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CONCLUSION
  The NRC and the U.S.  EPA take the view that there are no NRC-
U.S. EPA regulatory inconsistencies relative to mixed waste regulation.
Both agencies appear committed to address such inconsistencies brought
to their attention. The process for resolving regulatory inconsistencies
is unclear. Some  existing and prospective NRC-U.S. EPA  policy
statements could eliminate real or perceived regulatory inconsistencies.
In order to effectively eliminate real or perceived regulatory  incon-
sistencies, it would be preferable to vest one agency or the other with
exclusive or primary jurisdiction over mixed waste. Accomplishing this
designation could require a legislative change. No  such legislation is
pending.
  The RCRA hazardous waste land ban and storage restrictions place
mixed waste generators in a quandary. Untreated mixed waste may not
be stored or disposed of. There are inadequate mixed waste treatment
and disposal facilities. Although some covered waste is not land banned
until May 1992 under the third-third rule national capacity variance,
the situation may not be much different then.  Thus, mixed  waste
generators must obtain some form of regulatory relief or face potential
regulatory enforcement action.
  The  fact that some states exercise  NRC mixed waste regulatory
authority, that some state exercise the U.S. EPA mixed waste regulatory
authority, that some states exercise the U.S. EPA hazardous waste but
not mixed waste regulatory authority and that some states exercise in-
dependent hazardous waste  regulatory authority  not  derived from
RCRA, creates a potential patchwork of mixed waste regulatory pro-
grams at the state level. State radioactive waste regulatory policies may
differ from NRC radioactive waste regulatory policies. Therefore, the
degree to which a particular state exercises delegated federal mixed waste
regulatory authority or its own state regulatory authority will dictate
how certain mixed waste regulatory requirements are interpreted and
applied. Thus, the mixed waste generator must be aware of the regulatory
policies in the state in which it operates. It cannot rely solely on federal
regulatory policies which may or may not have been adopted by the state.


FOOTNOTES
1.  See 42 USC sec. 2224 (NRC agreement states) and 42 USC sec. 6926 (U.S.
   EPA-authorized states). State hazardous waste regulation may exist independent
   of EPA delegation. State radioactive waste regulations may exist indepen-
   dent of NRC delegation.
2.  The Atomic Energy Act (AEA) (42 USC sec. 2011-2296) and DOE Act (42
   USC sec. 7101-7375) authorize DOE to govern its own nuclear activities through
   the issuance of orders to protect public health, life and property, which could
   include standards controlling the design, location and operation of facilities
   associated with these activities. See 42 USC sec. 2201(i) (3). Doe nuclear
   activities include nuclear weapons production, uranium enrichment and
   nuclear research.
   DOE low-level radioactive waste management policy is contained in DOE
   Order 5280.2A and includes provisions on waste form acceptance criteria,
   site selection criteria, design criteria, operating procedures (including training,
   environmental monitoring, testing, site access and emergency planning) and
   closure and post-closure (including periodic surveillance and maintenance
   provisions). DOE hazardous and mixed waste management policy is con-
   tained in DOE Order 5400.3 and essentially invokes applicable U.S. EPA
   and state requirements.
3.  See Memorandum to NRC Licensees (Jan. 8,1987, as revised, Oct. 4,1989).
4.  See Memorandum to States and Low Level Waste Compacts (Mar. 13, 1987).
5.  See Memorandum to States, Compacts and Licensees (Aug. 3,  1987).
6.  The author has not seen the responses to this notice. However, a nuclear
   industry trade association has published a report comparing NRC and U.S.
   EPA mixed waste regulations and the impact of dual regulation on nuclear
   reactor and low-level radioactive waste disposal facility licensees. See "The
   Management of Mixed Low-Level Radioactive Waste in the Nuclear Power
   Industry," Nuclear management and Resources Council (January 1990).
7.  See U.S.  EPA Office of Solid Waste "Mixed Waste Training Course:
   1989/1990" summary outline at page  12.
                                                                                                                          TREATMENT    695

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            Remediation  of Solvent  Contaminated  Soils  by  Aeration
                                                     Andy Davis,  Ph.D.
                                                      Houston Kempton
                                                PTI  Environmental Services
                                                      Boulder, Colorado
                                                    Roger Olsen, Ph.D.
                                                 Camp,  Dresser  and McKee
                                                      Denver,  Colorado
ABSTRACT
  A bench-scale box test was performed to evaluate the feasibility of
rototilling  to  remediate  excavated  soils  contaminated  with
tetrachloroethylene  (PCE),  trichloroethylene  (TCE)   and
1,1,1-trichloroethane (1,1,1-TCA). Two soils containing different concen-
trations of the target analytes were tested. PCE in Soil A decreased
from 25,000 fig/kg to 5,053 /ig/kg within the first 24 hours (an 80%
decrease of the initial concentration) and to 834 /tg/kg after 407 hours.
PCE in Soil B decreased from 8,881 /*g/kg to 500 fig/kg (a 94% loss)
after 96 hours. The initial TCE concentration in Soil A was  1,100 /tg/kg,
decreasing to 30 jtg/kg after 408 hours. The initial TCE concentration
in Soil B was 1,573 jtg/kg decreasing to 37 fig/kg (a 98% loss) after
192 hours. The maximum PCE concentrations in the off-gas were 1.5
ng/mL and 0.8 ng/mL above Soils A and B respectively, during the first
24 hours of exposure. Subsequent air samples all were below 0.1 ng/mL
(the detection limit). Concentrations of TCE in the air above the soils
were below the detection limit (> 0.1 ng/mL) throughout the experi-
ment. Maximum 1,1,1-TCA air concentrations were 0.14 ng/mL during
the first 24 hours in Box A.

INTRODUCTION
  Chlorinated industrial solvents, e.g.,  tetrachloroethylene (PCE),
trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA), are among
the most common contaminants found at hazardous and industrial waste
sites.5 Remediation of soils contaminated with these compounds using
techniques such as solidification/stabilization, incineration, soil vapor
extraction, soil flushing or in situ biodegradation are expensive and
time-consuming alternatives.2'8 This contamination problem, requires
a simple and effective remedy; one such alternative is enhanced solvent
volatilization by excavation and  rototilling.
  A major concern with this option is the ensuing media transfer of
contaminants from the  soil to the urban atmosphere. However, once
exposed to ultraviolet radiation, these compounds readily photolyze in
the atmosphere (e.g., TCE t^ = 5.2 days3); while in the troposphere,
the unsaturated double bond is highly reactive,  rapidly degrading to
HCI, CO. CO, and  carboxylic acid with a rate constant of 3xl6ccmV
sec for TCE and 1.3xl6':cm'/sec for PCE." Consequently, volatiliza-
tion followed by degradation of the chlorinated compound in  the
atmosphere and troposphere appears lo be a simple, safe and effective
remedial option for soils contaminated with chlorinated  solvents.
  This study was designed to evaluate  the efficacy of a proposed aera-
uon technique (excavating, rototilling and exposing contaminated soils
to the atmosphere) in terms of the concentrations of solvents released
into (he atmosphere under ambient atmospheric conditions and the time
required to \ulaiilizc a significani «90"'c) proportion  of the con-
taminants To quantify removal rates of PCE. TCE and 1,1,1-TCA from
the contaminated soils, a bench-scale aeration test was performed in
an experimental environment similar to the anticipated field conditions.
Another facet of the investigation was to calculate the maximum mass
of PCE, TCE and 1,1,1-TCA potentially released to the atmosphere over
the course of the experiment.
  This study was undertaken to provide practical  data  on solvent
volatility from contaminated soils. Although the physical characteristics
of the three target compounds are well known, to date there has been
little investigation into their volatility from soils and water surfaces.
The only research that has been  reported12 focused on the release of
PCE from soil immediately following application. No work appears
to have been undertaken using soil that has been contaminated with
PCE for several years.

MATERIALS AND METHODS
  The aeration test apparatus consisted of two wooden boxes (60 cm
long, 30 cm wide and 15 cm deep) lined with aluminum foil to prevent
contaminant loss to the  wood. Two rectangular openings were cut at
each end, one a portal for a shaded pole fan and the other for an exit
vent. The fan was used to provide a constant 10 km/hr breeze over the
soil (characteristic of average wind speed  conditions  at the site)
monitored at each box exit using a hand-held anamometer.
  Two clay rich test soils were evaluated with Soil A containing >100
mg/kg  VOCs and Soil  B containing 10 to 20 mg/kg VOCs. After
sampling, the soils were shipped to  the laboratory on ice  in coolers
and maintained at 4°C until the start of the experiment. Each box was
filled with uncompacted soil to a depth of 30 cm, broken into clods
2.5 to 4 cm in diameter. These conditions were thought to be represen-
tative of a realistic depth  and the likely  size fraction resulting from
rototilling the soil. Samples from each box were then  taken in order
to establish initial soil conditions. After sampling, the boxes were closed
and placed in a ventilation hood.  The box fans were turned on and air
samples were collected  immediately. Every 24 hours  the entire soil
column was overturned and soil samples were collected after rototilling.
  The greatest variable in the soils was the moisture content of the clods,
determined using ASTM D2216-80,'  so this factor was incorporated
into the sampling strategy. After the soil had been tilled, four clods,
apparently representing  the range of moisture observed in the soil at
the time of sampling, were selected from each box. The clods were
aggregated and the blended soil was analyzed. Due to the volatile nature
of the compounds of interest, processing was performed quickly and
the composited samples  were placed in a glass vial containing as little
head space as possible. To evaluate solvent diffusion out of the clods,
the interior and exterior (rind) of Soil A clods were sampled on four
occasions. These samples were collected by removing and compositing
the exterior one centimeter from each of three clods. Moisture, PCE
       TREATMKNT

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and TCE were measured hi both rind and interior samples.
  Each representative sample weighed approximately 80 grams. Of this
amount, 30 grams were used for moisture analysis, 30 grams were split
into three 10-gram aliquots for chemical analyses and  the rest was
discarded. At the time of sampling, the relative humidity, wind speed
and temperature of the air in  the box  were recorded.
  Air sampling commenced immediately after the soils were placed
hi the boxes. Air samples were obtained using a 5-mL syringe through
the exit port at hourly intervals for the first 4 hours and men again after
30 hours. The fan on Box A was turned off overnight after the second
day and the box was sealed tightly in order to test the buildup of gas
over Soil A. Subsequently, air samples were collected before the fan
was  turned  on, 15 minutes  after  and  again after  rototilling.  To
characterize air quality over Soil B, three samples were collected over
a 1.5-hour period on the first  day and over a 1.5-hour period on the
second day. Between samples,  the syringes used to collect the samples
were flushed 10 times with air.
  Three separate 5-gram aliquots of soil were extracted in reagent grade
methanol following U.S. EPA method 5030, the extracts were analyzed
separately and the results averaged or the extracts combined and analyzed
together or the soil splits were combined prior to extraction. The ex-
tracts were analyzed for PCE, TCE and 1,1,1-TCA using a Purge and
Trap/Temperature Programmable Gas Chromatograph with a Hall detec-
tor hi the halogen specific mode (following U.S. EPA method 8010a).
  Quality assurance for the measurement of halogenated compounds
was monitored  four ways: by relative percent difference (RPD) of
duplicate analyses, by soil spiking, by adding blanks and by introducing
of a surrogate compound. To ensure analytical replicability, one duplicate
sample was run from Soil A each day.  For soils, the acceptable RPD
limit is +/-35%.10 With the exception of one TCE data point at a low
soil concentration,  the duplicate extractions all met this criterion.
  A blank was run to test for:  (1) cross contamination of soils during
the extraction step, (2) contaminants in the methanol extractant, (3)
contaminants on the glassware and (4) other contamination introduced
during analysis. No contamination was detected in any blank over the
course of the bench test. Each  day a split of blended Soil B was spiked
with a 1-mL mixture of the halogenated compounds of interest to deter-
mine a percent recovery for each analyte. The spike concentration
decreased with  time to reflect the decreasing soil analyte concentra-
tion in the unspiked soil. The spike recovery range for all analytes fell
between 60-140%,  also meeting the criteria established by  the U.S
EPA.10
  To ensure that the purge/trap extraction mechanism and the Hall
Detector were working properly, 100 ng of dichlorobromomethane were
added to each extract  and the percent  recovery of the surrogate was
calculated. The acceptable surrogate recovery range for soil methods
is 75-125%.10 The percent recovery of surrogate from these samples
ranged from 82 to  110% and averaged 95%.

RESULTS AND DISCUSSION
  Both soils were clay rich ranging in color from dark brown when
moist to light brown when dry.  The soil dried into clods that were very
difficult to break. Soil moisture averaged  18% at the start of the ex-
periment, decreasing to 2% after 7 days (Fig. 1). Percent moisture values
for rinds and ulterior samples fell below bulk percent moisture values
for both soils, although the rind and interior values measured after 24
hours lie within a similar percentage range. These data are indicative
of the heterogeneity of the soil  clods in contrast  with the more
homogenized sample used for the bulk soil test.
  The highest analyte concentrations determined were PCE, followed
by TCE and 1,1,1 TCA. Concentrations decreased most rapidly within
the first 24 hours, approaching an asymptote after approximately 150
hours. The initial PCE  concentration in Soil A was 25,000 /tg/kg,
decreasing to 5053 /tg/kg within 24 hours; a loss of 80% of the initial
concentration (Fig. 2). The PCE concentration decreased to 3330 /tg/kg
(an 87% decrease) after 48 hours and to 1000 /tg/kg  after 192 hours
(a 96% decrease).
  In Box B, the initial PCE concentration was 8880 /ig/kg (Fig. 2),
decreasing to 6290 /tg/kg after 24 hours (a 29 % decrease), to 2410 /tg/kg
after 48 hours (a 73% decrease) and to 500 /tg/kg after 192 hours (a
94% decrease). For both the rind and interior PCE analyses, the rind
concentration was less than the average clod concentration, which was
less than the interior PCE concentration. These data suggest that a dif-
fusive mechanism controlled release of PCE from the interior of the
clod (Fig. 2).
                100
                            200         300
                              Time (Hrs)

                            Figure 1
                       Soil Moisture Content
                                                    400
                                                                500
                             200       300
                              Time (Hrs)
                                               400
      8000000J


      6000000


      4000000


      2000000
                    100
                             200      300
                              Time (Hrs)
                                                       soo
                            Figure 2
              Concentration of PCE in Soils A and B
  TCE in Soil A was initially 1100 /tg/kg (Fig. 3) decreasing to 144
/tg/kg after 24 hours (an 87% decrease) and to 25 /tg/kg after 192 hours
(a 98% loss). In Soil B, the initial concentration of TCE (1573 /tg/kg)
was higher than Soil A.  An 84% loss of TCE (to 250 /tg/kg) was
measured in the first 24 hours. After 192 hours, the concentration had
decreased to 25  /tg/kg (a 98% loss).
                                               TREATMENT    697

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                           200       300
                            Time (Mrs)
                 100        200       300       400
                            Time (Hrs)

                             Figure 3
               Concentration of TCE in Soils A and B
  Both rind and interior samples taken after 24 hours contained less
TCE than the bulk sample soils. Soil A clods collected after 48 hours,
however, spanned the bulk concentration (Fig. 3).
  1,1,1-TCA  in Soil A behaved in a similar fashion to both TCE and
PCE, decreasing from 793 /ig/kg to 211 /«/kg (a  73% loss) after 24
hours and to 47 jig/kg (a 94% loss)  after 194 hours. A similar concen-
tration of 1,1,1-TCA (883 /ig/kg) was found in Soil  B. The evaporative
rate loss was similar; 87% after 24 hours and 96% after  194 hours.
  The initial PCE in Soil A air was 1.5 ng/mL and 0.8 ng/mL in Soil
B air. Air samples taken 24 hours after initial rototilling measured less
than 0.1 ng/mL (the detection limit) for both boxes.  The fans were then
turned off for  12 hours to allow a build-up of gas.  An air sample was
collected before the fans were turned on (PCE = 4.0 ng/mL)  and fifteen
minutes after the fan was turned on, at which time a concentration of
<0.1  ng/mL PCE was measured. No TCE concentrations above detec-
tion limits (0.1 ng/mL) were  measured at any time. Initial 1,1,1-TCA
soil gas concentrations were 0.14 ng/mL in Box A and  <0.1  ng/mL
in Box B. The 24 hour air sample  was below the  detection limit (0.1
ng/mL). After gas accumulated over the 12 hour period, 1,1,1-TCA was
0.18 ng/mL, but was below the detection limit 15 minutes after the fan
was turned on.
  Calculation of the mass flux of solvents from the soil to the atmosphere
on a daily basis demonstrates that the bulk of PCE,  TCE and 1,1,1-TCA
is released  over the first 24 hours  (Table 1), after which the solvent
flux decreased substantially.
  The initial rapid loss of volatiles followed by a slow, longer term
decline in solvent concentrations suggests a dual release mechanism.
The initial rapid decrease in soil concentrations probably corresponds
to evaporation of interstitial water containing high solvent  concentra-
tions, a "labile" fraction. Solvents in this fraction  would  be lost to the
atmosphere  at a rate governed by the  vapor phase concentration and
the gaseous diffusion. These parameters are well-known from Henry's
Law constant and the diffusivity coefficient, so it is not surprising that
PRZM accurately simulated the initial volatilization rate.
  The more lightly bound "refractory" fraction comprises only a small
perceni of the  total solvent mass, but is responsible for the asymptotic
behavior of the soil concentration  curve after the labile fraction has
volatilized. This refractory solvent content ranged  from 2.7% (TCE in
                                                                         Soil A) to 8.1% (TCA in Soil B). PCE had the highest refractory frac-
                                                                         tion of the total mass, consistent with its high Kow.. Research by Zytner
                                                                         et al.12 demonstrated that the volatilization rate of pure PCE after a
                                                                         recent soil application is 4 to 5 times slower than PCE dissolved in
                                                                         water, indicating that the volatilization rate of PCE  from soil also
                                                                         depends on the form in which PCE enters the unsaturated zone. In ad-
                                                                         dition,  Petersen  et al.6  found that TCE partition coefficients were
                                                                         higher for dry soils than for moist soils, while Smith et al.7 in a field
                                                                         study at Picatinny Arsenal, New Jersey, also demonstrated that TCE
                                                                         sorption was  highly dependent  on the soil  humidity.
                                                                                                               * M.t.und t.l.l-TCA

                                                                                                              	 Mod«l«d 1,1.1-TCA
                                                                                                   200       300
                                                                                                     Time (Hrs)
                                      * M.«.ur.d 1,1,1-TCA

                                     	 Uod*l«d 1.1,1-TCA
                          200       300       400       600
                            Time (Hrs)
                           Table 1
            Loss of Solvents From Soils A and B
              PCE
                                  TCE
                                                    1.1.1-TCA
        Day 1
                  Day 2
                            Day 1
                                     Day 2
                                                Day 1
                                                          Day 2
Soil A 1.30
Soil B 0.46
0.16
0.07
0.06
0.08
0.01
0.01
0.04
0.05
0.003
0.004
  All these investigations support the labile/refractory hypothesis ad-
vanced here. The practical effect of the dual volatilization mechanisms
on the simulated soil concentrations is to overestimate solvent degass-
ing, hence underestimating residual soil concentrations after volatiliza-
tion of the labile solvent fraction. However, it is important to note that
the refractory solvent fraction is invariably less than 10% of the total
concentration, so that the error introduced in the simulations is not great.

REFERENCES
 1. American Society for Testing and Materials. Standard Method for Deter-
   mination of Wuer (Moisture) Content of Soil, Rock and Soil-Aggregate Mix-
   tures. Section 04.08, ASTM, Philadelphia,  PA., 1986.
       TREATMENT

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2. Boyer, J.D., Ahlert, R.C. and Kosson, D.S., Pilot plant demonstration of
  in-situbiodegradationof 1,1,1-Trichloroethane. JWPCF, 60pp. 1843849,1988.
3. Cuppitt, L.T. Fate of Toxic and Hazardous Materials in the Air Environ-
  ment. EPA-600/53-80-084. U.S. EPA, Athens, GA,  1980.
4. Davis, S.N. "Porosity and Permeability of Natural Materials,"  in Flow
   Through Porous Media, Ed. R.J.M. DeWiest, pp. 54-89, Academic Press,
   New York, NY, 1969.
5. Hallstedt, P.A., Puskar, M.A. and Levine, S.P. "Application of the hazard
   ranking system to the prioritization of organic compounds identified at hazar-
   dous waste remedial action sites," Haz.  Hfcste Haz. Mat., 3, pp 221-232,1986.
6. Peterson, M.S., Lion, L.W. and Shoemaker, CA. "Influence of vapor-phase
   sorption and diffusion on the  fate of trichloroethylene in an unsaturated
   aquifer system." Environ.  Sri. Technol., 22, pp.  571-578, 1988.
7. Smith, J.A., Chiou, C.T., Rammer, T.A. and Kile,  D.E. "Effect  of soil
   moisture on the sorption of trichloroethene vapor to vadose-zone soil at
    Picatinny Arsenal, New Jersey." Environ. Sci. Technol., 24, pp. 676-683,
    1990.
 8.  Stief, K. "Remedial Action for Groundwater Protection Case Studies Within
    the Federal Republic of Germany," in Proc.  5th National Conference on
    Management of Uncontrolled Hazardous Waste Sites, HMCRI, Washington,
    D.C., 1984.
 9.  U.S.  EPA.  Test Method* for Evaluating Solid  Waste Physical/Chemical
    Methods, SW-846, 3rd edition. U.S. Office of Solid Waste and Emergency
    Response. U.S. EPA, Washington, D.C., 1987.
10.  U.S.  EPA. Contract Laboratory Statement of Work for Organic Analysis,
    Multi-Media, Multi-Concentration. U.S.  EPA, Washington, D.C., 1988.
11.  Yung, Y.L., McElroy, M.B. and Wofsy, S.C. "Atmospheric halocarbons:
    a discussion with emphasis on chloroform."  Geophysical Res.  Letters, 2,
    pp. 397-399, 1975.
12.  Zytner, R.G., Biswas, N. and Bewtra, J.K. "PCE volatilized from stagnant
    water and soil."./.Environ. Eng., 115, pp. 1199212  1989.
                                                                                                                                  TREATMENT    699

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           The Challenge oflteating  Contaminated Superfund Soil


                                                   Carolyn K. Offutt
                                        U.S. Environmental Protection Agency
                                   Office of Solid Waste and Emergency Response
                                                   Washington, D.C.
                                                 Joan O'Neill Knapp
                                         CDM Federal Programs Corporation
                                                    Fairfax,  Virginia
  ABSTRACT

     The purpose of this paper is to provide an analysis of the effective-
  ness of treatment technologies for contaminated soil and debris in
  response to the recommendation in the 1989 U.S. Environmental
  Protection Agency Superfund Management Review to "carefully
  evaluate the impact of RCRA land ban and other rules on the use of
  alternative technologies."  This analysis provides support to Re-
  gional decisions to employ treatability variances for complying with
  the RCRA Land Disposal Restrictions as applicable or relevant and
  appropriate requirements (ARARs) for Superfund actions involving
  contaminated soil and debris.

  INTRODUCTION

     The 1989 Superfund Management Review (also known as the 90-
  Day Study) by the U.S. Environmental Protection Agency acknowl-
  edged that Superfund response actions may not be able to meet
  treatment standards based on "best demonstrated available technol-
  ogy" (BOAT) under the Land Disposal Restrictions (LDRs). This
  regulation may limit the potential treatment technologies available
  for Superfund cleanups, with  technologies  such as  soil washing,
  stabilization  and biological treatment being precluded because they
  may not meet the highest level of performance required by LDRs. In
  contrast, the 90-Day Study encouraged the greater use of innovative
  technologies and urged the reduction of nontechnical barriers, such
  as regulatory and policy constraints, that inhibit the use of treatment
  technologies, while preserving the intent and spirit of applicable
  RCRA regulations.
     Office of Solid Waste and Emergency Response (OSWER) pro-
  gram offices recognized the potential limitation on treatment tech-
  nologies for Superfund actions and developed a process to use LDR
  treatability variances for soil and debris. Guidance was issued to the
  Regions through the Superfund LDR Guide 6A, "Obtaining a Soil
  and Debris Treatability Variance for Remedial Actions," (OSWER
  Directive 9347.3-06FS) in  July  1989 and  revised in  September
  1990.' Superfund LDR Guide 6B, "Obtaining a  Soil and Debris
  Treatability Variance for Removal Actions," (OSWER Directive
  9347.3-07FS) was issued in December 1989 and revised in Septem-
  ber 1990.4 These guides describe the treatability variance process,
  include alternaic treatment levels to be obtained under treatability
  variances and identify treatment technologies which have achieved
  ihc recommended levels.   OSWER recognizes  that the use of
  ireaiabilii v variances represents an interim approach and is currently
  in ihe process of acquiring additional daia for developing a regulation
  on treatment standards for contaminaied soil and debris.
  On November 30,1989, the Office of Emergency and Remedial
Response (OERR) issued a memorandum on the  "Analysis of
Treatability Data for Soil and Debris: Evaluation of Land Ban Impact
on Use of Superfund Treatment Technologies," (OSWER Directive
9380.3-04).2 This memorandum was in response to the concern in the
Superfund Management Review regarding limitations to the use of
alternative technologies at Superfund sites: it included an analysis
summarizing the effectiveness of treatment technologies applied lo
soils and other environmental wastes. The memorandum provides
support for decisions by the Regions to use treatability variances,
when appropriate. The analysis identifies some of the key technical
considerations to be evaluated in obtaining a treatability variance
when there is a reasonable doubt that a technology operated at full-
scale cannot consistently meet the BOAT treatment standards for the
soil and debris to be treated.

ANALYSIS OF TREATMENT EFFECTIVENESS

  An extensive  effort was  undertaken during 1987  and  1988 to
collect data on the treatment of soil, sludge, debris and related
environmental media. The results from several hundred studies were
collected and reviewed. All applicable treatment information from
67 studies was extracted, loaded into a data base and analyzed to
determine the effectiveness of technologies to treat different chemi-
cal groups (Summary of Treatment Technology Effectiveness for
Contaminated Soil, U.S. EPA, EPA/540/2-89/053).1
  Although some of the data on which the analysis is based have
limited quality  assurance information,  the data, nevertheless, do
indicate potential effectiveness (at least 90% to 99% reduction of
concentration or mobility of hazardous constituents) of treatment
technologies to treat Superfund wastes. Some reductions in organic
concentrations or organic mobility of more volatile compounds may
actually represent the removal of those compounds as a direct result
of volatilization.  Technologies where this is most likely to occur
include dechlorination, bioremediation, soil washing or immobiliza-
tion, and consideration of appropriate emission controls is required.
Percentage removal reductions (removal efficiencies) are not always
a good measure of effectiveness, especially when high concentra-
tions remain in the residuals. Some of the performance observations
are based upon a relatively small number of data points and may not
extrapolate well to the broad array of soils requiring treatment.
  Based on this analysis, a number of technologies commonly used
in the Superfund program provide substantial reduction in mobility
and toxicity of wastes as required in Section 121 of the Superfund
Amendments and Reauthorization Act (SARA) of 1986.  For ex-
ample:
"00   TREATMENT

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• Thermal destruction has been proven effective on all organic
  compounds, usually accomplishing well over 99% reduction of
  organics.
• Although the data indicate that PCBs, dioxins, furans and other
  aromatic compounds have been dechlorinated to approximately
  80%, more recent  data indicate that removal efficiencies may
  approach 99.9%.
• Bioremediation successfully treats many halogenated aliphatic
  compounds, nonhalogenated aromatics, heterocyclics and other
  polar compounds with removal efficiencies in excess of 99%.
• Removal efficiencies for low temperature  thermal  desorption
  have been demonstrated with averages up to 99% for nonpolar ha-
  logenated aromatics and with treatment often exceeding 90% for
  other polar organics.
• Soil washing data  on organic compounds indicate average re-
  moval efficiencies of approximately 90% for polar nonhaloge-
  nated organics and 99% for halogenated aromatics, with treatment
  often exceeding 90% for polynuclear aromatics.  The chemical
  extraction process, with optimized solvent selection, has demon-
  strated removal efficiencies often exceeding 90% for volatile and
  nonvolatile metals.
 • Immobilization processes, while not actually destroying the or-
  ganic compounds, reduce the mobility of contaminants an average
  of 99% for polynuclear aromatic compounds.  Immobilization
  may not effectively stabilize some organic compounds, such as
  volatile organics, and the long-term effectiveness of immobiliza-
  tion of organics is under evaluation. Immobilization can achieve
  average reductions in mobility of 93% for volatile metals, with
  reductions in mobility often exceeding 90% for nonvolatile met-
  als.

  A more detailed summary of the data follows, extracted from the
 "Summary of Treatment Technology Effectiveness for Contami-
 nated Soil."

 TECHNOLOGY LIMITATIONS TO BE CONSIDERED

  The data available suggest that the treatment of soil and debris
 with organic contamination by technologies  other than thermal
 destruction will not consistently achieve BDAT standards.  There-
 fore, other technologies should be used for those wastes only if
 approved under a treatability variance.
  The residual concentrations in contaminated soil treated by tech-
 nologies other than thermal destruction are highly dependent upon
 the concentrations in the untreated soil. Therefore, when evaluating
 technologies other than thermal destruction, the ability of those
 technologies to treat high concentrations  of organics should be
 considered.
  Site conditions and characteristics must be carefully considered
when designing and operating materials handling, pretreatment and
treatment requirements. High variability in contaminant concentra-
tions of untreated soil may have an adverse effect on the ability to
achieve treatment levels using technologies  other than thermal
destruction. Consideration should be given to the need for blending
wastes. In selecting technologies for contaminated soils and sludges,
the number and types of contaminants must be carefully screened,
and, in some cases, different technologies may be necessary for soils
and sludges.

UNIQUE CONSIDERATIONS OF SOIL TREATMENT

  The complex nature of solid waste matrices, such as contaminated
soil from a Superfund site, severely complicates  the  treatment
process. Soil is a nonhomogeneous living medium and the propor-
tion of clay, organic matter, silt, sand, debris and other constituents
can affect the treatability of a contaminated soil.  In addition, the
distribution of contaminants often is also nonhomogeneous and is
dependent on patterns  of contaminant  deposition and  transport.
Collectively, these conditions make the treatment of contaminated
soil a formidable technical challenge. Discussions of some impor-
tant considerations relevant to the selection of soil treatment proc-
esses follow.
  A critical element in soil treatment is materials handling. Special
approaches to waste transfer throughout the treatment system are
particularly important for solids and viscous sludges where tradi-
tional conveyance methods are frequently ineffective.   Slugs of
material or debris tend to jam treatment equipment, resulting in
breakage, downtime and the potential for uncontrolled releases to the
environment. Materials handling equipment should be tested on the
waste as part of any treatability testing program. Experiments should
be conducted on an untreated waste as well as on any intermediate
mixtures exhibiting changes in viscosity, particle size, density, etc.
  The preprocessing of waste to maximize homogeneity and modify
the waste characteristics is important to successful treatment tech-
nology operation.  Any treatment  technology will operate most
efficiently and cost effectively  when it is designed and utilized to
treat a homogeneous waste with a narrow range of physical/chemical
characteristics. If contaminant types and concentrations,  waste
viscosity, BTU content,  moisture content, acidity, alkalinity,  etc.
vary widely, control of the system can be difficult and costly to
maintain. Many of these waste  characteristics can be modified and
improved with appropriate preprocessing.
  In addition, the most effective technology performance is achieved
when the soil particle size is small and the  maximum amount of
surface area is exposed.  This condition facilitates intimate contact
between the contaminant sorption sites and the driving force of the
technology (i.e., microorganism, solvent, warm air, etc.). The key to
achieving this contact, and subsequent contaminant destruction,
transfer to  another medium or bonding,  is often achieved only
through significant preprocessing.
  Materials handling and preprocessing technologies with potential
application for soil are currently in use in the construction, agricul-
ture and mining industries. All  of these industries routinely handle
large quantities of soil or rock.  The use of technologies from these
industries should be considered during all soil remediation activities.
Materials handling and preprocessing techniques should also be
incorporated in treatability testing programs.  The results of such
tests will better define the range of waste characteristics which the
actual treatment technology will have to address.

CONCLUSIONS REGARDING SOIL TREATMENT
TECHNOLOGY EFFECTIVENESS

  Contaminated soils  can  be treated through three basic mecha-
nisms: (1) destruction of the contaminants through chemical altera-
tion to a less toxic compound (e.g., thermal destruction, dechlorina-
tion and bioremediation); (2) physical transfer of the contaminants
to another waste stream for subsequent treatment or recovery (e.g.,
low temperature thermal desorption and chemical extraction and soil
washing); and (3) permanent bonding of the contaminants within a
stabilized matrix to prevent future leaching (e.g., immobilization).
In general, the destruction technologies effectively reduce the toxic-
ity of many organic contaminants. The physical transfer technolo-
gies reduce the toxicity and often the volume of selected organic and
inorganic contaminants.  While  the bonding technologies most
effectively reduce the mobility  and, therefore, the toxicity of inor-
ganic contaminants, some increasing effectiveness is being demon-
strated on selected organic contaminants as well. Figure 1 presents
a summary of these basic conceptual conclusions.  A more detailed
discussion follows.
  The technologies that have been widely demonstrated on soils are
thermal destruction for organic contaminants and immobilization for
inorganic contaminants.  While  these two  technologies may be
highly effective in treating particular classes of compounds, neither
provides  an ideal solution to  complex mixtures of organic  and
inorganic contaminants which are common at Superfund sites.  The
inherent difficulty in treating contaminants in a soil matrix,  where
                                                                                                               TREATMENT   701

-------
wasle conveyance and mixing are in themselves complicated unit
operations, contributes to the need to find special solutions. Other
issues, such as landfill capacity and cost, cross-media impacts and
natural resource conservation, also support the need to develop and
use alternative and innovative treatment technologies for contami-
nated soil.
Contaminant
Volatile
Organics
Semi-Volatile
Organics
Metals
Technology
Physical Transfer
or Recovery
•
Q
e
Destruction
•
•
X
Stabilization
X
9
•
      •  Demonstrated Effectiveness  X Not Effective, Not Advised

      ®  Potential Effectiveness
         (More Data Required)

                           Figure 1
          Soil Treatment Effectiveness - Conceptual Approach

   Because of the U.S. EPA's ultimate goal of developing LDRs for
 contaminated soil and debris,  this study evaluates a number of
 treatment options that are applicable to excavated soils. In situ soil
 techniques, such as some types of bioremediation, soil vapor extrac-
 tion, in situ immobilization and combined groundwater and vadose
 zone soil treatment were not included in the scope of this evaluation.
 In situ techniques should  also be considered  when researching
 remediation measures for a contaminated soil problem. When in situ
 technologies are used at Superfund sites, the LDRs may not be
 applicable  because the waste has not been excavated and subse-
 quently "placed" in a landfill or other RCRA unit.
   Based upon the data collected and evaluated by OERR from more
 than 200 soil treatment tests, conclusions were developed regarding
 the effectiveness of six soil treatment technology groups on each of
 11 contaminant treatability groups.  For  destruction and physical
 transfer technologies applied to organic contaminants, the removal
 efficiency was analyzed. This evaluation factor was replaced by the
 reduction in mobility for immobilization for organics and inorgan-
 ics,  and for chemical extraction and soil washing of inorganics.
   In Figure 2, "Predicted Treatment Effectiveness for Contaminated
 Soil," summary information is provided for each of 11 contaminant
 treatability groups and six treatment technology categories. For each
 treatability group, the effectiveness of various technologies is evalu-
 ated using the following ratings:
 •  Demonstrated Effectiveness: A significant percentage of the data,
   at least 20%, is from pilot- or full-scale operations, the average
   removal efficiency for all of the data exceeds 90% and there are at
   least 10 data pairs.
 •  Potential Effectiveness: The average removal efficiency for all of
   the data exceeds 70%.
 •  No Expected Effectiveness: The average removal efficiency for
   all of the data is less than 70% and no interference is expected to
   this process as a result of this group.
 •  No Expected Effectiveness: Potential adverse effects to the envi-
   ronment or the treatment process may occur.  For example, high
  concentrations of metals  may interfere with biological treatment.

   In some cases, a different rating was selected when additional
 qualitative  information and engineering judgment warranted. Two
 ratings were  selected if the compounds within a treatabilily group
 were so variable thai a range of conclusions could be drawn for a
 particular technology.

                                                                                          o'
                                                                                          o'
                                                                                                   O'
                                                                                                  ox'
                                                                                                  ox
                                                                                                           o'
                                                                                                           o'
                                                           e1
                                                                                                                             e'
                                                                                                                             e1
                           Figure 2
        Predicted Treatment Effectiveness for Contaminated Soil

Thermal Destruction (See Figure 3)

Principle of Operation
• Thermal destruction uses high temperatures to incinerate and
  destroy hazardous wastes, usually by converting the contaminants
  to carbon dioxide, water and other combustion products in the
  presence of oxygen.

Effectiveness on Organics
• This technology has been proven effective on all organic com-
  pounds, usually accomplishing well over 99% removal.
• Thermal destruction technologies are equally effective on haloge-
  nated, nonhalogenated, nitrated, aliphatic, aromatic and polynu-
  clear compounds.
• Incineration of nitrated compounds such as trinitrotoluene (TNT)
  may generate large quantities of nitrous oxides.

Effectiveness on Inorganics
• Thermal destruction is not an effective  technology  for treating
  soils contaminated with high concentrations of some metals.
• High concentrations of volatile metal compounds (lead) present a
  significant emissions problem which cannot be effectively con-
  tained by conventional scrubbers or electrostatic precipitators due
  to the small particle size of metal-containing particulates.
• Nonvolatile metals (copper)  tend to remain in the soil when
  exposed to thermal destruction; however, they may slag and foul
  the equipment.

Dechlorination (See Figure 4)

Principle of Operation
• Dechlorination is a destruction process that uses a chemical reac-
  tion to replace chlorine atoms in the chlorinated aromatic mole-
  cules with an ether or hydroxyl group. This reaction converts the
  more  toxic compounds into less toxic, more water-soluble prod-
  ucts. The transformation of contaminants within the soil produces
  compounds that are more readily removed from the  soil. An
  evaluation of the end products is necessary to determine whether
  further treatment is required.

Effectiveness on Organics
• PCBs, dioxins, furans and other aromatic compounds (such as
  pentachlorophenol) have been dechlorinated to approximately
     TREATMENT

-------
TREATABIUTY GROUP
NON-POLAR
HALOSENATED
AROMATICS


PCB4,
HALOSENATED
DIOXINS. FURANS.
AND THEIR
PRECUSORS
(W02)

HALOGENATEO
PHENOLS, CRESOLS,
AMINES, THIOLS.
AND OTHER POLAR
(WM)

HALOSENATED
ALIPHATIC
COMPOUNDS
(W04)

HALOGENATED CYCLIC
ALIPHAT1CS, ETHERS,
ESTERS, AND
(W05)

NITRATED
COMPOUNDS
(W06)


HETEROCYCUCS
AND SIMPLE
NON-HALOSENATED
AROMATICS
(W07)


POLYNUCLEAR
AROMATICS
(W06)

OTHER POLAR
NON-HALOSENATED
ORGANIC
COMPOUNDS
(W09)

NON-VOLATILE
METALS
(W10)

VOLATILE
METALS


NUMBER AND WALE
OF AVAILABLE DATA
32 PAIRS
	 ?_% BENCH
9* * PILOT
0 XFULL

161 PAIRS
	 3% BENCH
83 % PILOT
1* %FULL

	 91 PAIRS
92 % BENCH
2 * PILOT
6%FULL

« PAIRS
21 % BENCH
79 * PILOT
°%FULL

11BPAIR3
	 ?Z* BENCH
33* PILOT
O*FULL

142 PAIRS
	 73* BENCH
27% PILOT
OSFULL

42 PAIRS
	 7_* BENCH
88 % PILOT
5 *FULL

24 PAIRS
33 % BENCH
59% PILOT
	 8_%FULL
34 PAIRS
35 % BENCH
65 % PILOT
0 «FULL

	 0 PAIRS
	 0% BENCH
0% PILOT
0 SFULL

	 0 PAIRS
	 °% BENCH
0 % PILOT
°%FULL

AVERAGE CONCENTRATIONS (ppm)
AND % REMOVALS
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 590 >99 %
TREATED 0.024

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
|ppm) EFFICIENCY
UNTREATED 1,100 >99 %
TREATED 0.055

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 550 96 *
TREATED 0.70

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 41 >99 %
TREATED 0.016

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 790 99 %
TREATED 17

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 98,000 99 %
TREATED 200

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 740 >99 %
TREATED 0.077

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 1.200 >99 %
TREATED 0.32
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 990 	 98. %
TREATED 0.28

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 0 0 T.
TREATED 0

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 0 On.
TREATED 0

GENERAL OBSERVATIONS
This technology works very well at optimum operating conditions on a variety of Initial concentrations.
Bromlnated compounds will Inhibit dame propagation.
High levels of acid gases produced In the presence of oxygen will attack the refractory walls and
exposed metal surfaces.


• This technology works very well at optimum operating conditions on a variety of Initial concentrations.
• High levels of acid gases produced In the presence of oxygen will attack the refractory walls and
exposed metal surfaces.


• This technology works well at optimum operating conditions on a variety of Initial concentrations.
• Oxides of nitrogen and sulfur can create potential serious cross media Impacts If not removed
from gas emissions.
• High concentrations of add gases produced In the presence of oxygen will attack the refractory walls
and exposed metal surfaces.

• This technology works well at optimum operating conditions on a variety of Initial concentrations.
• If this Is the only treatablllty group present, low temperature thermal desorption may be more cost
effective.
• High levels of acid gases produced In the presence of oxygen will attack the refractory walls and
exposed metal surfaces.

• This technology works well at optimum operating conditions on a variety of Initial
concentrations.


• This technology works well at optimum operating conditions on a variety of Initial concentrations.
• High amounts of nitrous gases may be released Into the atmosphere If not controlled by a nitrous
oxide burner.


• This technology works very well at optimum operating conditions on a variety of Initial
concentrations.
• Low temperature thermal desorption may be more cost effective.


• This technology works very well at optimum operating conditions on a variety of Initial
concentrations.

• This technology works well at optimum operating conditions on a variety of Initial
concentrations.

• The physical and/or chemical characteristics of the constituents of this treatablllty
group Indicate that this technology would not be effective.
• Pyrolysls and Infrared thermal destruction of wastes with metal concentrations over 500 ppm may


• This technology Is not recommended If the waste contains high concentrations of volatile metals,
due to potential volatilization of these metals with subsequent cross media Impacts.
• Pyrolysls and Infrared thermal destruction may reduce the mobility of these metals by binding the
metals Into the solid residue.


                        Figure 3
Final Conclusions by Treatment Technology - Thermal Destruction
                                                                              TREATMENT    703

-------
TDCATUil/TT (MOUT
NOHJXXAB
HALOGENATED
AftOMATICS

pea.,
HALOGENATED
DIOJUNS. FURANS.
PRECURSORS
fWOJ)

HALOQENATED
PHENOLS. CRESOLS.
AMNES. THKX3.
AND OTHER POLAR



OTHER POLAR
NON-HALOGENATED
OBQANIC
(W0»|

NON- VOLATILE
UETALS


VOLATILE
METALS


NUMKR AMD SCALE
Of AVAILABLE DATA
	 ? PAIRS
100 x BENCH
OXPILOT
OXFUU.
	 31 PAIRS
_W%BENCH
3* PILOT
0 %FULL

	 8 PAIRS
tOO % BENCH
0% PILOT
0%FULL

	 16 PAIRS
'00% BENCH
OxPILOT
o XFUU.

	 0 PAIRS
	 0% BENCH
OXPILOT
OXFULL

	 0 PAIRS
	 Ox BENCH
OXPILOT
Ox FULL

24 PAIRS
100 X BENCH
0 X PILOT
0 XFUU.

5 PAIRS
100 % BENCH
0 X PILOT
0 XFULL

_J! PAIRS
100
	 X BENCH
o
X PILOT
o
XFULL

	 0 PAIRS
	 °_XBENCH
°X PILOT
0 XFULL

	 0 PAIRS
°XBENCH
OXPILOT
°XFULL

AVERAGE COttCEMTHATlOKS (ppm)
AMD X REMOVALS
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(pp.) EFFICIENCY
UNTREATED 190 98 X
TREATED 1.6
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(pen) EFFICIENCY
UNTREATED 130 83 X
TREATED 1.6

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppn! EFFICIENCY
UNTREATED 98 96 X
TREATED 2.4

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(Ptm) EFFICIENCY
UNTREATED 330 98 X
TREATED 0.44

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm) EFFICIENCY
UNTREATED 0 Ox
TREATED 0

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppn) EFFICIENCY
UNTREATED 0 Ox
TREATED 0

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
Ippm) EFFICIENCY
UNTREATED 2,200 98 X
TREATED 23

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm| EFFICIENCY
UNTREATED 3.600 91 X
TREATED 190

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm| EFFICIENCY
UNTREATED 1.700 96 X
TREATED 30

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
Ippnj EFFICIENCY
UNTREATED 0 0 X
TREATED 0

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
Ippn) EFFICIENCY
UNTREATED 0 0 X
TREATED 0

GENERAL OtSCTVATtONS
• Data were for chtorobenzene only. These data suggest that this technology Is potentially effective
In certain situations.

• This technology Is potentially effective, especially for sandy soils.
• Data on sludges show better removal due to more uniform distribution of contaminants and better
reagent contact.
• Lower Initial concentrations give lower removal efficiencies.
• Parade size and soil matrix affect reagent penetration and process effectiveness.
(des Roslers. 1986).
• Data were lor pentachlorophenol only. These data suggest that this technology Is potentially
effective In certain situations.
• Recent data Indicate that greater than 99% of contaminants can bo destroyed
(des Hosiers. 1988).


• These data suggest that this technology Is potentially effective In certain situations.
• Some halogenated aliphatics react with the APEG reagents to form explosive compounds,
especially In the presence of heavy metals. The potential for this to occur should be evaluated
• The high removal efficiency may be the result of volatilization or the APEG process acting as a

• Data were not available for this treatabillty group. Data for compounds with similar
physical and chemical characteristics suggest that this technology Is potentially effective
In certain situations. Treatabillty studies will be needed to confirm the technology's
effectiveness.


• Data were not available available for this treatabillty group.
• The physical and/or chemical characteristics of the constituents of this treatabillty
group Indicate that this technology would not be effective.


• The physical and/or chemical characteristics of the constituents of this treatabillty
group suggest that this technology would ool be effective.
• The high removal efficiency may tie the result of volatilization or the APEG process
acting as a soil washing process.


• The physical and/or chemical characteristics of the constituents of this treatabillty
group suggest that this technology would not be effective.
• The high removal efficiency may be the result of volatilization or the APEG process
acong as a soil washing process.


• The physical and/or chemical characteristics of the constituents of this treatabillty
group suggest that this technology would not be effective.
• The high removal efficiency may be the result of volatilization or the APEG process
acong as a soil washing process.


• The physical anovor chemical characteristics of the constituents of this treatabillty
group suggest thai this technology would not be effective.


• The physical and/or chemical characteristics of the constituents of this treatabillty
group suggest that this technology would not be effective.


                                                                      Figure 4
                                              Final Conclusions by Treatment Technology - Dcchiorination
-IU    TRFATMENT

-------
       removal, with more recent data indicating that removal
  efficiencies may approach 99.9%.
• Other limited laboratory data suggest potential applicability to
  other halogenated compounds including straight-chain aliphatics
  (such as 1,2-dichloroethane).  The removal indicated by the data
  may be due in part to volatilization.
• Although no data were available for halogenated cyclic aliphatics
  (such as dieldrin), it is expected  that dechlorination will be
  effective on these compounds as well.
• When nonhalogenated compounds are subjected to this process,
  volatilization may occur.

Effectiveness on Inorganics
• Dechlorination is not effective on metals, and high concentrations
  of reactive metals (such as aluminum), under very alkaline condi-
  tions, hinder the dechlorination process.

Bioremediation (See Figure 5)

Principle of Operation
 • Bioremediation is a destruction process that uses soil microorgan-
  isms including bacteria, fungi and yeasts to chemically degrade
  organic contaminants.

 Effectiveness on Organics
 • Bioremediation appears to successfully treat many halogenated
  aliphatic compounds (1,1-dichloroethane), nonhalogenated aro-
  matics (benzene), heterocyclics (pyridine) and other polar com-
  pounds  (phenol) with  removal efficiencies in excess of  99%;
  however, the high removal implied by the available data may be
  a result  of volatilization in addition to bioremediation.
 • More complex  halogenated (4-4'DDT), nitrated (triazine) and
  polynuclear aromatic (phenanthrene) compounds exhibited lower
  removal efficiencies, ranging from approximately 50% to 87%.
 • Polyhalogenated compounds may be toxic to many microorgan-
  isms.

 Effectiveness on Inorganics
 • Bioremediation is not effective on metals.
 • Metal salts may be inhibitory or toxic to many microorganisms.

 Low Temperature Thermal Desorption (See Figure 6)

 Principle of Operation
 • Low temperature thermal desorption is a physical transfer process
  that uses air, heat and/or mechanical agitation to volatilize con-
  taminants into a gas stream, where the  contaminants are then
  subjected to further treatment. The degree of volatility of the
  compound rather than the type of substituted group is the limiting
  factor in this process.

Effectiveness on Organics
• Removal efficiencies have been demonstrated by these units at
  bench, pilot and full scales, ranging from approximately 65% for
  polynuclear aromatics (naphthalene) to 82% for other polar organ-
  ics (acetone) and 99% for nonpolar halogenated aromatics (chlo-
  robenzene).

Effectiveness on Inorganics
• Low temperature thermal desorption is not effective on metals.
• Only mercury has the potential to be volatilized at the operating
  temperatures of this technology.

Chemical  Extraction and Soil Washing (See Figure 7)

Principle of Operation
• Chemical extraction and soil washing are physical transfer proc-
  esses in  which contaminants are disassociated from the soil, be-
  coming  dissolved or suspended in a liquid solvent.  This liquid
  waste stream then undergoes subsequent treatment to remove the
  contaminants and the solvent is recycled, if possible.
• Soil washing  uses  water as the  solvent  to separate the  clay
  particles, which contain the majority of the contaminants, from the
  sand fraction.
• Chemical extraction processes use a solvent which separates the
  contaminants from the soil particles and dissolves the contaminant
  in the solvent.

Effectiveness on Organics
• The majority of the available soil washing data on organic com-
  pounds indicates removal efficiencies of approximately 90% for
  polar nonhalogenated organics (phenol) to  99% for halogenated
  aromatics (chlorobenzene), with lower values of approximately
  71% for PCBs to 82% for polynuclear aromatics (anthracene).
• The reported effectiveness for treatment  of these compounds
  could be due in part to volatilization for compounds with higher
  vapor pressures (such as acetone).
• This process is least effective for some of the less volatile and less
  water soluble aromatic compounds.

Effectiveness on Inorganics
• The chemical extraction process, with optimized solvent selec-
  tion, has demonstrated removal efficiencies of 85% to 89% for
  volatile metals (lead) and nonvolatile metals (copper), respec-
  tively.

Immobilization (See Figure 8)

Principle of Operation
• Immobilization processes reduce the mobility of contaminants by
  stabilizing them within the soil matrix without causing significant
  contaminant destruction or transfer to another medium.
• Volatile organic compounds will often volatilize during treat-
  ment, therefore an effort should be made to drive  off these
  compounds in conjunction with an emission control system.

Effectiveness on Organics
• Reductions in mobility for organics range from 61% for haloge-
  nated phenols  (pentachlorophenol) to 99%  for polynuclear aro-
  matic compounds (anthracene).
• Immobilization is also effective (84% reduction) on halogenated
  aliphatics (1,2-dichloroethane).
• Some organic mobility reductions of the more volatile compounds
  may actually be removals as a direct result of volatilization during
  the exothermic mixing process and throughout the curing period.
• The immobilization of organics is currently under investigation,
  including an evaluation of the applicability of analytical protocols
  (EP, TCLP and total analysis) for predicting long-term effective-
  ness of immobilization of organics. The preliminary  available
  data indicate that significant bonding takes place between some
  organic contaminants and  certain organophilic species in the
  binding matrix; however, immobilization  may not effectively
  stabilize some organic compounds, such as volatile organics.

Effectiveness on Inorganics
• Immobilization can accomplish reductions in mobility of 81% for
  nonvolatile metals (nickel) to 93% for volatile metals (lead).

REGULATORY IMPLEMENTATION

  The data indicate potential limitations of technologies that are
used to treat Superfund wastes when attempting to meet existing
BOAT standards for industrial process wastes.  Superfund LDR
Guide 6A outlines the treatability variance process for Superfund
soil and debris and identifies alternate treatability variance levels.
The levels in LDR Guide 6A (Figures 9 and 10) should be followed,
when appropriate, until OSWER completes a  regulation with treat-
ment standards for contaminated soil and debris. The limitations on
technologies identified here should be taken into  account when
evaluating, selecting, designing and implementing Superfund re-
sponse actions.
                                                                                                                TREATMENT   705

-------
TMUTAMUTr OKOur
NDHPOLAH
HALOaENATED
AflOUtTCS

pea..
HALOGENATED
DIOXIHS. FUHANS.
PRECURSORS
(WB)
HALOGENATEO
PHENOLS. CRESOLS.
AMINES. THOU.
AND OTHER POLAR
IW03)

HALOGENATED
ALIPHATIC
COMPOUNDS
(W04)

HALOGENATED CYCUC
AUPHATICS. ETHERS.
ESTERS. AND
KETONES
(WOS|

NITRATED
COMPOUNDS
(W06|


HETEROCYCUCS
AND SIMPLE
NON-HALOQENATED
AROMATIC*
(WOT)

POLVNUCLEAR
AROUATICS
(WM|

OTHER POLAR
NON- HALOGENATED
OROANC
(W»>

WON- VOLATILE
METALS

VOLATILE
METALS


NUUK* AMD KALI
Of AVAILABLE DATA
	 8* PAIRS
'SxBENCH
S XPILOT
0 %FULL
	 1 PAIRS
	 OXBENCH
100% PILOT
0 %FULL
	 3 PAIRS
	 O.X BENCH
100 xPILOT
Ox FULL

	 27 PAIRS
	 0% BENCH
100 % PILOT
0 XFULL

	 0 PAIRS
	 Ox BENCH
Ox PILOT
Ox FLU.

	 22 PAIRS
	 Ox BENCH
100 X PILOT
Ox FULL

	 54 PAIRS
	 0 » BENCH
JOO.XPILOT
" %FULL

	 37 PAIRS
	 l^X BENCH
81 XPILOT
0 XFULL

22 PAIRS
	 °X BENCH
100 XPILOT
0 XFULL

	 0 PAIRS
	 Ox BENCH
OXPILOT
0 XFUU
	 0 PAIRS
	 £x BENCH
0 XPIOT
0 XFULL

AVEJUOf COHCEHTIUTIOH9 (Ppml
AND X REMOVAL)
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(pp.) EFFICIENCY
UNTREATED 2.9 53 x
TREATED 0.79
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
ton) EFFICIENCY
UNTREATED 2.000 99 x
TREATED 0.12
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
to») EFFICIENCY
UNTREATED 83 74 x
TREATED 17

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppn) EFFICIENCY
UNTREATED 23 >99 X
TREATED 0.027

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(pin) EFFICIENCY
UNTREATED 0 Ox
TREATED 0

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
ton) EFFICIENCY
UNTREATED 13.000 82 x
TBFiTFD 1.*00

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
Ippm) EFFICIENCY
UNTREATEO_220 >99 X
TRFATFn 0.025

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
ippm) EFFICIENCY
UNTHEATED__!20 	 87. X
TREATED 3.8

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
tPpfli) EFFICIENCY
UNTREATED 64 >99 ,.
THEATFD 0.32

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
lpfm> EFFICIENCY
UMTRFATFn 0 0 ...
TPJATFD 0
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(pun) EFFICIENCY
UNTREATED 0 0 »
TWATFD 0

OCNEHAL OmnVADONl
• This technology Is not effective for all contaminants In (his class; however, there Is potential for
effectiveness tor low Initial concentrations with further development.
• The presence of these contaminants at low concentrations Is not expected to Interfere with the
treatment of applicable wastes.
• The effectiveness of this iechnology may be different than the data Imply, because the Initial

• The tone data pair Is PCBs.
• Ongoing research suggests that this technology may be potentially effective for this group.

• This technology Is potentially effective for low Initial concentrations.
• Btoremedladon requires uniformly mixed media with small pa/tide sizes.
• Toxic compounds such as cyanides, arsenic, heavy metals, and some organlcs adversely affect the
treatment.
• Bloremediation Is a slow process.

• This technology Is potentially effective for low Initial concentrations.
• Bloremedlation requires uniformly mixed media with small particle sizes.
• Toxic compounds such as cyanides, arsenic, heavy metals, and some organlcs adversely affect the
treatment.
• Preprocessing Includes mixing and nutrient and organism addition.
• Bloremedladon has low costs relative to other technologies.

• Data were not available for this treatablllty group. Data for compounds with similar physical
and chemical characteristics suggest that this technology may be potentially effective In certain
situations with low Initial concentrations.


• This technology Is potentially effective on these contaminants, especially at low concentrations.
• Some of the available data for this treatablllty group were based on very high Initial concentrations;
however consideration should be given to the ability of the technology to treat high Initial
concentrations.
• Bloremedlation requires uniformly mixed media with small particle sizes.
• Toxic compounds such as cyanides, arsenic, heavy metals, and some organlcs adversely affect the
• Preprocessing Includes mixing and nutrient and organism addition.
• Bloremedlation Is a slow process.
• Bloremedlation has low costs relative to other technologies.
• This technology Is potentially effective for low Initial concentrations.
• The high removal Indicated by the data may actually represent volatilization during
preprocessing and treatment.
• Bloremedlation requires uniformly mixed media with small particle sizes.
• Toxic compounds such as cyanides, arsenic, heavy metals, and some organic compounds
adversely affect treatment.
• Preprocessing Includes mixing and nutrient and organism addition.
• Bloremedlation has low costs relative to other technolooles.
• This technology Is potentially effective for low Initial concentrations.
• Bloremedlation requires uniformly mixed media with small particle sizes.
• Toxic compounds such as cyanides, arsenic, heavy metals, and some organic compounds
adversely affect treatment.
• Preprocessing Includes mixing and nutrient and organism addition.
• Bloremedlation Is a slow process.
• Btoremedladon has tow costs relative to other technologies.
• This technology Is potentially effective tor low Initial concentrations.
• Bloremedlation requires uniformly mixed media with small particle sizes.
• Toxic compounds such as cyanides, arsenic, heavy metals, and some organic compounds
adversely affect treatment.
• Preprocessing Includes mixing and nutrient and organism addition.
• BtoremedlaOon Is a slow process.
• Bloremedlation has tow costs relative to other technologies
• Removal may actually represent volatilization during preprocessing and treatment
• High concentrations ol heavy metals may adversely affect particular organisms.
• The physical and/or chemical characteristics of the constituents of this treatablllty group
suggest that the technology would not be effective.

• High concentrations of heavy metals may adversely affect particular organisms.
• The physical and/or chemical characteristics ol the constituents of this treatablllty group
suggest mat the technology would not be effecttve.


                                                                     Figure 5
                                             Final Conclusions by Treatment Technology - Biorcmediation
"06    TRE\TMKNT

-------
TREATAHUTV OROUP
NON-POUR
HALOGENATED
AHOMATICS


PCB«.
HALOGENATED
DIOXINS. FURANS.
PRECUSORS
(W02)

HALOQENATED
PHENOLS. CRESOLS.
AMINES. TWOS.
AND OTHER POLAR
(W03)

HALOGENATED
AUPHATIC
COMPOUNDS
(W04)
HALOGENATED CYCUO
AUPHATCS, ETHERS,
ESTERS. AND
(W05)

NITRATED
COMPOUNDS
(W06)


HETEROCYCLJCS
AND SIMPLE
NON-HALOSENATED
AROMATICS
(W07)


POLYNUCLEAR
AROMATICS


OTHER POLAR
NON-HALOSENATED
ORGANIC
(W09)

NON-VOLATILE
METALS
(W10)

VOLATILE
METALS
(WI1)

NUMBER AND SCALE
OF AVAILABLE DATA
29 PAIRS
_*.% BENCH
* % PILOT
-------
•rmATA»Lrnr onour
NON-POLAR
HALOOENATEO
AHOUATCS
(WW|
PCB*.
HALOGENATED
DIOXJNS. FURANS.
AND THEIR
PRECURSORS
(WQB)
HALOGENATED
PHENOLS. CRESOLS.
AMINES. THKXS.
AND OTHER POLAR
AROUATICS
(W03|
HALOGENATED
AUPHATIC
COUPOUNOS
rW«>
HALOGENATED CYCUC
AUPHATICS. ETHERS.
ESTERS. AND
KETONES
(W06|
NITRATED
COMPOUNDS
(WW)
HETEROCYCUCS
AND SIMPLE
NON-HALOGENATED
AROMATICS
(WOT)
POLYNUCLEAR
AROMATICS
(W0«|
OTHER POLAR
NON-HALOGENATED
ORGANIC
COMPOUNDS
(WOO]
NON- VOLATILE
METALS
(WIO|
VOLATILE
METALS
(W\l>
NUMBER AND SCALE
OF AVAILABLE DATA
20 PAIRS
100 X BENCH
0 % PILOT
0 XFULL
22 PAIRS
_ 82 XBENCH
* % PILOT
1* XFULL

	 5 PAIRS
100XBENCH
°%PILOT
OXFUU.
40 PAIRS
J00 XBENCH
OXPILOT
0 XFULL

	 fl PAIRS
	 Ox BENCH
	 P.XPILOT
0 XFULL
	 3 PAIRS
100% BENCH
0% PILOT
0 XFUU.

55 PAIRS
. M % BENCH
0 XPILOT
	 2_xFUU.
24 PAIRS
	 T!X BENCH
0 % PILOT
29 XFULL
M PAIRS
	 ?*» BENCH
0 % PILOT
5 XFULL

M PAIRS
100 X BENCH
0 XPILOT
0 XFUU.
	 M PAIRS
'00 XBENCH
OXPIUJT
OXFUU.

AVERAGE COMCEKTRATIOHS Ippm)
AMD % REMOVALS
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(p(m> EFFICIENCY
UNTREATED 170 >99 X
TREATED 0.30
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(Km) EFFICIENCY
UNTREATED 9500 71 x
TREATED 4.000

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppm| EFFICIENCY
UNTREATED 87 72 »
TREATED 18
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppml EFFICIENCY
UNTREATED 290 >99 »
TREATED 0.22

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
tppml EFFICIENCY
UNTREATED ... 0 0 •*.
TREATED 0

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ff*) EFFICIENCY
UNTREATED 8.900 >B9 »
TREATED 4.7
AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(Pfm) EFFICIENCY
UNTREATED 1,700 >99 x
TREATED 3-8

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppml EFFICIENCY
UNTREATED 1.600 82 %
TREATED 380

AVERAGE AVERAGE
CONCENTRATIONS REMOVAL
(ppml EFFICIENCY
UNTREATED 70,000 91 „
TREATED 1 5.000

AVERAGE AVERAGE
CONCENTFiATlONS MOBILITY
lppm| REDUCTION
UNTREATED 3* 89 x
TREATED '.'
AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppnl REDUCTION
UNTREATED 71 85 X
TREATED 10

GENERAL OBSERVATIONS
• This technology Is potentially effective on these contaminants out all data are from bench scale.
• Surfactants may adhere to the soil and reduce soil permeability.
• Possible volatile emission losses may occur during treatment.
• This technology Is potentially effective on these contaminants with further development.
• Some of the available data for this treatablllty group were based on very high Initial concentrations;
however consideration should be given to the ability of the technology to treat high Initial
concentrations.
• The presence of oil In the matrix enhances removal.
• The removal efficiency decreases as the percent of clays and clayey silts Increases.
• Surfactants may adhere to the soil and reduce soil permeability.
• Data were from pentachlorophenol only.
• This technology Is potentially effective on these contaminants, especially for treating sandy soils.
• Surfactants may adhere to the soil and reduce soil permeability.
• This technology Is potentially effective on these contaminants, but all data are from bench scale.
• This technology may be more applicable to sandy soils.
• Surfactants may adhere to the soil and reduce soil permeability.
• Volatile emissions may occur during treatment.
• Data were not available for this treatablllty group. Data for compounds with similar
physical and chemical characteristics suggest that this technology Is potentially effective In
certain situations.
• Surfactants may adhere to the soil and reduce soil permeability.
• This technology Is potentially effective on these contaminants. However, data are limited and
testing was conducted at bench scale.
• This technology Is potentially effective on these contaminants but nearly all data are from bench
scale.
• Volatile emissions may occur during treatment.
• Surfactants may adhere to the soil and reduce soil permeability.
• This technology Is potentially effective on these contaminants with further development.
• Some of the available data for this treatablllty group were based on very high Initial concentrationi;
however, consideration should be given to the ability of the technology to treat high Initial
concentrations.
• Surfactants may adhere to the soil and reduce soil permeability.
• This technology Is potentially effective on these contaminants.
• Some of the available data for this treatablllty group were based on very high Initial concentrationi;
however, consideration should be given to the ability of the technology to treat high Initial
concentrations.
• Treatment effectiveness should be evaluated on a case-by-case basis.
• Surfactants may adhere to the soil and reduce soil permeability.
• Volatile emissions may occur during treatment.
• This technology Is potentially effective on these contaminants.
•Water and HjSO4 atapHol 1.0 and a 3:1 molar ratio of EDTA at a pH of 12.0 can
both achieve good levels of extraction.
• Iron (1-2%) may cause solvent regeneration problems.
• This technology Is potentially effective on these contaminants, especially for sandy soils.
• Silty and dayey soils are not as effectively treated.
• Arsenic may be difficult to extract due to low solubility.
                                                                    Figure 7
                                                    Final Conclusions by Treatment Technology •
                                                       Chemical Extraction and Soil Washing
"OS
       TREATMENT
-------
TRSATAKLITYOBOUP
NON-POLAR
HAL06ENATEO
AROMATICS


POBi,
HALOGENATEO
DKJXINS.FUHANS,
AND THEIR
PRECUSORS
|WM)
HALOGENATED
PHENOLS, CRE90L3.
AMINES. THOLS.
AND OTHER POLAR
(W03)

HAL03ENATED
AUPtMTIC
COMPOUNDS
 BENCH
" % PILOT
0 %FULL

	 0 PAIRS
	 ?.% BENCH
°% PILOT
0 *FULL
	 * PAIRS
100
_2L% BENCH
°X PILOT
°*FULL

	 'PAIRS
_!?£% BENCH
°X PILOT
°*FULL

	 9 PAIRS
	 E* BENCH
0 X PILOT
°XFUU_

	 OpAIRS
	 °> BENCH
0 It PILOT
°%FULL

12 PAIRS
100 % BENCH
0 % PILOT
0 *FULL

	 ? PAIRS
100*BENCH
°% PILOT
0 %FULL
	 I PAIRS
100 % BENCH
0 14 PILOT
°%FULL

24 PAIRS
67 % BENCH
33* PILOT
0 SFULL

33 PAIRS
100* BENCH
0% PILOT
0 SFULL

AVERAGE CONCENTRATIONS (ppm)
AND * AVa MOBILITY REDUCTION
AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED. ,3.1 83 *
TREATED 0.65

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED, 0 0 *
TREATED 	 .0
AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 2.5 61 %
TREATED ._J.-J.

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 11 88 %
TREATED 0.24

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 0 0 It
TREATED . 0

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 0 0 %
THEATED 0

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 23 73 »
TREATED , ...6.8

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 3.0 99 *
TREATED 0.03
AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
IINTBFATED 20 T7 V.
TREATED 5.6

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 28 81 It
TREATED 0.34

AVERAGE AVERAGE
CONCENTRATIONS MOBILITY
(ppm) REDUCTION
UNTREATED 610 93 <
TREATED 1.4

OENERAL OBSERVATIONS
• Data were for chlorobenzene only.
• These data suggest that this technology Is potentially effective In certain situations,
particularly where the Initial concentration Is low.
•The treatment mechanism for the more volatile compounds may be volatilization as opposed to
Immobilization. Air pollution control systems may be necessary to minimize cross media
Impacts from these volatile emissions.

• Incomplete quantitative data were available to evaluate treatment effectiveness. These
quantitative data and additional qualitative Information suggest that this technology Is
potentially effective In certain situations, particularly where the Initial concentration Is low.
• It Is not recommended that this technology be selected If this Is the only treatablllty group present.
• Data were from pentachlorophenol only. These data suggest that this technology Is potentially
effective In certain situations, particularly where the Initial concentration Is low, the effectiveness
of this technology on these contaminants may be different than the data Imply, due to limitations In
the test conditions.
• It Is not recommended that this technology be selected If this Is the only treatablllty group present.

• Though these data suggest that this technology Is potentially effective In certain situations,
particularly where the Initial concentration Is low the reductions In mobility may be due to
volatilization of the volatile compounds during treatment.
• Air pollution control systems may be necessary to minimize cross media Impacts from
these volatile emissions.
• It Is not recommended that this technology be selected If this Is the only treatablllty group present.

• Data were not available for this treatablllty group. Data for compounds with similar physical
and chemical characteristics suggest that this technology Is potentially effective In certain
situations, particularly where the Initial concentration Is low.
• It Is not recommended that this technology be selected If this Is the only treatablllty group present.


• Data were not available for this treatablllty group. Data for compounds with similar physical
and chemical characteristics suggest that this technology Is potentially effective In certain
situations, particularly where the Initial concentrations are low.


• Though these data suggest that this technology Is potentially effective In certain situations,
particularly where the Initial concentration Is low, the reductions In mobility may be due to the
volatilization of volatile organic compounds during treatment.
• Air pollution control systems may be necessary to minimize cross media Impacts from these volatile
• It Is not recommended that this technology be selected If this Is the only treatablllty group present.

• These limited data suggest that this technology Is potentially effective In certain situations, particularly
where the Initial concentration Is low.

• These limited data suggest that this technology Is potentially effective In certain situations, particularly
where the Initial concentration Is low.
• The treatment mechanism for the more volatile compounds may be volatilization as opposed to
Immobilization. Air pollution control systems may be necessary to minimize cross media Impacts
from these volatile emissions.
• It is not recommended that this technology be selected If this Is the only treatablllty group present

• This technology works well on these contaminants.
• High levels of oil and grease may Interfere with the process.
• Soluble salts of K/lg, Sb, Zn, Cu, and Pb may Interfere with the pozzolan reaction.
• High levels of sui fates may Interfere with the process.

• Based on the pilot scale data this technology works well on these contaminants. Some bench scale
data was not representative of optimum conditions.
• High levels of oil and grease may interfere with the process.
• High levels of sulfates may Interfere with the process.
• Pretreatment may be required to Increase pH.
                      Figure 8
Final Conclusions by Treatment Technology - Immobilization
                                                                           TREATMENT    709
-------
Structural
Functional
Group
Halogenated
Non-Polar Aromatics
Dioxins
PCBs
Herbicides
Halogenated
Phenols
Halogenated
Aliphatics
Halogenated
Cyclics
Nitrated
Aromatics
Heterocyclics &
Non-Halogenated Aromatics
Polynuclear
Aromatics
Other Polar Organics
Concentration
Range
(ppm)"
0.05-10

0.00001 - 0.05
.01 -10
0.002 - 0.02
0.5 - 40

0.5-2

0.5-20

2.5-10

0.5 - 20

0.5-20

0.5-10
Threshold
Concentration
(ppm)"
100

0.5
100
0.2
400

40

200

10,000

200

400

100
Percent
Reduction
Range
90-

90-
90-
90-
90-

95-

.90-

90.9

90-

95-

90-
99.9

99.9
99.9
99.9
99

99.9

99.9

- 99.99

99.9

99.9

99.9
 * If the constituent concentration of the untreated waste is less than the threshold concentration, use the
  concentration range; if it is more than the threshold concentration, use the percent reduction range.

" Total Waste Analysis                               Fj  re g
                                                   LDR Guide 6A
                                   Alternate Treatability Variance Levels for CS&D - Organics*
Structural
Functional
Group
Antimony
Arsenic
Barium
Chromium
Nickel
Selenium
Vanadium
Cadmium
Load
Mercury
Concentration
Range
(ppm)"
0.1 -0.2
0.27 -1
0.1 40
0.5-6
0.5- 1
0.005
0.2- 22
0.2-2
0.1 -3
0.0002 - 0.008
Threshold
Concentration
(Ppm)"
2
10
400
120
20
0.08
200
40
300
0.06
Percent
Reduction
Range
90
90
90
95
95
90
90
95
99
90
-99
-99.9
-99
-99.9
-99.9
-99
-99
-99.9
-99.9
-99
      If the constituent concentration of the untreated waste is less than the threshold concentration, use the
      concentration range; if it is more than the threshold concentration, use the percent reduction range.

      TCLP Analysis                                  Figure 10
                                                   LDR Guide 6A
                                   Micrnjic Trcjtabilii\ Variance Levels for CS&D - Inorganics

      I Ki  M Mi M
-------
AVAILABLE TECHNOLOGY TRANSFER ASSISTANCE

  It is recommended that treatability studies be conducted for each
site containing soil and debris which requires treatment. To assist in
the process of planning and performing these treatability studies, a
number of sources of pertinent current information exist. In terms of
guidance documents and technical resources, the following  are
important sources of information:
• Summary of Treatment Technology Effectiveness for Contami-
  nated Soil, U.S. EPA, EPA/540/2-89/053
• Superfund Treatability Clearinghouse Abstracts, U.S. EPA, EPA/
  540/2-89/001
• Technology Screening Guide for Treatment of CERCLA Soils and
  Sludges, U.S. EPA, EPA/540/2-88/004
• Guide for Conducting Treatability Studies Under CERCLA, U.S.
  EPA, EPA/540/2-89/058
• Inventory of Treatability Study Vendors, U.S. EPA, EPA/540/2-
  90/003a
• Various Superfund Innovative Technology Evaluation (SITE)
  Program Reports

  In addition to the abovementioned references, there also is a
valuable network of U.S. EPA and other Agency, university, vendor
and consulting engineering personnel focusing on the challenging
technical issues of waste treatment. Some elements of this network
include the following:
• Superfund Technology Support Project (TSP)
• Superfund Technical Assistance Response Teams (START)
• OSWER Technology Innovation Office (TIO)
• National Advisory Council for Environmental Policy and Tech-
  nology (NACEPT)

CONCLUSION

  The data and conclusions presented in this paper represent the
most current information available in the Superfund program. The
U.S. EPA recognizes that with each additional treatment test per-
formed, more valuable information will be generated regardless of
whether the test was successful or unsuccessful.   Timely and
complete technology transfer is the key to establishing the necessary
justifications for treatability variances  as well as to developing
appropriate  land disposal restrictions for contaminated soil and
debris based upon best demonstrated available technologies. There-
fore,  the U.S. EPA continues to seek all  treatment results for
evaluation for regulatory development and for timely technology
transfer.
  In  order to participate in  this important technology transfer
process, please send all available information on the treatment of
contaminated soil and debris to U.S. EPA OERR or to CDM Federal
Programs Corporation at the following addresses:

Carolyn K. Offutt/Richard Troast
Hazardous Site Control Division (OS-220)
U.S. Environmental Protection Agency
401 M. Street, S.W.
Washington, D.C. 20460
(703) 308-8330/308-8323

Joan O'Neill Knapp
CDM Federal Programs Corporation
13135 Lee Jackson Memorial Highway
Suite 200
Fairfax, VA 22033
(703) 968-0900

REFERENCES

1. U.S. EPA, Summary of Treatment Technology Effectiveness for Contami-
  nated Soil. U.S. EPA, Washington, DC, EPA/540/2-89/053, June 1990.
2. U.S. EPA, Memorandum on "Analysis of Treatability Data for Soil and
  Debris:  Evaluation of Land Ban Impact on Use of Superfund Treatment
  Technologies" (OSWER Directive 9380.3-04) in response to Superfund
  Management Review: Recommendation 34A., U.S. EPA, Washington, DC,
  November 30,1989.
3. U.S. EPA,  Superfund LDR Guide #6A, "Obtaining a Soil  and Debris
  Treatability Variance for Remedial Actions," OSWER Directive 9347.3-
  06FS, U.S. EPA, Washington, DC, July 1989, Revised September 1990.
4. U.S. EPA,  Superfund LDR Guide #6B, "Obtaining a Soil  and Debris
  Treatability Variance for Removal Actions," OSWER Directive 9347.3-
  07FS, U.S. EPA, Washington, DC, December 1989, Revised September
  1990.
                                                                                                              TREATMENT   711
-------
               Weathering  Resistance of  Stabilized  Petroleum  Sludge
                                                       Stephen Zarlinski
                                                         Geosyntec, Inc.
                                                       Norcross, Georgia
                                                Jeffrey C Evans, Ph.D., RE.
                                                      Bucknell University
                                                    Lewisburg, Pennsylvania
ABSTRACT
  A multiyear research project has been undertaken to investigate the
stabilization/solidification of a petroleum sludge. Recent papers have
presented the results of short-term testing (TCLP) of the stabilized
material. In order to evaluate long-term environmental effects, durability
testing was conducted on samples of the stabilized  petroleum sludge.
Conclusions and recommendations based on these durability tests are
presented in this paper.
  Under current laboratory procedures, the stabilized sludge samples
cure in a humid environment for 2 weeks before further testing. A study
was conducted to determine whether the test results were significantly
affected by the curing time. Individual samples were tested at daily and
weekly intervals up to 4 weeks and monthly thereafter. Results indicate
that the maximum unconfined compressive strength occurs at approxi-
mately 28 days. Depending upon the stabilization  reagents, the total
organic carbon (TOC) concentration in the extract increased or remained
unchanged  with increased curing time beyond 28 days.
  To further study long-term environmental effects, a wet/dry study
was conducted. Each sample was placed in a bath of water for 24 hours
and oven-dried for 24 hours. This 48-hour cycle was repeated 12 times
on each sample. Very limited physical degradation was apparent for
each mix during cycles of wetting and drying. The sludge stabilized
with cement kiln dust was not as resistant to wet/dry testing as sludge
stabilized with a mixture of attapulgite, fly ash quicklime and cement.
  Since the project is located in the mid-Atlantic region, the stabilized
material may also be subjected to freeze/thaw stresses. The freeze/thaw
samples were frozen for 6 hours and thawed for 42 hours. The process
was repeated for 12  cycles on each sample.
  Consolidation data are used to predict the total settlement and time-
rate of deformation due to an applied load of overlying material.
Although additives used to solidify the sludge are cementitious,  the
resulting strength and stiffness is  not  that of concrete. The compres-
sion indices indicate  that the stabilized mass has the properties of a
stiff clay.
  Permeability tests were performed to determine the rate of transport
of fluids through the stabilized sludge. The average hydraulic conduc-
tivity of the material is 2 x 10~6 cm/sec. The TOC of the effluent was
an order of magnitude greater than the influent concentration indicating
a release of encapsulated organics due to permeation with tap water.

INTRODUCTION
  The refinery processes used in the past to produce lubricating oil
from crude oil  generated significant  quantities of acidic petroleum
sludge. The common practice was to dispose of this sludge in open
lagoons. In the early  1970s, the manufacturing process was altered to
eliminate the production of acidic sludge—but the lagoons remained.
Among the alternative remediation techniques identified for these sludge
lagoons is stabilization/solidification, the subject of the research reported
in this paper. Remedial technologies are sought which result in more
permanent solutions than landfilling. Such solutions include bioremedia-
tion, incineration, vitrification and  stabilization/solidification.  A
multiyear research project has been undertaken to evaluate the effec-
tiveness of stabilization/solidification for the acidic petroleum sludge.
  Stabilization is a process employing additives to reduce the hazardous
nature of a waste by converting the waste and its hazardous constituents
into a form that: (1) minimizes the rate of contaminant migration into
the environment or (2) results reduced toxicity. Solidification is the
process of improving the engineering properties of a material through
the addition  of stabilization reagents. This paper will use the term
stabilization  to denote both stabilization and solidification processes.
  The first year of the research included a review of existing literature
and the development of the laboratory testing procedures. A survey of
stabilization  vendors also was conducted. The second year included
laboratory testing of 250 stabilized  test mixes. Laboratory testing
included unconfined compression and Toxicity Characteristics Leaching
Procedure (TCLP). The final phase of the project will include a field
study of sludge stabilization.
  The laboratory testing focused upon two aspects of stabilized sludge
performance. The first aspect was short-term evaluation of the toxicity
reduction and engineering properties of the stabilized samples.1 The
second aspect of laboratory testing, the focus of this paper, studied the
durability  of the stabilized monolith under weathering conditions in-
cluding freeze/thaw and wet/dry stresses.

STABILIZATION REAGENTS
  Reagents for the stabilization of the acidic petroleum sludge were
classified into two groups: binders and sorbents. Binders include those
materials which,  when added to the contaminated material, improve
the strength  of the material. Fly ash and lime, cement and kiln dust
are binders used for the solidification studies described in this paper.
  Sorbents for the stabilization of the organic waste were added in order
to reduce the contaminant transport rates from the treated waste. The
sorbent materials used in the studies described in this paper include
bentonite,  attapulgite  and organically  modified clays.

LABORATORY TESTING PROGRAM

Physical Property Tests
  Each  stabilized sample was mixed using a 500-gram sample of
untreated sludge. Upon sampling, the density, moisture contest, loss
on ignition and pH were determined for the untreated  material. A
mechanical rotary mixer was used to mix the reagents with the untreated
       TREATMFNT
-------
material. The samples were then compacted into a 2.8-in. diameter cylin-
drical mold using standard proctor energy. The compacted samples were
allowed to cure in a humid environment for 2  weeks.
  After the 2 week cure period, the samples were extruded and tested
in unconfined compression.  The  specimens  were tested  to  their
maximum unconfined compressive strengths,  or  15% axial strain,
whichever occurs first. The pH of the sludge  averaged 3.2 with an
average loss on ignition of 78.2 % and an average water content of 45.6 %.
Thus, the sludge is both very acidic and very organic.

Chemical Tests
  Once the sample was crushed in unconfined compression, it was
further disaggregated by passing the material through a 3/8-in. sieve.
The disaggregated material was extracted using a modified form of the
Tbxicity Characteristic Leaching Procedure (TCLP).  The test procedure
has been modified to use sulfuric  acid instead of acetic acid as the
extraction acid. This  modification allows for the measurement of the
total organic carbon concentration (TOC) in the extract. Studies have
shown that no significant difference exists between  the use of sulfuric
acid in place of acetic acid for these sludges.2
  Samples of the extract  were analyzed for TOC and metals. A 1-L
aliquot of the remaining  extract was used for a methylene  chloride
acid/base extraction.  The extract was then condensed to 1 mL for in-
jection into a Hewlett-Packard gas chromatograph/mass spectrometer.
The concentrations of individual organic contaminant present in the
sludge was then measured. The TCLP extract was found to have varying
concentrations (depending upon the stabilization mix) of several organics
including phenol, methyl phenol and naphthalene.  The average  TOC
in the  extract from all stabilized mixes was 187 mg/L.

CONCLUSIONS AND RECOMMENDATIONS BASED  ON
LABORATORY TESTING
  Candidate mixes for the stabilization of the acidic petroleum sludge
were selected from these studies.3 For the durability studies  reported
in this paper, the following two types of mixes were used: (1) cement
kiln dust and (2) fly ash, quicklime, cement and attapulgite. For the
second type of mix, that with fly ash, quicklime, cement and attapulgite,
two mix  formulations were used with different sludge to attapulgite
ratios.  As measured in the extraction fluid from the TCLP, the following
parameters were selected to evaluate stabilization effectiveness:
   Total organic carbon concentration
   Phenol
   Methyl phenol
   Naphthalene
   Chromium
   Lead
   Mix cost
   Unconfined compressive strength
   Volume increase

DURABILITY TESTS
  The laboratory analyses discussed above effectively evaluated the
mixes  in  the short-term. The test parameters are effective for initial
evaluation of the stabilized/solidified mixes. It is  recognized that under
long-term environmental  stresses  (i.e., weathering),  physical  and
chemical degradation of the samples may occur. The remainder of this
paper discusses the evaluation of the effects of long-term stresses upon
the stabilized samples.
  Results of the short-term testing have been previously presented.1|4'5
From these results, three candidate  mixes were  selected for the long-
term durability analysis.  The mix proportions are shown in  Table 1.
The following section of this paper describes the tests conducted on
each of the samples and discusses  the results of these tests.

DURABILITY TESTING PROGRAM AND RESULTS

Curing Time Study
  The  short-term laboratory procedure had employed a 2-week cure
time. A study was conducted for each of the selected test mixes to
evaluate the  characteristics  and property changes of the stabilized
monolith as a function of time. For each of the three candidate mixes,
samples were tested at curing times of 1, 7,  14, 21 and 28 days, and
2 and 3 months. With the exception of the curing time, the laboratory
procedures remained  unchanged for these replicate samples.
  Shown in Figure 1 is the relationship between the curing time and
the unconfined compressive strength for the three candidate mixes. For
each test  series, the unconfined compressive strength increases by
approximately 300% from 1  day to 28 days  of curing.  Series I used
cement kiln dust as the solidification agent; it exhibited the lowest
strength of the three tested. Series n and m both used attapulgite, fly
ash, quicklime and cement in the solidification process. Series n had
an attapulgite to sludge ratio of 0.6, whereas Series HI had an attapulgite
to sludge ratio of 0.4. The higher attapulgite to sludge ratio resulted
in higher strengths as expected, although the increase is not dramatic.

                             liable 1
             Mix Ingredients and Proportions (by weight)
  Sludge/cement kiln dust                     1/1.5
      (S/CKD)
  Sludge/attapulgite/fly ash/quicklime/cement 1/.6/.75/.25/.5/.3
      (S/A/FA/QL/C)
  Sludge/attapulgite/fly ash/quicklime/cement 1/.4/.75/.25/.5/.j
      (S/A/FA/QL/C)
  440
                       28  35   42  49   56
                           Curing Time (days)
                                                      77  84
                            Figure 1
        Relationship Between Unconfined Compressive Strength
                        and Curing Time
  The reduction in the TOC of the extract was studied as a function
of curing time as shown in Figure 2. In the case of the cement kiln
dust-stabilized sample, the reduction in TOC (in the extract) decreased
as curing time increased. For the candidate mixes using attapulgite,
curing time has little effect upon the TOC in the extract. The data also
show that cement kiln dust was not as effective as the attapulgite mixes
in reducing the TOC of the extract in the TCLP.

Wet/Dry Testing
  Wet/dry testing was conducted to quantify the resistance  of  the
stabilized materials to degradation as a result of wet/dry cycles following
the procedure outlined in ASTM D-4843. The samples were mixed,
compacted using standard proctor energy, allowed to cure for 1 week
and extruded for testing. For each candidate mix, three test samples
and three control samples were formed. The  test samples were sub-
                                                                                                                    TREATMENT   713
-------
jected to 12 cycles of wetting in deionized water for 24 hours and drying
at 60 °C for 24 hours. Each 48-hour segment of wetting and drying con-
stituted one cycle.
  100

  90

  BO


i7°
y 60

!«
£ 40

* 30

  20

  10
                                                 •    Series I
                                                 «    Series II
                                                 A    Series a
               14  21
                        2B   35   42   49   56   63  70   77
                            Curing Time Idaysl
                              Figure 2
          Relationship Between TOC Reduction and Curing Tune
  The corresponding control samples were not subjected to the stress
of drying. Instead, these samples were placed in a humid environment
for 24 hours. The total material loss was obtained by drying and weighing
the material which spilled off the sample. The relative material loss
is the difference between the total  material loss for the test samples
and the total material loss for the control samples. Samples were tested
for metal and organic contamination using the modified TCLP described
above.
  Results of wet/dry testing are presented in Table 2.  As shown in
Table 2, the total material loss was greatest for the cement kiln dust-
stabilized sample. The total material loss was least for the sample having
an attapulgite to sludge ratio of 0.4., although the sample having an
attapulgite to sludge ratio of 0.6 was similar in magnitude. Since the
relative material loss  is quite small when  compared  with the total
material  loss, the tests demonstrated that the material degradation was
primarily a result of the wetting cycles with little impact from the drying
cycles. All mixes were quite resistant to physical degradation due to
wetting and drying as indicated by the low values of material loss. Failure
usually is defined  as a relative  material loss of 30%.
                            Tbble2
                      Wet/Dry Test Results
Stabilization Mix
fc Proportions

S/CKD
(1/1.5)
S/A/FA/QL/C
(1/.6/.75/.25/.5/.3)
s/V'VQVC
(1/.4/.75/.25/.5/.3)
Total
Material
Loss (*)
1.81

1.09

0.90

Relative
Material
Loss (*)
0.15

0.26

0.28

TOC
Reduction
(*)
72.3

66.9

71.0

environment for 1 week. After curing, test samples were placed in the
freezer for 24 hours at a temperature less than -20°C This freeze period
was followed by 24 hours erf thawing in deionized water.
  The results of the freeze/thaw testing are shown on Table 3. As with
previous data, the cement kiln dust-stabilized samples did not perform
as well as the samples stabilized with fly ash, quicklime, cement and
attapulgite. The reduction in TOC was greatest for the sample having
an attapulgite to sludge ratio of 0.6, which was only slightly better than
an attapulgite to sludge ratio of 0.4. The material loss was greatest for
the sample stabilized with cement kiln dust and essentially  the same
for the attapulgite-stabilized samples. Since the relative material loss
is quite large when compared with the total material loss, the tests
demonstrate that the material loss is primarily due to the freezing cycles.
  A comparison of the freeze/thaw  test results  with the wet/dry test
results indicates that the freeze/thaw  stresses are more critical than the
wet/dry stresses with respect to physical degradation. With respect to
TOC, the wet/dry stresses are more critical.
                                                                                                   Ihble3
                                                                                           Freeze/Thaw lest Results
Stabilization Mix
& Proportions
S/CKD
(1/1.5)
S/A/FA/QVC
(1/.6/.75/.25/.5/.3)
S/A/FA/QL/C
(1/.4/.75/.25/.5/.3)
Total
Material
Loss (*)
6.46
2.69
2.41
Relative
Material
Loss (%)
5.22
1.62
1.43
TOC
Reduction
(*)
72.4
91.4
89.6
One-Dimensional Compression
  In order to assess the time rate and magnitude of the settlement of
the stabilized mass, consolidation tests were run on the three candidate
mixes. For this test, a 1-in. thick by 2.5-in. diameter specimen of the
cured stabilized material is subjected to increasing vertical pressure and
constrained from lateral deformation (one-dimensional compression).
Loads were  applied to stress the samples to 0.25, 0.5, 1, 2, 4, 8 and
16 tons per square foot. The samples were then unloaded to stresses
of 8, 2, 0.5 and 0.001 tons per square foot. The time rate of deforma-
tion  was  recorded for all  loading increments. The compressibility is
indicated by the compression index, defined as:
Cc = de/d\oga\                                            (1)

where
de, = change in void ratio
dloga\ = change in applied stress

  The results of the consolidation testing are summarized in Table 4.
Note that the values of the compression index are in the range of those
typical for stiff clays. The  data also show a significant apparent precon-
solidation pressure for the samples stabilized with attapulgite. Thus,
stabilized materials loaded hi the field at stresses less than these values
will  not be subject  to large deformations.
                                                                                                   Table 4
                                                                                           Consolidation Test Results
Freeze/Thaw Testing
  Freeze/thaw testing was conducted to evaluate the resistance of the
stabilized materials to cycles of freezing and drying. The literature in-
dicated that freeze/thaw  cycles  often are more destructive  than the
wet/dry cycles. Samples for the freeze/thaw testing were mixed and com-
pacted into plexiglass cylinders 1.75 inches in diameter and 3.00 inches
in length. As with the wet/dry analyses, test and control samples were
prepared  for each candidate  mix. Samples were cured  in  a  humid
Stabilization Mix
I Proportions
S/CKD
(1/1.5)
S/A/FA/QVC
(1/.6/.75/.25/.5/.3)
S/A/FVQL/C
(1/.4/.75/.25/.5/.3)
Pre-
Consolidation
Prensur*
(tsf)
0.6
4.5
3.5
Co»pr«siion
Index
0.218
0.217
0.475
'14    TREATMENT
-------
PERMEABILITY
  Permeability tests were conducted on the stabilized monoliths in order
to assess the hydraulic conductivity of the materials and to examine
the contaminant transport from the stabilized material as a result of
water infiltration.  Triaxial permeability tests were  conducted at an
effective consolidation pressure of 10 psi, a backpressure of SO psi and
a differential seepage pressure of 5 psi. The permeant was potable tap
water with a TOC  of 10 mg/L. Chemical analyses were conducted on
the effluent  to determine the extent of transport from the sample.
  Presented in Figure 3 are the permeability test results for a sludge
sample stabilized with cement kiln dust. The hydraulic conductivity,
which was initially 3xlO~6 cm/sec, decreased to 2xlO~6 cm/sec after
5 days.  The slight decrease in conductivity is typical of cementitious
materials  which continue to hydrate with time  after mixing.
   10-3
J 1(H
u
>\
•I
8 10-5
I

   10-7
       0     1000   2000    3000   4000    5000   6000    7000
                          Total Elapsed Time (min)

                             Figure 3
                  Hydraulic Conductivity Test Results
   1200


   1000


    800


    600


    400


    200
       0.0  0.5   1.0   1.5   2.0  2.5   3.0   3.5   4.0   4.5   5.0   5.5
                          Pore Volume Displacement

                              Figure 4
               TOC of Hydraulic Conductivity Test Effluent
  Chemical analysis of the effluent (Figure 4) show an initially high
(>100 mg/L) TOC decreasing with time, i.e., pore volume displace-
ment. It is postulated that the initially high TOC is the result of free
organics within the stabilized matrix. The lower TOC reflects a steady-
state diffusion from the stabilized matrix to the permeating water.

CONCLUSIONS
  As a result of the studies  of the stabilization of acidic petroleum
sludges described herein, we have concluded that:

• The unconfined compression strength increases with curing time to
  approximately 28 days with little increase beyond that time.
• The initial TOC reduction decreased with increased curing time.
• No significant physical degradation occurred due to wet/dry testing
• Freeze/thaw testing resulted in greater physical degradation  of the
  samples than  wet/dry testing.
• Mixes containing fly ash, quicklime, cement, and attapulgite were
  more effective in stabilizing the acidic petroleum sludge than cement
  kiln dust.
• Compression  characteristics of the stabilized sludge are similar to
  those of stiff  clays.
• The hydraulic conductivity of the stabilized materials is low (in the
  range of 2xlO~6 cm/sec).
• Permeation with tap water caused release  of organics from the
  stabilized monolith.
• The release of organics decreased with the duration of permeation.

ACKNOWLEDGEMENTS
  The support of Sun Refining & Marketing Co., The Pennsylvania
Ben Franklin Partnership and The Earth Technology Corporation is
gratefully acknowledged. The authors appreciate the review comments
of Dr. Michael  LaGrega. Appreciation is extended  to Diane Hall,
Dr. Elaine Keithan, Jim Spriggle, Lewis Albee, Holly Borcherdt,  Bill
Farthing,  Yasodha Sambasivam,  Robert Semanek,  Eric Smalstig,
Kristine Smith, Kevin Spigelmyer and Jason Strayer for assistance with
this project.

REFERENCES
1. LaGrega, M.L., Evans, J.C., Acuna, CO., Zarlinski, S.J. and Hall, D.F.,
  "Stabilization of Acidic Refinery Sludges," Journal of Hazardous Materials,
  Elsevier Science Publishers, B. V., Amsterdam,  1990, (in press).
2. Toner, K.B, Keithan, E.D. and Pancoski, S.E., "A Comparison of the Toxicity
  Characteristic Leaching Procedure (TCLP) and a Modified TCLP in an
  Evaluation of a Stabilized Oil Sludge," Proceedings of the fifth Annual Sym-
  posium on Waste Testing Quality Assurance, Lewis Publishers, Chelsea, MI,
  July,  1989.
3. Zarlinski, S.J. and Evans, J.C., "Durability Testing of a Stabilized Petroleum
  Sludge," Toxic and Hazardous Wistes: Proceedings of the Twenty-Second Mid-
  Atlantic Industrial Waste Conference, pp. 542-556, Philadelphia, PA, July,
   1990.
4. Evans, J.C. and Pancoski, S.E., "Stabilization of Petroleum Sludges," Pro-
  ceedings of the 10th National Conference on the Management of Uncontrolled
  Hazardous Wiste Sites, Washington, DC, p.  292-297, HMCRI, Silver Spring,
  MD,  November 1989.
5. Evans, J.C. LaGrega, M.D., Pancoski, S.E. and Raymond, A., "Methodology
  for the Laboratory Investigation of Stabilization/Solidification of Petroleum
  Sludges," Proceedings of the  9th National Conference on the Management
  of Uncontrolled Hazardous Waste  Sites, Washington, DC, pp.  403-408,
  HMCRI, Silver Spring, MD, November 1988.
                                                                                                                         TREATMENT    715
-------
                       Selecting  Innovative  Treatment  Technologies:
                                            A  Practitioner's  Guide

                                              Walter  W. Kovalick, Jr. Ph.D.
                                                        John Kingscott
                                                Technology Innovation Office
                                          U.S.  Environmental  Protection Agency
                                                        Washington, DC
                                                        Daniel Sullivan
                                                       ICF Incorporated
                                                        Fairfax,  Virginia
ABSTRACT
  The U.S. EPA provides a number of tools for decision-makers who
must evaluate technologies to remediate contaminated soils and ground-
water. This paper provides a "road map" to guide the reader through
the variety of U.S. EPA resources available on innovative treatment
technologies.
  Some of the available resources include screening guides that assist
site managers in matching waste types with appropriate technologies;
a bibliography, entitled Selected Alternative and Innovative Treatment
Technologies for Corrective Action and Site Remediation, listing rele-
vant and current U.S. EPA reports on remedial technologies and how
to obtain them; the ROD System (RODS) data base, which contains
information on  technologies selected for individual sites; Superfund
Innovative Technology Evaluation (SITE) reports, which provide per-
formance data on innovative technology demonstrations; and the Alter-
native Treatment Technology  Information Clearinghouse (ATTIC),
which is a computerized library of treatability studies.
  Additional resources to be available in the near future include infor-
mation on technologies used at removal and remedial sites and their
implementation status;  an expert system to help select appropriate
biological treatment processes for remedial sites;  and an enhancement
of ATTIC with  treatment technology case histories from the Depart-
ment of Energy, the Department of Defense and the Department of the
Interior.

INTRODUCTION
  SARA mandated the use of permanent remedies at Superfund sites.
By definition, these remedies reduce the toxicity, mobility and volume
of contamination.  As noted in the Management Review of the  Super-
fund Program (commonly referred to as the 90-Day Study), decision-
makers are hesitant to select newly developed or innovative technologies
for a variety of informational, institutional and economic reasons. The
Technology Innovation Office (TIO) was created in 1990 within the U.S.
EPA's Office of Solid Waste and Emergency  Response (OSWER)  to
identify and remove impediments to the broader application of innovative
technologies to  hazardous waste remediation.  One of TIO's primary
goals  is to assist those who select hazardous waste cleanup technologies
to identify and use new or innovative technologies when remediating
contaminated soils and groundwater.
  A principal impediment to the use of innovative and alternative treat-
ment technologies is the lack of up-to-date, objective data  with which
to initially  evaluate a technology's performance  and cost. Such data
must be available early in the  remed> screening process in order for
an innovative technology to be fully considered during the feasibility
study. In an effort to overcome this particular roadblock, the U.S. EPA
has created a  number of reference  sources  for use bv  U.S. EPA
employees and others. These resources include computerized data bases,
a reference  library, numerous publications and the availability of
dedicated  groups of technical experts.  Many  of these resources are
available to the general public with no user fees.
  The  purpose of this paper is to publicize these computerized,
bibliographic and technical resources, to encourage  their use and to
present a  "road map"  or logical approach to their efficient applica-
tion. The "Practitioner's Guide to Identifying Innovative Technologies"
Preliminary
Information
    Database
     Search
    Bibliographic
      Search
      EPA Technology Screening Guides
              ATTIC
                       BODS    COLIS
                        Hazardous Waste
                       Collection Database
      Abstracts, Summaries, Detailed Reports
         Books, Records of Decisions
          Bibliographic Brochures:
V1    "elected Alternatives & Innovative Treatment
       Technologies for Corrective'Action
          ;   & Site Remediation        -;:

        Selected Technical Guidance lor
             Superfund Projects
                A
        Comparing
         Specific
       Technologies
                           Technical Experts:
               E«PeriBnced  Technology
               Peers      Vendors
                         "
                                    FOCUSING
                                        IN
               Site
              Specific
            Applications
           Treatability Protocols
        \Trealablllly Study Guidances/

            Technical Experts;

            reatabitrty Assistance ,
               «Program v
GETTING
SPECIFIC
                             Figure 1
         Practitioner's Guide to Identifying Innovative Technologies
 •|fc    FRhMMEM
-------
                            Table 1
     U.S. EPA Screening Guidelines for Treatment Technologies

 Technology Screening Guide for Treatment of CERCLA Soils and Sludges
 EPA/540/2-88/004
 Treatability Potential  for EPA Listed Hazardous Wastes in  Soil NTIS
 PB89-166581
> Treatability Potential for 56 EPA Listed Hazardous Wastes in Soil NTIS
 PB89-1744446
> Treatability of Hazardous Chemicals in Soils:  Volatile and Semi-Volatile
 Organics NTIS DE89-016892
• Bioremediation of Contaminated Surface Soil NTIS PB90-164047
1 Treatment Technology Fact Sheets:
     Innovative Technology: Soil Washing
     OSWER Directive 9200.5-250-FS (Fact Sheet)
     Innovative Technology: In-Situ Vitrification
     OSWER Directive 9200.5-251-FS (Fact Sheet)
     Innovative Technology: BEST-TM Solvent  Extraction Process
     OSWER Directive 9200.5-253-FS (Fact Sheet)
     Innovative Technology: Glycolate Dehalogenation
     OSWER Directive 9200.5-254-FS (Fact Sheet)
(Fig. 1) provides an ordered approach to using the various data bases,
publication sources and technical experts currently available from the
U.S. EPA. This Guide can be used as a first step in identifying poten-
tial technologies that may be applicable to a specific contaminated site,
as well as serving as a final check on available cost and performance
data concerning various innovative remediation technologies that have
already been identified through other means.

THE FIRST STEP
  The streamlining of the Superfund remedial program in recent years
requires the identification of remedial technologies during the early
data gathering phases of the RI. During  the early identification of
technologies in die RI, the analyst needs to sift quickly through available
information and identify what might be worth examining in more detail.
A similar analysis may be conducted when time permits an engineering
evaluation prior to a removal action.
  The U.S. EPA has prepared several screening documents which sup-
port an initial assessment of the possible application of technologies
at sites. These documents (Table 1) provide  an  overview of potential
technology use based  on physical site characteristics and contaminant
information. This information will help the  analyst begin to identify
potentially feasible technologies, to identify interfering waste and/or
site characteristics and to identify process limitations. The screening
guides should help focus attention on important technical issues and
help identity key words or phrases for use during computer searches.
Following this initial screening, data bases may be searched to identify
useful references.
  The U.S. EPA has created four data bases that are useful places to
begin bibliographic technology research: ATTIC, the Hazardous Waste
Collection Data Base, RODS and COLIS. The most recently developed
of these four data bases, and likely the most pertinent to a technology
search, is ATTIC—the Alternative Treatment Technology Information
Clearinghouse. ATTIC is the primary technology transfer mechanism
for disseminating information concerning the Superfund Innovative
Technology Evaluation (SITE) program and also contains abstracts and
executive summaries  from  more than 1,500 technical documents  and
reports from states, industry, NATO, DOD, DOE other countries, Super-
fund RODs and various Superfund treatability studies. ATTIC can be
accessed  through modem-equipped personal computers or through a
systems operator. The system is designed to search for key words with
minimum effort, a site manager can receive  short abstracts and sum-
maries of possible applicable technologies. Should these summaries
seem relevant, full copies of reports can be obtained through several
sources including the  U.S. EPA Library. Access to the on-line ATTIC
system is available through the ATTIC system operator. Technical
information requests also can be made by calling the system operator
at (301) 816-9153.
  The second data base of potential use during an early technology
 search is the Hazardous Waste Collection Database (HWCD), housed
 within the U.S. EPA Headquarters library. The HWCD, established in
 1986 to support the information needs of the U.S. EPA's Superfund
 office, is  a bibliographic data base containing abstracts of U.S. EPA
 and other government agency reports, trade books, policy and guidance
 directives, legislation and regulations concerning hazardous waste.
 Although the subject matter of HWCD is far more wide-ranging than
 the topic of innovative technologies, it is searchable by subject, reference
 title and key words using  a menu. A data base thesaurus is available
 to aid users in designing efficient searches. One may contact Felice
 Sacks, the U.S. EPA Headquarters Head Hazardous Waste Superfund
 Librarian, at (202) 382-5934 for more information concerning the
 HWCD system.
  A third useful data base  is the Records Of Decision System (RODS)
 data base. The RODS data base contains the text of the signed Super-
 fund Records of Decision. It facilitates comparing technologies used
 at sites with similar physical characteristics and waste conditions. The
 data base is menu-driven and provides rapid information searches. A
 search can be conducted on such fields as site name, remedy, key con-
 taminants or the full text of the ROD. RODS is maintained on the U.S.
 EPA's IBM mainframe computer, which is located in Research Triangle
 Park, North Carolina. The RODS data base is available to the general
 public through the CERCLIS  Hotline at (202) 252-0056 or the RODS
 staff at (202) 245-3770.
  The fourth data base of interest is COLIS—the Computerized On-
 Line Information Systems. COLIS is part of the U.S. EPA's Risk Reduc-
 tion Engineering Laboratory's (RREL) Technical Information Exchange.
 Three  COLIS data bases are  currently in operation:

• Case History  File:  This  file  contains  information  on  site
  characteristics, respond methods, costs and cleanup problems related
  to spills, waste sites and underground storage tank management.
• Library Search System: This subsystem allows free form searching
  through catalog cards and full length abstracts of documents in the
  TIX library. Users may conduct their own literature searches using
  their own key words—they are not limited to a standard set of key
  words.
• SITE Application Analysis Report File: This subsystem allows free
  form searching of reports containing  cost and performance data
  gathered from the U.S.  EPA's SITE demonstration program. The
  reports  are on-line in their entirety.


  COLIS is accessible through the ATTIC  system,  or the system
 operator can be contacted at  (201) 906-6871.
  In addition to data bases services, the U.S.  EPA also has  prepared
 two brochures that will help identify U.S. EPA documents concerning
 the use of innovative and alternative remedial technologies. These
 brochures are titled Selected Alternative and Innovative Treatment
 Technologies  for  Corrective  Action  and  Site  Remediation
 (EPA/540/8-90/008, Oct. 1990) and Selected Technical Guidance for
 Superfund Projects (EPA/540/8-89/004, May 1989). Each of these two
 brochures lists more than  70 U.S. EPA documents relating to Super-
 fund and remedial technologies. Both of these brochures are available
 free from the U.S. EPA's Center for Environmental Research Informa-
 tion (CERI) at (513) 569-7562.

 FOCUSING IN
  Each of these four computerized information sources allows users
 to gather a large number of potentially useful references in a relatively
 short period of tune.  The next step,  therefore, is to pare down the
 reference  list to those documents truly of interest. The technology
 screening guides listed in Table 1 should be helpful in this regard by
 assisting site managers to obtain a sense of the relevancy of individual
 references. The U.S. EPA and other sources also  make  available
 technology-specific publications and  technical experts  that can be
 consulted for detailed information regarding potentially useful remedia-
 tion technologies.
                                                                                                                      TREATMENT    717
-------
 Technology Specific Publications
   By using general knowledge of site characteristics and an overview
 of potentially  effective treatment technologies  obtained  from  the
 screening guides mentioned above, the site manager has at this point
 identified  references to a relatively small number  of remediation
 technologies that are potentially useful. The next step  is to locate and
 review documents concerning these technologies so that these few
 technologies can be compared with each other.
   During the review of screening documents and technical literature,
 the analyst may become aware of important site characteristics which
 will determine the feasibility of some treatment processes. These factors
 may concern the physical or chemical character of the waste and suggest
 the need to promptly gather additional site data. Thus,  an iterative pro-
 cess  may  develop where  additional site data  will be  necessary to
 thoroughly assess technologies prior to conducting treatability studies.

 Technical Experts
   One of the challenges facing site managers is the need to assess the
 value of an innovative technology  for the specific characteristics of a
 site.  When reviewing the literature and considering technologies,  the
 analyst should  be  aware  of the  developmental status of  different
 technologies. By definition, innovative technologies are neither fully
 commercialized nor ready for "off-the-shelf use. These technologies
 have  limited performance and cost data and  lack  extensive field
 experience. The status of these processes  may rapidly change, and new
 information is constantly being generated as demonstration projects and
 treatability studies are completed.  Therefore, especially  for new
 technologies, personal contact with technical experts, experienced peers
 and technology vendors is very important.
   The U.S. EPA's Risk Reduction Engineering Laboratory (RREL) and
 Robert S. Kerr Environmental Research Laboratory (RSKERL) have
 experts on numerous treatment technologies that  can  quickly steer a
 site manager to pertinent and relevant information. The  U.S. EPA spon-
 sors several programs through each laboratory to provide this type of
 consultation. At the RREL, the U.S. EPA has established:
 •  The Engineering and Treatment Technical Support Center
 •  The Treatability Assistance Program
 •  The Superfund Technical Assistance Response Team
   These three programs offer expertise in contaminant source control
 particularly in: above ground treatment units; materials  handling; treat-
 ment of soils, sludge and  sediments; and treatment of aqueous and
 organic liquids.  They are intended to serve  U.S.  EPA site managers
 primarily, but are available to the public on a limited basis. For further
 information regarding these programs, one can contact Ben Blaney at
 (513) 569-7406.
   Similarly, at the RSKERL, the U.S. EPA has established a Technical
 Support Center  to deal with in  situ  biorestoration of soils and
 technologies affecting groundwater. For further information concerning
 these programs, one can contact Richard Scoff at (405) 332-8800.
   The U.S. EPA has published reference guides to help identify ongoing
 programs and individuals who are working in specific technical areas.
 These guides are listed in Table 2.  In addition, the SITE program has
 ben actively working with developers of innovative technologies for the
 last 4 yr. The program has a technology transfer effort intended to pro-
 vide support to those in the hazardous waste site remediation community.
 The annual  SITE  Program brochure lists the U.S.  EPA Office of
 Research and Development  project managers  and their associated
 technologies of interest. For additional information, one can contact
 John Martin at (513) 569-7758.
   The five Hazardous Substance Research Centers are another source
 of technical expertise funded  by the U.S. EPA (Table 3).  These
 university-based centers, each of which has established special rela-
 tions with a pair of U.S. EPA Regions, focus  on problems common
 within their geographic regions, with emphasis on a specific area of
 research. These areas of specialization include groundwater remedia-
 tion, incineration, bioremediation, recovery of metals and other physical
 and chemical treatment of surface and subsurface contaminants. The
 centers perform long- and short-term research on all aspects of hazar-
 dous substance generation, management, treatment and disposal. The
 centers are committed to technology transfer, as well. The activities
 of these centers are  described more fully  in  Hazardous Substance
 Research Center: Annual Report FY1989 (January 1990). For a copy
 of this report or more information regarding these research centers,
 one can contact Karen Morehouse at (202) 382-5750.
                             TableS
         Hazardous Substance Research Centers and Directors

  Dr. Richard Magee, Director
  Hazardous Substance Management Research Center
  New Jersey Institute of Technology
  Newark, New Jersey 07102
  201/596-3233
  Region-Pair 1/2: CT, MA, ME, NH, NJ, NY, PR, RI,  VI, VT

  Dr. Walter J. Weber, Jr.
  Dept. of Civil Engineering
  2340 C.G. Brown Building
  University of Michigan
  Ann Arbor, Michigan 48109-2125
  3D/763-2274
  Region-Pair 3/5: DC, DE, IL, IN, MD, MI, MN, OH, PA, VA, WI,
  WV
• Dr. Michael R. Overcash
  Dept. of Chemical Engineering
  North Carolina State University
  Raleigh, North Carolina 27695-7001
  Region-Pair 4/6: AL, AR, FL, GA, KY, LA, MS, NM, NC, OK, SC,
  TN, TX

• Dr. Larry E. Erickson
  Dept. of Chemical Engineering
  Durland Hall
  Kansas State University
  Manhattan,  Kansas 66506
  913/532-5584
  Region-Pair 7/8: CO, IA, KS,  MO, MT, ND, NE, SD,  UT, WY

• Dr. Perry L. McCarty
  Center Director
  Dept. of Civil Engineering
  Stanford University
  Stanford, California 94308
  415/723-4D1
  Region-Pair 9/10: AK, American Samoa, AZ, CA, Guam, HI, ID,
  Northern Mariana Islands, NV, OR, WA
                             Table 2
             EPA Reference Guides to Technical Experts

• Groundwater Research: Technical Assistance Director)'
  EPA/600/9-89/048
• Environmental Protection Agency. Office of Research and Development:
  Technical Assistance Directory CERJ-88-84
• ORD Topical Directory EPA 600"9-86 006
• Technical Support Services for Superfund Site Remediation:
  EPA Mfl 8 
-------
are available through the Superfund Docket and CERI, respectively
(Table 2).
  Through the Risk Reduction Engineering Laboratory, the U.S. EPA
sponsors the previously mentioned Treatability Assistance Program.
This program offers a list of contractors available to perform treatability
studies,  a comprehensive data base of all aqueous treatability studies
and brief bulletins describing the applicability of various technologies.
The Treatability Assistance Program is also in the process of developing
generic  technology specific treatability study protocols.
CONCLUSION
  The U.S. EPA is assembling a comprehensive set of materials to make
hazardous waste site managers aware of the resources available con-
cerning innovative remedial technologies and to help steer them toward
use of innovative remedial technologies. A logical approach to use of
these materials is:
•  To reference screening guides and assess overall technology potential
•  To conduct a series of comprehensive data base searches
•  To consult available bibliographies
•  To  screen the  computer-generated reference  lists, abstracts  and
   bibliographies  and obtain those publications and documents iden-
   tified as having direct relevance to the project
•  To contact recognized experts in the field of hazardous waste site
   remediation and engineering
•  To conduct treatability studies using site-specific conditions and wastes
  The Technology Innovation Office continues it's efforts to make more
technology-specific information available to the hazardous waste site
remediation community. Future plans call for the development of an
innovative technology vendor data base, the expansion of the ATTIC
system to include other data bases (thereby offering one-stop shopping),
the development of a computerized expert system to assist in the selec-
tion of appropriate types of biological treatment and an expansion and
improvement of SITE program information availability.
  A critical factor in the success of the innovative technology informa-
tion systems is the timeliness of the information it contains.  "Innova-
tion"  by definition means "new," and all data in the U.S. EPA systems
need to be continually updated or the system becomes simply one more
impediment to  using  innovative technologies. Data  and information
concerning innovative technologies must be made widely available before
these  technologies can be fully evaluated and their potentials realized.
  The U.S. EPA's Technical Innovation Office would also like to integrate
information from outside sources, such as remediation contractors, other
federal agencies and private industry, into its various technology transfer
mechanisms. We have begun an outreach program designed to help col-
lect and collate cost and performance data for innovative remediation
technologies wherever it is available.

DISCLAIMER
  The opinions expressed in this article are those of the authors, and
do not necessarily reflect the policy position of the  U.S. EPA.
                                                                                                                     TREATMENT    719
-------
 Considerations in the Design of Pump-and-Treat  Remediation Systems
                                                  James W.  Mercer, Ph.D.
                                                   David  C  Skipp, M.S.
                                                        GeoTrans, Inc.
                                                       Sterling,  Virginia
ABSTRACT
  A common means to contain and/or remediate contaminated ground-
water is to extract the water and treat it at the surface. This process
is referred to as pump-and-treat technology. Practical considerations
in the design of pump-and-treat systems are reviewed, with emphasis
on the "pump" portion of the technology. Pre-design analysis and post-
implementation monitoring also are emphasized. Basic guidance is given
on how to use hydrogeological and chemical data to determine when,
where and how pump-and-treat technology can be used successfully.
  Factors which affect the time required to achieve a specific ground-
water cleanup goal also are discussed. These  factors include certain
combinations of hydrogeological conditions and geochemical proper-
ties. The variables also include the presence of nonaqueous phase liquids
(NAPLs), chemical desorption from the soil  matrix and media that
exhibit significant spatial variability. Such conditions and properties
result in  longer remediation performance periods for all corrective
actions, including pump-and-treat  technologies.
  Case studies illustrate the proper design of pump-and-treat technology.
As with any remedial technology, limitations at various sites may require
that different remedial technologies be combined to improve remedia-
tion performance.

INTRODUCTION
  Sources of groundwater contamination can range from leaky tanks,
landfills and  spills to the less obvious, such as chemicals in the soil
dissolving from nonaqueous  phase  liquids (NAPLs) or chemicals
desorbing from the soil matrix. Several options can be used to attempt
containment and/or cleanup of groundwater contamination.
  First, however, a distinction needs to be made between source removal
and  groundwater cleanup. Source removal typically  refers to excava-
tion and removal of wastes and/or contaminated soil. It also can include
vacuum extraction. Source containment includes chemical fixation or
physical encapsulation; if effective, its result is similar to source removal
in that it eliminates the potential for continued chemical transport from
the waste source to groundwater.
  Groundwater containment/cleanup options include physical contain-
ment (e.g., construction of low-permeability walls and covers), in situ
treatment (e.g., bioreclamation) and  hydraulic containment/cleanup
(e.g.. extraction wells and intercept trenches/drains). To ensure com-
plete cleanup, several methods may be combined to  form a treatment
tram. This paper focuses only  on  hydraulic containment/cleanup, in
particular, pump-and-treat technology.
  In  a pump-and-treat system,  contaminated groundwater or mobile
NAPLs are captured and pumped  to the surface for treatment. This
pnvess requires locating the groundwater contaminant plume or NAPLs
in three-dimensional space, determining aquifer and chemical proper-
ties, designing a capture system and installing extraction (and in some
cases injection) wells. Monitor wells/piezometers used to check the
effectiveness of the pump-and-treat system are an integral component
of the system. Injection wells are used to enhance the extraction system
by flushing contaminants (including some in the vadose zone) toward
extraction wells or drains. A pump-and-treat system may be combined
with other remedial actions, such as low-permeability walls, to limit
the amount of clean water flowing to the extraction wells, thus reducing
the volume of water to be treated.
  Whether the objective of the pump-and-treat system is to reduce
concentrations of contaminants to an acceptable level (cleanup) or to
protect the subsurface from further contamination (containment), the
system components are:
• A set of goals  or objectives
• Engineered components such as wells, pumps and a treatment facility
• Operational rules and monitoring
• Termination criteria
Each of these components must be addressed in the design and evalua-
tion of a pump-and-treat technology.
  Pump-and-treat technology is appropriate for many groundwater con-
tamination problems.1'2  However,  the physical-chemical subsurface
system must allow the contaminants to flow to the extraction wells. Con-
sequently,  the subsurface must have sufficient hydraulic conductivity
to allow fluid to flow readily and the chemicals must be transportable
by the  fluid, thus making  the use  of  pump-and-treat systems highly
site-specific.
  One way to evaluate the effectiveness  of a remediation technology
is through a  study of case  histories. Lindorff and Cartwright'discuss
116 case histories  of groundwater contamination and remediation. The
U.S.  EPA 4J presents 23 case histories of groundwater remediation.
More recently, groundwater extraction has been  evaluated via case
histories.6 Based  on these  reviews, conditions which inhibit  the easy
flow  of contaminants to pumping wells  include:
• Heterogeneous aquifer  conditions  where low-permeability zones
  restrict contaminant flow toward extraction wells
• Chemicals that are sorbed or precipitated on the soil and slowly desorb
  or dissolve back  into the  groundwater  as  chemical  equilibrium
  changes in response to  the extraction process
• Immobile  nonaqueous phase liquids (NAPLs) that may contribute
  to  a miscible contaminant plume by prolonged dissolution (e.g.,  a
  separate phase gasoline at residual saturation)
The main limitation of pump-and-treat technology is the long time that
may be required to achieve an acceptable level of cleanup. Limitations
are discussed further in Mackay and Cherry7 and Mercer et al.2 for
these limitations,  modifications to pump-and-treat technology, such as
      TREATMFN'T
-------
pulsed pumping, may be appropriate. Pump-and-treat technology also
may be combined with other remedial alternatives, such as vacuum
extraction and/or bioremediation. One should realize that  no single
technology is a panacea for subsurface remediation under complex
conditions.

CONCEPTUAL DESIGN AND LIMITATIONS

When to Select Pump-and-Treat Systems
  Figure 1 presents a decision-flow diagram for groundwater contamina-
tion. For groundwater contamination, the first decision concerns whether
a remedial action (G3) is necessary. If a risk assessment shows the need
for a remedial action, then the options shown in Figure 1 are contain-
ment (G4), in situ treatment (G5) or pump-and-treat (G6). If G5 is
selected,  then other decisions are necessary but not discussed here.
If G4 is selected, then the containment can be  either physical (G7) or
hydraulic (G8). Physical containment generally has not worked well8
and is not discussed further; hydraulic containment is achieved by pump-
and-treat technologies (Gil). As indicated previously, if the  source of
the groundwater contamination is not removed, then containment may
be necessary as opposed to G5 or G6.
  If pump-and-treat (G6) is selected, the next decision is whether to
use wells (G9) or drains (G10). If the hydraulic conductivity is suffi-
ciently high to allow  flow to wells, then select  wells.  For  low-
permeability material,  drains may be required. If wells have been
selected, a decision must be made whether to use extraction wells (G12),
injection wells (G13) or a combination. Injection wells will reduce the
cleanup time by flushing contaminants toward the extraction wells. For
the extraction wells, decisions need to be made  concerning continuous
pumping (G16), pulsed pumping (G17) and/or pumping combined with
containment. Continuous  pumping  maintains an inward  hydraulic
gradient;  pulsed  pumping  allows  maximum  concentrations to be
extracted efficiently; containment can be used to limit the  inflow of
clean water that needs to be treated. The injected water can be treated
water (G19); for biodegradable contaminants, it can contain nutrients
and/or electron acceptors (G20) to enhance in situ biodegradation; or,
for NAPLs, it can consist of enhanced oil recovery (EOR)  materials
(G21). For problems involving groundwater contamination, some form
of pump-and-treat technology almost always will be  used.
                                            LIQUID: LIQUID
                                            PARTITIONING
         GROUNDWATER VELOCITY  —>•

                           Figure 2
                 Liquid Partitioning Limitations of
            Pump-and-Treat Effectiveness (from Keely20)


Limitations of Pump-and-Treat Systems
  For pump-and-treat technology to remediate an aquifer in a timely
fashion, the contaminant  source  must be eliminated.  Otherwise,
unremoved contaminants will continue to be added to the groundwater
                                                                                                                    G16
                             G2
    G1
     ground-water
     contamination
                                                              Figure 1
                                           Decision-flow Diagram for Groundwater Contamination
                                                                                                                  TREATMENT    721
-------
 system,  prolonging  cleanup. Excavation is  one of several options
 available for source removal. NAPLs at residual saturation are one of
 the most difficult sources of groundwater contamination with which
 to deal. Particular difficulty is posed by substances such as halogenated
 aliphatic hydrocarbons, halogenated benzenes,  phthalate esters and
 polychlorinated biphenyls  (PCBs) which, in their pure form, are
 DNAPLs.  When NAPLs are trapped in pores by interfacial tension,
 diffusive liquid-liquid partitioning controls dissolution. Flow rates during
 remediation may be too rapid to allow aqueous saturation levels of par-
 titioned contaminants to be reached locally (Figure 2).  If insufficient
 contact time is allowed, the affected water may be advected away from
 the residual NAPLs before approaching chemical equilibrium and
 replaced by water from upgradient. Because groundwater extraction
 generally does not efficiently clean up this type of source, some other
 remedial action may be required.
   Mobile chemicals may be treated using pump-and-treat technology.
 For sorbing compounds, however, the number of pore volumes that will
 need to be removed depends on the sorptive tendencies of the contami-
 nant,  the geologic materials through which it flows and the ground-
 water flow velocities during remediation. If the velocities are too rapid
 to allow contaminant levels to build up to equilibrium concentrations
 locally (Figure 3), then the affected water may be advected away before
 approaching equilibrium. Efficiency in contaminant removal may be
 low and will tend to decrease with each pore volume  removed.
   The  hydrogeological  conditions  favorable  to  pump-and-treat
 technology are high permeability (greater than about 10~5 cm/sec) and
 homogeneity. If the hydraulic conductivity is too low (less than about
 10~7 cm/sec) to allow a sustained yield to a well, groundwater extrac-
 tion via pumping wells is not  feasible. Determining pump-and-treat
 feasibility  is site-specific; a hydraulic conductivity range that works
 at one site may not work at another site. For example,  if the plume
 is small and the natural hydraulic gradient low, a pump-and-treat system
 pumping at a very low rate in a low-permeability  unit may be feasible.
                      ORGANIC  CARBON OR
                     MINERAL OXIDE SURFACE
                                            ADVECTION
                    EQUILIBRIUM CONCENTRATION
                         INITIAL RAPID
                         DESORPTION
                             TIME —*-
                            Figure 3
               Sorpuon Limitations to Pump-and-Treat
                    Effectiveness (from Keely20)
 However, this same permeability may result in containment failure at
 another site.
   For heterogeneous conditions (Figure 4), advected water will sweep
 through zones of higher hydraulic conductivity, removing contamina-
 tion from those zones. Although heterogeneous conditions only are
 illustrated  in the vertical in Figure 4, they  are  generally a three-
 dimensional phenomenon. Movement of contaminants out of the low
 hydraulic conductivity zones is a slower process than advective transport
 in the higher hydraulic conductivity zones. The contaminants either are
 slowly exchanged by diffusion with the flowing water present in larger
 pores or move at relatively slower velocities in the smaller pores. A
 rule of thumb is that the longer the site has been contaminated and the
 more lenticular (layered) the geologic material, the longer will be the
 tailing  effect. The water and  contaminants  residing in the more
 permeable zones are those first mobilized during pumping. Thus, pump-
 and-treat technologies work in heterogeneous media, but cleanup tunes
 will be longer and more difficult to estimate than for similar systems
 in more homogeneous media.
 ts^S-r SANDY CLAY 3
       - CLAY	
            -A' &5
                                  AVERAGE VELOCITY
                                                 DIFFUSION & CONVECTION
   VERTICAL SECTION
   THROUGH AQUIFER
VELOCITY
PROFILE
  DOMINANT
FLOW PROCESS
                                                                                                   Figure 4
                                                                                     Effect of Geologic Stratification on Tailing
                                                                                                (from Keely20)
Using Models for Pump-and-Treat Design
  At many sites it is advantageous to have multiple extraction wells
pumping at low rates rather than one well  pumping at a high rate.
Analytical or numerical modeling techniques are used to evaluate alter-
native designs and help determine optimal well spacings, pumping rates
and cleanup times.9 For example, a generic modeling study examining
the effectiveness of various restoration schemes is presented in Satkin
and Bedient.10 There also  are  approaches  combining groundwater
models with linear and nonlinear optimization." Fluid pathlines and
travel times in groundwater systems also can be estimated from particle
tracking codes.12 In addition, there are numerous analytical solutions
that may be used to estimate pumping rates and well spacings once
aquifer properties are known. These solutions are included in Ferris
et al.,D Bentall,14 Walton" and Jacob.16 In the following examples, both
numerical and analytical models were used to estimate well spacings,
pumping rates and cleanup  times.


Numerical Model Example
  A proposed pump-and-treat system for a hazardous waste site was
evaluated using a numerical model and described by Ward et al.17 The
goal of the pump-and-treat system was to contain and clean up con-
tamination. The results of the transport simulations are  summarized
in Figure 5. This figure shows the distribution inventory of the mass
of volatile organic compounds (VOCs) at the site over time. At any given
time, the initial VOC mass can be distributed in three categories: 0)
mass remaining in groundwater, (2)  mass removed by the extraction
system and (3) mass leaving the domain unremediated. The mass in
groundwater diminishes with time. However,  some mass leaves the
system uncaptured by the proposed corrective action. Thus, this pump-
and-treat system  will fail to contain  the contamination.
->22   TREATMENT
-------
                                                                                                 MASS UNREMEDIATED
                                                                                                     LEAVING  GRID
 PROPOSED
    PLAN
                               MASS IN GROUNDWA TER
                                                                   DOUBLED
                                                                   PUMPING
                                                                     RATES
             NOTE: Conversion Factor
                    1lb   0.4535kg
                                                                                                         1000
                                                            TIME  (days)
                                                             Figure 5
                                                 Calculated VOC Inventory versus Time
                                                         (from Ward et al.17)
  To assess the effect of increasing discharge and injection rates on
 plume capture, simulations were performed in which the total extrac-
 tion and injection rates were doubled. The increased pumping rates
 reduced the VOC mass left in groundwater, but still failed to contain
 a portion of the plume (indicated by the dashed line in Figure 5). Thus,
 final pumping rates will need to be even greater. These results show
 the importance of plume capture analysis and emphasize the need for
 performance monitoring and the use of a model in monitoring program
 design.
  The analysis of the above pump-and-treat system indicated declining
 contaminant concentration at the seven proposed extraction wells with
 time (Figure 6). Most wells exhibit a decreasing trend after a few weeks
 of operation. For each tenfold increase in the time of system opera-
 tion, the concentration of VOCs decreases by a factor of ten. Some
 wells exhibit a temporary increase in concentration as zones of con-
 tamination are flushed toward the extraction wells. The effect of sorp-
 tion also was examined with the model. A nearly linear relationship
 exists between retardation and time of remediation for a specific level
 of contaminant.

 Analytical Model Example
  Scoping calculations to estimate the pumpage required to capture a
 plume in a confined aquifer may be performed using the semi-analytical
 model RESSQ.18-19 RESSQ is  applicable to two-dimensional contami-
 nant transport subject to advection and sorption (no dispersion, diffu-
 sion or degradation can be considered) in a homogeneous, isotropic,
confined aquifer of uniform thickness when regional flow, sources and
sinks create a steady-state flow field. RESSQ calculates groundwater
flow paths  in the aquifer, the location of contaminant fronts around
sources at various times and the variation in contaminant concentra-
tion with time at sinks.
                                                                         10.000
       1.000
  -
 °0
 ZQ.
 OS   100
 Bo
         10
 g<
 8°
                              1 ppb •
          0.1
                                  10
                              TIME (days)
                                              100
                                                         1,000
                            Figure 6
          Calculated Extraction Well Concentrations versus Time
                        (from Ward et al.17)
  For example, the site is located in glacial deposits and consists of
a leaking landfill with an associated plume (Figure 7). The goal is to
design a capture well network for the plume. The site is more complex
than the conditions simulated with RESSQ. A sand lens (not shown)
                                                                                                               TREATMENT    723
-------
causes the plume to narrow with distance from the landfill. For these
scoping calculations, the flow system considered is at the front of the
plume where the wells are placed. For this location, a  groundwater
velocity of 0.205 ft/day (75 ft/yr) was estimated using Darcy's equa-
tion. The aquifer is 30 feet thick and the plume width is approximately
600 feet. The regional flow rate is 600 ft x 30 ft x 0.205 ft/day = 3690
ft'/day or  19.2 gpm. The  total pumping  rate of the wells will need to
be approximately 20 gpm to capture the plume.
                                              IEXTRACTION WELLS]

                            Figure 7
              Simulation to Capture Front of the Plume:
           10 Wells, 25 Feet Apart, Pumping at 2 gpm Each

  Next, the maximum pumping rate that is sustainable without the wells
going dry must be determined. The computation of drawdown at a single
well in a multiple-well installation is not precise when a single water
table aquifer of infinite extent is assumed. For 10 wells pumping at 2
gpm each, the maximum drawdown is calculated using the Theis solu-
tion and superposition15  as 32  ft.  This is  an  overestimate,  as  the
leakage from  the layers below and other sources (e.g., delayed yield)
in the vicinity are not considered. Therefore,  10 wells at 2 gpm is con-
sidered acceptable from the considerations of drawdown. An optimum
well spacing of 25 ft was determined based on guidelines provided by
Javandel and  Tsang."
  Streamtubes representing uniform regional flow were generated using
RESSQ (Figure 7). The  Streamtubes trace the movement of the con-
taminants  in the plume by advective transport. To  ensure that con-
taminants do not escape between wells, the two Streamtubes at the middle
of the plume  were divided into 5-foot wide spacings. The resulting
calculations using RESSQ confirmed that the proposed pumping system
would effectively capture the plume.

OPERATION AND MONITORING
  Whatever remediation system is selected for a particular site,  the
following need to be described clearly:
• Performance standards (remedial objectives)
• Monitoring program
• Contingencies (modification to the existing remediation)
Remedial action  objectives are the goals of the overall remediation.
To ensure that these are met, appropriate monitoring must be conducted.
If the monitoring indicates that the goals are not being met, then con-
tingencies must be specified concerning changes to the remediation
system that will ensure that the goals are reached or will specify alter-
nate goals where original goals cannot be practically achieved.
  According to Keely,20 numerous compliance criteria and compliance
point locations are used as performance standards. Compliance criteria
can txr divided into three categories: chemical, hydrodynamic and  ad-
ministrative control. Chemical compliance criteria are risk-based21 and
include Maximum Contaminant Limits  (MCLs), Alternate Concentra-
tion Limits (ACLs),  detection limits and  natural  water  quality.
Hydrodynamic compliance criteria may include demonstrated preven-
tion or minimization of infiltration through the vadose zone, maintenance
ol an inward  hydraulic gradient at the boundary- of the contaminant
plume,  or  providing  minimum flow  to  a  surface  water body.
Administrative  control  compliance  criteria  range from  reporting
requirements, such as frequency and character of operational and post-
operational monitoring, to land-use restrictions, such as drilling bans
and other access-limiting restrictions.
  Once the remedial action objectives are established and a remedial
system is designed to meet these standards, the next step is to design
a monitoring program that will evaluate the success of the remedial
system. The monitoring criteria will be important in establishing the
required monitoring program. Water quality monitoring is important;
water-level monitoring also is important and is less expensive and sub-
ject to less uncertainty.
  The location of monitor wells is critical to a successful monitoring
program. For pump-and-treat technology, extraction and injection wells
produce complex flow patterns locally, where previously there were
different flow patterns.20 Another possibility is that previously clean
portions of the aquifer may become contaminated. Thus, monitor well
locations should be based on an understanding of the flow system as
it is modified by the pump-and-treat system.  Modeling techniques
discussed previously can be used to help in site-specific monitoring
network design.
  To determine the flow system generated by a pump-and-treat system,
field evaluations must be made during the operational phase.  Conse-
quently, in addition to data collection for site characterization, data need
to be collected during and after pump-and-treat system operation. Post-
operational monitoring is needed to ensure that desorption or dissolu-
tion of residuals do not cause an increase in the level of contamination
after system operation has ceased. This monitoring may be required
for approximately 2 to 5 years after system termination and will depend
on site conditions.
  Because of the uncertainties involved in subsurface characterization,
a pump-and-treat system may require modification during the initial
operational stages. Modifications may result from  improved estimates
of hydraulic conductivity or more complete information on chemistry
and loading to the treatment facility. Other modifications may  be due
to mechanical failures of pumps, wells or surface plumbing.
  Switching from  continuous  pumping  to pulsed pumping  is one
modification that may improve the efficiency of contaminant recovery.
Pulsed pumping is the intermittent operation of a pump-and-treat system.
The time when the pumps are off can allow the contaminants to diffuse
out  of less permeable zones  and into adjacent higher hydraulic con-
ductivity zones until maximum concentrations are achieved in the latter.
For sorbed contaminants and residual NAPLs, this  nonpumping period
can allow sufficient time for equilibrium concentrations to be reached
in local groundwater.  During the subsequent pumping cycle,  the
minimum volume of contaminated groundwater can be removed at the
maximum possible concentration for the most efficient treatment. The
durations of pumping and nonpumping periods (approximately  1 to 30
days) are site-specific and only can be optimized through trial-and-error
operation. By occasionally cycling only select wells, possible stagna-
tion (zero or low flow) zones may be brought into active flowpaths and
remediated.20
  If plume capture must be maintained, it will be necessary to main-
tain pumping on the plume boundaries and perhaps only use pulsed
pumping on the interior of the  plume. Termination of the pump-and-
treat system occurs when the cleanup goals are met. In addition to
meeting concentration goals, termination also may occur when optimum
mass removal is achieved and it is not practical to reduce contaminant
levels further.

REFERENCES
 1. Ziegler, GJ., "Remediation Through Groundwater Recovery and Treatment,"
   Pollution Engineering, July, pp. 75-79, 1989.
 2. Mercer, J. M., Skipp, DC and Giffin, D., Basics of Pump-and-'Real Ground-
    Water Remediation  Technology.  EPA-600/8-90/003, Robert  S.  Ken
   Environmental Research Laboratory, U.S. EPA, Ada, OK, 1990.
 3. Lindorff, D.E. and Cartwright, K., "Ground-water Contamination: Pro-
   blems and Remedial Actions," Environmental Geology Notes No. 81, Hlinoi*
   State Geological  Survey, Urbana, IL, 58  pp., 1977.
724    TREATMENT
-------
4. U.S.  Environmental Protection Agency,  Case Studies  1-23: Remedial
   Response at Hazardous mste Sites, EPA-540/2-84-002b,  U.S.  EPA,
   Cincinnati, OH, 1984.
5. U.S. Environmental Protection Agency, Summary Report: Remedial Response
   at Hazardous mste Sites, EPA-540/2-84-002a, U.S. EPA,  Cincinnati, OH,
   1984.
6. U.S. Environmental Protection Agency, Evaluation of Growd-Wtter Extrac-
   tion Remedies, Vols. 1 and 2 (Draft), Prepared by CH2M Hill, Contract
   No. 68-W8-0098, U.S. EPA, Washington, DC, 1989.
7. Mackay, DM., and Cherry, J.A., "Groundwater Contamination: Pump-and-
   treat Remediation," Environmental Science & Technology, 23  (6), pp.
   630-636,  1989.
8. Mercer, J.W., Faust, C.R., Truschel, A.D. and Cohen, R.M., "Control of
   Groundwater Contamination: Case Studies," Proc. Detection, Control and
   Renovation of Contaminated Ground  Water, pp.  121-133, EE Div/ASCE,
   Atlantic  City, 1987.
9. U.S. Environmental Protection Agency,  Modeling Remedial Actions at
   Uncontrolled Hazardous  Waste Sites,  EPA-540/2-85/001,  U.S.  EPA,
   Cincinnati, OH, 1985.
10. Satkin, R.L. and Bedient, P.B., "Effectiveness of Various Aquifer Restoration
   Schemes Under \fcriable Hydrogeologic Conditions," Ground Water, 26 (4),
   pp. 488-498, 1988.
11. Gorelick, S.M., Voss, C.I., GUI, P.E., Murray, W., Saunders, M.A. and
   Wright,  M.H., "Aquifer Reclamation Design: The Use of Contaminant
   Transport Simulation Combined with Nonlinear Programming,"  miter
   Resources Research, 20, pp. 415-427, 1984.
12. Shafer, J.M., GWPATH: Interactive Ground-Water Flow Path Analysis,
    ISWS/BUL-69/87, Illinois State Water Survey, Champaign, IL, 1987.
13.  Ferris, J.G., Knowles, D.B., Brown, R.H. and Stallman, R.W, Theory of
    Aquifer Tests, U.S. Geological Survey Water Supply  Paper, 1536-E, pp.
    69-174, 1962.
14. Bentall, R., Methods of Determining Permeability, Transmissibility and
    Drawdown, U.S. Geological Survey, Water Supply Paper, 1536-1, pp. 243-341,
    1963.
15.  Walton, W.C., Groundwater Resource Evaluation, McGraw-Hill Book Co.,
    New York, NY, 1970.
16.  Jacob, C.E., "Flow of Groundwater, in Engineering Hydraulics, Ed. H.
    Rouse, pp. 321-386, John Wiley,  New York, NY,  1950.
17.  Ward, D.S., Buss, DR., Mercer, J.W. and Hughes, S.S., "Evaluation of
    a Groundwater Corrective Action of the Chem-Dyne Hazardous Waste Site
    Using a Telescopic Mesh Refinement Modeling Approach," Witer Resources
    Research, 23 (4), pp. 603-617, 1987.
18.  Javandel, I., Doughty, C. and Tsang, C.F., Groundwater Transport: Hand-
    book  of Mathematical  Models,  American  Geophysical Union, Water
    Resources Monograph 10, Washington, DC, 228 pp., 1984.
19.  Javandel, I. and Tsang, C.F., "Capture-Zone Type Curves: A Tool for Aquifer
    Cleanup," Ground Water, 24 (5), pp. 616-625, 1986.
20. Keely, J.F., Performance Evaluations of Pump-and-Treat Remediations, U.S.
    EPA Superfund Ground Water Issue,  EPA-540/8-89,  U.S. EPA, Washington,
    DC, 1989.
21.  U.S. Environmental Protection Agency, Superfund Public Health Evalua-
    tion Manual, EPA-540/1-86/060, U.S. EPA, Washington, DC, 1986.
                                                                                                                               TREATMENT    725
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                  Application  of Innovative  Treatment  Technologies
                                                    At NPL  Sites

                                             Walter  W. Kovalick,  Jr., Ph.D.
                                                       John Kingscott
                                                        Linda Fiedler
                                     United States Environmental Protection Agency
                                                       Washington, B.C.
INTRODUCTION
  SARA fundamental changes in the U.S. EPA's approach to hazardous
waste site remediation by providing a clear preference for the use of
permanent  remedies. The NCP'  codifies  the  U.S.  EPA's policy
preference for treatment as well. Consistent with this direction, the
Agency has made significant progress in this area. For the last 2 fiscal
years (FY 88 and FY 89), more than  70% of our RODs for source
control remedies included provisions for treatment of some portion of
the waste at sites. These treatment technologies include several well-
known technologies which are available for "off the shelf use on con-
taminated  soils  and sludges  such as  rotary kiln incineration and
solidification/stabilization. However, concerns regarding the costs or
effectiveness of these methods under a  variety of site conditions have
caused the Agency  to actively seek  the development of new and
innovative technologies to remediate hazardous waste sites.
  Our ability to develop and use new technologies leading to more cost-
effective site cleanups may well determine the eventual success of the
nation's efforts to implement the Superfund and RCRA corrective action
programs. The Agency's recent Superfund Management Review (90-Day
Study)2 recognized the importance of this issue and called for the
creation of a separate U.S. EPA office charged with the responsibility
of stimulating the use of new technologies at Superfund sites. The
Technology Innovation Office was created by the U.S.  EPA this year
to work with both the public and private  sectors to accomplish this goal.
  The goals of this Office support a strategy to overcome impediments
that restrict the broader use of new technologies. These impediments
are regulatory, institutional and informational in  nature.
  Regulatory impediments relate primarily to regulatory and permitting
requirements under RCRA. The evaluation of new hazardous waste treat-
ment technologies is an unusual area of new product engineering which
requires a permit to develop such technologies in addition to a permit
for operation. The recently completed RCRA Implementation Study3
highlights areas for attention which will make it easier for technology
developers to perform testing with hazardous wastes not on Superfund
sites.
  Institutional impediments have their roots in human nature: people
are reluctant to take unnecessary risks. U.S. EPA project managers may
not see sufficient advantage in trying something new, or private con-
sulting engineering firms may not be willing to risk their reputations
and company assets on untried technologies. PRPs and owners/operators
do not want to pay twice for solutions. The Technology Innovation Of-
fice will be sponsoring a number of outreach initiatives to provide more
training and create incentives to overcome these  barriers.
  Informational impediments concern both technical and market issues.
The Agency's Office of Research and  Development has an ongoing
program to assist vendors in developing innovative and emerging
technologies. The Superfund Innovative Technology Evaluation (SITE)
program provides an opportunity for developers to demonstrate their
capabilities to the U.S. EPA. The program produces performance and
cost data which are necessary for the engineering evaluation of new
technologies. The Technology Innovation Office is also undertaking
initiatives to develop a computerized vendor information system and
to better define the hazardous waste remediation market. These efforts
will help foster greater communication between firms that are developing
new technologies, the financial  community and potential  users.

MARKET FOR CONTAMINATED  SITE REMEDIATION
  The potential market for new and innovative technologies is very broad
and rapidly evolving. In addition to problems at Superfund sites, which
are discussed later in the paper, a recent Congressional Budget Office
report1 estimates a future obligation of nearly $150 billion over the next
30 years to remediate hazardous waste problems at federal facilities.
These facilities primarily include Department of Defense and Depart-
ment of Energy sites. Federal facilities may present unique opportunities
for innovative technology because of the unusual  nature of the  sites.
Often these sites are contaminated with pollutants related  to the pro-
duction of munitions or nuclear  devices not commonly found on sites
owned and operated by individuals. These sites may contain very large
quantities of contaminated material if they were operated for long periods
of time.
  In addition, all facilities issued a RCRA permit after November 8,
1984, must take corrective action for  contamination at or from the
facility, including releases that result from past disposal. The primary
responsibility for corrective action belongs to the owner/operator of
the individual facilities. In the recent RCRA Implementation Study, the
U.S. EPA estimates that approximately 80% of 4,700 treatment storage
or disposal facilities may require some form of corrective action.
  Leaking underground storage tanks represent another potential market
for innovative technologies.  Estimates  of the  number  of  leaking
underground tanks vary, but current data suggest at least 10% of more
than  2 million tanks may be leaking. Based on information supplied
from states, approximately  50% of these sites are petroleum  product
retailers and 5% involve hazardous waste.
  Moreover, some individual states have site inventories which rival
the number on the Federal NPL. Non-NPL sites include those that the
U.S. EPA or states have assessed and found to be ineligible for the  NPL,
unassessed or unscored sites that may  or may not be eligible for the
NPL, sites that states have not reported to the U.S. EPA and undiscovered
sites. Accurate data are not available on the number of non-NPL sites,
since  many still have not been  identified. A December  1987  GAO
report5 stated that neither states nor the U.S.  EPA has identified all
potential sites. The report estimates that between 130,000 and 425000
72(>    TREATMENT
-------
sites may eventually have to be evaluated for possible cleanup action.
Some states have active site discovery programs underway, while other
states rely solely on citizen reports of potential sites.
  The contamination problems at this broad array of sites vary widely
with various combinations of volatiles, semivolatiles, metals and radioac-
tive mixed waste. In addition, assumptions regarding cleanup levels vary
depending on whether Federal or  state agencies are responsible for
remediation. As a result, no single technology is expected to dominate
the cleanup market. Combinations of technologies with several unit pro-
cesses hi series will often be required, but narrow market niches will
also develop. This suggests an overall market  capable of supporting
a variety of technologies.

MAKING INNOVATING TECHNOLOGY MORE AVAILABLE
  Interest in the hazardous waste site remediation market on the part
of technology developers is evident from the response to SITE program
requests for proposals.  Approximately 115 proposals were received from
five solicitations for the SITE innovative demonstration program, while
210 proposals were received from four solicitations for emerging
technologies program.
  The  Technology Innovation Office is  interested in achieving  an
increase hi the supply of new technologies to help satisfy the diverse
and growing demand for remediation services. In the Superfund
program, innovative technologies  are being chosen  with increasing
frequency. In FY 1987,  almost 80% of the treatment technologies chosen
for source control were conventional. By contrast, in  FY 89 less than
50% of the chosen technologies were conventional. At present, however,
relatively few innovative technologies have been employed hi actual
cleanup efforts. It is obviously important to have firms with commer-
cial equipment available to bid competitively for work when it is adver-
tised. Improving the  balance between supply  and demand  for new
technologies can be enhanced through better communication between
technology developers, investors and site managers.
   The Technology Innovation Office is initiating an effort to provide
an opportunity for innovative technology developers to display infor-
mation about the performance and status of their units. A series of ques-
tions are being compiled to profile new technologies for source control
and in situ groundwater remediation.  Vendors  will provide informa-
tion to the U.S. EPA which will be entered into an on-line data base
and made available through ATTIC, the Office of Solid Waste and
Emergency Response Electronic Bulletin Board  and other sources. The
system will help PRPs, government representatives and  then: consultants
keep informed about the latest information on new technologies.
   A second initiative to increase communication involves a compila-
tion of information on the market or potential  demand for new tech-
nologies. This market assessment is intended to help developers and
investors make long-term strategic decisions and to help  alert the remedi-
ation community to upcoming opportunities to bid on specific projects.
The analyses will be published periodically in monographs devoted to
this subject. The analysis which follows was prepared as part of the
initial effort in this area.

SUPERFUND TECHNOLOGY SELECTION
  Table 1 provides an overview of Superfund source control remedies
by fiscal year since the 1986 Amendments. The table shows an increase
in the selection of treatment remedies and in the number of RODs speci-
fying innovative treatment technologies.
  Figure 1 provides a  more detailed look at the chosen technologies.
The data are derived from RODs and anticipated design and construc-
tion activity. A comparison of similar compilations prepared separately
for FY 87, FY 88 and FY 89 shows a trend away from the selection
of solidification/stabilization and incineration (both on-site and off-site).
Correspondingly, the largest increases are in the selection of vapor ex-
traction and bioremediation  technologies.

SITE CHARACTERIZATION
  Table 2 groups NPL sites into 14 categories. Since sites may fall into
multiple categories, the total number of sites given exceeds the NPL
inventory of 1218 which was used for this analysis. The table also gives
                              Table 1
                Overview of Source Control Remedies
                           FY 1987-1988
FY
87
88
89
RODS Signed
77
151
143
Source Control
RODS
(Final t Interim
SO
99
104
RODs Selecting
One or Hore
Treatment
Technologies for
25
70
70
RODs selecting
Innovative
Treatment
Technologies for
8
31
43
                                            ROD=Record of Decision
            Treatment Technologies Specified - 210
                      Number of RODs -165
          Solidification/
          Stabilization
             (52)
                      On-site
                    Incineration"
                        (36)
   Thermal
  Desorption
     (9)
 Chemical
Destruction
   (2)
   In-situ
 Vitrification    /
     (2)      /
         Other
          (7)
                                                           Off-site
                                                         Incineration
                                                            (28)
                             Soil
                            Washing
                              (7)
                 Vaci
                  Vapor
                 Extraction
                   (29)
                        Chemical
                        Extraction
                          (6)
 In-situ
  Soil
Flushing
  (10)
Bioremediation
    (22)
     Sources include solids, soils, sludges and liquid wastes; waste sources do not include ground water
     or surface water
     Also includes sites where location of incineration is to be determined
     Number ol times this technology was selected

                             Figure 1
                      Source Control Treatment*
                        Fiscal Year 1987-1989
the categories for sites with signed RODs through FY 89. These figures
include RODs for groundwater and source control.
  Table 3 provides background  on the criteria used to develop this
classification system. Waste source, site description and constituent
information primarily come from site summaries which are prepared
when sites are proposed for inclusion on the NPL. Data for the five
primary contaminants come from ROD Summaries. All this informa-
tion has been placed into a new data base which provides technical
characteristics for NPL sites.
  Table 4 shows the distribution of selected innovative technologies for
the site categories. However, when sites are categorized by the presence
of a specific compound, that compound may not necessarily be targeted
by  the selected technology. Table  5 provides  a  summary of the
occurrence of contaminated media for the  different site categories.
                                                                                                                       TREATMENT   727
-------
                                                          Table 2
                                            Number of NPL Sites in Each Site Category
                                             (Total Number of Sites with RODs = 465)
                                               (Total Number of NPL Sites = 1218)
Category
WOOD PRESERVING
BATTERY /LEAD
PLATING
PCB
PETROLEUM
MINING WASTE
MUNICIPAL LANDFILL
INDUSTRIAL LANDFILL
DIOXIN
VOLATILE ORGANICS
MIXED WASTE
ASBESTOS
PESTICIDES
OTHERS
Nuaber of sites
with RODs
25
8
10
63
16
18
42
124
20
237
7
8
39
92
Total number
of sites
60
25
48
156
43
37
145
361
30
702
39
16
114
178
                                Note:  Analysis based
                                summaries.  Each site
                                      on information from
                                      may fall under more
RODs and NPL site
than one category.
              Waste  Source
Wood          Lumber and  Wood
Processing    Products

Battery/Lead  Batteries
Plating

PCB


Petroleum
                                                          Table3
                                            Site Categories, Criteria Used for NPL Site
                                         Analysis, and Five Primary Contaminants for Sites
                                                 with RODs in Each Category
                                         site
                                      Description
Electroplating
              Petroleum  Refining
              and Related
              Industries
Mining Waste  Metals,  Coal,  Oil
              and Gas,
              Nonmetallic  Metals

Municipal
Landfill

Industrial
Landfill

Dioxin
Volatile
Organics

Mixed Waste
                       Municipal
                       Landfill

                       Industrial
                       Landfill
Asbestos
Pesticides


Others
•Contaminanta of equal frequency
                                                       Constituent
                                        PCB
                                                       Dioxin
                                        All VOCs
                                        Radioactive
                                        Plutonium,
                                        Radium,
                                        Strontium,
                                        Thallium,
                                        Thorium,
                                        Uranium

                                        Asbestos
                                        All Pesticides
 Five Primary Contaminants
 Arsenic,  chromium, Polynuclear Aromatic
 Hydrocarbons,  Benzene, Pentachlorophenol

 Nickel,  Cadmium,  Arsenic, Chromium Polynuclear
 Aromatic Hydrocarbons

 Chromium,  Cadmium Trichloroethene Lead, Zinc

 PCB,  Lead,  Toluene Trichloroethene Polynuclear
 Aromatic Hydrocarbons

 Volatile Organics, PCB, Arsenic Trichloroethene
 Benzene
                                                         Lead, Cadmium,  Arsenic,  Zinc, Benzene
 Lead,  Vinyl Chloride Benzene, Chromium
 Trichloroethene

 Lead,  Chromium, Benzene 1,1,2,2
 Tefcrachloroethylene, Trichloroethene

 Dioxins,  Benzene, Arsenic, Polynuclear  Aromatic
 Hydrocarbons, Pentachlorophenol

 1,1,2,2 Tetrachloroethylene, Volatile Organics,
 Chromium,  Lead, Trichloroethene

 Radium, Radioactives, Trichloroethene*,  Toluene*,
 Total  Xylenes*, Chlorobenzene*
 Asbestos,  Nickel, 1,1,2,2 Tetrachloroethylene,
 Trichloroethene, Benzene*, Toluene*,  Ethyl
 Benzene*

 Pesticides,  Chromium, Lead, Benzene,  Delta-BHC,
 Trichloroethene

 Chromium,  Lead, Zinc, Nickel, Cadmium
     TREATMENT
-------
                             Table 4
                Frequency of Innovative Technologies
                      at NPL Sites with RODs
CATEGORY
WOOD
PRESERVIHG
BATTERY/LEAD
PLATING
PCB
PETROLEUM
HIHISO VASTE
MUNICIPAL
LAHDFILL
INDUSTRIAL
LANDFILL
DIOXIN
VOLATILE
ORCANICS
MIXED WASTE
ASBESTOS
PESTICIDES
OTHERS
Vacuon/
vapor
extraction



3
1

1
1

22


4
3
Biorene-
diation
9


2
3

1
2
5
14


1
4
SOIL
vaihlng
4
I





2

6




Solvent/
chemical
extraction



3



2
1
4




ChuicaL
dechlori-
nation



3





2




Themal
decorption



3



1

9



1
In- situ
vitrifi-
cation






1
1

1




                              Tables
      Occurrence of Contaminated Media at NPL Sites with RODs
                         (Number of Sites)
 Note:  Sons sites are categorized by Che presence of a specific conpound which is
 necessarily targeted by the selected technology.
Category
WOOD PRESERVING
BATTERY/LEAD
PLATING
PCB
PETROLEUM
MINING WASTE
MUNICIPAL LANDFILL
INDUSTRIAL LANDFILL
DIOXIN '
VOLATILE ORGANICS
MIXED WASTE
ASBESTOS
PESTICIDES
OTHERS
Boil
18
7
6
55
6
4
13
49
17
133
5
6
31
10
Sludge
5
1
0
5
1
0
1
5
2
14
0
0
3
1
Sediments
4
4
0
21
1
1
3
11
3
30
1
1
6
2
  At the time of writing this paper, additional analyses were being con-
ducted to be presented verbally at the Superfund '90 Conference. Some
of the additional work will include: total volumes of waste to be remedi-
ated will be determined by media. These data will include waste volumes
for all technologies specified in RODs including land disposal, inciner-
ation, solidification/stabilization and innovative technologies. Average
volumes will then be calculated for each site category leading  to an
estimate of total volumes by category and media. The CERCLIS data
base will then be used to determine the status of remedial design and
remedial action activities. This information should help vendors better
understand the market and plan for commercializing their technologies.


ACKNOWLEDGEMENTS
  The authors gratefully acknowledge the contributions of Teresa
Pagano, Joan Rnapp and Bill Kaschak of CDM Federal Programs Cor-
poration and Hung Pham,  Pat White and Mark Walsh  of Planning
Research Corporation (PRC)  in the preparation of this paper.
DISCLAIMER
  The opinions expressed in this article are those of the authors and
do not necessarily reflect the policy or position of the U.S. EPA.
REFERENCE
1.  The National Oil and Hazardous Substances Pollution Contingency Plan,
   March 8, 1990, FR 8666-8865.
2.  U.S. EPA A Management Review of the Superfund Program, U.S. Govern-
   ment Printing Office: 1989-623-682/10263.
3.  U.S. EPA The Nation's Hazardous Waste Management Program  at a
   Crossroads - The RCRA Implementation. Study, foe U.S. EPA/530-SW-90-069,
   U.S. EPA, Washington, DC, July 1990.
4.  CBO Federal Liabilities under Hazardous Waste Laws and its supplement,
   Federal Agency Summaries, Congressional Budget Office, Washington, DC,
   May 1990
5.  GAO Superfund: Extent of Nation's Potential Hazardous Wbste Problem Still
   Unknown, GAO/RCED-88-44, GAO, Washington, DC,  Dec. 1987
                                                                                                                       TREATMENT    729
-------
                   Treatability Studies  on  Soil  Contaminated  With
                   Heavy  Metals,  Thiocyanates,  Carbon Disulfate,
              Other Volatile and  Semivolatile  Organic  Compounds
                                                    Sarah Hokanson
                                                Roxanne Breines Sukol
                                                     Steve Giti-Pour
                                                      Greg McNelly
                                                   PEI Associates,  Inc.
                                                     Cincinnati, Ohio
                                                    Edwin Earth,  m
                                        U.S. Environmental Protection Agency
                                                     Cincinnati, Ohio
ABSTRACT
  On behalf of U.S. EPA, PEI Associates, Inc. performed laboratory
screening level treatability studies to support the ongoing RI/FS for
the Halby Chemical site in Wilmington, Delaware. These studies were
designed to address the applicability of solidification/stabilization and
xanthate flotation for treatment of metals in soils. In addition to these
technologies, low-temperature thermal desorption was evaluated as a
pretreatment step to remove compounds in soils that may impede the
solidification/stabilization process and biological treatment was evaluated
for treatment of carbon disulfide and those thiocyanate compounds that
were present at high levels in soils and groundwater.
  The results from these studies indicate that: (1) aerobic and anaerobic
carbon disulfide-  and  aerobic-thiocyanate degrading organisms  are
present in soils and biodegradation of carbon disulfide and thiocyanate
compounds (as indicated by microbial growth and  oxygen consump-
tion) can occur in the laboratory with the indigenous microbial popula-
tion under aerobic conditions and sufficient amounts of nutrients; (2)
while  low-temperature thermal desorption may  not be needed as a
pretreatment step prior to solidification/stabilization,  it can successfully
remove most volatile and semivolatile organic compounds in soils at
temperatures between 300° and SOOT and between  15 and 30 minutes
residence time; and (3) the soils, themselves, do not leach appreciable
amounts of metals under TCLP test conditions and of the two binders
studied (asphalt and cement), asphalt appears to be the better binder
for reducing leachate concentrations of arsenic and copper. Significant
flotation/separation of metals from soils using xanthates was not achieved
in our limited laboratory studies; however, further studies may be needed
to more fully evaluate the applicability of this technology for removing
heavy metals from  soils. Additional feasibility and treatability studies
are recommended prior to remedy selection.

INTRODUCTION
  Since the enactment of SARA. RI/FS have included detailed evalua-
tion of treatment alternatives for soils and groundwater. Recently, the
U.S. EPA developed general procedures and guidelines for conducting
treatability studies  during the RI/FS as part of the remedy selection
process reported in the U.S.  EPA's ROD documents.1 This guidance
document, entitled Guide for Conducting Treatabiliry Studies Under
CERCLA (Interim Final), established three general levels of treatability
testing that can be  used to provide the necessary technological infor-
mation to support the FS and remedy selection  process.
  This paper presents results from laboratory screening level treatability
studies performed on soils contaminated with volatile and semivolatile
organic compounds, as w«ll  as heavy metals and inorganic com-
pounds.: This work was conducted by PEI Associates. Inc. on behalf
of U.S. EPA. Office of Research and Development under the U.S. EPA
Contract No. 68-03-3413, Work Assignment No.  2-60. The overall
approach for these studies was modeled after the policies and guidelines
given in U.S. EPA's guidance document.1
  Four treatment technologies were evaluated for treatment or removal
of organic and inorganic compounds found in soils collected from the
Halby Chemical  Site in Wilmington, Delaware.  They are low-
temperature thermal desorption, solidification/ stabilization, xanthate
flotation and biological treatment. Each technology was evaluated as
a primary treatment step, except low-temperature thermal desorption,
which was  evaluated as a pretreatment step  prior  to solidifica-
tion/stabilization.  The biological treatment study was conducted as a
critical first step to evaluate the feasibility  of biological treatment for
selected compounds. Xanthate was evaluated as a flotation/separation
agent to remove heavy metal particles from other soil material. All four
technologies were evaluated at the laboratory screening tier, as defined
in the U.S. EPA treatability study guide.1
SITE DESCRIPTION
  The Halby Chemical site covers approximately 14 acres in a highly
industrialized area in Wilmington, New Castle County, Delaware. As
Figure 1 illustrates, the  site is  situated in a tidal marshland that is
bordered on the north and west by Interstate 495, on the east by Con-
rail Railroad and on the south by Terminal Avenue. The Christina River
and adjacent marsh area are located east of the site.
  The Halby Chemical Company and the Witco Chemical Company
produced sulfur compounds from 1948 to 1977. Specific raw materials
used in the manufacturing process are shown in Table 1 and  the pro-
ducts and associated byproducts known to have been produced at the
plant are shown in Table 2. The principal chemicals that were manufac-
tured or  used at the chemical  facility include carbon disulfide,
ammonium thioglycolate (ATG), isooctyl thioglycolate (IOTG) and
ammonium thiocyanate. In addition to these compounds, pyrite ore (iron
sulfide) with trace amounts of heavy metals and coke piles have been
stored on and adjacent to the site.
  From 1948 to 1964,  the wastewater, cooling water and surface run-
off were  discharged  into an unlined lagoon.  The lagoon waters
discharged to the  Christina River through a drainage ditch connected
to Lobdell Canal  southeast of the site. The lagoon presently  receives
run-off from the railroad tracks on the east side of the site and from
the highway northwest of the site. Currently, a drainage ditch along 1-495
drains the lagoon waters during tidal fluctuations into the Christina River.
Although chemical production activities stopped in 1977, the site is still
used for storage  of carbon disulfide in above  ground tanks. Areas
adjacent to the site also  are used for storage of coke piles (north of
the site) and for truck washing (west of the site).
      TRKATMHNT
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                                                           N
        FEET
                           Figure 1
       Map of Halby Chemical  Site in Wilmington, Delaware


                            Table 1
              Raw Materials Used at the Halby Site

                      Ammonium hydroxide
                      Anhydrous ammonium
                      Carbon disulfide
                      Potassium Hydroxide
                      Sodium hydroxide
                      Monochloroacetic acid
                      Isooctyl alcohol
                      Isopropyl ether
                      Monoethanolamine
                      p-Toluene sulfonic acid
                      Solvay dense soda ash
                      Sulfun'c acid
                           Table!
       Products and Byproducts Produced at the Halby Site

                  Ammonium thioglycolate (ATG)
                  Isooctyl thioglycolate (IOTG)
                  Ammonium thiocyanate
                  Sodium sulfide
                  Sodium thiocyanate
                  Sodium hydrosultide
                  Potassium thiocyanate
   	Monoethanolamine thioglycolate	

SOIL CONTAMINATION
  The site soils and sediments are contaminated by a complex chemical
mixture of VOCs (including carbon disulfide, chlorinated ethylenes and
benzene compounds), semivolatiles (including pyrene, benzp[a]pyrene,
phenanthrene, fluorene, chrysene,  fluoranthene and acenaphthene) and
inorganic compounds (ammonium thiocyanate, arsenic, copper, cobalt,
lead, manganese, mercury, vanadium and zinc) at widely varying con-
centrations ranging from approximately 100 ppb to 1%. In the sediments
and surface soils, the highest concentrations of these compounds appear
to be located at the southern end of the site near the tanks and chemical
plant building, with lower levels in the northern and eastern portions.
Subsurface soils are also contaminated with similar VOCs, semivolatiles
and inorganic compounds to a  depth of approximately 10 feet.
  The lateral and vertical extent of contamination at the Halby Chemical
site is complex and variable. The coexistence of various classes of com-
pounds means that several treatment technologies, either as operable
units or combined in treatment trains, may need to be evaluated in the
feasibility study. In addition, because the area is primarily industrial,
the use of in situ treatment methods for remediating soils and ground-
water may be evaluated in the RI/FS.

TECHNOLOGY DESCRIPTIONS
  Several soil treatment technologies were identified by PEI and the
U.S. EPA for further study during the technology screening stage of
the RI/FS. Of these, solidification/stabilization and xanthate flotation
were evaluated for applicability as primary treatment processes for treat-
ment of the metals in the soils. Low-temperature thermal desorption
was tested as a pretreatment step prior to solidification/stabilization.
Microbial activity on site was assessed as an indicator of the site's poten-
tial for supporting bioremediation of organic contaminants, especially
carbon disulfide and thiocyanate compounds that are present at high
levels in soils and water.
  Figure 2 presents the overall treatability scheme for this project and
Table 3  presents  the  experimental plan. Table 4  summarizes  the
analytical testing program for the  soil,  groundwater and  treatment
residual fractions. Soil collected from the Halby Chemical site was sub-
jected  to physical, chemical and biological characterization tests to
delineate the soil characteristics that may influence treatment  effec-
tiveness. Each separate soil sample (surface soil and sediment) was
homogenized prior to chemical analysis and testing to ensure that
representative samples are tested for each technology and that the results
from those technologies with similar starting matrices can be compared.
The soil was analyzed for a select list of indicator compounds (Table
4) to provide initial concentration data for determining the effectiveness
of the  technologies.
               8lod«gr«liHon  I
                             Figure 2
                  Overview of Treatability Scheme

  The low-temperature thermal desorption studies were performed at
two temperatures (300° and 500 °F) and two residence times (15 and
30 minutes). The VOC, semivolatile and inorganic/metal indicator com-
pounds were measured in the soil residues from all tests. The tests were
                                                                                                                        TREATMENT    731
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conducted using soil that contained high levels of VOCs and semivolatile
contaminants.
                            Table 3
                       Experimental Plan
                                        Test condition*
                                                      HO. of     Total
                                                      repli-    Ho. of
                                                      cate*	tut ore
LOM-taapiraturt tKcrval
drtorptlon

tolldlflcatlon/iiabltlia-
ttan

Sol(dlf(catlon/itatot11 ra-
tion
                   Surface !oll/»«di«ent
                    Sad la«m /ground wtrr
                    coapoaltt
                                      3 taaparaturet
                                      2 rctfd«ncet
                                      2 blnderi x 2 «lx
                                      * ratio* * 4 blanks
                                      I binder x 2 «l* ratio*
                                      1 reagent * 1 raagant/
                                      frotKer
                                      2 traatawnt! *
                                      2 control!
8


12
  The solidification/stabilization studies were performed on thermally-
pretreated soils from the low-temperature thermal desorption (SOOT
and 30 minutes) test run and on soil samples that were not thermally
treated. For the thermally-pretreated soils, two binders (asphalt and
Portland cement Type H) were evaluated each at two binder/waste mix
ratios (0.25 and 0.4 for cement and 0.5 and 1.0 for asphalt). Asphalt
was considered as a binder agent, because an asphalt plant is located
near the site. For the previously  untreated soils, only cement was
evaluated at the same two mix ratios used for the thermally-pretreated
soils (i.e., 0.25 and 0.4). The starting materials and the stabilized pro-
ducts were subjected to leach testing using the U.S. EPA's TCLP test
                    and the extracts were analyzed for the metal indicator compounds. In
                    addition, unconfined  compressive  strength  tests were  run on  the
                    stabilized products.
                      Xanthates are the reaction products of carbon disulfide and alcohol
                    and an alkali-metal hydroxide. The initial alcohol/hydroxide reaction
                    forms an alkoxide, which then reacts with carbon disulfide to give the
                    alkali-metal xanthate. Alkali metal xanthate salts are soluble in water
                    and readily decompose  in acidic environments  to liberate carbon
                    disulfide and the corresponding alcohol. Xanthates are used extensively.
                    in the minerals processing industry as collectors in the selective separa-
                    tion  of  nonferrous  metal sulfide ores  from gangue (mixtures of
                    undesirable ores, silicates and non-ore material).
                      This process exploits a surface chemistry phenomenon, where  the
                    xanthate compound selectively coats the metal sulfide particle increasing
                    its hydrophobicity and affinity to gas bubbles. The bubbles lift the metal
                    sulfide particles to the surface where they can be skimmed off and
                    collected in a separate vessel. The degree of flotation accomplished
                    is dependent upon the particular  xanthate chosen and the presence of
                    activators, such as cupric sulfote,  or depressants, such as cyanide salts.
                    Frothing agents can be added to  enhance the life  of the bubbles and
                    allow for a more efficient separation.3 Although this process has been
                    previously used in the mining industry,  it has not been previously
                    demonstrated on contaminated  soils. Nevertheless, the presence of high
                    concentrations of carbon disulfide in the surface soils and in above
                    ground tanks on-site caused us to consider testing this mining process
                    at the laboratory screening level using a pre-formulated xanthate reagent
                    (potassium amyl xanthate) with a  frothing agent (2-ethylhexanol). The
                    soil and the recovered froth would be analyzed for the metal indicator
                    compounds.
                                                                  Table 4
                                                        Summary of Analytical Testing
Low- temperature thermal Solidification/
desorption stabilization Xanthate flotation Biological studies
Parameter
VOCS
Semivolatiles
Metals
Other inorganics
Biological
parameters
Other parameters
Untreated Untreated Untreated
soil Treated soil soil Treated soil soil Treated soil Water
2 8
2 8
s Q b b
284 16 2 4
2 8
2
248 2
Composite




8
a
   VOCs

   Carbon disulfide
   Tetrachloroethene
   Hethylene chloride
   Toluene
   2-butanone
   Other parameters
                           Semivolatiles

                           Chrysene
                           Pyrene
                           Fluoranthene
                           Benzo(b)fluoranthene
                           Benzo(k)f luoranthene
                           Benzo(a)pyrene
Metals

Arsenic
Chromium
Cobalt
Copper

Mercury
Zinc
        Inorganics

        Ammonia
        Cyanide (total)
Biological  Parameters

TOC (total  organic carbon)
Oxygen consumption
Hicrobial density
Nitrogen  (as ammonia)
Orthophosphate
pH
   UCS (s/s)
   Moisture content  (LTTD)
   Particle size analysis (LTTD)
   TCLP extracts analysis.

   Because no visible  separation occurred,  these analyses were  not performed.


  :   TREATMENT
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  The biological studies involved an initial assessment of the biological
 and chemical characteristics of site soil and groundwater, followed by
 a series of treatments evaluating the degradative activity of the indigenous
 microbial population. Microbial growth and oxygen consumption were
 measured to evaluate the potential for biological treatment of carbon
 disulfide and ammonium thiocyanate in soils and groundwater.

 PROJECT OBJECTIVES
  The objective of these treatability  studies was to determine the ap-
 plicability  of the four treatment technologies to treat or remove the
 organic and inorganic indicator compounds in soil. For low-temperature
 thermal  desorption,  the specific test  objectives  were to remove
 semivolatile organic compounds and those compounds,  such as car-
 bon disulfide, ammonia and cyanide/thiocyanate compounds, that may
 impede the solidification/stabilization process. For biological treatment,
 the test objectives were to identify and evaluate conditions under which
 indigenous microorganisms will degrade carbon disulfide and  thio-
 cyanate compounds. The test objective for xanthate flotation was to
 reduce inorganic indicator compounds from soils and the objective for
 solidification/stabilization was to reduce the leachate concentration of
 inorganic indicator compounds.  Table 5 includes specific target levels
 for the semivolatile organic indicator compounds for the low-temperature
 thermal desorption and metal indicator compounds in soils for xanthate
 flotation. These target levels are based on site-specific human health
 and environmental risks. Under the solidification/stabilization studies,
 the preliminary target levels for metals indicator compounds in TCLP
 leachate is 1 mg/L.
                             Tables
            Treatment Objectives for Treatability Studies
   Indicator compound
                                             Soil'
                                                          TCLP
                                                        extract15,
                                                          mg/L
   Semivolatiles (low-temperature
    thermal desorption studies)
     Benzo[a]pyrene                              8 mg/kg"        NA
     Chrysene                                  8 mg/kg'         NA
     Fluoranthene                               8 mg/kg          NA
     Benzo(b)f Luoranthene                         B mg/kg          NA
     Benzo(k}f luoranthene                         8 mg/kg          "A

   Metals (solidification/stabilization
    and xanthate flotation)
     Arsenic                                   50 mg/kg         1
     Cobalt                                   1,000 mg/kg'        1
     Copper                                    300 mg/kg         1
     Chromium                                    HS            1
     Zinc                                     260 mg/kg         '
     Mercury                                    1 mg/kg          1

   Physical parameters (solidification/stabilization)
     UCS	50 psi"	HA
 a Based on HOAA-recommended levels for sediments in the marsh area next to the Halby site,
  except as noted.
 b
  Arbitrarily values set for study.
  US = Hot specified.
  HA = Hot applicable.
  Based on 10* human health risk levels.
  Based on preliminary target cleanup levels for hunan health


 EXPERIMENTAL DESIGN AND PROCEDURES

  The following discussion summarizes the experimental design and
 testing procedures, including  sample  collection and preparation,
 biological treatment, xanthate flotation, low-temperature thermal desorp-
 tion treatment and solidification/stabilization studies. A discussion of
 the analytical results and  interpretation follows this section.

 Sample Collection  and Preparation

  Samples of surface soil and sediment were collected at two locations
 in the process plant area of the Halby Chemical site. These surface
 soil and sediment samples were combined in a 30-gallon steel  drum
and  used  for the  low-temperature  thermal desorption,  solidifica-
tion/stabilization and xanthate flotation studies. A separate, sterilized
container was used to collect the sediment sample for the biological
 studies.  Groundwater from well SMW-01  was  collected in three
 sterilized, 1-gallon, amber glass jars for the biological treatment study.
 Prior to  groundwater sampling, four well volumes were bailed from
 the well. In addition to these samples, subsurface soils were collected
 at two locations in the lagoon area (Fig. 1) in anticipation of performing
 additional treatability studies.
   The sediment and groundwater samples for biological studies were
 packed in ice and sent to  the bioremediation testing laboratory (IT
 Corporation, Knoxville, Tennessee) for analysis and treatability testing.
 The 30-gallon drum containing surface  soils and sediments was
 manifested as hazardous waste and shipped to the U.S. EPA T & E
 facility in Cincinnati, Ohio, for treatability testing.  Upon receipt at the
 T & E facility, the 30-gallon drum was placed in an insulated drum
 overpack with dry ice for proper storage in the hazardous waste storage
 area prior to testing.
   Soil/sediment samples were withdrawn from the drum  using an
 aluminum scoop and homogenized by hand for 10 minutes in a stainless
 steel pan under a laboratory hood. Large fragments and debris were
 removed by hand from the  pan during mixing and placed back in the
 steel drum. The soil was mixed  until uniform in color and texture.
 Homogenized soil used hi  all the treatability studies was stored in a
 5-gallon  stainless steel container at 4°C. Stainless steel spoons were
 used to transfer the soils from the container to the testing apparatus
 and appropriate sample containers for analysis.

Biological Studies
   Prior to testing, the sediment and groundwater samples were stored
at 4°C. Water samples were taken by pipette. Sediment samples were
homogenized and pulverized with a mortar and pestle, with large-sized
particles  removed by sieve.
   The biological studies involved an initial biological characterization
step followed by a series of treatment test runs. Under the biological
characterization step, the sediment and groundwater were tested for the
following parameters:
•  Microbial enumeration of heterotrophic bacteria,  as well as specific
   thiocyanate-  and carbon disulfide-degrading bacteria
•  Nutrient analysis for nitrogen (as ammonia) and orthophosphate com-
   pounds in groundwater and lagoon sediment
•  Ph of soil and groundwater
•  Total organic carbon (TOC)  in groundwater
   Under the treatment test runs, a composite sample consisting of 1
part sediment and 10 parts groundwater (by volume) was subjected to
one of four treatments:
•  Treatment  1 (nutrients  and  oxygen) —  Restore™ 375 brand
   microbialnutrients (1000 mg/L) were added to the treatment vessel.
   The head space, which constituted 50% of the total volume, was filled
   with air.
•  Treatment 2 (oxygen only) - No nutrients were added; the head space
   was filled with air.
•  Treatment 3  (nutrients only)  - 1000 mg/L of Restore™ 375 brand
   nutrients were added; the head  space ambient air was purged and
   replaced with helium.
•  Treatment 4  (biologically inhibited) - 100 mg/L mercuric chloride
   was added to inhibit all biological activity.
  The treatment vessels were sealed with Teflon® -lined silicon septa.
Sulfide and thiocyanate compounds were added to the composite treat-
ment runs. Oxygen levels were measured at frequent intervals for a
period of 14 days by taking  50  /tl of head space gas with a gas-tight
syringe and injecting the gas sample into a quantitative oxygen sensor.
Injections of air were also made at each sampling point. Microbial
growth was also monitored at the start and finish of the two-week period.

Xanthate Flotation
   Soil was homogenized and a portion was sampled for analysis of the
metal indicator compounds. The homogenized soil was then mixed with
deionized water and potassium amyl xanthate in a 4-liter glass beaker.
A frothing agent, 2-ethylhexanol, was added to the beaker. The mix-
                                                                                                                        TREATMENT    733
-------
ture was stirred and air was bubbled through to facilitate flotation of
the insoluble metal sulfides present. Figure 3 illustrates the xanthate
flotation process evaluated in the study. The froth was then skimmed
from the surface and collected in sample containers for analysis of metal
indicator compounds. The liquid was decanted and the remaining soils
were collected for analysis of metal indicator compounds.
                                            Froth/metal concentrate
                                        Procedure:
                                        1) Add water
                                        2) Begin stirring
                                        3) Slowly add untreated soil
                                        4) Add xanthate
                                        5) Begin bubbling
                                        6) Collect froth/metal in flask
                             Figure 3
                        Xanthate Flotation
Low-Temperature Thermal  Description
  Thermal treatment of homogenized soils was performed by placing
approximately 800 g of soil in a 4-liter reaction flask with a stirring
paddle and heating indirectly  and gradually until the soils reached the
target temperature (300 °F or 500 °F).  Figure 4 illustrates the testing
apparatus used in the study. The soil was then heated at that temperature
(±  7%) for 15 or 30 minutes.  The reactor  vessel was continuously
purged with nitrogen gas to reduce the possibility of fire or explosion.
After completion of the test run, the heating mantle was turned off and
the sample allowed to cool to ambient temperatures,  prior to transferring
the solid residue to sample containers for analysis.  Eight samples (two
temperatures x two reaction times x two replicate runs) were generated
at the end of the experiments.  To prepare samples of thermally-treated
soil for solidification/stabilization, additional 800-g soil samples were
heated at 500 °F for 30 minutes. The evolved gases from the 500 °F and
30 minute test runs were condensed in a cold-finger condenser, collected
in a 1-liter volumetric flask and composited for analysis of the indicator
compounds.

Solidification/Stabilization
  Portland cement Type II was added to the thermally-pretreated and
untreated soil samples at binder/waste mix ratios of 0.25 and 0.4 (by
weight). Sufficient water (approximately 25% by weight of total solids)
was added to the  mixtures  to pass  the slump test. In the case of the
thermally-pretreated soils,  petroleum-based asphalt was pre-heated to
approximately 140 °C and soils were heated  to 60 °C and then added
at binder/soil mix ratios of 0.5 and  1.0 (by weight). In addition, blank
samples were prepared by  mixing clean sand and  the binder (cement
or asphalt) at the above mix ratios. The mixtures were poured into rigid
plastic molds and allowed to cure in zip-lock storage bags for a minimum
of 14 days.  A total of 12 stabilized products  (two  binders x two mix
ratios x two replicates + four blanks) for the thermally treated soils
and 4 stabilized products (one  binder x two mix ratios x two replicates)
for ihe untreated soils were generated and subjected  to unconfined com-
pressivc  strength  and TCLP tests for metal  indicator compounds.
                             Figure 4
                    Diagram of Desorption Vessel
RESULTS AND DISCUSSION
  The following paragraphs summarize the analytical results and discus-
sions for each of the four treatment technologies. Overall conclusions
concerning the applicability of these technologies for remediation of
the soils are presented in the following section.

Biological Studies
  The initial biological characterization produced the following results
(Tables  6 to 9):
• Ph of the groundwater is within acceptable range for bioremediation
  and the soils are only slightly acidic
• Groundwater is deficient in orthophosphate
• Aerobic carbon disulfide and thiocyanate degraders were present in
  sediment samples; however, the microbial population in groundwater
  is low. Aerobic thiocyanate) and carbon disul fide-degrading microbes
  comprised approximately 10%  of the total aerobic microbial popula-
  tion found in the sediment and water
• Anaerobic carbon disulfide degraders were detected in sediment and
  groundwater. A relatively high concentration of anaerobic carbon
  disulfide degraders was found in the sediment sample. No anaerobic
  thiocyanate degraders  were  observed in  sediment or groundwater
• Metabolic activity and microbial growth were observed on the organic
  carbon contained in the site water samples.
Based on these results, we conclude that site  soils contain adequate
amount of aerobic and anaerobic carbon disulfide degraders and aerobic
thiocyanate degraders. Site groundwater contains lower levels of both
aerobic and anaerobic carbon disulfide degraders, but little or no thio-
cyanate degraders.
  The results from the four treatment runs are shown in Table 10 and
Figure  5. The results of these experiments  indicate that  addition
stimulates the  growth and metabolism  of carbon  disulfide- and
thiocyanate-degrading microbes (Treatments 1 and 2). A deficiency of
s appears to inhibit the growth of thiocyanate degraders,  only (Treat-
ment 2). The results for  microbial population density in  Treatment 3
are not  valid because of a leak in the treatment vessel that introduced
oxygen  to the system. The presence of oxygen in Treatment 3 probably
inhibited the growth of anaerobic microbes. The increased population
density  of heterotrophs and carbon disulfide degraders observed  in the
killed control treatment (Treatment 4) may be indicative of the presence
of mercury-resistant organisms. Based on these results, thiocyanate
degraders appear to be able to grow only in the presence of oxygen
and nutrients; carbon disulfide degraders are able to grow under aerobic
conditions with  or without nutrients.
       TREATMENT
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                            Table 6
     Inorganic Nutrient Concentration and pHof Site Samples
Sanple
Sediacnt
Water- 1
Uater-2
Uater-3
water-4
Orthophosphate, ppn
190
-------
• TCLP leachate concentrations of arsenic, chromium and mercury
  from the thermally-pretreated soils and untreated soils are well below
  the TCLP regulatory levels  that are used to classify  wastes as
  characteristically hazardous (40 CFR Part 261.24). In addition, for
  these unsolidified soil samples, leachate concentrations of all metal
  indicator compounds are at or below the treatment target level of
  1 mg/L.
• Although leachate concentrations are low, those for arsenic and copper
  are significantly reduced by asphalt binder at both mix ratios; the
  cement binder did not perform as well as the asphalt and in the case
  of arsenic and  copper, it resulted in increased concentrations.
• Both  the asphalt and cement binders significantly reduced concen-
  trations of zinc in the leachate.
• Increased chromium concentrations observed in leachate  from
  cement-based products may have resulted from chromium in either
  the portland cement material or the tap water used during the mixing
  process, since the levels are comparable to those found for the two
  blank samples.  Chromium is generally known to leach more readily
  under basic conditions such as those created by the cement process.
  Chromium is present at levels near or below detection limits in the
  leachate from the asphalt-based products.
• Leachate levels of the metal indicator compounds are similar for the
  cement-based products of thermally-pretreated soil and untreated soils.
   As shown in Table 11, the moderate to high concentrations of metals
 (between 200 and 150 mg/kg) present in the thermally-pretreated and
 untreated soils apparently do not readily leach in appreciable amounts
 under TCLP test conditions. Leachate concentrations of these metals
 may be much greater, however, in multiple extraction tests or other leach
 tests that are designed to address long-term leaching rate over  time.
 The need for solidification/stabilization of soils should be investigated
 by conducting additional leach  testing of the soils.
                                                    While the asphalt appears to be the better binder of the two studied
                                                  for arsenic and copper, the lower leachate levels reported for the asphalt-
                                                  based products may be partially due to higher dilution by asphalt than
                                                  by cement (i.e., higher binder to soil mix ratios). In addition, several
                                                  issues should be evaluated further prior to selecting asphalt as the solidi-
                                                  fying/stabilizing agent for previously  untreated soils:  (1) need  for
                                                  dewatering of the soils prior to mixing, (2) potential VOC  emissions
                                                  during mixing and (3) potential leaching of volatile and semivolatile
                                                  organic compounds. Therefore,  additional feasibility analyses and bench-
                                                  scale studies may be warranted to evaluate these issues, if solidifica-
                                                  tion/stabilization is deemed necessary for reduction of metals leaching
                                                  from soils to  surface and ground waters.

                                                  CONCLUSIONS AND RECOMMENDATIONS
                                                    Based on these preliminary studies, the following overall conclusions
                                                  are drawn:
                                                  • Bacteria capable of degrading carbon disulfide and thiocyanate are
                                                    present in the soils under aerobic conditions with sufficient nutrient
                                                    supply. The presence, growth and metabolism of aerobic carbon
                                                    disulfide and thiocyanate degraders suggests the possibility of using
                                                    an above ground bioreactor treatment system.
                                                  • Xanthate flotation/separation of heavy metals from soils was not suc-
                                                    cessful under the limited experimental conditions tested.
                                                  • While low-temperature thermal desorption at temperatures between
                                                    300° and SOOT and between 15 and 30 minutes residence time can
                                                    successfully remove VOCs and semivolatile organic compounds from
                                                    soils,  it may not  be  needed as a  pretreatment step  prior  to
                                                    solidification/stabilization.
                                                  • The soils, themselves, do not leach metals at appreciable levels under
                                                    TCLP test conditions. However, among the two binders tested, asphalt
                                                    binder appears to be the much better binder material  for reducing
                                                                 Table 11
                                                    Analytical Results for Untreated (Raw)
                                                       and LTTD Treated Soil Samples
Metals and inorganics.


Untreated
(raw) sol 1
tamp Let
A
B
Average
LTTD treated
soil aaoples
(300'f,
IS Bin)
A
S
Average
LTTD treated
coll staples
(300'F,
30 Bin)
A
B
Average

""j


116
115
115




196
195
195




196
185
190


AS


217
248
232




288
283
285




344
J22
333


Cr

c
HA
HA
HA




317
310
313




297
JOB
302


Co


11.0
11.7
11.3




19
19
19




17.1
17.5
17.3


Cu


285
328
306




377
406
391




351
398
374

pg/g

CH


41.0
32.6
36.8




16.0
22.8
19.4




37.4
43.5
40.4

Volatile organics, fig/kg

In


1380
1230
1305




1410
1580
1495




1130
1490
1310


2-But

d e
HD (10)
HO
HO




190
220
205




300
220
260


CS2


HO (5)
HD
HO




17
22
19




23
7
15


HeCl


21
24
22




180
190
185




110
46
78


TCE


180
150
165




5
7
6




a
6
7


Tol


370
150
260




160
140
150




130
60
95


Chry


4800
3500
4150




2200
2400
2300




3200
4900
4050


Pyr


7100
8300
7700




1400
2400
1900




5000
HO (660)
<2830

Semi volati les, Ms/kg

Fluor


7800
7900
7850




3700
4600
4150




6400
HD (660)
<3530


B(b)F


4500
3800
4150




2500
3000
2750




4000
HO (660)
<2330


B(k)F


1600
1900
1750




1300
1500
1400




1800
HO (660)
•0230


B(»P


1900
1700
1800




NO (660)
NO
NO




910
2700
1805

Per-
cent
•oil-
ture


20.1
20.1
20.4




0.05
0.21
0.1]




0.24
0.4S
0.34

 LTTD treated
 soil taopltB
 (500-F.
 15 «ln)       275   349
  A         287   300
  I         281   324
 Average
272   17.9  390   6.26  1480
234   16.0  379   6.19  1600
253   16.9  384   6.22  1540
29      10    310     6  170      HO (660)  HO (660)   HO (660)   NO (660)   NO (660)   HO (660)   0.09
89       62005  140         HO       HO       HD       HO       HO       NO      0.0!
59       a    255     5  155         HD       HO       HD       »       HO       HD      0.07
LTTO treated
soil samples
(iOOM,
JO .In) 224 316
A 286 313
1 255 314
Average
? tut • 2-autenone
Ct, • Carbon dltullide
Heel • ftethylene chloride
TCI • TetracMoroethene
Tol • Toluene

c
HA - eot anal yied.
a
«i * eot detected.
t
•.jttirrs in parentheses are


255 17.8 363
274 17.7 370
264 17.7 366

B
Diry .
Pyr .
Fluor
l(t»P
B(k)P
l(a>P




ir-. -i -oo detects


6.71 1180 15 ID (5) 79, 5 5
9. JO 1IJO 43 10 680 5 62
8,00 1255 29 <7 379 5 33

Chrysene
Pyrerw
• Fluoramhene
• aento(b)f luoranthcne
• Ienlo4k)f luorentnene
• BemoCa)* luorenthene




li.lt. .


HD (660) HD (660) HO (660) NO (660) HO (660) NO (660) 0.2!
HO NO ID HO «0 ID 0.10
ID NO HO HO HO HO 0.17












       TREATMENT
-------
leachate concentrations of the metal indicator compounds, although
dilution of soils by the binder was not taken into account. Additional
feasibility and treatability studies are needed if solidification/stabiliza-
tion is deemed necessary to reduce metal leaching from soils to sur-
face and groundwater.
                                        i
                II
                                   18345
                                     Carbon Bisulfide
                              180
                              160
                              140
                              120
                              100
                              80
                                  12345
                                    Telrachloroethene
                               1 = Untreated soil
                               2 = LTTD treated soil (300°F, 15 minutes)
                               3 = LTTD treated soil (300°F, 30 minutes)
                               4 = LTTD treated soil (500°F, 15 minutes)
                               5 = LTTD treated soil (500°F, 30 minutes)

                               • All concentrations in ng/kg.

                             19 =  Below detection limits
                            Figure 6
            Effectiveness of LTTD Process in Removal
                  of Volatiles from Soil Samples
   12345
   Benzo (b) Fluoranthene
12345
Benzo (k) Fluoranthene
                                                         Benzo (a) Pyrene
                  1   Untreated soil
                  2 = LTTD treated soil (300°F, 15 minutes)
                  3 = LTTD treated soil (300°F, 30 minutes)
                  4 = LTTp treated soil (500°F, 15 minutes)
                  5 = LTTD treated soil (500°F, 30 minutes)

                  • All concentrations in/jg^kg.

                 jjjj    Below detection limits
                             Figure 7
            Effectiveness of LTTD Process in Removal
                of Semivolatiles from Soil Samples
                                                        1234
                                                             Chromium
                                                                                  1  = Untreated soil
                                                                                  2 = LTTD treated soil (300°F, 15 minutes)
                                                                                  3 - LTTD treated soil (300°F, 30 minutes)
                                                                                  4 = LTTD treated soil (500°F, 15 minutes)
                                                                                  5 = LTTD treated soil (500°F, 30 minutes)

                                                                                  • All concentrations in jio/g.
                                                                                 Figure 8
                                                                 Effectiveness of LTTD Process in Removal
                                                                  of Various Inorganics from Soil Samples


                                                                                 Table 12
                                                     Results of TCLP Leachate Analysis for Untreated (Raw), Treated
                                                                and Cement-based Solidified Soil Samples
                                                                                  (mg/L)
Type of sample
Untreated (ran) soil
A

Average
LTTD treated soil (500'F,
30 min)
A
B
Average
Solidified raw soil
(B/S = 0.25)
A
B
Average
Solidified raw soil
(B/S = 0.40)
A
B
Average
Solidified LTTO treated
soil (B/S = 0.29}
A
B
Average
Solidified LTTO treated
toil (fl/S » 0.40)
A
B
Average
Arsenic

0.0131
0.0141
0.0136


0.0281
0.0331
0.0306


0.0515
0.0455
0.0485


0.0295
0.0285
0.0290


0.0741
0.0701
0.0721


0.0131
0.0121
0.0126
Chromium

KD8 (0.003)b
HD
HD


HD (0.003)
ND
NO


0.213
0.204
0.208


0.115
0.123
0.119


0.132
0.121
0.126


0.17
0.14
0.15
Cobalt

HD (0.03)
HD
ND


0.044
0.060
0.052


HD (0.03)
KD
HD


NO (0.03)
HO
ND


HD (0.03)
HO
HD


HO (0.03)
HD
HD
opper

.201
.107
.194


.400
.419
.409


.846
.814
.830


.071
.077
.074


.037
.025
.031


.440
.371
.405
Mercury

ND (0.0001)
ND
HO


ND (0.0001)
KD
KD


HD (0.0001)
HD
HD


HD (0.0001)
ND
HD


NO (0.0001)
ND
NO


HD (0.0001)
HD
HD
Zinc

1.62
1.51
1.56


6.10
8.05
7.07


HD (0.02)
HD
HD


KD (0.02)
ND
NO


ND (0.02)
NO
HD


HO (0.02)
KD
HD
                                                                                  Solidified blank s
                                                                                  
-------
  (4) xanthate flotation agent and concentration and (5) frother con-
  centration/bubbler flow speeds.
• Additional TCLP or other leach testing (preferably a multiple waste
  extraction test or long-term leach study) of soils to adequately deter-
  mine the need for solidification/stabilization to reduce the leaching
  of metals from the soils to the surface and groundwaters.
• Upon determining the need for solidification/stabilization of soils,
  perform feasibility analysis comparing costs for cement-based and
  asphalt-based solidification/stabilization processes taking into account
  the need for dewatering prior to using asphalt. Upon determining
  the more feasible solidification/stabilization process perform addi-
  tional banch-scale studies evaluating leachate levels of semivolatile
  and metal indicator compounds and VOC emissions during mixing,
  at binder to soil mix ratios between 0.5  and 0.25 (for asphalt) or
  between  0.25 and  0.40 (for cement).
These additional studies could not be performed under the existing scope
and budget, but they are needed to build upon data presented in this
paper and to help further refine the design,  cost and performance for
soil treatment alternatives.

                             Tiible 13
               Results of TCLP Leachate Analysis for
      LTTD-Treated and Asphalt-based Solidified Soil Samples
                             (mg/L)
                      0.0281
                      0 QJJ1
                      0 0106
0,0*4
0.060
0.0*2
                                                     > (0.0001)   .10
Solidified llfD trtit*d
M»ll (l/f • O.iO)

1
Av.rW
fattdlflwJ I no irviiod
Mil {•/•! - 1.00)
A
•
*v«r«p«
latldlMrt blank soil
(•/I • O.W)
A
Av«rig.
ioltSIf l«d bl*nk toil
lift • 1.00)
A
Average


HO (0.005)
DO
HO


HD (0.005)
ND
HD


HD (0.005)
ND


MO (0,005)
NO


0.006
0.008
0.007


NO (0.003)
HI
HD


ND (0.00!)
MD


HO (0.00))
HO


ID (0 03)
MO
HO


HO (0.03)
HD
MD


ND (0.025)
HO


«D (0.025)
MO


0,165
0.017
0.091


0.013
0.015
O.OU


HD (0.005)
H>


HD (O.OOi)
HD


HD (0.0001)
W>
HD


HD (o.oooi >
HD
HD


HD (0.0001)
HD


HD (0.0001)
HD


553
329
Ml


H6
276
411


292
292


335
335
   HD • Hot (tatrcted.

   HiMtwrl In p*r*nth«e* i
                    • method detection Halt
ACKNOWLEDGEMENTS
  The authors would  like to thank  the  following people for their
assistance and guidance throughout the treatability studies and for their
review of this paper: Duane Graves of IT Corporation in Knoxville,
Tennessee (who conducted the biotreatability study); Judy Hessling and
Mike Taylor of  PEI Associates, Inc. (who provided direction and
guidance throughout the project); Jeff Davis of PEI Associates, Inc.
(who developed the QAPJP and  was part  of the initial scoping phase
of this project); Paul Mraz, Jr. and John  Murphy of PEI Associates,
Inc. (who reviewed and gave helpful comments on this paper); Roberta
Riccio of U.S.  EPA Region ID. (who directed and managed the RJ/FS
and treatability studies for the Halby Chemical site); and Harry Harbold
of U.S. EPA Region in (who reviewed this paper on behalf of U.S.
EPA). This project was performed  under U.S. EPA Contract No.
68-03-3413, Work Assignment No. 2-60 for Edwin Earth, ffl of U.S.
EPA Office of Research and Development in Cincinnati, Ohio.  U.S.
EPA Region HI provided  the funding for the treatability studies.

REFERENCES
1.  U.S. EPA. Guide for Conducting Treaiability Studies  Under CERCH.  In-
   tcnm Final. U.S.  EPA. Washington, DC,  1989.
2  PEI Associates.  Inc.. "Trcatability Study Report for Contaminated Soils and
   Sediments from the Halby Chemical Site. Wilmington, Delaware." Prepared
   for U.S. EPA. Office of Research and  Development under U.S. EPA Con-
   tract No. 68-03-34H, Work Assignment No.  2-60, PEI Associates, Inc, Cin-
   cinnati. OH.  1990
3.  Rao. S.R.. XaniHaifi and Related Compounds. Marcel Dekker. Inc., New
   York.  NY.  1971
                                                            Untreated soil
                                                            LTTD treated son (SOO'F, 30 minutes)
                                                            Solidified raw soil (B/S - 0.2S)
                                                            Solidified raw soil (B/S - 0.40)
                                                            Solidified LTTD treated soil (B/S - 025)
                                                            Solidified LTTD treated soil (B/S • 0.40)
                                                            Solidified blank soil (B/S - 0.25)
                                                            Solidified blank soil (B/S - 0.40)
    • All concentrations In mg/L
   m , Below detection limits

              Figure 9
Results of TCLP Leachate Analysis for
   Cement-based Solidified Samples
                                    0035
                                     003
                                    0025
                                     002
                                    0015
                                     001
                                    0005
                                       0

                                         12345
                                               Arsenic

'

0.25 	
0.2- _-
0 15- -•-
01-t
UU3 HB

1

•
•
1 	
1 	
•
• •
• I _

00008-
00007-
0.0006-
0.0004-










wa IH m m m m
23456 123456
Capper Mercury
                                                                                             23458
                                                                                                BIB
                                                          1    Untreated soil
                                                          2   LTTD treated soil
                                                          3   Solidified LTTD treated 80(1 (B/S - 0.50)
                                                          4   Solidified LTTD treated soil (B/S - 1.00)
                                                          5   Solidified blank soil (B/S - 1.00)
                                                          6   Solidified blank soil (B/S - 0.50)

                                                          •  All concentrations in mg/L

                                                         mm • Below detection limits
                                                                    Figure 10
                                         Results of TCLP Leachate Analysis for Asphalt-base Solidified Samples
       TREATM1NT
-------
                       Acid Extraction  and  Chemical Fixation  of
                                      Metal—Contaminated  Soil

                                              Hsin H. Yeh, Ph.D., RE.
                                            Dev R. Sachdev, Ph.D., RE.
                                             Ebasco Services Incorporated
                                                 Lyndhurst,  New Jersey
                                                  Joel A. Singerman
                                        U.S.  Environmental Protection Agency
                                    Emergency and Remedial Response Division
                                                  New York, New York
ABSTRACT
  A detailed bench-scale treatability  study of acid extraction and
chemical fixation was conducted on the metal-contaminated (cadmium,
nickel and cobalt) soil at the former battery plant grounds of Marathon
Battery Company Superfund Site situated in the Village of Cold Spring,
New \brk. For acid extraction,  five  variables, including leaching
solvent, pH, soil concentration, contact time and number of extraction
stages, were studied. In addition, other related treatment processes,
including base recovery, settling and dewatering, also were studied. For
chemical fixation, a proprietary reagent consisting of Portland cement,
silicate and other additives was used. The most optimum reagent ratio
was determined through a screening procedure. TCLP and MEP were
performed on the chemically-fixated soils to determine the leachability
and persistence. The objective of this  paper is to present the treata-
bility study results so that the findings and conclusions can be used
to support the remediation of other Superfund or hazardous waste sites
with similar contamination.

INTRODUCTION
  As part of the RI/FS  performed on the former battery plant grounds
portion of the Marathon Battery Company Superfund Site, acid extrac-
tion and chemical fixation were evaluated for the remediation of the
metal-contaminated soils.1-2 Extensive bench-scale tests were designed
and conducted to confirm the applicability and treatability of these two
remedial technologies. This paper presents the treatability test methods
and results. It is hoped  that the findings and conclusions presented in
this paper can be used to support  the remediation of other Superfund
or hazardous waste sites with similar  contamination.

BACKGROUND
  The Marathon Battery Company site, situated in the Village of Cold
Spring, Putnam County, New York, is located across the Hudson River
and slightly north from the United States Military Academy at West
Point. The  site is approximately 40 miles north of New York City. The
Marathon Battery Company site  is comprised of three study areas:
Area I, which consists of East Foundry Cover March and Constitu-
tion Marsh; Area n, which encompasses a former batter manufacturing
facility, its  grounds and the adjacent residential yards; and Area  HI,
which includes East and West Foundry Coves and the Hudson River
in the vicinity of the Cold Spring pier (Fig.  1).
EXTENT OF CONTAMINATION
  Cadmium, nickel, and cobalt, contamination have been detected in
the sediments (Areas I and ffl) and soils (Area IT) in all three areas.1"8
The source of the contamination  is the former Ni-Cd battery manu-
facturing plant (located in Area H) which operated from 1952-1979.
  The measured concentrations of Cd, Ni and Co in the Area  n soils
are 10 to 5,580 mg/kg, 26 to 2,046 mg/kg and 7 to 161 mg/kg, respec-
tively. Only the surface soils, i.e., upper 2 to 3 ft, are contaminated
with these heavy metals. Generally, the soil which is closest to the
surface has the highest metal concentrations. The concentration dis-
tribution patterns of these metals are very similar. Based on the results
of a risk assessment1 and the recommendation of the Agency for Toxic
Substances and Disease Registry, a Cd cleanup level of 20 mg/kg was
selected for the site (while Ni and Co contamination are also present,
Cd was used in the analysis since it is the most toxic of the three metals).
Employing the 20 mg/kg cadmium remediation level, the total volume
of metal-contaminated soil requiring remediation was estimated to be
5,250 yd3.
 EB492O
                            Figure 1
                      Marathon Battery Site
           East Foundry Cove Marsh and Constitution Marsh
                                                                                                             TREATMENT   739
-------
  TCLP tests were conducted on the soil samples with cadmium con-
centrations ranging from 114 to 5,580 mg/kg.' The results indicate that
cadmium concentrations ranging from 3.9 to 97.6 mg/L in the extracts
exceed the regulatory limit  of  1.0 mg/L. Therefore, the cadmium-
contaminated soil at the former battery plant grounds may be considered
hazardous under the RCRA.  There are no TCLP limits for nickel and
cobalt.

TREATABILITY TEST METHODS
  Both acid extraction and chemical fixation bench-scale tests were con-
ducted in a U.S. EPA mobile laboratory located on the former battery
plant grounds. Acid extraction tests were performed by Ebasco Services
Incorporated (Ebasco) and the liquid and solid samples generated during
the tests were analyzed  by Hittman-Ebasco Associates Incorporated
(HEAT). Chemical fixation tests were performed in the on-site laboratory
by Chemfix Technologies, Inc. (Chemfix) and the fixated soil samples
were shipped to an off-site Chemfix laboratory for further testing and
analysis. For conducting these bench-scale tests, a total of approximately
4.0 kg of soil were collected from the area showing the highest levels
of Cd, Ni and Co contamination. In order to determine the metal con-
centrations in the collected soil, 20 samples were taken and analyzed
for Cd, Ni and Co. The results indicate that the concentration ranges
for Cd, Ni and Co are 856 to 2,873 mg/kg, 585 to 1,829 mg/kg and
40.3 to 84.2 mg/kg, respectively and their corresponding average con-
centrations are 1,420 mg/kg, 1,060 mg/kg and 52.4 mg/kg, respectively.
These results also show that the metal concentrations are quite variable
in the soil and therefore, for the acid extraction tests, metal concentra-
tions must be determined for both liquid and  solid phases in order to
make an accurate evaluation of the effectiveness of this treatment process.

Acid  Extraction Test
  Acids have often very successfully extracted and recovered metals.
The primary purpose of this bench-scale treatability test was to iden-
tify an acid which could effectively extract the metals from the con-
taminated soil so that the metal residual concentrations in the soil would
meet the remediation  level.
  Several  variables can affect the  amount of metals extracted  from a
given contaminated soil. For this test, the following five major variables
were selected to determine  their effects on acid extraction:
•  Leaching  Solvent:  Six leaching  solvents  were  evaluated (i.e.,
   hydrochloric acid, sulfuric acid,  nitric acid (HNOj) and  three mixed
   solutions of sulfuric acid and ferric sulfate designated as Ml,  M2
   and  M3  and defined in Table 1).

                             Table 1
            Acid Extraction  Bench-Scale Treatability  Test
                        Testing Conditions
               	Testing Conditions	
   Leaching
   Solvent
   Soil
   Concent rat Ion
   Contact
   Tt»e
   Nuafcer of
   Extraction
   Stage*
Leaching
Solvent

HC1, H2SOt,.
RN03. Ml*,
N2* L N3*

HC1
H,SOt
HC1
HjSO,,
                                 Concentration   Tine      Ext
                             pH    (I by vt. 1     (Hrs. I     	S.
                             1.0      5          1



                             1.2 I 3   5          1


                             1.0      S, 10 I 15    1
                                                          abet of
                                                          raction
                             1.0
                                                1.2.',
                                                12, 24 L 48
                                                          1,2,3,
                                 CHe. 1 c.l Ccapodtloo.
                             tin 1.0 liter dgioniged Hater)
                             1C |r H;504
                             10 IT I.SOx.
                             ••0 ,r ijso^
                        !>0  if Fej (50^)3
                        10  fr Fez J
                         3  |r Fej (804)3
                                                                       • pH: Three pH levels were evaluated (i.e., pH of 1, 2 and 3).
                                                                       • Soil Concentration: Three soil concentrations were evaluated (i.e.,
                                                                         5%, 10% and 15% by weight).
                                                                       • Contact Time: Six contact times were evaluated (i.e., 1, 2, 4, 12,
                                                                         24  and 48 hours).
                                                                       • Number of Extraction Stages: Six extraction stages were evaluated.

                                                                         Table 1 summarizes the testing conditions used to evaluate the effects
                                                                       of the aforementioned variables on the effectiveness of acid extraction.
                                                                       As indicated in the table,  when one variable was evaluated, the other
                                                                       variables were held at preset constant conditions.
                                                                         Each acid extraction test was carried out by simply mixing a leaching
                                                                       solvent with the  metal-contaminated soil at the  preset testing condi-
                                                                       tions of pH, soil concentration, contact time and  number of extraction
                                                                       stages (Table  1). The mixing continued until the specified contact time
                                                                       was reached and  the mixture was then separated into liquid and solid
                                                                       phases by vacuum filtration. Samples were taken  from both the filtrate
                                                                       and filtered solids for analyses to determine the mass distributions of
                                                                       Cd, Ni and Co in the liquid and solid phases. The  percentage of a metal
                                                                       extracted from the  soil was be calculated  by the following equation:
                                                                       Percent Metal Extracted (%)  =.
                                                                                                            MML
                                                                                                          x  100%    (1)
                                (MML -t- MMS)
where: MML = Metal Mass in the Liquid Phase (or leaching solvent)
       MMS =  Metal Mass in the Solid Phase (or soil)
  For the cases of multiple stages of extraction, no samples were taken
from the solid phases during intermediate stages. In addition, fresh
leaching  solvent was  used at  each stage  of the multiple stages of
extraction.
  As a part of the acid extraction treatability test, a base recovery test
was conducted to examine the possibility of recovering the metals from
the spent leaching solvents through precipitation at higher pH levels.
Sodium hydroxide was used to raise the pH and three pH levels, i.e.,
7, 9 and 11, were evaluated by running ajar test. In addition, zone settling
rate tests and Buchner Funnel vacuum filtration tests were performed
on the metal sludge generated during the base recovery tests to deter-
mine the settleability and dewaterability of the metal sludge. The testing
procedures for conducting  these tests can be easily found elsewhere9'10
and are not discussed in this paper.

Chemical Fixation Test
  The purpose of this bench-scale test was to confirm whether the metals
present in the soil could be chemically stabilized  and/or physically
encapsulated  in the soil so that the metal-contaminated soil could be
transformed into a material which:
• Would not  exceed  maximum allowable concentration in  sample
  leachate  when subjected to the RCRA TCLP
• Would satisfy the Multiple Extraction Procedure  (MEP) which has
  been used to estimate the long-term stability of chemically fixated
  soil under  conditions simulating  1,000 years of acid  rain
  If  successful,  the  metal-contaminated soil  would be  considered
nonhazardous and suitable for disposal in a nonhazardous waste landfill.
  The reagent used by  Chemfix to  chemically  fixate  the  metal-
contaminated soil consisted of Portland cement, silicate and other pro-
prietary additives. The optimum reagent ratio was determined by first
running a screening test on ten 100-gram soil samples, each mixed with
a different reagent ratio.  Unconfined  compressive strength  (UCS)
readings were performed at various time intervals during the curing
process of these ten mixtures. Once UCS trends were established, three
of the best  reagent ratios were selected. New samples of these three
selected reagent ratios were made and shipped  to an off-site Chemfix
laboratory for UCS and TCLP tests. The  mixture  which passed the
TCLP test and yielded the best UCS readings was selected for the MEP
test.  If the mixture passed the  MEP test, the associated reagent ratio
would be considered as the optimum one to chemically fixate the metal-
contaminated soil.  A  duplicate soil sample was  thus made with the
"40
       TREATM1NT
-------
optimum reagent ratio and it was tested again for UCS, TCLP and MEP
to confirm the reproducibility of the results.

TREATABILITY TEST RESULTS
  The results of the bench-scale treatability tests of acid extraction and
chemical fixation on the metal-contaminated soil are discussed below.

Acid Extraction Test Results
  All of the leaching solvents tested achieved greater than 90% extrac-
tion of cadmium from the contaminated soil (Table 2). For nickel and
cobalt, HjSO^ Ml, M2 and M3 appear to be more effective than HC1
and HNO3 to leach out these two metals from the contaminated soil.
Since cadmium was the most hazardous contaminant among the three
metals of concern and since the cleanup requirement for cadmium was
the most stringent, the effectiveness in extracting cadmium from the
contaminated soil became one of the important factors in selecting a
leaching solvent. The other factors considered were  chemical cost and
number and amount of chemicals used. After evaluation of these factors,
HC1 and  HjSO,,  were selected and the  remaining variables  were
studied using only HC1 and H2SO4.
                             Table 2
              Effect of Various Leaching Solvents On
            Acid Extraction of Metal-Contaminated Soil
   Leaching
   Solvent
   Ml*

   M2*

   H3*
    Percentage of Metal Extracted. I**

Cadmium          Nickel         Cfltfllt
 92.8

 91.0

 91.5

 90.9

 92.5

 91.1
63.8

81.0

68.4

82. y

88.5

82.z
59.9

74.3

56.1
76.0

83.0

75.8
                                                   0
                                                   g
                                                   <
                                                   E
                                                   u.
                                                   O
                                                   ui
                                                                          U
                                                                          cc
                                                                          Ul
                                                                          Q.
                                                       S
                                                       E  60

                                                       1  40
                                                       3
                                                          20
                                                                                                       +-..A  I
           Figure 2
Effect of pH on Acid Extraction of
    Metal-Contaminated Soil
   * See Table 1 for definition.

   ** Average values of two tests.
  The pH levels can significantly affect the effectiveness of a leaching
solvent (Fig. 2). A high percentage of metal extraction was achieved
when the pH levels were maintained at 1.0 or lower. For HC1, 96.4%
Cd, 81.2%  Ni and 95.9% Co were extracted from the contaminated
soil and for  H2SO4,  90.3%  Cd,  85.6% Ni and 96.3%  Co  were
extracted. It should be mentioned that Figure 2 was plotted based on
the final pH levels measured during the tests. For those tests with an
initial pH of 3.0, it seemed that the pH levels could not be held at 3.0
throughout  the tests.
  Under the mixing condition used during testing (i.e., 100 rpm; Phipps
and Bird multiple mixer Model No. 7790—300), the effectiveness of
the leaching solvents was not affected when soil concentration was up
to 10% by weight (Fig. 3). At 15% by weight soil  concentration, the
percentage of metal extracted was generally decreased. This result could
be due to inadequate mixing. Localized soil settlement was observed
during the testing of the 15% by weight soil concentration.
  Increasing the contact time between soil and the leaching solvents
generally increased the amount of metals leached from the contaminated
soil (Fig. 4). After 12 hours of contact, no significant increase in metals
leached from the soil was observed. After 12 hours of contact, approxi-
mately 96% Cd,  93%  Ni and 87%  Co were extracted from the soil.
  Increasing the number of successive extraction stages increased the
amount of metals being leached from the contaminated soil (Fig. 5).
After three successive extraction stages, no significant increase in metals
leached from soil was observed. Approximately 95% Cd, 83% Ni and
78% Co were leached from the soil after three successive extraction
  By combining the optimum conditions of the tested variables, it is
estimated that at least 94% Cd, 84% Ni and 75 % Co can be removed
                                                         100

                                                          90

                                                          80

                                                          70

                                                          60

                                                          SO
                                                          6----
100
90
SO
70
60
50



-
-
I





I I
                                                         100,—
                                                       3
                                                       I-
                                                            J              5             10

                                                                        SOIL CONCENTRATION, % BY WT

                                                                             Figure 3
                                                             Effect of Soil Concentration on Acid Extraction
                                                                     of Metal-Contaminated Soil
                                                                                                                      TREATMENT    741
-------
100

95
S
1 "
O 85

80
75



cf£i"*Qf • *
"^ •— 0— HCI

- -A- - HjSO,
-
1 1 1 1 1 1 1 1 1 1 1 1 J

(~d






, |
                                                                                  100

                                                                                   80
*
a
6
i
u.
O
u
O
g
IE
UJ
Q.
   je
   o"
   o
   <
   o
   a:
   m
          100

           90

           80
           50

           40


          too

           90

       I  80

       1  70
       o
       u
           60

           SO

           40
             _i
                I    I   I    I    I   I    l   i    i   i   I    I   j,   i
                    4       8       12      16      20      24      48
                             CONTACT TIME, HOURS
                              Figure 4
                Effect of Contact Tune on Acid Extraction
                      of Metal-Contaminated Soil
          100

          95
       S
       a  90

       0  85
       5
          100


          90
       I  80
       si
       a  80
                          NUMBER OF CONTACT STAGE
                              Figure 5
          Effect of Number of Contact Stages on Acid Extraction
                      of Meal-Contaminated Soil
                                                                        ID   s.
                                                                        -J   LJ
                                                                        tu   g

                                                                        fe
                                                                        Ul
                                                                        <
                                                                        o
                                                                        a:
                                                                        UJ
                                                                        O.
100

 80

 60

 40

 20

 0


100

 80

 60

 40

 20

 0
                                                                            I

                                                                            I
                                                                            8
                                                                                                              10
                                                                                                       pH, UNIT

                                                                                                   Figure 6
                                                                                       Effect of pH on Metal Removal from
                                                                                         Spent Acid Extraction Solution
                                                                     from the contaminated soil by using either HC1 or H2SO4.
                                                                       Figure 6 indicates that more than 99% of the Cd, Ni and Co in the
                                                                     spent leaching solvents  can be removed (or recovered) at pH  11. As
                                                                     the pH level decreased from 11 to 7, the percentage of metal removal
                                                                     decreased. The settling  test results indicate that the sludge generated
                                                                     during the base recovery tests was completely settled within 30 minutes.
                                                                     The solids concentration of the settled sludge ranged from 3.4 to 6.3%
                                                                     by weight. The filterability test results indicate that the sludge can be
                                                                     further dewatered by vacuum filtration or the like and the solids con-
                                                                     centration can be increased to 15% by weight in the dewatered sludge.
                                                                     The calculated specific resistance is in the range of 109 to 1010 sec/gr;
                                                                     therefore, chemical additives may  be  required for assistance during
                                                                     sludge dewatering.
                                                                       Since the cleanup level for cadmium was 20 mg/kg, the contaminated
                                                                     soil with Cd concentration greater than 330 mg/kg would not be cleaned
                                                                     up to the desired level at the leaching efficiency of 94%. It was estimated
                                                                     that approximately 40%  of the metal-contaminated soil had a cadmium
                                                                     concentration greater than 330 mg/kg. Thus, additional treatment may
                                                                     be needed for that volume of the metal-contaminated soil. Therefore,
                                                                     based on the  above treatability test results, acid extraction was deter-
                                                                     mined not to  be a viable remedial technology for  cleanup of the con-
                                                                     taminated soil at the site.

                                                                     Chemical Fixation Test Results
                                                                       Tables 3 through 5  and Figure 7 summarize the chemical fixation
                                                                     test results. These results are discussed below.
                                                                       The results of the TCLP test on the three selected reagent ratios (i.e.,
                                                                     A, B and C)  indicate that  a very low quantity of metals leaches from
                                                                     the fixated soils (Table 3). For the three metals of concern, the  con-
                                                                     centrations of Cd, Ni and Co in the  leachates from  the TCLP tests were
                                                                     <0.005 to 0.29 mg/L, 0.33 to 0.41 mg/L and 
-------
metals leaches from the fixated soils during each of the ten leaching
steps (Tables 4 and 5). The concentrations of Cd, Ni and Co in the
leachates from the MEP tests were < 0.005 mg/L to 0.29 mg/L, <0.04
to 0.53 mg/L and <0.05 mg/L, respectively. Again, all the Cd con-
centrations were less than the TCLP Cd limit of 1.0 mg/L.
  Figure 7 shows that the unconfined compressive strength (USC) in-
creased rapidly as the curing time increased. With a curing time of
10 hours,  the USC can reach 1500 Ib/ft2 and at the end  of two-day
curing  time, the USC can reach approximately  5 tons/ft2.
  During the application of the Chemfix fixation process  to treat the
                             Table3
                 TCLP Results on Chemfix Products
                          (Heavy Metals)
PARAMETERS
Arsenic
Barium
Cadmium
Chromium
Cobalt
Lead
Mercury
Nickel
Selenium
Silver

RATIO
A
0.015
0.9
0.194
0.11
0.05
<0.05
0.0011
0.33
<0.002
<0.01
2/12/88
RATIO
B
0.011
0.3
<0.005
0.13
<0.05
<0.05
0.0013
0.41
<0.002
<0.01

RATIO
C
(me/11
0.004
0.2
<0.005
0.16
0.06
<0.05
0.0015
0.41
0.003
CO. 01
2/29/88
RATIO
B
(nit/11
0.015
<0.1
0.290
0.21
<0.05
<0.05
0.0022
0.33
0.003
<0.01
TCLP
LIMITS
5.0
100.0
1.0
5.0

5.0
0.2

1.0
5.0
metal-contaminated soil at the former battery plant grounds, 70% by
weight of water had to be added into the soil-reagent mixture. After
curing, the final volume of the fixated soil was approximately double
the original volume of the contaminated soil.
  The above treatability test results indicate that the Chemfix fixation
process is capable of treating the metal-contaminated soils at the former
battery plant grounds. The extraction procedures performed (TCLP and
MEP) on the fixated soil samples resulted in leachate contaminant con-
                                                                         £§
                                                                         i£  '
                                                                         O
                                                                         z1    1
                                                                                                    1500 LBS/SQUARE FOOT
                                                                                                                      I     I
                                                                                                     20          30

                                                                                                   CURING TIME, HOURS
    NOTE: TCLP limits for cobalt and nickel are not available.
                             Figure 7
           Unconfirmed Compressive Strength vs Curing Time
                                                                 Table 4
                                                  MEP Results of Ratio B Chemfix Product
                                                              (Heavy Metals)
PARAMETERS
Arsenic
Bari urn
Cadmi urn
Chromi um
Cobal t
Lead
Mercury
Nickel
Selenium
Silver
MEP
1
(ma/1)
0.014
0.2
0.021
0.20
<0.05
<0.05
0.0020
0.53
0.020
<0.01
MEP
2
(ma/1 )
0.012
<0.1
<0.005
0.05
<0.05
<0.05
0.0015
<0.04
<0.002
<0.01
MEP
3
(ma/1 )
0.010
<0.1
<0.005
<0.05
<0.05
<0.05
0.0010
<0.04
<0.002
<0.01
MEP
4
(ma/1)
<0.002
<0.1
<0.005
<0.05
<0.05
<0.05
0.0013
<0.04
<0.002
<0.01
MEP
5
(ma/1)
<0.002
<0.1
0.019
<0.05
<0.05
<0.05
0.0016
<0.04
<0.002
<0.01
MEP
6
(ma/1)
<0.002
<0.1
0.007
<0.05
<0.05
<0.05
0.0012
<0.04
<0.002
<0.01
MEP
7
(ma/1)
<0.002
<0.1
0.021
<0.05
<0.05
<0.05
0.0018
<0.04
<0.002
<0.01
MEP
8
(ma/1)
0.004
<0.1
0.033
<0.05
<0.05
<0.05
0.0019
<0.04
<0.002
<0.01
MEP
9
(ma/1)
<0.002
<0.1
0.029
<0.05
<0.05
<0.05
0.0015
<0.04
<0.002
<0.01
MEP
10
(ma/1)
0.004
<0.1
0.010
<0.05
<0.05
<0.05
0.0018
<0.04
<0.002
<0.01
Tables
MEP Results of Ratio B Chemfix Product
(Heavy Metals)
PARAMETERS
Arsenic
Barium
Cadmi um
Chromium
Cobalt
Lead
Mercury
Nickel
Selenium
Silver
MEP
1
(ma/1 )
0.015
<0.1
0.290
0.21
<0.05
<0.05
0.0022
0.33
0.023
<0.01
MEP
2
(ma/1)
0.012
<0.1
<0.046
0.06
<0.05
<0.05
0.0011
0.04
<0.002
<0.01
MEP
3
(mg/1)
0.005
<0.1
0.050
<0.05
<0.05
<0.05
0.0015
0.04
<0.002
<0.01
MEP
4
(ma/1 )
<0.006
<0.1
0.099
<0.05
<0.05
<0.05
0.0021
<0.04
<0.004
<0.01
MEP
5
(ma/1)
<0.002
<0.1
0.120
<0.05
<0.05
<0.05
0.0015
<0.04
<0.002
<0.01
MEP
6
(ma/1)
0.002
<0.1
0.092
<0.05
<0.05
<0.05
0.0020
<0.04
<0.002
<0.01
MEP
7
(ma/1)
0.005
<0.1
0.103
<0.05
<0.05
<0.05
0.0017
<0.04
<0.002
<0.01
MEP
8
(ma/1)
0.002
<0.1
0.146
<0.05
<0.05
<0.05
0.0022
<0.04
<0.002
<0.01
MEP
9
(ma/1)
<0.002
<0.1
0.154
<0.05
<0.05
<0.05
0.0020
<0.04
<0.002
<0.01
MEP
10
(ma/1 )
<0.002
<0.1
0.130
<0.05
<0.05
<0.05
0.0024
<0.04
<0.002
<0.01
                                                                                                                      TREATMENT    743
-------
 centrations well within the regulatory limits.  This chemical fixation
 treatment can change  the hazardous characteristics of the metal-
 contaminated soil to become nonhazardous.

 CONCLUSIONS
   Based on the results of the above-described  bench-scale treatability
 tests, the following  conclusions are made:
 • Since the selected soil cleanup level for the Area n portion of the
   Marathon  Battery Company site is 20 mg/kg Cd, acid extraction is
   not a viable stand-alone remediation approach  for this site.
 • Chemical fixation (e.g., the Chemfix fixation process) is capable of
   eliminating the hazardous characteristics of the metal-contaminated
   (Cd,  Ni and Co)  soil at the former battery plant grounds.

 ACKNOWLEDGMENT
   The work described in this presentation was funded by the U.S. EPA
 under U.S. EPA Contract No. 68-01-7250 with Ebasco Services Incor-
 porated. The contents do not necessarily reflect the views and policies
 of the U.S. EPA,  nor does mention of trade  names or commercial
 products constitute endorsement or recommendation for use.

 REFERENCES
  1. Ebasco Services Incorporated, Supplemental Remedial Investigation Report,
    Marathon Battery Company Site (Former Battery Plant Grounds), Village
    of Cold Spring, Putnam County, New York, A draft report submitted to the
    U.S.  EPA,  April 1988.
  2. Ebasco Services Incorporated, Supplemental Feasibility  Study  Report,
    Marathon Battery Company Site (Former Battery Plant Grounds), Village
    of Cold Spring, Putnam County, New tort, A draft report submitted to the
    U.S. EPA, May 1988.
 3.  Ebasco Services Incorporated, Supplemental Remedial Investigation Report,
    Marathon Battery Company Site (Constitution Marsh  and East Foundry
    Cove), Village of Cold Spring, Putnam County, New fork, A final report
    submitted to U.S. EPA, August 1986.
 4.  Ebasco  Services Incorporated, Supplemental Feasibility  Study Report,
    Marathon Battery Company Site (Constitution Marsh  and East Foundry
    Cove), Village of Cold Spring, Putnam County, New Kirk, A final report
    submitted to U.S. EPA, August 1986.
 5.  Ebasco Services  Incorporated, Supplemental Remedial Investigation Report,
    Marathon Battery Company Site (East and Hfor Foundry Cove and the Pier
    Area), Village of Cold Spring, Putnam County, New tork, A revised draft
    report submitted to the U.S. EPA, May 1989.
 6.  Ebasco  Services Incorporated, Supplemental Feasibility  Study Report,
    Marathon Battery Company Site (East and Wist Foundry Cove and the Pier
    Area), Village of Cold Spring, Putnam County, New York,  A final report
    submitted to the U.S. EPA, May 1989.
 7.  Acres International Corporation, Remedial Investigation at Marathon Battery
    Federal Superfund Site, Cold Spring, New York, A draft report submitted
    to New York State Department of Environmental Conservation, August 1985.
 8.  Acres International  Corporation, Feasibility Study at Marathon Battery
    Federal Superfund Site, Cold Spring, New York, A draft report submitted
    to New York State Department of Environmental Conservation, August 1985.
 9.  APHA-AWWA-WPCF, Standard Methods far the Examination of Water and
    Wistewater, 15th Ed., American Public Health Association, Washington,
    D.C.,  1980.
10.  Cushnie, G.C. Jr., Removal of Metals from Ubstewater, Neutralization and
    Precipitation, Noyes Publications, Park Ridge, New Jersey, 1984.
744    TREATMENT
-------
                      Extraction  and  Washing  Contaminated Soils
                    Using High  Pressure  Jet  Grouting  Techniques
                                                   George R. Grisham
                                                   Hayward Baker Inc.
                                                   Odenton, Maryland
                                           DR-ING  Wolfgang Sondermann
                                                 Keller  Grunbau  GmbH
                                                Offenbach, West Germany
ABSTRACT
  Contamination in the ground, particularly under a structure on a con-
    Turban site, poses a unique problem requiring a unique solution.
   ; small site in Hamburg, Germany, presently occupied by three old
factory buildings, was contaminated with-phenpl, a chemical substance
which was used in IfieTnanufacture of disinfectants. The old factory
buildings had subsequently been renovated and are now occupied by
a community center and various commercial enterprises.
  An extensive site investigation revealed contamination concentrated
between and under the buildings. Since off-site disposal of contaminated
soils in Germany is difficult and cost-prohibitive, it was necessary to
develop reliable methods of removal and on-site treatment of the con-
taminated soils. Remedial measures on this site required decontamina-
tion of soils adjacent to and under the structure while providing adequate
ground support  of the foundations.
  An on-site pilot program was devised using jet grouting techniques
to extract and wash contaminated  soils. This process  utilizes a high
pressure air/water jet which erodes and washes away the contaminated
substance from the granular soils. Contaminated soil was displaced to
the surface where it was collected and cleaned of phenolic contamina-
tion by oxidation in a completely self-contained unit. After decontamina-
tion, the cleaned material was separated according to composition and
then filtered. Cleaned soils were mixed with cement and replaced. The
City of Hamburg's Environmental Commission performed tests that
indicated levels  of phenol in the soil were well below the maximum
acceptable limits.
  This process,  using the combination of jet grouting  technique, on-
site soil washing and recycling of clean materials has proven successful
on this project.

INTRODUCTION
  Thousands of hazardous waste sites are known to  exist in North
America and Europe. Evaluations of many of these sites and their poten-
tial for damage (or further damage) to the environment have produced
a vast array of remedial techniques. Traditionally, excavation and
transport of the  contaminated  soil  to an off-site landfill has been the
most commonly used method of site remediation. However, due to land
ban legislation and the extremely high cost of off-site disposal, there
has been an industry shift to containment and/or on-site/in situ  treat-
ment of contaminated soils.
  Congested urban areas  with  contamination in the ground pose
particularly difficult challenges for the remediation contractor. Remedia-
tion of contaminated soils must make sure that all contaminated soils,
even in difficult to access areas (i.e., under developed sites), can be
decontaminated while the planned  use of the area and integrity of the
existing structures is retained. This paper explains  how one proven
geotechnical technique, jet grouting, was adapted and combined with
a new technology, soil-washing, to address a unique environmental
problem.

CONTAMINATED SITE
  An urban site in Hamburg, West Germany, was occupied by a small
manufacturing facility that produced disinfectant until the beginning
of the 1960s. The site, with an area of approximately 5,000 square
meters,  is bordered by a canal on the south side. Three  old, but
renovated, factory buildings exist on the site, one of which is used as
a community center. The other two buildings are occupied by various
commercial enterprises. Because of the  production and improper
handling methods used, the soil and groundwater became contaminated
with various concentrations of phenol. West Germany currently has
no national approach to establishing cleanup goals for contaminated
land. Cleanup control is by provincial governments with use of the
"Dutch List" for general guidance and screening.1
  An extensive site investigation program was undertaken to determine
the type and extent of contamination. The soil structure was basically
horizontal with layers of peat and sand over a layer of mud at approxi-
mately 7 meters below the surface. The center of the contaminated area
was located in front of, and underneath, the former disinfectant plant,
as shown in Figure 1. Phenol concentrations were determined in both
the groundwater and the soil. The highest concentration of contamina-
tion was determined to be approximately 2 to 3.5 meters beneath the
surface.2 When the highly concentrated chemicals came into contact
with air, they produced an intense odor which made excavation of the
soils in this urban area impractical.
  The spread of contamination underneath the structures posed a major
problem because the integrity of the buildings and the soils they were
resting on had to be maintained. It was necessary to find a suitable
method of treating the contaminated soils under the structures.

TREATMENT REQUIREMENTS
  This complex site required the development of treatment methods
that met the following criteria:
• Little or no contact with the contaminated material
• No air emissions during the decontamination process other than
  properly filtered air
• No open pit excavations
• The program should be able to extract and decontaminate soils
  underneath the buildings without compromising the support of the
  structure
• No groundwater lowering could be allowed because you would poten-
  tially  have to treat  large volumes  of contaminated water and the
  dewatered peat layers would likely cause settlement of the structure
                                                                                                              TREATMENT    745
-------
                                         Phenol-Index mg/kg
                                         I      l<»
                              Figure 1
                       Extent of Contamination
                       with Respect to Structures
•  Little  or no off-site transportation and disposal of contaminated
   materials would be required
   Several remedial methods were considered. Because of the high con-
centration of phenols and their considerable odor, on-site techniques
using open-pit excavation methods were neither practical nor did they
address contamination underneath the structure. Biological treatment,
which was attempted in a prior project, was unsuccessful because of
the differing soil conditions (sand and peat with different organic
contents   and  thickness)  and  rapid  changes  in  contamination
concentrations.

TREATMENT SYSTEM
   A geotechnical process known  as jet grouting  by the triple system
method was combined with an on-site soil-washing process. Jet grouting
is  a Ground Modification system used to create in situ cemented
geometries of soil (soilcrete). This system was developed primarily for
underpinning and/or excavation support but also has been adapted for
stabilization of soft soils and more recently has been used for pollution
control projects. The triple system (or a triple rod system as it is also
known) of jet grouting uses the combination of  high pressure water
(5,000 to 6,000 psi)  shielded in a cone of air to  cut  and lift the soil
to the surface (Fig. 2).  In underpinning applications,  the void created
is  simultaneously tremie filled with a pre-engineered backfill (usually
a cement slurry).3
  The water jet is surrounded by a concentric collar of compressed
air which concentrates the jet, particularly below the water table. This
high pressure water and air stream was designed to erode the surrounding
soil but also washes certain contaminants from the coarser grained soils.
This medium also becomes the source for the air lift system for displace-
ment of spoil to the  surface where it could be collected at the  top of
the drill hole. This controlled soil  removal and washing capability was
selected  for a full-scale pilot program on the Hamburg site.
  Five test columns were installed to monitor and analyze the success
of the procedure. The subsoil  to be cleaned is made air-tight with a
surface sealing work pad over the planned boring area.  After advancing
the drill through the  work pad  to the desired depth of treatment, high
pressure  water and air are forced through the drill rods. The drill rods
are rotated and retracted at a predetermined rate. The high energy cutting
stream leads to a displacement of the treated soil within a certain distance
from the  opening in  the drill rod. In this case, the treated volume of
the soil columns had an effective diameter of approximately 1.5 meters.
The soil is eroded and intensely cleansed and mixed with the outflowing
water.
   The radius of the eroded column can be regulated by altering stream
velocity,  rotary velocity and  suction velocity. This  process  allows
                               SoOcrete Column
                              under construction
Repetition of
theprocesa
                             Figure 2
                      Triple System Jet Grouting
variance in the system to account for differing soil conditions. This
cleansing process  continues to  the  surface  or upper limit of
contamination.
  During and after the production process, the stability of the column
walls is maintained by the pressure of the suspended  material in the
column. The use of additives in the cutting water (i.e., bentonite slurry)
can be used, if required.
  The diameter of the column (i.e., the treated volume of soil) can be
mechanically measured at the end of the operation by means of a folding
screen which is inserted in the column filled with suspended material.
This usually is done in the first test column(s) in order to set parameters
for the production work.
  The contaminated material consisting of water and soil coming out
of the drill hole through the work pad is fed directly into an enclosed
soil washing decontamination system (Fig.  3). An oxidation process
was used to degrade the phenols.4 After decontamination, the cleaned
material was removed, leaving the fine soil which was separated into
dry material and filtrate.
  This soil washing process can be repeated as often as desired. The
process results in very little contaminated material that has to be disposed
of in a secure landfill.
  The suspended material remaining in the test column now has to be
exchanged for an uncontaminated mixture in the next step of the process.
  The clean materials were mixed with purified filtrate water and a
bonding agent (in this case cement) to form a competent  filling material.
This material was then reinjected into the open column displacing the
suspended medium which is collected at the  surface and treated and
reused in the next column.
  Soil extraction and treatment was continued in alternating columns
refilling one column before jetting the adjacent column. This procedure
is standard practice in conventional underpinning and prevents under-
mining of the structure. The columns are overlapped to ensure decon-
tamination of the entire volume  of soil  targeted.

CONCLUSION
  This method of contaminated  soil extraction and on-site treatment
in a closed system  proved quite successful in this pilot project. The
final product showed a 98% reduction in the level of phenol. Confirming
tests by the regulating authority showed that the levels  of phenol found
in the soil were well  below required levels.  The combination of the
jet stream procedure  for eroding and washing the contaminated soil
"46    TREATMENT
-------
    Column I
                                                                                                                             — Filling
                                                                                                                  Column 2
                                                                   Figure 3
                                                Technology of High Pressure Washing and Treatment
followed by a direct decontamination and recycling of the resulting
displaced mixture has several advantages:
• Site access is not as significant an issue as it would be in an excava-
  tion and replacement procedure; the triple rod system method of
  jetting can be done with small jet grouting rigs, if necessary, to access
  very restrictive locations
• The procedure also has the potential of targeting pockets of contamina-
  tion in deep or otherwise in accessible locations such as under existing
  structures
• Due to the closed system of treatment, there is very little contact
  of the contaminated materials with the surrounding environment
• No lowering of the groundwater is necessary
• The process results in very little off-site disposal of contaminated soil
• The process can potentially be adjusted to treat specific contaminants

  Care must be taken during the extraction process not to  increase the
amount of contaminated water in the treatment zone. Properly staging
and planning the remedial program will minimize this problem. Potential
chemical reactions of the treatment reagents with the soils and con-
taminants must be carefully considered.  Since most hazardous waste
sites contain a mix of contaminants.  A treatment approach that may
neutralize one contaminant may render another more toxic or mobile.5
  Jet grouting techniques can be used  to support structures while con-
taminants are removed beneath them and to wash the  coarser soil
particles in-place and bring the fines with the contaminants to the sur-
face for additional treatment.
  Further development of this technique includes using hot water and/or
adding steam to the flushing and cutting jet to greatly increase the degree
of decontamination of particular pollutants. Addition of a  biologically
active  substance to the jet stream  is also  a viable option under
consideration.

REFERENCES
1. Sigrist, R., "International Perspectives on Cleanup Standards for Con-
   taminated Land," Proc. Third International Conference on New Frontiers
   far Hazardous Waste Management, U.S. EPA, Pittsburgh, PA, pp.348-359,
   September, 1989
2. Sondermann, W. and Zarth, M., "High Pressure Soil Washing and Soil Treat-
   ment  by Extraction,"  International Meeting  NAFO/ccms  Pilot Study
   Demonstration of Remedial Axion Technologies for Contaminated Land and
   Groundwater, Bilthoven, Netherlands, November, 1988
3. Welsh, J., Rubright, R. and Coomber, D., "Jet Grouting for Support of Struc-
   tures,"  Grouting for Support of Structures, Geotechnical Session, ASCE
   Spring  Convention, Seattle, WA, April, 1986
4. Grisham, G., "Contaminated and In situ Treatment of Contaminated Sites,"
   Proc. of the Seminar on Contamination and the  Constructed Project, spon-
   sored by Connecticut Society of Civil Engineers  (CSCE) in association with
   Connecticut Groundwater Association (CGA), Berlin, CT, November, 1989
5. Wagner, K. et al., "Remedial Action Technology for Waste Disposal Sites,
   in Second Addition," Pollution Technology Review No. 135, Noyes Data Cor-
   poration, Park Ridge, NJ, pp. 367-437, 1986

ACKNOWLEDGEMENTS
  The in situ soil extraction and treatment pilot program was  performed jointly
by the following companies:
* Keller Grundbau GmbH
*S&I
  Schlammentwasserung
  GmbH & Company KG
* WUE
  Umwelt  - Engineers GmbH
                                                                                                                          TREATMENT   747
-------
                       Cost  of  Controlling Air  Stripper  Emissions

                                                   Gary L. Saunders
                                               John P.  Carroll, Jr., P.E.
                                                    David R. Dunbar
                                                   PEI Associates, Inc.
                                                 Durham, North Carolina
                                                      Joseph Padgett
                                         U.S.  Environmental Protection Agency
                                        Research Triangle  Park, North Carolina
ABSTRACT
  Air stripping is a proven technology that frequently is used at Super-
fund sites to treat groundwater contaminated with certain volatile organic
compounds (VOCs). It may be desirable or required by regulations to
control the air emissions from air strippers when emission rates of VOCs
exceed certain levels. The cost of controlling these air emissions is of
interest to the U.S. EPA and  others involved in evaluating costs of
remedial technologies. This study evaluated cost trends for air stripping
with vapor-phase carbon adsorption controls and graphically presents
the control costs  in terms of dollars per ton of pollutant removed versus
groundwater concentration for various treatment rates.
  Cost data on existing air stripping operations at Superfund sites are
generally very limited in terms of uniformity of data reported and lack
of cost category. To produce consistent results, preliminary air strip-
per and carbon adsorber designs were developed and estimated costs
were calculated based on some simplifying assumptions. Three com-
pounds,  1,1-dichloroethylene  (DCE), trichloroethylene (TCE)  and
1,2-dichloroethane (EDC),  were used  at various  concentrations in
groundwater for the purposes of this study. These compounds are
commonly found at Superfund  sites and have small maximum contami-
nant levels (MCLs) used as cleanup standards. They represent a range
of Henry's Law  constants and each may be adsorbed in vapor phase
by activated carbon at different holding capacities. VOC inlet flow rates
investigated varied from 0.05 to  10 Ib/hr and liquid flow rates varied
from 500 to 3500 gal/min at a fixed air-to-water ratio.  Air strippers
were designed using the Sherwood-Holloway Model  and vendors
supplied design  and cost data for the carbon adsorption units.  Both
regenerative and nonregenerative carbon systems were  evaluated.
  Estimated  capital  costs,  operation  and  maintenance  costs  and
annualized costs are presented for the air strippers, carbon adsorption
units and the combined systems. Control costs are presented and trends
are discussed in  terms of cost per ton of VOC adsorbed and cost/1000
gallons of groundwater treated.

INTRODUCTION
  PEI Associates, Inc. (PEI) was asked by the U.S. EPA  to evaluate
the cost of controlling air emissions from air strippers used in ground-
water remediation at Superfund sites. This study was initiated to provide
additional data for the Office of Emergency and Remedial  Response's
(OERR) Air Stripper Control Policy in terms of evaluating control costs
per ton of pollutant removed.  The study also was useful as a tool in
evaluating cost trends for air stripping and vapor-phase carbon adsorp-
tion controls.
  Cost data on existing air stripping operations at Superfund sites have
been found to be very limited  in terms of uniformity of data reported
and lack of cost breakdowns. To produce consistent uniform results for
this study, it was necessary to develop preliminary air stripper and
carbon adsorber designs and to calculate estimated costs based on some
simplifying assumptions.
  The results of the control cost analysis are summarized in Figure I.
Figure 1 is a plot of the cost per ton of volatile organic compound (VOC)
adsorbed on the activated carbon versus the groundwater concentra-
tion for three different treatment rates. For regenerative carbon adsorp-
tion systems at air concentrations greater than 4 ppm, the costs per
ton are very similar for the three chemicals investigated because equip-
ment costs predominate. Therefore, one set of lines represents the 500,
1500 and 3500 gal/min flow rates. The inlet pollutant rates (0.5 Ib/hr
to 10 Ib/hr) for the regenerative systems also are shown in Figure 1.
Below 4 ppm the nonregenerative carbon adsorption systems show dif-
ferent costs per ton for each chemical because the different carbon use
rates control  these costs.  Best fit  lines  have been plotted for the
nonregenerative carbon adsorption systems used to control each pollu-
tant at low air concentrations.
                                   COST OF CONTROLLING
                                   AIR STRIPPER EMISSIONS
                                                          ooooo »
                   100           1000          10000
                    GROUNDWATCH CONCENTTVUTON, ufl/Iltw

                            Figure 1
       Cost per ion of VOC Adsorbed vs. Groundwater Concentration
 CHEMICAL SELECTION
   Three chemical compounds were selected  for the study based on
 logical criteria. These chemicals are VOCs commonly found in con-
 "M8    TREATMENT
-------
taminated groundwater at Superfund sites and the groundwater cleanup
levels required are significantly small  for each chemical.  Both air
stripping and vapor-phase activated carbon adsorption are technically
feasible treatment methods for each chemical. The three chemicals
represent a high, medium and low range of Henry's Law constants (a
measure of a compound's ability to be stripped).  Trichloroethylene
(TCE) was selected first because it is a VOC frequently found at Super-
fund sites, it is a common target for air stripping and it has a midrange
Henry's Law constant. Selection of the other two chemicals was aided
by consulting the chemical data table in the Superfund Public Health
Evaluation Manual (SPHEM)1 and reviewing the Superfund Records
of Decision System (RODS) data base.2 1,1-Dichloroethylene (DCE)
was selected as the VOC with a higher range Henry's Law constant
and 1,2-Dichloroethane (EDC) was selected as the VOC with a low-
range Henry's Law constant that could be removed from groundwater
by air stripping. Tables 1 and 2 present selected data for each chemical.
In this study, VOC concentrations in groundwater up to 40,000 /tg/liter
were investigated.

                            Table  1
              Data on Three Compounds Selected for
               Study of Air Stripper Control Costs
Compound
1,1-Dichloroethylene (DCE)
Trichloroethylene (TCE)
1,2-Dichloroethane (EDC)
Molecular
weight
97
131
99
Henry's Law
constant
3.4 x 10'2
9.1 x 10'3
9.8 X 10'*
Vapor
pressure,
mm hg
600
57.9
64
                            Table 2
             Typical Concentrations at Superfund Sites
 Compound
           Range of concen-
Frequency"  trations, jig/Hter
Approximate
 mean con-
centration,   MClb,      WQCC
  pg/liter   pg/liter   fig/liter
DCE
TCE
EDC (DCA)
6
18
4
1.7 52,000
8 70,000
5 7,000
400
1,600
200
7
5
5
0.033
2.8
0.94
 28 sites with air stripping.
 TICL - Proposed maximum contaminant level  for drinking water.
 CWQC = Hater quality criteria (for 1 x 10-6 cancer risk).
 ASSUMPTIONS USED FOR PRELIMINARY DESIGN
 AND COST ESTIMATES
  This section presents the assumptions and data items used in the design
 and cost analysis. The following assumptions were used to design the
 air stripper and the outlet results were used to size the carbon adsorber:
 • The carbon adsorber and air stripper designs were produced for treat-
  ment of three chemicals independently:  TCE, DCE and EDC.
 • The VOC flow rates investigated ranged from 0.05 to 10 pounds/hour
  in the liquid influent. The inlet rates were assumed to be constant.
  No "safety fector" for variation in concentration or nonideal effects
  was included.
 • Liquid flow rates of 500, 1500 and 3,500 gal/minin were investigated.
 • The air-to-water ratio used in each case was 35 to 1. This ratio was
  found to provide an adequate air stripper design for the cost estimates
  on a comparative basis.
 • The outlet water concentration was set at 5 micrograms/liter.  This
  parameter also controls the air stripper design efficiency.
 • Air and water temperatures were assumed to be 60° F.
  With these parameters, the air stripper was designed for optimum
 height  and diameter using the Sherwood-Holloway  Model.3 An
 assumption used in designing the air stripper was that column dimen-
sions would allow operation at 50 percent of the flooding loadings of
water and air. In some cases, there was no feasible single air stripper
design and multiple parallel air strippers were used. Once the optimum
designs were identified, vendors were contacted to obtain prices for
the accompanying carbon adsorbers. The capital costs for the air strip-
per were calculated from the PDQ$ costing program.4 The cost for
the 1.5 inch Berl saddles packing was obtained from Peters and Tim-
merhaus.5 The operation and maintenance costs for the air strippers
were assumed to be 62 percent  of the capital costs. The operation and
maintenance costs for the carbon adsorbers were individually calculated
based on carbon use and other factors.
  Carbon adsorber costs  were obtained  from vendors for  both
regenerative and nonregenerative carbon systems. The regenerative unit
is fully  automated and has low operating costs (mostly utilities). On
the other hand, the nonregenerative unit has  a low initial capital cost,
but a large cost for off-site regeneration of the spent carbon. The total
annualized costs for each type of system were compared to determine
whether a regenerative or  nonregenerative system should be used.
  The annualized costs for both the stripper  and the carbon adsorber
were obtained by assuming a 10-year project life (operating  life and
capital recovery period) and a 10 percent interest rate. Costs presented
are in 1989 dollars. A number of assumptions were made in determining
the adsorber and stripper costs including: the site is accessible and
utilities  are available, minimum site work is necessary for installation,
the system is in continuous operation, operating labor requirements are
minimal, the salvage value or disposal cost for the recovered VOC is
negligible and there is no salvage value for the used equipment at project
end.
  The vendors  supplied details and  costs  of exchangeable carbon
adsorption units (carbon tanks)  and steam-regenerative systems based
on air flow volume. General adsorption capacities of carbon for the
three chemicals at 4 ppm were used to calculate  carbon use for the
nonregenerative units. These estimated capacities were reduced by
50 percent at VOC concentrations below 1 ppm. The annualized cost
of the carbon adsorber was divided by the tons of VOC removed/year,
based on an assumed efficiency of 92 percent, to obtain the cost per
ton of VOC removed.
  The capital and operating costs estimated include basic installed equip-
ment costs, minimum expected operation and maintenance costs and
minimum operating labor requirements. Many other direct or indirect
costs associated with groundwater cleanup may be applicable to Super-
fund site remediation depending on site-specific conditions. Items that
were not included in the cost estimates include design, engineering,
treatability studies, shipping costs, installation of utilities, groundwater
collection systems,  auxiliary equipment, heating of gas stream (if re-
quired), unscheduled repairs and administrative costs.
  It is important to note that if all the above  cost factors are considered,
the cost of the basic air stripping operation may be a small portion of
the total site remediation costs.

TECHNICAL AND ECONOMIC FEASIBILITY OF
CARBON REGENERATION OF ADSORBERS  TREATING
AIR STREAMS WITH LOW VOC CONCENTRATIONS
  When treating air streams with low VOC concentrations, carbon
adsorbers that make one time use of the carbon  (nonregenerative
systems) and carbon adsorbers  that regenerate the carbon on-site for
reuse are competitive from both a cost and technical standpoint. Vendors
were contacted in an effort to learn at  what VOC concentrations
nonregenerative carbon use becomes preferable on both technical and
economic grounds. One area of agreement was that boundaries were
very situation-specific  and the information presented is strictly  a
generalization.617 The specific comparisons cited are only good for the
10 year  operating life.

Economic Considerations
  Regenerative systems have a much higher initial  capital cost and,
therefore, incur large fixed costs due to capital recovery, maintenance,
taxes, insurance, etc., whether or not the system operates. Variable costs,
i.e.,  operating labor (the system is essentially automated and small)
                                                                                                                     TREATMENT    749
-------
and steam for carbon regeneration, are low.
  The nonregenerative systems have low initial capital costs, mainly
for fans and ductwork, but operating costs are high due to the cost of
carbon. Large air flows favor regenerative systems because carbon ad-
sorber costs do not vary linearly with size.  For example,  a system
handling 12,000  cfm has only twice the costs of a system handling
2,300 cfm.
  Regenerative systems appear to be less costly at VOC concentrations
of approximately 3  ppm at 2,300 and 7,000  cfm and approximately
2 ppm at 12,000 and 16,000 cfm. The technical  feasibility of on-site
steam regeneration of carbon beds at these low concentrations, however,
has been questioned by the carbon system vendors.
  The minimum cost of a small (300 to 800 cfm) regenerative carbon
adsorber is approximately $80,000. Minimum requirements also include
instrumentation and controls and metal fabrication work. Allowing for
an additional cost of 50 percent for installation and $5,000 for a steam
generator and air compressor, the minimum cost of a regenerative carbon
adsorption system of this type is $125,000. Therefore, due to fixed costs
such  as capital recovery,  maintenance, taxes,  insurance, etc.,  a
nonregenerative  system would be preferable if annualized  costs are
$35,000 or less.

Technical Considerations
  There was agreement among carbon vendors  that  nonregenerative
systems should be considered at concentrations below 10 ppm as well
as at higher concentrations. The technical feasibility of a regenerative
system  was questioned at  or below  3  ppm. The dividing line  is
somewhere  between 4 and 10 ppm with  the considerations being:
(1) the hydrocarbon being adsorbed, (2) the air flow rate and (3) the
temperature and relative humidity of the air stream being fed  to the
adsorber.6'7 For the  purpose of this analysis, if the air concentrations
were 4 ppm and below, a nonregenerative system  was selected because
a regenerative system may  not be technically feasible.
   In a regenerative  system, more VOC is adsorbed on virgin carbon
than on carbon that has been regenerated by stream. This operational
phenomenon occurs because steam stripping only removes part of the
adsorbed VOC, thus reducing the capacity of subsequent cycles.  For
example, if virgin carbon can adsorb 10 percent of its weight in VOC,
then that is considered to be the capacity  of the carbon. But  steam
regeneration  may remove only 70 percent of the VOC from the. car-
bon, leaving 0.03 pounds of VOC/pound of carbon still on the carbon.
Because the carbon  capacity remains at 0.10 pounds of VOC/pound of
carbon, the working capacity of the carbon is 0.10 - 0.03 or 0.07 pounds
of VOC/pound of carbon. For the purpose of analysis, it was assumed
that the regenerative systems lost one-third of their capacity due to the
inability to completely regenerate the  carbon beds.

RESULTS AND DISCUSSION OF COST ESTIMATES
  This section of our paper presents the design  results and cost data
for air stripping and vapor phase carbon adsorption. The costs per ton
of VOC removed by stripping and adsorption are discussed as well as
the costs/1000 gallons of ground water treated.

Air Stripping
  Table 3 shows the estimated air stripping costs for the chemicals TCE,
DCE and EDC. The stripper dimensions  shown are inside packing
dimensions. The values reported are based  on the results of the Sher-
wood Holloway packed column model. Other models exist that are more
complex and  would give somewhat different tower dimensions. In
addition, design practice would dictate rounding tower diameters to con-
venient increments for manufacturing and recalculating packing height
and mass transfer rates based on actual dimensions. The total column
height used for cost estimates includes five extra feet for internal distribu-
tion at column inlet and outlet.
  The capital  costs, annual operation and maintenance (O&M) costs
and annualized costs for air  strippers generally increase as the air flow
and the inlet water concentrations increase. For TCE  the capital costs
range from S35jOOO to S216,000, and the O&M costs range from S22.000
to S134.000-year. The annualized costs range from S28.000 to $169,000.
For DCE, the air stripper costs are only slightly higher than for TCE
by 2 to 4 percent.  The air stripper costs for EDC are highest,  at
1.2 to 2 times the costs for TCE.
  The costs per ton of TCE removed from groundwater by air stripping
range from $1900/ton up to $430,000/ton. These unit costs decrease
as the quantity  of TCE being treated increases and as the size of the
air stripper (air flow) is reduced. The costs per ton of DCE and EDC
removed are higher  as compared to TCE, in the same proportions as
the air stripper costs for those chemicals.
                            Table 3
             Estimated Air Stripper Costs for Removal
                of Three Chemicals in Groundwater
TalCMLOWCTMTLENE (TCE)
use  voc FLOW WATER VATEH
•0.   KLEI  FLO» CMC.
    (L8/WO  (GPH) (PPB)
   CE
UR FLOW AIR COHC.STRIPPER DIMENSION
(ACFN) (PPHV) TOWtRS HEIGHT OIA.
              (FTI  (FT|
CAPITAL
 COST
0.05 500 200 1340 1.03
0.
0



0 0
0.
1
0.
!


1
TKTL
C Fl
"LET
B/W
0.0
0
0
1


0.0
1
0.


1
DJtOf.
•LET
6/t*
O.O1
0
a.
1


0
0
1

1
0
1


1
500 400 2340 2.06
500 2000 2340 10.31
SCO 6000 2340 30.93
500 12000 2340 61.87
500 20000 2340 103.11
1500 67 7020 0.34
1SOO 133 7020 0.69
1500 13300 7020 68.74
3500 28i 6400 1.47
3SOO 856 6400 4 41
3500 1712 6400 6.63
3500 2854 6400 14.71
3500 5707 6400 29.42
7.
9.
I
IS.
16.
1
5.

17.
8
II
12.
13.
15.








1


1
1
1
HE(DCE)
FlOV COK (ACFN) (PPNV) TOVEHS KEIbHT DI
(GPH) (PPfl) if ) (f
500 200 2340
500 400 2340
500 2000 2340 1
500 6000
500 12000
500 20000
1500 67
1500 13300
3500 285
1500 856
1500 1712
3500 2654
1500 5707
HMEtEOC)
FLOV COHC. [«
(6PM) (PP8)
500 200
500 400
500 2000
500 6000
500 IZOOO
500 20000
1500 133
1500 666
1500 2000
1500 4000
1500 11300
340 4
340 &
340 13.
020
020 9
400
MOO
400 1
MOO I
MOO 3
.39
.79
.93
.78
.55
.26
46
84
,99
96
92
87
.74

FH) (PPHV) TOWER

140
340
340 1
140 4
140 6
140 13
020
020
020 )
020 2
020 9
3500 265 16400
3500 856 16400
3500 1712 16400 |
3500 2854 16400 1
36
.73
64
93
.87
,44
.91
.55
64
29
,96
95
84
68
47
3500 5707 16400 18 94

1 .
j
1 .
10.
19.

IB.
I
13.
14.
IB.

HEIGH
(FT)
Ifl.
20.
JO.
37
42
45.
13.
23.
30
35.
42
18
25.
29.
1
37







10
11
11
11
11

DIA
(n






1
1
1
1
10
11
16
11
11
11
35000 1201
31000 2301
47000 29«
&2000 1201
54000 3301
58000 3601
12000 6901
03000 64CH
07000 6601
94000 12001
90000 lie«
91000 11BOX
99000 123W
16000 13401

COST COST

36000 21 0(
16000 24M
48000 3001
53000 J3«
58000 )60(
S9000 37«
114000 71 0<
111000 690C
186000 1S«
196000 230(
207000 26tt
224000 190C

COST COST

53000 330C
6)000 390C
78000 480C
9)000 560C
100000 620(
105000 650C
90000 56M
14000 BJOC
59000 990C
76000 «0(
11000 320C
49000 54M
65000 640<
48000 160(
J4000 )20(
39000 720(
URUUIZCO VOC
COST «EHOVtD
on • lea ions
H695
row
1664)
40460
417B6 1
45437 I
87R2
60758
634D9 4
1S1U4
148913
149076 1
155377 I
169143 «
UNIMLIZED VOC
COST ItEWn
on i in TONS
17(57
301 U
37810
416Z3
4M37 1
41599 I
69548
620*4
87060 4
156540
141282
ISSII5 1
111 179 I
17S44S 4]
UNULLUEQ VOC
COST RtMft
on • iox TORS
4162)
49250
60691
73131
76270 i
82064 t
74457
70643
04601
14869
17U5 1
51727 f
66»5 4
94511
IOMI6
272KO i
292850 t
n
11
.43
.18
.56
,13
.89
,»
<;
78
IS
53
10
86
76

to
Tl
11
43
IB
56
13
09
20
4(
78
IS
U
10
86
76

0
I
fl
43
IB
56
13
to
10
41
17
SI
II
M
78
15
53
10
66
OOST/TOI
voc
•WDYIO
lUXXW
67000
DOOO
000
UOQ
1100
410000
IttOM
1100
roooc
(3000
now
'100
1W
OUT/TOM
VOC
REwno
110000
7MOO
17000
uoo
3500
flOO
44ION
I950W
rooo
HOOD
HOOD
11000
MOD
tow
C011/TM
vac
icwvto
195000
114000
two
HOC*
WOO
1-00
M'OOD
IIUOO
MOM
ItOOO
10000
7000
3*M
torn
HMO
now
IUOO
Carbon Adsorption
  Table 4 shows estimated costs for the carbon adsorption controls for
the chemicals TCE, DCE and EDC. The costs presented are additional
control costs to be added to the cost of air stripping. Both regenerative
and nonregenerative carbon systems were  used in  this study.  The
regenerative systems were more economical for treating highly con-
centrated outlet air streams. For cases where the outlet air concentra-
tions were lowest, the nonregenerative systems were found to be more
economical. Nonregenerative systems were used in all cases at or below
4 ppm air concentration because of the performance concerns regarding
regenerative systems as previously discussed.
  The capital costs for the carbon adsorbers are the same for all three
chemicals under the same operating parameters. The nonregenerative
capital costs  range from $14,000 to $24,000, while  the  regenerative
capital costs range from $207,000 to $453,000. The operating costs for
the nonregenerative systems depend mainly on the carbon replacement
costs. The nonregenerative  operating costs/year for TCE range from
524,000 to $475,000. For DCE the range is  $62,000  to $547,000. For
EDC the range  is $51,000 to $443,000.  The operating  costs for
 7V1    TREATMENT
-------
regenerative systems depend on fixed costs and steam and vary by
5 to 20 percent between different chemicals. Annual operating costs
for regenerative systems for the three chemicals range from $20,000
to $54,000. The total annualized costs for controlling TCE range from
$26,000 to $479,000. The range for DCE is $54,000 to $551,000 and
the range for EDC is $53,000 to $446,000. Except for the cases where
nonregenerative systems were  chosen  over regenerative systems for
technical reasons, costs are reduced when the system size is reduced
and the quantity of VOC treated is reduced.
                             Table 4
                Estimated Carbon Adsorber Costs for
                 Controlling Air Stripper Emissions
TRICHLOROETHYLENE(TCE
CASE VK FLOW WATER
HO. INLET FLOW
(LB/HR) (GPH)
1 TCE 0.05 500
2 TCE 0.1 500
3 TCE 0.5 500
4 TCE 1.5 500
5 TCE 3 500
6 TCE 5 500
7 TCE 0.05 1500
8 TCE 0.1 1500
9 TCE
10 TCE
11 TCC
12 TCE
13 TCE
14 TCE
10
0.5
1.5
3
5
10
1500
3500
3500
3500
3500
3500
WATER
CONC.
(PPB)
200
400
2000
6000
12000
20000
67
133
13300
285
856
1712
2854
5707
AIR FLOW AIR COKC. SYSTEM CAPITAL
(ACFH) (PPHV) TYPE COST
2340 1.03 N/R 14000
2340 2.06 H/R 14000
2340 10.31 REGEH 207000
2340 30.93 REGEH 209000
2340 61,87 REGEH 212000
2340 103.11 REGEH 212000
7020 0.34 H/R 17000
7020 0.69 H/R 17000
7020
16400
16400
16400
16400
16400
68.74 REGEN
1.47 H/R
4.41 H/R
8.83 REGEN
14.71 HEGEN
29.42 REGEN
339000
24000
24000
452000
452000
453000
0 & H
COST
24000
39000
20000
21000
21000
21000
38000
69000
31000
163000
475000
36000
37000
40000
ANNUALIZED VK
COST ADSORBED
10YR 1 10X TONS/YR
26278 0.20
41278 0.40
53679 2.01
55004 6.04
55492 12.06
55492 20.14
40766 0.19
71766 0.39
86155
166905
478905
109540
110540
113703
40.28
1.98
6.01
12.05
20.11
40.26
COST/TON
VK
ADSORBED
134000
104000
27000
9100
4600
2800
219000
185000
2100
84000
80000
9100
5500
2800
0!CHLOROETHYLENE{KE) :
CASE
HO.

1 KE
2 DCE
3 DCE
4 DCE
5 DCE
6 DCE
7 DCE
8 KE
9 DCE
10 KE
11 KE
12 KE
• 13 KE
14 KE
fOC FLOW
INLET
LB/HR)
0.05
0.1
0.5
1.5
3
5
0.05
0.1
10
0.5
1.5
3
5
10
WATER
FLOW
(6PM)
500
500
500
500
500
500
1500
1500
1500
3500
3500
3500
3500
3500
WATER
CONC.
(PPB)
200
400
2000
6000
12000
20000
67
133
13300
285
856
1712
2854
5707
AIR FLOW
(ACFH)

2340
2340
2340
2340
2340
2340
7020
7020
7020
16400
16400
16400
16400
16400
AIR CONC. SYSTEM
(PPMV) TYPE

1.39 N/R
2.79 N/R
13.93 REGEH
41.76 REGEH
83.55 REGEH
139.26 REGEH
0.46 H/R
0.93 H/R
92.84 REGEN
1.99 N/R
5.96 REGEH
11.92 REGEH
19.87 REGEH
39.74 REGEK
CAPITAL
COST

14000
14000
207000
209000
212000
212000
17000
17000
339000
24000
439000
452000
452000
453000
0 & H
COST

62000
117000
21000
23000
24000
25000
110000
219000
39000
547000
37000
40000
44000
54000
ANNUALIZED
COST
10YR 8 10X
64278
119278
54679
57004
58492
59492
112766
221766
94155
550905
108425
113540
117540
127703
VOC
ADSORBED
TOHS/YR
0.20
0.40
2.01
6.04
12.08
20.14
0.19
0.39
40.26
1.98
6.01
12.05
20.11
40.26
COST/TON
VK
ADSORBED
327000
300000
27000
9400
4800
3000
605000
572000
2300
278000
18000
9400
5600
3200
1.2-DICKLDROETHAKE(EK}:
CASE \
HO.

1 EK
2 EK
3 EDC
4 EDC
5 EK
6 EK
7 EOC
BEQC
9 EDC
10 EK
11 EK
12 EK
13 EDC
14 EK
15 EK
16 EK
17 EK
18 EK
•OC FLOW
INLET
LB/HR]
0.05
0.1
0.5
1,5
3
5
0.05
0.1
0.5
1.5
3
5
10
0.5
1.5
3
5
10
WATER
FLOW
(GPHJ
SOD
500
500
500
500
500
1500
1500
1500
1500
1500
1500
1500
3500
3500
3500
3500
3500
WATER
CONC.
(PPB)
200
400
2000
6000
12000
20000
67
133
666
2000
4000
6700
13300
285
856
1712
2854
5707
AIR FLOW
(ACFH)

2340
2340
2340
2340
2340
2340
7020
7020
7020
7020
7020
7020
7020
16400
16400
16400
16400
16400
AIR COKC. SYSTEM
(PPHV) TYPE

1.36 H/R
2.73 H/R
13.64 REGEH
40.93 REGEN
81.87 REGEN
136.44 REGEH
0.45 H/R
0.91 H/R
4.55 H/R
13.64 REGEN
27.29 REGEN
45.48 REGEH
90.96 REGEH
1.95 H/R
5.84 REGEN
11.66 REGEN
19.47 REGEN
38.94 REGEH
CAPITAL
COST

14000
14000
207000
209000
212000
212000
17000
17000
17000
334000
334000
334000
339000
24000
439000
452000
452000
453000
0 & H
COST

51000
95000
21000
22000
23000
24000
90000
177000
443000
30000
32000
35000
37000
439000
36000
39000
42000
50000
ANNUALIZED
COST
10YR * 10X
53278
97278
54679
56004
57492
58492
92766
179766
445766
B4342
86342
89342
92155
442905
107425
112540
115540
123703
VK
ADSORBED
TONS/YR




1
2




1
2
4


1
2
.20
.40
.01
.04
.06
.14
.19
.39
.00
.03
.07
.13
.28
.sa
.01
.05
.11
40.26
COST/TON
VK
ADSORBED
271000
244000
27000
9300
4800
2900
498000
464000
223000
14000
7200
4400
2300
224000
16000
9300
5700
3100
Cost per ton of VOC Adsorbed
  The costs per ton of VOC controlled by the carbon adsorber range
from a low of $2100/ton to highs of $219,000/ton for TCE, $605,000/ton
for DCE and $498,000/ton for EDC. The costs per ton decrease as the
quantity of VOC being treated increases and the system size decreases.
  As previously noted, Figure 1 shows the cost per ton of VOC adsorbed
plotted against the groundwater concentration on a log-log scale. For
the regenerative systems at air concentrations greater than 4  ppm, the
costs per ton are very similar for the three chemicals. These have been
plotted as one set of lines for the 500, 1500 and 3500 gal/minin flow
rates. The VOC inlet rates for the regenerative systems are also shown,
from 0.5 Ib/hr to 10 Ib/hr. It can be seen that for a given groundwater
concentration, the cost per ton decreases when the water flow rate is
increased because the VOC quantity being adsorbed also increases.
Below 4 ppm, the nonregenerative systems show different costs per ton
for each chemical because of the different carbon use rates. Best-fit
lines have been plotted to show the general cost trends for these systems.

Combined  System Costs
  Table 5 shows the calculated annualized costs for air stripping, carbon
adsorption controls and the combined systems. The control costs per
ton of VOC adsorbed are shown for the three chemicals.
  The annualized costs for the air stripper and the carbon adsorption
systems were discussed in the previous sections. In comparing these
costs,  the  additional costs for controls were found to  range from
36 percent of the air stripping cost up to 426 percent of the air stripping
cost for the extreme case. The smaller percentage additional control
costs are generally found in the larger regenerative systems. It can be
seen that the total cost of air stripping with controls generally increases
as the system size and ground-water concentration increases. These total
annualized costs range from $54,000 to $628,000  for TCE,  $92,000
to $707,000 for DCE and  $95,000 to $637,000 for EDC. Costs for the
air stripper, carbon adsorber and the combined system were lowest for
TCE. The highest costs for the air stripper and combined system were
for EDC, while the highest carbon adsorber cost  was for DCE.
                                                                                                    Tables
                                                                                     Estimated Air Stripper/Carbon Adsorption
                                                                                              Control System Costs
TRICHLOROETHYLEHE(TCE):
CASE V
HO.

1 TCE
2 TC
3 TC
4 TC
5 TC
6 TC
7 TC
8 TC
9 TCE
10 TCE
11 TCE
13 TCE
14 TCE
OC FLOW
INLET
(LB/HR)
0.05
0.1
0.5
1.5
3
5
0.05
0.1
10
0.5
1.5
S
10
WATER
FLOW
(GPH)
500
500
500
500
500
500
1500
1500
1500
3500
3500
3500
3500
INLET
CONC.
(PPB)
200
400
2000
6000
12000
20000
67
133
13300
285
656
2854
5707
AIR FLOW
(ACFH)

2340
2340
2340
2340
2340
2340
7020
7020
7020
16400
16400
16400
16400
AHNU
TRIPPER

27695
29020
36647
40460
41786
45437
80758
83409
151564
148913
155377
169143
ALIZED CO
HDSORBER

26278
41278
53679
55004
55492
55492
71766
86155
66905
78905
10540
13703
STS:
TOTAL

53973
70298
90326
95464
97278
100929
152524
169564
318469
627618
265917
282846
VK
REMOVED
TOHS/YR
0.21
0.43
2.18
6,56
13.13
21.89
0.20
0.42
43.78
2.15
6.53
21.86
43.76
TOTAL COSTS
COST/TON ST« PP
VOC
253000 0
163000 0
41000 0
15000 0
7400 0
4600 0
632000 0
PER 1000 GA
ING CONTROL

.11 0.10
.11 0.16
.14 0.20
.15 0.21
.16 0.21
.17 0.21
.11 0.05
3900 0.11 0.11
148000 0
S6DOO 0
12000 0
6500 0
08 0.09
08 0.26
08 0.06
09 0.06
LLONS:
TOTAL

0.21
0.27
0.34
0.36
0.37
0.38
0.16
0.22
0.17
0.34
0.14
0.15
DICHLOROETHYLEHE(DCE):
CASE V
HO.

1 KE
2 DCE
3 KE
4 DCE
5 DCE
6 KE
7 DCE
8 KE
9 KE
10 KE
11 KE
12 DCE
13 DCE
14 DCE
OC FLOW
INLET
(LB/HR)
0.05
0.1
0.5
1.5
3
5
0.05
0.1
10
0.5
1.5
3
5
10
WATER
FLOW
(GPH)
500
500
500
500
500
500
1500
1500
1500
3500
3500
3500
3500
3500
INLET
CONC.
(PP8)
200
400
2000
EOOO
12000
20000
67
133
13300
285
856
1712
2854
5707
AIR FLOW
AHNU
LI ZED CO
(ACFH] STRIPPER ADSORBER

2340
2340
2340
2340
2340
2340
7020
7020
7020
16400
16400
16400
18400
16400

27857
30183
37810
41623
45437
46599
69546
82084
87060
156540
145262
155215
161679
175445

64278
119278
54679
57004
58492
59492
112766
221766
94155
550905
106425
113540
117540
127703
TS:
TOTAL

92135
149461
92489
96627
103929
106091
202314
303850
181215
707445
253667
268755
279219
303148
VOC
TOTAL COSTS
PER 1000 GA
REMOVED COST/TON STRIPPING CONTROL
TONS/YR
0.21
0.43
2.18
6.56
13.13
21.89
0.20
0.42
43.78
2.15
6.53
13.10
21.86
43.76
VOC
431000 0
346000 0
4200D 0
15000 0
7900 0
4800
998000
721000
4100
329000
39000
21000
13000
6900

11 0.24
11 0.45
14 0.21
16 0.22
17 0.22
18 0.23
11 0.14
10 0.26
11 0.12
09 0.30
08 0.06
08 0.06
09 0.06
10 0.07
LOKS:
TOTAL

0.35
0.57
0.35
0.38
0.40
0.40
0.26
0.39
0.23
0.38
0.14
0.15
0.15
0.16
1 . 2-OICHLORO£THANE( EDC) :
CASE V
NO.

1 EDC
2 EDC
3 EDC
4 EDC
5 EK
G EDC
7 EK
8 EDC
9 EDC
10 EDC
1 EDC
2 EK
3 EK
4 EK
5 EK
6 EK
7 EK
18 EK
3C FLOW
INLET
LB/HR)
o.QS
0.1
0.5
1.5
3
5
0.05
0.1
0.5
1.5
5
10
0.5
1.5
3
5
10
WATER
FLOW
(GPH)
500
500
500
500
500
500
1500
1500
1500
1500
1500
1500
3500
3500
3500
3500
3500
INLET
CONC.
(PPB)
200
400
2000
6000
12000
20000
67
133
666
2000
6700
13300
285
856
1710
2850
5707
AIR FLOW
(ACFH] S

2340
2340
2340
2340
2340
2340
7020
7020
7020
7020
7020
7020
16400
16400
16400
16400
16400
ANHIH
TRIPPER *

41623
49250
60691
73131
78270
82084
74457
70643
104802
124669
152727
166655
194512
207116
272620
2928SO
343425
LI ZED CO
DSORBER

53278
97276
54679
56004
57492
58492
92766
179766
445766
84342
89342
92155
442905
107425
112540
115540
123703
TS:
TOTAL

94901
146528
115370
129135
135762
140576
167223
250409
550568
209211
242069
258810
637417
314541
385160
40B390
46712B
VOC
REMOVED
TONS/YR
0 21
0 43
2 18
6 56
13 13
21 69
0 20
0 42
2 17
6 55
21 88
43 78
2 15
6 53
13 10
21 86
43 76
TOTAL COSTS
OST/TOH STRIPP
VOC
444000 0
339000
53000
20000
10000
6400
825000
594000
253000
32000
11000 0
5900 0
296000 0
48000 0
29000 0
19000 0
ER 1000 GA
KG CONTROL

16 0.20
19 0.37
23 0.21
28 0.21
30 0.22
31 0.22
09 0.12
09 0.23
13 0.57
16 0.11
19 0.11
21 0.12
11 0.24
11 0.06
15 0.06
16 0.06
11000 0.19 0.07
LONS.
TOTAL

0.36
0.56
0.44
0.49
0.52
0.53
0.21
0.32
0.70
0.27
0.31
0.33
0.35
0.17
0.21
0.22
0.25
Cost Estimates by Volume of Groundwater Treated
  In evaluating the costs of groundwater treatment technologies, as well
as  drinking  water  and wastewater  treatment  technologies,  the
cost/volume of water treated frequently is used as a basis for comparison.
Table 5 shows these costs in $/1000 gallons of groundwater treated. It
can be seen that the costs range from 8 cents 31V1000 gallons for air
stripping alone. When carbon adsorption controls are added, the total
costs range from 14 to 70C/1000 gallons.
  The costs per 1000 gallons of water treated generally is reduced when
the size of the stripping operation is increased and the groundwater
concentration is reduced. This trend is opposite from the trend indicated
by the  cost per ton of VOC treated. The cost/1000 gallons may be a
better indicator for evaluating system costs because the treatment rate
                                                                                                                     TREATMENT    751
-------
for grouodwater is constant and variations in groundwater concentra-
tion do not drastically affect these costs.  The costs per ton of VOC
treated, however, are directly affected by the groundwater concentra-
tion, which is likely to fluctuate. In many applications, groundwater
is moving through an aquifer and it is impossible to accurately predict
the quantity of VOC that will be removed over a given period of time.
When an air stripping system is only removing a fraction of a  ton of
VOC/year of operation, the cost per ton of VOC treated becomes a large,
abstract number  that does not necessarily reflect  the  actual cost
of the system.

DATA LIMITATIONS  AND CONCLUSIONS
  The  cost data generated are  based on simplified assumptions and
theoretical models and are valid only for the single chemicals in ground-
water. The adsorption capacity  of carbon actually varies with varying
chemical concentration and can vary with different brands of carbon.
This variation in treatability can have a significant impact on carbon
use and the cost for the  nonregenerative units. The design of a prac-
tical air stripping system with vapor phase carbon adsorption controls
at a specific Superfund site would require a more detailed analysis than
was possible to include in this study. For example, the costs generated
by PDQ$ for the air stripping columns are for carbon steel. In many
cases an FRP (fiberglass reinforced plastic) or a stainless steel column
may be more desirable, at a different cost. Most Superfund sites con-
tain a variety of different chemical contaminants. The air stripper must
be designed for the chemical with  the worst  stripping characteristics,
while the carbon adsorption system  must be designed for chemical com-
binations with potentially complex adsorption relationships. The air
stripper also should be designed for  the lowest expected operating
temperatures.
  The cost per ton of VOC removed is extremely sensitive to the
tons/year of VOC adsorbed. A minor variation  in tons/year of VOC
at low concentrations will produce a significant change in the cost per
ton of VOC removed. The system with the lowest VOC input and lowest
annualized cost can also have the highest cost per ton of VOC removed.
  The cost data presented may be used as relative  indicators of cost
trends for air stripping and carbon adsorption control systems. Real
world systems at Superfund sites may vary widely from these numbers
depending on a variety of site-specific conditions.

REFERENCES
1. U.S. EPA, Superfund Public Health Evaluation Manual, EPA-540/1-86-060,
   OERR, U.S. EPA, Washington, DC, Oct. 1986.
2. U.S. EPA, Records of Decision (RODS) data base. Research Triangle Park,
   NC, accessed May 1989.
3. Roberts, P. V., et al., "Evaluating Two-Resistance Models for Air Stripping
   of Volatile Organic Contaminants in a Countercurrent, Packed Column," En-
   viron. Sci. Techn., 19(2), pp. 164-173, 1985.
4. PDQ$ software,  Version 032889,  PDQ$, Inc. 1987.
5. Peters, M. S. and Timmerhaus,  K.  D., Plant Design  and Economics far
   Chemical Engineers, 2nd Ed., McGraw-Hill, New York, NY,  1968.
6. Telephone contact between T. Cannon, D. Dazell, N. Shaw, Vic Manufacturing
   and J. E. Spessard, PEI, May 1989.
7. Telephone contact between C. Polinsky, M. Bourke, Calgon Corp. and J.  E.
   Spessard, PEI, May 1989.
75:
       TREATMENT
-------
                        High  Energy  Electron  Beam  Irradiation:
                     Quantitative  Evaluation  of  Factors  Affecting
             Removal  of  Toxic Chemicals From Aqueous  Solution
                  William J. Cooper, Ph.D.
                 Michael G. Nickelsen,  M.S.
                      David  E. Meacham
                      Eva Maria Cadavid
               Drinking Water Research  Center
               Florida  International University
                         Miami,  Florida
       Thomas D. Waite, Ph.D., P.E.
      Charles N.  Kurucz, Ph.D., P.E.
             University of Miami
             Coral  Gables, Florida
ABSTRACT
  Irradiation of water with high energy electrons results in the forma-
tion of three reactive free radicals: e"(aq), H • and OH •. Once formed,
these free radicals react with organic solutes in aqueous solution. Full-
scale experiments, conducted at our Electron Beam Research Facility,
will be compared to parallel bench-scale studies, conducted at a ^Co
facility, for the removal of chloroform and carbon tetrachloride from
aqueous solutions. Additional results obtained at the E-Beam facility
will describe removal efficiencies obtained for chemicals of interest in
site remediation. The results of these studies have  led to a better
understanding of the factors affecting the removal  of the organic
compounds of interest to Super fund.

 INTRODUCTION
  Soils, sediments and groundwater have been contaminated with hazar-
 dous compounds in many areas of the country, many of which may
 persist for considerable periods in the environment. Because of this
 contamination and the recalcitrant nature of many of the chemicals,
 it is of interest to develop processes  which will effectively and effi-
 ciently remove these compounds from aqueous solutions. Effective
 technology might be defined as that technology which results in the
 ultimate disposal of the chemicals, not merely a transfer from one en-
 vironmental compartment to another. Efficiency should consider not
 only the cost question, but also the overall effectiveness of the process
. in solving the problem.
  High energy electron irradiation is an innovative treatment process
 which is being developed as an ultimate disposal process for toxic and
 hazardous organic chemicals. Experiments conducted to  date  have
 focused upon their removal from aqueous solutions of varying water
 quality, i.e., raw wastewater to potable water. Recently, experiments
 have been initiated which indicate that the process also will  work well
 on sludges.
  Table 1 outlines the most frequently found hazardous chemicals at
 Superfund sites in the United States. Table 2 outlines organic compounds
 recently added to the list of compounds to be regulated as hazardous.
 Many of the organic compounds on these lists have been studied at the
 Electron Beam Research Facility in Miami, Florida.  It is possible to
 use ^Co gamma irradiation to simulate the high energy electron ir-
 radiation process. The advantage of conducting  studies using gamma
 irradiation is that smaller volumes can be used and the solutes can be
 studied in distilled water arid in aqueous solutions of defined composi-
tion. Reaction byproduct analyses can be conducted much easier in a
well-defined aqueous medium and the results confirmed at full-scale
and in natural waters.
  This paper focuses upon the results of full-scale high energy elec-
tron irradiation and  batch ^Co gamma irradiation for the removal of
chloroform and carbon tetrachloride from aqueous solutions. Studies
conducted at both the ^Co and the Electron Beam Research Facility
will be compared and a quantitative relationship defined to relate removal
efficiency under both conditions.

RADIATION CHEMISTRY OF NATURAL WATERS
  The purpose of this section is to provide an overview of aqueous-
based radiation chemistry. This brief introduction should assist the
reader in understanding the application of high energy electron irradia-
tion to the treatment of toxic and hazardous organic wastes in natural
waters.

                          Thblel
   25 Most Frequently Identified Substances At 546 Superfund Sites
   Adapted from McCoy & Assoc., "Haz. Waste Consult." 3:2(1985))
Table 1. 25 Host Frequently Identified Substances At 54C
Superfund Sites (Adapted from McCoy t Assoo., "Ha.*.
Waste Consult." 3i2 (1985)1.
Rank
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Substance
Trlchloroethylene
Lead and Compounds
Toluene
Benzene
Polychlorlnated Biphenyls (PCBs)
Chloroform
Tetrachloroethylene
Phenol
Arsenic and Compounds
Cadmium and Compounds
Chromium and Compounds
1,1, 1-Trichloroethane
Zinc and Compounds
Ethylbenzene
Xylene
Hethylene Chloride
££an£-l , 2-Dichloroethylene
Mercury
Copper and Compounds
Cyanides (soluble salts)
Vinyl Chloride
1 , 2-Dichloroethane
Chlorobenzene
1 , 1-Dichloroethane
Carbon Tetrachloride
Percent of Sites
33
30
28
26
22
20
16
15
15
15
15
14
14
13
13
12
11
10
9
8
8
8
8
8
8
                                                                                                        TREATMENT   753
-------
                            Table!
          Organk Compounds Recently Added to the List of
              Chemicals to be Regulated as Hazardous
TtM« 1. organic Coapoaada »»oantly &dd»d to the Ll«t of
Chaical* to b* Rwjnlatcd a* Haiardotu.
coHpomd
Benzane
Carbon Tetrachlorlde
Ctilordane
Chlorobenzene
Chloroform
C-Cr«»ol
«-Cr««ol
B-Cr«sol
1,4-Dichlorobenzene
1 , 2 -Dichloroethane
1, 1-Dichloroethylene
2 , 4-Dinitrotoluene
Hcptachlor
Hexachlorobenzene
Hexachloro-1, 3-butadiene
Hcxachloroathan*
Hethyl Ethyl K«ton«
Nltrobenzan*
Pentachlorophenol
Pyrldln*
T«tmchloro«thyl«n«
Trlchloro«thyl«n»
2,4, 5-Trichloroph«nol
2,4, 6-Trlchloroph«nol
Vinyl Chlorid*
(•gulatorr L«v«l (mq L~')
0.5
O.S
0.03
100.0
6.0
200.0
200.0
200.0
7.5
0.5
0.7
0.13
0.008
0.13
0.13
3.0
200.0
2.0
100.0
5.0
0.7
0.5
400.0
2.0
0.2
  The literature relating to radiation chemistry most often reports ex-
periments conducted in pure water. The extrapolation of pure water
data to natural waters is complicated by the presence of inorganic and
organic matter (primarily humic substances) found in natural waters.
These compounds may interact with the reactive species formed during
irradiation and lead to side reactions not  observed in pure water.
Examples of these processes are the reactions of hydroxyl radical with
carbonate and halide ions.
  Irradiation of pure water with fast electrons has been studied exten-
sively with numerous excellent reviews on the subject.1"3 The fast elec-
trons  can be generated either by ^Co or by electron accelerators.  It
is thought that the initial radiation process (lO^-lO"14 sec) results in the
formation of excited molecules HjO',  H2O+  and e" 4   As these
excited state molecules and electrons interact and transfer their energy,
several secondary reactive species are formed:
H,0 -/ \
H, (0.45),
/ \   / \->
                     (2.6),  H  (0.55),  OH
H202 (0.71), H30+ (2.7)
                                                         (2.7),
                                                            (1)
  The efficiency of the conversion of energy from ionizing radiation
to chemical energy is described by G values. G is defined as the number
of radicals, excited states or other products, formed (or lost) in a system
absorbing 100 eV of energy. The G value for the formation of the secon-
dary products of irradiation are indicated in parenthesis in Equation (1).
  The three free radicals formed are the most reactive species.  The
e (aq) and H  are reducing radicals and the OH  is  an  oxidizing
radical.58 Of these radicals, the aqueous electron and hydroxyl radical
account for greater than 90% of the reactive species. Thus, the chemistry
of primary interest in this process is that of these two species. However,
it is possible that the presence  of HjO2  may also contribute to the
removal of organic toxic and hazardous wastes.

Aqueous Electron
  The reactions of the aqueous electron, e~(aq), with specific organic
and inorganic compounds has been studied extensively.**9 The e'(aq)
                                                        is a powerful reducing reagent with an E° (e'(aq) + H —> VtH^ of
                                                        2.77. The reactions of the e~(aq) are single electron transfer, the general
                                                        form of which is:

                                                          e-(aq) -1- SN	> SN-'                                     (2)

                                                        The e~(aq) reacts with numerous organic chemicals and of particular
                                                        interest to the field of toxic and hazardous wastes are the reactions with
                                                        halogenated compounds. A generalized  reaction is shown  below:
                                                                        e-(aq) + RC1	>  R + Cl
                                                                                                                   (3)
                                                                      Thus, reactions involving the e~(aq) may result in the dechlorination
                                                                      of organohalogen compounds. Further reaction of the organic radical
                                                                      formed could result in the complete destruction of the compound and
                                                                      specific examples  are given below. The e'(aq) also reacts with other
                                                                      organic compounds and would contribute to the removal of these com-
                                                                      pounds from aqueous solutions. Examples of the rate constants of reac-
                                                                      tions of interest in this area are presented later in this paper.

                                                                      Hydrogen Radical
                                                                        The reactions of H- with organic and inorganic compounds have also
                                                                      been summarized.10  The hydrogen atom accounts for approximately
                                                                      10% of the total free radical concentration in irradiated water. The H
                                                                      undergoes two general types of reactions with organic compounds,
                                                                      hydrogen addition and hydrogen abstraction.
                                                                        An example of a typical addition reaction with  an organic solute is
                                                                      that of benzene:
                                                                        H  +C6H6	>                                        (4)

                                                                      The second general reaction involving the H  is hydrogen abstraction:

                                                                        H  +  CH3OH	> R2 + CHjOH                        (5)

                                                                        Since most natural waters likely to be encountered will be oxygenated,
                                                                      the predominate reaction for H- will be:
                                                                        H
                                                               O2 —
                                                                         HO
                                                                                       '2                                      (6)

                                                                    This reaction has a second order rate constant of 2.1 x 10K/m. sec.
                                                                    Therefore, it is assumed that the H  is of minimal importance in the
                                                                    removal of toxic and hazardous organic compounds from oxygenated
                                                                    aqueous solutions.
Hydroxyl Radical
  Reactions of the hydroxyl radical, OH-, with inorganic and organic
compounds has been well-documented.6 Compilations of rate constants
have been published.7'10 OH- can undergo several types  of reactions
with chemicals in aqueous solution. The types of reactions that are likely
to occur are addition, hydrogen abstraction, electron transfer and radical-
radical recombination.
  Addition reactions occur readily  with  aromatic  and  unsaturated
aliphatic  compounds. The resulting compounds  are hydroxylated
radicals:
                                                                        OH  +
                                                                                > HOCHj-CHj
                                                                                                                   (7)
                                                        Hydrogen abstraction occurs  with  saturated and many unsaturated
                                                        molecules, e.g., aldehydes and ketones:

                                                          OH  + CH3-CO-CH33	> CHjCOCH, + HjO           (8)

                                                        Reactions involving halogen ions (X') may also be significant:

                                                          OH  + X	> X + OH                               (9)
                                                          X  + X •
                                                                                                                   (10)
                                                        The Xj can further react with organic molecules possibly forming
                                                        halogenated organic compounds. The halogens of most interest are CT
                                                        and Br.
                                                          Another inorganic radical likely to be involved is the carbonate radical,
                                                        CO3. C03 is formed by OH reaction with CO32-. The importance
                                                        of the carbonate radical is as yet unknown, but because of its relatively
      TREATMENT
-------
low reactivity with organic compounds, it probably will play a relatively
unimportant role in their removal from aqueous solution. However, the
presence of high  concentrations of CO32" may have a positive effect
on the effective concentration of e'(aq) by removing OH from solu-
tion. This situation would result in an increased removal efficiency of
compounds which primarily react with e'(aq).

Hydrogen Peroxide
  In oxygenated aqueous solutions, the reactions of O2  with e'(aq)
and H  occur and compete for the reactive intermediates formed in
Equation 1. Both of these reactions result in the formation of reduced
oxygen:
                                                                1000 Krad  = 1.0 x 10s erg/g  = 2.39 cal/g
                                                                                                                               06)
e-(aq)
H  +
          O2 -----
O2
                  HO2
(11)
(12)
The products of Equation (11) and (12) are in equilibrium, with a pKa
 = 4.5. These products also lead to the formation of additional H2O2:
202- + 2H+
2H0  — ->
                     0
               0
                                                           (13)
                                                           (14)
      2 — -       -j     2

 One of the interesting reactions that has been studied is the following:

  e-(aq) +  Uf)2 — > OH + OH'                          (15)

 with a second order rate constant of 1.2-1.4 x 1010/m. sec. In our study,
 with the high and continuous radiation dose, it appears that H2O2
 might serve as a secondary source of OH .

 ELECTRON BEAM RESEARCH FACILITY

 Plant Description
  The Electron Beam Research Facility is located at the Virginia Key
 (Central District) Wastewater Treatment Plant. It was originally installed
 as a substitute technology for heat-treatment disinfection of sludge and
 was declared operational on September 25, 1984. The actual project
 construction costs at that time were approximately 1.7 million dollars.
  The accelerator is a horizontal 1.5 MeV electron beam, rated at 50
 mA. The beam current is continuously variable from 0 to 50 mA,
 providing doses of 0 - 850 krads.
  The research  facility was designed to treat 460 L/min (120 gpm);
 however, experiments have been conducted using flows of up to 610
 L/min. The minimum flow is approximately 380 L/min (100 gpm).
 Originally designed to disinfect digested sludge, 2-8% solids, the pre-
 sent configuration allows for several influent streams. The influent
 streams directly connected to the plant are potable (drinking) water,
 a secondary wastewater effluent and anaerobically digested sewage
 sludge. The secondary wastewater is the effluent of an extended (pure
 oxygen) aeration process. The effluent is chlorinated immediately (0.5
 - 1 min.) prior  to the intake of  the electron beam.
  In addition to the three flow streams described above, we have the
 capacity to conduct large-scale (22,400 L) batch experiments using tank
 trucks. Batch experiments may be used for groundwater and any other
 source of contaminated water for  which treatability studies are desired.
 The minimum batch experiment is 7,600 L.
  The electron beam (E-Beam) research facility has been instrumented
 to continuously monitor  and  record various operating  parameters;
 accelerating voltage, beam current,  water flow and absorbed dose. The
 absorbed dose is measured using five resistance temperature devices
 (RTDs). The five RTDs are mounted in the influent (2 sensors) and
 effluent (3 sensors) stream immediately before and after the beam. All
 of the variables are connected via an interface board (Strawberry, Inc.)
 to a portable computer (Compaq, Inc.) which continuously reads and
 records temperatures.


 Measurement of Absorbed Dose
  Absorbed dose is a measure  of energy transfer to the irradiated
 material, in this case .water. In a continuously flowing aqueous system,
 the absorbed dose can be estimated by measuring the temperature dif-
 ference of the water stream before and after irradiation  as follows:
                                                              By converting cal/g to temperature in degrees centigrade, 1000 Krads
                                                              is equivalent to a temperature change of 2.39°C. Therefore, the total
                                                              absorbed dose (Dt) in pure water is calculated using the equation:
                                                                      Dt =
                                                                          - t,)
                                                                      (17)
                                                              where t, and tj  are the before and after irradiation water temperature
                                                              of the flowing stream in °C, respectively; and K is the constant of
                                                              proportionality:
                                                                      K  = 418 krads/°C
                                                                                                                         (18)
  The measurement of D, provides an estimate of absorbed dose in
natural waters. A slight error results from the deviation from unit den-
sity (pure water) of the natural waters. The application of temperature
difference to estimate the absorbed dose in irradiated sludges would
result in an error which would increase with increasing solids content.

Electron Utilization Efficiency
  It is possible to estimate the electron utilization efficiency of the system
at the Electron Beam Research Facility described above. Assuming that
the system is operated at full power,  i.e., 1.5 MeV and 50 mA, total
beam power of 75 kW and a flowrate of 470 L/min, then the efficiency
may  be determined as follows:
                                                                1 W =  860 cal/hr
                                                                75 kW = 6.45 x 107 cal/hr
                                                                                                                              (19)
                                                                                                                              (20)
                                                              Assuming that 1 cal results in a 10 C increase in temperature per gram,
                                                              complete conversion of electrical energy (beam power) to heat would
                                                              result in a D, of:
                                                                D, = 6.45 x 107 cal/hr / 2.73 x 107 mL/hr = 2.36°C
                                                                                                                              (21)
                                                              We observed a 1.54°C increase in temperature (645 krads). Therefore,
                                                              the efficiency of the conversion of beam energy to heat was:
                                                                efficiency (%) =  1.54°C/2.36°C x 100 = 65.3
                                                                                                                              (22)
                                                                      In limited experiments at high water flowrates, 610 L/min the dose
                                                                    was unchanged, i.e., 645 krads or 1.54°C increase in temperature and
                                                                    the efficiency approached 86%. The reasons for the increase in effi-
                                                                    ciency probably were related to the more complete absorption of the
                                                                    fast electrons in the solution (increased depth of the water) and at the
                                                                    higher flowrate, the water cascaded over the weir nearer to the elec-
                                                                    tron gun window, reducing energy losses in the air between the window
                                                                    and the water.

                                                                    "Co GAMMA SOURCE RESEARCH FACHJTY
                                                                      More than 20 years of research have demonstrated the reduction of
                                                                    chemical and microbiological contaminants from aqueous-based systems
                                                                    with "Co-Gamma radiation.U>H "Co represents an unstable nucleus
                                                                    of cobalt. 59Co, when placed in a reactor, will absorb a neutron and
                                                                    become "Co:

                                                                                                                              (23)
                                                                59Co + 'n	>
                                                              As the "Co returns to a stable condition, it releases mass-energy in
                                                              the form of one beta particle and two gamma rays. This process results
                                                              in the stable isotope "Ni.

                                                                «>Co	> ^Ni + /3~ + 2r                             (24)

                                                              Beta (ff) particles are electrons and have very little penetrating ability
                                                              when released from "Co.13 When "Co is  encapsulated in stainless
                                                              steel, all of the beta particles are stopped and only the highly penetrating
                                                              gamma rays escape into the surrounding medium. Gamma rays are not
                                                              deflected by an  electric or magnetic field and have no charge. They
                                                              are electromagnetic waves with extremely short wavelengths and are
                                                              very penetrating.
                                                                Gamma rays in  water produce a decomposition  of water similar to
                                                              that observed with high-energy electrons. Interaction of gamma rays
                                                              and water is on the molecular level and not on the nuclear level. Gamma
                                                                                                                   TREATMENT   755
-------
rays must possess at least 1.50 MeV of energy to enter a nucleus and
even at this elevated energy level, photonuclear cross sections are ex-
tremely small.14 Because  gamma rays  from ^Co are  emitted at
energies of 1.17 and 1.33 MeV, residual nuclear activity in the water
or wastewater is not observed.

MCo Reactor Description
  The "Co reactor is a 5000 Ci gamma source located at the Univer-
sity of Miami Radiation Control Center. The gamma source is located
at the center of concentric circles of 10, 20, 30, 40, 50, 60, 70 and 100
cm. A linear regression of a In/In plot of distance versus dose rate was
generated to determine the dose rate at any distance from the '"Co
source:
  In (dose rate) =  -1.958 x In (distance)  + 13.356
(25)
REMOVAL OF SELECTED ORGANIC CHEMICALS
IN AQUEOUS SOLUTION
  We have conducted numerous experiments on organic chemicals that
may be of interest in: water treatment, trihalomethanes; groundwater
contamination, halogenated ethanes and ethenes; leaking underground
storage tanks, benzene and substituted benzenes; as well as other organic
chemicals now regulated as hazardous wastes. Before presenting removal
efficiencies, a brief discussion and summary of the rate constants is
presented for the compounds that have been studied or are of interest
in the area of toxic and hazardous wastes.

Rate Constants
  The rate constants of interest are those for the reaction of the reac-
tive intermediates formed when water is irradiated (Equation 1), e'(aq),
H  and OH . with toxic and  hazardous organic chemicals and in-
organic chemicals likely to be found in natural waters. A review of the
literature10 for selected rate constants applicable  to toxic and hazardous
wastes  is summarized in Table 3.

Removal Efficiencies
  Most of the results shown below, conducted  on a large-scale  treat-
ment facility, appear to be qualitatively explained using available rate
constants. However, other results do not fit the available rate data. These
differences are not surprising given that the rate  data reported in the
literature usually are obtained in pure  solutions  under controlled
experimental conditions. Thus, there  may be several reasons for the
apparent discrepancies. First, all of the experiments have been con-
ducted  in raw or secondary treated wastewater or potable water. These
waters  are of widely  varying (water)  quality and present a complex
matrix  for detailed examination of removal data.  Secondly, not  all of
the applicable rate constants are known for the compounds of interest.
  Tb date, the only compound which has been studied at both the  Elec-
tron Beam  Research  Facility and the  '"Co  Research  Facility is
chloroform. Chloroform is listed as the sixth most frequently identified
substance at 546 Superfund Sites (Table 1). Others have reported studies
using electron  and  gamma  irradiation  of aqueous  solutions of
chloroform.15'16 We have observed removal efficiencies  of CHCL of
approximately 99.9% in distilled water  (Figs 1 and 2) using ^Co
irradiation. This removal was not affected by the initial concentration
of CHC13 when it was varied from 125 to 1250 ug/L. At the electron
beam research facility, similar studies were conducted using potable
water (Figs.  3 and 4). Experiments not shown  in secondary and raw
wastewater have shown removal efficiencies of 85  - 95%.
  A proposed mechanism for the decomposition of CHC13 and the for-
mation  of reaction byproducts  has been suggested:16
  e (aq) +  CHC1,
  H  -I- CHC1,
  OH  +  CHC1,
  CHC1, -t-  H,O
  CC1, "+ 2H,0
  COOH  +  COOH
	> Cl + CHCL;
	> H,+  CO,
	> HC1+ CHCU
	> H,O+ CC1/
	> CHO-I- 2HC1
	> COOH + 3HC1
	> HOOC-COOH
(26)
(27)
(28)
(29)
(30)
(31)
(32)
CHO +  HCCLj +  H/)
H + CHC13
CHCL, -I- CHCL;
CCL, + CHCLj
CC13 + CC13
H + CHO
                                        -> HCOOH + CO2           (33)
                                        -> CHCLj -I-HCOOH  + HC1  (34)
                                        -> CH^CL,                    (35)
                                        -> CHCLjCHClj              (36)
                                        -> CCljCHClj                (37)
                                        — >  CC13CC13                (38)
                                        -> HCHO                    (319)
CHC13 + O2
CC13  +  02
                                            O2CHC13
                                            02CC13
                                            and in solutions with high O2 concentrations the following reactions
                                            are also possible:

                                                                                                     (40)
                                                                                                      (41)

                                            with the exact fete of these radicals unknown.
                                              The major differences between the work which resulted in the above
                                            reaction mechanism16 and our work are: (1) the concentration of the
                                            CHC13 was 70 mm, whereas the concentration range we have been
                                            studying is 1000-fold less and (2) the irradiation doses we use are up
                                            to 100-fold higher. In our studies, conducted at  low solute concentra-
                                            tions, none of the halogenated reaction byproducts have been observed.
                                            The liquid-liquid extraction method used for the quantification of the
                                            CHC13 would also have determined the presence of the chlorinated
                                            ethanes at detection limits of 0.01 /iL.  The authors12 found that the
                                            presence of O2 enhanced the decomposition of the CHC13. This finding
                                            is important because many of the systems in which this process poten-
                                            tially will be used involve solutions  which will  have been aerated or
                                            at least contain some O2.
                                        Thble 3
                 Rate Constants (1/m. sec.) of Selected Organic Chemicals and
                  the Free Radicals Formed in Irradiated Aqueous Solution10
Table 1. Rate Conatanta (Ma1) of selected Organic
Chemiaala and the Free Radical* Formed ia
Irradiated Aqueoua Solution (12) .
compound
Benzene
Bromodichlorone thane
Bromoform
carbon Tetrachloride
Chlorobenzene
•3H.ftotofm-'f,^j(i&!"-' •'
fl-Creaol
ii^crSgdlr r,'ji-. ."„..•.'...
D-Cresol
•Dibromochlorome thane
1, 2-Dichlorobenzene
l.^-Dichlorobenzene
1, 4-Dichlorobenzene
1, 1-Dichloroe thane
1, 2-Dichloroethane
1, 1-Dichloroethylene
Siana-1 < 2-Dichloroethylene
2 , 4-Dinitrotoluene
Ethylbenzene
Hexachlorobenzene
Hexachloro-l, 3-butadiene
Hexachloroethane
Hethylene Chloride
Methyl Ethyl Ketone
Nitrobenzene
Pentachlorophenol
Phenol
Pyridina
Tetrachloroethylene
Toluene
1, 1, 1-Trlchloroe thane
Trichloroethylene
2,4, 5-Trichlorophenol
3,4 , S-Trichlorophenol
Vinyl Chloride
fl-Xylane
m-Xylene
B-Xylene
•"u*
9.0 X 10°
NP"
NF
1.6 X 1010
5.0 X 101
3.0 X 10™
NF
NF
4.2 X 107
NF
4.7 x 10*
S.2 X 10*
5.0 X 10*
NF
NF
NF
7.5 x 10*
NF
NF
NF
NF
NP
NF
NF
3.7 x 10"
NF '
2.0 X 10T
1.0 X 10*
1.3 X 10™
1.4 X 107
NP
1.9 X 10*
NF
NP
2.5 X Ifl'
NF
NP
NP
H-"
9.1 X 10*
":HF
NP
d.s x v>7
1.4 X 10
i.i x ior
NF
• -'NF • ;
NF
'• *&'"
NP
NF
NP
NF
NP
NF
NF
NP
NF
NP
NF
NF
NF
"^
1.0 X 10
• "; up '', '
1.7 X 10*
7.8 X 10*
NP
2.6 X lO*
NF
NP
NF
HP
NP
2.6 X 10*
2.0 x 10*
3.2 X 10*
OH
7.8 X 10*
iV 'j|f
NF
-NF
5.5 X 10
,# 5 X 10*
1.1 X 10™
J^^ T NF JttjjtL1',
1.2 X 10
'y ivf^iffi.
HP
HP
NF
'•- 
-------
  Whether the above mechanism describes the actual breakdown pro-
cess in natural waters will never be known quantitatively. The impor-
tance of the above mechanism (Equations 26-41) is that it provides a
point of departure for determining other possible reaction products.
We have observed, in preliminary research, that oxidized organic com-
pounds, such as formaldehyde, are formed. Continuing research is
underway using analytical methods for the determination of very low
concentrations of aldehydes and carboxylic acids.
  Another group of organic chemicals mat have been studied at our
treatment facility are the halogenated solvents. The compounds most
commonly found are trichloroethylene (TCE) and tetrachloroethylene
(PCE). Radiation-induced decomposition of TCE in aqueous solutions
has been the subject of several recent studies.17'22 An example of the
removal efficiency we have obtained in raw wastewater is shown in Figure
5. In most of the referenced studies conducted to date, the complete
destruction of TCE was observed. Although  the preliminary  data
indicated a relationship between removal efficiency and second order
reaction rate constants of OH , it is also possible that the e'(aq) may
be in part responsible for the removal of TCE. We have also conducted
studies on the removal of tetrachloroethylene in secondary chlorinated
wastewater (Figure 6).
                                                     POTABLE WATER
 o
                          DISTILLED WATER
                                            60,
                                              Co source
               125


             -•100
                  s
             ••75 ii


             ••50


             ••25
                                   100
                       APPLIED DOSE (Krads)
                                                 150
                             Figure 1
      Removal of CHCL3, using ^Co, at several irradiation doses in
        distilled water at an initial concentration of approximately
      125 ug/L (error bars indicate one standard deviation from mean,
      where no error bars are seen the error is within the data point)
                               1000-
                                         100   200  300  400   500   600   700   800
                                                 ABSORBED DOSE (Krods)

                                                        Figure 3
                                 Removal of CHCL3, using ^Co, at several irradiation doses in
                                   distilled water at an initial concentration of approximately
                                 100 ug/L (error bars indicate one standard deviation from mean,
                                 where no error bars  are seen the error is within the data point)
                                                                                                  POTABLE WATER
                                                                            5000:
                                                                        f  4000-
                                    0    100   200   300  400  500   600   700   800
                                                 ABSORBED DOSE (Krads)

                                                       Figure 4
                               Removal of CHCL3, using the Electron Beam Research Facility, at
                                     several irradiation doses indistilled water at an initial
                                          concentration of approximately 600 ug/L
                                error bars indicate one standard deviation from mean, where no
                                     error bars are seen the  error is within the data point)
                          DISTILLED WATER
                                                                                                    RAW WASTEWATER
1E4<
s-\
1 8000-
•*-*
g 6000-
o
0 4000-
° 2000-
0-
! 60Co source
\
\
E \
' x--__
! ' : 	 o
	 1 	 1 	 1 	 1 	 1 	 1 	 v- 	 1
-1250
-1000
750
500
•250
hO
                    50
                                100
150
                                                         200
                       APPLIED DOSE (Krads)
                             Figure 2
      Removal of CHCL3, using ^Co, at several irradiation doses in
        distilled water at an initial concentration of approximately
     1250 ug/L (error bars indicate one standard deviation from mean,
      where no error bars are seen the error is within the data point)
                                                                           7000
                                                                                                                                   900
                                          100    200    300     400
                                                       DOSE (krads)
                                                                                                                     500     600
                                                        Figure 5
                                      Removal of TCE at several irradiation doses in raw
                                   wastewater (error bars indicate one standard deviation from
                                     mean, where no error bars are seen the error is within
                                                      the data point)
                                                                                                                        TREATMENT   757
-------
                     SECONQWr CHLORlH/kTED WASTEKAItR
J.WJ •
"S
u 150°-
s
i
o 1000-
o
_J
i

| 500-
i
0-
.It T ,
I 1 \TX^ j
*

\
\

A — A tmcxr
*, 	
- • — »^^ v — T EmjuocT
^""~^\^
, ; 	 ; 	 r-
300

•250
•200
•150


•100

•50
.n



r
i

%"-'




               100    200     300    400
                           DOSE (krods)
500
       600
                             Figure 6
             Removal of PCE at several irradiation doses in
          secondary wastewater (error bars indicate one standard
       deviation from mean, where no error bars are seen the error
                       is within the data point)

  Considerable research has also been reported on the irradiation of
aqueous solutions of PCE. ""^ 22'25 As with TCE, it appears that com-
plete destruction occurs as evidenced by chloride ion mass balance.
This observation, insofar as loss of the parent compound PCE, has been
confirmed in our studies in potable water. In secondary wastewater,
removal was < 95 % while in raw wastewater the removal was > 95 %
(Fig. 6). It is remarkable that there is little, if any, difference in the
removal efficiency of PCE in raw and secondary wastewater. A possi-
ble explanation of this phenomenon is that the presence of relatively
high concentrations of organic compounds in these two waters results
in less recombination of the e"(aq) and OH . By reducing the recom-
bination of these two species, their effective concentrations in solution
increase and result in similar removal efficiencies. Mechanisms for the
destruction of both TCE and PCE have been proposed and presently
are under investigation  in continuing studies.
  Another example of a removal efficiency using high energy electron
irradiation is shown in Figure 7 for carbon tetrachloride. This chemical
is persistent in subsurface environments and is not effectively treated
using other oxidation processes. High energy electron irradiation ap-
pears  to be an excellent choice  for its destruction.
                     SECONQAmr CHLORINATED WASTCWMm
    ISOOi
                                                          200
000 -H

500-

n-
.
I i — » WUJCKT
\ "'"" '
^^
i r^»> . — « — ^ — t . — • i i i — . i — «
-150
100 i

•50
• n
               100    200
                             300
                                     400    500
                                                   600
                           DOSE (krods)
                              Figure 7
       Removal of carbon letrachloride at several irradiation doses in
          secondary wastewater (error bars indicate one standard
        deviation from mean, where no error bars are seen the error
                        is within the data point)

  A third group of compounds which we have studied are benzene and
substituted benzenes. Numerous studies have been reported on the ef-
fect  of irradiation of aqueous solutions of benzene.26"33 In other studies
                            we have also shown that benzene is very effectively removed from an
                            oxygenated secondary wastewater effluent. Shown in Figures 8 and 9
                            are the removal efficiencies of chlorobenzene and ethylbenzene in secon-
                            dary wastewater. We have shown that at low irradiation doses, phenols
                            are formed. However at higher doses, these compounds are removed
                            with a net removal of total phenols of approximately 50%. Vife also were
                            able to identify formaldehyde and glyoxal in sub-pM concentrations
                            in several samples. Several other aldehydes were observed, but the struc-
                            tures of these reaction products have not yet been determined. Addi-
                            tional studies are underway to determine all of the reaction byproducts.
1OUU-
i
1000:
500-
(
A — A •VUMT •
L .^ -U 	 ^
p
X
D 100 200 300 400 500 600
150
100
50

                                                          DOSE (krada)

                                                          Figure 8
                                      Removal of chlorobenzene at several irradiation doses in
                                      secondary wastewater  (error bars indicate one standard
                                    deviation from mean, where no error  bars are seen the error
                                                   is within the data point)
                                 1500
                            ~   1000-F
                            UJ
                                  500--
                                                                                         100
                                                                                                 200
                                                                                                         300
                                                                                                                 -+-
                                                                                                                         -+-
                                                                                        •150
                                                                                        ••100
                                                                                          50
                                                                                                                 400    500
                                                                                                                                600
                                                                                                       DOSE (krada)
                                                          Figure 9
                                      Removal of ethylbenzene at several irradiation doses in
                                      secondary wastewater (error bars indicate one standard
                                    deviation from mean, where no error bars are seen the error
                                                    is within the data point)


                             CONCLUSIONS
                               The results reported here are part of an ongoing project which will
                             extend the data base to other chemicals of concern to Superfund. The
                             use of high energy electron beam irradiation appears to be an efficient
                             process for the destruction of all organic compounds of interest in site
                             remediation.
                             REFERENCES

                              1. Pikaev, A.K. Pulse Radiolysis of Wuer and Aqueous Solutions. Indiana Uni.
                                Press. Blooraington, IN.,  1967.
                              2. Bielsld, B.HJ. and Gebicke J.M., "Species in Irradiated Oxygenated Water.
                                Adv. Radiation Chemistry," 2 pp. 177-279, 1970.
                              3. Draganic, I.G. and Draganic,  Z.D. The Radiation Chemistry of Wkaer.
                                Academic Press, New York, N.Y., 1971.
758    TREATMENT
-------
4. Bensasson, R.U., Land, E.J. and Truscott, T.G., Flash Photolysis and Pulse
   Radiolysis,  Contributions  to the Chemistry  of Biology and Medicine.
   Pergamon Press. New York,  N.Y., 1983.
5. Anbar, M.,Bambenek, M. andRoss, A.B. "Selected Specific Rates of Reac-
   tions of Transients from Water in Aqueous Solution. 1. Hydrated Electron."
   Nat. Stand. Ref. Data Ser.  Nat. Bur. Stand. 43 pp.1-54, 1973.
6. Ross, A.B. "Selected Specific Rates of Reaction of Transients from Water
   in Aqueous Solution. Hydrated Electron, Supplemental Data." Nat. Stand.
   Ref. Data Ser. Nat. Bur. Stand. 43, Supplement, pp. 1-43 Mar, 1973.
7. Dorfman, L.M. and Adams, G.E. "Reactivity of the Hydroxyl Radical in
   Aqueous Solution." Nat. Stand.  Ref. Data Ser. Nat.  Bur. Stand. 46pp.l-59,
   1973.
8. Allen, A.O. The Radiation Chemistry of Wtter and Aqueous Solutions, van
   Nostrand-Reinhold. Princeton,  NJ, 1961.
9. Hart, E.J. and Anbar, M., The Hydrated Electron. Wiley-Interscience, New
   York,  N.Y., 1970.
10. Buxton, G.V., Greenstock,  C.L., Helman, W.P. and Ross, A.B. "Critical
   Review of Rate Constants for Reactions of Hydrated Electrons, Hydrogen
   Atoms and Hydroxyl Radicals (• OH/ • O") in Aqueous Solution." J. Phys.
   Chem. Ref. Data, 17 pp.513-886, 1988.
11. Woodridge, D.D., Cooper, P.C., Garrett, W.R., "Effect of Gamma Rays
   on Bacteria and Chemicals in Secondary Effluent," Interim Report, Prepared
   for U.S. Army Mobility Center, Research and Development Division, by
   Florida Institute of Technology, University Center for Pollution Research.,
   Melbourne, FL. 1974
12. Wxxteidge, D.D., Garrett, W.R., Cooper, P.C "Making Water Safe for Use,"
   mter Sew. W>rks, 38, 1975
13. Oldenberg, O. and Rasmussen, N.C Modern Physics for Engineers, McGraw-
   Hill Publishers, New York, NY, pp. 299-307, 1966.
14. Tipler, P. A. Foundations of Modem Physics, Worth Pub., Inc., New York,
   NY, pp.  463^87, 1969.
15. Rezansoff, B.J., McCallum, K.J. and Woods, R.J. "Radiolysis of Aqueous
   Chloroform Solutions." Can. J. Chem.  48 pp.271-276 1976.
16. Dickson, L.W., Lopata,  V.J., Toft-Hall, A., Kremers, W. and Singh, A.
   "Radiolytic Removal of Trihalomethanes from Water." Proc. from the 6th
   Symp. on Radiation Chemistry, pp.173-182, 1986.
17. Gehringer, P., Proksch, E., Szinovatz, W. and Eschweiler,  H. "Der Strahlen-
   chemische  Abbau  von Trichlorathylen) und Perchlorthylenspuren in
   Trinkwasser." Z. Wisser-Abwasser-Forsch.  19 pp.186-203, 1986.
18. Gehringer, P., Proksch,  E., Szinovatz, W. and Eschweiler,  H. "Decom-
   position of trichloroethylene and tetrachloroethylene in  drinking water by
   a combined radiation/ozone treatment." Water Res. 22 pp.645-646, 1988.
19. Gehringer, P., Proksch, E., Szinovatz, W. and Eschweiler, H. "Radiation-
   induced decomposition of aqueous trichloroelhylene solutions." Appl. Radial.
   hot. 39 pp.1227-1231, 1988b.
20. Proksch, E., Gehringer, P., Szinovatz, W. and Eschweiler, H. "Radiation-
    induced decomposition of small amounts of perchloroethylene in water."
    Appl. Radiat. Isot. 38 pp.911-919,  1987.
21. Proksch, E., Gehringer, P., Szinovatz, W. and Eschweiler, H. "Radiation-
    induced decomposition of small amounts of trichloroethylene in drinking
    water." Appl Radiat. Isot. 40 pp.133-138, 1989.
22. Proksch, E., Gehringer, P., Szinovatz, W. and Eschweiler, H.  "Decom-
    position of chlorinated ethylenes in drinking water by combined ozone/radia-
    tion treatment." Paper presented at International Ozone-Symposium, Berlin,
    Germany, 1989.
23. Gehringer, P., Proksch, E. and Szinovatz, W. "Radiation-induced degradation
    of trichloroethylene and tetrachloroethylene in drinking water." Int. J. Appl.
    Radiat.  Isot. 36 pp.313, 1985.
24. Getoff, N. "Radiation induced decomposition of biological resistant pollutants
    in water." Appl. Radiat.  hot. 37 pp.1103, 1986,
25. Raster R. and Asmus K.D. "Pulse radiolysis studies of halogenated organic
    compounds in aqueous solutions." Proc. 3rd. Tihany Symp. on Radiation
    Chemistry Eds. Dobo J. and pp. Hedvig Adademiai Kiado, Budapest, 2,
    pp.  1095,  1972.
26. Dorfman, L.M.,  Taub, I.A. and Bhler, R.E., "Pulse Radiolysis Studies.
    I. Transient Spectra and Reaction-Rate Constants in Irradiate Aqueous Solu-
    tions of Benzene." /.  Chem. Phys. 36 pp.3051-3061, 1962.
27. Neta, P. and Dorfman, L.M. "Pulse Radiolysis Studies.Xffl. Rate Con-
    stants for the Reaction of Hydroxyl Radicals with Aromatic Compounds
    in Aqueous Solutions." Adv. in Chem. Series 81, American Chemical Society,
    Washington D.C., Chapter 15, pp. 222-230, 1968.
28. Vysotskaya, N.A., Bortun, L.N.  and Rekasheva, A.F. "Radiation-Chemical
    Conversions of Condensed Aromatic Hydrocarbons in Aqueous Solutions."
    Presented at the 5th Symp.  on Radiation Chemistry, L.V. Pisarzhevsky
    Institute of Physical Chemistry, Ukrainian SSR Academy of Sciences, Kiev,
    USSR, 1982.
29. Phung, pp.V. and Burton, M. "Radiolysis of Aqueous Solutions of Hydrocar-
    bons Benzene, Benzene-d6, Cyclohexane'." Rod. Res.  7pp.l99-216, 1957.
30. Goodman, J. and Steigman, J. "Products of the Radiolysis of Water Con-
    taining Benzene and Air." J. Am. Chem.  Soc. 62 pp.1020-1022, 1958.
31. Stein, G. and Weiss, J. "Chemical Actions of Ionizing Radiations on Aqueous
    Solutions. Part n. The Formation of Free Radicals. The Action of X-Rays
    on Benzene and Benzoic Acid." J.  Chem Soc., pp.3245-3254, 1949.
32. Daniels,  M., Scholes, G. and Weiss, J. "Chemical Action of Ionizing Radia-
    tions in Solution. Part XV. Effect of Molecular Oxygen in the Irradiation
    of Aqueous Benzene Solutions with X-Rays." J. Chem. Soc., pp.832-834,
    1956.
33. Michael, B.D. and Hart, E.J.  "The Rate Constants of Hydrated Electron,
    Hydrogen Atom  and  Hydroxyl  Radical   Reactions  with Benzene,
    1,3-Cyclohexadiene, 1,4-Cyclohexadiene and Cyclohexene." J. Phys. Chem.,
    74 pp.2878-2884, 1970.
                                                                                                                                 TREATMENT    759
-------
        U.S.  EPA's  Mobile  Volume  Reduction  Unit  for  Soil Washing
                                                      Bernard Rubin
                                                        Roger  Gaire
                                                     Porfirio Cardenas
                                            Foster Wheeler Enviresponse, Inc.
                                                  Livingston,  New Jersey
                                                       Hugh Masters
                                         U.S. Environmental Protection Agency
                                         Risk Reduction  Engineering  Laboratory
                                                 Releases Control Branch
                                                    Edison, New  Jersey
ABSTRACT
  This paper discusses the design and initial operation of the U.S. EPA's
Mobile Volume Reduction Unit (VRU) for soil washing. Soil washing
removes contaminants from soils by dissolving or suspending them in
the wash solutions (which can be treated later by conventional wastewater
treatment methods) or by volume reduction through simple particle size
separation techniques. Contaminants are primarily concentrated in the
fine-grained (0.0025 inches) soil fraction. The VRU is a pilot-scale
mobile system for washing soil contaminated with a wide variety of
heavy metal and organic contaminants. The unit includes state-of-the-
art washing equipment for field applications.
  The VRU equipment was originally conceived by the U.S. EPA. It
was designed and fabricated by Foster Wheeler Enviresponse, Inc. under
contract to U.S. EPA's Risk Reduction Engineering Laboratory (RREL)
in Edison, New Jersey, with the following objectives:
•  To make available to members of the research community and to the
   commercial sector the results of government research on a flexible,
   multistep, mobile, pilot-scale soil washer  capable of running treat-
   ability studies on a wide variety of soils
•  To demonstrate the capabilities of soil washing
•  Tb provide data that facilitate scale-up to commercial size equipment
  The design capacity of the VRU is  100 Ib/hr of soil, dry-basis. The
VRU consists of process washing equipment and  utility support ser-
vices mounted on two heavy-duty semitrailers. The process trailer equip-
ment accomplishes material  handling,  organic vapor recovery, soil
washing,  coarse soil  screening, fine particle  separation,  floccula-
tion/clarification and steam generation via a boiler. The utility trailer
carries a power generator, a process water cleanup system and an air
compressor. The VRU is controlled and monitored by conventional in-
dustrial process instrumentation and  hardware.
  Shakedown operations are  currently in progress, and future plans
include testing U.S. EPA-produced synthetic  soil matrix (SSM) spiked
with  specific   chemical pollutants.  The  addition of novel,
physical/chemical treatment processes, such as sonicAiltrasonic cleaning
and acid leaching, will expand the VRU's extraction capability in soil
decontamination.

INTRODUCTION
  Section 121(b) of the CERCLA  mandates the U.S. EPA  to select
remedies that "utilize permanent solutions and alternative treatment
technologies or resource recovery technologies to the maximum extent
practicable" and to prefer remedial actions in which treatment "per-
manently and significantly reduces the  volume, toxicity, or  mobility
of hazardous substances, pollutants and contaminants as a  principal
element,"
  In most cases, soil washing technologies are used in conjunction with
other remedial methods for the separation/segregation and volume reduc-
tion of hazardous materials in soils, sludges and sediments. In some
cases, however, the process can deliver the performance needed to
reduce contaminant concentrations to acceptable levels and, thus, serve
as a stand-alone technology. In treatment combinations, soil washing
can be a cost-effective step in reducing the quantity of contaminated
material to be processed  by another technology, such  as  thermal,
biological or physical/chemical treatment. In general, soil washing is
more effective on coarse sand and gravel; it is less successful in cleaning
silts and clays.
  A wide variety of chemical contaminants can be removed and/or con-
centrated through soil washing applications. Removal efficiencies depend
on both the soil characteristics (e.g., soil geology and particle size)
and the processing steps contained within the soil washer. Experience
has shown that volatile organics can be removed with 90+ % efficien-
cy. Semivolatile organics are removed to a lesser extent (40-90%). They
usually require the addition of surfactants to the washwater. Surfactants
are surface-active or wetting agents that reduce the surface tension at
the interface between the hydrophobic contaminants and the soil, thereby
promoting release of the contaminants  into the  aqueous extraction
medium.
  Metals which are less soluble in water often require acids or dictating
agents for successful  soil washing. A chelating  agent,  such as
ethylenediaminetetraacetic acid (EDTA), bonds with the metal and
facilitates solubilization in the  extraction medium.
  The VRU process can be applied to the treatment of soils contaminated
with  hazardous wastes such  as  wood  preserving chemicals (pen-
tachlorophenol and creosote),  electroplating residues (cyanides and
heavy metals), organic chemical production residues and petroleum/oil
residues. The applicability of soil washing to general contaminant groups
and soil types, which is shown in Table 1, has been reproduced from
a U.S. EPA report, "Treatment Technology Bulletin - Soil Washing,"
dated May 1990.
  The U.S.  EPA  has  developed  the VRU to  meet the following
objectives:
• To make available to members of the research community and to the
  commercial sector the results of government research on a flexible,
  multistep, mobile, pilot-scale soil washer capable of running treat-
  ability studies on a wide variety of soils
• To  demonstrate the capabilities  of soil washing
• To  provide data that facilitate scale-up commercial size equipment
  The U.S. EPA plans to investigate other extraction processes which
may be added  to the VRU at a later data. The addition to  the VRU
of novel physical/chemical treatment processes, such as sonic/ultrasonic
760   TREATMENT
-------
cleaning and acid leaching, will expand its overall extraction capabili-
ty in soil decontamination.
                             Table 1
              Applicability of Soil Washing to General
               Contaminant Groups for Various Soils

Contaminant Croups



j.
i
O



,
£
5

|
1
•
T
Q
Halogenated volatile*
Halogenated semivolatiles
Nonhalogenated volatile*
Nonhalogenated semivolatiles
PCBs
Pesticides (halogenated)
Dtoxins/Furans
Organic cyanides
Organic corrosives
Volatile metals
NmvrJatllo mAtalt
Asbestos
Radioactive materials
Inorganic corrosives
Inorganic cyanides
Oxfdizers
Reducers
Good to excellent ApptobBty: Hlghp
successful
^Applicable: Expert opinion that te<
Matrix
Sandy/ SUty/Clay
Gravelly Soils Soils
•
T
•
T
T
T
T
T
T
•
•
a
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
T
Q
T
T
T
T
T
«o»bHity that technology v«H be
raw care in choosing technology
ihnology will not work
 SYSTEM DESCRIPTION
  The VRU is a mobile, pilot-scale washing system for stand-alone field
 use in cleaning soil contaminated with hazardous substances. The VRU
 is designed to decontaminate certain soil fractions using state-of-the-
 art washing equipment. The total system consists of process equipment
 and support utility systems mounted on two heavy-duty, semitrailers.
  Figure 1, General Block Diagram, shows the VRU basic pilot plant
 subsystems as  follows:
 • Soil handling and conveying
 • Organic vapor recovery
 • Soil washing and coarse screening
 • Fines/floatables gravity separation
 • Fines flocculation/water clarification and solids disposal
 • Water treatment
 • Utilities - electric generator, steam boiler and compressed air unit
  The generator, air compressor, water heater, water filters/carbon ad-
 sorbers, recycle water pump, gasoline tank (for the generator) and
 delisting tank are located on the utility trailer. All remaining equip-
 ment is located on the process trailer. The VRU system is controlled
 and monitored by conventional industrial process instrumentation and
hardware, including safety interlocks, alarms and shutdown features.
PROCESS DESCRIPTION
  Figures 2, 3  and 4 present the Process Flow Diagram for all VRU
subsystems in terms of their process equipment functions.
Soil Handling and Conveying
  Raw soil is delivered from battery limits to a vibrating grizzly that
separates the particles greater than 0.5 inches into a drum for redeposit
and collects the smaller particles (-0.5 inches +0) for transfer to the
feed surge bin. (The maximum particle size that can be handled in the
miniwasher is 0.5 inches, but smaller screen sizes may be selected.)
From this bin, the soil less then 0.5 inches in size is conveyed through
a steam-jacketed screw conveyor where the volatile organics and water
are vaporized. Both live steam and jacketed steam can be introduced
so that the efficiency of the steam extraction can be determined. The
conveyor flow is adjusted by a speed controller on the conveyor motor.
The solids pass through a motor-operated rotary valve (which prevents
air infiltration), then into the feed hopper of the mini-washer.

Organic Vapors Recovery
  Volatiles stripped from the soil in the screw conveyor are either
collected in the VOC condenser  and fall by gravity into the process
condensate seal tank or are adsorbed in vapor-phase activated carbon
containers located upstream  of the vent blower.
  The spent carbon will be periodically replaced based on vent gas
analyses. The vapor train is maintained under vacuum by an induced
draft blower. The vacuum level is adjusted by manual admittance of
atmospheric air upstream of the blower to maintain a slight negative
pressure on the vapor system. Clean vapors, leaving the blower, vent
to the atmosphere.

Soil Washing  and Coarse Screening
  Soil is fed to the miniwasher at a controlled rate of approximately
100 Ib/hr by the screw feeder. Filtered washwater, which can be heated
to 150T (maximum),  is added to soil in the feed hopper and also sprayed
onto an internal slotted trommel screen (with a 10-mesh (0.079 inches)
slot opening) miniwasher. Five manually controlled meters can con-
trol the flow up to approximately 10:1 overall weight ratio water to soil.
Hot water should be more efficient in extracting contaminants, but
heating  is optional. When required, dilute surfactant/detergent and/or
caustic can be metered at a controlled rate into  the feed hopper.
  Two vibrating screens, equipped with antiblinding devices, are pro-
vided to continuously segregate soil into various size fractions.  These
screened fractions can be collected to measure the effectiveness of con-
taminant removal for each soil fraction recovered and to determine the
effectiveness of soil washing in cleaning a particular contaminated soil
fraction to achieve sufficient volume reduction.
  Miniwasher overflow, containing the coarser solids, fells onto the first
10-mesh (0.079 in/2 mm) vibrascreen. First vibrascreen overflow (-0.5
inches  +  10 mesh) solids flow by gravity down to a recovery  drum.
The underflow is pumped at a controlled rate, using a progressing cavity
pump, onto the second 60-mesh (0.0098 in/0.25 mm) vibrascreen where
it is joined by the miniwasher underflow.
  The overflow from the second vibrascreen (- 10-mesh  + 60-mesh),
is gravity fed to another recovery drum. Second vibrascreen underflow
(a fines slurry) drains into an agitated tank. The VRU is designed with
the following flexibility:
• The mesh sizes for both the miniwasher and vibrascreens can be
  varied [i.e., the screen size could be 20- or 30-mesh (0.033  inches
  or 0.023 inches)].
• Additional soil cleaning by use of water sprays or steam sprays will
  be evaluated for each vibrascreen.
• Screened soil fractions, collected in the recovery drums, can be
  redeposited if sufficiently cleaned or further cleaned by addition of
  rinse water, followed by reslurrying and pumping the slurry back
  over the screens (recycle mode). In the future, these soil fractions
  will be sent for treatment by various extraction units currently under
  development by U.S. EPA's RREL in Edison, New Jersey.

Fines/Floatables Gravity Separation
  Slurry from the second screen (fines slurry) tank, containing par-
ticles less than 60-mesh (0.0098 inches/0.25 mm) in size, is pumped
to a Corrugated Plate Interceptor (CPI).  Material lighter than water
                                                                                                                      TREATMENT    761
-------
              Raw
          contaminated
              soil
                                                                                         Fines
       -3-
  So1l  washing
       and
coarse  screening
                                           Make up/
                                           recycle
                                           water
                                  -5-
                          Fines flocculation/
                          water clarification
                          and solids  disposal
                                   -7-
                           Utilities
                               Electric  generator
                               Boiler
                               Compressed air
                                                 To  posttreatment
                                                                                         Fleatables    To posttreatment
        -4-
 F1nes/fleatables
gravity separation
                -1/2" +10-mesh  (0.079"/2mm)  solids
                                  To redeposit or
                                  further  treatment
  -10  +60 mesh  (-0.079"[2mm] +  0.0098"[0.25 mm])
                                 To redeposit or
                                 further  treatment
                                                                                           Makeup water
                                                    To  delisting/disposal
                                     B1 owdown	or  posttreatment   _
                                                                                           Clay/silt sludge  To posttreatment.
                                                                Figure 1
                                                          General Block Diagram
 (floatables such as oil) will overflow an internal weir, collect in a com-
 partment within the CPI and drain by gravity to a drum for disposal.
 CPI-settled solids [soil particles - 60- to about 400-mesh (- 0.0098 inches
 to about 0.0015 inches)] will be discharged by the bottom auger to a
 recovery drum. The VRU has the flexibility to redeposit or further clean
 these settled soils, if required, by addition of rinse water followed by
 pumping the slurry back through the CPI. As mentioned above, these
 soils could also be sent, in the future, to an extraction unit.
Fines Flocculation, Water Clarification and Solids Disposal
  Aqueous slurry, containing  fines less  than about  400-mesh (34
um/0.0014 inches), overflow the CPI and gravity feed into an agitated
tank. The slurry is then pumped to a static flash mixer located upstream
of the floe clarifier's mix tank. Flocculating chemicals are introduced
into this static flash mixer. Typically, liquid alum and aqueous polyelec-
trolyte solutions are metered into the static flash mixer to neutralize
the repulsive electrostatic charges on colloidal particles (clay/humus)
and promote coagulation. The fines slurry is discharged into the floe
chamber which has a varispeed agitator for controlled floe growth (sweep
flocculation). Sweep flocculation refers to the adsorption of fine  par-
ticles onto the floe (colloid capture) and continuing floe growth to  pro-
mote rapid settling of the floe and its removal from the aqueous phase.
The floe slurry overflows into the clarifier (another corrugated plate
unit). Bottom solids are gravity fed by an auger to a drum for disposal,
or to the sludge  slurry tank (depending on solids concentration) for
subsequent concentration in a filter package unit. Concentrated cake
from the filter is  discharged to another drum for disposal. This system
has the ability to clarify the process water and dewater the sludge.  The
efficiency of iolids dewatering can be determined  and cost savings
estimated, for trucking waste sludge to  a disposal/treatment site.
                Water Treatment
                  Clarified water is polished with the objective of reducing suspended
                solids and organics to low levels that permit recycle of spent washwater.
                Water is pumped from the floe settler overflow tank at a controlled rate
                through cartridge-type polishing filters operating in parallel, in order
                to remove soil fines greater than 10-um (3.94X10"4 inches). One um
                (3.9xlO'3 inches) cartridges are available, if required.
                  Water leaving the cartridge filter flows through activated carbon drums
                for removal of hydrocarbons. The carbon drums may be operated either
                in series or parallel and hydrocarbon breakthrough monitored by
                sampling. A drum  will be replaced when  breakthrough  has  been
                detected.
                  In order to recycle water and maintain suitable dissolved solids and
                organic levels, aqueous bleed (blowdown) to  the boiler delisting tank
                may be initiated at a controlled rate. Delisted material will be sealed
                in drums and sent for disposal in accordance with respective state and
                local regulations. Treated recycle  (recovered) water  is sampled for
                analysis before it flows into the process water storage tank. Supplemen-
                tary water is fed into this tank from a tank truck. Recovered and added
                water is pumped by the water recycle pump (and optionally fed to the
                water heater) for subsequent feed to the  miniwasher. A side stream from
                the water recycle pump is utilized  as cooling  water in the VOC con-
                denser and either returned to the process water storage tank or sent
                to the sewerage system.

                Utilities Systems
                  The VRU is equipped with a steam  boiler,  electric generator and a
                compressed air  system.

                Field Operations
                  While in the field, the VRU would be supported  by a decontamina-
      TREATMENT
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                      Figure 2
                Process Flow Diagram
U.S. EPA Mobile Volume Reduction Unit for Soil Washing
                      Figure 3
                Process Flow Diagram
U.S. EPA Mobile Volume Reduction Unit for Soil Washing
                                                                            TREATMENT    763
-------
               MUSHING FILTERS
                                       i   i
                                                                                                          T-7
                                                                                                       PROCESS arts
                                                                                                       STOtAGC T1W
                                        Jtl
                                      tlTEB IOTOI
   UTD)
   IHOUP-)
                                                            F-l 1 2
KOVCK1I UTCH
POLISH!* FIUU
                      KLISTED MTCIIAL
                      ro DISPOSAL
                                 C-3 t CH
                                 L10UID PHASE
                                                AOUEMUS BLMiaM
                                                                   Figure 4
                                                             Process Flow Diagram
                                             U.S. EPA Mobile Volume Reduction Unit for Soil Washing
tion trailer, a mobile treatability laboratory/office and a storage trailer
for supplies, spare parts, miscellaneous tools, etc.


SUMMARY OF VRU FEATURES
  Listed below are the various features, operational parameters and
capabilities of VRU:
• The VRU  is a mobile, pilot-scale washing  system for field use in
  cleaning soil contaminated with hazardous materials, using state-of-
  the-art washing equipment and support utilities.
• The unit  has the ability to  remove  VOCs by  steam  heating and
  stripping.
• It is capable of washing with  water  (in combination  with  surfac-
  tants/detergents) up to a 10:1 water to soil ratio  while  also varying
  water  temperature from ambient to 150 °F.
• The miniwasher screen and vibrascreens can be varied in mesh size.
  Additional use of soil cleaning by water or steam sprays  on the
  vibrascreen decks can be evaluated.
• Four screened soil fractions (including CPI-settled solids) can be fur-
  ther cleaned by slurrying with the addition of rinse water and recycling
  the slurry  over the vibrascreens or the CPI.
               • The floc-clarifier system has the ability to clarify the process water
                 and dewater the  sludge.
               • Additional treatment of the clarified process water through polishing
                 filters and activated carbon should allow, in most cases, reuse of this
                 water as recycle  to the washing circuit.
               • Side streams  from the  VRU  will  be treated  using various
                 physical/chemical extraction units currently under development by
                 U.S. EPA.
               • The VRU offers a unique method for conducting treatability studies
                 on various contaminated soils.

               REFERENCES
               1. Foster Wheeler Enviresponse, Inc., "Cleaning Excavated Soil Using Extrac-
                  tion Agents:  A State-of-the-Art Review,"  January,  1990,   U.S.
                  EPA/600/S2-89/034.
               2. Foster Wheeler Enviresponse, Inc., "Workshop of Extractive Treatment of
                  Excavated Soil," December,  1988.
               3. US. EPA Treatment Technology Bulletin, "Soil Washing," Draft issued May,
                  1990.
               4. Traver, R.P., "Development and Use of the U.S. EPA's Synthetic Soil Matrix
                  (SSM/SARM)."  U.S.  EPA  Releases  Control Branch,  Risk Reduction
                  Engineering Laboratory, Edison, NJ, 1989.
7M    TREATMENT
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                             Baird  and  McGuire  Superfund  Site:
       Design of a  GWTP  Fume  Collection  and  Treatment System
                                               Cinthia L.  Rudasill,  RE.
                                                     Mary E.  Doyle
                                                 Metcalf and Eddy, Inc.
                                               Hazardous Waste Division
                                                Wakefield,  Massachusetts
ABSTRACT
  A groundwater extraction system and treatment plant has  been
designed by Metcalf and Eddy to restore groundwater quality at the
Baird and McGuire Superfund Site in Holbrook, Massachusetts. The
site, which formerly housed chemical mixing and batching operations,
currently ranks 14th of 989 sites on the NPL.
  The groundwater at the  site has been contaminated with metals,
(including arsenic and lead), volatile and semivolatile organics and
pesticides. Included among the VOCs found in the groundwater are vinyl
chloride, methylene chloride, trans-1, 2-dichloroethane, benzene, toluene
and xylenes. The groundwater treatment plant will treat 200 gpm of
contaminated groundwater by a series of unit operations including metals
precipitation, biological treatment, filtration and granular activated
carbon adsorption.
  Due to the high concentration of VOCs present in the groundwater,
the need for collection and treatment of contaminated air from the
process tanks located inside the treatment plant building and from the
biological aeration tanks located outside was assessed to ensure the safety
of the treatment plant operators and the surrounding community. In
order to determine whether collection and treatment of the air would
be necessary, the OSHA permissible exposure limits (PELs) of the con-
taminants and Henry's Law constants were reviewed.  Additionally,
samples of air emissions were collected during bench-scale treatability
testing and submitted to an analytical laboratory for VOC analysis by
GC/MS. Test results confirmed the need for collection and treatment
of air from all process tanks through the treatment train up through
biological aeration.
  Two methods of off-gas treatment were considered; fume incinera-
tion and vapor-phase carbon adsorption. Fume incineration was selected
since this process provides essentially complete destruction of the VOCs
without producing a waste  byproduct. An air collection system was
designed to collect the contaminated air from the plant and aeration
tanks and feed it to a 1,000-cfm incinerator. The incinerator will be
fueled by natural gas and operate at a minimum temperature of 1,400 T.

INTRODUCTION
  The Baird and McGuire Superfund site currently ranks 14th of 989
sites on the NPL. Baird and McGuire, Inc., operated a chemical mixing
and batching facility in Holbrook, Massachusetts, for more than seventy
years. Operations at the facility included production of household and
industrial products such as floor waxes, wood preservatives, pesticides
and solvents,1 and resulted in widespread contamination of the Baird
and McGuire property, and the surrounding property by numerous toxic
organic and inorganic  compounds.  In September, 1986, following a
number of investigations, the U.S. EPA issued the ROD for the Remedial
Alternative for the site. Included in the ROD was remediation of con-
taminated groundwater by metals precipitation, biological treatment and
carbon adsorption. The ROD also included remediation of soil by
incineration.

Site Contamination
  Investigations have been conducted at the Baird and McGuire site
by several parties including consultants for Baird and McGuire, Inc.,
the town of Holbrook, the U.S. EPA, the Massachusetts Department
of Environmental Quality Engineering, Goldberg-Zoino Associates2
and GHR Engineering Associates. Most recently, Metcalf and Eddy
conducted a comprehensive groundwater sampling effort to provide sup-
port for design activities. The analytical data from this sampling round
documented extensive  groundwater  contamination  by  metals,
semivolatile and VOCs and pesticides.
  VOCs were of special interest in the design of the groundwater treat-
ment plant since the need for fume collection and treatment, as well
as removal  of these  constituents from  the groundwater, had to be
assessed.  The VOCs detected in the groundwater during the most recent
phase of  sampling are shown in Table 1.
                           Table 1
                 VOCs Found in Groundwater at
                   the Baird and Mcguire Site3

                                  Concentration (ug/1)
Parameter
Chlorome thane
Vinyl Chloride
Methylene Chloride
Acetone
1 , 1-Dichlorethane
Trans-1 ,2-Dichlorethene
1,1,1 -Trichloroe thane
Trichlorethene
Benzene
Toluene
Ethylbenzene
Total Xylenes
Detection Limit
<5
<5
<5
<25
<2
<2
<2
<2
<2
<2
<2
<2
Max Imum
550
130
190(11008)
710
7.5
3700
5.7
130
1100
1500
1200
9000
Ave («)
11
13
133
78
2.3
315
2.2
5.1
62
127
153
870
     ased on not detected = detection limit
 B - Compound found In blank
DESIGN OF THE GROUNDWATER TREATMENT PLANT
  As part of the Baird and McGuire site remediation, Metcalf and Eddy
designed a groundwater treatment plant (GWTP). The plant was
designed to produce an effluent which will meet drinking water stan-
                                                                                                             TREATMENT    765
-------
dards as is required for infiltration to the aquifer. The standards are
specified by the federal Safe Drinking Water Act (SDWA) Maximum
Contaminant Levels (MCLs) or the Massachusetts Groundwater Quality
Standards, whichever is lower. The plant was designed to treat 200 gpm
of groundwater contaminated with metals, volatile and semiVOCs and
pesticides. Treatment processes include two-stage metals precipitation,
biological treatment by activated sludge process, filtration and granular
activated carbon adsorption.
  During  predesign activities conducted by M  and E to confirm or
develop design parameters, it was determined that the need for con-
trols to eliminate volatile emissions during GWTP operations had to
be assessed. This measure was not required to comply with the ROD
since, unlike off-gas from an air stripper, off-gas from a biological aera-
tion tank does not require treatment under Massachusetts regulations.

Predesign Activities
  The predesign activities, which were conducted as part of the design
effort, included a groundwater pumping test and a bench-scale treat-
ability study. These investigations developed data for the design of the
groundwater extraction system and confirmed the ability of the pro-
posed  treatment processes to meet the  discharge limitations;  the
treatability  study developed treatment system design data.  Water
produced during the pumping test was temporarily stored on-site in an
open 300,000-gallon above ground tank. Due to past odor  problems,
community concern and the potential for health impacts, a review of
the need for temporary controls to prohibit release of VOCs from the
tank to the atmosphere was conducted at this time.
  The review was conducted to evaluate airborne VOC concentrations
in the vicinity of the tank and at the property boundary. Henry's Law
was used to estimate the  concentration of contaminants in the air at
the air/water interlace, and a simple U.S. EPA dispersion model was
used to estimate contaminant concentrations at the property  boundary.
The estimated air concentrations were then compared with OSHA per-
missible exposure limits (PELs) and what was then called Massachusetts
proposed allowable ambient levels (AALs). Only organic contaminants
that had been defined as critical in the public health risk assessment,
conducted  as  part of the Feasibility Study,4 and which  had been
detected in the groundwater were included in the evaluation. Conser-
vative assumptions were used in this comparison, including  maximum
measured  contaminant concentrations, high ambient temperature for
the time of year the pumping test would run (77 °F) and low wind speeds
(1 m/sec to 2 m/sec). In addition, comparing a water/air interface con-
centration with an OSHA  PEL is very conservative, since the concen-
tration where workers are exposed should be lower.
  The evaluation determined that five contaminants were greater than
the OSHA PELs indicating the potential to exceed PELs in the vicinity
of the tank and that 12 to  14 of the compounds exceeded the AALs.
The estimated property boundary concentrations were as high as 1,000
times the state AAL. This evaluation was based on very conservative
assumptions; however, concentrations up to 1000 times the state's AALs
indicate the potential for contaminants to volatilize from an uncovered
tank at concentrations above AALs even under less conservative con-
ditions than those used in the models. The results of this evaluation,
as well as the concern for  potential odors, indicated the need to install
a floating cover on the 300,000-gallon tank. The evaluation also indicated
a need to incorporate emissions controls into the design of the  full-
scale treatment plant. A program for measuring  loss of volatiles from
the groundwater to the air was incorporated as part of an ongoing bench-
scale treatability  testing program. The goal of the sampling program
was to quantify volatile contaminants that would pose a threat to the
operators of the proposed GWTP and the surrounding community.
  Two methods were used to determine quantities  of volatiles being
transferred  from the water to the air. The first calculation involved a
simple mass balance around a batch aerated tank. Loss of volatiles to
the air was determined by measuring VOCs in  the waste before and
after aeration over  a 4-hour test period.
  The second method involved the collection of air samples from two
covered tanks, one unacraied and one aerated, over a measured period
 of time. An aeration tank containing biomass from activated sludge test
 was used as the aerated test vessel. The biomass was added to the tank
 in order to help account for loss of VOCs due to biodegradation. Con-
 taminated groundwater was added to the tank and a sample of the con-
 taminated  air was collected using  a volatile organic sampling train
 (VOST).
  The VOST consists of a series of vapor traps, condensers and a
 vacuum pump that allow vapor to flow through the apparatus and capture
 organic contaminants in a trap containing a carbon medium.  The
 apparatus was set up to draw samples from an exhaust stack stemming
 from each of the enclosed tanks. Air was sampled for 0.5 rh at a rate
 of 1 L/min, which equaled the diffused air flow rate into the test aera-
 tion tank.  A vent in the tank cover allowed the flow of air into the test
 apparatus.
  The results of the mass balance around the aerated tank are shown
 in Table 2. These data indicate that at an air flow rate of 1 L/min, 15
 L of waste yield 82.5 mg of volatile compounds over the 4 hour test
 period. This amount equals 344 mg/m3 of VOCs leaving the aeration
 tanks. Analytical results could not be obtained for the samples collected
 by the VOST method since VOC concentrations on the carbon collection
 media were higher than the GC/MS calibration limits for the test. This
 result indicated that the air VOC concentrations were extremely high.
                            Table!
               VOCs Concentrations in Groundwater
                    Before and After  Aeration
 Parameter
                        Raw Groundwater
                                  Concentration (ug/l)(*l
                                                 Aerated Groundwater
 Trans-1,2-dlchloroethane
 Benzene
 Toluene
 Ethylbenzene
 Total Xylene
     Total Volatlles
1100
 160
 900
 660
2700
5520
  21
 1.6
 9.6
 1.5
  33
69.7
 • Only volatile organics detected Ln the test sample have been reported.

lest Conclusions
  Results of the mass balance indicated that loss of VOCs to air would
be high enough to warrant the collection of fumes off the GWTP aera-
tion tanks and the application of Best Available Control Technology
to the contaminated air collected from the tanks. In addition, since all
process tanks that precede the activated sludge process were to be located
inside a building, a decision was  made to cover the  tanks and collect
the contaminated air in the tank head-space for treatment as  well,  in
order to ensure operator safety.

Design of the Fume Collection  and Treatment System
  Based on the test results and the sampling data presented in Table
1, a fume collection and treatment system was designed. Two methods
of off-gas treatment were considered for the full-scale GWTP; fume
incineration and  vapor-phase carbon adsorption.
  The two alternatives were evaluated based on their ability to remove
or destroy the contaminants of concern, their applicability to the Baird
and McGuire site and cost. A technical evaluation of the two alternatives
indicated that carbon has low adsorption capacity for several of the con-
taminants of concern, including methylene chloride and vinyl chloride.
This finding was of particular concern due to the potential for high con-
centrations of some of these organics in the air. Incineration, under
proper operating conditions, will  result in virtually complete  destruc-
tion of all the organics of concern, regardless of concentration.
  An additional consideration evaluated was community reaction to the
two alternatives. Due to the low adsorption capacity of carbon for some
of the contaminants and the potentially high concentrations expected
in the air stream, frequent carbon replacement or on-site steam regenera-
tion would be required. Replacement or regeneration would  result in
additional traffic to and from the site through the bordering residential
area, either delivering  and removing carbon, or removing the concen-
      TREATMENT
-------
trated  solvent  waste  that  would  result  from  regeneration.  The
community's reaction to another incinerator on the site was of concern.
                         Cost Comparison

Design Basis:
Capital Cost
Annual Operating
Carbon Adsorption
1,000 cfn
1,000 Ibs carbon/adsorber
*no,ooo("
$ 15,000
Incineration
1,000 cfm
1,100 °F
$ 90,000
( 20,000
     Cost

   Net Present
     Value1"'
$152,000
$212,000
 1.  Includes adsorbers and steam regeneration system
 2.  Present value assumes an annual Interest rate of 10} over a 15 year
    project life.

 However, it was found that any increase in traffic, particularly if the
 vehicles would be transporting hazardous materials, seemed to be of
groundwater into the air, the tendency of some of the VOC contaminants
found in the groundwater to deplete the capacity of carbon at a high
rate and the need for disposal or on-site regeneration of carbon with
regenerant disposal, the fume incineration option was selected. This
option will provide essentially complete VOC destruction  without
producing  a waste byproduct requiring disposal.
  All process tanks preceding and including the biological aeration tanks
and clarifiers were covered, and exhaust gas  from these tanks were
vented at a rate of 800 to 1000 cfm through FRP ductwork and fans
to a fume incinerator located outside the treatment plant building. FRP
was selected due to the presence of chlorinated organics. Vents were
included in the tank covers to allow air to be drawn by two induced-draft
fans to the incinerator. A process flow diagram is shown in Figure 1.
  Due to the low BTU value of the contaminated air and aeration tank
off-gas, an air-to-air heat exchanger was included to recover heat from
the incinerator stack gas to preheat the incoming air to approximately
700 °F.  The VOC  contaminants  will be  thermally  oxidized in  the
incinerator at a minimum temperature of 1400 °F. The system is design
to achieve 99.99 % destruction of organics. The incinerator burner will
be fueled by natural gas.
                                                                                                                                  Stack
           Equalization
             Tank
       Rapid     Retaliation     Clarifier
        Mix       Tank
       Tank
               Rapid
                Mix
               Tank
  Flocculation    Clarilier     Neutralization
    Tank                  Tank
                                                                                                                                 Natural
                                                                                                                                  Gas
                                                                   To Effluent
                                                                  ' Polishing System
                               Aeration Tanks
                                   (2)
                                                                  Figure 1
                                                            Process Flow Diagram
 greatest concern to the surrounding community.
  Finally, incineration was found to be the more economical solution
 for treating the contaminated air at this site. Although equipment costs
 of the two proposed alternatives are comparable and both use fairly
 low maintenance equipment, the need to frequently replace or regenerate
 the carbon drives up the operating cost of this process. A cost com-
 parison is presented in Table 3.
 CONCLUSIONS
  Due to the potentially high concentration of VOCs removed from the
                                                 REFERENCES

                                                  1. GHR Engineering Associates, Inc.; Remedial Investigation Report, Baud and
                                                    McGuire Site, Holbrook, MA, Volume I; 1985.
                                                  2. Goldberg-Zoino and Assoc., Inc.; Site Assessment, Baird and McGuire,
                                                    Holbrook, MA; July 1983.
                                                  3. Metcalf and Eddy, Inc., Groundwater Sampling Technical Memorandum for
                                                    the Baird and McGuire Superfund Site, Holbrook, MA; Dec. 20, 1988.
                                                  4. GHR Engineering Associates; Final Feasibility Study Report, Baird and
                                                    McGuire Site, Holbrook, MA; July 1986.
                                                                                                                        TREATMENT    767
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                        Chemical  Oxidation  of Dissolved  Organics
                    Using  Ultraviolet-Catalyzed Hydrogen  Peroxide
                                              Frederick £. Bernardin, Jr.
                                                   Emery M. Froelich
                                                Peroxidation Systems, Inc.
                                                     1\icson,  Arizona
INTRODUCTION
  The development of the perox—pure™ UV/Peroxidation process
was started in the late 1970s. Today, while there are more than 30 full-
scale treatment units in operation or in the final stages of design and
installation,  the development and improvement of the  process is
continuing.
  This advanced oxidation process using ultraviolet (UV) light-catalyzed
hydrogen peroxide is a cost-effective treatment for a wide array of
organic compounds found in contaminated groundwater, toxic waste
leachates and industrial wastewaters. Recent improvements in the perox-
pure™ Process have reduced the operating cost for total destruction
of these toxic organics by up to 50%. In addition, the oxidation rate
of many  of the  "difficult to  oxidize"  compounds such  as
1,1,1-trichloroethane (TCA),  1,1-dichloroethane (DCA), chloroform
(CHC13)  and methylene chloride (MeCl) have been increased up to
three-fold. These advances increase the cost-effectiveness of on-site
destruction processes versus transfer technologies and broaden the ap-
plicability of chemical oxidation as the technology of choice.

perox-pure™ PROCESS
  In this process, UV light converts the hydrogen peroxide (HjO2) in
solution to hydroxyl radicals (HO') and "activates" many of the organic
molecules to make them easier to oxidize. The photolysis reaction which
forms HO can be shown as follows:
                         UV
                              -> 2 HO
(1)
  The activation of the organic molecules can range from direct oxida-
tion by UV absorption and disassociation to the formation of organic
radicals or other reactive intermediates. With enough time and reac-
tants, organic compounds can be completely destroyed to CO2, Hf>
and, if present, the  appropriate inorganic salt.
  Most early UV oxidation processes used low pressure mercury vapor
lamps combined with ozone (Oj). The perox-pure™ Process utilizes
a proprietary high intensity UV lamp combined with HjOr This pro-
vides  a number of advantages for chemical oxidation of aqueous
solutions.
  Three process considerations which manifest advantages include:
• UV Intensity - The higher intensity allows for a more compact equip-
  ment design as well as lower capital cost. In addition, the higher
  UV intensity gives better penetration in wastewater or high concen-
  tration  waters  and  allows for  treatment  of  a wider range of
  applications.
• UV Spectra - Since activation of organic compounds plays a key role
  in the destruction process, the broad spectra of the high intensity
           lamps are better suited for most applications than the narrow spec-
           trum low pressure mercury lamps.
         • Hydrogen Peroxide   Because H^Oj is completely  miscible with
           water, it can easily be added in any desired concentration. This wide
           range of permissible concentrations combined with high intensity
           lamps allows for simplicity of reactor design and short reaction times
           for both groundwater and wastewater applications. In addition, there
           are no toxic gas emissions or stripping of volatile organics into the air.

         BENCH-SCALE TESTING
           Over the last 5 years, Peroxidation Systems, Inc.  (PSI) has tested
         hundreds of water and wastewater samples from clients using bench-
         scale equipment. In addition, an ongoing research and development
         program has contributed to the large body of information available on
         the oxidation of organic compounds by UV peroxidation. These data
         are stored in a computerized data base that can be used to generate
         preliminary process design and cost estimates for a given set of influent
         and effluent specifications. Table 1 is a partial listing of the compounds
         in the data base.
                                    Table 1
                             perox-pure™ Data
                           Organic Compounds
Acenaphthene
Acenaphtylene
Acetic Acid
Acetone
Acetonitrile
Acrolein  (Propenal)
Acrylic Acid
Acrylonitrile
Alachlor
Alcohols
Aldicarb
Aldrin
Aniline
Anthracene
Benzene
Benzoic Acid
Benzyl butyl phthalate
Bis (2-chloroisopropyl)
 ether
Bis (2-ethylhexyl)
 phthalate
Bronodichloronethane
Butyric Acid
Butyl  Acrylate
Butylbenzene
Carbon tetrachloride
Chloroaniline
Chlorob«nzene
Chlorodane
Ch1oro«thane
Chloroform
ChloroBethane
2-Chloronaphthalene
base
Listing

  2,4-Dichlorophenol
  Dichloropropane
  Oichloropropene
  Oinitrophenol
  Dieldrin
  EDTA
  Endrin
  Ethylbenzene
  Ethylene Dlamine
  Fluoranthene
  Pluorene
  Formaldehyde
  Formic Acid
  Hexachlorobenzene
  Hydrazines
  Isophorone
  Methyl ethyl ketone (HEK)
  Methyl isobutyl keton*
    (MIBK)
  Methylene chloride
  HTBE
  Napthalene
  Nitroglycerine
  Nitrophenol
  Nitrosamine
  PCBs
  Pentachlorophenol
  Phenanthrene
  Phenol
  Tetrachloroethane
  Tetrach loroethene
  Tetrahydrofuran
768   TREATMENT
-------
                                          Toluene
                                          Trichlorobenzene
                                          1,1,1-Trichloroethane
                                          1,1,2-Trichloroethane
                                          Trichloroethene
                                          Trichlorofluoromethane
                                          2,4,6-Trichlorophenol
                                          Trichlorophenols
                                          Vinyl chloride
                                          Xylene
Chlorophenol
Cresol
Chlorotoluene
Cyanide
Cyc lohenanone
l,2-Dibromo-3-
 chloropropane
Dibromoohloromethane
1,2-Dibromoethane
Dichlorobenzene
Dichlorobenz idine
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
1,2-Diohloroethene
 PROCESS CONSIDERATIONS
   Like most other chemical oxidations, the UV/Peroxidation process
 is dependent upon a number of reaction conditions which can affect
 both performance and cost. Some process variables are inherent to the
 properties of the contaminated water while other process variables can
 be controlled by the treatment system design and operation. Some of
 the more important process variables are summarized in Table 2.
                            Table 2
                UV/Peroxidation Process Variables
      Variables related  to the  contaminated water:
      •     type and concentration of organic  contaminant
      •     light  transmittance  of the water
            (color/suspended solids)

      Variables related  to treatment process  design  and
      operation:
      •     UV and H202 dosages
      •     pH and temperature conditions
      •     Use of catalysts
 TREATMENT EQUIPMENT
  While the UV/Peroxidation process is based on well-known chemistry,
 the equipment and the use of a high  intensity UV source such as is
 embodied in the perox-pure™ equipment is a more recent develop-
 ment. Figure 1 presents data which illustrates the relationship between
 the UV power employed and the oxidation rate for trichloroethylene
 (TCE).
  As is shown, the reaction rate improves significantly and is more
 than 10 tunes faster for the high output UV sources employed in the
 perox-pure™ equipment than for the older conventional sources. In
 practice,  for UV/Peroxidation reaction, this relationship results  in a
 four-lamp 80-gallon reactor being able to provide equivalent treatment
 to a system requiring 200 lamps in a 1500-gallon reactor. The increased
 lamp power costs are more than off-set by the much simpler and lower
 capital cost equipment.
  This smaller, simpler design has significance with regard to space
 requirements, the number of potential replacement parts and the  cor-
 responding maintenance costs. A schematic design of a high intensity
 UV/Peroxidation system is shown in  Figure 2.
  In practice, tLf>2 stored on-site in polyethylene or aluminum tanks
 at 50% concentration is fed via small chemical metering pumps directly
 into the incoming water. The solubility of HjOj in water obviates any
 need for mixing or dispersion devices other than the inlet piping.  The
 mixture passes into the bottom of the oxidation chamber and then up-
 ward over horizontally mounted UV  lamps. Mechanical design and
 hydraulic principles ensure mixing during the oxidation process.  The
 unit  contains  no  moving  parts,  further  minimizing  maintenance
 problems.
  Individual oxidation chambers can contain up to 15 lamps which can
 be controlled in increments which match the UV dosage to the treat-
 ment needs based on the incoming flow and organic concentration. As
 treatment flow increases or higher concentrations are treated, the
modular oxidation chambers are mounted in series or parallel depending
on whether longer contact times or higher flow capacities are required.
Modular systems have been constructed which have hydraulic capacities
up to 1500 gpm. As shown schematically in Figure 2, the majority of
equipment on each skid-mounted system is devoted to the electrical feed
and control system which provides output readings on lamps, power
controls, alarm readouts and the option for remote and automatic opera-
tion and control.


     EFFECT OF UV INTENSITY ON DESTRUCTION RATE
          1.0-1
                                                                         0.5-
                                                                         0.2-
                                                                               0.1
                                                                          y o.os-
                                                                     UJ
                                                                     u
                                                                     >-
                                                                     Ul
                                                                     g
                                                                     3
                                                                     E
                                                                        0.02-
                                                                     CC
                                                                     u.
                                                                        0.01
                                                                                          10
                                                                                                  20       30
                                                                                                 TIME.(MINUTES)
                                                                                                                   40
                                                                                                                            50
                                                                     LINE A -  DATA FROM SUNDSTROM? AT 2.5 WATTS © 254 NM/UTER
                                                                     LINE B -  DATA FROM HAGER1AT 230 WATTS TOTAL UV/UTER
                                                                     LINE C -  DATA FROM RECENT PEROXIDATION SYSTEMS TESTING AT
                                                                             OVER 500 WATTS TOTAL UV/UTER

                                                                                          Figure 1
                                                                             Effect of UV Intensity on Destruction Rate

                                                               FULL-SCALE OXIDATION
                                                                 Of the 30 full-scale perox-pure™ systems in operation or final con-
                                                               struction/installation, approximately 10 are treating wastewaters with
                                                               organic concentrations between 10 mg/L and 1%. The remainder of
                                                               the 30 on-line units are treating groundwater. Table 3 shows a partial
                                                               list of the organic compounds being  treated by these installations.
                                                               Operating costs for these treatment systems range from approximately
                                                               $0.25/1000 gallons for low concentration groundwater containing TCE
                                                               and DCE to approximately $0.12/gallon for the highest concentration
                                                               wastewaters.

                                                               APPLICATION OF THE PROCESS
                                                                 Examples of treatment systems and their performances are presented
                                                               below to illustrate the application of the process.
                                                                 Because of the low flow estimated for treatment (25-50 gpm) and
                                                               the bench-scale success, the smallest perox-pure™ production model,
                                                               an LV 60, was chosen for the on-site demonstration. Specifications for
                                                               the LV 60 are shown in Table 4. Other process components included
                                                               an  air stripper, equalization tank, piping and well pumps.
                                                                 In order to make maximum use of both air stripping  and the
                                                               UV/Peroxidation system, the treatment system was plumbed to allow
                                                               UV/Peroxidation first followed by the air stripper. Data from this treat-
                                                               ment sequence are presented in Table 5. As is shown, the UV/Perox-
                                                               idation destroyed virtually all contaminants with the exception of TCA
                                                               which is subsequently reduced to below 2 /tg/L by the air stripper. The
                                                               result of this sequence is higher quality effluent water as well as much
                                                               lower atmospheric emissions of chlorinated hydrocarbons.
                                                                                                                  TREATMENT    769
-------
                                                                                       LAMP POWER
                                                                                       CONVERTERS
      H202 8TORAQE
        AND FEED
INFLUENT
                                                                                                           CONTROL PANEL
                SIGHT QLA88
                                                                              UV LAMPS
                                                                   OXIDATION CHAMBER
                                                          Figure 2
                                             Equipment Arrangement and Process Water
                                                 Flow for the UV/RjOj System
                        Table3
             perox-pure™ Operating Systems
                 Organic Chemicals List
                                                           TableS
                                              UV/Peroxidation Performance Ahead of
                                                         Air Stripper
Acrylic  Acid
Aniline
Benzene
Bis 2-ethylhexyl
 phthalate
Butyl Acrylate
Chlorinated phenols
Chlorobenzene
Chloroform
1,1-DCA
1,1-DCE
1,2-DCE
Dimethyl Nitrosamine
  Ethyl Benzene
  Hydrazines
  Isopropanol
  MeCl
  PCE
  Pentachlorophenol
  1,1,1-TCA
  TCE
  Total Toxic Organics
  Vinyl Chloride
  Xylene
                        Table 4
          Specifications for the perox-pure™ LV 60
  Contaminant

  MeCl
  1,2-DCE
  1,1,1-TCA
  TCE
  PCE
        Influent
         fun/11

         75
        3480
        1980
        1480
        4990
 3.8
  ND
1430
  ND
  ND
                        Table 6
           Contaminated Groundwater Treatment
                                     Contaminant

                                     Hydrazine
                                     Acetone
                                     Phenol
                                     Aniline
                                     Bis.  2-ethyl hexyl
                                      phthalate
                                     TOC

                                        Oxidation time:
                                        H202:  300 mg/1
                                                                                           Influent
                                                                                            (ua/11

                                                                                           180,000
                                                                                                41
                                                                                                14
                                                                                               730
                                                                                               170
                          31,000
                                                                                      18 Bin.
                                           2,000
 Maximum GPM:
 Inlet:
 Outlet:
 Power  Supply:
 Electrical  Enclosure:
 Material
   Wotted  Parts:
   External  Parts:
 Weight:
 Size:
 No.  of  Lamps:
160
2 1/2"   \50t Flange
2 1/2"   ISO/ Flange
3/60/360-480/60 KW,  70 KVA
NEMA 3R

316 SS, Quartz, Viton, TFE
Enamelled Steel
3000 Ibs.
2'l"v x B'l x 6'h
4  individually controlled
                        Table?
            Comparison of UVfBJO1 and GAG
Contaminant

TCE (Ave. 6 Mos)
      CAC1	
Influent   Effluent
                                             CAC'
                     Influent   Effluent
                      (uo/11     (no/11
                    756
                              3.8
                                         4016
                                                    <1
  1.   GAC usage 1.2  Ibs./100 gal.. Contact time  50 »in.
  2.   H202 usage 50  mg/l, oxidation tine <1 min.
     TREATMINT
-------
  The perox-pure™ system on this site is being operated on a Full Ser-
vice Contract which eliminates capital expenditure and includes regular
service, all parts and labor for maintenance, delivery of H^ and a
guarantee of system performance. The cost to destroy the organics as
shown with  the perox-pure™  system is approximately  $2.69/100
gallons treated including capital amortization, chemicals, electricity and
all maintenance parts and labor, but excluding air stripping costs.

OTHER EXAMPLE INSTALLATIONS
  In order to illustrate the range of treatment applications, two more
sets of performance data are presented. Table 6 shows treatment of water
principally contaminated with hydrazine with other trace organics
present.
  While it is notable that all treatment objectives were met, it also is
 interesting to note that the total organic carbon (TOC) content of the
 water was reduced more than 93 % indicating that most of the organics
 have been converted to COr
  Table 7 is a  comparison of 6 months  of averaged data on  a TCE-
 contaminated site which operated  both  a granular activated carbon
 (GAC) and UV/Peroxidation system.
  The principal difference in the operation was that while the GAC
 system was operated on a production well, the UV/Peroxidation system
 operated on a monitoring well with nearly six times higher concentra-
 tion. Twelve months of  operating data showed the UV/Peroxidation
system capable of producing a significantly better effluent at an operating
cost of $0.83/1000 gallons compared to $3.05/1000 gallons for GAC.

CONCLUSION
  The use of chemical oxidation and particularly the use of ultraviolet
light-catalyzed hydrogen peroxide systems, is a proven,  very effective
technology for removal of organic contamination from water. It is
economically competitive with adsorption and operationally simpler
than other technologies which may produce sludges, air emissions or
other secondary disposal problems. The UV/Peroxidation process is
relatively easy to evaluate and demonstrate and should be included in
any evaluation of treatment technology alternatives.

SOURCES
1.  D.G. Hager and Smith, C.E., "The Destruction of Organic Contaminants
   in Water by Chemical Oxidation" in Proc, of the Hoztech International Con-
  ference and Exhibition; Institute for International Research, Denver, CO, pp.
   215-231, 1986
2.  N.W. Gossett, Bausano,  J. and Oldham., J., "Start-up of an Innovative
   UV/Peroxidation Groundwater Treatment System," in Proc.  of the 10th Na-
   tional Superfund Conference and Exhibition; HMCRI, Silver Spring, MD,
   pp. 306-308, 1989
3.  D.W.  Sundstrom, Klei,  H.E., Nalette,  T.A.,  et ah, "Destruction  of
   Halogenated Aliphatics by Ultraviolet-Catalyzed Oxidation with HjOj" Haz.
   Waste Haz. Mat. 3(1): 101 (1986)
                                                                                                                      TREATMENT    771
-------
        Hazardous Material  Control  Versus  "End of  Pipe"  Disposal
                                                     Alvin F.  Meyer, PE
                                             A.F.  Meyer and Associates,  Inc.
                                                      McLean,  Virginia
ABSTRACT
  This paper  describes current industrial interest in the subject of
pollution prevention, gives some historical perspectives on it and then
addresses, as  a case study, a program of the U.S. Navy to reduce
hazardous waste by 50% during the next five years. An overview of
the specifics of key elements of the Navy's Hazardous Material Control
and Management Program is presented as an example of one approach
that brings together all the elements of environment, safety and health
by a life-cycle approach to management.'

INTRODUCTION
  This paper presents a brief overview of the regulatory maze governing
pollution control, the resulting philosophies of regulatory action and
compliance and associated economic implications. It then addresses
concepts and  approaches developed by the U.S. Navy to reduce the
amounts and costs associated with using hazardous materials and the
disposal of their ultimate waste.
  At the outset it must be understood that in both industry and  in the
defense establishment there always will be processes, systems and oper-
ations that require the use of materials with properties hazardous  to
human health safety and/or the environment. As J. Clarence Davies
stated in his remarkable text almost twenty years ago, "We can not stop
all the activities which introduce potentially dangerous substances into
the environment, because to do so would be to sacrifice most  of the
benefits of modern society."3 He also pointed out that the prevailing
philosophy then was we could build treatment plants and install control
devices if money  and political power were brought  to bear on the
problem. From an economic viewpoint,  it is  interesting to note that
in 1970 it was  estimated that the control costs to bring down air, water
and solid waste pollution to the then acceptable levels was $300 billion
in 1970 dollars over a  thirty year period.
  Events and costs have overtaken the political, social and engineering/
technical philosophies that national environmental goals can best be
met through control technology. Environmental control procedures have
been based on the premise that the best solution will come from ever
increasingly stringent codes, standards and regulations directed at re-
quiring achievement of the best available  technology. A recent article
on occupational hazard illustrates that this approach is rapidly being
recognized as bad policy.
  A rethinking of these traditional approaches began in the early  1980s.
Waste minimization as an alternative to disposal has rapidly become
a recognized industry objective. That process is defined by DuPont as
"reducing the quality and toxicity of materials to be wasted by end-of-
the-pipc treatment."-" While large companies and government agencies
have been committed to source reduction and waste minimization, the
large outlay of funds thai may be imolved results in many small and
medium size companies concentrating on treatment and disposal proce-
dures with all of the associated permit  requirements.
  Beginning in 1986, the U.S. Navy began to address the questions of
both hazardous material control and hazardous waste minimization.
After extensive study of ongoing efforts in several naval activities, in-
cluding the Naval Aviation Depot Pensicola, Florida, broad-scale in-
vestigations led to the development and issuance of the Navy directive
on Navy Hazardous Material Control and Management. This approach
has been recognized by the General Accounting Office as being a unique
approach wormy of being emulated by other Federal agencies. The prin-
ciples and procedures are applicable to  the private sector as well as
the Defense and Aerospace community.

BACKGROUND OF REGULATORY  REQUIREMENTS AND
ECONOMIC IMPLICATIONS
  Among the driving forces affecting the widening recognition that a
true preventive management and engineering approach is needed for
hazardous materials and hazardous waste is the high cost of complying
with the wide variety of Federal, State and local regulations. Signifi-
cant  also are the  regulations' indirect impacts.
  Among these indirect impacts are the costs of training the people
working with hazardous materials to meet the Hazardous Communi-
cation Standard of OSHA; the costs associated with installation of ever
increasingly complex new equipment to meet such requirements as Fossil
Organic Compound  Controls;  medical  examinations for personnel
routinely working with hazardous materials and hazardous waste; and
the sharply increasing costs of storage facilities. The General Accounting
Office has estimated that it costs the Defense establishment approxi-
mately $1.10 for waste  disposal for each $1.00 actually spent in pro-
curing a hazardous material. Thus economic implications begin to take
a major role in a search for alternatives to pollution control technology.

FUNDAMENTAL CONCEPTS OF HAZARDOUS MATERIAL
CONTROL AND MANAGEMENT
  As envisioned  by the U.S. Navy, Hazardous Material Control and
Management is not waste minimization  alone.  Waste minimization is
an element of a  multifaceted approach bringing together all  of the
requirements associated with environment, safety and health. As shown
in Figure  1, it is a  program which provides  for  policy, action and
followup by all of the interested and affected elements of the Navy struc-
ture. It recognizes that there is a relationship between the life-cycle con-
trol and management of acquisition procurement and use of hazardous
materials and the control and waste minimization efforts and  proce-
dures. Highlights of the most important elements of the Navy policy
embodied in  its directive,  OPNAV  Instruction  4110.2,  Hazardous
Material Control and Management, are provided  below.6
      TRE.ATMFNT
-------
                             HMCfcM

                      POLICY, ACTION, FOLLOW UP


                      (CERCLA, RCRA, OSHA, CAA, ETC)
                  UP FRONT


                      LIFE CYCLE


       ACQUISITION


        NVENTORY CONTROL


       AUTHORIZED USE LIST


       HAZARDS COMMUNICATION


       ISSUE USE CONTROL


       SPECIFICATIONS
     WASTE WIN.


 POLLUTION


CONTROL/    RE-DESIGN


        PROCESS DESIGN


        REVERSE ENGINEERING


        TREATMENT/CONTROL


        PROCESS CHANGE


        SUBSTITUTION
                             Figure 1
                 HMC&M Concept/Inter Relationship
Policy and Goals
  The basic Navy policy is that the Navy will control and reduce the
amounts of hazardous material used and hazardous waste generated
through a life-cycle approach. A central element of the policy is the
establishment of an integrated effort encompassing the health and safety
of Navy workers  and procedures to protect the environment. A  firm
goal of achieving a 50% reduction in weight of hazardous waste gener-
ated by the Navy  by 1992 is also established. In view of the fact that
some observers are looking at a 25%  reduction of waste from most
generators by the year 2000, this goal may seem overly optimistic, but
at least it represents a reasonable target.

The Life-Cycle Approach
  In essence,  the Navy program calls for institution of hazardous
material control and management procedures and actions throughout
two related life-cycles of Navy systems and equipment. The first of these
relates to the life-cycle of systems and equipment as shown in Figure
2. Consideration of the need for use of hazardous material and resulting
hazardous waste reduction must begin from the time of conception to
the new system of procedure throughout  its research, engineering
development, production, installation, use and ultimate disposal.  The
systematic application of hazardous material control and management
studies and analyses as part of system development is intended to result
in inputs to the Navy's authorized use list discussed later in this paper.
  There is another life-cycle which is  also recognized in the Navy
process.  It is described in Figure 3. A second life-cycle is at the  acti-
vity  or installation level.  It involves the local  facilities' ordering of
materials,  their  receipt, storage,  distribution, use and  ultimate
disposition. Li a manufacturing installation or other similar commercial
facility, this same life-cycle exists.  It involves raw materials, trans-
portation and handling;  plant and process operations; storage, distri-
bution and transportation of the finished product; and use by an ultimate
consumer. It also includes final disposition of the waste streams in the
manufacturing  process and of  the  finished  products distributed
in commerce.
  In effect, in both the military installation and the civilian situation,
there are two distinct phases in controlling  a hazardous material.  The
first  control phase is the in-plant one involving exposures of person-
nel, equipment and facilities to the hazards associated with the materials.
The  second control phase involves the external environment using a
systems engineering  process. These process must be  addressed  con-
                             Figure 2
                 Life Cycle of System and Requirement
currently. The approach taken by the Navy and its Hazardous Material
Control and Management Plan clearly recognizes these interfaces and
provides for them in a cohesive fashion.

Assignments of Actions and Responsibilities
  Any program for comprehensive hazardous material control bringing
together environmental safety and health concerns requires a clearly
defined assignment of actions and responsibilities from the top level
of management to the lowest operating level. The Navy directive does
this in unmistakable terms. Responsibilities are assigned commanders
of systems command and fleet commanders in chief, and additional
specific assignments are provided to those elements concerned with
systems development, acquisition and research for education and training
and to commanders of Navy facilities.
  A key element to ensure the program's success is to assign the Naval
Inspector General to make the project a  special  interest item. Past
experience has indicated that this action will result in the necessary
responsiveness at all echelons of the organizational structure.

Authorized Use List Concept
  The OSHA Hazard Communications Standard (29 CFR 1910.1200)
requires that employers (and the Navy,  as well as other Federal agen-
cies, is considered an employer) must maintain inventories of hazardous
materials  in the workplace and provide workers with material safety
data sheets on those materials. Literally  tens of thousands of hazardous
materials  are currently in use throughout American industry and the
Navy is no exception.
  As in industry, many of the materials used by the Navy used are speci-
fied by plant process, production and operational design staff.  Far too
often, little or no consideration has  been given or had to be given to
whether or not a less hazardous material than the one called for might
be more suitable.
  Instead of approving the use of hazardous materials on an  uncon-
trolled basis or operational need, the Navy is now changing its method
of dealing with this problem. It is requiring an "up front" analysis and
control at the earliest possible moment. The objective is to help the
Navy avoid excessive costs associated with hazardous waste disposal
and the acquisition of hazardous materials.
  To that end, the Navy directive calls for the establishment at activity
level and at the Navy level of "Authorized Use List." Such a program
has been adopted by the Navy for its forces afloat and is now being
carried over into the entire Navy establishment. Accomplishment of
hazards analysis, risk assessment and economic analysis of an appro-
priate level of detail to the intended usage is required as part of the
decision process involved in the selection and use of hazardous materials.
  Recognizing that there are many specifications and standards calling
for the use of hazardous  materials applicable to existing systems and
equipment, the Navy program provides for a 36 month time period for
the establishment and implemention of plans to  take the necessary
actions to review these and develop  plans and procedures for the sub-
stitution  of less  hazardous materials  as  appropriate.  One  unique
procedure now being investigated by the Navy is the use of reverse
engineering/value engineering  techniques to  determine if existing
                                                                                                                        TREATMENT   773
-------
requirements for the use of hazardous materials can be changed or
modified.
Plan of Action Requirement
  In addition to the inspection program through the Naval Inspector
General, an important feature of the Navy's program which is directly
applicable in a civilian sector is the requirement for a formal plan of
action and milestones for implementation of the program and overview
of progress  in meeting the requirements by the "Corporate Head-
quarters,"  namely the office of the Chief of Naval Operations.


PERCEIVED OUTPUTS/BENEFITS
  Although the primary objective of the Navy program is to reduce
hazardous waste by 50% in a finite time period, there are many other
perceived outputs and benefits of the Navy program which are applicable
to the civil sector as well as to other Federal agencies. Some of these
benefits have already been cited in this presentation. In addition, the
following  are of critical importance:
• Avoidance of both resources (dollars and time) to deal with litiga-
  tion, citations and fines associated with environmental impacts or
  violations and/or occupational safety and health requirements.
• Avoidance of the costs of new control equipment to comply with the
  requirements of the pending Clean Air Act and OSHA permissible
  exposure limit regulations.
• Reduction in impacts on productivity because of requirements for
  use of personal protective equipment, preventive measures,  etc.
• Reduction in the costs for compensation for occupational  injuries
  and illnesses.
• Cost containment associated with accident and emergency response
  requirements.
• Lessened technical administrative and management needs to deal with
                                                hazardous materials.
                                              • Reduction in specialized hazardous materials/hazardous waste storage
                                                facilities.
                                              • Improve public and worker perception of the organizations policies,
                                                procedures and actions.4


                                              SELECTION PROCESS FOR HAZARDOUS MATERIALS
                                                One major need  associated  with the Navy program and similar
                                              hazardous material control and management programs in the civilian
                                              sector (in this author's view) is the lack of uniformly acceptable proce-
                                              dures for evaluation and selection of the least hazardous material to
                                              achieve specific  needs. While  the  concept of substitution of lesser
                                              hazardous materials has been a longstanding philosophy of industrial
                                              hygiene and environmental engineering, no definitive guidance currently
                                              exists. In addition to lexicological and other environmental, occupa-
                                              tional health and safety and public health hazard information (for ex-
                                              ample, fire and explosion potential), such considerations as the number
                                              of persons  exposed, the frequency and duration of exposure and the
                                              circumstances of use need to be taken into account.
                                                While  there is a lot of literature relating to  "risk analysis" in rela-
                                              tion to environmental impacts5, there is a need to compare the use of
                                              one solvent with another in a particular industrial setting. A number
                                              of methods currently used to evaluate occupational exposures may be
                                              utilized to meet this need. Among these are the procedures for "deriv-
                                              ing risk assessment codes for health hazards" developed by the U.S.
                                              Army Environmental Hygiene Agency and adaptations to include en-
                                              vironmental concerns total Air Force Occupational Safety and Health
                                              Standard 161-ll,"Work Place Monitoring."7 These both use numerical
                                              rating systems which allow a comparative analysis of the potential haz-
                                              ards and  other concerns associated with the specific workplace situa-
                                              tion. This  is an area which requires much more study within the
                                              hazardous materials control community.
                                                                       MISSION
                                                                       RQMNTS
                                                                         SPECS
                                                                     JOB  STDS
                                                                                                                           AIR
                                                                                                                          SOLID
                                                                                                                          WASTE

                                                                                                                         LIQUID
                                                                                                                          WASTE
                                                                                                                   TO:  DRMO
            DOT
                                                                                             DOT
                                             OSHA
                       REQUIREMENTS
                       PROCUREMENT ACTION
         M . i . . . .1
         •••III
SUPPLIES

WASTE
                                                                                                     EPA
77.4   TREATMENT
                                        Figure 3
                         Hazardous Material Management Regulatory
                            Requirements and Life Cycle Concept
-------
CONCLUSION
  The end-of-the-pipe air, water pollution and solid waste control so-
lution still is required for many waste streams. Hazardous materials
control by "up-front" procedures is not a panacea, but it is essentially
more cost-effective and less wasteful than the former mode of opera-
tion. From an overall national economic viewpoint, addressing a re-
quirement for waste minimization and process control, when conducted
in conjunction with measures to improve productivity and moderniza-
tion of production processes, has built-in benefits as an important ele-
ment in improving American competitiveness.
DISCLAIMER
  This paper represents the opinions of the author only and is not an
official U.S. Navy view or position.
REFERENCES
 1.  Yaroschak, P.J., New Directions in Navy HM/HW Management, Proc. In-
    ternational  National Congress on Hazardous Material  Management,
    PP.461-468, ICEP, Techny, IL, 1987.
 2.  La Ban, G., Dupont Watching Its Waste, Occupational Hazards, pp.51-54,
    July 1990.
 3.  Davies m, J.C., The Politics of Pollution, Pegasus, New York, NY, 1970.
 4.  Meyer, A.F., New Dimensions for Environmental and Occupational Health
    Surveys, Journal American Institute of Plant Engineers, 14(4), pp.100-104,
    1982.
 5.  Cohissen, J.J. and Couello, U.T., Risk Analysis, A Guide to Principles and
    Methods for Analyzing Health and Environmental Risks, NTIS, US Depart-
    ment of Commerce, Springfield, VA, 1989.
 6.  U.S. Department of The Navy. OPNAVINST 4100.2, Hazardous Material
    Control and Management (HMC&M), Washington, DC, 1989
 7.  U.S. Department of Air Force. AFOSH Standard 1&-11, Work Place
    Monitoring, Washington, DC, 1980.
                                                                                                                        TREATMENT    775
-------
 Case  Study:  Degradation  of Diesel  Fuel With  In Situ  Microorganisms
                                                        Chee-Kai Tan
                                                       Gregory Gomez
                                                         Yeonn Rios
                                                Southwest Research Institute
                                                     San Antonio, Texas
                                                     M. Neal  Guentzel
                                                         Joy Hudson
                                         The  University of Texas at San Antonio
                                                     San Antonio, Texas
ABSTRACT
  Following a diesel fuel spill of approximately 1,400 gallons a por-
tion of the contaminated soils was obtained for studies of bioremedia-
tion with  an indigenous microbial  consortium. These soils were
characterized for existing microorganisms and hydrocarbon concentra-
tion.  The  predominant microbial  species  found  in  the  diesel-
contaminated soils consisted of Pseudomonas putida, P. fluorescent,
Acinetobacter calcoaceticus var. anitratus, A. calcoaceticus var. Iwof-
fi and other Pseudomonas species.  The  initial total heterotrophic
bacterial population was 2 x 105 CFU/g, the final population was 6 x 108
CFU/g and the soil contained approximately 14,000 jig/g of diesel fuel.
  In 150 days of treatment, approximately 87% of the hydrocarbons
were mineralized to carbon dioxide and water. In another reactor where
additional oil-degrading microbes were added along with the nutrients,
the degradation of diesel fuel was 84%. A degradation study with oxygen
consumption was  also  conducted with a six-reactor respirometer.
Mineralization of 97% of initial concentrations of 100 and 300 ppm
of diesel fuel was  obtained  in 60 days.

INTRODUCTION

  Human and animal populations have demonstrated chronic and acute
toxicity to organic chemicals.1"3 Stricter federal and state regulations
for organic pollutants have required owners to clean up their toxic wastes
from  the  contaminated environment.4"6 Although incineration
technology often is the optimum choice for destruction of toxic  and
concentrated organic wastes, it is not economically feasible for organics
sorbed to soils over a wide area.
  The cleanup of persistent organic contaminants that have been strongly
adsorbed to soils  is  difficult  and expensive. One promising  and
economically feasible approach is through in situ biodegradation of the
organic contaminants.7""  Theoretically,  any organic compound  can
serve  as a carbon source for microorganisms. Metabolism of organics
with naturally existing living microorganisms  may be  encouraged by
adding nutrients,  oxygen and  minerals. When naturally-occurring
degradative microorganisms are absent or low  in  numbers, preac-
climatized cultures may be  added  along  with  nutrients  to  the
environment.
  The specific  objectives of the research were:  (1) to evaluate the
capability of a fertilizer formulation to serve as a nutrient source for
promoting indigenous bioactivities, (2) to determine the indigenous
microorganisms  present in degrading diesel fuel and (3) to compare
the biodegrading capability among the indigenous microorganisms, as
well as the activated sludges obtained from an industrial wastewater
treatment plant and a municipal wastewater treatment plant.
EXPERIMENTAL

In Situ Bioreactor
  The soil samples obtained from the site were separated into two por-
tions and  placed into two 55-gallon glass reactors called AQUA-1  and
AQUA-2.  The design of the reactors is shown in Figure 1. AQUA-1
was designed to use naturally existing microbes for degrading the diesel
fuel. A mixture of Pseudomonas, Enterobacter, Acinetobacter, Kleb-
siella and Bacillus was added along with the nutrient during injection
into AQUA-2. The nutrients were applied during treatment of the soils
in both reactors and the soils were continuously aerated with the PVC
pipe. The excess nutrients were recycled back to the container. The
nutrient was a fertilizer containing urea as a nitrogen source, phosphoric
acid as a  phosphorous source and metals.
 Nutrient Recyclln<
ecycllnq
                                         Nutrient Jet
                                                Diesel Fuel
                                                Contaminated
                                                Soil
                                          Perforated
                                          Manifold
                   Air Blower
                           Figure 1
              Design of In Situ Bioreactor for Degrading
                  Diesel Fuel in Contaminated Soil
Closed System Bioreactor - The Electrolytic Respirometer
  The reaction vessels used  in the  study were 1-L flasks with side
openings so that septa were easily inserted into them allowing sampling
of the reaction mixture. The experiments consisted of duplicate flasks
of two concentrations of diesel fuel (100 mg/L and 300 mg/L) in each
flask. The indigenous microorganisms were isolated  from the con-
taminated soils. Besides the indigenous microorganisms, mixed con-
     BIOTREATMENT
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sortium inocula also were obtained from an industrial wastewater treat-
ment plant at Kelly Air Force Base, San Antonio, Texas and the San
Antonio City Municipal Wastewater Treatment Plant. The seed inocula
were suspended in a nutrient mixture containing ammonium chloride,
calcium chloride, potassium phosphate,  sodium phosphate and trace
metals (magnesium sulfete, ferric chloride, sodium molybdate, cobalt
chloride, copper sulfete, zinc sulfete) as nutrients. The respirometric
control system consisted  of (1) nutrient/substrate  control  (diesel
fuel/sterile water/nutrient) and (2) nutrient/substrate/inoculum control
(diesel fuel/nutrient/inoculum). At specified times, 25-mL aqueous
samples were removed from the respirometer vessels and analyzed for
diesel fuel aliphatic, aromatic compounds and related metabolites using
gas chromatography/mass spectrometer (GC/MS). When necessary, the
pH was adjusted to ensure that the environment remained optimal for
microbial growth. The electrolytic respirometer was developed as a
means of providing a more accurate and complete measurement of the
BOD than normally is obtained by the standard dilution BOD methods.
The BOD is determined by precise measurement of the oxygen uptake
reaction. This system eliminates many technical problems encountered
with other methods for determining oxygen demand and the rate at which
it is exerted.
   The electrolytic respirometer consists of three basic components: (1)
a reaction vessel, (2) an electrolysis cell and (3) an electronic control
unit. Together, these components comprise a large-volume respirometer
which provides continuous and  automatic adjustment of the oxygen
pressure within the enclosed reaction vessel.12
   As oxygen is consumed by the biological reaction within the reac-
tion vessel, metabolically produced carbon dioxide is absorbed in a
KOH scrubber solution. A slight vacuum is  thereby created, causing
a decrease in the electrolytic level in  the outer chamber of the elec-
trolysis cell. When an approximate 1-mm change in electrolyte level
has occurred, the outer electrolyte surface breaks contact with the switch
electrode. This signal activates the electronic control unit and causes
a controlled direct current to flow through the electrolyte.  Oxygen is
produced at the positive electrode according to Faraday's  Law. This
oxygen is added to the reaction vessel in precise increments until the
original internal pressure is reestablished and electrolyte contact is made
at the switch electrode. Oxygen production is monitored electronically
by counting the increments of input needed to equalize the pressure.
 Hydrogen produced at the negative electrode is vented to the atmosphere
 at the outside top of the electrolysis cell.

Microbial Analyses of Soil  Samples
   Soil  samples  were collected in  sterile  vials  and refrigerated
 immediately upon receipt. These diesel fuel contaminated soil samples
 were used to characterize the indigenous microbial population growth.
 Serial tenfold dilutions of the soil samples were made using sterile 0.85 %
 saline solution. Aliquots (0.1 mL) of the dilutions were spread plated
 onto plate count  agar, MacConkey's agar, Pseudomonas agar P  and
 Sabouraud dextrose agar plates.
   Gram-negative isolates were identified using the API-20E system
 (Analytab Products,  Plainview, New York).  The system  contains
dehydrated chromogenic substrates that are activated with the addition
of the bacterial  suspension.  The reactions are assigned numbers
according to the result that occurs, and a seven or eight digit combina-
tion of these numbers is then decoded in the data base. The methodology
used to detect the other microbial parameters was that described in the
latest edition of Bergey's Manual of Systematic Bacteriology, Volumes
I and n.B The techniques selected for identification were those which
should yield the greatest degree of sensitivity for the samples examined.

RESULTS AND DISCUSSION

Oxygen Uptake
   Results of the respirometry experiments were based on the oxygen
uptake from each reactor vessel (containing 100 and 300 ppm, respec-
tively) and the mineral nutrients.
   1) 100 ppm diesel fuel/nutrients in  sterilized water
  2) 100 ppm diesel fuel/nutrients/industrial aerobic sludge
  3) 100 ppm diesel fuel/nutrients/indigenous microbes
  4) 300 ppm diesel fuel/nutrients/industrial aerobic sludge
  5) 300 ppm diesel fuel/nutrients/indigenous microbes
  6) 300 ppm diesel fuel/nutrients/municipal microbes
  The oxygen uptakes are shown  in Figure 2. The figure displays
cumulative oxygen consumption with respect to duration time illustrated
by oxygen uptake kinetics. Oxygen uptake in the nutrients with the
100-ppm diesel fuel began after approximately 2 days  lag time and
leveled off  at approximately 180 mg/L  through 30 days. In  the
substrate/nutrient/inoculum control studies, inocula obtained from the
industrial wastewater treatment plant showed a better initial bioactivity
comparing the indigenous and municipal wastewater cultures.  The
activity of the industrial inoculum could be traced to the acclimation
and selection of the inoculum to hydrocarbons at the treatment plant.
     800
     700-
0 1
• 100 ppm Diml/Nutrtonu/lnduttnM Amfefc Sudj«
O 300 ppm DtcM/NutrMnM/lnduMW AcroMc SluOgt
9 100 ppm OltMVNulrfefitt/ln S«u MterobM
6 300 ppm Oimi/Nuutofia/ln SKu Mferaton
                     171    261   351    441   531   621    693

                                 TIME (hr)
                             Figure 2
       Cumulative Oxygen Consumption in Respirometry Experiments
 Oxygen consumption showed a cumulative oxygen uptake plateau at
 780 mg/L at a 300-ppm initial diesel fuel concentration in the industrial
 inoculum culture. The maximum oxygen uptake values for the in-
 digenous soil microbe inoculum were 320 mg/L and 450 mg/L at 100
                                                                                                                   BIOTREATMENT    777
-------
ppm and 300 ppm initial diesel fuel concentration for 60 days incuba-
tion. Figure 2 only shows 30 days of incubation.

Microorganism Analysis
  Growth data indicated significant increases of growth of the indigenous
oil degrading microorganisms at the end of the 60-day incubation period.
                             Table 1
            Microorganisms Extracted from in Situ Diesel
          Contaminated Soils and Cultured in the Laboratory
   Colonies Count (Plate Count Agar) = 1.2 x 10* cfu/mL

   1.  Pseudomonai aeruginosa
   1.  Pseudomonas fluoresctns
   3.  Pseudomonas putida
   4.  Acine'.obocter calcooceticus var. anitratus
   5.  Acinetobacter calcoaceticus var. Iwoffi
          MICROORGANISMS OBTAINED FROM INDUSTRIAL
                   AEROBIC ACTIVATED SLUDGE

   Colonies Count (Plate Count Agar) = 2.8 x 101 cfu/mL

   1.  Pseudomonas aeruginosa
   2.  Pseudomonas pseudomallei
   3.  Pseudomonas fluorescent
   4.  Pseudomonas cepacia
           MICROORGANISMS OBTAINED FROM MUNICIPAL
                   AEROBIC ACTIVATED SLUDGE

   Colonies Count (Plate Count Agar) = 1.1 x 10' cfu/mL

   1.  Pseudomonas pseudomallei
   2.  Enterobacter cloacae
   3.  Aeromonas hydrophila
   4.  Acinetobacter calcoaceticus var. anitratus
Plate counts demonstrated that the number of organisms increased from
2.1B105 cfu/mL on the soil samples to 6B108 cfu/mL after 60 days of
incubation in the respirometric reactors. The total heterotrophic bacteria
count seemed to level off after the first 2-3 weeks of incubation.
hydrocarbons degrading capability in the literature. *° An attempt to
characterize the aerobic activated sludges obtained from Kelfy Air force
Base, Texas, and the San Antonio Municipal Hbstewater Treatment Plant
is shown in Table 2.
Gas Chromatographic/Mass Spectrometry Analysis Information
  Table 2 illustrates the GC/MS analysis in culture samples obtained
from respirometric vessels. This analysis demonstrates almost com-
plete mineralization of the aliphatic and aromatic hydrocarbons in these
experimental systems at the end of 60 days incubation in Reactions 2-5.
Significant biodegradation of diesel fuel at 100 mg/L and 300 mg/L
occurred with inocula obtained from the industrial wastewater treat-
ment plant and acclimated indigenous soil microbiota. This result also
shows that higher concentrations of diesel fuel in the inlet stream of
municipal treatment plant may upset the activated aerobic sludge of
the plant.  The blank  control  experiment in Vessel  1  using  the
respirometric approach provided evidence that more than 90% of the
diesel fuel  remained in the sample at 60 days post-inoculum.
  The Fourier transform infrared  analysis technique was applied to
analyze the samples obtained at 60 days. These samples were extracted
by Freon 113 and  hydrocarbons monitored at 2930 nm.
  Biodegradation data for diesel fuel contaminated soils at approximately
14,000 ug/g are shown in Table 3. Control studies were conducted with
air aerated at 10 psig throughout the soil for 10 days. Soil samples
obtained from the reactors on the 3rd, 6th and 10th days demonstrated
that the high molecular weight aliphatic (mle = 57) and aromatic (mle
= 91) hydrocarbons are strongly absorbed by the soil matrix. The con-
centrations remained at a homogeneous level with 2,900 ppm of aliphatic
hydrocarbons and 13,000 ppm of aromatic hydrocarbons for  reactor
AQUA-1 and 3,100 ppm of aliphatic hydrocarbons and 13,000 ppm of
aromatic hydrocarbons in reactor AQUA-2.
  On the llth day,  sprinkle-type injection systems were set up on both
aerated reactors and the soil moistures were controlled to near 40-60%.
For reactor AQUA-1, only buffered fertilizer medium was applied to
the soils while hydrocarbon preacclimatized microbes were added into
the buffered fertilizer medium to enhance the degradation rate of the
AQUA-2 soils.  During applications, the nutrient conditions were
monitored and maintained at pH 7 and room temperature. The samples
obtained after 30 days showed a drastic drop in concentrations of the
residual diesel fuels. In AQUA-1 60% and 50% of the initial aliphatic
and aromatic hydrocarbons, respectively, were degraded; at the same
time the soil samples obtained from AQUA-2 demonstrated 74% and
62% degradation of the aliphatic and aromatic hydrocarbons, respec-
tively. In both reactors, the recycled nutrients in the bioreactors do not
                                                                Table 2
                                                Respirometer Study with Diesel Fuel Exposed
                                                          to Acclimated Inocula


Sample ID
1. 100 ppm Diesel Fuel/Nutrient
2. 100 ppm Diesel Fuel/Nutrient/Industrial Wastewater Inoculum
3. 100 ppm Diesel Fuel/Nutrient/Indigenous Soil Inoculum
4. 300 ppm Diesel Fuel/Nutrient/Industrial Wastewater Inoculum
5. 300 ppm Diesel Fuel/Nutrient/Indigenous Soil Inoculum
6. Diesel Fuel/Nutrient/Muncipal Wastewater Inoculum
Amount (pg/g)
By GC/MS
T=ODay
100
100
100
300
300
300
T=15 Day
105
113
96
197
192
392
T=30 Day
82
98
88
214
179
207
T=60 Day






By FTIR (TPH)
T=60 Day
120
1.3
3.3
20
7.3
86
  As shown in Table 1, the inoculum composition was characterized
for the component and microbial species. The contaminated soils con-
tained  Pseudomonas  arruginosa,  Pseudomonas  fluorescens,
Pseudomonas putida. Acinetobacier calcoaceticus var. anitratus and
.•icinrtabacter calcoaceticus var. hvoffi. The organisms have established
contain any hydrocarbons. In the total population counts, a 50% in-
crease in bacteria density was obtained in both reactors. In 150 days
of treatment, approximately 87% of the hydrocarbons were mineralized
to carbon dioxide and water in AQUA-1. In AQUA-2, the degradation
of diesel  fuel was 84%. It is anticipated that the soils will be cleaned
~?8   B1OTREATMENT
-------
up in another 4 months.
  Analytical respirometry and the in situ bioreactor technique were
shown to be a valuable experimental  approach  for testing biode-
gradability of the diesel fuel formulations in contaminated soil matrices.
                              Table3
          Biodegradation Control Studies with the Diesel Fuel
       Contaminated Soils Obtained from a Diesel Fuel Spill Site
CONTROL AQUA-1
T =
3
6
10
%DryWl
95.1
91.6
93.5
CONTROL AQUA-2
T =
3
6
10
%DiyWt
88.4
88.6
91.9
SOIL AQUA-1
T =
30 days
60dayi
90 day.
150 days
%DryWl
79.5
76.5
75.1

SOIL AQUA-2
T =
30 days
todays
90 days
150 days
*DryWt
80.0
75.7
793

m/z = 57 amount
ng/gWa
2,863
2.815
2,972
pg/gDiy
3,011
3,073
3.179
m/z = 57 amount
pg/gWa
2,756
2571
2,804
pg/g Dry
3.118
3353
3,051
m/z = 57 amount
ug/gWa
956
341
685

Pg/g Dry
1,203
450
912

m/z = 57 amount
pg/gWa
621
723
350

Pg/g Dry
776
960
441

m/z » 91 amount
pg/gWa
"~ 11353
12362
12,626
Pg/g Dry
12,569
13,496
13^04





m/z = 91 amount |j
pg/gWa
13,201
14,774
14,605
pg/g Dry |
14.933 1
16,675
15,892
m/z = 91 amount
Pg/gWa
5519
2,965
1,548

pg/g Dry
6365
3,800
2,064

ro/z = 91 amount
pg/gWa
3,822
3,499
1,898

Pg/g Dry
4.778
4,600
2393


FTIR Amount
pg/g Wa pg/g Dry

3,247 3,820
1348 1,821
TPH Amount
Pg/g Wa pg/g Diy

3.961 4.660
1.789 2.181
 CONCLUSIONS
   Respirometric and bioreactor biodegradation data have demonstrated
 a significant enhancement of biodegradation of diesel fuel with the use
 of fertilizer and mineral nutrients. In situ stimulation of the growth of
 indigenous microbes from diesel-contaminated soil with nutrients per-
mitted the mineralization of hydrocarbons to environmentally accep-
table products, carbon dioxide and water. Inoculum from an industrial
wastewater treatment plant were an alternative source of microbes per-
mitting degradation of hydrocarbons. The results of this experiment have
promoted an on-site pilot study of the diesel fuel spill site. We anticipate
the cleanup of the contaminants will be accomplished within a year.

ACKNOWLEDGEMENT
  The authors are grateful to Southwest Research Institute for finan-
cial support through internal research funding. We also wish to thank
Dr. J.-P. Hsu, Mr. B. Wheeler and Ms. P. Millard for performing the
GC/MS analyses.

REFERENCES
 1.  Stroller, P.  Time, 6,  1985.
 2.  Sax,  N. I.,  Weisburger, E. K., Schottenfeld, D., Haas, J., Feiner, B.,
    Castleman and B. I., Lewis, R.  J., Jr., "Cancer Causing Chemicals," Van
    Nostrand Reinhold Company, New York, NY, 1981.
 3.  U.S. EPA, "Guidelines Establishing Test Procedures for the Analysis of
    Pollutants," Federal Register, 44,  p. 233, 1979.
 4.  The Comprehensive Environmental Response, Compensation and Liabili-
    ty Act (CERCLA), 1980.
 5.  The Superfund Amendments and Reauthorization Act  (SARA),  1986.
 6.  Resource Conservation and Recovery Act (RCRA), Public Law 94-580, 1976.
 7.  Gibson, D. T., Ed., "Microbial Degradation of Organic Compounds," Marcel
    Dekker, New York, NY, 1984.
 8.  Van Demark, P. J. and Batzing, B. L., "The Microbes; An Introduction
    to Their Nature and Importance," The Benjamin/Cummings Publishing Com-
    pany, Inc.,  1987.
 9.  Rochkind, M. L., Blackburn, J. W., Sayler, G. S., Sferra, P. R. and Glaser,
    J. A., "Microbial Decomposition of Chlorinated Aromatic Compounds,"
    U.S. EPA, Cincinnati, OH, 1986.
10.  Barenberg, S. A., (Ed.), "Degradable Materials: Definitions, Case Studies,
    Issues and Needs," CRC Press, Inc., Bocca Raton, FL,  1990.
11.  Fitter, P. and Chudoba, J., "Biodegradability of Organic  Substances," CRC
    Press, Inc.,  Bocca Raton,  1990.
12.  Bioscience Management, Inc., ER-100 Electrolytic Respirometer, Operating
    Manual.
13.  Sneath, P.H.A., Mair, N.S., Sharpe, M. E.  and Holt, J. G., "Sergey's
    Manual of Systematic Bacteriology, Volumes I and n," Williams and Wilkins,
    Baltimore, MD, 1986.
                                                                                                                       BIOTREATMENT    779
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                           Biodegradation of  Aromatic  Compounds
                                                William R.  Mahaffey, Ph.D.
                                                 Geoffrey Compeau, Ph.D.
                                                     ECOVA Corporation
                                                    Redmond, Washington
ABSTRACT
  An overview of current knowledge on the capacity of microorganisms
to degrade polycyclic aromatic compounds (PAH) will be reviewed.
Bioremediation of PAH compounds such as pentachlorophenol (PCP),
creosote, naphthalene and phenanthrene will be demonstrated through
case histories.
  A former railroad tie-treating plant on the NPL list is contaminated
with creosote in soil and groundwater. PCP, naphthalene and phenol
have migrated from site ponds and have contaminated shallow ground-
water beneath the site and a nearby river. Contamination at the site ranges
from oil-saturated sands and gravel to groundwater containing /ig/L con-
centrations of dissolved contaminants.
  ECOVA conducted a 20-month treatability study and process develop-
ment program to evaluate the effectiveness of oil recovery and develop
advanced in situ soil washing and bioremediation treatment techniques.
Laboratory bench-scale studies provide a thorough analysis of site soils,
and a series  of micro-column studies determined the effectiveness of
bioremediation. The  results confirm  that the  PCP can  be rapidly
degraded in  the highly contaminated soil and water at this site. This
study confirmed that the PAHs could be successfully biologically
remediated in the contaminated soil and  water.  The rates of loss are
extremely rapid in a soil slurry system, with concentrations reaching
nondetectable levels in  four weeks  in some cases.  Similarly, water
biotreatment can be extremely rapid and  complete. Finally, the com-
pounds can be effectively (90%) removed from soil  by simulating in
situ soil washing which has  tremendous potential for hastening on-site
remediation  of heavily-contaminated sites.
  The Brio Refining Superfund Site has a large volume of soil containing
styrene still bottom tars and  chlorinated hydrocarbon solvents. The site,
located adjacent to a housing development, contains  approximately
60,000 yd3 of waste. VOCs, ethylbenzene, styrene and toluene, were
detected at maximum concentrations  of 4,400 ppm,  240 ppm and
510 ppm, respectively. The contaminant of particular concern is phenan-
threne, detected in  ranges from 0.44 to 170 ppm.  ECOVA conducted
a process development and treatability  study to bioremediate the soil.
  A site assessment and laboratory study demonstrated that phenan-
ihrene could be degraded to < 1  ppm using biological techniques. A
four-month pilot demonstration of solid-phase bioremediation was con-
ducted.  The treatment  area  was  enclosed  into greenhouse-type
enclosures to capture vapor  emissions during treatment and eliminated
the need to  control or treat rainwater.  An overhead  spray system
distributed water, nutrients and inocula. Organic  vapor emissions were
controlled by adcorption on  carbon and the greenhouse helped control
dust. Approximately 200 yd' of contaminated soils were successfully
treated during the 94 days of operation. VOCs were reduced by more
than 99$. Sermvolatile organic compound concentrations were reduced
an average of 89 %, and phenanthrene concentrations reduced an average
of 84%. the average phenanthrene half-life was 33 days, significantly
less than reported half-life values of 69-298 days in other solid-phase
bioremediation systems. The data indicated that approximately 131 days
would be required for the phenanthrene concentration to reach 0.33
ppm, the analytical detection limit using U.S. EPA-approved procedures.

INTRODUCTION
  Bioremediation is the controlled use of microbiological agents, com-
monly bacteria and fungi, to reclaim soil and water contaminated with
substances which are deleterious to human health and the environment.
The biological agents are often indigenous microorganisms  inhabiting
the polluted matrix. However they also may be seed organisms which
have been isolated from another environment on the basis of their ability
to degrade a specific class of substances. It is due to the wide diversity
of microbial metabolic potential that  bioremediation is possible.
  PAHs represent a class of organic compounds which are ubiquitous
in the environment. They  are present in fossil fuels and are formed
during the incomplete  combustion of organic material. Creosote has
been used extensively to treat wood products against fungal  and insect
attack or to impart fire resistance. The creosote found in wood treat-
ment wastes  is a coal tar distillate  boiling from 200  to 400°C.
Chemically, creosote is a complex  mixture predominantly of PAHs,
plus a minor fraction of phenolic substances. The major  PAH con-
stituents are 2-, 3-, 4- and 5-ring compounds, including; naphthalene,
acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene,
benzopyrene and methyl derivatives of these compounds. PAHs, as a
class of organic compounds exhibit low volatility and low aqueous
solubility. As the molecular weight of these compounds increases, there
is an exponential decrease in both solubility and volatility. PAHs ex-
hibit a strong tendency to adsorb onto soils and sediments due to their
hydrophobic character,  which is an intrinsic function of molecular size.
  The microbial degradation of individual PAHs by pure cultures' as
well  as  mixed populations is  well documented.2 In  addition, the
degradation of PAHs has been evaluated in complex mixtures such as
petroleum refining wood  preserving wastes. Numerous  laboratory
studies have been performed which demonstrate the biodegradabiliry
of these compounds under a wide range of soil types and environmen-
tal conditions.4-5*
  Generally, the factors which seemed  to have the greatest influence
on the rates of biodegradation were moisture content of soils, pH, in-
organic nutrients, loading rates, initial concentrations and the presence
of an acclimated microbial population.
  Feasibility studies are an essential component for the development
of a bioremediation strategy. These studies are performed in a phased
testing program which is designed to accomplish a number of objec-
"'80
       BIOTREATMENT
-------
lives.  These objectives include:
• Establish the existence of an indigenous microbial population with
  the appropriate degradative potential on-site contaminants
• Define the rate limiting factors for enhanced microbial degradation
  of the contaminants
• Perform process optimization studies to define the optimal treatment
  in terms of rates  and cleanup levels attainable
• Develop design parameters  for field operations
  The first half of this paper presents a case study on a feasibility testing
program and the implications of the results for the development of a
site-specific remediation strategy. The second half will present a review
of a pilot-scale demonstration program treating soils containing styrene
still bottoms and chlorinated hydrocarbon solvents presented at this con-
ference in 1987.7

CASE HISTORY: TREATABILITY STUDY
  The site is a  former wood treating facility which was in operation
for almost 100 years. Wood  preserving agents used in the process
included zinc chloride, creosote oil and pentachlorophenol. Wastes were
disposed of at the plant according to the standards of the era, resulting
in approximately 100 acres at the site becoming contaminated by present
standards. Contamination consists largely of an immiscible, denser than
water mixture of creosote and PCP. The principal compounds of concern
are PCP and PAHs. The range of site contamination varies from oil-
saturated sands and gravel to groundwater with ^g/L concentration of
dissolved  phenols,  PCP PAHs  and  other petroleum hydrocarbon
fractions.
  The site was  secured with a contaminant isolation system installed
; on-site. Actions over the past three years have focused on cleanup of
«the  site through  on-site  contaminant removal  and  biotreatment
technologies. Due to the tightness of the bedrock formations and the
high porosity of the soils, this site is well-suited to in situ bioremedia-
tion techniques.

RESULTS

Phase 1: Microbial Biotreatability Evaluation
  A microbiological evaluation was performed to determine whether
the microorganisms currently present in the soils and groundwater at
the site were capable of degrading the site contaminants under condi-
tions conducive to biodegradation.  Soil  and water  samples  were
incubated under aerobic conditions with sufficient nutrients for 4 weeks.
The loss of contaminants was monitored by GC/MS. Half of the samples
received growth factors and a surfactant to determine whether these
chemical treatments could enhance biodegradation.
  The results indicated that substantial biodegradation of contaminants
could be achieved in all of the areas sampled. Contaminant reduction
was greatest in the groundwater  samples (93%),  followed by the
saturated soils  (80%) and the unsaturated soils (66%). The percent
reduction hi individual target contaminant levels was not related to the
initial concentrations in all samples. However, the total biodegradation
was related to  total contaminant concentration in all samples. The
residual hydrocarbon after a 4-week incubation appeared to be related
to the inherent biodegradability of the contaminants present in a given
sample. Most of the individual compounds were readily biodegraded.
The average loss of 2 - 3 ring polynuclear aromatic hydrocarbons (PNAs)
was 80 to 90%. In those sites showing residual hydrocarbon, the com-
pounds were those showing slower rates of biodegradation such as penta-
chlorophenol (PCP) and the 4 - 6 ring PAHs (approximately 65 % loss
on average). No effect of the growth factor and surfactant addition was
observed.
  Although  the results  indicate substantial biodegradation of  con-
taminants, it was necessary to confirm that microorganisms present at
the site are capable of mineralizing the contaminants (i.e., convert
organic carbon to carbon dioxide). To confirm mineralization, selected
14C-labeled compounds were incubated with enrichment cultures
selected during the previous activity and mineralization was monitored
by measuring the evolved 14CO2.
  The results showed  that the 2 - 3 ring PAHs tested (naphthalene,
phenanthrene and fluorene) were rapidly mineralized by most of the
enrichment cultures when present as sole carbon source. The 4- and
5- ring PNAs tested (pyrene and benzo(a)pyrene, respectively) were
not mineralized when present as the sole carbon  source. However,
14CO2 was evolved by some enrichments when contaminated soil (con-
taining additional hydrocarbon substrate) was added. This is evidence
that mineralization  of 4- and 5-ring PNAs may be achieved through
cooxidation by stimulating microbial activity on other organic substrates
(i.e., microbes are  growing related simpler contaminants). PCP was
mineralized when present as sole carbon  source only by enrichments
from some of the surface and unsaturated soil samples. Microorganisms
responsible for mineralizing PCP appeared to be lacking from the
groundwater and saturated  soil  samples. The apparent lack of this
metabolic potential in these areas probably is due to the lack of oxygen.
An acclimated culture capable of PCP mineralization was under develop-
ment and testing.
  The initial studies have shown that the site contains microorganisms
capable of extensive biodegradation of all target contaminants.  Many
of the  simpler compounds can be biodegraded as sole carbon source
and these apparently can induce the production of enzymes  capable
of degrading the  more complex compounds as well. These bacteria
apparently are not distributed evenly throughout the site. Thus, the extent
of biodegradation of PCP or more complex PNAs was highly variable
between samples and there was no  conclusive evidence that  the
microorganisms present in any one sample could degrade all of the con-
taminants.  However,  the results establish the potential for in situ
biological treatment for both contaminated groundwater and soils at
the site.
  The  following conclusions can be drawn from this work:
• The  total contaminant concentration at the site varies with sampling
  site (location) and/or medium (groundwater,  surface, subsurface soil).
• The  potential to biodegrade all of the contaminants present in the
  soil  and  water  exists  in the  metabolic  capabilities  of  the
  microorganisms present at the site.
• The  fraction of the total contaminant load which was biodegraded
  in a given time period was related to  the location of the  sample
  (groundwater >  saturated soil > unsaturated soil).
• The total contaminant biodegraded in a given time period was related
  to the total concentrations  of contaminants as well as the concentra-
  tion  of 4 - 5 ring PNAs or PCP.
• The  amount of  contaminant biodegradation achieved was  not
  increased by addition of growth factors, or surfactants.
• Inoculation of microorganisms or substrates may be  necessary to
  redistribute the biodegradation potential at the site  to achieve total
  bioremediation.
• Mineralization  of most the compounds tested  can  be  achieved by
  microorganisms present in the site.
• Cooxidation  or the addition  of specific  organic  substrates may
  stimulate the biodegradation of other compounds (4-5 ring PNAs
  and  PCP).

Phase  2: Bioremediation Process Optimization
  From the Phase  1  studies it  was concluded that  the indigenous
microorganisms possessed the contaminant biodegradation potential
required for an effective in situ bioreclamation process. The focus for
the Phase 2 studies was on determining how best to use these capabilities
in a site-specific bioreclamation process and on preliminarily evaluating
the cleanup levels that can be achieved over tune.
  Several specific in situ bioreclamation processes were developed and
tested.  These processes include surface bioreclamation, in situ subsur-
face bioreclamation after  free product recovery and  in situ subsurface
bioreclamation following  soil washing using an alkaline polymer sur-
factant (APS). Each process relies on stimulating the  contaminant
biodegradation activity of native microorganisms by managing the soil
environment. Process specific techniques include altering and main-
taining pH and moisture levels within a preferred range, supplemen-
tation with inorganic nutrients that would  otherwise be present in limiting
concentrations and  providing sufficient oxygen  for optimal aerobic
                                                                                                                   BIOTREATMENT    781
-------
activity. Laboratory results suggest that surface bioreclamation following
primary  product recovery and  in situ  subsurface  bioreclamation
following soil washing each has potential as a viable, cost-effective
remediation technique.

Surface Bioreclamation
  Surface bioreclamation  is based on the microbial degradation  of
organic contaminants in soils in a land surface treatment system. Surface
bioreclamation essentially consists of stimulating contaminant degrada-
tion in a relatively shallow  (< 18 inch) surface soil layer. Contaminant
biodegradation is stimulated by providing an environment conducive
to optimal microbiological activity.  Aerobic conditions are maintained
by optimizing atmospheric contact and oxygen diffusion through surface
soil and may be aided by soil tilling methods. Inorganic nutrients and
other soil amendments can also be tilled into the soil while the moisture
content is maintained within a range  conducive to microbial activity.
  The most effective surface bioreclamation methods were evaluated
by measuring contaminant reduction in soils treated by different methods
in microcosm studies. The surface bioreclamation microcosm studies
were carried out in  small open pans containing approximately 3 kg of
soil spread to a depth of approximately 10 cm. Daily tilling and watering
were carried out to maintain soil moisture content at approximately 50%
to 70% of the water holding capacity. Treatments evaluated in these
studies included the following:
•  Soil amendment  with inorganic  nutrients
•  Amendment with various levels of manure
•  Inoculation plus  amendment with  nutrients
  Figure 1 illustrates the results obtained for the biodegradation of the
PAH fraction  in  the surface  soils under evaluation  for surface
bioreclamation.
                             labtel
          Residual Contaminant Levels Achieved in Surface
                    Bioreclamation Pan Studies
                             pit*. IM vilu* In ptrtnlKmn i
that it may be beneficial to add nutrients hi small multiple increments.
  The most important implication of the laboratory soil pan studies
is that surface bioreclamation does indeed appear to be a viable means
of reducing the contaminant levels in the surface soils. It should be
further investigated in field pilot studies.

Soil  Washing
  Laboratory column studies, which are designed to simulate an in situ
treatment process, have provided data on the effectiveness of the APS
soil washing process. These studies confirm the contaminant removal
effectiveness of the APS soil washing technique as summarized in
Table 2.  Generally, better removal efficiencies (>89%) were observed
in  the more heavily contaminated Trench 4 soil.
                             Figure  1
        PAH Removal Results for Laboratory Simulation of Surface
                         Soil Bioreclamation
                                                                                                    Table 2
                                                                                Contaminant Removal in APS Soil Washing Studies
  The contaminant removal kinetics observed in these studies were on
the high end of the range obtained in similar studies reported in the
available literature. Similar results were observed for the oil and grease
component of the site contamination. As observed in other studies, the
higher ring PAHs (i.e. > 4-rings) exhibit degradation rates which are
lower than for the 2-to 3-ring PAHs. This results in a lower overall
biodegradation efficiency of the larger PAHs during the study  period
(Table 1).  Given the limited duration of these studies (i.e., 8 weeks),
the rales should be considered initial rates at best for the higher ring
PAHs and  therefore the residual contaminant levels achievable for these
compounds cannot be accurately assessed.
  These laboratory simulations suggest a number of factors that may
be important for surface bioreclamation pilot studies. For example, it
appears that while the addition of manure did not significantly enhance
the rate of biodegradation. it did enhance the physical character of the
soil making it easier to till. This operational factor alone warrants the
use of manure for field pilot studies. The laboratory studies also suggest
  In situ soil washing is a two-step process consisting of delivery of
the APS solution followed by an aquifer reequilibration step designed
to purge residual polymer and surfactant and to establish base line pH
conditions. The high pH values subsequent to the APS wash are not
conducive to microbial activity. In addition, the alluvium will contain
high residual concentrations of polymer and surfactant. This contamina-
tion may contribute to an increased oxygen demand and result in the
preferential biodegradation of this material over the target contaminants.
  As pan of the laboratory studies,  various treatment evaluations were
performed on soil columns that had been subjected to the APS washing
process. One series of columns was treated by flushing the soil  with
0.001 N phosphoric acid solution to return the soil to near neutral pH.
The other  series of columns  was treated  by flushing  neutral  pH,
oxygenated water through the columns to slowly reequilibrate the soil.
As  summarized in  Table 3, higher concentrations of polymer,  surfac-
tant and target contaminants  were leached with neutral water solution
than with the acid solution.  This  suggests that aquifer rehabilitation
will be most effectively accomplished with non-pH-adjusted  water.
       BIOTRF-ATMENT
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                             Tables
    Contaminant Removal During Simulated Aquifer Rehabilitation
Contaminant
Concentration
Parameter After Soft Ue-
•Mn.
Chemical Oxygen Oe-
: mand
Total Petroleum
Hydrocarbons 	
Total PHAs
Pentach lorooheno L
49,000
10,208
2.406
57
1 ?F Lushed with Neutral Water
flushed with phosphoric acid solution
cHot detected at the method detection I In
Note: Concentrations In no/kg.
After Aouffer Rehabilitation
Treatment 1* TrMtJttnt 2 and 3b
Percent Percent
Concentration Reduction Concentration Reduction
10,350
985
139
HDC
t.
79
90
91


27,500
1,425
185
NDC
44
86
89


Subsurface Bioreclamation
  Subsurface bioreclamation may be implemented in two distinct soil
environments. One scenario is implementation immediately following
primary oil recovery in which case the soil environment would be heavily
contaminated. In the second scenario, primary oil recovery would be
Mowed by in situ soil washing with in situ bioreclamation  as the
polishing step to achieve final cleanup levels. The soil environment
would be characterized by much lower target contaminant levels, the
presence of residual polymer and surfactant from the wash step and
potentially altered microbial populations and  metabolic capabilities.
  Laboratory studies were performed to evaluate in situ bioreclama-
tion in both washed and unwashed soils. The discussion of the  results
from this study is therefore presented in two sections: bioreclamation
in unwashed soils and bioreclamation  in washed soils.
  Studies performed to evaluate in situ bioreclamation in unwashed soils
were designed to answer the following questions:
* Considering the toxicity of certain site contaminants, could microbial
  degradative activity be stimulated in the heavily contaminated soils
  present after primary oil recovery?
• What specific treatments are required to most effectively stimulate
  activity in these soils?
• What cleanup levels are achievable as a function of time  in the
  specified process?
  The ability to stimulate microbial activity in heavily contaminated
unwashed soils was evaluated in column studies designed to simulate
in situ subsurface bioreclamation. Soils  from two site locations, Trench
1 and Trench 4, were used in these studies. Trench 4 soil had the highest
contaminant levels, approximately four times greater than Trench 1 soil.
Approximately 400 g of soil were placed in columns 20 cm long with
a diameter of 5 cm. Simulated groundwater containing combinations
of treatment agents (e.g., oxygen, nutrients, peroxide and inoculum)
was then passed through the saturated soil column. Data were obtained
                                                       OXYGEN PLUS
                                                       250 PPU HYDROGEN
                                                       PEROXIDE
            NO NUTRIENTS
            OflNOCULUM
            (TREATMENT I 8 IA)
NUTRIENTS ADDED

(TREATMENT 2A2A>
NUTRIENTS AND
INOCULUM ADDED
(TREATMENT 3 S3A)
                             Figure 2
     Contaminant Reduction in Trench 4 Soil During Column Studies
through influent and effluent analysis and through analysis of soil from
sacrificed columns.
  Results from the column studies demonstrated that microbial con-
taminant degradation could be stimulated in heavily contaminated Trench
4 soils. Oxygen consumption in the columns is indicative of aerobic
microbial activity since the aerobic biodegradation of the contaminants
will exert an oxygen demand on the system. Oxygen supplied to the
columns was generally rapidly and completely utilized in the columns.
The data suggested that higher oxygen delivery rates resulted in increased
contaminant biodegradation or removal. The greatest degree of con-
taminant reduction occurred in columns which received elevated oxygen
levels and inorganic nutrients. This result is illustrated in Figure 2 which
presents a summary of results obtained in studies conducted in the soil
columns.
  The level of cleanup achievable using in situ subsurface bioreclama-
tion and the tune required to attain a given cleanup level will  be two
criteria that will  determine the feasibility of this technique  for site
cleanup. The most pertinent data generated in the  bioreclamation
laboratory studies for cleanup levels are the data on contaminant con-
centrations in column leachates at the conclusion of the tests. These
data provide a measure for organic groundwater quality achievable as
subsurface contaminants are removed  and  biodegraded.
  Leachate from the columns was evaluated after 15 weeks of delivering
oxygen and nutrients to saturated soil columns. No PAHs or PCP were
detected in the column leachate at a detection limit of 10 /ig/L.  Levels
of total petroleum hydrocarbon (TPH)  were below the detection limit
of 1.0 mg/L. Another measure of the degree of cleanup achievable with
in situ bioreclamation immediately following primary oil recovery is
the degree to which specific contaminant concentrations in column soils
are  reduced. Table 4 contains data on soil contaminant levels at the
beginning and after 15 weeks of treatment in select column studies.
  It is apparent from these data that significant reductions in all con-
taminants were observed; however, this result was not considered
representative of the ultimate degree of cleanup attainable. Most of the
oxygen being supplied to the columns was still being consumed in the
columns at the  time  these data  were collected.
  Select columns were operated through 92 weeks of treatment before
the columns were sacrificed and analyzing soil samples were analyzed
for  residual contaminant levels. Generally,  oxygen consumption had
subsided considerably and nutrient levels in column effluents approached
those of the influent.  This was taken as an indication that microbial
degradative activity had subsided. Trench 1 soils continued to exhibit
further reductions in all PAHs. In the more heavily contaminated Trench
4 soil columns, further reductions in contaminant levels were observed
only in those columns receiving inorganic nutrients and aerated ground-
water. Columns receiving additional oxygen in the form of hydrogen
peroxide showed no  significant reductions in PAHs after the first
15 weeks of treatment. The indication is that treatment with hydrogen
peroxide can substantially reduce the time frame of in situ bioreclama-
tion and achieve the maximum cleanup levels attainable. Table 5 pro-
vides a summary  of the results obtained for specific bulk contaminant
parameters such as COD, oil and grease, TPH and total PAHs. These
data suggest that while though peroxide treatment resulted in optimal
PAH  removal during the first 15 weeks of treatment,  further signifi-
cant reductions in COD and TPH could be achieved through longer
treatment times. The data can also be interpreted to indicate that PAHs
are preferentially biodegraded in comparison to the total organics. Table
6 provides a summary of the reductions obtained in specific target con-
taminant levels  for Trench 1 (low PAH) and Trench 4 (high PAH) at
various treatment times. The results tend to indicate that the use of
hydrogen peroxide yielded optimum reduction  of all PAHs during in
the  shortest treatment interval (15 weeks).  When treatment consisted
of supplying oxygen via aerated groundwater, then both Trench 1 and
Trench 4 soils exhibited substantial reductions in PAHs with extended
treatment periods.
  Laboratory studies were performed to evaluate in situ subsurface
biodegradation of contaminated subsurface soil following in situ  soil
washing with an APS solution. These studies were designed to answer
the following questions:
                                                                                                                   BIOTREATMENT   783
-------
                                                                 Table 4
                                               Residual Contaminant Levels Achieved in Select
                                               Surface Bioredemation Studies AAer 15 Weeks
Parameter
Chemical Oxyaen Demand
Total Petroleun Hydrocarbons
Oil I Creese
2 • and 3-Ring PNAs
4- and 5 Ring PNAs
Total PNAs
Treatment 1a Treatment Z6 Treat»ent 3°
After 15 After 15
Initial Ueeks Reduction Initial Weeks Reduction
7,900
415
325
59.4
70
129.4
3.800
123
207
ND
14.6
14.6
52
70
36
100
79
88.7
16.500
650
964
365
175
540
11.500
70
72
76.4
157.4
233.8
30
90
92
79
10
56
Initial
13.000
300
580
189
138
329
After 15
Ueeks
17.250
300
^o
62
81
143
Reduction
..
0
21
67
41
56
?Treated with aerated water.
"Treated with aerated water containing inorganic nutrients.
Treated with aerated water containing inorganic nutrients and inoculum.
                              TableS
          Contaminant Reduction in Representative Subsurface
                    Bioreclemation Column Studies
                              Table 6
      Residual Contaminant Achieved in Representative Subsurface
                   Bioreclamation Column Studies
                                  (rng/W
           • ».•....—«,:«.
  To what extent will microbial populations and metabolic capabilities
  be altered by the APS soil washing process?
  What  measures are required following  soil  washing  to restore
  microbial degradative activity towards site contaminants?
• What  cleanup levels  are achievable using  in  situ  subsurface
  bioreclamation following in situ soil washing?
  A major concern about the in situ soil washing process followed by
in situ bioreclamation as a polishing step was the potential adverse effect
of the APS solution on microbial populations and metabolic capabilities
towards site contaminants. The saline, alkaline, APS solution  could
drastically reduce microbial numbers  and metabolic capacity during
the washing cycle. It was hypothesized that a soil washing agent that
effectively liberates and displaces oil from the subsurface soils  could
flush the associated microbial biomass from the soils as well.
  The degree to which microbial populations and metabolic capabilities
were altered by the soil washing process was evaluated in a series of
column experiments. Approximately 400 g of Trench 4 soil were placed
in columns 20 cm long with a diameter of 5 cm. Four pore volumes
of the APS solution were then passed through the columns. After soil
washing, various treatments for rehabilitating the soil were evaluated.
Simulated groundwater containing combinations of treatment agents
(i.e., phosphoric acid, oxygen, nutrients, peroxide and inoculum) were
then passed through the  saturated soil column. Data  were obtained
through influent and effluent analysis and through analysis of soil from
sacrificed columns. Evidence of restoration of microbial activity can
be divided into three categories:
•  Oxygen consumption in the columns
•  AJI increase in microbial numbers during the bioreclamation  phase
•  Contaminant removal during bioreclamation
  After the  soil washing process, Trench 4  soil samples exhibited a
reduction in microbial populations from 2 x 10s viable heterotrophic
bacteria per gram of soil to  less than  104 gram of soil. Trench  2 soil
showed a more  drastic reduction in microbial  populations from 3 x 107
to 1 x lOVgram of soil  (Table  1). Subsequent to cycling water con-
taining oxygen and nutrients through the soil columns, microbial counts
increased to 2 x 107/gram of soil. This increase in numbers is another
indication that microbial activity can be reestablished in soils after APS
washing.
  The effect of the  simulated  soil washing process on microbial
biodegradation  capabilities was evaluated by  measuring phenanthrenc
mineralization during incubation of soils subjected to the soil washing
process. Mineralization was measured using a WC - radioisotope of
phenanthrene and monitoring  for the  production of WCO2.
   As can be seen by the results presented in Table 7, phenanthrene
mineralization was reestablished in Trench 4 soils but apparently was
not reestablished in  Trench 2  soil.
   Nearly all oxygen supplied to the columns  was consumed during the
bioreclamation phase. In columns with an influent dissolved oxygen
of 12 mg/L, the effluent dissolved oxygen was always less than 1.5 nig/L.
784    BIOTREATMENT
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                             Table?
  Reestablishment of Biodegradation Potential After APS Soil Washing
Percent of 14-C as CO.
C»a/k9 total pnenanthrene}
SauLe ueek 2 Ueefc 4 Ueek 6
TRENCH 2:
Unwashed
Washed, untreated
Washed + HQSQ, tuH 7.0)
Washed * kyo.CDH 7.0)
Washed + HjPQf+N
Washed + KjPO, * N + Inoculum
7.29(18.7)"
0.17 (0.02)
ND
ND
ND
1.01(0.13)
8.65(22.2)
1,15 (0,15)
HO
0.86(0,11)
ND
0.71(0.09)
12.4(31.9)
«0b
ND
ND
HD
1.17(0.15)
TRENCH 4:
Unwashed
Washed, untreated
Washed * H-SOf (uK 7.0)
Washed * H-jPO, (pH 7.0)
Washed + H,POf + N
Washed + tUPO, * H + Inoculun
1.95(12.4)
0.79(0.51)
5.17(3.4)
3.12(2.0)
NO
ND
4.37(27.8)
2.93(1.9)
13.9(9,0)
7.77(5.1)
ND
NO
7.30(46.5)
4.27(2.8)
13.4(8.7)
14.0(9.1)
ND
0.72(0.47)
^one detected after subtraction of sterile controls. Sterile controls produced an average of 1.65
percent of the total 14-C as C02 after 6 weeks.
                             Thble 8
           Results of Bioreclamation Column Studies After
                 APS Soil Washing and Restoration
Soil Concentration
>-.i - -:':? .:..•>•••-'... Initial Final
Removal
Removal
Rate
X Removal ng/kg/day
Treatment 1 : Washed Soi I Leached Groundwater
PNA -
Total 2-3 Ring
Total 4-5-6 Ring
TOTAL
COD
TPH
OSG
Plate Count (cfu)
59.4
70.0
129.4
7.900
.415
325
2x105
ND
14.6
14.6
3.800
123
207
2x105
<95%
79%
88.7X
52X
70%
36%

0.57
1.05
2.19
39.0
2.8
1.1

Treatment 2: Washed Soil Leached with Nutrient Amended Grounduater
PNAs
Total 2-3 Ring
Total 4-5-6 Ring
TOTAL
COD
TPH
OSG
Plate Count (cfu)
365
175
539
16.500
650
964
2x1 05
76.4
157.4
233.8
11.500
70
72
2x1 06
79%
10%
56%
30X
90%
92%

2.75
0.33
5.80
48
5.5
8.5

Treatment 3: Washed Soil Leached with Nutrient Amended, Inoculated Groundua-
ter
PNAs
Total 2-3 Ring
Total 4-5-6 Ring
TOTAL
COD
TPH
OiG
Plate Count (cfu)
189.0
138.4
328.4
13.000
300
580
2x1 05
61.7
81.4
143.0
17.250
300
290
2x106
67%
41%
56%
..
0%
50%

2.42
1.09
3.53
.-
..
2.7

Although these data suggests that significant microbial activity was
restored, there is no certainty whether the target contaminants (PAHs)
or residual polymer surfactant were being degraded.
  As part of this study, replicate columns were sacrificed and the soil
was analyzed at the conclusion of the soil washing and again at the
conclusion of the bioreclamation process. Although it  is possible to
state, based on these data, that aerobic microbial degradative activity
was restored in these columns, it is difficult to conclude to what degree
the capability of soil microorganisms to degrade target contaminants
was affected.
  This conclusion is due in large part to the excellent contaminant
removal efficiencies attained in the soil washing phase. The concentra-
tion of target contaminants (PAHs and PCP) in the column soils at the
conclusion of soil washing was generally near nondetectable levels. Some
further reduction in target contaminant concentrations was achieved
during the bioreclamation phase of the study (Table 8). It is not possi-
ble to differentiate between contaminant loss resulting from microbial
activity in the column and contaminant loss resulting from the leaching
of a mixture of residual polymer, surfactant and target contaminants.
  It is important to note that the lowest contaminant levels were attained
in the soil columns that were  not subjected to rapid pH adjustment with
phosphoric  acid. These  columns were simply  treated by  cycling
oxygenated ground water through  the column.

CONCLUSIONS
  The most important conclusion from the bioreclamation column
studies described previously is that in situ subsurface bioreclamation
is a viable process  under either of the following  scenarios:
•  Directly following primary oil  recovery where very high contami-
   nant levels will be present
•  Directly following soil washing with an APS solution as a polishing
   step.
  Microbial contaminant biodegradation was stimulated in soils con-
taining relatively high residual contaminant levels. Providing sufficient
oxygen appeared  to be the most important parameter for stimulating
microbial degradative  activity. Supplementation  with  nitrogen  and
phosphorous as inorganic nutrients was also beneficial, but only if suf-
ficient oxygen was provided.
  In situ, subsurface bioreclamation following soil washing also appears
to be a viable treatment scenario. Although the APS soil washing process
did have some impact on microbial populations, the laboratory study
results suggest that microbial contaminant biodegradation activity can
be  restored  and  stimulated.   In the   laboratory column studies,
bioreclamation following soil washing successfully lowered the residual
concentrations of target contaminants (PAHs and PCP) in the soil to
levels near or below the analytical detection limit.
  Preliminary indications of the time required to achieve cleanup were
obtained in the column studies. It is believed that the time required
to achieve cleanup by  in situ bioreclamation may be  determined
primarily by the rate at which oxygen is delivered to the subsurface.
The laboratory studies suggest that the subsurface oxygen demand that
must actually be met to achieve cleanup may be substantially less than
the predicted oxygen demand  based on in situ mineralization of the gross
organics present. Thus, depending upon the oxygen delivery rate actually
achievable under  field conditions, actual cleanup  times could poten-
tially  be lower than theoretical predictions.
  As  previously  stated,  the laboratory results suggest that  in  situ
bioreclamation is a viable treatment alternative for the remediation of
this site and field  pilot testing  was recommended. Based  on the
laboratory results, it was  suggested that one of the major objectives
of the field program should be the correlation of oxygen delivery with
contaminant removal. Developing the correlation will require deter-
mining the relative extent of contamination reduction through several
mechanisms. Monitoring the following parameters will be critical tasks
in field  pilot studies:
   Mass of oxygen delivered
   Mass  of oxygen  consumed and definition of the  zone of  aerobic
   treatment
   Contaminant reduction in the  aerobic zone
   Contaminant reduction in anoxic zones
   Nature and extent of contaminant removal through leaching from the
   subsurface
CASE HISTORY: PILOT-SCALE DEMONSTRATION
  A pilot-scale, solid-phase air stripping and biological treatment facility
was constructed at the Brio Refining Superfund Site, Texas, in order
to demonstrate the feasibility of bioremediating affected soils and organic
residues on-site. The site has a large volume of affected soils containing
                                                                                                                    BIOTREATMENT    785
-------
 styrene  still bottom tars and chlorinated hydrocarbon solvents.
   The biodegradability of the site material was determined by Microtox
 testing. Of 11 areas tested, two areas were found suitable for biodegrada-
 tion without dilution. Of these two areas, the one with the lowest con-
 centration of volatile organic compounds was selected as the source
 of material for the pilot-scale biodegradation demonstration. This area
 was designated as Pit O during the RI/FS. Additional samples of the
 Pit O backfill were collected in order to conduct a bench-scale evalua-
 tion of the  biodegradability of the organic compounds present in the
 backfill. This testing indicated that the ketones, short-chain chlorinated
 hydrocarbons,  chlorinated  aromatic hydrocarbons  and  aromatic
 hydrocarbons found in the pit backfill could be removed by air stripping
 or biologically destroyed by indigenous microorganisms. On this basis,
 the decision  was made  to undertake a pilot-scale demonstration of
 biodegradation of backfill material from  Pit  O.
   The treatment facility  consisted of an enclosed, lined treatment bed
 containing  200 yd3 of affected soil from one of the backfilled storage
 lagoons located at the site. The liner  was an  80-mil HDPE synthetic
 membrane with heat-welded seams. A sand drainage layer was placed
 on top of the liner and a 6-inch thick layer of affected soil was placed
 on top of the sand. Nutrients and inoculum were applied to treatment
 bed through an overhead spray  system. The treatment bed was tilled
 daily to increase soil surface area and provide aeration. Volatile emis-
 sions from the treatment bed were contained by a plastic-film greenhouse
 and routed to carbon adsorption units.
   Following construction of the treatment facility, approximately 200
 yd3 of soil were transferred to the treatment facility. The excavated soil
 was placed on top of the prepared treatment bed. Due to the cohesiveness
 of the clay soil, the pit backfill material was allowed to dry before final
 grading. For several days the tracked front-end loaders were run back
 and forth over  the pit backfill to break up large blocks of soil and
 distribute  material evenly  over the treatment bed. After  3 days  of
 manipulation, the clay was amendable to tillage by a power rototiller
 attached to a tractor. Soil moisture content was low enough after 6 days
 to add nutrients.
4  The soil treatment bed was divided  into four lanes so that different
 methods of optimizing microbial activity and biodegradation rates could
 be evaluated. A control  lane, which  received only tilling and water
 additions,  was established to provide a base line for evaluating the
 effectiveness of the following three treatment processes: (1) nutrient
 addition, (2) single microbial inoculation  and (3) multiple microbial
 inoculations.
   The pilot-scale treatment facility was operated for 94 days. The soil
 in the treatment facility  was tilled daily to optimize contact between
 microorganisms and the organic constituents present in the pit backfill
 material and to ensure adequate aeration for microbial activity. Tilling
 also facilitated the air stripping of VOCs.  Soil moisture content, soil
 temperature and soil pH  were monitored to ensure that they remained
 within ranges conducive to microbial activity.  Water, nutrients and
 inocula were added as required to the treatment bed through the overhead
 spray system.

 Sample  Collection Analysis
   Soil samples were collected on Day  0, Day 21, Day 58 and Day 94.
 Soil samples were analyzed for volatile and semivolatile organic com-
 pounds in order to determine the rate  of organic compound degrada-
 tion and measure the effectiveness of the  three treatment processes.
 In addition, the soil samples were analyzed for soluble  ammonium,
 nitrate and phosphate to determine if the concentrations of these nutrients
 were sufficient to ensure maximum microbial growth and organic com-
 pound degradation.

 Removal of Volatile Organic Compounds
   The predominant VOCs detected in the Pit O backfill material placed
 in the treatment facility were ethlybenzene, styrene and toluene. These
 compounds were detected at maximum concentrations of 4,400 ppm,
 240  ppm   and   510  ppm,   respectively.  Methylene  chloride  and
 l,I.2-trichloroeihane  were also detected but at lower concentrations.
 Meihylene chloride concentrations ranged  from 0.53 ppm to 20 ppm.
while 1,1,2-trichloroethane concentrations ranged from 0.52 ppm to IK)
ppm.  Acetone;  2-butanone;  chlorobenzene;  1,1-dichloroethane;
methylene chloride; 1,1,2,2-tetrachloroethane, 1,1,2-trichloroethane; and
xylene were detected at concentrations ranging from 3.1 to 88 ppm;
3.7 to 54 ppm, 3.4 to 26 ppm; 2.3 to 200 ppm; 0.53 to 20 ppm; 4 to
5.1 ppm; 0.52 to 110 ppm and 0.55 to  180 ppm, respectively.
  The concentrations of the volatile organic compounds in the treat-
ment facility were reduced by more than 99% over the 94 day period
of operation (Table 9). Most of this reduction occurred within the first
21 days of operation and was predominantly due to air stripping, \blatile
compounds of both high and low volatility were removed with equal
efficiency. For example, the concentrations of methylene chloride and
1,1,2-trichloroethane, both highly volatile compounds, were reduced
by more than 99%. The concentrations of ethylbenze and styrene, both
low volatility compounds, also were reduced by more than 99%.
  Two methods were used to estimate the amount of volatile organic
compounds removed  from the affected soils by air stripping: (1) con-
centration of volatile compounds adsorbed in the activated carbon units
and (2) air emissions data collected during facility operation. The
amount of volatile compounds air stripped from (he affected soils ranged
from 137 kg to 159 kg, a removal rate of approximately 7 kg per day.
                            Table 9
   Volatile Organic Compound Removal, Pilot-Scale Bioremediation,
               Brio Refining Site, Friendswood, Texas
                        Total Volatile Omanlcs fPPBl
Lane
Control
Nutrient Adjusted
Single Inoculation
Multiple Incduallon
Day 0
25.972
39.460
273.184
101.868
Day 21
81
40
13
10
Day 58
17
14
16
19
Day 94
29
12
25
27
Reduction-
9969%
99.90*
99.99%
99.9%
• Reduction Alter 21 Days ol Operation
Degradation of Semi-Volatile Organic Compounds
  Phenanthrene was the predominant semivolatile organic compound
detected in the Pit O backfill material placed in the treatment facility.
Phenanthrene concentrations  ranged  from 0.44 to 170 ppm and the
average phenanthrene concentration was 36.3 ppm. 2-Methylapthalene
concentrations ranged from 6.2 to 170 ppm, with an average concen-
tration of 50. ppm. Naphthalene concentrations ranged from 0.13 to
96 ppm and the average concentrations was 19.5 ppm. Over the 94 day
operation of the pilot-scale biological treatment facility, semi-volatile
organic compound concentrations were reduced an average of 89%
(Table 10).

                            Table 10
            Serai-Volatile Organic Compound Degradation,
   Pilot-Scale Bioremediation,  Brio Refining Site, Friendswood, Texas
                  Total Sernl-Volalle Organic Compound! fPPBI
Lane
Control
Nutrient Adjusted
Single InocUallon
MJUpfe Inocutotlon
DayO
18,900
16.100
56.983
16.496
Day 21
9,346
6.999
4,610
6.028
Day 58
6,078
5,325
3.967
6,611
Day 94
2.928
1.402
2.023
2.800
Reduction
6451%
91.29%
9645%
8303%
Phenanthrene Degradation
  Due to its predominance in the affected soil from Pit O, phenanthrene
was used to determine the effect of the various treatment processes on
the degradation rate of semivolatile organic compounds. Over the 94
days of facility operation, phenanthrene concentrations were reduced
an average of 84% (Table 11). During the first 21 days of operations,
phenanthrene degradation occurred at a relatively rapid rate.  For the
remainder of the demonstration project, the phenanthrene degradation
rate  was  approximately  124 pg/kg/day.  At this degradation  rate,
approximately 131 days would be required for the phenanthrene con-
 7g6   B1OTREATMENT
-------
centration to reach 0.33 ppm, the analytical detection limit using the
U.S. EPA-approved procedure.
                             lablell
        Phenanthrene Degradation, Pilot-Scale Bioremediation,
               Brio Refilling Site, Friendswood, Texas
Phenanthrene Degradation, Plot-Scale Bioremediation.
Brio Refining Site, Friendswood, Texas
Phenanthrene Concentration iPPB)
Lane
Control
Nutrient Adjusted
Single Inoculation
Multiple Inoculation
Initial Day 0
27,850
19.400
73.600
24,360
Final Day 94
5,725
2,712
5,750
5.275
Reduction
79.44%
86.02%
92.19%
78.35%
Half-life (Days)
40.8
33.0
25.7
43.3
   Phenanthrene half-life values for the control, nutrient-adjusted, single
 inoculation and multiple-inoculated lanes were 40.8, 33.0, 25.7 and 43.3
 days, respectively. A statistical analysis of the data demonstrated that
 there was no significant difference in the rate of phenanthrene degrada-
 tion in the different treatment lanes; the initial phenanthrene concen-
 tration was apparently the parameter controlling the rate of phenan-
 threne degradation. The data collected during this demonstration project
 suggested that aeration  and the amount  of contact between the
 microorganisms and the affected soil also were parameters that governed
 the rate of phenanthrene degradation.
   Since there was no significant difference in the rate of phenanthrene
 degradation  observed in the different treatment lantes, all of the date
were pooled to determine the rate of phenanthrene biodegradation in
the treatment facility. The average half-life was 33 days, significantly
less than reported half-life values of 69 to 298 days in other solid-phase
biodegradation systems.

CONCLUSION
  The pilot-scale biological treatment facility constructed at the Brio
Refining Superfund Site conclusively demonstrated that target com-
pounds such as 1,2-dichloroethane, 1,1,2-trichloroethane and phenan-
threne could be removed effectively from soils using an on-site treat-
ment technology other than incineration. The process removed volatile
organic compounds by air stripping and destroyed semivolatile organic
compounds by biodegradation.

REFERENCES
1.  Gibson, D.T. and Subramanian, V. "Microbial degradation of hydrocarbons,"
   In D.T. Gibson (ed.) Microbial degradation of organic compounds. Marcel
   Dekker, New York, NY 1984.
2.  Cerniglia, C. "Microbial metabolism of polycyclic aromatic hydrocarbons."
   Adv. Appl. Microbiol. 30:30-70, 1984.
3.  Sims,  R.  "Waste/soil  treatability studies  for  four  complex  wastes:
   Methodologies and Results." U.S. EPA Publication No. EPA/600/6-86/003b,
   U.A. EPA, Washington, DC, 1986.
4.  Dibble, J.T. and Bartha, R. "Effects of environmental paramaters on the
   degradation of oil sludge." Appl. Environ. Microbiol. 37: pp. 729 - 739, 1979.
5.  Sims, R.C. and Overcash, M.R. "Fate of Polynuclear aromatic compounds
   in soil-plant systems." Residue Review,  83: pp.  1 - 88.
6.  Bossert, I.W. and Bartha, R. "Fate of hydrocarbons during oily sludge
   disposal." Appl. Environ. Microbiol. 47: pp. 763-767, 1984.
7.  Yare, B.S., Ross, D. and Aschom, D. "Pilot Scale Bioremediation at the Brio
   Refining" Proc. Superjund  '87. Washington, DC. pp. 313-319, 1987.
                                                                                                                        BIOTREATMENT   787
-------
                   Biotreatment of Red Water with Fungal Systems

                                                TenLin S. Tsai, Ph.D.
                                                   Robert J. Turner
                                                  Cynthia Y.Sanville
                                         Environmental Research Division
                                            Argonne National Laboratory
                                                   Argonne, Illinois
ABSTRACT

  Red water generated during the manufacture of trinitrotoluene
(TNT) is  an  environmental  concern  because  it contaminates
ground surfaces and groundwaters. Past methods for the man-
agement of this hazardous waste stream either did not meet pollu-
tion compliance or were not cost-effective. Biodegradation of
TNT by bacteria has been reported, but no conclusive evidence
supports its biotransformation to harmless  products or its com-
plete mineralization to  CO.  and HjO. The lignin peroxidase
(ligninase) secreted by the white rot fungus (Phanerochaete chry-
sosporium) has been shown  to degrade a broad  spectrum of
organic pollutants. In this study, the efficacy of treating red water
with the P. chrysosporium system was investigated.

INTRODUCTION

  Red water is a waste stream generated during the manufacture
of explosives. During TNT purification, a red colored waste water
is produced that is rich in sodium sulfite (sellite) and sulfonates of
various isomers of TNT. Red water has been classified by the
U.S. EPA as hazardous and has been an environmental concern
not only to U.S. Army ammunition plants, but also to the general
public because it can contaminate ground surfaces and ground-
waters.
  Disposal of untreated  red water by direct  discharge into water-
ways and sewer systems is not acceptable. Tighter pollution regu-
lations have prevented paper mill  companies from  recycling the
red water  for its sodium and sulfur content for use hi pulping
operations.' The conventional method of disposal by incineration
is expensive and energy-intensive, and the ash accumulated from
incineration can cause a leachate problem when it is land filled.2
The Sonoco process,' which converts red water into a sellite solu-
tion for reuse in TNT purification, has been tried in several opera-
tions, but the capital cost of the equipment  and the cost of plant
operation are astronomical. In addition, the quality of the recov-
ered sulfite remains questionable.
  An average Army ammunition plant, such as the Joliet Army
Ammunition  Plant (JAAP),  generates red water at rates of
approximately 80,000 gal of liquid per day and 250,000 Ib solids
per day during full operation.  Samples taken from different sites
at JAAP indicated that  past operations have caused contamina-
tion of the soils, sediments, surface water and groundwater. Un-
til a solution for effective red water treatment is found, all United
States ammunition plants must be maintained in a standby mode,
and no TNT may be produced.
  One of the most cost-effective methods for on-site remediation
is microbial biodegradation. However,  the effectiveness of this
treatment depends heavily on the survival, adaptability and activ-
ity of the microorganisms. Initial efforts at biological treatment
of wastewater containing TNT were not  satisfactory. Bacteria
generally reduce nitro groups of the TNT,  but no conclusive evi-
dence exists that they cleave the aromatic  ring. In addition, the
bacterial transformation created a sludge  disposal problem and
produced an effluent that was more toxic to fish than the un-
treated samples.4 Therefore, an economical and environmentally
safe method needs to be developed to treat red water.
  Direct enzyme treatment of hazardous compounds and en-
vironmental contaminants is  a relatively  new concept.  Lignin
peroxidase (ligninase) secreted by a white rot fungus has been
shown  to nonspecifically break many aromatic and substituted
aromatic rings.9 Ligninases play a key role in the degradation of a
broad spectrum of organic pollutants including DDT, polychlor-
inated biphenyls, benzopyrene, pentachlorophenol and dioxins.'
In this study, red water samples were treated with ligninase pre-
pared from the fungal  culture or with the fungal culture itself,
under  various  conditions.  Different analytic and  toxicologic
parameters were tested to evaluate the efficacy  of  the various
treatment protocols. The best biotreatment protocol  can be used
as the basis for further development of field application and on-
site, large-scale demonstrations.

EXPERIMENTAL
  The  red water samples obtained from  Canadian Industries,
Limited (McMasterville, Quebec)  are  representative of waste
streams from continuous production  lines in the  U.S. Army
ammunition plants. The "as received" (AR) red water was refrig-
erated, and the solid precipitate  (identified as Glauber's salt,
Na,SO4 •  10 H,O) formed upon  refrigeration was  removed to
yield the salt-reduced (SR) form.7  Both AR and SR red water
samples were treated with the fungal system.
  The white rot fungus P. chrysosporium (BOK-f-1767, ATCC
24725)  originally from  T.K. Kirk (U.S. Department of Agricul-
ture, Forest Products  Laboratories, Madison,  Wisconsin) was
cultured according to  the procedures of  Tien  and Kirk.1 The
ligninase activity secreted into the fungal culture media during the
ligninolytic phase of fungal growth was extracted. The ligninase
activity was measured at room temperature by monitoring the in-
crease in absorbance at 310 nm.'  One unit of ligninase  activity
(U) is defined as that which catalyzes oxidation of one micromole
of veratryl alcohol to veratryl aldehyde (which absorbs intensely
at 310 nm) per minute under specified conditions.
  The extracted ligninase preparation was  concentrated by Ami-
con CH2PRS and 8200 concentrators (Amicon Division, W.R.
"88    BIOTREATMENT
-------
Grace & Co., Danvers, Massachusetts) using a membrane with a
cutoff at 10,000 molecular weight. Dialysis of the concentrated
ligninase preparation (CLP), removal of mucilagenous materials
after the CLP was frozen or partial purification of the extra-
cellular enzyme followed, depending on the experimental design.
The stability of the ligninase activity was evaluated at various
temperature to ensure that the storage and activity of the enzyme
preparation were proper for laboratory use or for long-term field
application.
  The CLP collected from several batches of shake flask culture
of P. chrysosporium was  used in various biotreatment incuba-
tions. Both the AR and the SR red water, undiluted and diluted
(1:10- 1:20), were incubated with CLP  at  25 °C.  The whole
fungal culture was sampled when peak ligninase  activity was ob-
served. The peak fungal broth (PFB) was used to treat the SR red
water sample at 39° C. The biodegradation rate  of the whole
fungal culture treatment was compared  to  that  of the .direct
enzyme (CLP) treatment. Biotreatment controls (with no CLP or
no red water) were also set up for proper comparison.
   An aliquot of the SR red water was preexposed (at room temp-
erature) for three days to a Philips back-light lamp (with greater
than 96% of its energy peaked at 365 nm) from four directions
in a sealed structure made in-house. Ultraviolet light (UV) ex-
posure is known to cause photolysis and to weaken the structure
of the organic ring. The effects on biodegradation of UV pretreat-
ment and the addition of veratryl alcohol (known to stabilize the
ligninase activity) were also tested in the SR red water.
   Treated sample aliquots were taken from the  incubation mix-
ture at 4 hr, 1 day, 3 days and 7 days. These samples were stored
at -20° C until the time of  assay. Samples collected from vari-
ous  biotreatment plans were analyzed for decolorization and
ligninase activity and by UV spectral analysis, high-performance
liquid chromatography (HPLC) metabolite analysis  and Micro-
tox™ bacterial toxicity screening.10
   Two  different HPLC  column  systems with UV detection
(230 nm) were developed to analyze specific reactants in the red
water and  their biodegradation products. The  Supelcosil LC-8
column (4.6 mm x 33 mm, 3-um packing, from Supelco,  Inc.,
Bellefonte, Pennsylvania)  was heated at 30 °C. Sample (20 ul)
was injected onto the column through a 0.5-um  pore stainless
steel precolumn frit filter. Standards of structures similar to the
organic compounds commonly found in red water were chosen to
calibrate the column. The standards, used in  95% glacial acetic
acid  (GAA) were 2,4,6-trinitrobenzenesulfonic acid (picrylsul-
fonic acid, PSA), TNT, 2,4-dinitrotoluene (2,4-DNT) and 2,6-
DNT. The column was eluted for the first 4 min with 100% 1 mM
GAA (at 0.5 mL/min) and for the next 10 min with a solvent sys-
tem consisting of 30% of 1 mM GAA (at 2 mL/min).
   The second HPLC system, developed to analyze biodegrada-
tion metabolites, used a longer column (Beckman Ultrasphere
Octyl 5-um column, 4.6 mm x 250 mm, from Beckman Instru-
ments, Inc., San Ramon,  California) and a longer elution time
(30 min) for better resolution of the earlier peaks derived from
the treated samples. Samples (20 uL), diluted in 1 mM GAA, were
injected onto the column at 40° C. From 0 to 7 min, a 10% solu-
tion 2% THF in methanol in 90% water was used as mobile phase
at a flowrate of 0.3 mL/min. From 7 to 30 min, the mobile phase
was changed to 30%:70% and the flowrate increased to 2.5 mL/
min.
   To get even better  resolution  of the major sample peaks,
samples were run isocratically on the Beckman column at 40 ° C
for 25 min. The mobile phase used was a 10% solution of 2%
THF in methanol in 90% water at a flowrate of 0.3 mL/min.
   Samples collected at different time points of the biotreatment
incubation were screened for biotoxicity with the Microtox bio-
assay (Microbics Corporation, Carlsbad, California). This assay
involves exposing luminescent bacteria to red water and measur-
ing any decrease in light output, which is indicative of the degree
of sample toxicity. When the treated red water is subjected to the
same test, an increase in light output over that for the untreated
sample reflects degradation and detoxification of the red water.
The Microtox  test was conducted on a Luminescence Biometer
(DuPont Instruments, E.I. DuPont deNemours & Co., Wilming-
ton, Delaware).

RESULTS AND DISCUSSION

Stability of Ligninase

  In vitro stability of ligninase is important in determining the
economic and technical feasibility of its application in bioremed-
iation or industrial uses. The ligninase activity of two different
CLPs was compared at 25 ° C. The high-activity (3580 U/L prepa-
ration, without mucilagenous material,  showed a slow decrease
in activity, finally staying at 70% of its original activity at 7 days.
However,  the  low-activity  preparation (750 U/L), containing
mucilagenous material, dropped to only 3% of its original activity
in 24 hr. Ligninase activity of a CLP (1540 U/L, mucilates re-
moved) first decreased and then stayed at 70 to 80% of its initial
activity over a period of 7 days when it was stored at 25 ° C (Fig.
1) or 39° C (Fig. 2). When the original enzyme activity (1540
U/L, IX) was  diluted to 0.2X, 0.1X or  0.02X, the stability pat-
tern remained the same. The same ligninase stability pattern was
also  observed  with  a CLP of 1050 U/L  (mucilates removed)
stored at -70° C, -20° C or 4° C for 28 wk. If the mucilagen-
ous material is removed from the crude enzyme preparation, the
ligninase activity apparently will remain at 70  to 80% of its orig-
inal value at starting activity levels ranging over two orders of
magnitude (30 to 3500 U/L). The polysaccharides or protease
present  in the mucilates may have detrimental effects  on the
ligninase activity.

Decoloration and UV Spectral Analysis

  The red color intensity was measured  in all samples by absor-
bance at 400 nm. A loss of red color suggests that biotransforma-
tion of the red water has occurred. The red color intensity was
     60
       01234
                               Days
                           Figure 1
       Stability of Ligninase Activity at 25 ° C (IX = 1540 U/L).
     60
                      234567
                               Days
                           Figure 2
        Stability of Ligninase Activity at 39 °C (IX = 1540U/L).


                                        BIOTREATMENT   789
-------
         4 hr l day  3 day      1 week        2
               Time
                           Figures
      Effect of UV Pretreatment on Enzyme-Treated SR Red Water
If
if
o «
    100
80-

60-

40-

20-

 0
               39-C
                                  ! 0.5-
         4 hr 1 day  3 day      1 week        2    2.5    3    35
               Time                           102 nm
                          Figure 4
      Effect of Temperature (25 ° C vs. 39 ° C) on Enzyme-Treated
                        SR Red Water
        4 hr l day  3 day      1 week        2    25    3    35
               Time                            !02nm
                           Figure 5
       Effect of Enzyme (Ligninase) Treatment on AR Red Water
                      and SR Red Water
reduced in all samples from 30 to 0% of the original value after
only 1 day of treatment with the fungal system. The diminished
absorbance in the region 200 to 300 nm may result from UV spec-
tral changes associated with the reduction of NO2 groups of TNT
isomers, a general bathochromic shift and the degradation of aro-
matic rings by enzyme hydrolysis. The decoloration of treated red
water (Figs. 3A, 4A and 5A) corresponds with changes in the UV
spectral profile (Figs. 3B, 4B and SB). Figure 3  (A and B) shows
that red color and UV absorbance (at 200 to 300 nm) were re-
duced when SR red water received UV treatment before enzyme
(CLP) treatment. When SR red water was treated at two different
temperatures, the 39 ° C incubation caused more biodegradation
than the 25 ° C incubation as decoloration (Fig. 4A) and UV spec-
tral results (Fig. 4B) demonstrate.  Both red color intensity data
(Fig. 5A) and UV spectral analysis (Fig. 5B) demonstrated that
the fungal enzyme degrades AR red water  more effectively  than
SR red water.
  More decoloration was observed (Fig. 6) when SR red water
was treated with whole fungal culture (PFB) than with the fungal
enzyme (CLP). The  addition of vcratryl alcohol (V-OH), a sub-
strate for ligninase, further reduced the red color.
  The decoloration and UV spectral results both suggested that
SR red water is more toxic (see following toxicity data)  and less
biodegradable than AR red water. The UV pretreatment makes
the SR red water more  amenable to fungal biotreatment.  The salt
                                                                                                 SR/CLP/39
                                                                                                 SR/CLP/39
                                                                                                 SR/PFB+V-OH/39
            1      T         T
          4 hr   1 day    3 day

                         Time
1 week
                    Figure 6
Comparison of Direct Enzyme (Ligninase) Treatment with
          Whole Fungal Culture Treatment



0355 -


0265-

0177-



0088-



f
|
s t
o_]
«
s






gi
o 11
lj\

	 btanaaros
	 SR/CLP/25-C,
- 4-hr Sample
il
3 I
2 1
1
t
- 1 ~
A iO fc m S
- g I S |I

fin i S 5 0~
5 g «• i '• S
i 21 "• r^ 1 ""5
1 v 1 n 1 1 *o
i,is A » 1 J~
U(M 	 li

                                                                         n     i      i      i     i      i      i     r
                                                                   009    179   349   519    689   859   1029    1199   12 84
                                                                                       Retention Time (mm)

                                                                                      Figure 7
                                                                   HPLC (Supelcosil LC-8 column) Profile of CLP-Treated
                                                                 SR Red Water Sample (4-hr Time Point) Spiked with Standards
                                                            that was removed from the AR red water may be important to
                                                            the enzyme activity and the biotreatment regime.
                                                            HPLC Analyses of Red Water Biodegradation Metabolite*
                                                              Data from HPLC analyses revealed that biotreatment with fun-
                                                            gal enzymes altered red water components. An aliquot from the
                                                            4-hr sampling of the CLP-treated (at 25 ° Q SR red water was
                                                            spiked with 0.1%  PSA, 77 mg/L  TNT, 109 mg/L 2,4-DNT and
                                                            93 mg/L 2,6-DNT and the mixture was applied to the Supelcosil
                                                            column. The elution profile with its respective  retention time
                                                            (min)  is given in  Figure 7. Five  distinct peaks were recovered
                                                            from  the treated red water sample. The applied PSA standard
                                                            was resolved into three earlier peaks (PSA-A, PSA-B and PSA-Q
                                                            which were mingled with the five  peaks derived from the treated
                                                            sample. The TNT, 2,4-DNT and 2,6-DNT peaks appeared toward
                                                            the end of the elution.
                                                              The calibrated Supelcosil column system was used to analyze
                                                            samples taken from  biotreatment incubations. The results are
                                                            summarized in Table 1. All samples initially had  low levels (less
                                                            than 0.5% of the total peak height) of TNT isomers. After CLP
      BIOTREATMENT
-------
  0.109 —i
                     35?
                     CO O
-------
                             Table 3
          Summary of Red Water Biotreatment Tenacity Data


A.


B.






C.



D.



Protocols"
AR Red Hater
SR Red Water
SR UV
SR Red Water
SR/CLP/25
SR UV
SR-UV/CLP/25
AR Red Water
AR/CLP/25
AR(1:10 dill /CLP/25
SR/CLP/25
SR(1:20 dil)/CLP/25
AR/CLP/25
SR/PFB-V-OH/39
SR/CLP/39
SR/PFB/39
SR/PFB-V-OH/39
Deqree c
4 hr
10
100
33
100
14
33
4
10
4
4
14
8
4
42



>f Toxicitv %
1 wk










6
3
1
4
5
11
4
         •Abbreviations:  AR,  as-received red water;
          SR,  salt-reduced red water; CLP, concen-
          trated ligninase preparation; 25, 39, red
          water sample  treated at 25'C or 39'C; 4 hr,
          1 w)t,  sample  aliquots taken at 4 hr or
          1 wk of red water biotreatraent incubation;
          UV,  SR red water subjected to UV pretreat-
          ment for 3 days before biotreatment; PFB,
          peak fungal broth (whole fungal culture
          collected for biotreatment incubation when
          it contains the highest ligninase
          activity); V-OH, veratryl alcohol (115
          namomoles/ml) added to the incubation
          mixture.
the extracellular ligninase preparation. Certain  aromatic com-
ponents of the red water waste were biotransformed, and the red
color intensity and biotoxicity  were reduced after the biotreat-
ment. The ligninase activity was stable (at 70 to 80% of its orig-
inal level) for a minimum of 7 days at 25 ° C or 39 ° C. Pretreat-
ment of the  red water with UV seems to make the waste more
sensitive to biodegradation.

ACKNOWLEDGEMENT

  This work was supported under  a  military interdepartmental
purchase request from the U.S. Department of Defense, U.S.
Army, Materiel Command, through U.S. Department of Energy
Contract 9311-1410.  We appreciate  the gift of a fungal culture
brought from Michigan State University by Dr. Satyr Kakar and
his initial introduction of fungal culturing techniques in our lab-
oratory.
REFERENCES

 1.  Tien, M., "Properties of Ligninase from Phanerolchaete chrysos-
    porium and their Possible Applications, CRC Critical Rev. in Micro-
    biol., 15(2), pp. 141-168, 1987.
 2.  Helbert, Jr., W.B. and Stull, H.L., Red Water Pollution Abatement
    System, Final Report, AD-B082717, DAAA09-77-4007, Hercules.
    Inc., Radford, VA, pp. 56.1984.
 3.  Pal, B.C. and Ryon, M.G., Database Assessment of Pollution Con-
    trol of the Military Explosives and Propellants Industry, Oak Ridge
    National Laboratory Final Report, ORNL-6202, Prepared for U.S.
    Army Medical Research and Development Command, POiC83PP3802.
    pp. 134-136, Feb. 1986.
 4.  Kaplan, D.L. and Kaplan, A.M., "Thermophilic Biotransforma-
    tions of 2,4,6-Trinitrotoluene  under Simulated Composting  Con-
    ditions," Appl. Environ. Microbiol., 44, pp. 757-760,1982.
 5.  Bumpus, J.A., "Biodegradation of Polycyclic Aromatic Hydrocar-
    bons by Phanerochaete chrysosporium,  Appl. Environ. Microbiol,
    5J(l),pp. 154-158, 1989.
 6.  Bumpus, J.A., Tien, M., Wright, D. and Aust, S.D., "Oxidation of
    Persistent  Environmental  Pollutants by a  White Rot Fungus,"
    Science, 228, pp. 1434-1436, 1985.
 7.  Chaiko, D.J., Reichley-Yinger, L., Orth, E.R., VanDeventer, E.H.,
    Vandegrift, O.F.,  Coleman, R.D., Kakar, S.N..  Tsai, T.S.. Hellt,
    J.E., and  Sather,  N.S., "Development of a  Process for Treating
    Red Water by Organic/Inorganic Separation and Biodegradation,"
    14th Annual Army Environmental R&D Symposium, Williamsburg,
    VA, Nov. 1989.
 8.  Tien, M. and Kirk, T.K., "Lignin Peroxidase of Phanerochaete
    chrysosporium, "MethodsinEnzymology, 161, pp. 238-249,1988.
 9.  Tien, M. and  Kirk, T.K., "Lignin-Degrading Enzyme from Phanero-
    chaete chrysosporium: Purification, Characterization, and Catalytic
    Properties of a Unique H2O2-requiring Oxygenase,"  Proc. of Na-
    tional Academy of Science, USA, 81, pp. 2280-2284, 1984.
10.  Symons, B.D. and Sims, R.C., "Assessing Detoxification of a Com-
    plex Hazardous Waste, Using the Microtox™  Bioassay," Arch.
    Environ. Contam. and Toxicol., 17, pp. 497-505, 1988.
      B1OTRF.ATME-NT
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                        Biodegradability  of Sixteen  Chemicals  in  a
                                     Hazardous  Waste  Site  by  an
                                Indigenous  Microbial Consortium

                                            Martina Bianchini-Akbeg, M.S.
                                         Analytical Bio-Chemistry  Laboratories
                                                    Columbia, Missouri
                                                William J. Adams, Ph.D.
                                                 Edward J.  Valines, RE.
                                                David E. McKenzie, M.S.
                                                B. Mason Hughes, Ph.D.
                                                    Monsanto Company
                                                    St. Louis,  Missouri
ABSTRACT
  A laboratory, batch biodegradation study was conducted to evaluate
the biodegradation potential of soil from a hazardous waste site con-
taining chemicals associated with polystyrene waste. The study focused
on: (1) total waste biodegradability; (2) quantitative losses of certain
volatile  compounds  added, i.e., 1,2-dichloroethane  (DCE) and
1,1,2-trichloroethane  (TCE); and (3)  kinetic removal rates for all
chromatographable organic compounds in the waste.
  Sixteen nonvolatile chromatographable compounds were monitored
in seven bioreactors hi a 14-day study.  The experimental design con-
sisted of two open bioactive reactors, a sealed bioactive reactor, two
sterile open control reactors to measure abiotic degradability and two
open reactors not exposed to wastes as background controls for quality
control. All bioreactors were spiked with DCE and TCE to quantitate
losses due to volatility.
  High resolution GC/MS analyses indicated that a major fraction of
the organic components was biodegraded with reaction half-lives ranging
from 24 hours to 72 hours.  All nonvolatile chromatographable com-
pounds were reduced to less than the limit of detection (1.0 ppm).
Difference between the volatile and nonvolatile chemicals  was suc-
cessfully measured. Organic chemicals with GC retention times shorter
than  biphenyl, including DCE and TCE were rapidly volatilized.
Enumeration of microorganisms confirmed an active microbial con-
sortium present at all times of the study except in the control reactors.
Acute toxicity analysis using Microtox confirmed a decrease in toxicity
of extracts from  the bioactive reactors over tune.

INTRODUCTION
  Hazardous wastes produced by  industry must be disposed of in a
manner  which  is  both  environmentally acceptable  and  cost-
effective.1'3'6'7'15  The  waste disposal problem includes past disposal
sites that now must be cleaned  up. The remediation method chosen
for each site is a key  factor affecting the cost of any  site remediation
project.7 Since the reauthorization  of CERCLA, incineration has been
the primary technique  for  waste site remediation of organic con-
taminants.  Incineration may be cost-effective and efficient in specific
instances where wastes contain high levels of organic components and
high BTU content. However, when the site consists primarily of soil
containing less than approximately 5% organic components, microbial
treatment is a viable and cost-competitive alternative to incineration.
It has been demonstrated that, under favorable environmental condi-
tions, biodegradation of contaminated organics such as hydrocarbons
and oily sludges  may occur in soils.6'7'8-13
  Since most hazardous waste sites contain mixtures of many chemicals,
a microbial technology must demonstrate the removal of  all  listed
chemicals to acceptable levels. This paper summarizes results from a
 laboratory-scale biological treatment study which was conducted to
 demonstrate the feasibility of biologically treating soil contaminated
 with polystyrene tars. The objectives of this study were: (1) total waste
 biodegradability; (2) measurement of quantitative vapor losses of certain
 volatile  compounds  added,  i.e.,  1,2-dichloroethane (DCE) and
 1,1,2-trichloroethane (TCE)  and (3)  kinetic  removal rates  for all
 chromatographable organic compounds in the waste.

 MATERIALS AND METHODS

 Experimental Design
   Seven glass bioreactors (2-L beakers) were used to conduct the study.
 Each bioreactor, except reactor D, contained  1450 mL of soil-water
 slurry. Reactors A and B were duplicate vessels to which 300 mg of
 HgCLj (Granular, Mallinckrodt Chemical Works, St. Louis, Missouri)
 were added on Day 0 and again on Day 10. The absence of microbial
 activity in these reactors  should provide information about abiotic
 degradation processes. Reactor C contained all components except the
 waste to provide quality control. Reactor D was sealed with no headspace
 to eliminate volatility and demonstrate quantitative recovery of the
 chemicals at the end of the experiment. It consisted of a 1-L glass bottle
 filled up to the neck in order to eliminate all headspace and sealed with
 a foil-lined cap. Reactors E and F were bioactive duplicates of A and
 B and were the key reactors for monitoring biodegradation of the waste
 chemicals. Reactor G served as secondary control for analytical pur-
 poses and contained only well water, DCE and TCE.  All reactors ex-
 cept C and G were amended with nutrients and a surfactant. Previous
 research  has shown that nutrient supplementation may  enhance
 biodegradation  of organics4'9  and that soils  contaminated  with
 hydrophobic or slightly hydrophilic organics have been previously treated
 with surfactants.7
 Procedures
   All waste and surface soils were collected from the waste site and
 characterized as containing polystyrene tar polymers  and chlorinated
 organics.18 Two duplicate composite soil mixtures containing 20% total
 solids (wet wt/vol) were used to prepare the test soil water slurry. The
 mixtures were homogenized in small increments with a blender. The
 first mixture was then transferred into a 4-L Erlenmeyer  flask and further
 stirred with a spatula. The second mixture was further handmixed in
 a 6-L Erlenmeyer flask. Equal volumes of each mixture were trans-
 ferred into 2-L beakers and  allowed to stir on heavy duty magnetic
stirrers for 18  hr in a closed environmental chamber  (Vollrath, River
 Falls, Wisconsin) at 22 °C. During this mixing period, a portion of the
 styrene polymers contained in the waste was visibly  adsorbed to the
 stir bars. The stir bars coated with styrene tars were removed and a
 new stir bar was added to each reactor prior  to test  initiation. After
                                                                                                           BIOTREATMENT   793
-------
stirring, the mixtures were transferred back into the large Erlenmeyer
flask and rehomogenized with a Talboys Model 101 homogenizer (Cole
Farmer Lnstr.,  Chicago,  Illinois).  Aliquots of 1450 mL  were then
transferred into 2-L open glass vessels. The first batch  provided the
slurry  for reactors A and E, and the second for B, D and F.
   Assuming a total organic carbon content of 1 % of the soil slurry,
nutrients (K2HPO4 and NH4NO3)  were added at a C:N:P ratio of
 100:10:1. Surfactant, Triton x 100 was added at a concentration of 200
ug/mL, and DCE and TCE were both added at 61.1 ug/mL to all reactors
but D  to which 86.8 ug/mL were added. The pH was adjusted to pH
7.8 for all reactors. All  reactors were incubated on heavy duty stirrers
in a closed environmental chamber  at 22 °C. A light source consisting
of 50% Gro-Lux and 50% Cool White fluorescent bulbs provided a
light intensity of 175 ftc ±5% at reactor liquid level. A  16 hour light
period was alternated with an 8 hour dark period. The lack of humidity
control in the environmental chamber necessitated daily adjustment of
the liquid level in all reactors but D, which was  sealed.
   Samples for analytical  work were withdrawn for Volatile Organics,
Gas Chromatography/Mass Spectrometry (GC/MS) Extractables, acute
toxicity as measured with Microtox and enumeration of microorganisms.

Enumeration of Test Organisms
   Microorganisms were collected from contaminated surface soil from
the site (0 to 6 in. depth). This soil was used to prepare a soil slurry
of 20% waste (wet weight/vol) with well water. The soil slurry was
placed in an open glass container and continuously stirred on a heavy
duty magnetic stirrer and periodically amended with nutrients and waste
for a period of 2 months. This slurry was used as inoculum for the
present study.  Thirty mL of the slurry  was used as an inoculum for
each flask. Enumeration of  microorganisms was performed  using
disposable presterilized Millipore Total-Count™ Water Testers.17 Each
sample was plated in duplicate using serial dilutions of the waste. Two
sterile controls with autoclaved distilled  deionized dilution water were
also plated to test for contamination in plates, pipettes and dilution water.
The Total-Count™ samplers  were  incubated at 35 °C for 24 hours.
Growth of heterotrophic bacteria was determined  by visual detection
of colonies or turbidity. Results were reported in colony forming units
per mL (CFU/mL).

Isolation  of Microorganisms
   Microorganisms were  isolated from reactors using an enrichment
medium  consisting of  minimal  inorganic salts14 supplemented with
wastes containing the mixture of organics (0.02% total organic carbon)
as the  sole source of carbon.  A series of 500-mL  Erlenmeyer  flasks
containing 200 mL of this medium was prepared, autoclaved, inoculated
with 1  mL of slurry from reactors E and F and incubated at 22 °C. Con-
trol  flasks lacking wastes were also inoculated. Bacterial populations
in the  flasks were measured by  plating  onto minimal inorganic salts
solidified  with purified  agar and  on  nutrient  agar (Bacto,  Difco
Laboratories, Detroit, Michigan). Nineteen microbial isolates were ob-
tained  from the plating studies. Pure cultures of each microbial isolate
were examined with a Zeiss Axioskop light microscope  (Zeiss, West
Germany) for cellular morphology and gram stain reactions. The isolates
were further characterized and identified with a Vitek AMS microbial
identification system (McDonnell  Douglas Health Systems Co., St.
Louis,  Missouri) using the gram-negative GN1 identification card (Vitek
No.  51-1306).

Acute  Toxicity
   One method of defining the potential  toxicity of chemical residues
is the use of bioassays such as the Microtox™ test. A major advantage
of microbial toxicity testing over chemical analysis is the direct assess-
ment of potential biotic impact without extrapolation from chemical
analysis of uncertain completeness.D A Beckman Model 2055 Toxicity
Analyzer (Beckman Instruments, Inc., Microbics Operations,  Carlsbad,
California) was used to measure the toxicity of the liquid fraction of
the wastes to the marine bioluminescent bacterium  Photobacterium
phosphoreum in a temperature-controlled photometer (15 °C). The pro-
cedure for the a>sa> is  detailed in the Microtox™ System Operating
Manual. Bioreactor sample aliquots (7 mL) were placed in 20-mL scin-
tillation vials on Days 0, 7 and 14 and stored in the refrigerator at 4°C
until analysis. A statistical analysis method was used to determine the
percent normalized light decrease for all dilutions.10 The decrease in
toxicity is reported as normalized percent light decrease.

Method of Analysis
  Instrumental analysis methods (GC/MS) were developed to quantify
the major volatile and nonvolatile extractable chromatographable com-
pounds in the waste from each bioreactor. Since some of the wastes
at the site contained large amounts of DCE and TCE, which were absent
in the present samples, 70 uL of these two compounds were added at
day 0 to all bioreactors. This addition resulted in a beginning concen-
tration of 61.1 ug/mL of DCE for all  reactors but D, which contained
86.8 ug/mL. The beginning  concentration for TCE was 70 ug/mL for
all reactors but D, which contained 99.5 ug/mL. Reactor D was  the
only vessel that was sealed immediately after spiking; therefore no loss
of chemical occurred before the time zero samples could be collected.

Volatile Organics Analysis
  Duplicate  samples  were collected  and analyzed at each sampling
period. A 10-mL aliquot of bioreactor sample was pipetted into a W-mL
Pierce vial, and 1 mL of n-dodecane was added to each vial. The vials
were sealed  with Teflon-lined caps.  The samples were vortexed  for
approximately 2 min and the  phases were allowed to separate. The vials
were then  stored at 4°C until further extraction.  The extraction was
completed after bringing the vials to room temperature, shaking them
and withdrawing 0.5-mL samples,  which were placed in  1.6-mL
autosampler vials. An aliquot of this extract was placed with an equal
volume of n-dodecane which contained 100 ug/L benzene-d6 internal
standard. The samples were  analyzed by  split injection on an HP 5985
Capillary GC/MS. The chromatographic column used was a 30-meter
fused silica  J&W DB-5 (250 u) with a wide  bore (0.32-mm I.D.).
Column temperature program was held at 10 °C for 4 min and then in-
creased at  8°C/min to the final temperature of 300 °C. Typically, data
were acquired for 40 min.  Masses were monitored from  10 to 250
Atomic Mass  Units.  The concentrations of  DCE and TCE were
determined by using an internal standard quantitation method. Relative
response factors for these compounds were determined by  analyzing
a standard solution  containing these two compounds. Samples  for
volatiles were not collected after day 3 because  analysis showed 100%
removal by day 1.

Extractables Analysis
  Ten mL  of bioreactor sample were pipetted into a 40 mL Pierce vial
and serially extracted with 20 mL of methylene chloride three times.
After each 20 mL addition, the vial  was agitated and the methylene
chloride was removed. The three methylene chloride extracts were com-
bined and  concentrated to a  final volume of 10 mL. An aliquot of this
extract was added to an equal volume of methylene chloride which con-
tained 100 ug/mL anthracene-dIO internal standard. The samples were
analyzed by splitless injection using an HP 5985 Capillary GC/MS as
previously described. Column temperature program was held at 50°C
for 4 min  and then increased at 8 °C/min to the final temperature of
300°C. Typically, data were acquired for 40  min. Masses were
monitored from 10 to 500 Atomic Mass  Units.  The concentrations of
the major extractable  compounds were calculated by dividing the total
ion areas  of the organic compounds by the  total ion  area  of  the
anthracene-dK) internal standard and by performing the same calcula-
tion using the selected ion areas.  All values are reported on a wet weight
basis and  are not corrected  for extraction efficiency.
  The  experimental  design required that  16  compounds,  in seven
biodegradation reactors, at 10 different days, be analyzed in duplicate.
This requirement resulted in the analysis of 16 compounds in approxi-
mately 100 reactor samples. Approximately two-thirds of these samples
contained  the 16 compounds of interest, with the  remaining one-third
being method blanks, reactor blanks and QA/QC samples  which  did
not contain the total array of analytes. This procedure resulted in the
generation of 3,200 concentration values and 4300 additional values
       B1OTRH \TMHNT
-------
which required  summing,  averaging  and displaying in an efficient
manner. Thus the GC/MS  study was  divided into a data acquisition
part collecting data in the MS system, and a data analysis part trans-
ferring the data to Lotus 1-2-3 and performing calculations. Both parts
of the process were designed to be interrelated and to produce high
quality data in a cost-effective manner.
  Analyte concentrations were calculated by using the total ion (or
selected ion) areas of the analytes,  the total ion (or selected ion) area
of the internal standard and the concentration of the internal standard
to calculate the "Total Ion Concentrations" or "Selected Ion Concen-
trations." Detailed compound identification can be accomplished best
only after all possible isomers of identified compounds are obtained
and retention times  of authentic standards are compared to the reten-
tion times of the components in the waste. However, this detailed iden-
tification was not considered critical to the present study since degrada-
tion profiles of compounds and relative changes in concentration, were
of primary concern. Therefore, compounds which were not uniquely
identified by standard library search  algorithms were identified by
molecular formula and/or molecular weight, when possible.

GC/MS Quality Control

false Positives
   Bioreactors C and G served as Quality Control reactors to which no
wastes had been added. Therefore, analysis of these bioreactor samples
would indicate whether contamination was occurring which would have
resulted in the reporting of false positive values. In addition,  extrac-
tion method blanks were prepared and analyzed in order to detect any
source of contamination in the extraction of samples. No method blanks
contained any of the analytes. Finally, either methylene chloride or
n-dodecane  was analyzed using capillary GC/MS to identify whether
instrument contamination could be causing the measurement of false
positives.  Again, no analytes were detected  in any of the instrument
blanks analyzed.

False Negatives
   An instrumental analysis protocol was developed which assured that
adequate levels of detection and system performance were maintained
so that the incorrect reporting of analytes did not occur. This analysis
protocol included the analysis of a system performance standard which
contained compounds of wide volatility to evaluate chromatographic
performance, and decafluorotriphenylphosphine which evaluated mass
spectrometer performance.  In addition, all bioreactor extracts were
analyzed at random times so that there could be no systematic bias pro-
duced in one set of bioreactor samples. Therefore, in a given set of
analyses, there would be Day 7 extracts from Reactors A and B which
showed the presence of a large number of components which were pre-
sent on Day 0, and also  Day 7 extracts from Reactors E and F which
showed the absence of almost all of these components. These data were
analyzed in  a blind manner so that  no bias would result in human in-
terpretation  where preconceived biasses may exist.


RESULTS

Biodegradation  of  Chromatographable Chemicals
  Analytical  measurements  indicated  rapid   removal  of  all
Chromatographable compounds in the bioactive reactors (Table 1). The
data for the average total ion (TI) concentrations for duplicate samples
for Bioreactors A, B, D, E  and F are shown in Figure 1. Reactors C
and G are not included in this Figure, since they served as quality con-
trol reactors  and did not contain any of the analytes of interest. Three
disappearance patterns are evident. Reactors A and B, sterile duplicates,
showed some degradation within the first 7  days of the experiment.
This degradation  may be due to unidentified abiotic loss, but is thought
to be partially due to microbial activity,  as evidenced by an increase
in microbial  cell  counts  (Table   2).  It  is  believed  that these
microorganisms contributed to the overall TI removal of 49.5% for
Reactor A and 48.8% for Reactor B. The second addition of HgCLj
eliminated further degradation in both reactors.
 ^
  O)
  U

  O
 O
 O)
 <
                            Figure 1
        Average Total Ion (IT) Concentrations for all Bioreactors
                             Table 1
     Biodegradation (% removal) of Nonvolatile Chromatographic
             Chemicals at the End of the Study (Day 14)
                                Percent Removal in Bioreactors
Compound*
Identification
#01 =
#02 =
#03 =
#04 =
#05 =
#06 =
#07 =
#08 =
#09 =
#10 =
#11 =
#12 =
#13 =
#14 =
#15 =
#16 =
#17 =
anthracene-dlO
biphenyl
ethylbiphenyl isomer #1
ethylbiphenyl isomer #2
bibenzyl
methyldiphenyl isomer
diphenylpropane isomer #1
diphenylbutane isomer #2
diethylbiphenyl isomer #1
diethylbiphenyl isomer #2
ethylenebiphenyl isomer
phenanthrene
1 -phenylnaphthalene
2-phenylnaphthalene
elemental sulfur
diphenylthiophene isomer # 1
diphenylthiophene isomer #2
Total Cone, of all SI Compounds
Total Cone, of all TI Compounds

A
0
£99.0
93.4
70.2
90.2
80.0
51.1
40.9
42.8
34.2
30.8
24.7
15.3
13.2
-37.5
29.7
27.0
56.6
49.5

B
0
£99.0
93.2
68.9
88.6
78.4
42.3
9.7
35.8
23.5
12.9
£99.0
-9.8
-9.6
- 206.3
11.8
19.8
58.1
48.8

D
0
63.9
30.2
23.4
32.8
27.1
21.4
21.7
18.3
14.4
16.6
85.4
7.1
8.7
£99.0
19.5
17.9
29.5
27.3

E
0
£99.0
£99.0
£99.0
2:99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
95.2
98.9
£99.0
96.0
93.9
98.9
99.5

F
0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
£99.0
91.8
£99.0
£99.0
94.2
92.8
99.1
99.5
*    compound identification was done with selected mass.

SI    Estimated level of detection is 0,1 ng/mL for most compounds.

TI    Estimated level of detection is Ijjg/mL for most compounds.
                                                                                                                   BIOTREATMENT   795
-------
                              Tabk2
             Enumerations of Microorganisms (CFTJ/mL)
 Buxeacux
               Day 1 (CFU/mL)   Day 7 (CFU/mL) Day 14 (CFU/mL)
A
B
C
D
E
F
G
Control"
<]
<1
<]
3.0 X 105
> 3.0 X 105
> 3.0 X 105
2.0 X 103
<1
5.5 X 102
>3X 104
> 3.0 X 102
4.7 X 105
2.3 X 107
I.OX 107
> 3.0 X 102
<1
<1
<\
1.4 X 105
6.3 X 105
2.0 X 107
2.8 X 107
5.5 X 104
<1
 Samples too numerous too count arc reported as > the highest tested dilution.
 Values are averages of duplicate measurements.
 * A control was plated using sterile dilution water.


   Reactor D showed 27.3% TI removal.  Since it  was sealed, volatile
components were prevented from escaping and reoxygenation was
eliminated. The minor degradation which did occur could be attributed
to microorganisms utilizing the dissolved oxygen  in the aqueous frac-
tion as an electron acceptor for the metabolism of some of the organics.
   Reactors E and F showed TI removal  rates of 99.5%. A lag phase
required by the microbiota to adapt to the system explained the low
degradation rates during the first day. Almost linear degradation rates
were  observed from Days  2 to  5. Since neither the sealed nor the
sterilized reactors exhibited similar removal rates under equal condi-
tions, the degradation was  interpreted as being microbial.
   Reasonably good  agreement was obtained between the TI and SI
chromatographable measurements. The response factors for the SI con-
centrations are slightly lower than for the TI concentrations (Fig. 2).
The detection limits were 1 ug/mL for TI and 0.1 ug/mL for SI con-
centrations. Seventeen compounds were identified with Selected Ion
Mass (Table 1). The  first compound, anthracene-dlO, was used as an
internal standard in all cases. Biphenyl  (Compound  #02) was completely
removed in Reactors A, B, E and F, however at different rates. While
6 and 5 days were needed in Reactors A and B, respectively, to remove
biphenyl >99%, it degraded in 3  and 2 days, respectively, in the Bioac-
tive Reactors E and F to below the detection limit. The total TI removal
of biphenyl in Reactor D was 61.0%. Since volatilization  was excluded
in this system, it is assumed that biphenyl  was microbially degraded
in Reactor D. However, biphenyl may have partially degraded and/or
partially volatilized in Systems A, B,  E and F. Compounds #2-12 and
compound  #15 (elemental sulfur) were removed 100% in Reactors E
and F, while they partially  persisted  in Bioreactors A,  B and D.
   Plots  of the chemical concentrations  over time  are presented  for
2-phenylnaphthalene  and phenanthrene as  typical  examples
demonstrating the biodegradation of all  16 chromatographable com-
pounds  (Figures  3 and 4). 2-Phenylnaphthalene and phenanthrene
degraded rapidly below the  detection limit. Previous literature reports
indicate  the ability of bacteria and fungi to utilize naphthalene and
phenanthrene as a source of carbon.2-1-13 It was expected, therefore,
that these compounds or isomers would be  biologically oxidized. The
two compounds typically were not removed in the  sterile and sealed
bioreactors with the exception of phenanthrene in sterile reactor B which
exhibited significant  microbial activity by  Day 7. This  result clearly
indicated that the compound was  biodegraded and not volatilized. The
estimated half-life under the given environmental conditions was less
than 36 hours. If one takes  into consideration the fact that the experi-
ment  consisted of a batch microbial system  with a small amount of in-
oculum,  the initial lag phase where no degradation occurred is not unex-
pected.  Therefore it appears possible to design a system that would
reduce the lag phase and the amount of time required to degrade the
chemicals.
                                                                               220 -i
                                                                                                                        D Avg TI
                             Figure 2
             Average Total Ion and Selected Ion (TI and SI)
                  Concentrations for All Bioreactors
  The presence of elemental sulfur was monitored by GC/MS (Fig.  5).
It was observed to rapidly disappear from the bioreactors containing
bacteria. Sulfur is required as an essential constituent for bacterial cell
growth and used in the synthesis of amino acids. Most bacteria assimilate
sulfur in the form of soluble sulfates or  reduced organic sulfur com-
pounds, but elemental sulfur can be utilized.5-16 The process of the ox-
idation of elemental sulfur has been  studied in detail.5 In all the reac-
tors containing bacteria (D, E and F), elemental sulfur was completely
removed, while it persisted in the Sterile Controls A and B (Fig. 5).
Some sample variability for Reactors A and B may be due to the fact
that elemental sulfur is insoluble, but it  was consistently observed in
all studies that it was removed in active bioreactors.  It is thought that
the sulfur  was  microbially  converted  to a form  which  was  not
chromatographable.
  The data obtained on the removal  of volatile compounds (DCE and
TCE) indicate that these chemicals are in  fact removed by volatiliza-
tion and not biodegradation under the conditions of this test (Fig. 6).
Concentrations of both chemicals in Bioreactors A, B, E and F  dropped
to less than 10 ug/mL (initial concentration was 70 ug/mL) after 1 hour.
However, the concentrations of both DCE and TCE in Bioreactor D
were only slightly below the initial concentration of 99.5 ug/mL. This
result was interpreted  as evidence  that these two compounds were
volatilized and not biodegraded. No data are shown for DCE, Reac-
tors B and F, in Fig. 6, because the  values were less than the method
limit of detection (1  ug/mL).
Enumeration of Microorganisms
  The enumeration of microorganisms in Bioreactors E and F increased
approximately two orders of  magnitude from Day 1  to Day 7  and
       BIOTREATMENT
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remained in the order of 107 CFU/mL over the last 7 days (Table 2).
The highest enumeration of heterotrophic bacteria occurred in Reactors
E and F and correlated with the highest compound removal in these
reactors. All other reactors that had received the same initial nutrient
amendment as E and F did not exhibit such high cell counts. These
data indicated that the bacteria in Reactors E and F used the organics
present in the waste as a carbon source for cell growth. Reactor  D
exhibited a steady increase in enumerations of microorganisms over
the time of the experiment. The biomass  in this reactor doubled from
the first to the last day of the experiment, suggesting that nutrient sources
were available to support growth. The microbial population in Reactor
G also increased over time but remained below the reactors containing
waste.

Acute Toxicity
  The  Microtox™ test measures the   toxicity of  chemicals to a
phosphorescing bacterium by measuring a loss in its ability to produce
light. The Bioactive Reactors E and F exhibited 82.2% and 78.2% light
loss,  respectively, on Day 0, while on Day 14, the percent light loss
was only 13.9% and 18.1%, respectively.  Thus, these reactors showed
the highest reduction hi toxicity over time. These data correlated well
with results obtained  using GC/MS which showed the largest reduc-
tion in chemicals for these two reactors. Reactor G, like Reactor  C,
served  as a quality control. The only difference between Reactors C
and G consisted in the amount of surfactant added. Reactor C received
the same amount of surfactant as all other bioreactors;  Reactor G did
not receive surfactant. This difference explains the lack of toxicity and
light loss over time in Reactor G while Reactor C exhibited some toxicity
at Day 0 as evidenced by a 57.4% light loss.  However, this light loss
dropped to 23.2% on Day 14, suggesting metabolism of the surfactant
by bacteria hi the reactor.

                                                   Bioreactor
      160 -i
120
                            DAY
                          Figure 4
        Phenanthrene Removal  Expressed as a Percentage of
         Day 0 Using Average  Selected Ion Concentrations
                                                                              600
                               DAY
                            Figure 3
        2-phenylnaphthalene Removal Expressed as a Percentage
         of Day 0 Using Average Selected Ion Concentrations
                                                                                                                     10    12    14
                           Figure 5
         Disappearance of Elemental Sulfur Expressed as a
   Percentage of Day 0 Using Average Selected Ion Concentrations
                                                                                                                    BIOTREATMENT    797
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                             Table 3
                   Microtox Normalized % Light
                        Decrease Over Time
   Bioreaclor
                      DayO
Day 7
Day 14
A
B
C
D
E
f
C
100
100
57.4
77.66
77.9
83.0
1.7
75.3
80.6
14.6
74.1
25.1
23.9
0
ND'>
ND")
23.2
64.4
13.9
18.1
1.1
         Daia are presented for the highest tested dilution mixed with Microtox diluent in a

         1:1 ratio

         ND=  Not Determined


                                                     Bioreactor
     80
     70
     60 -
 O>
 a.  50
 c
 O   40
4^
 (0
 £  30
 O
 O
 C
 O  20
O
    10 -

b
                1,2-DCE
        1,1,2-TCE
                         COMPOUND
                              Figure 6
             Concentrations of Volatile Compounds One Hour
                        After the Study Started
  The normalized percent light decrease for Days 0, 7 and  14  is
presented in Table 3. Both sterile controls. Reactors A and B, exhibited
a 100% light decrease on  Day 0 due to the presence of HgCLj. The
toxicity of these samples  decreased 20% to 25% by  Day 7, which
indicates  a  lack of complete sterility  and correlates  well with the
microbial growth in these bioreactors and the degradation shown  in
Fig. 1. A  second addition of HgCl, on Day 7 was necessary to insure
sterility during the remaining 7 days. Reactor D showed a minor decrease
in toxicity correlating with a small amount of degradation occurring
in this reactor.
Characterization of Microorganisms
  After approximately 3 to 5 weeks of enrichment, a clear difference
in growth and number of colonies between the plates from the test flasks
(with waste) and plates from the control plates (no waste) was evident.
Nineteen microbial isolates were initially obtained and studied by light
microscopy. Colonial morphologies ranged from yellow to white and
from oval to circular with a predominance of round white and bright
yellow colonies. All isolates were nonfermenting obligate aerobes and
gram negative short rods with the exception of one strain which was
a gram positive rod. This gram positive strain, however, was always
found in combination with a gram negative culture and could not be
isolated into a pure culture.
  Four of the  isolates were  tentatively identified as Acinetobacter
calcoaceticus (98%, 98%, 91% and 99% probability), two strains as
Pseudomonas vesicularis (96% and 99% probability) and one strain
as Pseudomonas paucimobilis (99% probability). Tentative identifica-
tion of the other strains showed 49% probability for Flavobacterium
sp. and 23% probability for Pseudomonas stutzeri. Eight isolates could
not be identified by the Vitek system.

DISCUSSION
  The concept of using biological treatment as a remediation technology
for  contaminated waste is an  attractive idea because of the potential
cost savings. Additionally, bioremediation offers the advantages  that
the  chemicals of interest are destroyed, future liability is eliminated
and  the  remediation can be done on-site.  The present study  has
demonstrated that 16 chemical constituents associated with styrene tar
polymers can be removed in a biological treatment system to acceptable
levels.  Acceptability of this process is based on: (1) reduction of key
chemical constituents to acceptable levels;  less than  1.0 mg/kg  was
achieved for 16  chromatographable compounds, (2) significant reduc-
tion in the toxicity of the soil slurry to Photobacterium phosphoreum
as measured in  the Microtox test; (3)  demonstration that biodegrada-
tion is  the primary route of degradation, not volatilization for most of
the   16  chromatographable  chemicals;  (4)  rapid  growth  of
microorganisms in the active  treatment reactors; and  (5) demonstra-
tion of removal  rates that are rapid enough to allow for this bioprocess
to be scaled up and used on a field scale.
  It is recognized under the test conditions used that chlorinated solvents
were most likely air stripped and the lower molecular weight organics
such as biphenyl were at least partially air stripped. Full-scale use of
this  technology would most  likely require carbon adsorption of the
bioreactor gasses.
  It was demonstrated in this study that the indigenous microflora was
adapted to the system and capable of rapidly metabolizing the major
chromatographable compounds present. The persistence of most of the
compounds in the sterile control reactors and the sealed reactor was
interpreted as proof that losses of these compounds in the reactors con-
taining the bacteria can best be explained by biodegradation and not
volatilization. No new chromatographable components were detected
during the study, indicating that no new chromatographable degrada-
tion products were produced  during  biodegradation.  It is not clear,
however, if one or several dominant species were responsible for the
metabolism or if cometabolism played a major role. It is not known
what role the individual isolates played in the overall degradation
processes, but it does warrant further investigation. Since cometabolism
may play a significant role, chemical degradation may be dependent
on the presence  of all or a mixture of some members of the consortium.
  The data presented in this paper have been used to justify a field pilot
study for a biodemonstration of this  method. The data suggest  that
adequate treatment could be achieved on a full-scale level using a 4-day
batch treatment of a 20% soil/water  slurry.


ACKNOWLEDGEMENTS
  We thank W. J. Renaudette, B. J. Simpson and  M.  W.  Tucker for
their excellent  technical assistance and Michael A.  Heitkamp for
reviewing the manuscript.
       B1OTRE\TMI NT
-------
REFERENCES
 1.  Atlas, R.M., (Ed), Petroleum Microbiology. MacMillan Publishing Com-
    pany, New York, NY, 1984.
 2. Atlas, R.M., "Microbial  degradation  of petroleum hydrocarbons:  an
    environmental perspective," Microb. Reviews, pp. 180-209, 1981.
 3.  Bianchini, M.A., Portier, R.J., Fujisaki, K., Henry, C.B., Templet, P.H.
    and Matthews, J., "Determination of Optimal Toxicant Loading for Biological
    Closure of a Hazardous Waste Site," In Aquatic Toxicology and Hazard
    Assessment, Ed. W. J. Adams, G. A. Chapman and W. G. Landis, pp.503-516,
    10th Volume, ASTM  STP 971,  1988.
 4. Bossert, I., Kachel, W.M. and Bartha, R., "Fate of hydrocarbons during
    oily sludge disposal in soil," Appl. and Environ. Microbiol., 47, pp. 763-767,
    1984.
 5.  Brock, T.D, Thermophitic Organisms and Life At High Temperatures. Springer
    Verlag, New York, NY, pp. 126-148, 1978.
 6.  Dibble, J.T. and Bartha, R.,  "Effect of environmental parameters on the
    biodegradation of oil sludge," Appl. and Environ. Microbiol., 37, pp. 729-739,
    1979.
 7.  Ellis, W.D., Payne, J.R. and MacNabb, G.D., Treatment of Contaminated
    Soils  With Aqueous Surfactants, EPA Rept. No. 600/S2 85/129,  U.S. EPA,
    Washington, DC, 1985.
 8. Elsavage, R.E. and Sexstone, A.J.,  "Biodegradation of a dilute waste oil
    emulsion applied to soil," Journ. oflnd. Microbiol. 4, pp. 289-298, 1989.
 9. Fedorak, P.M. and Westlake, D.W.S., "Microbial degradation  of organic
    sulfur compounds in Prudhoe Bay crude oil," Can. Joum.  of Microbiol.
    29, pp. 291-296, 1983.
10. Finney, D.J., Probit Analysis, 3rd ed., Cambridge University Press, Lon-
   don,  1971.
11. Ghisalba, O., "Microbial degradation of chemical waste: an alternative to
   physical methods of waste disposal," Experientia 39, pp. 1247, 1983.
12. Greene, J.C., Miller, W.E., Debacon, M.K., Long, M.A. andBartels, C.L.,
   "A comparison of three microbial assay procedures for measuring toxicity
   of chemical residues,'M/r/i. Environ. Contam. lexical. 14, pp. 659-667, 1985.
13. Heitkamp, M.A. and Cerniglia, C, "Effects of chemical structure and ex-
   posure on the microbial degradation of polycyclic aromatic hydrocarbons
   in freshwater and estuarine ecosystems," Environ. Tax.  and Chem. 6, pp.
   535-546, 1987.
14. Leadbetter,  E.R.  and Foster, J.W.,  "Studies on some  methane utilizing
   bacteria," Archiv fa_ar Microbiologie 30, pp. 91-118, 1958.
15. Portier, R., Bianchini, M., Fujisaki, K., Henry, C. andMcMillin, D., "Com-
   parison  of  effective  toxicant  biotransformation  by  autochthonous
   microorganisms and commercially available cultures in the in situ reclama-
   tion of abandoned industrial sites," Schr.-Reihe Verein WaBoLu 80,  pp.
   273-292, (Gustav Fischer Verlag, Stuttgart, West Germany- 1988.
16. Stanier, R.Y., Adelberg, E. A. and Ingraham, J., The Microbial World, Mac-
   Millan Publishing Company, New York, 1976.
17. ASTM Standard Method F 488-79,  Test Method for Total Bacterial Count
   in Water, in ASTM Standards on Materials and Environmental Microbiology,
   1st Ed.  American Standards for Testing and Materials,  Philadelphia, PA,
   pp. 176-179, 1987.
18. Hughes, B.M., McKenzie, D.E., Bianchini-Akbeg, M., Adams, W.J., Simp-
   son, B.J., Lee, J.M. and Kimerle,  R.A., ASMSProc. 36, pp. 288-289, 1988.
                                                                                                                               BIOTREATMENT    799
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                 In  Situ  Bioremediation  of TCE  and Other  Solvents

                                                Michael J.K.  Nelson, Ph.D.
                                                        John  A.  Cioffi
                                                       Harlan S. Borow
                                                     ECOVA  Corporation
                                                    Redmond,  Washington
 ABSTRACT
   In situ bioremediation of industrial solvents, hydrocarbons, and pes-
 ticides has been demonstrated as an effective alternative to aboveground
 treatment using physical processes such as air stripping and carbon ad-
 sorption. These competing physical cleanup methods do not destroy
 the compounds of concern but merely transfer them from one medium
 to another. Biological treatment is an alternative treatment process that
 could result in complete destruction of TCE, hydrocarbons and related
 compounds. As an overview, in situ biological treatment techniques will
 be presented followed by a discussion of several field case histories.
   Chlorinated solvents such as TCE are  ubiquitous and  persistent
 groundwater contaminants. Currently, physical processes such as air
 stripping and carbon adsorption are used to remove these compounds.
   Biological degradation was demonstrated by ECOVA in a continuous-
 flow bioreactor with influent TCE concentrations of 1 to 5 mg/L being
 degraded to below detectable levels. The results indicate the utility of
 the system for field applications using surface bioreactors in pump-and-
 treat processes. Subsequent laboratory studies identified conditions that
 would maintain TCE and thus be suitable to use in situ. Utilizing these
 conditions, ECOVA tested a pilot system in the field for developing and
 maintaining TCE-degradative activity within an aquifer. Initial concen-
 trations ranged from 2500 to 3500 ug/L TCE. After 24 hr of treatment,
 a downgradient monitor well had less than 500 ug/L TCE; the concen-
 tration decreased less than 100 ug/L TCE  after 7 days  of operation.
 The test results indicate that in situ biological removal of TCE can be
 achieved in subsurface aquifers.
   ECOVA has designed and installed an in situ bioremediation system
 for groundwater contaminated with 4-chloro-2-methyl-phenol (4C2MP).
 Prior to the design and installation of the bioremediation  system,
 hydrogeological and microbiological evaluations were  conducted to
 determine if in situ bioremediation was a viable treatment technology
 for the contaminated  groundwater. The microbiological evaluation
 demonstrated that the groundwater contained a high existing 4C2MP
 biodegradation  potential.  Under laboratory conditions, the existing
 microorganisms in groundwater samples removed from the site generally
 reduced the 4C2MP concentration by more than 90% after 7 days of
 incubation. The hydrogeological evaluation demonstrated that aquifer
 permeabilities and subsurface mass transport parameters were amenable
 to in situ bioremediation. A groundwater model for the site was deve-
 loped to determine optimum spacing of the groundwater recovery and
 rcinjection wells. The in situ bioremediation system consists of aera-
 tion and recycling of recovered groundwater to stimulate the existing
 microorganisms to degrade the 4C2MP. In the initial 3  mo of opera-
 tion, the lotal contaminated plume exhibited a 25% to 35% reduction
 in size; after 6 mo. a 50% reduction  was  observed.
   In MIU biotrcaimeni is being implemented in a multicomponent
cleanup program currently underway at a former marketing fuel terminal
in the Western United States. Two separate zones of contamination are
being treated in situ via series of trenches and wells for recovery and
recharge of groundwater contaminated with petroleum hydrocarbons
at a mean concentration of 2,660 mg/L. The primary contaminants are
weathered gasoline and diesel. Recovered water is pumped to the sur-
face bioreactor where free product is reclaimed, contaminant concen-
trations are reduced and the treated water is amended with oxygen and
specific nutrients and recharged into the subsurface. Soil oxygenation
is also being used to provide oxygen to the zones where in situ treat-
ment is underway and remove limited amounts of volatile compounds
from the shallow unsaturated soil above the in situ biotreatment zone.
This remedial program will reduce total petroleum hydrocarbon con-
tamination from the mean concentration of 2,660 ppm to less than 15
ppm cleanup criteria for groundwater. To date, the in situ system oper-
ation is effectively producing biodegradation in the subsurface.
INTRODUCTION
  Groundwater beneath industrial sites is commonly contaminated with
a variety of organic chemicals.' The contaminants originate from sur-
face lagoons, tanks and pipelines and percolate into aquifers where they
migrate in both the free and dissolved phase. The standard approach
for solving this problem is to install a series of recovery wells which
pump the contaminated groundwater to above ground treatment systems.
The most commonly used treatment systems are air strippers and/or
activated carbon filters.
  Both of these treatment methods are really transfer technologies; that
is,  they transfer the  contaminants from the  water  into either the
atmosphere or onto the carbon. Alternatives to this standard approach
are required for two reasons: (1) transferring the contaminants merely
results in contamination of another medium, and (2)  pump-and-treat
technology fails to achieve site cleanup goals. The U.S. EPA has recog-
nized that while pump-and-treat systems  are generally effective in con-
taining contaminant plumes, full system optimization (pumping rates,
screened intervals and well locations) and cleanup goals have not been
attained.2 The in situ biological removal of organic groundwater con-
taminants addresses both concerns.  The contaminants are degraded (not
transferred to another medium) and,  thus, more efficiently removed
from  the subsurface.
  The successful implementation of in situ degradation systems requires
an  in-depth understanding of the  subsurface environment generally
followed by a  three-phased development program: (1) laboratory treat-
ability evaluation, (2) pilot-scale demonstration and (3) full-scale system
implementation. This approach ensures that only the most effective treat-
ment  program is implemented for full-scale remediation.
800   BIOTREATMENT
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THE SUBSURFACE ENVIRONMENT
  The subsurface groundwater environment consists of three compo-
nents; physical,  chemical and biological. Each component plays an
integral part in the evaluation, design and implementation of in situ
treatment systems. The physical system governs the rate at which ground-
water contaminants move through the subsurface and the ease with which
they will be removed. Contaminant chemistry defines the geometry and
behavior of the contaminant plume while an assessment of subsurface
microbiological  activity determines the presence  of contaminant
degrading microorganisms  and the subsurface oxygen conditions. To
engineer an  effective  in situ biotreatment  system, each  of  these
components must be defined and understood.

Hydrostratigraphy
  Subsurface geological strata are defined by  drilling soil borings and
collecting soil/rock samples. Stratigraphic profiles are developed that
delineate various hydrostratigraphic units: water bearing aquifers and
low permeability aquitards. Measurements of hydraulic gradients and
conductivity are used to determine groundwater flow velocities and the
rate of contaminant plume  migration.

Hydrochemistry
  The chemical  compositions of the aquifer matrix and the ground-
water are defined through the analysis of soil and groundwater samples.
The ability of the contaminants to dissolve and migrate through the
aquifer is determined together their ability to absorb on the solid matrix.

Hydrobiology
  Microorganisms represent the biological component of the subsur-
face environment.  To survive, they must obtain a variety of inorganic
substances, carbon and a source of energy. When these conditions are
met,  the microbial population flourishes and in so doing transforms
the chemical contaminants to harmless byproducts.

IN SITU BIOTREATMENT
  In situ bioremediation is the controlled management of microbial sub-
surface processes. In situ systems generally utilize aerobic processes
and involve the introduction of oxygen, nutrients and sometimes specific
microorganisms, to the subsurface. Two key  criteria for hi situ treat-
ment are: (1) a permeable matrix to allow rapid oxygen and nutrient
transport and (2) contaminant-degrading microorganisms.
  In  situ treatment systems involve  either: (1) pumping the contami-
nated groundwater to the surface from a downgradient recovery well,
passing it through a surface treatment unit, amending it with nutrients
and oxygen and reinjecting it into the subsurface via an upgradient
injection well; or (2) directly stimulating microbial activity in the aquifer
via direct injection.

 PROGRAM DEVELOPMENT
   The key to successful hi  situ biotreatment of contaminated ground-
 water is to understand the complete hydrobiological system. For example,
 some hydrogeologic environments may contain sufficient nutrients,
 others may not require the addition of oxygen (if anaerobic conditions
 are preferred), or low permeability may cause accumulation of biomass
 in the treatment zone. An in situ program generally involves three steps:
 (1) laboratory treatability study,  (2) pilot program and (3)  full-scale
implementation.

Treatability Studies
   The purpose of a treatability study is to determine the:
 • Biodegradability of the groundwater contaminants
 • The rate at which they degrade
 • The amounts of oxygen and nutrients required to sustain the reaction
• The interaction between the degrading compounds and the aquifer
   media (plugging potential).
  There are two basic types of treatability studies: (1) the flask study
and (2) the column study.
  For flask studies, the contaminated groundwater is analyzed for
organic, inorganic and metallic compounds. A minimum of three test
conditions are generally performed over a period of 6 to 8 wk. During
this time, the tests are periodically analyzed to determine the rate of
biological degradation. The basic test conditions are: sterile, unamended
and nutrient-amended. Typical data are shown in Figure 1. At the com-
pletion of the study, a preliminary treatment design is prepared that
specifies the anticipated rate of contaminant reduction (cleanup tune)
and the amounts of oxygen and nutrients required.
  Column studies employ the same approach as flask studies with the
added benefit of measuring the effect of the aquifer media on the bio-
logical reactions. Glass columns are filled with soil samples, and con-
taminated groundwater  is percolated through the columns;  sterile and
nutrient-amended columns also are evaluated. While the columns do
not accurately recreate actual in situ  conditions, they do provide an
indication of the likely effects of compound adsorption and precipitation.

System Design
  Thought must be given to the design of the in situ system such that
several key questions are addressed. The treatability study determines
if the site contaminants are biodegradable and the rates at which they
degrade under laboratory conditions.  The next step is to run a field
pilot test to confirm these experimental results under "real "conditions,
quantify the effects of dilution on contaminant concentrations and evalu-
ate hardware components that will be used in the full-scale system.

Pilot Program
  The pilot test must be capable of simulating full-scale operations and
yet be brief enough to obtain data that can be fed into the system design.
The ideal setup for the in situ program is to monitor groundwater flow
and  quality up and downgradient of the injection location.  The
monitoring wells should be located within several days hydraulic travel
                 ACETONE
                                         LEGEND:
                                         0	Killed
                                         O	A«rat»d
                                         H	Aerottd-Nutrlent
                Tlmo (days)
                              Figure 1
            Compound Concentrations in Aerobic Culture Flasks
                                                                                                                   BIOTREATMENT    801
-------
 tune of the injection well so that the biological process can be monitored
 rapidly following injection.
   Before performing the biological pilot test, a preliminary test using
 clean, unclorinated water should be run without oxygen and nutrients.
 This test determines the potential effects of water injection (dilution)
 on contaminant concentrations and is used as a base line against which
 the effects of biological test  are compared. A conservative tracer can
 be used at this stage to help define  groundwater velocities and flow-
 paths in the vicinity of the injection well and identify potential zones
 of anisotropy within the aquifer and  hence the ability of the feed stock
 to reach the contaminants.

 Full-Scale System
   The full-scale system must be capable of degrading the entire plume
 without causing the spread of contaminants through pumping and
 injection.  For complex sites, this  information can be obtained by
 simulating a variety of scenarios using computer models.  The model
 aids in locating injection and recovery wells and estimating cleanup time.
   A series of case histories is presented  to illustrate the details of the
 three steps of an in situ program. Separate projects  were selected  to
 illustrate the application to different organic contaminants.

 CASE HISTORY: PILOT-SCALE DEMONSTRATION
   The aerobic  biodegradation of trichloroethylene  (TCE) has been
 demonstrated in laboratory  treatability  tests.4  A  pilot program was
 designed to demonstrate the viability of using this process in situ.5
   The test site is underlain by a thick and extensive sand aquifer (Up-
 per Aquifer) that contains two zones (shallow and deep) contaminated
 with TCE. The  pilot program was performed upgradient of the plant
 production well  N-l. This well  pumps 200 gpm from the deep zone
 of the Upper Aquifer and runs the effluent through a carbon filter be-
 fore delivering  it to the plant water system. An injection  well (EI-1)
 and up (EU-1) and downgradient (ED-1, M-1A) monitoring wells were
 installed for the  test program. Figure 2 shows the locations and layout
 of the test wells.
   A tapline, installed downstream of  the N-l carbon unit, conveyed
 clean, unclorinated water to an aeration column, nutrient/bacteria feed
 system and into  the Upper Aquifer via injection well EI-1. To ensure
 a  maximum feed rate,  the delivery  zone was vertically restricted by
 means of  an inflatable packer.  Dedicated,  submersible, air-driven
 sampling pumps were  installed  in monitoring wells ED-1  and M-1A.
   A two-phased  pilot program was implemented. Phase 1 involved the
 injection of TCE-free water  containing a sodium chloride tracer into
 the aquifer to quantify the effects of dilution on groundwater TCE con-
 centrations. Phase  2 involved the injection of oxygen, nutrients and a
                                     IfCTNO
                                       __	, in.
                                                      0  *^*-u- •«-
 strain of TCE-degrading bacteria (G-4) into the aquifer to quantify the
 effect of in situ microbial degradation of TCE.

 Phase 1   Tracer Test
   Sodium chloride was selected as the tracer; an increase in specific
 conductance in the monitoring wells would indicate the migration of
 the tracer. The saline solution was fed to the water stream which was
 injected into the well (EI-1) at a rate of 5 gpm. Before starting the test,
 base line conductivity measurements were taken in the three monitoring
 wells; injected water was detected in both the up and  downgradient
 monitoring  wells.  Groundwater velocity in the lower permeable unit
 was calculated to range between 2 and 5 ft/hr. This figure was deter-
 mined by dividing the time taken for the first occurrence  of tracer at
 the two downgradient wells by their respective distances from the in-
 jection well.
   The issue of dilution is a key point in verifying the validity of the
 in situ biotreatment process. TCE values were plotted versus conduc-
 tivity to determine if there was a correlation between TCE and salt con-
 centration. An increase in conductivity would parallel the ingress of
 the injected water. If the freshwater injection was diluting the contami-
 nated groundwater, then a decrease in TCE levels could be expected
 to correspond with an increase in conductivity.
   By  calculating the  daily flow of groundwater in injection zone and
 comparing it with the amount of water injected, it is possible to calcu-
 late the expected dilution effect. The receiving zone had  a saturated
 thickness of 14 ft and a width of 20 ft (minimum, based on the appear-
 ance of tracer at all monitoring wells), an effective porosity  of 25%
 and a flow velocity of 48 ft/day. Based on these data, approximately
 25,000 gal/day (gpd) were flowing through the receiving zone. By com-
 parison, the injection stream was run at a steady rate of 5 gpm (7,200
 gpd) representing 29% of the flow into which it was placed. Based on
 this calculation, a 30% decline in TCE levels could be ascribed to
 dilution in ED-1, the directly downgradient well. No evidence of dilu-
 tion was seen in wells EU-1 or Ml-A. By contrast, the overall reduction
 (95%) in TCE values achieved  during the subsequent biological test
 far exceeded the effects of dilution.
  Direct measurements of the injected salt concentrations were not made
 in Salt Test  1 and therefore dilution estimates could only be approxi-
 mated. In Salt Test 2 influent salt concentration was measured, allowing
 the calculation of dilution at the monitor wells. The results of the test
 are presented graphically in Figure 3. The time-weighted average con-
 centration of the saline feed was determined by weighing the data points
 using  the length of time between the readings.  Using the time-weighted
 average smoothed the injection concentration data that would  improperly
 skew  the test results.
  In Salt Test 2, Wells ED-1 and  EU-1 recorded the greatest break-
through of salt solution from the injection well EI-1. Well Ml-A showed
                            Figure 2
                Upper Aquifer. Deep Hydrochemistry
                              Figure 3
                          Sail Injection Test
Mi;    H10TR!--\TMFNT
-------
very little breakthrough (one peak at 500 mg/L over background).
Dilution (of groundwater) was calculated from the following formula:

   DILUTION  = (SAMPLE CONC.-BACKGROUND CONC./
        (INJECTION CONC. BACKGROUND CONC.)         (1)

  Figure 4 represents the calculated percent dilution during the test for
all the wells. Dilution in the upgradient and downgradient wells (EU-1,
ED-1) was the most significant; the greatest calculated dilution was 40%
and only then for one sampling. Well Ml-A showed only minimal dilu-
tion effects of the injected water, less than 13%. These data suggest
that dilution is a very localized process and would become insignifi-
cant during full-scale operations. The large fluctuations are due to fluc-
tuating water demands by production well Nl. Time weighted averages
of dilution calculated for wells ED-1 and EU-1 (not including the lag
phase)  were 23% and 20%, respectively.
  From the Salt Test 1 data we calculated that dilution by the injection
stream would account for a 29% decrease in TCE plume concentra-
tions. This number was calculated using flowrate ratios between the
injection stream and groundwater flow in the aquifer.  However, no data
were taken during the first test on the exact salt concentrations being
injected; therefore, the exact dilution could not be calculated. In the
second test, we monitored the salt concentrations being injected through-
out the test, this allowing exact concentrations to be  calculated.
Phase 2 - Biotreatment Test
   The  in  situ biotreatment system utilized the same injection and
monitoring wells and the same injection rate (5 gpm) as the tracer test.
Clean unchlorinated water was injected for 1 day; nutrient feeds were
initiated the following day. \forious additions were made to the recharge
water to stimulate degradation of TCE. The water was oxygenated and
both inorganic and organic nutrients were introduced into the feed. In
addition, a culture of strain G4 was added during the  initial phase of
the test. Nutrients and oxygen were added continuously for 6 days.

Oxygen Concentrations:
   The addition of oxygen to the feed maintained high levels of oxygen
downgradient during the test period,  ensuring the necessary aerobic
conditions for treatment. The range of oxygen concentrations from in-
itiation of the test to termination of feed is summarized in Table 1 for
the three monitoring wells.  As expected, as treatment continued and
microbial activity was expected to increase, the oxygen levels decreased.
However,  at no  time did oxygen concentrations decrease to levels
approaching anaerobic  conditions.
                            Table 1
   Range of Oxygen Concentrations During the Pilot Treatment Test
    Well                       Oxygen Concentration (mg/L)
                              Min                 Max
    ED-1                       4.0                  14.6
    Ml-A                       4.0                  12.3
    EU-1                       2.8                  12.5

 Microorganisms:
  The monitoring wells were periodically tested for the presence of
 strain G4 suing a semi-selective plate count method. These results in-
 dicate that very low levels of strain-G4-like microorganisms were already
 present in the aquifer. The results for the following 5 days showed less
 than 103 cfu/mL of organisms in all three monitoring wells.
  Detectable increases in G4-like microorganisms were first detected
 at T=6.2 days, and they were 7.6 x  104 and 1.6 x 104 cfu/mL  in wells
 Ml-A and EU-1, respectively. Similar results were obtained at T=6.9
 days, which was the final test for microorganisms. In this instance, all
 three wells showed significant levels of microorganisms.
 TCE Disappearance:
  After 24 hr of feed (T=2 days), TCE concentration in the downgra-
 dient well (ED-1) had decreased from 2500 ug/L to 466 ug/L. By Day
 3 of the test, the concentrations had fallen below 200 ug/L. With the
 exception of one data point (T=5.8 days), all subsequent concentra-
                              Figure 4
                  Salt Injection Test,  Percent Dilution

tions were below 300 ug/L. Decreases in the concentration of TCE also
occurred in wells Ml-A and EU-a.  The time of response was longer
and the magnitude of the decrease was less than observed for ED-1.
These results were consistent with the results of the tracer studies, which
showed the most rapid communication between the injection well (EI-1)
and well ED-1, followed by well Ml-A and finally the upgradient well
(EU-1).

Results:
  Figure 5 summarizes before (T=0 days) and after (T=10 days) test
plume configurations. The effect of treatment continued after termina-
tion of the feeds. The pilot test allowed the following important con-
clusions to be made regarding  the in  situ treatment of TCE:
• The tracer test confirmed that the injection water spread up and down-
  gradient of the injection well and that groundwater flow velocities
  within the receiving zone were on the order of 2 to 5 ft/hr. A theo-
  retical dilution of TCE concentrations was calculated based on the
  ratios between the rate of injection and the flowrate of the receiving
  zone. Measurable dilution effects were only observed in the down-
  gradient monitoring well ED-1.
• The  tracer test was followed by the  introduction of TCE-degrading
  bacteria, organic and inorganic nutrients and oxygen into the lower
  permeable unit of the Upper  Aquifer over a 6-day period. Within
  8 hr of initiation, a measurable decline in TCE concentrations was
  observed. A corresponding decline  in oxygen levels was observed,
  suggesting that  microbial degradation had been activated.
• The  in situ  test demonstrated biological degradation of TCE-
  contaminated groundwater from a high value of 3,000 ug/L to a mean
  concentration of 135 ug/L, which was maintained form Day 3 to Day
  8. A further decline to a mean value of 78 ug/L was observed over
  the next 10 days.
  The pilot test proved that TCE can  be removed from groundwater
by in situ aerobic biodegradation. The rapid rates are very encouraging
as they indicate that under the right conditions, this contaminant can
be significantly reduced within a short time frame.

CASE  HISTORY: IN SITU BIODEGRADATION
OF HERBICIDES
  Shallow groundwater contamination was detected beneath a herbi-
cide formulation facility in 1981. The major contaminants were identi-
fied  as  chlorinated  phenols,  primarily 4-chloro-2-methylphenol
(4C2MP), and were present in a shallow (35ft. thick) glacial  aquifer
overlying bedrock. A pump-and-treat  system (consisting of 11  extrac-
tion wells feeding two activated carbon units)  was installed in 1983.
Effluent from the system was returned to the aquifer via  eight injec-
tion wells. To achieve a more rapid reduction  in contaminant levels,
an in situ program was evaluated in 1987.
                                                                                                                 BIOTREATMENT    803
-------
                                                              Looking NorUtMul
                                                                         960QOC
                                        T = 0 Doya
                                                                                      10 Days
                                                                 Figure 5
                                                     Pre and Post Test TCE Concentrations
   Aerobic laboratory culture techniques were used to assess 4C2MP
 biodegradation in the site groundwater. High 4C3MP biodegradation
 potentials were observed in groundwater samples obtained from three
 site wells (Table 2):
 Well
 1-4
 P-4
 P-8
                Ibble2
4C2MP Concentrations in Aerobic Cultures
   CJmg/L)        C.(mg/L)        CJmg/L)
   X = 1B3       X =  1133        X =  <41
   X
   X
3400
710
X  = 3800
X  = 710
X  =
X  =
                                      D80
X  = Average 4C2MP concentration (3 replicates).
CQ  = Initial Concentration.
Cfc = Final Control Concentration (7 days).
Cft  = Final Test Concentration (7 days).

  High 4C2MP  biodegradation  potentials were observed with no
nutrient adjustment. This study showed that only aeration was needed
to reduce 4C2MP concentrations in the groundwater. In 1988, the num-
ber of recovery wells was increased to 19 and two additional injection
wells were installed. Airlift pumps were placed in the recovery wells,
thereby increasing the oxygen concentration in the injected effluent.
Results
  Within the first year of system operation, the following results were
obtained:
• Reduction in off-site contaminant plume  size was effected by gra-
  dient control of the recovery system.
• Decreased dissolved oxygen concentrations were initially measured
  in the injection wells; this suggested that phenolic degrading microbial
  populations had been established adjacent to the injection wells.
• In the initial 3 mo  of operation, the total phenol  plume exhibited
  a 25  to 35% reduction in area; after 6 mo, a 50% reduction was
  observed.
  The system has continued to operate successfully and is expected to
result in total  site remediation within five years of initiation.

CASE HISTORVCS SITU BIODEGRAEAT1ON OF PETROLEUM
  A former marketing terminal in the Western United States had been
contaminated by losses incurred  during  the handling of petroleum
products during 65 yr of operation. More than 60,000 yd3 of soil are
contaminated with petroleum hydrocarbons at  a mean concentration
of 2,660 ppm. Groundwater analyses identified benzene as the com-
pound of concern. Ethylbenzene,  toluene and xylenes are present at
low levels.
  A laboratory treatability study evaluated treatment options and cleanup
levels achievable through bioremediation. Options studied included ex-
cavation and off-site disposal, off-site treatment and on-site treatment
focusing on bioremediation. Activities managed  in support of the
Remedial Action Plan (RAP) included preliminary design of cleanup
systems and regulatory liaison and public involvement activities.
  Two recommended treatment alternatives, on-site solid-phase biotreat-
ment  and in situ biotreatment, were selected because of the destruc-
tion of the contaminants and significant cost savings compared to off-site
disposal. Bioremediation of the contaminated soil reduces the hydrocar-
bon contaminant level to below the agreed to cleanup level of 200 ppm.
Water cleanup criteria  for  the contaminants  are  as follows:  total
hydrocarbons-15 mg/L, benzene-40 ug/L and ethylbenzene-3.5 mg/L.
Once  these levels are achieved, the  site will be rendered clean and suita-
ble for  development.
  The site is divided into four areas (Fig. 6). The in situ system plan
called for installation of trenches on either side of Area C and either
side of Area D. Figure 7 shows the general installation and operation
of the two situ systems.
  The in situ systems are comprised of extraction and reintroduction
trenches/wells and surface bioreactors.  Contaminated groundwater is
pumped from the extraction trench/well to the surface bioreactor. Baffles
on the influent end of the bioreactor separate  free product which is
pumped to an  oil/water separator  for further separation and eventual
reclamation. The contaminated water flows over a weir into the active
zone of the bioreactor. In this zone, oxygen (via diffused air bubblers)
and nutrients are added to promote optimal degradation. The residence
time of the water in the reactors  is controlled  to ensure degradation
of the contaminants.
  Once the contaminants are degraded, the treated water is  pumped
from the surface bioreactors through nutrient amendment and oxygen-
ation  contactors and reintroduced to the subsurface via the reintroduc-
tion trenches. The nutrient additions are monitored to maintain optimal
804    BIOTRF.ATMEVT
-------
                             LEGEND

                               -0- HYDROCARBON MONITOR

                                *  METEOROLOGICAL TOWER
SCALE IN FEET
                                                                 Figure 6
                                                                 Site Map
levels. The oxygenation is accomplished with both diffused air bubblers
and pure oxygen contactors. The oxygen is supplied by an on-site oxygen
generator, thereby avoiding the dangers associated with compressed
oxygen storage. The oxygen generator uses a molecular sieve bed that
selectively excludes nitrogen from an ambient air stream and allows
only oxygen to pass. As a result, a 98% pure oxygen stream can be
produced. The molecular sieve uses size exclusion to prohibit the nitro-
gen flow and is regenerated each cycle.
  The in situ system cleans contaminated zones by increasing the flow
above normal groundwater flowrates, promotes in situ degradation, pro-
motes mobilization of contaminants and treats unsaturated zones more
effectively. The higher flowrate through the zone of contamination pro-
motes soil washing. Any contaminants that are mobilized by the system
are captured by the extraction trench and treated in the surface bioreactor.
By supplying oxygen and nutrients to the subsurface, organisms present
in the soil reach optimal degradation rates and reduce the contaminants
                              Figure 7
                           In Situ System
   at the source. The enhanced biodegradation also assists in promoting
   mobilization of contaminants for capture and treatment by the extrac-
   tion trench and  surface bioreactor.
     The development of active biodegradation in the subsurface enhances
   mobilization of contaminants through the action of biosurfactants. The
   microorganisms produce extracellular proteins (biosurfactants) which
   liberate contaminant molecules from soil particle surfaces into solu-
   tion. Once in solution, the microbes can absorb and utilize the con-
   taminant molecule as direct or co-metabolic carbon sources. The active
   microbial culture is very efficient at producing biosurfactants but not
   as efficient at capturing and utilizing all of the mobilized contaminant.
   As a result, with the increased groundwater flowrates and the action
   of the biosurfactants, soil washing is enhanced and the extraction trench
   recovers the mobilized contaminants  for  treatment in  the  surface
   bioreactors.
     Finally, the reintroduction trench supplies treated and oxygen/nutrient-
   amended groundwater at a faster rate than the  subsurface strata can
   accept.  As  a result, the groundwater surface in the  area of the
   reintroduction trench is mounded. This mounding of the groundwater
   surface  saturates previously unsaturated soils and provides  a more
   optimal condition for in situ biodegradation.
     The Area C system is comprised of a 300-ft long extraction trench
   coupled to a 250-ft long reintroduction trench. The pipe invert for the
   extraction/reintroduction piping is 2 ft below static water surface, or
   approximately 13 ft below ground surface. The design flow rate for the
   Area C system is approximately 20  gpm.
     The Area D system is comprised of a series of 15  extraction wells
   on 50-ft centers. The wells were required because of lower permeabil-
   ities and restricted access problems. The extraction wells  are coupled
   to a 650-ft long reintroduction trench. The invert elevation for the ex-
   traction wells is between 5 to 10 ft below static water levels  and the
   pipe invert for the reintroduction trench is 2 ft below static ground-
   water levels. The design flow rate for the Area D system is approxi-
   mately 100 gpm.
     Included in the Area C and D in situ system trenches  are  vacuum
   lines that induce soil oxygenation in the contaminated zones. Ambient
   air is drawn into the subsurface from exposed surfaces within the zone
   of influence of the trench by a vacuum applied to the subsurface piping.
   The soil oxygenation pipe invert is 6 ft  above the groundwater surface
   and 4 ft below ground surface.
                                                                                                                    BIOTREATMENT    805
-------
  Figure 8 presents some process monitoring data collected during the
initial 8 mo of operation.  As can be seen from this figure, the in situ
system  has  clearly  affected the  subsurface.  The  concentration  of
ammonia nitrogen has increased consistently since operation of the
system began in early 1990. The other parameters, nitrate nitrogen, phos-
phate and dissolved oxygen also show potential increasing trends but
are not as clear as the trend for the ammonia nitrogen. Based on the
data collected to date, we project that the cleanup goals will be achieved
within 7 yr of initiation of treatment.

CONCLUSIONS
  In situ biotreatment of groundwater contaminated with organic com-
pounds is a proven remedial method that may provide an alternative
or  adjunct  to  conventional solutions. The method  uses  naturally
occurring microorganisms that are adapted to site conditions to remove
groundwater contaminants.  Laboratory treatability studies provide an
evaluation of the biodegradability of the contaminants.  Pilot testing
gathers information on the performance of the injection/recovery system
and determines the degree of dilution. Full-scale implementation results
in terminal  destruction of the contaminants and rapid site cleanup.

REFERENCES
1.  Kinsella, J.V., "The Impact of the Chemical Industry on Groundwater Quality:
   Three Case Histories," in Hazardous Waste Detection, Control, Treatment,
   ed. R. Abbou, Elsevier Science Publishers, B.V., Amsterdam, 1988.
2.  Cannon, J.Z.,  "Considerations in Groundwater Remediation at Superfund
   Sites," U.S. EPA Internal memorandum, Superfund Report, 111 (23): 9(1089).
3.  Rifei, H., Bedient, P.B., Borden, R.C., and Haasbeek, J.F,  "BIOPLUME
             T  "I	»	Y-
            JAN   |  UAP  |
                FTB    APR
                               MONTH (I9MO)
                               Figure 8
             Average Nutrients and Dissolved Oxygen vs. Tune

   n, Computer Model of Two-Dimensional Contaminant Transport Under the
   Influence of Oxygen Limited Biodegradation in Groundwater," U.S. EPA,
   Robert S. Kerr Environmental Research Laboratory, ADA, OK,  1988.
4. Nelson, M.J.K., Montgomery, S.O., Mahaffey, W.R., and Pritchard, PH.,
   "Biodegradation of Trichloroethylene and Involvement of an Aromatic Bio-
   degradative Pathway," App. Environ.  Microbio., pp. 949-954, May, 1987.
5. Nelson, M.J., Kinsella, J.V., and Montoya, T, "In Situ Biodegradation of
   TCE Contaminated Groundwater,"  in press, 1990.
       BIOTREATMENT
-------
       Selection,  Testing and  Design of an Integrated Biotreatment
            System for Remediation of a  Former  Oil Refinery Site

                                                 Ann C  Kuffner, RE.
                                                   Douglas E. Jerger
                                                 Patrick M.  Woodhull
                                          OHM Remediation Services  Corp.
                                  Technology Applications  and  Commercialization
                                                      Findlay, Ohio
INTRODUCTION
  OHM Remediation Services Corp. (OHM) was hired in 1985 by a
major Midwestern refiner to provide environmental services for a
petroleum refining site. The refinery operations had been previously
dismantled, but the site needed further assessment and remedial efforts
to address the residual contamination that had originated  from the
facility. During the last 5  years, OHM has  completed the  site
characterization, provided interim site mitigation measures to prevent
further groundwater contamination, performed biotreatability tests, con-
ducted bench-scale tests and completed a detailed design for an integrated
treatment system.  This system includes a variety of processes, but
biological treatment is the cornerstone of the process with carbon
adsorption used for polishing effluents.
  This paper discusses the tasks related to the development and design
of a treatment system to recover and treat benzene, toluene, ethylbenzene
and xylene (BTEX) contaminants in groundwater. Over a long period
of time these soluble petroleum hydrocarbon components (PHC) had
dissolved into the shallow groundwater aquifer. The primary objectives
of this project were to:
• Provide a  site perimeter groundwater containment system consisting
  of fully penetrating recovery wells designed to halt the off-site migra-
  tion of groundwater containing dissolved PHCs.
• Identify the optimal method to treat groundwater containing BTEX
  and dissolved PHCs to levels suitable for discharge into a surface
  drain under a NPDES permit.
• Design a full-scale treatment system for the selected remedial process.
  The information gained during the prior 4 years of hydrogeological
and biodegradation studies was used as a basis for  this design.
  The significance of this project is that it provides an excellent example
of how, by combining technologies, project costs can be reduced while
meeting the  established cleanup criteria. Although this groundwater
cleanup could have been achieved by using either carbon adsorption
or biological treatment alone, combining these technologies^ optimized
both the technical results and the cost-effectiveness.
BACKGROUND
  The site geology consists of a 75- to 80-foot thick interval of coarse-
to medium-grained sands that fine downward and overlay a blue silty
clay. The depth to groundwater ranges from 2 to 5 feet below grade.
The upper 20 feet of the water table aquifer possesses a hydraulic con-
ductivity of 1,000 gal/day/ft.2
  The contamination originated from the oil products that were pro-
duced by the refinery. Over the years of refinery operation, these pro-
ducts spilled and were  also discharged into ponds which most likely
leaked. The result was that the underlying soil and groundwater were
contaminated with PHCs.
  Table 1 lists the influent parameters and contaminant concentrations
for the design basis. Table 2 lists the discharge limitations as outlined
in the NPDES permit. The primary hydrocarbon constituents for which
regulatory agencies established cleanup criteria are BTEX. Other
hydrocarbon constituents are present in the water, but they have not
been regulated. The total influent BTEX concentration is 2 mg/L. The
treatment criteria establish that the total concentration of BTEX com-
pounds must be reduced to less than 20 parts per billion ^g/L (24-hour
sample) with a benzene limit of 5 jig/L.
  Available on-  and off-site  hydrogeological,  hydrochemical and
biological data were used to design a groundwater recovery treatment
system. Additional data generated from initial laboratory treatment
studies were also utilized to prepare the preliminary design and to
estimate operational costs.

                            Table 1
                         Design Basis
           Parameter

    Hydraulic Conductivity

    Porosity

    Ground-Water  Gradient

    Saturated Thickness

    Maximum Influent Flowrate

    Normal Influent Flowrate
       Value

1,000 gallons/day/ft2

0.3

0.0026

78 ft

400 gallons  per  minute

360 gallons  per  minute
Ground-Water Chemistry
Lead
Chromium
BTEX (total)
BOD5
Total Organic Carbon (TOO
Total Suspended Solids (TSS)

pH
Oil and Grease
Water Temperature
Nitrogen
Phosphorous

<0.05 ppm
<0.05 ppm
2 ppm
<10 ppm
40 ppm
5 ppm

6.7 SU
<10 ppm
55°F
3 ppm
0 ppm
                                                                                                          BIOTREATMENT   807
-------
                             Table 2
          Effluent Limitations and Monitoring Requirements
                                                      Suple
                                                      TYP'
                                                      Report Total
                                                      Daily Flo-
                         <  «g/l     ID ng/1    Weekly
                         S  B
-------
Materials and Methods
  The laboratory study involved operation of an upflow, attached film,
5-L, static bed reactor. The upflow operation assured maximum ground-
water/biomass contact and a minimum of short circuiting through the
bed. The reactor was filled with random packed, plastic pall rings and
enclosed to allow complete material balances to be performed. Air was
used as an oxygen source during the study to assess the effect of aera-
tion on VOC stripping. If necessary, high purity oxygen could be used
to minimize volatilization/stripping of the organics. The reactor was
operated on the site water supplemented with appropriate nutrients to
support the growth of biomass. The pH of the reactor was maintained
in the neutral range.  In order to establish the minimum temperature
and nutrients needed to achieve design effluent concentrations, two small
biotowers were constructed. Biotower I was operated at 70 °F to simulate
heated groundwater, while Biotower n was operated at 55 °F to simulate
the ambient groundwater temperature.
   The biotowers were constructed as 4-inch diameter Plexiglas columns
with flanged  top and bottom plates. The influent port was located on
the column bottom while the effluent was side discharged near the top
of the biotower. A port on the biotower top allowed off-gas to escape.
                       The packed volume of the reactor was 4 liters. Each column was packed
                       to a height of 29 inches, with 5/8-inch nominal Nor-Pac polypropylene
                       media to provide a support medium for biomass growth. One-half inch
                       glass beads were placed below the packing for air dispersion from the
                       influent throughout the column diameter (Fig. 1).
                         Each reactor was inoculated with activated sludge from the Findlay,
                       Ohio, wastewater treatment plant. A full recycle flow scheme was in-
                       itiated with an influent feed consisting of BTEX-spiked site  water
                       supplemented with acetate. The acetate was the primary carbon source
                       for the developing biomass since TOC and BOD concentrations  in the
                       site water were relatively low. Full recycle operation was continued until
                       sufficient biomass had developed on the column media.
                         For continuous flow operation, site water was pumped from barrels
                       into a header leading to the bioreactor influent port. Also connected
                       to the header was a line to the carbon/nutrient/BTEX source carboy.
                       This mixture contained measured amounts of ammonia-nitrogen and
                       phosphate-phosphorous nutrients for biomass support, a BTEX addi-
                       tion to increase influent concentrations and acetate to be added as a
                       primary carbon source when necessary. The  BTEX addition was
                       necessary due to volatilization of these contaminants from the site water
                            AIR FEED
                        AIR FLOWMETER
    AIR
                   NUTRIENT/BTEX/ACETATF
       NUTRIENT/BTEX/ACETATE
         ADDITION VESSEL
   SITE WATER FEED LINE
                                      c
                                                                                                                              EFFLUENT LINE
                                                                                                             GLASS BEAD PACKING
                                                             MAIN FEED LINE TO REACTOR
                                         SITE WATER
                                            PUMP
J
                                                                  Figure 1
                                                         Bench-scale Biowater System
                                                                                                                    BIOTREATMENT   809
-------
during collection and/or storage. On Biotower I, operated at room
temperature to simulate 70 °F (heated) groundwater, a compressed air
line was connected to the combined feed header before reaching the
column influent port. Biotower n was operated at 55 °F to simulate
ambient groundwater temperature.  The combined feed was  passed
through a copper tubing coil immersed in a temperature controlled water
reservoir to assure an influent temperature of 55 °F. An aeration line
was also connected into the chilled feed line to provide oxygen to the
biotower.
  Several operating conditions were  tested on each biotower from flow
initiation to the design 1-hour HRT (Tables 3 and 4). This operating
parameter required the adjustment of liquid feed rates and influent con-
centrations. A period of at least 2 to 3 weeks was allowed for biomass
acclimation after operating conditions were changed. Once the perfor-
mance had  stabilized, analytical data were collected over 3 days as
representative of steady-state performance (Table 5).

Results and Discussion
  Biological removal of  BTEX was the primary goal  of this study.
Greater than 99% treatment removal efficiency was achieved for BTEX
during operation of Biotower I at design steady-state conditions during
8 months of operation. An average influent BTEX concentration of 2
mg/L was treated to nondetectable levels in the effluent stream (Limit
of Detection [LOD] = 2 jig/L for each BTEX component) (Table 6).
A similar treatment efficiency (greater than 99%) has been achieved
for BTEX in Biotower II during 5 months operation at design condi-
tions  (Table 7). To  confirm that microbial degradation was  the
mechanism responsible for BTEX removal,  analyses of the vent gas
and biomass solids were performed on both biotowers. The data indicate
                             Table3
          Steady State Operating Conditions for Biotower I
                    (70  Degrees Fahrenheit)
Hydraulic
Residence
Time
2
1
1
1
hour
hour
hour
hour
35
35
35
35
35
17.
35
Influent Total
Organic Carbon
ppm
ppm
ppm
ppm
site water
acetate
site water
acetate
ppm site water
.5 ppm acetate
ppm
site
water
plus
plus
plus

 Condi tion

      1


      2


      3
 NOTE:  Condition  4  is  Design  Operating  Conditions



                               Table 4
            Steady State Operating Conditions for Biotower n

                     (55 Degrees  Fahrenheit)
 Condi tion

      1


      2


      3


      4

      5
Hydraulic
Residence          Influent  Total
  Time        	Organic  Carbon

 2  hour       35 ppm  site  water  plus
               35 ppm  acetate

 1  hour       35 ppm  site  water  plus
               35 ppm  acetate

1.5  hour      35 ppm  site  water  plus
               17.5 ppm acetate

1.5  hour      35 ppm  site  water

 1  hour       35 ppra  site  water
                                                 that the BTEX components were not detectable in the air or solids
                                                 process streams (Tables 8 and 9). These data clearly prove the effec-
                                                 tiveness of the upflow biotower design for treating BTEX in groundwater.
                                                   The total unidentified semivolatiies (total influent concentration =
                                                 0.999 mg/L) were not fully degraded by the biotower treatment systems.
                                                 Biotower I removed an estimated 67 % of the semivolatile contaminants
                                                 while Biotower n removes approximately 31% of these compounds.
                                                 Volatile or semivolatile compounds were not detected in the biomass
                                                                              Tables
                                                           Samples Collected and Analyses Performed During
                                                            Steady State Operation of Bench-scale Biotowers
Saaple Point       Analysis

Influent, Effluent  Volatiles
                  Total Organic Carbon
                  Oil and Grease
                  Base/Neutral and
                   Acid Extcactables,
                   Semi-Volatiles
                  NH,-N
                  foi-t
                  Total Suspended Solids
                  Chemical Oxygen Demand
                  Biological Oxygen Demand
                                                 Vent Gas

                                                 Biotover Biomass
                  Volatiles

                  Volatiles
                   Base/Neutral and
                   Acid Extraccables
                   Semi-Volatiles
                  ICP Metals
                  Total Solids
                                                                                          Method

                                                                                          SV-846, Method 8240
                                                                                          SV-846, Method 9060
                                                                                          600/4-79-020, Method 413.1
                        SV-846,  Method 8270
                        Standard Method 417E
                        Standard Methods 424F
                        Standard Methods 2090
                        Standard Methods S08C
                        Standard Methods 507

                        SV-846,  Method 8240

                        SV-846,  Method 8240
                                                                                          SW-846, Method  8270
                                                                                          SV-846, Method  6010
                                                                                          Standard Methods 209F
                                                  Composite suspended solid samples were collected  from the effluent
                                                 over a 3-veek.  period


                                                 SV-846:  USEPA Methods  for Organic Chemical Analysis of Municipal and
                                                 Industrial Vastevatec,  600/4-79-020, July 1982.

                                                 Standard Methods:  Greenberg,  A., R. Trussell, and L. Clesceri, Standard
                                                 Methods for the Examination of Water and Vastevater,  16th Edition,
                                                 American Public Health  Association, 1985.
                                                                              Table 6
                                                            Performance Summary of Bench-scale Biotower I
                                                           (70  °F) Operated to Achieve Design Conditions for
                                                                       Groundwater Treatment

                                                  Operating
Condi tions
1 )
2}
11
4 1
HRT 2 hrs
TOC 70 ng/L
HRT 1 hf
TOC 10 ng/L
HRT I hr
TOC 55 ng/L
HRT 1 hr
TOC 35 «g/L
Reduction
>99.2t
>98.9t
>99.2l
>99 .91
Reduction
541
651
421
161
Reduction
>99t
>99\
>99%
—
Reduction
fill
781
an
101
Reduction
SOI
77t
SM
!«»
                                                   BTEX Supplenented Site Mater (2 ppn)
                              Table 7
           Performance Summary of Bench-scale Biotower n
           (55 °F) Operated to Achieve Design Conditions for
                       Groundwater Treatment
Operating  .
Condition*

1i HRT 2 hrs
   TOC 70  «g/L

2) HRT 1 nr
   TOC ?Q  ag/L

j; HUT :.s f.n
   -z: 55  »g/L

* i hRT . 5 r. i s
   toe J<  .5/1.

b  HRT I rtr
   TK !S  «g.'l
Un
>SS 24


149.6>


)9S 11
42t


7.21


0.9t
eSt       121


121       lit
 N'OTE: Condition 5  is Design Operating Conditions


810    B1OTREATMENT
                                                                                                 •2 pp.'
-------
                              Tables
    Mass Balance of BTEX Components from Upflow Bench-scale
     Biotower I (70 °F) Operated at 1 Hour HOT and an Influent
    TOC Concentration of 35 mg/L Site Water Spiked with BTEX
Date
9-1
9-1
9-1
9-1
9-8
9-6
9-B
9-8
9-27
9-27
9-27
9-27
Component
Benzene
Toluene
E-Benzene
Xylenes
Benzene
Toluene
E-Benzene
Xylenes
Benzene
Toluene
E-Benzene
Xylenes
Influent (1)
38.9
32.2
33.0
26.2
63.9
62.1
49.7
44.7
69.8
74.9
53. B
58. 5
Effluent 11)
0.657
0.327
0.184
0.362
0.539
0.450
0.175
0.462
0.652
0.513
0.213
0.519

0.212
0.530
0.523
0.813
0.036
0.090
0.097
0.214
0.032
0.180
0.139
0.206

0.55
1.7
1.6
3.2
0.06
0.15
0.20
0.48
0.05
0.24
0.26
0.35
(1) Values are in units of:
                         us
                        5Tn
(2) i stripped -
              Influent-Effluent
131 Ait Clow:  209 ml/min

sludge indicating these compounds do not bioaccumulate within the
reactor.11
  In addition, acetate addition and the heated water (70 °F) would only
be required during the startup process.  Once the biotowers were opera-
tional, the acetate feed and water heating could be gradually eliminated.
The results from this study were used  as the basis of the final design.
                                Table 9
      Mass Balance of BTEX Components from Upflow Bench-scale
      Biotower II (55 °F) Operated at 1 hour HOT and an Influent
      TOC Concentration of 35 mg/L Site Water Spiked with BTEX
                                                                           Date    Component    Influent (11    Effluent (1)
                                                                                                                         Headqas (II    t Stripped  (21
                                                                           11-21   Benzene
                                                                           11-21   Toluene
                                                                           11-21   E-Benzene
                                                                           11-21   Xylenes

                                                                           11-22   Benzene
                                                                           11-22   Toluene
                                                                           11-22   E-Benzene
                                                                           11-22   Xylenes
                     46.7
                     36.1
                     15.7
                     25.2

                     46.0
                     35.6
                     15.5
                     24.9
 11-28
 11-28
 11-28
 11-28
                                                                                  Benzene
                                                                                  Toluene
                                                                                  E-Benzene
                                                                                  Xylenes
 BDL
 BDL
 BDL
 BDL

 BDL
 BDL
 BDL
 BDL

1.49
1.39
0.16
2.18
0.353
0.263
0.078
0.303

0.727
0.691
0.129
0.599
2.25
2.28
0.673
2.27
0.76
0.73
0.50
1.2

1.6
1.9
0.83
2.4

5.5
5.9
2.1
8.1
                                                                           (1) Values are in units of:
                          uj
                         nun
                                                                           (2) % Stripped •
                                                                                             Headqas
               Intluent-Eftluent
 (3) Air  Flow:  209 mL/min

FINAL FULL-SCALE DESIGN


   The final treatment system was designed to treat a maximum of 400
 gpm to the cleanup criteria previously described in Table 2. The process
 flow diagrams for the full-scale treatment system are presented in Figures
 2 and 3. The treatment system will include the following major systems:
                                           roi i FC-TION  WASTFWATFR
                                           TANK        FFFP. PUMP
                                                                                                                                  '\ TO SAND   \
                                                                                                                                  -4  FILTER    }
                                                                                                                                  1/5TD-D-201  /
                                                                                                                                   \  TO DWG.  \
                                                                                                                                   ~J  STD-201   I
WITH PUMP'S
                                                                    Figure 2
                                                              Process Flow Diagram
                                                                                                                         BIOTREATMENT    811
-------
  •  Groundwater recovery system
  •  Pre-conditioning system
  •  Biological treatment system
  •  Post-conditioning system

  Groundwater Recovery System
    The groundwater recovery system was specifically designed to prevent
  off-site migration of groundwater containing dissolved PHCs at the site
  perimeter via a network of recovery wells. Design assumptions were
  based upon several years of field investigation and numerical modeling.
  Each of the existing site-perimeter recovery wells is a fully penetrating
  well screened from 10 feet below land surface to the bottom of the water
  table aquifer (75 to 78 feet). The maximum flowrate of groundwater
  extracted will be 400 gpm, with a normal flowrate of 360 gpm.

  Preconditioning System
    This system and all subsequent treatment processes are designed to
  handle a maximum flowrate of 400 gpm. The preconditioning system
  will receive  water  from the recovery wells and adjust the  influent
  parameters to conditions more ideal for microbial growth before the
  water enters the recycle stream of the biological reactors.  Water from
  the recovery wells will be delivered to a carbon steel collection tank
  (8,000 gallons). Nutrients (nitrogen and phosphorus), a carbon source
(sodium acetate) and a defoaming agent will be added in-line prior to
entering the tank. Flow equalization will take place in this tank. Water
will be pumped from this tank by a horizontal, centrifugal wastewater
feed pump. (The system also includes one installed spare pump.) High
level and low level control in the collection tank will be connected to
the groundwater well pumps and the wastewater feed pump. The ground-
water will  be heated  in-line from the wastewater feed pump  to the
biotowers using a direct fired (natural gas), fin-tube water heater.

Biological Treatment System
  The aerobic biological treatment system will consist of two packed
biotowers.  The main  components of each biotower system are  the
biotower, the bioseeder and the recycle loop. Each system also con-
tains support components for pH adjustment and air addition.
  The total installed height of each biotower is 33 feet. The static growth
attachment medium used in the biotower is specified as plastic and will
have a total height of 22  feet.  The BOD loading of each tower is
estimated to be 20 pounds of BODj/l.OOO/ftVreactor volume/day. The
HRT in each tower is designed to be 1 hour, achieved by an influent
flowrate of 180 to 200 gpm per reactor. Centrifugal pumps will be used
to continuously provide recycle flow in each biotower. Oxygen  re-
quirements for each biotower will be met via a blower and an air distribu-
YFROM
 >BIOTOWERS
/STD-D-200/
\ 'ROM AiR  \
 YOI-.PBESSOR)-
/:-?-D-:O:/
                                                                                              PQ5T          TRFATFn WATFR
                                                                                              APR AT ION TANK  DisfHARfiF PUMP
                                                                 Figure 3
                                                           Process Flow Diagram
 812    B1OTREATMENT
-------
tion system at the bottom of each biotower. Approximately 60 scfm of
air at 15 psig will be supplied to each biotower. Higher air flowrates
will be used periodically to scour excess bacteria from the media. A
system will be used to supply an initial inoculum of active biomass
and to maintain a sufficient biomass in the biotower, as needed.

Post-Conditioning System
  The post-conditioning system consists  of  a sand filter,  a  solids
thickener, a supernatant tank, polishing filters and two 40,000-pound
twin-cell carbon adsorption  units.
  The filter (Parkson DynaSand) will continuously remove suspended
solids in the biotower effluent to an effluent quality of 10  mg/L of
suspended solids. The effluent will flow from the sand filter, by gravity,
into  the filtrate tank.
  The reject stream from the DynaSand filter, containing water and
solids, will flow to a 12-foot diameter, 10-foot high, cone bottom, carbon
steel solids thickener. A mixer mechanism (rake) in the thickener tank
is used to enhance solids settling and to convey the settled  solids to
the center of the conical bottom. The supernatant from the thickener
will  overflow to a 900-gallon carbon steel tank. The supernatant will
be pumped to the filtrate tank by a pump on level control. The solids
(approximately 2% solids by weight) will underflow from the thickener
and  be pumped with a mechanical diaphragm pump as waste solids
for disposal.
  The thickener waste solids will be applied  to an on-site land treat-
ment system during months  when the temperature is above freezing.
The  solids will be applied with a pump and a distribution system. During
the winter months, the solids will be pressed in a plate and frame filter
press and the pressed sludge will be stored in an outside staging area
until conditions permit land application. The sand filter effluent will
be collected in an 8,000-gallon carbon steel filtrate tank. Flow equaliza-
tion  for carbon adsorption cells will be achieved in this tank. One pump
will  feed the water to the polishing filters and the carbon units. Water
from the filtrate tank will be filtered to remove fine particles in the
range of 20 to 30 /aa using  an external backwashing multiplex filter
rated for a flow rate of 400 gpm.
  Two 40,000-pound total, dual-cell (20,000 pounds of carbon per cell)
carbon adsorption units will treat the biotower effluent. The valving
system will allow the units to be switched on- or off-line as needed.
Each twin-cell is capable of treating 200 gpm. Each cell will be filled
with 20,000 pounds of Filtrasorb 300 carbon. This carbon has a sur-
fece area of 950 to 1,050 m2/g and a bulk density of 27 to 28 pounds
per cubic foot.
  The water from the carbon cells will flow into a 6-foot diameter,
10-foot high, carbon steel post-aeration tank.  Approximately 20 scfm
of air will be supplied to increase the dissolved oxygen to 6 mg/L in
the water prior to discharge under a NPDES permit. The tank will also
provide enough head to permit gravity flow  to the discharge point.
  A rough order-of-magnitude cost estimate (in 1989 dollars) for the
design, equipment purchase, construction and operation (20 years) was
completed and is summarized in Table 10. Based on an average flowrate
of 360 gpm for 20 years, the cost to remediate the PHC-contaminated
groundwater is approximately $0.01/gallon.

ACKNOWLEDGEMENTS
  The authors would like to thank the following people for their in-
volvement on this project: Paul M. Sutton and William F. Mitchell for
their assistance in die design of the treatment system, Paul E. Flathman
for performing the laboratory feasibility studies, Brian P. Greenwald
                              Table 10
            Cost Summary for the Full-scale Groundwater
                   Treatment System (1989 Dollars)
  Design  Engineering

  Equipment Purchase

  Site Construction

        Field Labor

        Material

        Construction  Equipment

  Operation (20  years)

        Labor

        Materials

        Utilities

        Analytical

        Equipment Maintenance
         and Replacement
                                      TOTAL
$    850,000

   1,760,000



   1,160,000

     790,000

     110,000



   8,840,000

 10,200,000

   7,140,000

   7,390,000

   1,750,000


$39.990.000
for the operation of the bench-scale biotowers and Anne L. Hermiller
for her assistance and patience in preparing this paper.

REFERENCES
 1. Atlas, R. M., Petroleum Microbiology, p. 692, Macmillan Publishing Com-
   pany, New York, NY,  1984.
 2. Atlas, R. M.,  Microbial Degradation of Petroleum Hydrocarbons: An En-
   vironmental Perspective, Microbiol. Rev., 41 (1), pp. 180-209, 1981.
 3. Brown, K. W. and Deuel, L., Hazardous Waste Land Treatment, SW-874,
   U.S. EPA, Municipal Environmental Research Laboratory, Cincinnati, OH,
    1980.
 4. API Land Treatment Practices in the Petroleum Industry, Environmental
   Research and  Technology, American Petroleum Institute, Washington, D.C.,
    1983.
 5. Halmo, G., "Enhanced Biodegradation of Oil," Proc. 1985 Oil Spill Con-
   ference (Prevention, Behavior, Control, Cleanup), Los Angeles,  Califor-
   nia, American Petroleum Institute, U.S. EPA, pp. 531-537, API Publica-
   tion No. 4385, Washington, D.C., 1985.
 6. Senn, R. B. and Johnson, M. S., "Interpretation of Gas Chromatography
    Data as a Tool in Subsurface Hydrocarbon Investigations," Proc. Conference
   and Exposition on Petroleum Hydrocarbons and Organic Chemicals in
    Groundwater—Prevention, Detection and Restoration Houston, Texas, pp.
    331-357, American Petroleum Institute, Washington, D.C.; National Water
   Well Association, Dublin, OH; 1985.
 7. API The  Land Treatability of Appendix Vm  Constituents Present in
    Petroleum Industry Wastes, Environmental Research and Technology, API
   Publication No. 4379,  Washington, D.C., 1984.
 8. Tabak, H. H., Quave,  S. A., Mashni, C. I. and Earth, E. E, "Biodegrad-
   ability Studies with Organic Priority Pollutant Compounds," JWPCF, 53
    (10), pp. 1503-1518, 1983.
 9. Verschueren, K., Handbook of Environmental Data on Organic Chemicals,
   2nd Edition, p. 1310, Van Nostrand Reinhold Company, New York, NY, 1983.
10. Flathman, P. and Jerger, D., Biological Treatability of Groundwater Con-
   taminated with BTEX, OHM Remediation Services Corp., Findlay, OH, 1989.
11.  Greenwald, B. and Jerger, D., The Use of an Attached Film, Upftow Biotower
   to Treat Low Concentrations of BTEX in Groundwater, OHM Remediation
    Services Corp., Findlay, OH, May 1990.
                                                                                                                     BIOTREATMENT    813
-------
           Solid  Phase  Remediation  of Petroleum-Contaminated  Soil

                                               Geoffrey  C.  Compeau, Ph.D.
                                                        Harlan Borow
                                                        John C. Cioffi
                                                     ECOVA Corporation
                                                    Redmond,  Washington
ABSTRACT
  Biological processes have been used to remediate petroleum hydrocar-
bons, pesticides,  chlorinated  solvents and  halogenated aromatic
hydrocarbons. Biological treatment of contaminated soils may involve
solid-phase, slurry-phase or in  situ treatment techniques. This paper
will  review the general  principle of solid-phase bioremediation and
discuss the application  of this technique for the cleanup of total
petroleum hydrocarbons.
  Up to 280,000 cubic yards of  soil on the site of a former oil refinery
tank  farm are contaminated with up to  15,000 part per million (ppm)
of petroleum hydrocarbons and crude oil. The site posed significant
challenges due to its size as well as the depth and range of contamina-
tion.  The implementation of biological remediation required the design
of a Land Treatment Unit (LTU) and a remedial program which would
support the treatment of a significant amount of contaminated soil within
a restrictive time schedule.  Once this scenario was developed, the LTU
was prepared for treatment and  excavation and placement of soils was
initiated. Currently, the LTU area encompasses 27 acres of a 45-acre site.
  A  mobile laboratory  has been placed on-site and is  staffed with
chemists and microbiologists who analyze up to 150 soil samples per
day.  This laboratory  has been designed and equipped to provide the
necessary chemical and biological analyses to fully support the excava-
tion and bioremediation program. On-site biological treatment activities
include irrigating, aerating and tilling the soil to bring microorganisms,
contaminants and oxygen  into  contact  with each other to promote
biological degradation. Chemical and microbiological monitoring con-
ducted throughout the remediation process ensure that treatment levels
are being met.
  A multicomponent cleanup program is currently underway at a former
marketing fuel terminal in the Western United States. The site, owned
by a  major oil company,  contains approximately 60,000 cubic yards of
soil contaminated with petroleum hydrocarbons at a mean concentra-
tion of 2,660 parts per million  (ppm). The primary contaminants are
weathered gasoline and  diesel fuel.  Initial site  activities  involved the
development of a Remedial Action Plan which served as a basis for
negotiations between the client and lead regulatory agency and resulted
in the signing of a voluntary Consent Order. In addition, laboratory
treatability evaluations were conducted to assess treatment options and
cleanup levels achievable by those options.
  After demolition of existing  structures on the site, the majority  of
contaminated Area  1 soil (approximately 20,000 cubic yards) was
excavated, screened and  transported via conveyor system to Area 2 for
solid-phase biological treatment. Additional soil is being treated  in
Area I. Solid-phase treatment involves the excavation and processing
of the contaminated  soil with a carefully controlled combination  of
oxygen, water and specific  nutrient mixtures. This treatment promoted
the rapid growth of naturally occurring bacteria present in the soil to
metabolize and degrade the hydrocarbon contaminants. When treatment
is complete, the Area 2  soil (approximately 25,000 cubic yards) will
be treated in the same manner. Some of the treated soil may be used
as backfill and compacted.
  These remedial programs will reduce total petroleum hydrocarbon
contamination from the mean concentration of 2,660 ppm to less than
the 200 ppm cleanup criterion for soil and less than the 15pprn_cleanup
criterion for groundwater.  Over 20,000 cubic yards of soifhave been
treated by solid-phase treatment to date. The in situ system operation
is effectively producing biodegradation in the subsurface. The project
is approximately one third complete.

INTRODUCTION
  Carbon is distributed in the environment in a variety of chemical com-
pounds that range from gases (methane and carbon dioxide) to liquids
(benzene and toluene) to solids (simple sugars and polymers such as
cellulose, and asphaltic components of crude oil). The biological
degradation of many of these compounds is a naturally occurring reac-
tion. The rate of this reaction, however, is highly dependent on a variety
of factors including the  specific structure  of the compound;  the
availability of nutrients, oxygen and water for the microorganisms; and
the nature of the soil or other matrix in which the compound resides.
In some  cases, certain compounds can be biologically degraded in hours,
while other  compounds,  such as asphaltics, are  virtually totally
nondegradable.
  The susceptibility of petroleum products to biodegradation varies with
the types and sizes of the component molecules. Since there are several
hundred individual component molecules in any given crude oil, which
can vary with its origin, the rate and extent of degradation is not easily
predictable. Thus, the overall degradability  of a specific petroleum
product  will depend on the proportion of degradable compounds of
which it is composed. For example, alkanes of intermediate chain length
(Cnj-CjJ are degraded most rapidly. However,  very long chain alkanes
become  increasingly resistant to biodegradation,  and after exceeding
a molecular weight of 500 to 600, they cease to serve as carbon sources.
Branching structures  typical  of  asphaltics also  reduce the rate of
biodegradation, and aromatic compounds are degraded more slowly
than alkanes.  Some  hydrocarbons and hydrocarbon biodegradation
products are  highly  resistant to ultimate biodegradation, that  is,
mineralization. Condensed polycyclic aromatics and cycloparaffms, as
well as high-rnolecular-weight alkanes, are mineralized only very slowly.
Solid-phase biological treatment  processes  involve establishing an
environment conducive to  microbiological growth and degradation of
organic  contaminants. The availability of nutrients and oxygen have
significant effects on petroleum degradation. In particular, nitrogen and
814   BIOTREATMENT
-------
phosphorus fertilizers, as well as oxygen, accelerate biodegradation.
Additionally, proper pH and temperature also produce favorable effects.
  Techniques employed in bioremediation are designed to remove con-
straints which slow degradation rates, such as limited nutrients and
oxygen, in order to bring about rapid rates of degradation.  Because
of the variability in the source of petroleum hydrocarbon contamina-
tion, the chemical nature of contaminated soil and other concerns,
treatability studies of contaminant reduction in specific soils are the
most appropriate way of establishing proper treatment conditions. Such
conditions include nutrient concentrations, moisture levels and treat-
ment duration. Treatability studies also determine the extent of degrada-
tion that can be achieved for  a given compound.
  Biological treatment technologies for contaminated soils and ground-
water fall into four main categories: (1) solid-phase biotreatment (land-
farming); (2) slurry-phase biotreatment; (3) in situ biotreatment; and
(4)  combined technologies with chemical or physical treatment. The
specific treatment process required is a function of the physical/chemical
nature of the contaminant and the matrix in which it is found. The focus
of this paper is the solid-phase remediation of petroleum-contaminated
soils.

Solid-Phase Biotreatment
  Soil provides a rich source of microorganisms, many of which have
the potential to degrade hydrocarbons. Solid-phase biotreatment relies
on principles applied in agriculture in the biocycling of natural com-
pounds. The conditions for biodegradation are optimized by regular
tilling of the soil and by the addition of nutrients and water. The natural
indigenous microbial populations of soil are diverse and many of the
appropriate  microorganisms which degrade many  contaminants are
found in the contaminated soils.
  The rates of bioremediation of contaminated soils are enhanced by
optimizing the conditions of the site for oxygen levels, moisture con-
tent,  available nutrients such  as nitrogen and phosphorous, pH and
contact between the appropriate microorganisms and the contaminants.
This technique has been successfully used for years in the managed
disposal of oily sludge and other petroleum refinery wastes through
a process called landforming. Solid-phase biotreatment of contaminated
soils is probably the most widely used and cost-effective biotreatment
technology currently in application today. Typically, the process is used
for petroleum- and creosote-contaminated soils. Typical costs for this
type of treatment are $40 to $120/cubic yard but are highly dependent
on  conditions at the site and  materials handling costs. New federal
regulations (RCRA, Land Bans) may prohibit some current disposal
techniques and require alterations to the system due to fugitive emissions
and leaching of organics and metals. A variety of options are  available
to control these emissions.
  A solid-phase biotreatment  program involves careful manipulation
of oxygen, nutrient and water levels in the soil within the treatment
unit to promote optimal degradation rates. Oxygen is  supplied to the
soil by tilling either with disk aeration equipment or heavier recycling
equipment to a depth of 18 inches. Periodic turning of the soil to deeper
depths (24 inches) may occasionally be conducted. The tilling frequency
is determined by a number of factors including temperature, moisture
levels, contaminant concentration levels and soil type. The soil generally
is tilled with a frequency of 1 to 7 days depending on time and equip-
ment limitations.
  Nutrients normally are added in an aqueous form and applied with
either a spray assembly attached to the disk aerator or by specialized
equipment such as a terragator. Nutrient levels are monitored  and
nutrients are applied as needed to maintain optimum degradation rates
based on treatability data for specific con-taminants. Specific nutrient
formulations are added to the soil to maintain nitrogen, phosphorus
and other trace minerals.
  Moisture control is critical  to optimum operation of the treatment
unit. Low water activity restricts biological activity and results in less
than optimal treatment rates. More than optimal moisture can create
a number of significant difficulties, including slow treatment rates due
to lower aeration potential, difficulties in the operation of treatment
equipment and recontamination of the uppermost treatment lift by con-
taminants from lower lifts if tilling equipment cannot be maintained
at constant depth in the soil.
  Optimal moisture levels are typically in the 12 to 15 % by weight range.
However, presence of a clay fraction in otherwise sandy soil may result
in a 12 to J5 % moisture range creating a moisture content that is too
high. As a result, soil moisture levels are maintained at 10 to 12% to
promote optimal degradation rates in some soils and as high as  16 to
17% in other soils. A more consistent measure of water activity is field
holding capacity. Maximal microbial activity occurs at approximately
40 to 50% of the maximum field holding capacity.
  Moisture at the site is controlled by careful irrigation and rainfall
control, if required. An irrigation system at a small site (3 to 4 acres)
is comprised of a number of radial sprinkler lines that provide the ap-
propriate water application rate. At larger sites, this approach and the
logistics of implementation are not practicable and  a terragator type
water truck is most practical.
  In areas of high rainfall,  rainfall control  may be achieved through
the use of large plastic tarp systems that minimize the amount of rain-
fall that comes in contact with  the soil in the treatment unit. Tarps as
large as 50 feet by 650 feet have been successfully employed; they are
installed by a hydraulic roller attached to the bulldozer equipment used
during treatment. Modifications of typical solid-phase remediations may
include systems for control of volatile emissions and leachate collec-
tion as well as composting and  heap leaching. A modified solid-phase
bioremediation system was used  successfully by ECOVA to control
volatiles and leachate. The system consisted of a treatment bed lined
with a high-density liner. A perforated leachate collection system and
clean sand are placed on the liner for protection of the liner and proper
drainage and collection of contaminated water as it leaches from con-
taminated soils placed on the treatment bed. The lined soil treatment
bed is completely covered by a modified plastic film greenhouse. An
overhead spray irrigation  system contained within the greenhouse
provides for moisture control and a means of distributing nutrients
and microbial inocula (as needed) to the soil treatment bed.
  Volatile compounds released from the soil are swept through the struc-
ture to the air management system. Biodegradable volatile organic com-
pounds can be treated in a vapor phase bioreactor.  Nonbiodegradable
volatile organic compounds can be removed from the effluent gas stream
by adsorption on activated carbon.  Contaminated leachate which drains
from the soil is transported by the drain pipes and collected in a gravity-
flow lined sump. Leachate is then pumped  from the collection sump
to an on-site bioreactor for treatment. Treated leachate can then be used
as a source of microorganisms  and reapplied to the soil treatment bed
through an overhead irrigation system,  after adjusting for optimum
nutrients and environmental parameters.
  Soil heap bioremediation is a modification of solid-phase treatment
used when available space (area) is limited. In soil heap bioreclama-
tion, contaminated soil is excavated and stockpiled into a heap  on a
lined treatment  area to  prevent further contamination. Microbial
inoculum (as needed) and nutrients are applied to the surface of the
stockpile and allowed to percolate down through the soil. The pile can
be covered and an air emissions recovery system installed as described
above. A leachate collection system is used to collect the fluid, which
is recycled. An internal piping system may  also be installed  in order
to blow aii upwards through the soil and thus accelerate the biodegrada-
tion process through the addition of oxygen.  During operation, pH and
moisture content are maintained within ranges conducive to microbial
activity. Typical costs are similar to conventional solid-phase treatment.
  Composting processes are another modification of solid^phase treat-
ment in which  the  system is operated at higher temperature due to
increased biological activity. This technology is used for highly con-
taminated soils, treatment of poorly textured soils  and in areas where
temperature is critical to the sustained treatment process.  Contaminated
soils are mixed with suitable bulking agents, such as straw, bark or
wood chips, and piled in mounds.  The bulking agent  improves soil
texture for aeration and drainage. The system is  optimized for pH,
moisture and nutrients using irrigation techniques and can be enclosed
to contain volatile emissions. Care must be taken to control leaching,
to control volatile emissions, and to ensure that the bulking agent does
                                                                                                                   BIOTREATMENT   815
-------
not interfere with the biodegradation of the contaminants (preferential
carbon source).

CASE HISTORY: BIOREMEDIATION OF BUNKER C
FUEL HYDROCARBONS
  Soil remediation activities are being conducted at a former tank farm
facility in southern California. The soil undergoing remediation con-
sists of berm soils and soils underlying a former 20-acre concrete-lined
surface impoundment which was used to store bunker fuel oil.  The
quantity of soil treated will be in excess of 280,000 cubic yards and
is being treated in eight separate treatment cells at the site. The petroleum
contamination contained hydrocarbons in the range of C-10 to C-35
carbon chain length. The  oil-contaminated soil was found not to be
hazardous based on the 96-hour Acute Aquatic Toxicity Bioassay tests.

Treatment Concentrations
   An initial treatability evaluation was conducted to determine the
optimal concentration for treatment in the land treatment unit. It was
determined that a starting concentration of approximately 4000 ppm
total petroleum hydrocarbon would be optimal and that it was poten-
tially possible to treat up  to 5000 to  6000 ppm TPH in these soils.
   Since the excavation program required continued progress and the
sequential stacking of lifts  of soil to accommodate  the excavation
requirements, an  area was set aside at the treatment site and an LTU
was charged with 5500 cubic yards of high concentration (average 5595
ppm TPH) soil. The data from this LTU treatment verified the upper
limit of bioremediation to meet scheduling requirements.

TPH Monitoring
   The project involved treating more than 280,000 cubic yards of soil
contaminated with petroleum hydrocarbons in concentrations of up to
6,000 ppm  as total petroleum hydrocarbons (TPH).  The analytical
method used was U.S. EPA method 418.1 and the cleanup standard was
 1000 ppm TPH. In order to guide the excavation of the soil and facilitate
process monitoring of the solid-phase process,  a  mobile laboratory
(Figure 1) was placed on-site and staffed with environmental chemists
and microbiologists. The laboratory has analyzed up to 150 samples
per day during peak periods of production from the excavation and land
treatment units. More than 20,000 samples have been analyzed in the
laboratory at this stage of the project.
   During one phase of the project, a gas chromatograph was installed
in the laboratory to guide the remediation of light kerosene-like solvent
residues located in a separate disposal area on the site. For this aspect
of the remediation, the analytical protocol was U.S. EPA method 8015
and the cleanup standard was 100 ppm TPH. These soils  were incor-
porated into a separate LTU for treatment in several consecutive lifts.
                         The gas chromatograph also was used to qualitatively evaluate the
                         progress of the remediation by determining what fraction of hydro-
                         carbons had been treated and what fraction remained.
                         Nutrient and Biological Monitoring
                           In addition to contaminant chemistry, the site support laboratory
                         supported the nutrient addition program and monitored biological
                         activity in the LTUs. Ammonia and nitrate nitrogen as well as phosphate
                         were routinely analyzed for in the LTU. It was found that random
                         sampling of the LTU at approximately five samples per acre gave ade-
                         quate  coverage for the  nutrient,  moisture  and  microbiological
                         monitoring.
                           To evaluate biological activity, total heterotrophic organisms in the
                         treatment soils were enumerated. The microbial analysis program at
                         the site was augmented with plating of soil onto mineral media con-
                         taining specific hydrocarbons as the sole source of carbon for growth.
                         The development trends for the hydrocarbon-degrading population could
                         be evaluated in this way.
                           A variety of treatments were attempted to stimulate overall microbial
                         activity as  well as specific hydrocarbon degraders. These studies in-
                         dicated that treatments selected for scale-up effectively stimulated the
                         activity of the hydrocarbon-degrading populations.
                           Laboratory evaluations of the soil from the remediation and small-
                         scale studies were conducted to more clearly establish the population
                         of organisms involved and the community interactions responsible for
                         the degradation of hydrocarbons. Obvious changes  in the microbial
                         population occurred  over time  in  the  LTUs.  The evaluation of
                         hydrocarbon-degrading activity has helped to clearly define the im-
                         portance of these changes. A dominant organism in  the remediation,
                         distinguished  by a distinctive orange pigment,  was identified as
                         possessing the ability  to  metabolize a wide range of hydrocarbon
                         substrates. To better understand the full substrate range of the orange
                         organism, media plates were made using mineral salts broth, purified
                         agar and hydrocarbon. Clear evidence of growth was demonstrated on
                         pentadecane  (C-5),  octadecane  (C-18),  pristane (C-15 branched),
                         docosane (C-20) and hexacosane (C-26). A preliminary study on C-30
                         hydrocarbons also is being undertaken. Control plates which contained
                         no hydrocarbons did not demonstrate growth. Interestingly, the organism
                         produces a mucopolysaccharide when attempting growth on longer chain
                         hydrocarbons. These types of responses are known to be important in
                         the  solubilization of heavier hydrocarbons.
                            To follow the occurrence and development of these organisms, soils
                         from selected LTUs were plated on substrate specific hydrocarbons every
                         other  week. In this way, the  population of specific hydrocarbon-
                         degrading organisms was followed during the remediation. This required
                         no additional resources or expenditure for the project.
                FUcovary
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            M.J
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-------
Data Management
  The Laboratory Data Management System is a PC-based software
package designed and written for ECOV\ mobile laboratory operations.
The system provides direct data input for each sample from the moment
it is taken (via a laptop-mounted computer) through the actual analysis
to the final customized report. In addition, we can transfer selected
blocks of data between system modules and/or commercial software
packages such as spreadsheet or graphics programs.
  Data integrity is assured through the use of triple-redundant data bases,
automatic backup to floppy disk and a complete audit trail facility. The
audit trail facility tracks and records every change made to a sample
record. The audit trail data base is invisible to, and totally inaccessible
by, mobile laboratory personnel.
  Finally, the remote access feature uses a specialized telecommuni-
cations package which allows home office personnel to support the
system even while it is unattended. This system allows quality assurance
checks, data transfers or software modifications to be performed after
normal working hours, eliminating system downtime for  normal
procedures.

Summary of Remediation Data
  Figure 2 is a representative of TPH data from treatments employed
during the remediation. The pattern of degradation presents a similar
pattern to that observed in earlier LTU soils. A high initial rate  is
followed by a period of reduced rate as the composition of the petroleum
hydrocarbon and microbial community changes. After these changes,
the rate of remediation increases.
       2/11 2/21 2/28  3/7 3/14 3/21 3/2B 4/4  4/12 4/18 4/2G 6/2  6/9 6/18 6/23
— - AVQ.
(CFU/Q)
   AVERAGE (CFU/GRAM) X 10EOO
                              Figure 3
                              LTU 5-2
                      Overall Microbial Analysis
these pigmented organisms possess the ability to degrade an extremely
wide range of petroleum hydrocarbons from hexane (C-6) through hex-
adecane  (C-16), pristane  (branched C-15),  octodecane (C-18) and
hexadocosane (C-26). The physiology and ecology of this organism may
be pivotal to the control of the rate of hydrocarbon degradation in the
remediation. This is currently being evaluated.
            2/1612/21 2/28 3/7 3/14 3/21 3/28 tU  4/11 4/18 4/£6 5/2 6/B
  IAVERAQE TPH B04o|3666 3*4933002 2814 3026 2140 isoo 2014 1938 IBBO iso4 1400
                                                                          CPU (MILLIONS)
                                  WEHAQE TPH
                            Figure 2
                            LTU 5-2
                        Performance TPH
                                                                          3/7   3/14   3/21   3/Z8   4/4   4/11   4/18   4/26   6/2    6/9    6/18
                                                                               Orange/Flavo

                                                                               Yellow/Flsvo
                                     Agro/Whlle

                                     Alc/Pseudo/Tan
                            Figure 4
                            LTU 5-2
                      Analysis of Populations
   There is a critical period of time in the remediation in which the
 rate slows. This occurs during the period of from 6 to 9 weeks in soils
 which have a starting concentration of approximately 5,000 ppm. This
 phenomenon is not observed in LTU soils which have starting TPH
 concentrations below approximately 3,500 ppm.
   The significance of the changes in TPH degradation are borne out
 by the overall changes in nutrient concentrations and the heterotrophic
 (including petroleum hydrocarbon-degrading) microbial  populations
 which occur during this period. The increased presence  and activity
 of organisms that do not degrade hydrocarbons, but potentially com-
 pete for ammonia (an essential nutrient for hydrocarbon metabolism)
 is supported by the general, but  slight, decrease in heterotrophic
 organisms during the course of the remediation (Figure 3)  and changes
 in the ratio of forms of nitrogen present in the soil.
   The analysis of the heterotrophic population indicates  that signifi-
 cant changes occur after 7 weeks of treatment (Figure 4). Over the final
 5 weeks of the remediation, brightly pigmented bacteria emerge from
 the population. Heterotrophic organisms in general decrease; the pro-
 portion of the hydrocarbon degrading organisms increases. As stated,
  The nutrient concentrations attained during the study were sufficient
to evaluate the effect of increased concentrations on bioremediation.
The increased nutrient concentrations did not have an effect on the rate
of degradation. It is also possible that increasing the concentration of
nutrients may have the negative effect of stimulating populations of
organisms that do not  degrade TPH.

CONCLUSIONS
  The solid phase remediation program implemented for this site has
been extremely successful. More than 150,000 cubic yards of soil have
been treated and removed from the LTUs to date. Approximately 120,000
cubic yards  of soil remain to be treated. More than 20,000 samples of
soil from excavation, process monitoring, verification sampling of the
LTUs and backfilling operations have been taken throughout the course
of the  remediation. Several optimization studies are being conducted
on-site during the remediation at an incremental cost to the remedia-
tion. These studies  assure  that the optimal rate of remediation  is
occurring and provide valuable information to the client for use at other
sites which are candidates for bioremediation.
                                                                                                                   BIOTREATMENT   817
-------
CASE HISTORIES: PETROLEUM MARKETING
TERMINAL REMEDIATION
  A former marketing terminal in the Western United States had been
contaminated by losses incurred during the handling of petroleum
products during 65 years of operation. More than 60,000 cubic yards
of soil are contaminated with petroleum hydrocarbons at a mean con-
centration of 2,660 parts per million (ppm). Groundwater analyses iden-
tified benzene as the compound of concern.  Ethylbenzene, toluene and
xylenes are  present at low concentrations.
  ECOVA Corporation was hired to assist in the development of a
Remedial Action Plan (RAP)  for the fuel terminal site. A laboratory
treatability evaluation to assess treatment options and cleanup levels
achievable from those options was conducted. Options studied included
excavation and off-site disposal; off-site treatment; and on-site treat-
ment focusing on bioremedmtion. Activities managed in support of the
RAP included preliminary design of cleanup systems and regulatory
liaison and public  involvement activities.
  The RAP served as the basis for negotiations between the client and
the lead regulatory agency which resulted hi the signing of a voluntary
Order on Consent. The voluntary Order on Consent was finalized in
November 1988.
  Two recommended treatment alternatives, on-site solid-phase biotreat-
ment and in situ biotreatment, were selected because of the destruc-
tion of the contaminants and  significant cost savings compared with
off-site disposal. Bioremediation of the contaminated soil reduces the
hydrocarbon contaminant level to below the agreed to cleanup level of
200 ppm. Water cleanup criteria for the contaminants are as follows:
total nydrocarbons-15 ppm; benzene-40 parts per billion (ppb),  and
ethylbenzene-3.5 ppm. Once these levels are achieved, the site will be
rendered clean and suitable for development.
  ECOVA Corporation was awarded the full-scale remediation contract
in February  1989 after winning a competitive bid over 30 other major
environmental contractors. The multimillion dollar project is the largest
biological remediation project undertaken in the State of Washington.
  The first  task involved  preparation of a detailed Work  Plan  and
initiation of permitting. The Work Plan contained the final design of
the remedial systems and a detailed description of the installation and
operation procedures to be followed during  the remediation. Once the
necessary permits were obtained, the remedial program was initiated.
  The remedial program involved demolition, installation and opera-
tion of in situ systems and excavation and treatment of contaminated
soil. This paper describes the activities and results obtained  to date
related to the solid-phase biotreatment component of the remedial pro-
gram. A discussion of the  activities and  results to date related to the
in situ biotreatment component of the remedial program can be found
in another paper within these proceedings by Nelson and others.
  The site is divided into four areas (Figure 5). The original plan called
for contaminated soil from Area A to be treated in Area B and then
returned to Area A for replacement and compaction.  Transportation
of the contaminated soil to Area B is accomplished with a conveyor
system running through an existing pipe tunnel under the major street
separating Areas A and B. Solid-phase biotreatment of contaminated
soil in Area  B would then follow. Contaminated zones in Areas C and
D are treated by in situ biotreatment and soil oxygenation.
  Demolition activities began in May 1989.  Surface and subsurface
structures were demolished and significant quantities of demolition
debris, including concrete rubble, pipe, brick and wood were removed.
Excavation of contaminated soil in Area A indicated that the extent of
contamination was greater than  the preliminary investigation determined.
As a result of the increased volume of contaminated soil, Area A is
used as a solid-phase treatment area as well, and the treated soil from
Areas A and B is transported off-site for disposal after treatment to
below the 200 ppm cleanup criteria.  Solid-phase biotreatment began
in Area B in September 1989 and in Area A in October 1989.
  Figures 6  and 7  present  some operational data for the solid-phase
treatment program to date. Figure 6 indicates  that the average lift volume
is approximate!) 2,800 cubic  yards. The lift volume varies due to a
number of factors The area available for treatment vanes between treat-
      HYDROCARBON MONITOR
      METEOROLOGICAL TOWER
                             Figure 5
                             Site Map
ment area and the surface area which is affected by stockpile side-slope
requirements and other site activities. Also, the lift size varies depending
upon whether or not all cells within the lift  are treated to below the
treatment criteria. If there are cells that have not reached the treatment
criteria, these cells remain in the treatment unit and are incorporated
into the next  treatment lift.

                      345678
                               Lin NUMBER
                        D  CACM Lin    *  AVOEC'/.. .1

                            Figure 6
                   Average Treatment Lift Volume
  Figure 7 shows the actual treatment time required for each lift and
the running average treatment time for all lifts to date. The bench-scale
treatability studies for the site indicated that treatment times should be
in the 3 to 6 week time frame,  if optimal degradation rates are main-
tained. This optimal treatment range is represented in Figure 7 as two
horizontal lines. As can be seen in the  figure,  8 of the 12 lifts com-
pleted to date are within the 3- to 6-week treatment time frame estimated
by the treatability study. Four lifts have required longer treatment times.
  Lifts 4 through 6 were treated during the winter months when am-
bient temperatures were colder than normal and snow accumulated and
remained on  the  ground for 2 weeks.  This  colder  temperature sig-
nificantly reduced the treatment  rates. The general  rule of thumb is
that for every K)°F decrease in temperature, there is an associated 50%
decrease in degradation rates. In addition, the rainwater control tarp
systems were not fully operational. As a result, the soil moisture levels
SIS    BIOTRKATMFNT
-------
                                                   10   II   12
                              LIFT NUMBER
                       O  EACH LIFI    + AVCEflAGE
                            Figure 7
                     Treatment Tune by Lift


were higher than optimal which further contributed to the decreased
treatment rates and the associated increase in treatment times.
  The treatment time for Lift 8 was significantly longer than the 3-
to 6-week treatment time frame estimated by the treatability study. A
number of factors are responsible for the extended treatment time
requirements for this lift. The primary factor is excessive soil moisture.
  In early June, the lift was within 1 week of reaching the cleanup
criteria in more than 80% of the cells in the lift. However, before the
verification samples were collected, an unanticipated storm saturated
the upper 24 to 36 inches of the lift before the rainwater control tarp
systems could be deployed. Efforts to reduce the amount of soil moisture
by tilling resulted in contaminated soil and water from lower lifts be-
ing brought up to within the current treatment lift. As a result, the next
sampling indicated that the concentrations in all cells were at or above
the original starting concentrations. Therefore, the entire treatment pro-
cess had to stan again and resulted in a lift mat had a treatment time
approximately double (12.4 weeks) the maximum treatment time re-
quirement indicated by the treatability study.
  Figure 7 also indicates that subsequent treatment times have been
on the lower end of the 3- to 6-week treatment time range. This im-
proved performance is due to the warmer temperatures that occurred
during the later part of the summer and early fall. The average treat-
ment time, which has been shifted higher by the four lifts discussed
above, is back within the 3- to 6-week treatment time range.
  To date, approximately 32,000 cubic yards of contaminated soil have
been treated to below the 200 ppm cleanup criterion  and disposed off-
site. An additional 25,000 to 30,000 cubic yards of contaminated soil
from Areas A and B will be treated before the solid-phase component
of the remedial program is concluded.
                                                                                                                BIOTREATMENT    819
-------
      Abiotic  Immobilization/Detoxification  of  Recalcitrant  Organics
                                                        Gene Whelan
                                               Pacific  Northwest Laboratory
                                                 Richland,  Washington and
                                                   Utah State University
                                                         Logan,  Utah
                                                  Ronald C Sims, Ph.D.
                                                   Utah State University
                                                         Logan,  Utah
ABSTRACT
  In contrast to many remedial techniques that simply transfer hazar-
dous wastes from one part of the environment to another (e.g., off-site
landfilling), in situ restoration may offer a safe and cost-effective solu-
tion through transformation (to less hazardous products) or destruc-
tion of recalcitrant  organics.  Currently,  the  U.S.  Environmental
Protection Agency and U.S. Department of Energy are encouraging
research that addresses the development of innovative alternatives for
hazardous waste control. One such alternative is biotic and abiotic im-
mobilization and detoxification of poly nuclear aromatic hydrocarbons
(PNAs) as associated with the soil humification process. This  paper
discusses: (1) the possibility of using abiotic catalysis (with manganese
dioxide) to polymerize organic substances, (2) aspects associated with
the thermodynamics and kinetics of the process and (3) a simple model
upon which analyses may  be based.

INTRODUCTION
  Humic materials are natural  organic substances that are common in
the environment and are involved in a nonstop polymerization process
with organic molecules. Polymerization of humus material (humifica-
tion) involves the breakdown, convolution, and transformation of organic
matter into long, complex, amorphous organic molecules with numerous
reactive functional groups and bridges that are similar to the reactive
groups added to aromatic compounds by microbial enzymatic action.
Functional  groups include hydroxyl, carboxyl, ketonic, phenolic,
quinone,  ester,  ether,  carbonyl,  imino  and amino  groups,  with
dihydrodiol and  dione (e.g., quinone) structural formations  showing
promise in promoting polymerization. During humus formation, reac-
tive compounds are linked through biotic-enzymatic and/or abiotic-
chemical reactions, resulting in complexes of polymerized molecules.
Biotically induced polymerization, for example, can result in oxidative
coupling  of nonreactive organics (e.g., anilines) into active organic
polymerization  processes  (e.g.,  using  dichlorophenols).1  More
recently, scientists have noted that abiotically catalyzed polymeriza-
tion may also represent an important aspect of humification.2"5 For
example, manganese-bearing silicates have demonstrated catalytic effects
in enhancing the polymerization of polyphenols (e.g., hydroquinone).5

ABIOTIC CO-POLYMERIZATION
  Research at Utah State University (USU) has indicated that multiple-
ringed constituents might be humified. Soil samples spiked with  a I4C-
labelled benzo(a)pyrene [B(a)P]  [the structure of which  is  shown in
Figure  1] have shown activity in humic  and  fulvic acid soil samples,
which previously had been extracted with methylene chloride. The ex-
traction procedure did not remove all of the radiolabelled carbon, sug-
gesting some sort of  binding process between the B(a)P molecule or
a portion of it and the humus material. These results suggest that the
B(a)P [or B(a)P intermediate or product] was structurally bound in some
way to the humic/fulvic material and humin that was formed. These
results occurred for both sterile and nonsterile samples. The results
suggest that: (1) co-polymerization of multiple-ringed constituents might
be possible and (2) abiotically catalyzed polymerization may also be
occurring and may be as important as microbially mediated polymeriza-
tion in humification. If one reviews the structures of humus (Figure
2) and those of B(a)P metabolites (Figure 3), one notes functional-group
similarities. Jeftic and Adams6 presented a general reaction scheme for
the anodic oxidation of B(a)P,  illustrating its transformations and
polymerization properties.
  Bollag,2 whose  research  focuses  on  enzymatically  induced
polymerization, stated that abiotically mediated catalysis also may be
important. One result of his research was the indication that most reac-
tants appeared to move through a transitional quinone-like structure
prior to the final  humified product. Senesi and Schnitzer7 have pro-
posed similar pathways for abiotically  induced polymerization. They
suggested that hydroquinone [1,4-C6H4(OH)2] goes to the semiquinone
                            Figure 1
                    Structure of Benzo(a)pyrcne
S20   BIOTREATMENT
-------
radical [•C6H4O(OH)]  and that this  radical forms a  quinone
(1,4-C6H4O2) where all reactions are reversible (Figure 4):

  C6H4(OH)2 = •C6H40(OH) + H+ + e-                    (1)
  •C6H40(OH) =  C6H402 + H+  + e-                       (2)

  Shindo and Huang3-8 explained the polymerization of hydroquinone
in the following manner, using oxidation-reduction potentials (E°)9'10
for manganese dioxide (MnO2) and hydroquinone:

                                        E° =  +1.224 V  (3)
                                        E° =  -0.6992 V  (4)
MnO2 + 4H+ + 2e- = Mn2+ -,  -,v
C6H4(OH)2 = C6H402  + 2 H+ + 2 e-
Thennodynamically, the overall oxidation-reduction reaction is +0.525
V, indicating that the oxidation of diphenol (i.e., hydroquinone) by
manganese dioxide is favorable. Shindo and Huang" took a similar ap-
proach to explain the catalytic polymerization of hydroquinone by
primary minerals,  especially the olivine  tephroite (MnjSiC^).
Schnitzer12 suggested that the rate-determining step in the synthesis,
by oxidative polymerization of humic acids from simple phenols and
phenolic acids, is the formation of a semiquinone radical involving a
one-electron transfer reaction. These relatively unstable and reactive
semiquinone radicals will couple with each other to form a stable humic
acid polymer. Shindo and Huang5 noted that because the coupling of
radicals requires no activation energy (in contrast to electron transfer
reactions), coupling of semiquinones rather than the formation of
quinones should be kinetically the preferred reaction path. Therefore,
diphenols should be converted to humic acid through semiquinones
during the reduction of Mn(IV) oxides. Senesi and Schnitzer7 noted
that the semiquinone  radical can form a semiquinone radical ion
[(•C6H4O2)-] and then a semiquinone dianion [(C6H4O2)2'], where all
reactions are reversible (Figure 4):
  •C6H40(OH) = CC6H402)- + H+
  (•C6H402)- = e- = (C6H402)2-
           (5)
           (6)
                        In previous work, Kononova13 and Schnitzer and Kahn14 made a
                      statement similar  to that  of  Shindo and  Huang5  regarding the
                      polymerization of hydroquinone through a semiquinone radical.15'16
                      Wang et al.16 also reported that in the absence of an electrophilic
                      substituent in the ring of the hydroquinone, phenolic hydroxyl groups
                      act like weak acids, and with an increasing pH solution, the hydro-
                      quinone dissociates  to a semiquinone anion ([C6H4O(OH)]~):
                      C6H4(OH)2 = [C6H40(OH)]-  + H
                                                                                                                           (7)
                      Upon  oxidation by,  for  example,  a manganese  oxide  [in  which
                      manganese acts as an electron acceptor and becomes reduced (acting
                      as a Lewis acid)], the semiquinone anion is converted into a semiquinone
                      radical (Figure 4).
                      [C6H40(OH)]- = •C6H40(OH) + e'
                                                                                                                           (8)
                       Benzo(a)pyrene-cis-9,10-Dihydrodiol
                                                             Benzo(a)pyrene-3,6-Dione
                                                 Figure 3
                                      Structures of Biologically Mediated
                                        Benzo(a)pyrene Intermediates
                                                                 Under neutral or higher pH conditions and in the presence of air (i.e.,
                                                                 oxygen, which acts as an electron acceptor) and MnO2, the dissolved
                                                                 Mn2+ is rapidly oxidized to form MnO2 through auto-oxidation:
                                                                                     DH
                HOOC   H
       HQOC
                                                                                                                      COCH
                       HOQC
c^Lo-^i-M^T:S-a-S-Sz-i-K-g-t-S-g-M-a
v   /r^                    \__y      i             i          i
N  £H          C'Pc-CH              ^          9Hi      CDQH
N  Vn«        -U ~*^- ~t. ^^n
                                                         •DH
                                                             Figure 2
                                                    Illustrative Structure of Humus
                                                                                                             BIOTREATMENT   821
-------
* +  Vt O2 + H£> = MnO2  + 2
                                                               (9)
   The terminal electron acceptor of the abiotic-catalytic process is free
   oxygen.
Hydroquinone
                                 Seoiquinone Radical
                                                              Quinone
                         Seroiquinone
                         Dianion
                             Semiqu inone
                             Radical
                             Anion
                               Figure 4
        Proposed Relationships Between Quinone, Semiquinone Radical,
       Hydroquinone, Semiquinone Radical Ion and Semiquinone Dianion
              [After Senesi and Schnitzer7 and Wang et al.16]
   PROPOSED MODEL DESCRIBING REDUCTIVE
   DISSOLUTION AND AUTO-OXIDATION
     Stone17 notes that rates of reductive dissolution of transition metal
   oxide/hydroxide minerals are controlled by rates of surface chemical
   reactions and that transition metal oxides/hydroxides differ in their ability
   to oxidize organic compounds. He listed reduction potentials for nickel,
   manganese, cobalt and iron. Based on their thermodynamic data, their
   oxidant strength decreased in the following order: Ni3O4 > MnO2 >
   MnOOH >  CoOOH > FeOOH. Because manganese is a relatively
   strong oxidant that is readily found  in soil, its reductive dissolution
   and autooxidative characteristics  are reviewed.
     Stone and Morgan18 proposed a simple model for describing reduc-
   tive dissolution of Mn(III) with  phenol. Based on their work, a simple
   illustrative model is proposed herein for the reductive dissolution and
   autooxidation of Mn(TV) and transformation of hydroquinone.  The
   following assumptions apply to this  analysis:
   • Manganese(TV) represents the  oxidized form of the metal.
   • The oxidized organic product is represented as a radical,  because
     under aerobic conditions a radical represents the most likely pro-
     duct for polymerization reactions.5i8-11-15'26
   • Transport-controlled  reactions are assumed not to  occur.27  The
     dissolution rate is controlled  by the rates of surface chemical reac-
     tions (assuming for this paper inner-sphere complexation) and not
     by diffusion.28
   • The release of the reduced metal ion is independent of the product
     concentrations, indicating that the release of the reduced metal from
     the oxide surface is unidirectional.27
   • The availability of the oxidized metal surface [i.e.,  =Mn'v(OH)2]
     is not limiting in the proposed reactions, and the total number of
     surface sites remains constant as a new site is generated when a re-
     duced manganese ion is released. This assumption does not address
     the potential  for the oxide surface to readsorb reduced manganese
     (i.e., dissolved Mn2*)  or dissolved oxidized organics. Stone and
     Morgan27 investigated the potential for  readsorption of Mn2+ and
     determined that the loss of Mn:" was less than 2%  of the amount
     of manganese added. The number of moles of surface sites is assumed
     to equal 6"?  of the number of moles of total manganese  added to
  the system. Stone and Mat^aP estimated the number of manganese
  oxide surface sites (based on moles) in their experimental setup to
  be between 3.5 and 9.0% of the total oxide  added to the system.
• The organic substrate (i.e., hydroquinone) is in excess, and its mass
  changes negligibly in the system. The hydroquinone is assumed to
  represent a simple surrogate for other dione- and diol-configured
  organics.
This paper presents a simple model for describing reductive dissolu-
tion and autooxidation. It illustrates the importance of oxygen and the
impact that autooxidation has on Mn2"1" concentrations. The remaining
portions of this paper describe the general  stoichiometric  equations
associated with the process and present a brief analysis illustrating their
application.

Half Reactions and Inner-Sphere Mechanism for
Reductive Dissolution of Mn(TV)
  The half-reactions associated with the reductive dissolution of Mn(TV)
and the oxidation of hydroquinone (i.e., QHj) are presented in Table
I.29 Stone and Morgan18 have mechanistically described these equa-
tions in four steps: (1) precursor-complex formation (i.e., reductant ad-
sorption), (2) electron transfer, (3) release of oxidized organic product
and (4) release of reduced metal ion. Precursor-complex formation may
be either an inner-sphere reaction, when incoming organics bind directly
to the surface metal centers, or an outer-sphere reaction, where a layer
of coordinated hydroxyl groups or water molecules separate the organic
from the surface metal centers.18 Hydroxyl groups exist at the surface
of the manganese dioxide mineral [i.e.,  MnwO2(s)]; these hydroxyl
groups are used to balance the charge at the surface - water interface
and can be expressed as sMnlv(OH)2, where  " ="  refers to the ox-
ide surface. The following four steps can be used to describe the inner-
sphere complex formation between hydroquinone and the manganese
dioxide surface:18
• Precursor-Complex Formation (Reductant Adsorption):
                                                                   IV
                                                                   lv
EMn(OH), + 2  QH,   <
                                                                                                                            (10)
where k, and k, are rate constants in the forward and reverse direc-
tions, respectively.

• Electron Transfer:

                k2
               ==
                k
E«nIV(QH)2
^nH(-QH)2
                                                                                                                            (11)
                                                                                 -2
where
tions, respectively.
                                                                         and k 2 are rate constants in the forward and reverse direc-
                                                                   Release of Oxidized Organic Product:
                                                                   n
^ln"(-QH)2  +  H20   <=
                                                                                       k3
                                                                                       "-3
       ^lnnOH0
                                                                                                         2  (-QH)
                                                            (12)
                                                                where kj and k 3 are rate constants in the forward and reverse direc-
                                                                tions, respectively, and «QH is a Semiquinone radical. By noting that
                                                                Mn(II) still resides on the oxide surface, the Mn(II) products of Equa-
                                                                tion 12 can also be written as follows, because the right- and left-hand
                                                                sides of Equation  13 are equivalent:

                                                                        2           2*2'
                                                                where " sMnrvO2-(MnnOH7)" represents the reduced metal complex
                                                                on the  Mn(IV) surface prior to Mn(II) release.

                                                                •  Release of Reduced Metal Ion:

                                                                Stone and Ulrich30 noted that protons frequently assist in the metal-
                                                                detachment step of dissolution reactions and that studies have general-
                                                                ly found the number of protons involved to be equal to the valence of
                                                                the detached metal (i.e., 2).31 They continued to note that the actual
                                                                number of protons involved in reductive dissolution is not known with
          BIOTREATMENT
-------
certainty, because the presence of two or more oxidation states on the
metal surface may alter the pH dependence of the metal'release step.
The release of the reduced metal ion from the surface is expressed as
follows:

^lnIV02-(MnnOH2) + 2 H+	>  ^1nIV(OH)2 + Hn2+ + H20 (14)
where k4 is a rate constant. In experiments to determine the effect of
varying amounts of Mn2+ on the rate of dissolution of MnO2(s), Stone
and Morgan27 found that the initial rates of dissolution with varying
amounts of Mn2+ in solution had no effect on the kinetics.  Based on
these results, one might conclude that Equation  14 is not rate-limiting
and can be considered to be  unidirectional. The amount of Mn2+ in
solution does not influence the rate of its formation. This conclusion
appears to be confirmed by the fact that Mn(II) has a larger radius than
Mn(TV) and does not appear to fit  into the solid structure of MnO2(s)
very well. As such, the Mn(H) ion is readily released from the matrix.
                            Table 1
              Half Reactions for Reductive Dissolution

              HnIV02(s) + 4 H* t 2 e' =   Hn2'1' + 2 HjO
2 QH
                           2 (-QH) + 2 H+ + 2 e-
    net:   HnIV02(s) + 2 QH2 + 2 H+ -  MnZ+ + 2 (-QH) -f 2 H20
                                       (1)

                                       (2)



                                       (3)
 Proposed Polymeric Products of MnffV) Dissolution/Auto-Oxidation
  Research has indicated that oxygen promotes oxidative coupling reac-
 tions, creating dimers, trimers and other less soluble, more surface-
 active oxidation products.5-8-11'15'26 These reactions can be expressed as
 follows:
 •QH + -QH
   polymeric  oxidation products
                                             (15)
 Auto-Oxidation of Mn(II) to Mn(TV)
   Stumm and Morgan32 presented reactions for the oxidation of Mn(II)
 to Mn(TV). They felt that the reactions might be visualized as proceeding
 according to the reactions presented in Table 2. They also note that
 the  Mn2+  concentration  decreases  with time  with  an apparent
 autocatalytic effect. Based on Stumm and Morgan32 and Morgan,34
 Benefield et al.33 describe the autocatalytic oxidation of Mn(Q) in the
 following manner:
 d[Mn2+]/dt
-k5 [MnT]  [P0J  [OH']2
                   [Mn2+]
                               Hn2+]
(16)
 where k, is a rate constant, Mn,, is the total manganese in the system,
 and [PCr] is the partial pressure of oxygen. Although Mn(II) is ox-
 idized according to  Equation 16,  it is unclear what  valence that
 manganese is oxidized to [i.e., Mn(in) or Mn(TV)]. To be a true catalyst,
 Mn2+ would have to be oxidized to Mn(IV) to regenerate the oxidative
 surfaces and maintain zero net change.

 KINETICS OF REDUCTIVE DISSOLUTION AND
 AUTO-OXIDATION
   This section proposes algorithms describing the kinetics of reduc-
 tive dissolution and autooxidation. The analysis presented above does
                             Table 2
                  Half Reactions for Autooxidation
                              slow
                                        .IVn
          i Hn" + J 02 + ! H20  	>  1 Mnlv02(s) + H+

                              fast         w    n
            Mn2+ + } HnIV02(s)
                      J
                            t  H20
                                   slow
                      MnIV02(s)
   net:
              i_2+
02 + H20  = HnIV02(s)  + 2 H+
                                         (1)


                                         (2)


                                         (3)


                                         (4)
                                                    not account for the removal of radical products [Equation 12] that are
                                                    consumed in  the polymerization  process,  although Taylor  and
                                                    Battersby35 note that the rate of disappearance of phenolate radicals
                                                    through dimerization has been clearly shown to follow second-order
                                                    kinetics.
                                                      Figure 5 presents a schematic illustration of the surface-site mass
                                                    balance for reductive dissolution and autooxidation, based on Equa-
                                                    tions 10 through 14 and Equation 16. Included in this figure are for-
                                                    mulae for the characteristic times associated with the reaction for each
                                                    rate. Assuming that the only species that contribute to the surface mass
                                                    balance equation are =Mnw(OH)2,  ^Mnw(QH)2, sMnn(»QH)2 and
                                                    = MnnOH2 and that other  competing anions are not considered, the
                                                    surface mass balance equation can be written as  follows:
                                                            -  [=MnIV(OH)2]
                                                                                                                (17)
                                                     where ST is the total moles of surface sites per liter of solution (M).
                                                     Under the assumption that each reaction can be described as an elemen-
                                                     tary  reaction,  rate expressions are  proposed for  =MnIV(OH)2,
                                                         = MnIV(QH)2,
                                                        through 7:
                                                         [QH]
                                                        d[-«nIV(QH)2]/dt  -

                                                        k, [QH2]2 [«*tn'V(OH)2]
                                                                     Mnn(«QH)2, and  =MnnOH2,  using Equations 4
                                                                                                                   [H+]2
                                                                                k2) [«MnIV(QH)z]
                                                                                                                            -QH)2]

                                                                      '  (k
                                                                      _2
                                                                                                [-QH]
                                                                    {k_3 [-QH]
                                                                                                                                   (21)
                                                     The rate expressions for the remaining nonsurface-constituent concen-
                                                     trations (i.e.,  [Mn2+], [QH2], and [»QH]) are as follows:
                                                     d[Hn2+]/dt  -
                                                                                                         .2+1    (22)
k4 [H+]  [^ln11OH2]   k5 [HnT]  [P0J [OH']' [Mn'  ] [Mny  Hn'


d[QH2]/dt  =    2 kj  [QH2]2 [^1nIV(OH)2] + 2 k.j  [^nIV(qH)2]     (23)


                                                           (24)
d[-QH]/dt  -

2 k3 [dmn(-QH)2]   2 k_3 [-QH]2 [*nUOH2]   polymerized products
                                                        Solutions to the Kinetic Rate Expressions
                                                          This section presents an illustrative example of the effects of kinetic
                                                        rate constants and other parameters in determining the importance of
                                                        reductant adsorption, electron transfer, surface release of oxidized
                                                        organics, surface release of the reduced  metal Mn2+  and auto-
                                                        oxidation. The response to variations in parameters contained in Equa-
                                                        tions 10 through 14 and in Equation 16 are determined through solu-
                                                        tions of Equations 17 through 24, which have been solved using Euler's
                                                        method.36 The solutions to these equations assume that the systems are
                                                        well buffered (constant pH).
                                                          As noted earlier, Schnitzer12 suggested that the rate-determining step
                                                        in the synthesis, by oxidative polymerization of humic acids from sim-
                                                        ple phenolic constituents and acids, is the formation of a semiquinone
                                                        radical  involving a  one-electron transfer reaction. This  illustrative
                                                        example investigates the conditions when the formation and release of
                                                        the semiquinone radical is rate-limiting. To meet this condition, either
                                                        the electron transfer step [i.e., formation of the radical on the oxide
                                                        surface, Equation 11] or the release of the oxidized organic radical from
                                                        the oxide surface [Equation 12] is rate limiting. For illustrative purposes,
                                                        the latter (i.e., release of radical from the surface) is assumed to be
                                                        the rate-limiting step.
                                                                                                                   BIOTREATMENT    823
-------
  The assumptions associated with this analysis are presented in Table
3.  Stone and Ulrich30 arbitrarily assigned numerical values for the
parameters presented in this table, which have been modified for this
example. The initial concentrations for [ST]° [ = Mn^OIpj] °,  and
[QHj]0 are also given in Table 3. All other initial concentrations (i.e.,
[•QH],  [Me2*],  [sMn^QH^], [^Mir^OR,], and [ =
are assumed as zero.
[HnT Mr,2*])'1
Auto-Oxidatic
Hn2+
t
n
 (2  k,  [QH.,]2)-1
                                                      (2 k3)
                                                           -1
                                           (2 k_3  [-QH]2)'1
                             Figure 5
             Schematic Illustration of the Surface-Site Mass
         Balance Equations (Expressions containing rate constants
         represent characteristic times.) [After Stone and Morgan18]
                              Table 3
             Parameter Values for the Illustrative Example
    Parameter
      k,
                   Value
             1.50E+02 l/H'/min
             6.00E-02 1/min
             l.OOE+00 l/m1n
             5.00E-01 l/«1n
             l.OOE-03 I/rain
             O.OOE+00 l/MZ/m
-------
4. Flaig, W., Beutelspacher, H. and Rietz, E., "Chemical Composition and
   Physical Properties of Humic Substances," hi Soil Components, Vol. 1,
   Organic Components, Ed. J. E. Gieseking, Springer-Verlag, Berlin, 1975.
5. Shindo, H., and Huang, P.M.,  "Catalytic Effects of Manganese(TV),
   Iron(m), Aluminum, and Silicon Oxides on the Formation of Phenolic
   Polymers," Soil. Sci. Soc. Am. J. 48:927-934,  1984.
6. Jeftic, L., and Adams, R. N., "Electrochemical Oxidation Pathways of Ben-
   zo(a)Pyrene," J. Amer. Chem.  Soc,  92:(5)1332-1337, 1970.
7. Senesi, N., and Schnitzer, M., "Effects of pH, Reaction Tune, Chemical
   Reduction, and Irradiation on ESR Spectra of Fulvic Acid," Soil Science,
   £3:(4)224-234, 1977.
 8. Shindo, H., and Huang, P.M., "Role of Manganese(TV) Oxide in Abiotic
    Formation of Humic Substances in the Environment," Nature (London),
    298:363-365,  1982.
 9. Weast, R.C. Ed., CRC Handbook of Chemistry and Physics, 64th ed., CRC
    Press, Inc., West Palm Beach, FL,  1983.
10. Weast, R.C. Ed., CRC Handbook of Chemistry and Physics, 59th ed., CRC
    Press, Inc., West Palm Beach, FL,  1978.
11.  Shindo, H., and Huang, P.M., "Catalytic Polymerization of Hydroquinone
    by Primary Minerals," Soil Science, 139:(6)505-511, 1985.
12.  Schnitzer, M., "Quo Vadis Soil Organic Matter Research," Panel Discus-
    sion Papers, Whither Soil Research, Publications of the 12th Int. Congr.
    Soil Sci., New Delhi,  5:67-78, 1982.
13.  Kononova, M.M.,  "Humus of Virgin and Cultivated Soils," in Soil Com-
    ponents, Ibl.  I: Organic Components, Ed. J.  C. Gieseking, pp. 74-75,
    Springer-Verlag, New York, 1975.
14. Schnitzer, M. and Khan, S.U., Humic Substances in the Environment, Marcel
    Dekker, New York,  1972.
15.  Wang, T.S.C., Huang, P.M., Chou, C.-H. and Chen, J.-H., "The Role of
    Soil Minerals in the Abiotic Polymerization of Phenolic Compounds and
    Formation of Humic Substances," in Interaction of Soil  Minerals With
    Natural Organics and Microbes, Soil Science Society of America Special
    Publication No. 17, pp. 251-281, 1986.
16. Wang, T.S.C,Kao,M.-M., Huang, P.M., "The Effect of pH on the Catalytic
    Synthesis of Humic Substances by lUite," SoilScience, 129: (6)333-338,1980.
17.  Stone, AT., "Adsorption of Organic Reductants and Subsequent Electron
    Transfer on Metal Oxide Surfaces," in Geochemical Processes at Mineral
    Surfaces, eds. J. A. Davis and K. F. Hayes, pp. 446-461, American Chemical
    Society, Washington, D.C., 1986.
18.  Stone, A.T. and Morgan, J.J., "Reductive Dissolution of Metal Oxides,"
    in Aquatic Surface Chemistry, Ed. W. Stumm, pp. 221-254, John Wiley
    & Sons, New York, 1987.
19.  Shindo, H. and Huang, P.M., "Significance of Mn(TV) Oxide in Abiotic
    Formation of Organic Nitrogen Complexes in Natural Environments," in
     Nature (London), 308:57-58, 1984.
20.  Larson, R.A. and Hufnal, J.M., "Oxidative Polymerization of Dissolved
     Phenols  by Soluble  and  Insoluble  Species,"  Limmol.  Oceanogr,
     25:(3)505-512, 1980.
21.  Wang, T.S.C., Wang, M.-C. and Ferng.Y.L. "Catalytic Synthesis of Humic
     Substances by Natural Clays, Silts, and Soils," SoilScience, 135:(6)350-359,
     1983.
22.  Wang, T.S.C., Wang, M.-C. and Huang, P.M. "Catalytic Synthesis of Humic
     Substances by Using Aluminas as Catalysts," Soil Science, 136: (4)226-230,
     1983.
23.  Wang, T.S.C., Li, S.W. and  Ferng, Y.L.  "Catalytic Polymerization of
     Phenolic Compounds by Clay Minerals," Soil Science, 126: (1)15-21, 1978.
24.  Wang,  T.S.C.,  Li, S.W. and Huang, P.M.  "Catalytic Polymerization of
     Phenolic Compounds by a Latosol," Soil Science,  126: (2)81-86, 1978.
25.  Stone,  A.T., "Reductive Dissolution  of Manganese(ffl/IV)  Oxides by
     Substituted Phenols," Environ.  Sci.  Technol, 21: (10)979-988, 1987.
26.  LaKind, J.S. and Stone, A.T., "Reductive Dissolution of Geothite by Phenolic
     Reductants," Geochim. Cosmochim. Acta,  53:961-971, 1989.
27.   Stone, A.T. and Morgan, J. J., "Reduction and Dissolution of Manganese(m)
     and Manganese(TV) Oxides by Organics.  1. Reaction with Hydroquinone,"
     Environ. Sci. Technol, 18:(6)450-456, 1984.
28.  Stone,  A.T., The Reduction and Dissolution of Manganese (III) and (IV)
     Oxides by Organics, Ph.D. Dissertation, California Institute of Technology,
     Pasadena, CA, 1983.
29.  Lindsay, W.L., Chemical Equilibria in Soils, John Wiley & Sons, New York,
     1979.
30.  Stone, A.T. and Ulrich, H.-J., "Kinetics and Reaction Stoichiometry in the
     Reductive Dissolution of Manganese(IV) Dioxide and Co(IH) Oxide by
     Hydroquinone,"/ of Colloidal and Interface Science,  732:(2)509-522, 1989.
31.  Furrer, G. and Stumm, W, "The Coordination Chemistry of Weathering:
     I. Dissolution Kinetics of 5-A12O3 and BeO,"  Geochim. Cosmichim. Acta,
     50:1847-1860,  1986.
32.  Stumm, W. and Morgan, J.J., Aquatic Chemistry, John Wiley & Sons, New
     York,  1981.
33.  Benefield, L.D., Judkins, J.F. and Weand, B.L., Process Chemistry for Wttter
     and Wastewater Treatment, Prentice-Hall,  New York, 1982.
34.  Morgan, J.J., "Chemical Equilibria and Kinetic Properties of Manganese
     in Natural Waters," in Principles and Applications of Water Chemistry, Eds.
     S. D. Faust and J. V. Hunter, pp. 561-624, John Wiley & Sons, New York,
     1967.
35.  Taylor, W.I. and Battersby, A.R., Eds., Oxidative Coupling of Phenols,
     pp. vii, Marcel Dekker, New York, 1967.
36.  Carnahan, B., Luther, H. A. and Wilkes, J.O., Applied Numerical Methods,
     pp. 344-352, John Wiley & Sons,  New York, 1969.
                                                                                                                                 BIOTREATMENT  825
-------
                    Enhancement  of PCP and  TCE  Biodegradation
                                            By  Hydrogen  Peroxide
                                                Judith B. Carberry, Ph.D.
                                                   University of Delaware
                                                      Newark,  Delaware
ABSTRACT
  Two model toxic chemicals were previously identified as recalcitrant
to biodegradation by activated sludge and selected microbial consor-
tia.  Each model toxic chemical was subjected to chemical oxidation,
both by hydrogen peroxide and by Fenton's reagent. Chemical oxida-
tion rates and biodegradation rates before and after chemical oxidation
were measured. Fenton's reagent was a particularly effective oxidizing
agent. Subsequent microbial degradation was enhanced by Fenton's
reagent pretreatment.  Chloride ions were produced by both chemical
oxidation and microbial degradation.

INTRODUCTION
  Pentachlorophenol  (PCP) and its sodium salt are widely used
pesticides in the United States. The advantages of using PCP and its
derivatives are that they are effective biocides and  soluble in both oil
and water. Although PCP and its derivatives have many uses, by far
the major application is for wood preservation. Trichloroethylene (TCE)
is a very useful cleaner and spot remover and is widely used as an in-
dustrial, household and military degreaser.
  Economical bioremediation of contaminated soil can be carried out
before a plume of toxic chemical penetrates an underground aquifer.
Since recalcitrant  organics  in contaminated  soils  are degraded only
slowly, pre-oxidation of recalcitrants and persistent toxic chemicals into
more readily degradable  substances may be useful  to improve soil
bioremediation techniques.
  This enhancement occurs if the initial oxidation step of the sequen-
tial  microbial  mineralization process can be carried out chemically,
rather than biologically. The initial rate-limiting step for the microbes,
therefore, is bypassed by the addition of aqueous chemical oxidants and
the resulting partially oxidized products become more polar, more solu-
ble and more easily degraded than the parent toxic organic chemical.
In addition, the resulting residual decreased toxic chemical concentra-
tion becomes less toxic to the microorganisms and  is, therefore, more
quickly degraded.
  In our laboratory, a generic microbial  selection process is utilized.
Selected microbial consortia (SMC) for various model toxic chemicals
are developed  from contaminated soils obtained at  nearby toxic waste
sites prior to any remediation. Then reactor conditions are optimized
for each aqueous solution of specific  chemical and  its consortium and
resulting  biodegradation  rates  are  measured by  a respirometer.  A
replicate aqueous solution of each specific chemical is then subjected
to chemical oxidation by hydrogen peroxide solution and by Fenton's
reagent (a mixture of hydrogen peroxide and Fe*:). Respirometric
measurements due to microbial biodegradation of the resulting oxida-
tion products are then conducted as before. A replicate set of experiments
is also carried out using a stock culture  of activated sludge microbes
in order to determine any decrease in toxicity due to chemical pre-
oxidation treatment.

BACKGROUND
  In the United States, 78% of the PCP produced is used by the wood
preserving industry, 12% in production of Na-PCP, 6% in plywood and
fiberboard waterproofing, 3% in domestic use and 1% as a herbicide.1
Though PCP-treated products do not appear to represent a threat to
the environment, accidental spillage and improper disposal of PCP at
the approximately 600 United States manufacturing plants and at wood-
preserving facilities have resulted in extensive contamination of soil,
surface  water and  groundwater  aquifers.2'3 Pentachlorophenol is
presumed to be the most resistant chemical to microbial degradation;
however, the feasibility of biological treatment of pentachlorophenol
has been the subject of numerous research papers.4""
  Early studies on TCE biodegradation produced anaerobic  degrada-
tion products which were toxic.12'14 Wilson and Wilson15 cited TCE as
a compound resistant to biodegradation in  aerobic subsurface en-
vironments, but Parsons, et al.16 conducted experiments indicating that
biological  activity was responsible for tetrachloroethylene and TCE
transformations in aerobic microcosms containing  cultured  bacteria.
Recently, additional workers have been conducting aerobic studies with
methanogenic and other bacterial cultures.17'19
  Other researchers have investigated whether microbial degradation
could be enhanced if the toxic carbon source could be oxidized to a
metabolite  which is more readily degraded by microorganisms. Bishop,
et al.20 conducted an experimental study on uncharacterized municipal
wastewaters containing a wide variety of refractory organics  using
peroxide-ferrous ion solutions producing hydroxyl radical. Bowers, et
al.21  also  examined the  preoxidation of uncharacterized industrial
wastewaters with hydrogen peroxide and found reduced toxicity of
oxidation products  when compared to the original wastes. The reactions
to illustrate peroxide mechanisms are discussed below.
  Peroxide can dissociate into water and oxygen to provide an oxygen
source, as follows:
2H2O2
                      O
(1)
In contrast, Fenton's reagent reacts to produce both the hydroxyl ion
and the hydroxyl radical, as follows:
Fe+
                   Fe+2  + OH  +'OH
                                                           (2)
  The hydroxyl radical can then attract a hydrogen atom from an organic
substrate to produce an organic radical, as follows:
RH  + 'OH - -R
                         H2O
                                                                                                                               (3)
$:t.   BIOTRE.ATMENT
-------
  The organic radicals exist as transient intermediates and may be fur-
ther oxidized by Fe+3 oxygen, or hydroxyl radical to form final, stable
oxidation products.  The  oxidation products may be  more  easily
biodegraded than the  parent organic chemicals such as  PCP.
  The total oxidation reactions of PCP and TCE are expressed as
follows:
PCP C6OHC15
                            6CO
TCE C2HC13 + 4.5H22O2 -» 2CO2
                                                + 5C1

                                                 3Cr
  These reactions were used to determine peroxide and Fenton's reagent
doses that would only partially oxidize the model chemicals for subse-
quent microbial biodegradation.
  The  chemicals  were  subjected  to microbial  biodegradation
respirometric measurements before and after chemical oxidation, and
reactions rates were calculated using Equations 4 and 5.
  R - -
           A  St
                              -St  -  t.
                               (X0  +  Xt)  /2
                                                           (4)
where
    S is the substrate concentration
    t is time
    X is microbial biomass concentration

  Subscripts o and t represent initial and anytime t, respectively, and
superbar denotes an average value.
  The values of R at each S were then evaluated using a Michaelis-
Menten function, expressed in Equation 5:
  R=
       Ks
                                                            (5)
where
    ko is the maximum substrate uptake rate constant
    Ks is the half velocity  constant,  or substrate  concentration at
which specific substrate uptake, R, is half the maximum rate.

METHODS AND MATERIALS
  Details of  experimental  procedures  have been described  pre-
viously.22'23  Briefly,  the following  experimental  variations were
examined:
• Set 1.  Hydrogen peroxide and PCP or TCE
• Set 2.  Hydrogen peroxide, ferrous ion and PCP or TCE
• Set 3.  Hydrogen peroxide, PCP, or TCE and selected microbial
         consortia (or activated sludge)
• Set 4.  Hydrogen peroxide, ferrous ion, PCP or TCE  and selected
         microbial consortia (or activated sludge)
  Replicate reactors and controls were  run for  each respirometric
experiment. For each analysis, a 5-mL sample was withdrawn by syringe
through the rubber septum of each reactor vessel. For TCE determina-
tions, the aqueous sample was extracted using a MIXXOR (GENEX
Corporation, Maryland) in 5 mL of n-pentane with 20 strokes.  Two
mL of the extracted  TCE in  n-pentane was mixed with 2 mL of
dibromodichloromethane (DBDCM) in a 10-mL vial. One fiL samples
of this solution were analyzed by a Varian Gas Chromatograph equip-
ped with  an FID detector at  310 °C and a 30-m DB-5 (J  & W Scien-
tific) capillary column.  A temperature  program of 35 °C (1 min),
increasing to 70°C at 5°C/min temperature gradient was used.  The
injector temperature  was 85 °C. Nitrogen carrier gas flow rate was
10 mL/min. With the above  conditions, the retention times for TCE
and DBDCM  were 3.08 and 7.80 minutes, respectively.  The ratio of
peak heights was converted to concentration units using previously deter-
mined calibrations. This procedure minimized TCE volatilization losses
and experimental results were compared to control runs to insure
consistency.
  Residual PCP concentration was determined by HPLC (Varian Model
2550) using a reverse-phase column (25 cm NUCLEOSIL C18 packed
column) with a UV detector at 280 nm. The aqueous sample was filtered
through 0.22 /im (Millipore, MILLEX-GX) before each 40 /tL injec-
tion. The isocratic eluent was pumped at a rate of 1 ml/min and it was
composed of 88% methanol with 1% acetic acid and of 12% deionized
water with 1% acetic acid. The results were printed in analog and digital
modes on a Varian integrator, model 4290.
  Soluble chemical oxygen demand (SCOD) was determined by using
the micro COD digestion and titrimetric procedure manufactured by
the HACH Company. Chloride ion concentrations were determined with
a Fisher 825 MP digital pH meter equipped with a chloride-specific
electrode (Orion 94-17B). Chloride concentration was determined by
using a calibration curve plotted from the molarity of a series of KC1
standards versus millivolts. The potassium iodide-sodium thiosulfate
titration method was  used to  determine residual  concentration of
hydrogen peroxide in each system.24

RESULTS AND DISCUSSION

Chemical PreOxidation
  Chemical oxidation of PCP when preoxidized with Fenton's reagent
was fester and more extensive than when just peroxide was added alone.
The results of chemical oxidation by Fenton's Reagent are shown in
Figure 1.
                                                                       400
                                                                   CD


                                                                   O
                                                                   HI
                                                                   o
                                                                   z
                                                                   o
                                                                   o
                                                                   a
                                                                   o
                                                                   a.
                                                                           300  -
                                                                           200
                                                                       100
                                                                                    2       4        6        8       10       12

                                                                                                TIME (DAYS)
                                                                                             Figure 1
                                                                                Residual PCP Concentration Following
                                                                                    Oxidation by Fenton's Reagent
                                                                   By comparison, the chemical oxidation of TCE by both hydrogen
                                                                 peroxide alone and with Fenton's reagent was significant. Both a faster
                                                                 rate and higher level of oxidation with Fenton's reagent resulted,
                                                                 however, than when just hydrogen peroxide was used. TCE chemical
                                                                 oxidation using Fenton's reagent is shown in Figure 2. If Figures 1 and
                                                                 2 are compared, it is evident that chemical doses were relevant to both
                                                                 the rate and level of oxidation occurring for PCP. For TCE, however,
                                                                 a minimal dose of Fenton's reagent was just as effective as a dose 10
                                                                 times greater. Analyses of residual peroxide indicated that the oxidizing
                                                                 chemical was not detectable after four hours. These results indicated
                                                                 that the chemical reactions shown in Equations 1 and 2 for peroxide
                                                                 and Fenton's reagent occurred at approximately the same rate. Even
                                                                 though the disappearance of hydrogen peroxide in Fenton's reagent was
                                                                 very fast, the chain reaction described in Equation 3 for Fenton's Reagent
                                                                 occurred slightly  more slowly.
                                                                                                               BIOTREATMENT    827
-------
     150 r-
D)

o
 ut
 o
 8
     100
      50
                  2       4        6        8       10       12

                              TIME (DAYS)
                             Figure 2
                 Residual TCE Concentration Following
                    Oxidation by Fenton's Reagent
Chemical Oxidation Followed by Selected
Microbial Consortia Degradation
  When chemical oxidation was followed by microbial degradation,
the rate of PCP disappearance was faster than when due to chemical
oxidation alone. For systems to which a selected microbial consortium
(SMC) were added following chemical oxidation by Fenton's reagent,
the biodegradation rate constant was an order of magnitude larger than
that due to chemical oxidation alone.  Figure 3 illustrates the resulting
degradation following Fenton's  reagent preoxidation. Comparison of
Figure 1  for chemical oxidation alone and Figure 3 for subsequent
microbial degradation indicates that chemical dose became less rele-
vant for the selected microbes than for just chemical oxidation alone.
  For the TCE case, volatilization occurred, as indicated in the con-
trol plot of Figure 4. The loss due to volatilization was not apparent,
however, until repeated aliquots were removed from the reactor. In fact,
this plot defines a maximum loss due to volatilization, for in the other
plots showing microbial degradation, the TCE lost early to the gas phase
will  subsequently  be transferred back to  the  aqueous  phase as
biodegradation proceeds with time. This transfer back to the aqueous
phase is  caused by a shift  in the chemical potential  for TCE as
biodegradation depletes the aqueous concentration.  The decrease in
aqueous chemical potential compared to gas phase chemical potential
causes a spontaneous transfer from the gas phase, controlled by Henry's
Law constant for TCE, in order to reestablish a constant equilibrium
concentration ratio for TCE between the two phases.
  The degradation plots shown in Figure 4 for the three doses of Fenton's
reagent indicate that the level of biodegradation was a function of the
oxidant dose. This bacterial response with  respect to oxidant dose was
apparently different than for PCP where oxidant dose made less dif-
ference to the degradation by its SMC. Work is being carried out in
an attempt to identify both chemical oxidation products and intermediate
microbial metabolites by GC/MS, but a preliminary comparison can
be made by examining the microbial Cl~ production level, Cl~ produc-
tion rate and oxygen uptake rate for the two compounds. A typical Cl~
production rate for  the  PCP SMC is  shown in Figure 5. This figure
indicates a large concentration of Cl~ was produced at a significant rate
which was barely reaching an asymptotic value after 12 days. In addi-
tion,  the Cl'  production appears to  be independent of the Fenton's
reagent dose. In contrast, the Cl~ production by TCE selected microbial
consortium was one-fourth the  amount of the PCP case, the produc-
                                                                       O
                                                                      LU
                                                                      O
                                                                      z
                                                                      o
                                                                      o
                                                                      Q.
                                                                      O
                                                                      a
                                                                            400
                                                                            300
                                                                            200
100
                                                                                                                     O
                                                                                                                     A
                                                                                                                     D
                                                                                                                       SET 4 0.1:1
                                                                                                                       SET 4 0.5:1
                                                                                                                       SET 4 1:1
                                                                                                                            10
                                                                                                                                   12
                                                                                                    TIME (DAYS)
                                                                                                  Figure 3
                                                                                 Residual PCP Concentration Due to Biodegration
                                                                                  by a Selected Microbial Consortium Following
                                                                                    Chemical Oxidation by Fenton's Reagent
                                                                          150
                                                                                                   TIME (DAYS)
                                                                                                  Figure 4
                                                                                Residual TCE Concentration Due to Biodegradation
                                                                                  by a Selected Microbial Consortium Following
                                                                                     Chemical Oxidation by Fenton's Reagent
                                                                     tion rate diminished to a very low level after Day 4 and the production
                                                                     rate and level were proportional to the dose of Fenton's reagent. All
                                                                     of these observations suggest that Fenton's reagent is a much more ef-
                                                                     fective oxidant  for TCE than for PCP. Examination of the chemical
                                                                     oxidation reactions presented previously indicate that a three-fold molar
                                                                     ratio increase of oxidant was required for PCP degradation compared
                                                                     to TCE. Therefore, even a small dose of Fenton's reagent was effective
                                                                     for oxidizing TCE as shown in Figure 2. The subsequent microbial
                                                                     response was proportional to the oxidant dose for both the degradation
                                                                     rate of parent TCE and the production rate and level of Cl". All of
                                                                     these results are consistent with the hypothesis that the hydroxyl radical
                                                                     produced  from  hydrogen peroxide attacks the chJoro-substituents on
                                                                     the hydrocarbon skeletal matrices of TCE and PCP. The results for PCP
                                                                     oxidation and PCP preoxidation followed by SMC degradation indicated
K:S    B1OTREATMENT
-------
that comparable oxidant doses for this chemical were not large enough
to cause significant oxidation. Cumulative oxygen uptake rates were
comparable for both TCE and PCP SMC when each parent toxic
chemical was dosed either with hydrogen peroxide alone or with Fenton's
reagent. For both SMC, the oxygen uptake rates were slightly higher
when Fenton's reagent  was used.
  01
  "5
  §

  o

  cc
  UJ
  o
  8
  1
  5
                               TIME (DAYS)

                              Figure 5
              Chloride Ion Production Due to Biodegration
               of PCP by a Selected Microbial Consortium
            Following Chemical Oxidation by Fenton's Reagent
 Chemical Oxidation Followed by Activated Sludge Degradation
   Microbial degradation of both TCE and PCP by activated sludge was
 slower than by each SMC,  whether the parent toxic chemicals were
 untreated or pretreated by  hydrogen peroxide alone or by  Fenton's
 reagent.  Production of Cl" and oxygen uptake rates were also slower.
 Activated sludge degradation of both parent toxic chemicals was fastest
 following Fenton's agent pretreatment. Enhancement of activated sludge
 biodegradation of TCE was greater than for PCP.
                              Table 1
               Specific Substrate Uptake Rate Constants
              and Half Velocity Constants for PCP Under
                    Varying Treatment Conditions
  Environmental condition  k(AS)
                     k(SCM)
                      K(SMC)
  Untreated system
                       0.00022
                                  120.5
                                           0.00027
  Pretreated with hydrogen peroxide at molar ratios of
  hydrogen peroxide:PCP
  0.1:1
  0.5:1
  1.0:1
0.00031
0.00031
0.00044
126.3     0.00079
126.3     0.00092
115.8     0.00096
  Pretreated with Fenton's reagent at  molar
  ratios of peroxide:PCP
0.1:1
0.5:1
1.0:1
                       0.00147
                       0.00151
                       0.00189
          114.3
          119.0
          102.3
         0.00542
         0.00553
         0.00573
121.0
118.8
110.5
 91.5
 80.3
 72.5
 k(AS)    :  Biodegradation Rate by Activated Sludge
 k(SMC)   :  Biodegradation Rate by SMC  (Selected Microbial Consortium)
 K(AS)      Substrate  Concentration at  Half the Maximum Velocity for
           Activated  Sludge (Half Velocity Constant)
 K(SMC)     Substrate  Concentration at  Half the Maximum Velocity for SMC
           (Half Velocity Constant)
                                                    SUMMARY OF RESULTS
                                                      Data from all the degradation tests were used to calculate biodegrada-
                                                    tion rate constants and half velocity constants according to Equations
                                                    4 and 5. These tabulations indicate quantitative values of the differences
                                                    in results described above.

                                                                                   Table 2
                                                                   Specific Substrate Uptake Rate Constants
                                                                  and Half Velocity Constants for TCE Under
                                                                        Varying Treatment Conditions
                                                                             Environmental condition    KS(AS)  Km(AS)     Ks(SCM)
                                                                                                            Km(SMC)
                                                                             Untreated system
                                                                                                   0.00019
                                                                                                              78.0
                                                                                                                       0.00020
                                                     Pretreated with hydrogen peroxide at molar  ratios of
                                                     hydrogen peroxide:PCP
                                                     0.1:1
                                                     0.5:1
                                                     1.0:1
                                                                  0.00026
                                                                  0.00027
                                                                  0.00029
                                                       53.1    0.00027
                                                       50.8    0.00030
                                                       46.1    0.00031
                                                                             Pretreated with Fenton's reagent  at molar ratios  of
                                                                             hydrogen peroxide:PCP
                                                     0.1:1
                                                     0.5:1
                                                     1.0:1
                                            0.00034     51.9     0.00043
                                            0.00034     48.7     0.00040
                                            0.00036     46.7     0.00059
                                                         51.3
                                                         49.6
                                                         46.1
                                                                                                  49.6
                                                                                                  48.5
                                                                                                  44.7
  In addition, the half velocity constants and oxygen uptake rates in-
dicate that preoxidation treatment reduces the toxicity of the substrates
for both activated sludge and both SMC. The Cl~ production levels and
rates indicate that both the chemical oxidation and microbial degrada-
tion mechanisms sequentially remove chlorine substituents from the
molecule.

CONCLUSIONS
  Selected microbial consortia for TCE and PCP degraded these parent
toxic compounds faster and more efficiently than unacclimated activated
sludge microbes. Preoxidation of the parent model toxic chemicals
enhanced the subsequent microbial degradation by both activated sludge
and selected microbial consortia. Pretreatment of TCE and PCP with
oxidants, particularly with Fenton's reagent, reduced the toxicity of these
substrates to both activated sludge and selected microbial consortia.
Chloride ion was produced as a result of both chemical oxidation and
microbial degradation.

REFERENCES
 1.  Cirelli, D. P., "Patterns of pentachlorophenol usage in the United States
    of America; an overview." In: Rao, K.R., ed. Pentachlorophenol, New York
    Plenum Press, pp. 13-18, 1978.
 2.  Godsy, E. W., Georlitz, D. F. and Grabic-Galic D. "Anaerobic biodegrada-
    tion  of creosote  contaminants in natural and simulated ground water
    ecosystem." In: EPA Symposium on Bioremediation of Hazardous  Wastes;
    U.S. EPA's Biosystems Technologies Development Program. Arlington, VA.
    31-33, 1990.
 3.  Goerlitz, D. R, Trouman, D. E., Godsy, E. M. and Franks, B. J. "Migra-
    tion of wood-preserving chemicals in contaminated groundwater in a sand
    aquifer at Pensacola, Florida." Environ. Sd. Technol.  19, pp. 955-961,1985.
 4.  Kirsch,  E. J. and Etzel,  J.  E.  "Microbial decomposition of penta-
    chlorophenol." JWPCF. 45, pp. 359-364, 1973.
 5.  Etzel, J.  E. and Kirsch, E.  J. "Biological treatment of contrived and in-
    dustrial wastewater containing PCP." Dev. Ind. Microbiol. 16 pp. 287-295,
    1975.
 6.  Smith, J. A. and Novak, J.  T.  "Biodegradation of chlorinated phenols in
    subsurface  soils." Water Air Soil Poll. 33 pp. 29-42, 1987.
 7.  Chu, J. P. and Kirsch, E. J. "Metabolism of pentachlorophenol by an axenic
    bacterial  culture." Appl. Environ. Microbiol. 23 pp. 1033-1035, 1972.
 8.  Kuwatsuka, S. and Igarashi, M. "Degradation of PCP in soil." Soil Sci.
    Plant Nutri. 21(4) pp. 405-414, 1975.
 9.  Edgehill, R. U. and Finn, R. K. "Microbial treatment of soil to remove
    pentachlorophenol." Appl. Environ. Microbial. 45 pp.  1122-1125,  1983.
10.  Kaufman, D.  "Degradation of PCP in soil and by soil microorganisms."
    In: Pentachlorophenol, Rao, K. R. (ed.) New York Plenum Press, New York
    NY, pp.  27-39, 1978.
                                                                                                                         BIOTREATMENT    829
-------
 U.  Melcer, H. and Bedford, W. K. "Removal of PCP in municipal activated
     sludge  system." JWPCF. 60 pp. 622-626, 1988.
 12.  Bouwer, E. J. "Secondary utilization of Dace halogenated organic compounds
     in biofilms." Environ.  Progress. 4(1) pp. 43-45,  1985.
 13.  Kleopfer, R. D.. Easley, D. M., Haas, B. B., Jr., Geihl, T. G., Jackson,
     D. E. and Wurrey, C J. "Anaerobic degradation of trichloroethylene in Soil."
     Environ. Sd.  Techno!. 19 pp. 277-280, 1985.
 M.  Vogel,  T. M.  and McCarty, P. "Biotransformation of tetrachloroethylene
     to trichloroetbylene, dichloroetfaylene, vinyl chloride and carbon dioxide
     under methanogenic conditions." App. Environ. Microbiol. 49 pp. 242-243,
     1985.
 15.  Wilson, J. T.  and Wilson,  B. H. "Biotransformation of trichloroethylene
     in soil." Appl. Environ. Microbiol.  49 pp. 242-243,  1985.
 16.  Parsons,  E,  Wood,  P.   R.  and  DeMarco, J.  "Transformations of
     letrachloroethane and  trichloroethene in microcosms and  groundwater."
     JAWWA 76 pp. 56-59,  1984.
 17.  Little, C. D.,  Palumbo, A.  V., Heroes, S. E., Lidstrom, M. E., Tyndall,
     R.  L. and Gilmer, P. J. "Trichloroethylene biodegradation  by a methane-
     oxidizing bacterium." Appl. Environ. Microbiol.  54 pp. 951-956, 1988.
18. Fliennans, C R, Phelps, T. J., Ringelberg, IX, Mikell. A. T. and White,
    D. C "Mineralization of trichloroethylaie by heterotrophic enrichment
    cultures."  Appl. Environ. Microbiol. 54 pp. 009-1714, 1988.
19. Wackett, L. P. and Gibson, Dl T. "Degradation of trichkHoethylene by toluene
    dioxygenase in whole-cell studies with Pseudomonas panda F,." AppL En-
    viron. Microbiol. 54(7) pp. 1703-1708, 1988.
20. Bishop, D. F.,  Stern, G., Fleischman, M. and Marshall, L.S. "Hydrogen
    peroxide catalytic oxidation of refractory organics in municipal wasttwaters."
    In. Eng. Chem: Process Des. Develop. 7 pp.  110-113, 1974.
21. Bowers, A. R., Gaddipati, P., Eckenfelder, W. W., Jr. and Monsen, R. M.
    "Treatment of toxic or refractory waste waters with hydrogen peroxide." Hfaer
    Sci. Tech.  21 pp. 477-486, 1989.
22. Carbeny, J. B.  and Benzing, T. M. "Peroxide preoxidation of recalcitrant
    toxic waste to enhance biodegradation." fitter Sci.  Techno.
23. Carberry,  J.  B. "Evaluation of oxidation pretreatment to enhance the
    bioremediation of pentachlorophenol," presented at AICHE Summer Con-
    ference, San Diego, CA, August,  1990.
24. Encyclopedia of industrial chemical analysis. John Wiley and Sons, Inc.
    14 pp. 431-439, 1971.
830    BIOTREATMENT
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                 Treatability of Contaminated Groundwater Using
                                           Biological Processes

                                                   Mark £. Zappi
                                                  Cynthia L. Teeter
                                              Norman R. Francingues
                                       Environmental Engineering Division
                              U.S. Army Engineer Waterways Experiment Station
                                               Vicksburg, Mississippi
 ABSTRACT

  Treatability of contaminated groundwater from the  Ninth
 Avenue Superfund  Site,  Gary, Indiana, was evaluated using
 bench-scale biological reactors  (bioreactors). Aerobic treatment
 and aerobic treatment with the addition of powdered activated
 carbon (PAC) were evaluated. All bioreactors were configured to
 simulate a complete mix activated sludge system. The ground-
 water was contaminated with various organic contaminants  in-
 cluding: 278 mg/L total ketones, 25 mg/L chlorinated solvents,
 6 mg/L total phenols and  10 mg/L of benzene, toluene, ethyl-
 benzene and xylene (BTEX) compounds. The groundwater also
 contained  approximately 90  mg/L and 230 mg/L of iron and
 manganese, respectively.
  A microbial culture collected from a local municipal waste-
 water treatment system was acclimated over a period of 6 wk to
 the contaminants in the groundwater using a 15-L bioreactor.
 Once the microbial culture was acclimated, biological treatability
 testing was performed in four 3-L bioreactors. The groundwater
 influent had sufficient nitrogen, but the addition of phosphate
 was required.
  The reduced iron and manganese in the groundwater were oxi-
 dized and precipitated in the aeration chamber of the  bioreactors.
 The precipitate caused substantial bulking of the activated sludge;
 however, the bulking did not seem to affect the activity of the bio-
 mass. The organic contaminants were reduced to trace levels in
 both treatment systems. The aerobic bioreactors without PAC
 addition achieved a BOD reduction in excess of 95%, but only
 achieved COD and TOC removals in excess of 50%.  The aerobic
 bioreactors with PAC addition achieved a 95% BOD removal.
 The addition of PAC improved the percent removals of COD and
 TOC to over 80%. The PAC also increased microbial activity.

 INTRODUCTION

  The Ninth Avenue Superfund Site, which is listed on the NPL,
 is scheduled for cleanup under  the Superfund  Acts of 1980 and
 1986. The site is a 17-ac inactive chemical waste disposal area lo-
 cated in Gary, Indiana.
  Both solid and liquid wastes are reported to have been disposed
 at the site. Solid wastes deposited there include industrial con-
 struction and demolition wastes. Liquid wastes disposed at the
 site  include oils, paint solvents and  sludges,  resins, acids and
 other chemical wastes. Waste disposal operations took place be-
tween 1973 and 1980.
  The site  groundwater is contaminated with a variety of inor-
ganic and  organic contaminants.  Inorganic contaminants  are
mainly in the form of road salts (sodium chloride). Organic con-
taminants detected in significant concentrations in the ground-
water are ketones, benzene, toluene, xylenes, ethylbenzene and
chlorinated ethenes.
  This treatability study was performed for the U.S. Army Corps
of Engineers Omaha District and the U.S. EPA RI/FS Region V
  This treatability study was performed for the U.S. Army Corps
of Engineers Omaha District and the U.S.  EPA Region V as
part of the RI/FS. Four treatment technologies were evaluated by
the  U.S. Army Engineer Waterways Experiment Station during
the  treatability study. The technologies evaluated were activated
carbon, air stripping, activated sludge and activated sludge with
powdered activated carbon addition. The results of the evaluation
of the latter two technologies are presented in this paper.

STUDY OBJECTIVE

  The objective of this study was to evaluate, on the laboratory
bench-scale level, the potential of biological processes to remove
organic contaminants from a composite of groundwater samples
collected from six site observation wells. Activated sludge (AS)
and activated sludge with  powdered activated carbon  addition
(PAC/AS) were evaluated for their ability to reduce the biochem-
ical oxygen demand, chemical oxygen demand, total organic car-
bon and organic contaminants listed on the U.S. EPA's Priority
Pollutant List from the groundwater composite.

DESCRIPTION OF PROCESSES
Activated Sludge
  AS is a biological process that utilizes acclimated bacteria for
the aerobic degradation of contaminants in wastewater. Figure 1
is an  illustration of a  typical AS treatment system. The term
"acclimated" means that the bacteria consortium are capable of
utilizing the organic contaminants in the influent as their food
source.
  Biological  treatment processes (which  include both AS and
PAC/AS) are destruction technologies requiring no ultimate dis-
posal  of treatment residuals containing hazardous or toxic  con-
stituents (assuming that the waste sludges do not contain parent
and/or intermediate contaminants).  In contrast, activated carbon
or air stripping are not destruction technologies. They are phase
change technologies that simply transport the contaminants from
one phase to  another,  with activated carbon systems requiring
the disposal or regeneration of the spent carbon.
  The populations of bacteria in the aeration tanks of AS systems
are so great that the air-activated organic biological solids which
are  made up primarily of dense colonies of bacteria are referred
to as activated sludge. The activated sludge/wastewater slurry in
                                                                                                     BIOTREATMENT    831
-------
  iCBEtMED
  DEGRITTED RAW
  VASTCWITCK
                           Figure 1
                Activated Sludge Treatment System
the aeration tank is commonly known as the mixed liquor (ML).
The ML is kept in suspension in the aeration tank by using either
mechanical misers or diffused air. Since biological solids are vola-
tile, bacterial populations in the mixed liquor are often measured
using mixed liquor suspended solids (MLSS) or mixed liquor vol-
atile suspended solids (MLVSS).
  Influent is added to the aeration tank at a rate that is carefully
controlled to achieve a specific hydraulic retention time (HRT).
HRT has units of time and theoretically describes the amount of
time a particle of water and theoretically describes the amount of
time a particle  of water is retained in the aeration tank. As fresh
influent enters  the aeration tank, treated water or effluent flows
out of the aeration tank into the clarifier. The clarifier is a sedi-
mentation tank used to  separate the activated sludge  from the
effluent. To keep a constant population of bacteria in the aera-
tion  tank, a portion of the thickened sludge  is  returned to the
aeration tank.  Also, since bacteria  are constantly reproducing,
some of the thickened sludge must be wasted from the bottom of
the clarifier or directly from the aeration tank to maintain a con-
stant bacterial  population in the aeration tank.  The amount of
bacteria wastes is determined based on the solids retention time
(SRT) of the biological solids. The SRT or sludge age is theoreti-
cally the amount of time a particle of solid matter remains in the
aeration tank. SRT also has the units of time.

Powdered Activated Carbon/Activated Sludge
  PAC/AS is a treatment process that incorporates the benefits
of both activated carbon and activated sludge for the removal of
organic contaminants  from wastewater. PAC/AS systems  are
usually configured  identically to AS systems except that PAC is
periodically added  to maintain a specific PAC suspended solids
(PACSS) in the mixed liquor.
  The PAC/AS treatment process relies heavily on biological de-
gradation  for the removal of the majority of the organic com-
pounds from the influent.  However, if compounds that are  not
easily degraded are present, then these  compounds  can be  ad-
sorbed  into the PAC, thus preventing the loss of  these com-
pounds in the effluent resulting in incomplete treatment. PAC has
also been added to the AS system to reduce the amount of vola-
tile compounds from off-gasing the treatment system via volatili-
zation in the aeration tank. Once adsorbed, many of the adsorbed
contaminants can be degraded  directly from the PAC by either
the  suspended  bacteria coming in  contact  with them or  by
attached growth microbes using the PAC as a structural sub-
strate.

LITERATURE REVIEW
AS Treatment Process

  The  suitability of AS for the degradation of a variety of com-
plex xenobiotic compounds has been demonstrated by many re-
searchers.8'10- u Most of the research activities reviewed generally
used the same technical approach selected for  this study. The
technical approach uses a microbial consortium containing an ex-
tremely diverse variety of microbial types, such as mixed liquor
from an AS system, as a source of microbial  seed for biological
reactors. The microbes are slowly exposed to the contaminants in
the test influent until   all or a portion of the original bacterial
population become acclimated to the target contaminant(s). l n*
chance of successfully establishing a consortium of acclimated
bacteria is high because microbe populations capable of mineral-
izing the contaminants are usually present in activated sludge.
  Sanford and Smallbeck" used a mixed consortium of bactena
and yeast to degrade a synthetic wastewater comprised of 100
mg/L acetone, 50 mg/L 2-butanone and 125 mg/L methyl iso-
butyl ketone  in  bench-scale chemostats.  They  concluded that
treatment of ketones was successful within 48 hr of batch treat-
ment utilizing a stable consortium of microorganisms and yeast.
  Kim and Maier9 evaluated the acclimation and biodegradation
potential of chlorinated organic  compounds in the presence of
various cometabolites. They were able to acclimate a consortium
of bacteria from a municipal AS plant capable  of degrading
2,4-D (2,4 dichlorophenoxyacetic acid) and 3,5-DCB (3,5 dichlor-
obenzoate) under aerobic conditions.  Combined contaminant
concentrations as high as 100 mg/L were successfully degraded.
Kim and Maier concluded that seed bacterial consortia should
contain as diverse a population of microorganisms  as possible to
increase the probability of plasmid exchange.  In addition, they
also suggest that the acclimation phase begin with an influent con-
taining very low concentrations of the target compounds to avoid
inhibitory effects.
  Bieszkiewics and Pieniadz-Urbaniak2 evaluated  the effect of
benzene and xylene at concentrations as high as 75 mg/L and 150
mg/L, respectively,  on the  work of an AS system. They con-
cluded that increased concentrations of the target compounds
generally decreased the COD removals,  increased sludge volume
index (SVI), increased the number of bacteria and, finally, altered
the morphology of the bacterial floes.
  Rozich and Gaudy12 evaluated the response of an AS system to
quantitative loadings of phenol. Phenol concentrations of 500
mg/L were evaluated as a base influent concentration. Initially,
shock loadings of 1,000 mg/L of phenol were imposed on the AS
system without significant disturbances in treatment occurring.
The  AS system was then shocked  with 2,000 mg/L of phenol
which resulted in the collapse of the stability of the system. They
concluded that design engineers  should design AS systems that
will be treating possible inhibitory and/or toxic compounds with
high SRTs; especially systems that could be subjected to periodic
shock loadings of contaminants.

PAC/AS Treatment Process

  There has been considerable research on the feasibility of ap-
plying PAC/AS to treat a variety of wastewaters.4-5 Nayar and
Sylvester" evaluated PAC addition to an AS system for increased
removal of phenol. Concentrations of  phenol as  high as 1,300
mg/L were successfully removed. They  concluded  that the addi-
tion of  PAC to the aeration tank did not enhance bacterial
growth); however, PAC addition could be used to prevent shock
loadings of contaminants at toxic levels from disrupting the bio-
logical system.
  Chao, Yeh and Shieh1 evaluated the  use of PAC/AS systems
to remove total phenols and cyanides at concentrations as high as
160 mg/L and 80 mg/L, respectively. They concluded that the
PAC addition did not have an appreciable effect  on phenol re-
moval; however, they  did observe increased  cyanide removals
with PAC addition.
  Hoffman and Oettinger' investigated the performance of a
two-stage PAC/AS and activated carbon system for the removal
of trichloroethylene,  1,4-dichlorobenzene and  2-chlorophenol at
a combined concentration of approximately 100  mg/L from a
landfill leachate. They concluded that 99.8% removal of the con-
taminants could be achieved using the two stage system, with only
0.31% of the contaminants removed via air stripping from the
aeration tank.

TECHNICAL APPROACH
   The following steps were used to implement this study;
       B1OTREATMFNT
-------
                           Table 1
            Chemical Analysis of Groundwater Composite
Analyte
                                            Concentration
                                               (mg/1)
Priority Pollutants
Methylene Chloride
cis-l,2-Dichloroe thane
2-Butanone
Acetone
Toluene
Phenol
2,4-Dimethylphenol
2-Methylphenol
4-Methylphenol
Metals
Aluminum
Arsenic
Barium
Boron
Cadmium
Calcium
Chromium-Ill
Cobalt
Iron
Nickel
Lead
Magnesium
Manganese
Potassium
Zinc
Miscellaneous Analytes
BODS
COD
TOC
PH
0-Phosphate
T-Phosphate
TKN
Ammonia
Nitrate
Sulfate
Chloride
Salinity

11.00
16.00
260.00
18.00J
10.00
0.27
0.63
0.80
0.81

1.08
0.01
0.32
2.11
0.01
589.00
0.11
0.06
91.40
0.4B
0.04
234.00
7.41
37.70
0.88

2300
4010
1260
6.78
0.601
0.912
76.8
73.2
0.022
93.3
566
2400
 J:  Indicates concentration below statistical quantition limits
                                 Hydraulic Gradient
   Sludga Wailing
     Port
                    Aeration Tank
                           Figure 2
             Activated Sludge Bioreactor Used in Study
 •  Acclimate a consortium of bacteria to degrade the contami-
   nants in the groundwater composite using mixed liquor from a
   local activated sludge system treating municipal wastewater
 •  Determine an optimal SRT for an AS system using multiple
   bioreactors
 •  Examine the potential benefits of PAC addition to an AS
   system
 •  Determine an optimal PAC dose in a PAC/AS for reducing
   effluent pollutant concentrations.

 MATERIALS AND METHODS
 Materials

  The contaminated water used in this study was a composite of
 groundwater samples  collected from six site observation wells.
 Table 1  lists the major chemical constituents  detected in the
 groundwater composite.
  The bench-scale bioreactors used in this study are illustrated in
Figure 2. Two bioreactor sizes were used. The acclimation phase
used a single 20-L bioreactor having a 15-L  aeration chamber
and a 5-L clarifier, while the AS and PAC/AS phases of study
used multiple bioreactors with 2.0-L aeration chambers and 1.0-L
clarifiers. Influent was delivered to the aeration tank of the biore-
actors using peristaltic pumps. Sludge wasting was accomplished
through the sludge wasting port located on the side of the biore-
actor (Fig. 2). The waste sludge was settled in graduated cylinders
of various  sizes dependent on the amount of sludge requiring
wasting (determined by SRT).  The supernatant from the settled
waste sludge was mixed with effluent and returned to the bioreac-
tor to make up for the volume of water lost due to sludge wasting.
  A bacterial inoculum was obtained from the aeration tank of
the City of Jackson, Mississippi, Wastewater Treatment System
(JWWTS). This system is a contact stabilization process with a
50-mgd capacity.
  The PAC used in this study was obtained from the Calgon Car-
bon Corporation of Pittsburgh, Pennsylvania. A pulverized ver-
sion of Filtersorb 300 marketed as BL  Type PAC was selected
based on recommendations by Calgon personnel after review of
the chemistry of the groundwater composite contaminant concen-
trations.
Acclimation of Bacterial Consortium

  The 15-L acclimation bioreactor was completely filled with the
mixed liquor from the JWWTS. The bioreactor was initially fed
influent to a trickling filter of City of Vicksburg, Mississippi,
Wastewater Treatment System (VWWTS). Over a 4-wk period,
influent  to the  acclimation  bioreactor  was  proportionally
switched on a volumetric basis from VWWTS  influent  to  the
groundwater composite.  The groundwater composite contained
appropriate nitrogen levels in the form of ammonia; however,
phosphate nutrient was added to the influent in the form of potas-
sium monobasic phosphate to achieve a carbon to nitrogen to
phosphate ratio of appriximately 100:10:5. This C:N:P ratio was
considered adequate because analysis of the effluent indicated
that sufficient nitrogen and phosphate nutrients were present hi
the effluent to prevent the biological system from becoming nu-
trient-limited.
  Acclimation of the bacterial consortium to the contaminants in
the groundwater composite was based on the acclimation biore-
actor receiving a constant organic loading based on influent 5-day
BOD. The rate at which the ratio of groundwater composite to
VWWTS influent was increased was determined assuming that
the bacterial consortium would easily acclimate  to the ground-
water compolsite, with little  or no lag phase, when acclimated
using a constant system influent organic loading. Therefore,  the
acclimation bioreactor was operated at different HRTs depending
on influent composition and respective BOD. The SRT of the bio-
reactor throughout the acclimation phase was 10.0 days.
  During the acclimation period when groundwater was propor-
tionally replacing the VWWTS influent: BOD, COD and TOC re-
movals were determined twice weekly and the  MLVSS/MLSS
ratio daily. This monitoring was done to ensure that the contam-
inants in the groundwater composite were not adversely affecting
biological activity. If adverse effects such as significant reductions
in BOD, COD  and TOC removals or dramatic decreases in the
MLVSS/MLSS ratio were noted, then these effects could be re-
versed or minimized by decreasing the rate of groundwater com-
posite addition.
  The VWWTS influent had an average BOD of 70 mg/L; there-
fore glucose was added to increase the influent BOD to approxi-
mately 200 mg/L to achieve an organic loading of approximately
0.015 Ib BOD/day on the system. The organic loading was ad-
justed daily by changing system influent feed rates accordingly as
influent BOD changed due to the increased proportion of ground-
water composite making up the influent. Once the system influent
consisted only of groundwater composite, the acclimation biore-
actor was operated at a HRT of 3.0 days  and a  SRT of 10 days
(these operational parameters were selected prior to testing based
on a literature review of systems treating similar wastes). When
                                                                                                         BIOTREATMENT   833
-------
the percent removal of gross pollutants and the MLVSS/MLSS
ratios were constant, then the consortium  was considered accli-
mated. Acclimation of the bacterial consortium took approximat-
ely 6 wk,

Operation of the AS Bioreactors
  After the acclimation process was considered complete, ap-
proximately 3L of mixed liquor from the acclimation bioreactor
were added to the four 2-L bioreactors. Each AS bioreactor was
operated at an HRT of 1.0 day. The AS bioreactors different
from each other by SRTs of 2, 4, 8 and 16 days. The purpose of
varying the SRTs was to determine an optimal SRT.

Operation of the PAC/AS Bioreactors
  After completion of the AS study, the mixed liquors from each
of the four AS bioreactors were composited  into the  15-L bio-
reactor used in the acclimation phase of study. The compositing
of the mixed liquors was done to ensure that the bacterial con-
sortiums used in the PAC/AS bioreactors initially contained sim-
ilar microbial populations (AS systems operated at different SRTs
can contain different types of bacteria). The 15-L bioreactor was
operated at the optimal SRT from the AS study and an HRT of 1
day. The  large bioreactor was operated for a period of three
SRTs, then approximately 10 L of mixed liquor were added to
four of the 2-L bioreactors.
  The PAC/AS bioreactors differed by PAC dose. PAC dosages
of 1.0, 2.0, 5.0 and 8.0 mg/L were added to the 2-L bioreactors.
The amount of PAC removed each day in the waste sludge was
replaced with equal amounts of fresh PAC after sludge wasting
operations were  completed. New PAC was  added  into  the
PAC/AS bioreactors by slurrying the fresh  PAC with enough
effluent to make up for the volume of water lost from the  sludge
wasting activities.

Chemical Analyses
  All gross pollutant, suspended and volatile  solids, and oil and
grease analyses were performed using methods described in Stan-
dard Methods for the Examination of Water and  Wastewater.'
Priority  pollutant analyses were  performed using U.S.  EPA
Methods SW 846-8270 and SW 846-8260 for volatile compounds
and base  neutrals/acid  extractables, respectively.6  Chemical
analysis of bioreactor off-gases for volatile organic priority pollu-
tants was performed using gas-tight bioreactors equipped with
Tenax(™) traps. Approximately 3.0% of the total off-gas flow
from the bioreactors (52 mL/min) was passed through the Tenax
traps at a retention time of 12.0 min. The "loaded" Tenax traps
were then purged with helium to remove the contaminants. The
helium gas was analyzed for volatile organic compounds using a
modified version of U.S. EPA Method 846-8270.'

STUDY RESULTS
Acclimation of Bacterial Consortium
  The operational data for the acclimation bioreactor are pre-
sented in Table 2. Table 2 also presents the solids and influent
and effluent BOD concentrations over the 23 day period when the
influent was  proportionally being switched from  VWWTS in-
fluent to the groundwater composite. The BOD loading on the
acclimation bioreactor was kept at approximately 0.015 Ib BOD/
day throughout the acclimation phase of study (Table 2).
  The impact of the groundwater addition on the biological sys-
tem is illustrated in Figures 3 through 6. Influent  and effluent
BOD concentrations versus time  are presented in  Figure 3.  In
Figure 3, it can  be seen that  the effluent responded with very
slight increases in BOD concentration as influent BOD strength
increased; however, the effluent BOD concentration generally re-
mained constant throughout the  acclimation period. Figures 4
and 5 illustrate the variation in TOC and COD influent and efflu-
ent concentrations as a function of time. The TOC and COD data
did indicate a slight increase of these parameters in the effluent,
suggesting the existence of  some refractory compounds in the
groundwater composite. At the end of the acclimation period, the
bioreactor was achieving BOD, COD and TOC removals of 97.9,
71.4 and 74.8%, respectively.
  As the ratio of groundwater composite to VWWTS influent de-
                                                           Table 2
                                           Acclimation Bioreactor Operational Parameters
Influent
Component Amounts
Test
Day
0
1
2
3
4
5
6
7
8
9
10
11
12
13
1*
15
16
17
18
19
20
23
Sewage
(liters')
15,
13.
13.
12.
12.
10
10,
9.
9
7.
7,
6
6
<-<
14
-<
(4
1
1
1
0
0
.0
,5
.5
.0
.0
.5
.5
.0
.0
.5
,5
.0
.0
.5
.5
.0
.0
.5
.5
. 5
0
0
Ground H20
(liters)
0.0
0.5
0.5
1.0
1.0
1.5
1.5
2.0
2.0
2.5
2.5
3.0
3.0
3.5
3.5
3.0
3.0
A. 5
4.5
4.5
5.0
5.0
HRT
(days)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
.001
.073
.073
.157
.157
.255
.255
.370
.370
.509
.509
.653
.653
.860
.860
.125
.125
480
.480
,-,80
.976
.^76
SRT
(days)
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
MLSS
(mg/n
933.3
778.3
786.7


985.3
1178.3
1308.3
1508.3
1668.3


1805.0
1926.7
2173.3
2035.0
2870.0




5126.7
MLVSS
(mg/1)
723.2
633.3
640.0


815.7
1003.3
1013.1
1136.7
1195.0


880.0
1198.3-
1306.7
1158.3
1488.3

. _


2136.0
MLVSS/
MLSS
0.77
0.81
0.81


0.83
0.85
0.77
0.75
0.72


0.49
0.62
0.60
0.57
0.52



_ .
0.42
Influent
BOD
(me/1)
202
211
365




598
i
729


	

	
1455
1455

	
	
	
1716
Effluent
BOD
(me/1)
16
33

27



_ _

11
	
„ _
_ ,
	
„ _
16
15

	
_ _
	
53

F/M
(me/me)
0.28
0.31
0.53



	
0.43

0.40
	
..
..
„ _
m ,
0.59
0.46
_ _
„ _
- -
	
0.27
Organic
Loading
(Ibs.SOOAn
0.007
0.006
0.010



. _
0.014

0.016
	
..

..

0.023
0.023




0.019
S.U   BIOTRH.ATMEVT
-------
                               Tuldiy
                •   hflwnt           •  ElOutolXn

                            Figure3
             Acclimation Bioreactor Influent and Effluent
               BOD Concentrations versus Test Time
                               T.iUiy
                   D   hllu.nl           a   EIHIUM

                            Figure 5
             Acclimation Bioreactor Influent and Effluent
                COD Concentrations versus Test Time
                              T.il day
                   •   hlhnnl           A  EIBu.nl

                            Figure 4
             Acclimation Bioreactor Influent and Effluent
                TOC Concentrations versus Test Time
                              Tuldiy
                         •  SS     •   VSS

                            Figure 6
      Acclimation Bioreactor MLSS and MLVSS versus Test Time
 creased, the color of the mixed liquor changed from a light brown
 color to an orange-rusty color indicating that reduced iron and
 manganese in the influent were being oxidized and then precipi-
 tated in the aeration chamber. The accumulation of the precipi-
 tated cations  in the aeration chamber caused a dramatic increase
 in MLSS. Figure 6 illustrates the MLSS and MLVSS of the accli-
 mation bioreactor throughout the  acclimation period.   The
 MLVSS remained constant, while  the MLSS increased approxi-
 mately eight-fold.  The constant MLVSS values and gross pollu-
 tant (BOD, COD and TOC) removals indicated that a lag phase in
 biological activity did not occur. Surprisingly, the increased fixed
 solids concentration did not significantly affect  the gross pollu-
 tant removal  efficiencies of the bioreactor. An analysis of total
 iron and  manganese  in the waste  sludge indicated iron  and
 manganese concentrations of 35,700 mg/kg and 1,510 mg/kg, re-
 spectively.
  Table 3 presents the results of organic priority  pollutant analy-
 sis of the acclimation bioreactor effluent.  It can be seen from
 Table 3 that all priority pollutants  previously detected in the in-
 fluent were removed to levels below the analytical detection limit.

Activated Sludge Evaluation

  Table 4 lists the average operating parameters for each of the
four 2-L bioreactors. Also listed in Table 4 are  volatile organic
compound (VOC) measurements  of the headspace above the
aeration tanks of each of the  bioreactors which were measured
                            Table3
      Priority Pollutant Analysis of Acclimation Bioreactor Effluent

      Analyte                            Concentration
                                           (mg/1)
    Methylene chloride
    cis-1,2-Dichloroethene
    Toluene
    Acetone
    2-Butanone
    Phenol
    2,4-Dimethyl phenol
    2-Methylphenol
    4-Methylphenol
ND
ND
ND
ND
ND
ND
ND
ND
ND
    ND:  Not detected
using an HNU™  meter which measures air phase VOC concen-
trations using an ultraviolet photoionization detector. All of the
HNU readings were below 1.0 ppm, indicating that volatilization
of contaminants (detectable by a HNU meter) was minimal. This
information infers that the ambient air around a bioreactor oper-
ating in  the field probably  will contain little or  no measurable
VOCs.
  Chemical analysis for organic priority pollutants in the off-gas
from the eight day bioreactor (Bioreactor No. 3) using the Tenax
traps was performed to determine the fraction of organic priority
pollutants  being removed  via volatilization from the aeration
tank. This analysis indicated that approximately 4.0%  of the
                                                                                                             BIOTREATMENT    835
-------
                            Table 4
      Activated Sludge Bloreacton Avenge Operating Parameters

Parameter Ko.l
HRT (day) i.o
ORT (day) 2.0
Average DO (mg/1) s.e
pM B.53
Salinity (t) l.e
Conductivity (umhos) 2912
HLSS (mg/1) 2649.7
MLVSS (mq/1) 1196.0
KLVSS/MLSS u.451
F/M ratio* 1.45
Headr.pacr- HUU
Reading (ppftj <1.0

Ho. 2
i.O
4.0
5.6
8 . 55
1.7
2725
5260. «
1831.5
0.348
0. 94
< 1 . 0

No . 3
1 . 0
8.0
5.7
8.49
1.7
2829
7390. 1
2439.7
u. 330
0.71
«...

No. 4
1.0
16. u
5.7
8.53
i . 9
2844
16769.1
4609.6
U.275
0.38
<1.0
•  Based on BOD
                            TableS
          Average Gross Pollutant Concentrations and Percent
                Removals In Bloreactors and Control
Influent
Concentration
(mg/1)
BIOREACTOR NO. 1:
BOD
COD
TOC
BIOREACTOR NO. 2:
BOD
COD
TOC
BIOREACTOR NO. 3:
BOD
COD
TOC
BIOREACTOR NO. 4 :
BOD
COD
TOC

1729
3279
745

1729
3279
745

1729
3279
745.

1729.
3279.
745.

.1
.0
.0

.1
.0
.0

.1
.0
.0

1
0
0
Effluent
Concentration
(mg/1)

122
1260
302

130
1267
265

131.
1567.
296.

213.
1252.
271.

.2
. 0
.0

.9
. 0
.0

. 0
.0
0

7
0
0
Percent
Removal
m

92
61
59

92
61
64

92
52
60

87.
61.
63.

.9
.6
. 5

.4
.4
.4

. 4
.2
.3

, 6
8
6
results of this analysis are listed in Table 7. The sludge contained
detectable amounts of organics at concentrations very near the
detection limit of  the  respective  compounds, except  for the
ketones.  However,  the ketones could probably  be  further de-
graded if the AS  system were operated at SRTs greater than 16
days (i.e., extended aeration mode) or if biological sludge diges-
tion methods were used on-site to reduce  the quantity of sludge
requiring disposal, thereby further degrading the ketones.
  The results of the gross and priority pollutant organic analyses
of the AS bioreactor effluents indicated that the  four AS biore-
actors had lower contaminant removals than the acclimation bio-
                                                                                               Table 6
                                                                                Priority Pollutant Analysis of AS Effluents
ANALYTE
Methylene Chloride
cis-1, 2-Dichloroethene
Toluene
Acetone
2-Butanone
T-Xylene
Phenol
2,4-Dimethylphenol
2-Hethylphenol
4-Methylphenol
Isophorone
Bioreactoi
No. 1
0.0046J
0.0032J
ND
ND
ND
ND
ND
ND
ND
0.1760
ND
No. 2
0.0045J
0.0094
ND
ND
ND
ND
ND
ND
ND
0.1510
ND

0,
0,
1.
0.
0.

0.
0.
0.
0.
No. 3
ND
.0250
,0069
.0500
.1500
0062

0217J
0105J
1730
0128J
No. 4
ND
0.0069
ND
ND
U.0150J
ND

ND
0.0112J
0.0287J
ND
                                                                   J:   Indicates that  the concentration is below quantitational limits
                                                                   ND:  Not Detected
                                                                                               Table 7
                                                                            Analytical Data on Waste Sludge from AS Bloreactors
Analyte
Methlyene Chloride
Acetone
2-Butanone
Phenol
Phenanthrene
Dibutylphthalate
Fluoranthene
Pyrene
Chrysene
Benzo( a) Anthracene
Bis (2-Ethlyhexly) Phthalate
Benzo (b) Fluoranthene
Benzo (k) Fluoranthene
Concentration
(mg/kg)
4.4
18.2
16.2
0.71J
0.53J
0.12J
0.85J
1.2J
0.49J
0.40J
5.5
0.42J
0.13J
                                                                      J:  Indicates value is below statistical quantitation limits
organic priority pollutants were being removed due to volatiliza-
tion. Therefore, it was concluded that contaminant removal due
to volatilization from the aeration tank was minimal compared to
the amount of contaminant  being  biologically degraded. This
conclusion was consistent  with  the contaminant composition of
the groundwater which was comprised primarily of ketones which
are relatively nonvolatile at standard temperature and pressure.
  Table 5 contains influent and effluent BOD, COD and TOC
analyses along with the percent  removals achieved in each biore-
actor. There was little difference observed in the performance of
the various bioreactors for removal of the gross pollutants (BOD,
COD and TOC).  Therefore, at an HRT of  1 day there was no
appreciable difference in BOD,  COD and TOC removals for the
range of SRT evaluated.
  Table 6 lists the results of the priority pollutant analyses of the
four bioreactors' effluents. The effluent from Bioreactor  No.3
had  more organic contaminants detected than the other three
effluents.  However, except for acetone, the concentrations de-
tected in the Bioreactor No. 3  effluent were all near the analytical
detection limits of the respective contaminants.
  To complete the mass  balance of organic contaminants around
the AS bioreactors, a  priority pollutant analysis on a composite
of waste sludges from all of the bioreactors was performed. The
                            Table 8
         PAC/AS Bloreactors Average Operating Parameters
Bioreactor
Parameter No.l
HRT (day)
SRT (day)
DO (mq/1)
pH
Salinity (%)
Conductivity
in microahos
PACSS (mq/1)
TSS (rng/1)
KLSS (»q/l)
KLVSS <*g/l)
HLVSS/MLSS
F/M ratio*
Headspace KHU
Readings (ppn)
1.0
8.0
7. j
8.44
0.18
2776
1000
11436
10438
4394.0
0.421
u.37
<1.0
Bioreactor
No. 2
1.0
8. u
6.5
8.27
0. 17
2837
2000
10663
8663
4514
0. 521
0.36
-------
reactor. There are two factors that could have individually or
jointly contributed to the difference in the performance of the
acclimation bioreactor versus the performances of the four AS
bioreactors. The first factor was that  the hydrodynamic differ-
ence in terms of mixing efficiency between the large and small
bioreactors affected bioreactor performance by reducing the con-
tact frequency of the microbes with the contaminants. From vis-
ual observations made during both study phases, the larger biore-
actor seemed to mix the ML more efficiently than the smaller
units. The 2-L bioreactor had problems keeping the ML properly
suspended. The second, and probably more important, factor was
that the 2.0-L bioreactors were operated at a lower HRT,  indicat-
ing that some of the contaminants may require longer treatment
times.
PAC/Activated Sludge Evaluation
   The operating parameters and treatment conditions  for the
PAC/AS bioreactors are presented in Table 8. The PAC/AS bio-
reactors were operated at an HRT of 1  day and an SRT of 8 days.
The 8-day SRT was selected because relatively little difference in
the quality of the effluents from  the four AS bioreactors was
observed during the AS study. Of the  four bioreactors evaluated
in the AS study, the 8-day SRT bioreactor (Bioreactor No. 3) had
the lowest removals of TOC and COD. Since there was not an ap-
parent optimal SRT, an 8%-day SRT was selected to evaluate the
benefit of PAC addition to an AS system that was not removing
extremely high  percentages of the TOC and  COD from the in-
fluent.
   In Table 8, we report the concentrations of VOCs in  the off-
gases from each PAC/AS bioreactor  measured using the HNU
meter; all VOC concentrations were less than  1.0 ppm. Chemical
analysis for organic  priority pollutants in the off-gas from the
8.0-g/L PAC/AS bioreactor was performed to assess the amount
of contaminant removal achieved via volatilization. This analysis
indicated that approximately 2.6% of the priority pollutants  were
being removed via volatilization from the aeration tank of the
PAC/AS bioreactor. Therefore, as was the case with the AS bio-
reactor, it was concluded that the majority of the priority pollu-
tants were being removed due to biological degradation.
   To fully evaluate the benefits of PAC addition to the activated
sludge systems, the removal efficiencies obtained in the PAC/AS
bioreactors were compared to those of the 8-day SRT AS biore-

                           Table9
         Average Gross Pollutant Concentrations and Percent
          Removals in the PAC/AS and Control Bioreactors
                                                                    Table 10
                                             Priority Pollutant Analysis of PAC/AS and Control Bioreactors
                          Influent
                        Concentration
                           (mg/1)
                Effluent
              Concentration
                 (mg/1)
              Percent
              Removal
                 (*)
  PAC/AS BIOREACTOR NO. 1:
         BOD
         COD
         TOC
  PAC/AS BIOREACTOR NO. 2:
         BOD
         COD
         TOC
 PAC/AS BIOREACTOR NO. 3:
         BOD
         COD
         TOC

 PAC/AS BIOREACTOR NO.  4:

         BOD
         COD
         TOC

 CONTROL REACTOR:

         BOD
         COD
         TOC
1611.2
  3695
   775
1611.2
  3695
   775
1611.2
  3695
   775
1611.2
  3695
   775
1729.1
3279.0
 745.0
  80.2
1029.0
 297.6
 127.7
1063.0
 281.7
  53.2
 673.0
 175.9
  36.9
 490.0
 145.0
 131.0
1567.0
 296.0
95.0
72.2
61.6
92.1
71.2
63.7
96.7
81.8
77.3
97.7
86.7
81.3
92.4
52.2
60.3
                                                                            BIOREACTOR EFFLUENT
                                                                           No. 2   No. 3    No. 4  CONTROL
Methylene Chloride
cis-1, 2-Dichloroethene
2-Butanone
Acetone
Toluene
T-Xylene
Phenol
2 , 4-Dimethlyphenol
2-Methylphenol
4-Methylphenol
Benzole Acid
Isophorone
0.
0.




0,
0.

0,
0.
0,
.0109
.0172
ND
ND
ND
ND
.0012J
. OOOSJ
ND
.0027J
. 003 J
,012

0.




0.
0.

0.
0.
0.
ND
,0211
ND
ND
ND
ND
. 0053 J
,008J
ND
,20
. 0055J
,013
u.

u.



0.
0.

0,
0.
0.
.104
ND
. 0226J
ND
ND
ND
, 0035J
. 0017J
ND
,13
. 007J
.011
U.0738
ND
0.329
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
0.025
0.15
1.05
0.0069
0.0062
ND
0.0217J
0.0105J
0.1730J
ND
0.0128J
                                         J:  Denotes concentration is below statistical quantitiion limits
                                         ND:  Not detected

                                         actor. The 8-day SRT AS bioreactor will be referred to herein in
                                         this section as the control bioreactor.
                                           Table 8 also lists the ratios of MLVSS/MLSS for each PAC/
                                         AS bioreactor. As PAC dose increased, the MLVSS and MLVSS/
                                         MLSS ratio also increased, indicating an overall increase in bio-
                                         logical activity with increasing PAC dose. Several explanations
                                         for the increase in biological activity with increased PAC dosage
                                         were postulated. One explanation is that the PAC removed con-
                                         taminants that  were inhibiting biological activity resulting in a
                                         liquid phase more conducive to biological activity. A second ex-
                                         planation is that an attached growth population of microorgan-
                                         isms were using the PAC as a structural substrate. The attached
                                         growth consortium may be better suited for degradation of the
                                         more  difficult-to-degrade compounds  that were making up the
                                         TOC  and COD in the effluents from the AS bioreactors. The
                                         third explanation is that the PAC was adsorbing compounds that
                                         were kinetically slower to degrade. Once adsorbed, these com-
                                         pounds can be utilized by the bacteria as an additional food
                                         source. As PAC dose increased, the overall adsorptive capacity of
                                         the  bioreactor increased, thereby concentrating the amount of
                                         food available to the microbes.
                                           The results of the gross pollutant analyses of the four PAC/AS
                                         and control bioreactor effluents are presented in Table 9 and illus-
                                         trated in Figure 7. The removal of TOC and COD increased dra-
                                         matically with increasing PAC dose.  The removals of the gross
                                         pollutants also increased with increasing VSS/SS ratios which is
                                         illustrated in Figure 7. The observed increase in biological activity
                                         is further substantiated by the increased removal of the gross
                                         pollutants. The BOD removals achieved in the AS bioreactors
                                         were already high; therefore, only a slight improvement in BOD
                                         removals was observed with increased PAC dose (Fig. 7).
                   BODo:  Influent BOD
                   CODo:  Influent COD
                   TOCo:  Influent TOC
                                                                        (Thousand*)
                                                                     P AC do. J. mo/1
                                                                          A   COD/CODo
            Figure 7
     PAC/AS MLVSS/MLSS
Ratios and Gross Pollutant Removals
                                                                                                            BIOTREATMENT    837
-------
                            Figure 8
         Effect of Increasing PACSS on Oil and Grease Removal

  Table 10 lists the results of priority pollutant analyses  of the
four PAC/AS and control bioreactors. There was not an apprec-
iable difference between any of the bioreactors (including the con-
trol) in the removal of priority pollutant compounds. The 8,0-g/L
PAC bioreactor does indicate slightly better phenolic compound
removal due to the absence of these compounds in the effluent.
  Although not analyzed in the AS phase of study, the influents
and effluents from the four PAC/AS bioreactors were analyzed
for oil and grease concentrations. These data are summarized in
Figure 8. As the  PAC does increased, the removal of oil and
grease also increased.

CONCLUSIONS

  The acclimation phase of this study indicated that an inoculum
from a suspended growth municipal wastewater treatment plant
could be acclimated  to the contaminants in the Ninth Avenue
Site groundwater  composite samples  without an observed lag in
biological activity. Reduced iron and manganese in the ground-
water composites caused a dramatic increase in the MLSS  due to
cation oxidation.
  Based  on analysis  for  organic priority pollutants of the off-
gases from both biological systems (AS and  PAC/AS) and of a
composite sample of  waste sludge, it was concluded that biologi-
cal degradation accounted for a majority of the priority pollutant
removal achieved by both biological systems.
  The activated sludge process exhibited a potential for removing
contaminants in the site groundwater. BOD removals were  always
in excess of 95%. However, TOC and COD removals were only in
excess of 50%. Few priority pollutants were detected in the efflu-
ents  from the AS bioreactors. Those priority pollutants detected,
except for acetone, were at concentrations very near their respec-
tive analytical detection limits.
  The addition of PAC to the activated sludge did improve the
removal of COD and TOC from the influent. The removal of the
gross pollutants increased with increased PAC dose. A PAC dose
of 8.0 g/L  resulted in percent removals in excess of 80^0 for the
COD and TOC in the groundwater composite. Also, fewer prior-
ity pollutants were detected in the 8,0-g/L PAC dose bioreactor
effluent than the effluents from the other PAC/AS bioreactors.
   In summary, AS treatment augmented with the addition of
PAC seemed to be more effective than the AS biological system
alone for removing  the  gross pollutants and  organic  priority
pollutants from the groundwater composite.

ACKNOWLEDGEMENTS

   This work was funded by the U.S. Army Corps of Engineers,
Omaha District, in conjunction with U.S. EPA-Region V. The
authors would  like to thank Mr. Steven Rowe, COE Omaha Dis-
trict, and Ms.  Allison Hiltner, U.S. EPA-Region  V, for their
assistance and support for this study. Permission was granted by
the Chief of Engineers to publish this information.

REFERENCES

 1. American Water Works Association, Water Pollution  Control Fed-
   eration, and American Public Health Association, Standard Methods
   for Examination of Water and  Wastewater, Sixteenth Edition,
   AWWA, 1985.
 2. Bieszkiewicz, E. and Pieniadz-Urbaniak, A., "Effect of Benzene and
   Xylene on the Work of Activated  Sludge," ACT A  Microbiology
    'pollution, 33, (3/4), 1984.
 3. Shieh,  W.K., Chao, Y.M. and Yeh, T.F., "PAC-Activated Sludge
   Treatment of a Steel Mill Coke-Plant Wastewater," JWPCF, 58 (4).
   p. 333-338, Apr.  1986.
 4. Copa, W.M.  and Meidl, J.A., "Powdered Carbon Effectively Treats
   Toxic Leachate," Pollu. Eng., July 1986.
 5. Dietrich, M.J., Copa, W.M., Chowdhury, A.K. and Randall, T.L.,
    "Removal of Pollutants from Dilute Wastewater by the PACT Treat-
   ment Process," Environ. Prog., I, (2), pp. 143-149,1988.
 6. U.S. EPA, SW-846: Test Methods for Evaluating Solid  Wastes,
   U.S. EPA, Washington, DC, 1986.
 7. Hoffman, M.C.  and Oettinger, T.P., "Landfill Leachate Treatment
   with the PACT System," 60th Annual Meeting of the Central States
   Water Pollution Control Association, May 1987.
 8. Kelly, H.G.,  "Pilot Testing for Combined Treatment of Leachate
   from a Domestic Waste Landfill Site," JWPCF, 59, (5), pp. 254-261,
    1987.
 9. Kim, C.J. and Maier, W.J.,  "Acclimation and Biodegradation of
   Chlorinated Organic Compounds in the Presence of Alternate Sub-
   strates," JWPCF, 58, (1), pp. 35-40, 1986.
10. Kim, J.K., Humenick, M.J. and Armstrong, N.E., "A Comprehen-
   sive Study on the Biological Treatabilities of Phenol and Methanol,"
    Water Res., 15. (11), pp. 1221-1232,1981.
11. Nayar, S.C.  and Sylvester, N.D., "Control of Phenol in Biological
    Reactors by Addition of Powdered Activated Carbon," Water Res.,
13, (2), pp. 201-206, 1979.
12.  Rozich, A.F. and Gaudy, A.F., "Response  of Phenol Activated
    Sludge Process to Quantitative Shock Loadings," JWPCF, 15, (7),
    795-804, 1985.
13. Sanford, R. and  Smallbeck, D., "The Enrichment and Isolation of a
    Ketone Degrading Microbial Consortium by Continuous  Culture
   Techniques to Model Contaminated Groundwater Treatment," Ab-
    stracts from  the 1987 Annual Meeting of the American Society of
    Microbiology, 1987.
14.  Venkataramani,  E.S. and Ahlert, R.C., "Rapid Aerobic Biostabil-
    ization of High-Strength Landfill  Leachate," JWPCF, 56, (11),
    pp.1178-1184, 1984.
S.18   BIOTREATMhNT
-------
            Treatability  Study  of  Biological  Treatment System and
                 In  Situ  Remediation  at  a Remote  Superfund Site

                                          C.  Peter Varuntanya, D. Eng. Sc.
                                               James T. Volanski,  RE.
                                                 Donald G. Olmstead
                                           Killam Associates, DLA Division
                                               Warrandale, Pennsylvania
                                 A.A. Spinola                           R.J. McCarthy
                               USX Corporation                 Bethlehem Steel Corporation
                          Monroeville,  Pennsylvania               Bethlehem, Pennsylvania
ABSTRACT
  In January 1988, officials of a state environmental agency became
concerned about an ongoing accumulation of stormwater within an in-
active hazardous waste impoundment containing principally coke plant
wastes. The structural integrity of the impoundment was suspect, the
three million gallon stormwater accumulation was approaching the
impoundment's capacity and several downstream drinking water supplies
were threatened. The agency notified the U.S. EPA, which determined
that a CERCLA Section 106 removal action was required. A consent
decree requiring removal  of the impounded water  was issued in
August 1988.
  The initial treatment technology implemented evolved from an agency
recommendation and the practicalities of a remote site lacking utilities.
This technology (air stripping and activated carbon) was in place by
mid-December, and treated water discharge began in late December.
Discharging was stopped shortly thereafter due to elevated levels of con-
taminants in the discharge.
  The agency was satisfied that the immediate danger had been relieved
by the removal and treatment of 15%  of the accumulated  water.
Therefore, they agreed to postpone further removal until a laboratory
treatability study could be conducted by the consulting engineers re-
tained by the PRPs. The study demonstrated that biological treatment
offered the most effective and least costly treatment  approach. The
results from this study will be discussed.
  A temporary treatment basin was constructed adjacent to the first
impoundment in May and June of 1989. The wastewater was transferred
and seeded with bacteria in mid-July. An additional accumulation of
contaminated water was transferred in late August. Aeration/oxidation
time was nine weeks. The COD reduction was in general agreement
with the predicted oxygen transfer rate of the aeration equipment, and
wastewater quality was in agreement with that predicted from laboratory
studies. Approximately 82% percent removal of TOC was achieved.
  The paper will also illustrate the effectiveness of biological treatment
on a wide range of organic compounds, the predictability of full-scale
performance from bench-scale testing and the expeditious manner in
which biological treatment can  be implemented.

INTRODUCTION
  The Municipal and Industrial  Disposal Company (MIDC) operated
a hazardous waste disposal facility in Southeastern Allegheny County,
Pennsylvania from 1979 to August 1983. Operations ceased when the
Pennsylvania Department  of  Environmental Resources  (PaDER)
suspended the MIDC permit because of permit and consent order viola-
tions. The site has remained inactive since 1983. Waste materials known
to have been disposed at the site include coal tar decanter sludge, spent
solvents and metal-bearing wastes.
  The Phase I Disposal Pit was created by constructing dike walls above
the existing grade and then placing waste material within the lined diked
area. Waste material was not covered when operations ceased and rain-
water accumulated within the diked area. Through constant contact with
the  waste material, soluble chemical compounds contaminated  the
estimated 3.5 million gallons of accumulated water.
  In 1988, PaDER officials became concerned that a dike failure would
threaten several downstream drinking water supplies. PaDER notified
the U.S. EPA of their concerns at MIDC. After an assessment of the
situation, the U.S. EPA determined that a CERCLA Section 106 removal
action was warranted.
  Later that year, the U.S. EPA and the potentially jrfjpnnsihlp partifL
(PRPs) entered into a Consent Order and Agreement to conduct a
removal action at the MIDC site. One requirement of the Order was
to remove the liquid layer contained in the Phase I Disposal Pit.
  The initial treatment technology implemented evolved from an agency
recommendation and the practicalities of a remote site lacking utilities.
The  PRPs implemented the agreed  technology  (air stripping and
activated carbon),  and the treatment system was  in place by mid-
December. After verification of  the quality of the treated water by
sampling and analysis, discharge from the on-site treatment system began
in late December. Discharging was stopped shortly thereafter due to
elevated levels of contaminants in the discharge.
  The system could not respond to fluctuating influent characteristics
and overall influent concentrations which were greater than expected.
More rigorous sampling and characterization of the pond water showed
conspicuous stratification (Table 1)  and greater organic loads than
anticipated from the previously available data. Water treatment opera-
tions eventually revealed that the selected technology could not con-
sistently meet the stipulated technology based effluent quality limita-
tions. Acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone
(MIBK) proved particularly difficult to remove to the specified limits
by  the  selected  treatment scheme.  The treatment  system  was
subsequently dismantled and demobilized.
  Approximately  15 % of the impounded water had been treated and
discharged before cessation of operations. The agencies were satisfied
that the immediate danger posed by the site had been at least temporarily
relieved. Therefore they agreed to postpone further action until con-
sulting engineers retained by the PRPs could evaluate other alternatives.
  A number of on-site and off-site water management schemes were
considered. Off-site methodologies investigated were incineration, the
use of RCRA Treatment, Storage and Disposal Facilities and Publicly
Owned Treatment Works. On-site treatment schemes investigated were
incineration, solidification and biological treatment. Biological degrada-
tion of numerous solvents and of organics associated with coal coking
operations, was well documented.1"25 Table A-l  contains numerous
                                                                                                         BIOTREATMENT    839
-------
                              Table 1
         Phase I Disposal Pit Impounded Water Characterization
                     and Initial Discharge Limits
                             MH>C Site
PARAMETERS'
Suspended Solids
Dissolved Solids
Volatile Solids
Total Organic Carbon
Soluble Organic Carbon
Chemical Oxygen Demand
Phosphorus
Ammonia
Oil and Grease
Phenolics
Cyanide
Sullide
Selected Metals:
Arsenic
Magnesium
Selected Organic*
Phenol
2-Methyl Phenol
4-Methyl Phenol
Penlachlorophenol
Benzole Acid
Butanota Acid
Hexanoic Acid
Acelone
Methyl Ethyl Ketone(MEK)
Methyl Isobulyl Ketone(MIBK)
Shallow
Samples
mg/l
27
2800
1100
1500
1500
5600
0.19
24
4.4
13.9
0.78
1
Deep
Samples
mo/1
144
11800
5600
4900
4900
17000
2.2
108
8.4
17.8
3.7
2.8

1.8
80

2.3
0.3
1.4
NO
NO
2
6.2
5.1
4
0.4
3.5
280

9.1
1.3
4.8
Z1
51
24
12
100
57
18
Effluent limitations Applied lor
Stripping/Carbon Adsorption
Mo
Avg
mg/l








0.15
115
0.005


1.29





0.05



0.4
0.4
0.12
Daily
Max
mg/]








0.3
230
0.01

Inst
Max
mg/l








0.3
285
0.0125


2.58





0.1



0.8
0.8
0.24
3.2





0.125



1
1
0.3
  * Th« paramalcr* and •ffluanl limit* thown ar« not a oomp4«f« Uat.
  tlx abova ubk Hue only tha principal compound* and thak aaaodalad limllt.
  NO - Not DMaclad
citations of wastewater treatment efficiency for specific compounds based
on the type of treatment and source of the wastewater stream. The data
in this table  were  taken from a literature search in "Estimation of
Removal of Organic Chemicals During Wastewater Treatment," in 1986,
for the U.S.  EPA, The original data are from research conducted on
pilot- and full-scale treatment systems.
  The consulting engineers had participated in the successful utiliza-
tion of biological treatment for the organic chemicals of concern  and
were satisfied of its utility and cost-effectiveness. In addition, the PRPs
had had  good experience with  biological treatment of comparable
wastewaters within their own  facilities.
  The preliminary review of potential  treatment  and disposal
methodologies concluded that biological treatment processes held the
most  promise for  successful  management of the  impounded  water
because of their ability to remove a wide variety of organic compounds
from contaminated water at varying concentrations at a reasonable cost.
The agencies agreed to postpone further  removal until a laboratory
treatabiliry study could be conducted to demonstrate the effectiveness
of biological  treatment.

BACKGROUND
  Sampling of the feed to the air  stripper/carbon treatment system
showed inconsistencies with earlier data collected by the agencies in
1988.  To establish a basis for design of a new treatment system, it  was
necessary to accurately determine the volume and composition of the
impounded water.
  Liquid samples were collected from the Phase I Disposal Pit from
approximately one foot below the liquid surface and from approximately
one foot  above the waste/liquid interface.  The pit was divided  into
quadrants and samples were obtained at two depths in the center of
each quadrant.
  The samples were analyzed for the following indicator parameters
and nutrients:  Suspended Solids. Chemical Oxygen Demand, Dissolved
Solids, Phosphorus, Volatile Solids.  Ammonia. Total Organic Carbon,
 Oil and Grease (Freon Extractables), Soluble Organic Carbon, and
 Phenolics.
   These parameters were selected to:
 • Determine the physical nature of the majority of contaminants (dis-
   solved or suspended)
 • Evaluate  the  potential  for  biological  treatment  enhancement
   by nutrients
 • Determine initial operating parameters and loading for the biologi-
   cal treatability scenarios
   Results of these analyses  are presented in Table 1 for the shallow
 and deep samples.
   Composite samples generated from the set of shallow samples and
 deep samples  were subjected to these analyses: cyanide, sulfide,
 ignitability, Btu,  metals, acid extractable organics, and base  neutral
 extractable organics. The organic scans included the "tentatively identi-
 fied compounds" library search procedure on both fractions. Table 1
 also shows the analytical results.
   The final group of parameters is the volatile organic compounds,
 including a library search. Since the U.S. EPA protocols specify that
 samples intended for analysis of volatile compounds are to be grab
 samples, two discrete samples were selected; one shallow and one deep.
   These analytical data indicate  that contaminants in the impounded
 water are generally more concentrated closer to the waste material, i.e.,
 deeper in the liquid layer. Typically each analyte was three to five times
 more concentrated in the deep samples.
   Concurrent with  sample  activities,  depth soundings were taken
 throughout the impoundment.  From depth sounding  data,  it was
 estimated that approximately  3.5  million  gallons  of water had
 accumulated within the Phase I Disposal Pit as of the date of sampling.

BIOLOGICAL TREATABILITY STUDY
  Three scenarios were  considered  for the treatability study.  The
scenarios are described in the next sections  of the paper.
Scenario  No.  1: Blending   and Biological Treatment  at Nearby
 Coke Works
  A nearby coke works, owned by a PRP, utilized an activated  sludge
process to treat coal coking wastewaters. Phase  I Disposal Pit wastewater
and the coke works wastewater were blended at a 1:20 ratio consistent
with expected hauling and receiving capabilities. A bench-scale bio-
reactor was seeded with sludge from the coke plant and operated at
an  F/M  (Food/Microorganism  ratio  defined as the  gram COD
applied/gram MLVSS per day) of 0.3 after blending.
Scenario No. 2: Treatment On-Site Using Mobile Equipment
  For this scenario, modular, transportable equipment was envisioned
for treatment of the impounded water. A low load activated sludge system
was selected as the most promising approach, due to  availability and
proven performance. To simulate this scenario, a bench-scale activated
sludge process  was selected  for testing at F/Ms of 0.1 and 0.2.
Scenario No. 3: In Situ Treatment
  In situ treatment would consist of the introduction of surface aerators
to the Phase I Pit and the addition of seed bacteria and nutrients. The
seed bacteria preferably would have some degree of acclimation to the
pond organics,  as would occur with biological sludge from a nearby
coke works wastewater treatment plant. To simulate this scenario, a
small bench-scale reactor was operated.
  The experimental design is summarized in Table 2.

MATERIALS  AND METHODS
  A laboratory treatability study was conducted to evaluate all three
scenarios. Two activated sludge  reactors were  set  up to simulate
Scenarios 1 and 2. Each consisted of a stirred, aerated  compartment
of 5 gallons, separated by a vertical baffle to provide quiescent condi-
tions at the overflow. Operating conditions were set to allow the reactors
to operate at F/M ratios of 0.3 (Scenario 1), 0.2 and 0.1  (Scenario 2).
All reactors were seeded with sludge from a local coke works biological
wastewater treatment facility.  Nutrients were  added to the reactors to
supplement the bacteria and ensure new cell growth.
MO    BIOTRE^TMENT
-------
                                                          Table A-l
                                      Selected \fastewater Treatment Removal Efficiencies*
                                                     (22, 23, 24 and 25)
Chemical
Acetone
Anthracene
Anthracene
Anthracene
Napthalene
Napthalene
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Chemical
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Phenol
Percent Waste Stream
Removal
73.0
>96.0
>99.0
98.0
>99.0
>99.0
91.00
94.60
9?. 30
90.60
90.70
98.20
95.0
86.30
93.30
96.70
90.70
0-5
90.80
75.30
94.10
76.20
81.30
99.00
97.40
80.20
82.70

Coke processing plant
Coke processing plant
Coke processing plant
Coke processing plant
Coke processing plant
Indust Creosote Waste
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Municipal Sewage
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Ind. Wastewater
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes

Refinery Wastes
Refinery Wastes
Refinery Wastes
Percent Haste Stream
Removal
80.20
86.20
88.60
92.80
80.30
93.70
96.30
88.30
85.40
93.50
94.30
94.60
81.40
90-100
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Refinery Wastes
Coke Plant Effluent
Initial
Chem Cone

7.2 ug/1
85 ug/1
15 ug/1
560 ug/1
180 ug/1
47 mg/1
21.2 mg/1
16.2 mg/1
21.2 mg/1
22.7 mg/1
18.5 mg/1
50 ug/1
19.9 mg/1
13.5 mg/1
19.6 mg/1
21.1 mg/1
13-19 mg/1

20.3 mg/1
21.2 mg/1
20.6 mg/1
20.3 mg/1
39.6 mg/1
21.2 mg/1
21.2 mg/1
21.6 mg/1
Initial
Chem Cone
24.8 mg/1
24.5 mg/1
23 mg/1
21.1 mg/1
20.2 mg/1
21.2 mg/1
18.8 mg/1
25.7 mg/1
20.3 mg/1
21.2 mg/1
21.2 mg/1
21.2 mg/1
18.1 mg/1
655 mg/1
Treatment
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Activated Sludge
Microb Treat Tower
Aerated Lagoon
Cont Activated Sludge
Aerated Lagoon
Cont Activated Sludge
Cont Activated Sludge
Plug Flow A.S.
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Aerated Lagoon
Activated Sludge
Batch Activated Sludge
Cont Activated Sludge
Aerated Lagoon
Cont Activated Sludge
Cont Activated Sludge
Seg Batch Reactor
Aerated Lagoon
Cont Activated Sludge
Cont Activated Sludge
Treatment
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Aerated Lagoon
Cont Activated Sludge
Aerated Lagoon
Cont Activated Sludge
Cont Activated Sludge
Cont Activated Sludge
Aerated Lagoon
Aerated Lagoon
Aerated Lagoon
Cont Activated Sludge
.Activated Sludge
Scale
Pilot
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Pilot
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Scale
Full

Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Full
Pilot
Temp Susp Solids
C Cone
NR
NR
NR
NR
NR
NR
10
NR
6.00
NR
6.00
6.00
NR
6.00
6.00
6.00
NR
NR
NR
6.00
NR
6.00
6.00
24-26
NR
6.00
6.00
NR
NR
NR
NR
NR
NR
116 mg/1
227 mg/1
NR
285 mg/1
NR
NR
430 mg/1
NR
NR
NR
250 mg/1
931 mg/1
NR
NR
245 mg/1
NR
NR
NR
265 mg/1
NR
NR
Temp Susp Solids
C Cone
6.00
6.00
6.00
NR
6.00
NR
6.00
6.00
6.00
NR
NR
NR
6.00
NR
NR
NR
NR
290 mg/1
NR
260 mg/1
NR
NR
NR
282 mg/1
265 mg/1
260 mg/1
NR
45 mg/1
Hydraulic
Res. Time
8 hrs
NR
NR
NR
NR
NR
NR
12 days
7 hr
1 day
7 hr
7 hr
7 days
7 hr
7 hr
7 hr
3 days
NR
10 hr
7 hr
10 days
7 hr
7 hr
8-9 days
10 days
7 hr
7 hr
Hydraulic
Res. Time
7 hr
7 hr
7 hr
3 days
7 hr
7 days
7 hr
7 hr
7 hr
5 days
5 days
7 days
7 hr
NR
Acclimation Reference
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Klncannon et al,
Walters and Luthy
Walters and Luthy
Walters and Luthy
Walters and Luthy
Walters and Luthy
Vela and Ralston,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
no date
, 1984
, 1984
, 1984
, 1984
, 1984
1978
no date
no date
no date
no date
no date
Petrasek et al, 1983a
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Feller, 1979
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
no date
no date
no date
no date

no date
no date
no date
no date
no date
Herzbrun et al, 1985
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
no date
no date
no date
Acclimation Reference
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
NR
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
Mahmud and Thanh,
no date
no date
no date
no date
no date
no date
no date
no date
no date
no date
no date
no date
no date
Osantowski & Hendriks, no date
                        Table 2
Experimental Design; MIDC Impoundment Water Treatability;
                      MIDC Site
Scenario
Raw Waste
Reactor
Type
Description
F/M
1
95% Coke Plant
5% MIDC
R-1
Continuous
Activated Sludge
0.3
2
MIDC
R-2
Continuous
Activated Sludge
0.2
0.1
3
MIDC
R-3
Batch
Aerobic
Digestion
N/A
N/A
  To determine when stable conditions had been attained at a given
F/M, selected parameters were routinely monitored until constant values
were obtained. Total organic carbon (TOC), methyl ethyl ketone (MEK),
biochemical oxygen demand (BOD) and  flow were monitored in the
influent.  In the mixed  liquor, the  concentrations of mixed liquor
suspended solids (MLSS) and mixed liquor volatile suspended solids
(MLVSS) were monitored and, in the effluent, TOC  and MEK were
monitored. Weeks were required for reactor conditions to  stabilize;
during that time the biomass acclimated  to the new substrate. Large
variations in sludge and mixed liquor characteristics were  observed
during the  stabilization period.
  The batch reactor study to simulate the in situ treatment, Scenario
3, was designed based on initial toxicity tests (dissolved oxygen uptakes)
to determine at what concentration the pond water could be mixed with
                                                                                                            BIOTREATMENT    841
-------
 activated sludge without toxicity. Initial testing did not indicate any
 toxicity problems. Seventy-five percent of the pond water and twenty
 five percent of the coke plant aeration tank mixed liquor were combined
 for the uptakes. An 8-gallon reactor was used to simulate the Phase I
 Pit holding the impounded water. In order to be conservative, the reactor
 was prepared with  water  samples drawn from  the  bottom of the
 impounded water layer, where the highest organic levels were observed.
   The first batch reactor was  seeded to a MLVSS of approximately
 500 mg/L.  The reactor was then vigorously  aerated and monitored.
 A second test was conducted to check/confirm the results of the first
 test. The second reactor used all the settled sludge from the first reactor.
 After  adding  impounded water, the second  reactor was vigorously
 aerated and monitored. The treatment performances for the biological
 reactor were monitored  for BOD5, TOC, COD,  MEK and organic
 compounds analysis.

 RESULTS  AND DISCUSSION

 Reactor Performance
 Scenario 1: Blending and Biological Treatment at Nearby Coke Works
   The organic removal increased with time due to acclimation of the
 bacteria to the wastewater. After approximately four weeks of acclima-
 tion, the average organic removal based on BOD was 88%  (Table 3).
 MEK was removed by approximately one order of magnitude, but the
 required removal rate could not be achieved without the 20:1  dilution
 provided by the other wastewater streams. Overall, this reactor did not
 perform as  well as the on-site continuous or batch reactors.

                            Table3
   Summary of Reactor Performance; MIDC Impoundment Water
                  Treatability Study; MIDC Site
Scenario
R-1
(Continuous
Blend)
1
R-2
(Continuous)
2a
2b
R-3
(Batch)
3a
3b
Raw Waste:
TOC, mg/l
BOD, mg/l
MEK, ug/l
783
1110
613
1950
3100
11800
2020
2980
13500
2000
2800
13500'
1050
1400'
7150
Operating Parameter:
F/M
MLVSS
0.3
3000
0.2
4800
0.1
3700

3600

4400
Effluent:
TOC
BOD
MEK
245
127
79
1100
960
1725
524
88
89
453
26
<10.0
333
5
17
% Removal:
TOC
BOD
MEK
69
88
79
44
69
85
74
97
99
77
>99
>99'
68
>99-
>99
       •Estimated

       All data shown are averaged during steady state


Scenario 2:  Treatment On-Site Using Mobile Equipment
  The  continuous reactor showed better performance at a reduced
loading. The initial average F/M loading (gram COD/gram MLVSS/day)
was 0.2.  The  second F/M loading was 0.1.  At  these loadings, the
removals based on BOD were 69% and 97%, respectively (Table 3).
MEK dropped to below the expected 1000 ug/L effluent limitation at
the lower loading.
  Scenario 3:  In Situ Treatment
  The batch reactor showed the best performance overall (Table 3).
After 10 days of operation, the organic removal based on BOD exceeded
99•*  (Table 3). and the projected effluent limit for  MEK was achieved.
The second hatch test confirmed the results of the initial lest and showed
that MEK removal exceeded  99% after  10 days of operation.
  The operating data and the results of the batch reactor performance
 are summarized in Tables 3 and 4. In all cases, the previously applied
 discharge limits were attained or approached. In some cases, detection
 limits were too high to determine whether or not discharge limits could
 be attained. This finding was attributed to interferences from other
 organics in the matrix, which often occur in high strength wastewaters.
                             Table 4
             Operating Data for Batch Treatability Tests;
                            MIDC site

Volatile Suspended Solids (Avg)
Time for TOC removal, days
Time for MEK removal, days
Total test duration, days
Test A
3600
<6.0
13
24
TestB
4400
<3.0
13
13
  BOD removal was computed as an average value from mean per-
formance data.  Scenario 3 offered the best removals in the shortest
period of time for the least cost. Therefore, this scenario was recom-
mended for  implementation.  High detection  limits  occurred  in
Scenario 3 at least once with the following parameters: cyanide, MIBK,
phenanthrene, 2-hexanone, and fluoranthene. The discharge limits were
not achieved  for the following parameters: phenol,  arsenic, boron,
manganese and nickel. Therefore, one recommendation of the treatability
study was to renegotiate the limits applied to these compounds.
  Proposed limits were submitted to PaDER by the PRPs (Table 5).
The acceptability of these limits was vigorously debated by the PRPs
and the involved agencies and was not resolved until immediately before
discharge of the treated impoundment water.
                                                                                                  Table 5
                                                                                    Performance of Batch Treatability Tests;
                                                                                                 MIDC Site
Parameters
TOC
BOD
Phenolics (4AAP)
Cyanide
Arsenic
Methyl Ethyl Ketone(MEK)
Methyl Isobutyl Ketone(MIBK)
Test A
Influent
2000
2600
6.35
15.5
2.3
13.5
1.25
Effluent
450
26
0.1
0.05
1.7
0.01
0.01
TestB
Influent
1050
1400
4.35
15.5
1.7
7.3
0.79
Effluent
330
5
0.4
0.87
1.3
0,042'
0.2
Proposed
Effluent
Limitations
InsLUax


0.4
0.05
3.2
1

                                                                        Note: All concentrations are in the unit of mg/l.
                                                                         compound was detected In blank
FULL-SCALE IMPLEMENTATION
In Situ Biotreatment System Design
  The bench-scale reactors yielded performance data, but no data that
were readily utilizable for sizing aeration equipment. The bench-scale
reactors were vigorously aerated to assure that performance would not
be limited by oxygen requirements or by the quantity of biomass in
suspension and to demonstrate the concept in the available time. In full-
scale operation, aeration would be less vigorous to avoid disturbing
the wastes at the bottom of the impoundment. The minimum recom-
mended power level for mixing and aeration in lagoons is approximately
30 hp/mg.M  Typical horsepowers commonly used in aerated lagoons
range from 10 to 60 hp/mg. A range of anticipated performance infor-
mation is shown in Table 6. Based on an anticipated waste volume of
3.5 million gallons, initial volatile suspended solids of 400 mg/L and
aeration horsepower of 30 hp/mg were selected as objectives.
  Table 6 indicates that MLVSS would be rale-limiting and that the
required BOD  removal could be accomplished in 26 to  65 days
depending on oxygen transfer efficiency and on  the concentration of
       B1OTRKATMEM
-------
                            Table 6
           Anticipated In Situ Performance; MIDC Site
                                                                               TOC. COD. BOD, ma/I (llOEJ)
                                                                                                                    TS3. VSS. ma/I
Case
Total Mixing Power
total BOD in Pond
(Avo. of 3000 mg/l)
If Oxygen is 'Rate Limiting: .v-
Rate of Oxygen Delivery
Rate of Oxygen
Utilization (Estimated)
total total Oxygen Delivery
total BOD Removal
Time Required for BOD Removal
IfMLVSSisRatelinirSng -> «,*•,
Anticipated MLVSS
Uptake Rate
(Est. Avg. From Lab Data)
Rate of Oxygen Uptake
Oxygen Consumable by MLVSS
total BOD Removal
time required for BOD Removal
Units
HP
Ib
>•'.-. ^SiSyft-sfiS''-^
Ib/HP-hour
lbO2/
Ib BOD Removed
Ib/day
Ib/day
day
*V S°V WSfcfcX ^
mg/1
mg O2/1 mini
mg/1 MLVSS
mg/l-day
Ib/day
Ib/day
day
Expected
105
40000
.:. ' s ^V^Ss^ •• '
2.5
1.5
6300
4200
10
v. 5.V*
500
1.1E(-4)
79
2310
1540
26
Worst
105
40000
'::.'•'• i"K-',y
1.5
1.5
,_ 3700
1260
32
-i*-x J*>-
200
1.1E(-4)
32
924
616
65
 biomass (MLVSS) maintained in suspension. Additional time would
 be required for the seed to acclimate, to settle the biological solids and
 to discharge the treated water.  There also was concern that removal
 of organics could  be anticipated to become less efficient as the BOD
 decreased, which  would extend the treatment period. Total time from
 seeding to an empty pond was predicted to be twelve to eighteen weeks.

 Implementing On-Site Treatment
   In May 1989, another emergency condition was declared at the MIDC
 site due to increased seepage at the toe of the eastern dike and rising
 water levels within the Phase I Disposal Pit from heavy precipitation.
 An emergency construction project was initiated to  buttress  and
 strengthen the dikes. Although batch biological treatment within the
 Phase I Disposal Pit would have been the most  expeditious and effec-
 tive alternative to implement, two major drawbacks were evident:
 •  The persistent threat of dike overtopping by the rising water level
   would not be quickly alleviated because of the time period necessary
   for proper treatment and
 •  Leaving the impounded water in the Phase I Pit and in contact with
   the waste material would complicate the aeration application and
   possibly prolong treatment by enhancing  the flux of contaminants
   from the solid phase to the liquid phase
   The alternate plan developed to implement batch treatment involved
 construction of a lined treatment basin, transferring the water from the
 Phase I Disposal Pit into the treatment basin and proceeding with treat-
 ment. Since this plan eliminated the drawbacks of in situ treatment,
 it  was endorsed by the agencies.
   The temporary  treatment  basin was constructed adjacent to the
 Phase I Disposal Pit in approximately 6 weeks of extremely inclement
 weather. The aeration  system consisted of ten floating aerators posi-
 tioned throughout  the temporary basin. Nine 10-horsepower units and
 one 15-horsepower unit provided a total system aeration/mixing power
 of 105 horsepower (Table 6). As the water level in the Phase I Pit was
 drawn down, a minimal amount of infiltration was observed. However,
 one month after the initial water removal, another one foot of infiltra-
 tion and precipitation  had accumulated in the Phase I Pit and was
 transferred into the treatment basin.

 Startup
  To aid mixing, nutrients and biomass were added to the temporary
 basin during the transfer pumping of the impounded water from July 6
 to  July 13. A review of the nutrient characteristics of the raw water
 (Table 1) suggested that the available nutrients  could not support the
kind of biological growth anticipated to be necessary for expedient
biological degradation of the wastewater constituents. However, it was
believed that a high ratio of endogenous respiration and nutrient cycling
would occur.
                                                         1000
                                                                                                                                800
                                                                                                                             --600
                                                                                                                                400
                                                                                                                             --200
       0   10  20  30  40  50  60  70  80  90  100  110  120
                        DAYS OF OPERATION
           TOC   + COD   * TSS
                                         VSS
                                               x  BOD
                             Figure 1
               MIDC Impounded Stormwater Remediation
                      Process Monitoring Data
      12
         UEE CONCENTRATION. ma/I
                            20         30
                           DAYS OF OPERATION

                              D  MEK

                             Figure 2
               MIDC Impounded Stormwater Remediation
               MEK Concentration vs. Days of Operation


  Therefore, the consulting engineers elected not to supplement the
existing ammonia,  but  to  add  110 gallons of 75%  technical grade
phosphoric acid. Approximately 20,000 gallons of 5%  solids biological
sludge were shipped from the local coke plant wastewater treatment
facility and used to seed the new impoundment. Seeding took place
from July 11 to  14. Aeration began on July 12.
  The results of TOC, COD, TSS, VSS and BOD analyses performed
are summarized in Figure 1; MEK analysis results are shown in
Figure 2. A summary of the analytical data is shown Table 7. COD,
TOC, BOD and MEK levels appeared to decline exponentially.
Biological activity began approximately one week after seeding. Initial
                                                                                                                   BIOTREATMENT    843
-------
                                                                 Table?
                                               Biological Treatment Process Monitoring Data;
                                                               MIDCSite
Date
Jul. 14
Jul. 17
Jul. 20
Jul. 25

Aug. 4
Aug. 7
Aug. 11
Aug. 14
Aug. 18
Aug. 21
Aug. 25
Aug. 26
Aug. 31
Avg.
pH
S.U.
7.7





flfl
8.2
8.4
8.6
8.8
8.5
8.5
7.5
Avg.
DO
mg/l
0.56


0.59


4
5.8
2.3
7
6.1
0.4
5.1
6.7
TOO
mg/l
2150
2300
2050
1800

1250
1050
800
575
600
590
860
730
540
COD
mg/l

6850
7050
5200

3350
3150
2550
2250
2000
1600
2600
2150
1900
TSS
mg/l

400
485
850

385

390

115

1?R

74
MLVSS
mg/l

310

640

330

325

100

115

66
BOD
mg/l

3700

2355
MEK
mg/l

11.0

3.3
Acetone
mg/l




Phenols
mg/l




Ammonia
mg/l

24
19
23
Phosphate
mg/l

200
4
4

1400



230



43
N.D.



0.009



0.004
0.064



0.03



0.013
0.15



0.08



0.03
31



25

13.5

21.5
0.08

0.07

2.3

2.0

1.7
Cyanide
mg/l










<0.04


0.18
Arsenic
mg/l










2.0


1.8

Sept. 5
Sept. 8
Sept. 11
Sept. 13
Sept. 15
Sept. 18
Sept. 21
Sept. 25
Sept. 28

Oct. 2
Oct. 6
Oct. 9
Oct. 12
Oct. 16
Oct. 20
Ocl. 30
7.6
8.6
8.9
9.2
8.5
8.6

11.2
8.6
8.4
8.1
7.6

7.8
8.1

10.1
8.7
590
480
485

510
415
420
430
400
1850
1800
1800

1650
1500
1450
1500
1600

68

68
54





58

58
38








660








0.006







0.06
0.021








<0.05





17.5


13





0.16


7.0







0.02








2.2






9.1
8.9
9.1

8.9
9.1

10
8.8
11.4

9.3
10.7

450
400
410
395
400
380
385
1300
1300
1300
1300
1300
1250
1250






































































      Note: On August 23, an additional 81.000 gallons o( Impounded water was translered from the Phase I Pll lo the temporary basin.
      N. D. - Not Defined

                                                                       dissolved oxygen  concentrations were positive, indicating  that the
                                                                       aerators were adequately sized to match the initial load (Figure 3). Later
                                                                       dissolved oxygen levels rose as residual CODs dropped. Biological
                                                                       degradation was essentially complete in approximately one month.

                                                                                                     Tables
                                                                                      MIDC Site; Analysis of Biotreated Water;
                                                                                  Selected Parameters; Sampled September 21, 1989
14 -
13 -
12 -
1 1 -
io-
9 -
8 -
7 -
6 -
5-
4 -

3 -
2 -
1 -
n -

+
+ +
_l_
L
- - .. >: .-••••
•'+ + .
+ +
+
+





i 	 1 	 1 	 1 	 4 	 1 	 1 	 1 	 1 	 1 	 1 	 1 	
I z
~ 11
- 10

- 9
- 8
- 7
- 6
- 5
-4

- 3

-2
- 1
- n
            10  20  30  40  60  60  70   80  90 100  110
                         DAT1 OF OPC1ATIOK
                                                       120
                           pH
                                  +  DO
                             Figure 3
              MIDC Impounded Slormwaicr Remediation
                      Process Monitoring Data
PARAMETERS
Total Organic Carbon
Chem. Oxygen Demand
Arsenic. Total
Nickel. Total
OiG
Phenols (4AAP)
Total Cyanide
Acetone
Methyl Ethyl Ketone
Metnyl Isobutyl Ketone
Napthalene
Acenapthylene
Anthracene
Pyrene
Chrysene
Benzoft>)lluoranthene
Beruo(k)fluoranlhene
Benio(«)pyrene
Pftenantnrerw

TB-1
445
1450
2.4
0.82
3
0.26
<0.02
0.029
ND
NO
0.003
0.003
0.005
0001
0005
0.015
0.012
0.011
NO
ND
TB-2
410
1450
2.5
0.8
8
0.06
<0.02
ND
ND
NO
0.003
0.003
0.005
0.002
0006
0.021
0.01
0.013
ND
ND
TB-3
425
1450
2.2
0.72
11
0.06
<0.02
0.039
ND
ND
ND
ND
0.004
0.003
0.004
0.027
0.035
0.011
0.003
0.003
TB-4
415
1450
2.4
1.2
21
0.09
0.03
0.015
ND
ND
ND
0.003
0.004
0.002
0006
0024
0.012
0014
0.007
0.007
TB-S-
415
1450
2.2
1.2
20
0.07
0.02
0.02
ND
ND
ND
0.002
0.004
0.002
0.006
0.024
0.012
0.014
0.007
0.007
Note. Ai conuonuabons tie In UK unit a mgA
NO- Not Determined
' Dupfecate of TB-4
TB-6
410
1500
2.5
1.2
17
0.09
<0.02
0.056
ND
ND
ND
0.002
0.002
NO
0.003
0.016
0.006
0.009
NO
NO

104    BIOTREA.TMENT
-------
  The transfer of additional run-on and infiltration water from the
Phase I impoundment (on August 25, 1989) resulted in a 63% increase
in COD within the pond. Again biological degradation was essentially
complete in approximately one month. The pond completely exhausted
its potential for biological degradation in another three weeks. A sum-
mary of the monitoring data is shown in Table 7.
  Conclusion of the treatment process was indicated by three condi-
tions: leveling off of TOC valves, BOD below 50 mg/L, and MEK
(2-Butanone) below 1 mg/L. Representative samples were then collected
at five locations at varying depths (Table 8). The data demonstrated
that the pond was essentially homogeneous.
  Upon review of the data, the involved agencies agreed to a mass-
based discharge limit based on residual levels of several polynuclear
aromatic compounds. This limited the discharge rate from the pond
to 100 gpm. The water was discharged in 20,000 gallon batches. Each
batch was tested for soluble COD. Batches with CODs in excess of 1800
mg/L were returned to the pond. Discharge began on November 8, 1989
and concluded on January 28, 1990. Comparison of effluent analyses
between the bench-scale reactor and the biotreatment process is shown
in Table 9.
                            Table 9
       Comparison of Treatability Effluent and Pond  Effluent
             Analyses;  Selected Parameters; MIDC Site
PARAMETERS
Arsenic, Total
Nickel, Total
O&G
Phenols (4AAP)
Total Cyanide
Acetone
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Napthalene
Acenapthylene
Anthracene
Pyrene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluorantnene
Benzo(a)pyrene
Phenanthrene
Fluoranthene
TreatabUity
Effluent
Test A
1.7
0.4
9
0.1
0.05


<0.2
<0.2

<0.2


NO

ND
<0.2
<0.2
TestB
1.3
0.58
<5
0.4
0.87
0.17
<0.01
<0.01
<0.01

<0.01


0.019
<0.01
0.013

<0.01
Pond
Effluent
(average)
2.4
0.97
13
0.11
<0.02
0.032
0.004
ND
0.003
0.003
0.004
0.002
0.005
0.021
0.014
0.012
0.006
0.006
  Note: All concentrations are in the unit of mg/l.
  ND= Not Determined

Evaluation of Biokinetic Constants
  During the process of biooxidation of a complex substrate, the reac-
tion rate decreases independently of the decrease in substrate concen-
tration. As a result, efforts to describe the overall reaction rate by a
first order equation is considered.  At the same time, it is quite clear
that the reaction rate constant (k) from the first order equations will
decrease with the progress of the biochemical reaction of a complex
substrate. Typically, substrate levels are represented by an indicator
parameter such as BOD or COD.
  While kinetic data have not been studied extensively for this study,
it should be noted that the exponential decay coefficients for COD and
TOC varied with initial loadings. The biokinetic constants were deter-
mined by fitting TOC and COD data to the first order kinetic equation:
      S  = S0exp(-kt)
where S  = substrate concentration at time t
      So = initial substrate concentration
      k  = first order kinetic constant
      t  = time
(1)
            Estimation of the numerical values of the biokinetic constants presents
          a complex problem, because one has to choose an equation which fits
          the data. Several investigators have utilized non-linear regression tech-
          niques to fit the data and estimate the biokinetic constants. This ap-
          proach is applied with difficulty. It is possible to obtain numerical values
          which have little physical meaning; nonetheless, such a problem did
          not occur  in obtaining the numerical values of first order biokinetic
          constants for substrate concentrations measured as  TOC and COD,
          summarized in Table 10. The goodness of fit is also shown as correla-
          tion coefficients in the same table. The decay constants reported here
          seem  to be  comparable to one another (for both  TOC and COD
          measurements). In Phase I, k was 0.043 day"1, and 0.044 day"1 for TOC
          and COD, respectively.  In Phase H, k was 0.025 and 0.018 day"1 for
          TOC  and COD, respectively. MEK was removed at a faster rate of
          0.19 day-'.
                                       Table 10
                             Biokinetic Constants; MIDC Site
TOC DAT A
FIRST ORDER KINETIC CONSTANT (k). 1/day
INITIAL SUBSTRATE CONCENTRATION, mg/l
CORRELATION COEFFICIENTS (r)
COD DATA
FIRST ORDER KINETIC CONSTANT (k), 1/day
INITIAL SUBSTRATE CONCENTRATION, mg/l
CORRELATION COEFFICIENTS (r)
MEK DATA
FIRST ORDER KINETIC CONSTANT (k), 1/day
INITIAL SUBSTRATE CONCENTRATION, mg/l
CORRELATION COEFFICIENTS (r)
Phase 1
0.043
2050
0.975
Phase 1
0.044
7050
0.997
Phase 1
0.228
11
0.996
Phase II
0.025
860
0.892
Phase II
0.018
2600
0.93




  The physical, chemical and biochemical  characteristics of these
reported organic compounds become important during biological treat-
ment because of the combined possibilities of stripping, adsorption and
biological oxidation. Most kinetic design models available to date have
originated from a substrate mass balance assuming substrate removal
based on biological consumption. Stripping and biological adsorption
are not included in this balance, and the amount of substrate stripped
is not predicted.
  Tables 3 and 7 show the comparison of the MEK removal achieved
in batch reactors; one test was performed as a bench-scale experiment
and the other as a biological treatment process. In a bench-scale system
(Scenario 3), more than 99% of MEK was removed in 14 days; in the
pond treatment process, 99 % of MEK was removed in one month. This
difference might  reflect  rate limiting  conditions in the pond, i.e.
oxygen transfer.

CONCLUSIONS
  The batch biotreatment process achieved comparable  removals to those
found in the bench-scale study. Bench-scale testing was a good predictor
of reactor performance.

REFERENCES
 1. Forney, A.J., Haynes, W.P., Gasior, S.J., Johnson, G.E. and Strakey, J.P.,
   Analysis of Tars, Chars, Gases and Water Found in  Effluents from the
   SYNTHANE Process, U. S. Bureau of Mines, TPR 76, January  1974.
 2. Cousins, W.G. and Mindler, A.B., "Tertiary Treatment  of Weak Ammonia
   Liquor," Journal of Water Pollution Control Federation, 44, pp. 607, 1972.
 3. Kostenbader, P.D. and Flecksteiner, J.W., "Biological Oxidation of Coke
   Plant Weak Ammonia Liquor," Journal of Water Pollution Control Federa-
   tion, 41, pp.  199, 1969.
 4. Radhakrishnan,  I. and Ray, A.K., "Activated Sludge Studies with Phenol
   Bacteria," Journal of Water Pollution Control Federation, 46, pp. 2393,1974.
 5. Shimizu, T.,  Uno, Y., Dan, Y., Nei, N. and Ichikawa, K., "Continuous
   Treatment of Waste Water Containing Phenol by Candida Tropicalis" Fermen-
   tation Technology, 57(11), 1973.
 6. Shuckrow, A.J., Pajak, A.P. and Touhill, C.J., Management of Hazardous
   Waste Leachate, U.S. EPA, Office of Solid Waste and Emergency Response,
   Washington, DC, SW-871, September 1982.
 7. U.S. EPA Municipal Environmental Research Laboratory, Survey of Two
                                                                                                                  BIOTREATMENT    845
-------
    Municipal Wastewater Treatment Plans for Toxic Substances, Cincinnati,
    OH. March 1977.
 8. U.S. EPA, Background Document for Solvents to Support 40 CFR Pan 268
    Land  Disposal Restriction,  Volume  11,  U.S.  EPA,  Washington, DC,
    January 1986.
 9. Bess, F.D. and Conway, R.A., "Aerated Stabilization of Synthetic Organic
    Chemical Wastes," Journal of Waer Pollution Control Federation, 38, pp.
    939, 1966.
KX  Tibak, H.H., Quave, S.A., Mashni, CL and Earth, E.F., "Biod^radability
    Studies with Organic Priority Pollutant Compounds," Journal of Waer Pollu-
    tion Control Federation, 53, ppg. 1503,  1981.
11.  Tischler, L.F.  and Kocurek, O., "Biological Removal of Toxic Organic Pol-
    lutants," in Tone Materials-Methods for Control, N.E. Armstrong and A.
    Kudo, eds., pp. 939, The University of  Texas,  Austin, TX, 1983.
12. Olthof, M., Pearson, E., Mancuso, N. and Wittmann, I., "Biological Treat-
    ment of Coke Oven Wastewater Including  Provisions for Nitrification," Iron
    and Steel Engineer, 1980.
13.  Olthof, M. and Oleszkiewicz, J., "Benzol Plant Wastewater Treatment in
    a Packed Bed  Reactor," Proceedings 37th Annual Purdue Industrial Waste
    Conference, Purdue University, Lafayette, IN,  1982.
14. Benefield,  L.D. and Randall, C.W., Biological Design for Ubstewater Treat-
    ment, Prentice Hall Inc., Englewood,  NJ,  1980.
15.  Stover, E.L. and Kincannon, D.F., "Biological Treatability of Specific
    Organic Compounds found in Chemical Industry Wastewaters," Journal of
    Water Pollution Control Federation, 55,  pp. 97, 1983.
16.  Gaudy, A.F.,  Jr., et al., "Biological Treatment of Volatile Waste  Com-
    ponents," Journal of Water Pollution Control Federation, 35, pp.  75, 1963.
 17.  Freeman, R. A., et al., "Experimental Studies on the Rate of Air Stripping
    of Hazardous Chemicals from Waste Treatment Systems," Presented at the
    APCA Meeting, Montreal, Canada, 1980.
 18.  Kincannon, D.F., a al., "Biological Treatment of Organic Compounds Found
    in Industrial Aqueous Effluents," Presented at the Am.  Chan. Sac. 1981
    Nad. Meet., Atlanta, GA, 1981.
 19.  Stamoudis, V.C and Luthy, R.G., "Determination of Biological Removal
    of Organic Constituents in Ouency Waters Fro-High-BTU Coal-Gasification
    Pilot Plants," Waer Research, 14, pp. 1143, 1980.
20.  Lutby, R.G. and Tallon, J.T., "Biological Treatment of Coal-Gasification
    Process Wastewater,"  Water Research, 14 pp. 1266, 1980.
21.  Luthy, R.G., et al., "Biotreatment of Synthetic Fuel Wastewater," Journal
    of Environmental Engineering Division, American Society Civil Engineers,
    106 pp. 609, 1980.
22.  U.S. EPA, Estimating Releases and Wiste Treatment Efficiencies for the Toxic
    Chemical Release Inventory Form, Section 3D of the Emergency Planning
    and Community Right-to  Know Act  of  1986,  U.S.  EPA,  Washington,
    DC, 1987.
23.  Herzbrun, P.A., et al., "Biological  Treatment of Hazardous  Waste in
    Sequencing Batch Reactors," Journal of Waer Pollution Control Federa-
    tion, 57, pp.  1163, 1985.
24.  Petrasek, A.C., et al., "Fate of Toxic  Organic Compounds in Wastewater
    Treatment Plants," Journal of Water Pollution Control Federation, 55, pp.
    1286, 1983a.
25.  Snider, E.H. and Manning, F.S., "A Survey of Pollutant  Emission Levels
    in Wastewaters and Residuals From  the  Petroleum  Refining Industry,"
    Environmental International, 7 pp. 237, 1982.
84*    BIOTREATMENT
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                              Innovative Biological Processes for
                                Treatment of Hazardous Wastes

                                 Sanjoy K. Bhattacharya, Ph.D., P.E., M.B.A.
                                           Civil Engineering Department
                                                  Tulane University
                                              New Orleans, Louisiana
INTRODUCTION

  In this paper, the principles of biological treatment have been
reviewed. This first section of the paper includes a discussion of
the environmental requirements and kinetics  of biological sys-
tems. This introductory material is followed by a discussion of the
fundamental reasons for limitations of conventional bioprocesses
in treating hazardous wastes. Identification of such fundamental
reasons leads to understanding how any innovative bioprocess
should be developed and evaluated for application to treatment of
hazardous wastes. Some examples show how the innovative pro-
cesses can enhance the successful biodegradation  of hazardous
organic compounds.

PRINCIPLES OF CONVENTIONAL BIOTREATMENT

Environmental Requirements

  The environmental requirements shown in Table 1 must be pro-
vided  for the growth of organisms to facilitate  bio treatment.
These requirements are only general conditions applying to all
microorganisms. For a specific organism or group  of organisms,
knowledge of more specific requirements is required.

                         Table 1
          Environmental Requirements for Bioprocesses
Carbon-Source
Electron Donor
Electron Acceptor
Macronutrients
Micronutrients
PH
Temperature
Absence of Toxicity
Mixing and Mass Transfer
SKT
  The organic matter in wastewater is used as substrate by the
organisms. These organics serve as the energy source (electron
donor) and carbon-source. The organisms also need an electron
acceptor for electron balance. Different groups of organisms need
different electron acceptors. For aerobic bacteria, the electron
acceptor is oxygen. Denitrifiers, which are anoxic organisms, use
nitrate (NO3~ ) as the electron acceptor. Sulfate reducing bacteria
use sulfate (SO4 ~) and methanogens use CO2 as electron accep-
tors. The organic matter serves as both electron acceptor and elec-
tron donor to fermentative bacteria.
  Using thermodynamics, it  can be shown that, energetically,
oxygen is the most preferred electron acceptor followed by ni-
trate, sulfate and carbon dioxide. A simple experiment makes this
concept clear. If a closed vessel contains a glucose solution (or
any other easily biodegradable substrate, i.e., electron donor),
oxygen, nitrate, sulfate and CO2,  the aerobic bacteria will start
biodegrading glucose as  long as dissolved oxygen is available.
After depletion of oxygen, the denitrifying bacteria will start bio-
degrading glucose using nitrate as the electron acceptor. After the
nitrate disappears, the sulfate reducers will start utilizing glucose.
Finally, the methanogens will start consuming CO2,  leading to
the formation of methane. From the hazardous waste perspec-
tive, it is important to note that various toxic organic compounds
may have different adverse effects on these different groups of
bacteria. One group of organic compounds may be biodegraded
effectively by one group of organisms, whereas the other groups
of organisms may fail to do so.
  Phosphorous and nitrogen are considered as macronutrients.
Some researchers consider sulfur as a macronutrient for methano-
genic bacteria. Examples of micronutrients are metals (such as Fe,
Mg, Ca, Co, Ni, etc.) and vitamins. In addition to the carbon
source and N,  P and S, the organisms need several elements in
minute quantities  for proper growth. Without these micronu-
trients, the organisms may still grow but such growth  will not be
"healthy" and there may be long-term adverse effects. From a
biotreatment perspective, the problem is  to know exactly which
micronutrients are necessary and more importantly what concen-
trations are optimum. Quantitative information often is lacking
in this area. Engineers are advised to add all these micronutrients
(especially the metals) to the feed if they were not already present
in the wastewater.
   Most organisms require a neutral pH for optimal growth. De-
pending on the process, the optimum temperature may vary. For
conventional aerobic treatment,  the optimum temperature is
normally 20 to 25 ° C whereas  for mesophillic anaerobic  treat-
ment, the optimum temperature is 35 ° C. Thermophillic anaero-
bic treatment requires a temperature of 55 ° C.
   One requirement for biotreatment is the "absence of toxicity."
The significance of this requirement is that the hazardous organ-
ics can be treated only if they were not  toxic to the organisms.
But toxicity is not a simple concept. Toxicity depends on concen-
tration, mode of  application, ability  to acclimate, etc. Almost
any substance could be toxic if the concentrations were very high.
A slug dose may have very different effects compared to a grad-
ual increase in concentration since the latter mode  of addition
                                                                                                      BIOTREATMENT   847
-------
gives the organisms the ability to acclimate to the toxic substances.
  Adequate mixing is necessary for the transport of substrate and
nutrients to the bacteria. Even if all other environmental require-
ments were fulfilled, lack of adequate mixing could lead to system
failure. Mixer design becomes a challenge for engineers when they
try to utilize biotreatment with sludge having a high solids con-
centration (> 5% total solids). Without an innovative  process,
engineers may fail when they try to apply biotechnology to the
treatment of contaminated soil. Permeability and other character-
istics of the soil such as particle size and type of soil also need to
be considered.
  The last factor in Table 1 is solids (i.e., bacterial) retention
time (SRT). SRT is  a measure of the length of  time the bacteria
spend in  a bioreactor. The longer the bacteria are in a reactor, the
higher the biodegradation is assuming all other  requirements
listed in Table 1 are fulfilled.  SRT is defined as the mass of organ-
isms in the system  divided by the mass of organisms removed
(wasted)  per day. The engineers can control the solids wasting rate
to control SRT. It is not unreasonable to say SRT is the most im-
portant variable in the biotreatment of both hazardous and non-
hazardous wastewaters. The discussion of kinetics in a later sec-
tion of this paper will clarify the importance of SRT.
  Another important point  to realize is the difference  between
hydraulic retention  time  (HRT) and SRT. For continuous-fed,
complete-mix  systems without solids (organisms)  recycle,  SRT
equals HRT. For continuous-fed,  complete mix systems with re-
cycle or continuous-fed, fixed-film systems, SRT could be many
times higher than HRT. In an ideal system, HRT is low and SRT
is high. Lp^HRJTsjUgwhigjier feed flow  rates  for the same bio-
reactor, "andhigh^  SRTs~lead to effective degradation of the
organic compounds.
Scope of Innovation

   Based  on the discussion thus far, the areas appearing to need
more R&D work are noted below.

Use of Various Types of Bacteria

   It is useful  to know which electron acceptor can best treat a
certain organic waste (electron donor). In other  words, more
work is required to know which types of bacteria (aerobic, anaer-
obic, etc.) are  most suitable for  biodegrading  various  toxic
organic compounds.

Use of Other Organisms

   Recently, there is a renewed enthusiasm with white rot fungi
for treatment of complex organics in wastewaters.  White rot
fungus belongs to a  family of wood-rotting fungi found through-
out the northern hemisphere. Lignin, normally resistant to decay,
is the primary noncarbohydrate constituent of  wood. White rot
fungus naturally produces a group of enzymes that degrade lig-
nin. White rot fungus enzymes are unique because they have a low
specifity, meaning  they can react with a wide variety of sub-
stances. '
   It is expected that white rot fungus will offer a potential  solu-
tion for  groundwater and soil cleanup problems that currently
cannot be managed using conventional methods.  Although re-
searchers expect the technology to be relatively low in cost, the
pilot-scale demonstrations will define specific costs. Other organ-
isms may prove to  be very useful in biodegrading toxic organic
compounds.'

Enhanced Bioavailability/Mass Transfer

  Engineers need to find a way to increase  mass  transfer for treat-
ment of wastes containing high solids and  contaminated soil. No
matter how simple it  sounds, a  successful innovative process
could be to "mix" domestic wastewater or domestic sludge with
contaminated  soils  for combined  treatment. The wastewater or
sludge will provide enough water content to facilitate mass trans-
fer in the mixed waste.
Innovative Techniques to Increase SRT
  During the 1980s, a significant amount of research was per-
formed in this area. Researchers have recognized that fixed-film
processes such as anaerobic filters, fluidized beds, etc., have an
inherent advantage over complete-mix systems. It is important to
realize that there is nothing innovative about this concept be-
cause this should be understood from the fundamentals of biokin-
etics. The part that is innovative is the design of a system that
satisfies the fundamental requirements. Unless a process is funda-
mentally  sound,  it is not going to be of any value. For this rea-
son, the  fundamental aspects have been stressed in this paper
while discussing the scope of innovation.

Kinetics of Bioprocesses
  Before successful evaluation of innovative biological processes,
the kinetics of bioprocesses need  to be understood. The less
understood areas in kinetic modeling need to be recognized.
  One popular model in biokinetics is the Monod Model.1 The
organic matter (C-source and electron donor) in a waste is the
substrate, S0, for the bacteria. The bacterial mass, X, increases as
S0 is utilized. The utilization of substrate and the growth of bac-
teria are simultaneous events. To quantify this phenomenon, a set
of simultaneous differential equations is used as follows:9
dt
 dX  =
 dt
           K   T  S
      Y  dS
          dt
b  X
                                  (1)
(2)
where:
dS_ =
dt
dX =
dt
k   =

Ks  =

Y   =
b
X
S
   rate of microbial substrate utilization per unit
   volume, mass per volume-time
   net growth rate of microorganisms per unit volume
   of reactor, mass per volume-time
   maximum rate of substrate utilization per unit
   weight of microorganisms, tune-l
   half velocity coefficient, equal to the substrate
   concentration when dS/dt  = 0.5 k, mass per volume.
=  growth yield coefficient, mass per mass
=  microorganism decay coefficient, time-'
=  microbial mass concentration, mass per volume
=  concentration of substrate surrounding the
   microorganisms, mass per volume
  Each organism has a characteristic set of kinetic parameter
values. For example, for acetate-utilizing methanogens, the values
are: k  =  2.5day-',Ks  =  lOmg/L, Y  = 0.05 and b  = 0.01
day-'.' These values are constants; the engineers cannot change
these values by using any innovative processes. However, when
the bacteria undergo mutation, these values might change.
  Mutation, which is commonly referred to as acclimation by en-
gineers, is possible after exposing the organisms to toxic chemi-
cals. Engineers regard mutation (or acclimation) as the ability of
the organisms to develop "some resistance" to toxicity and also
the ability to develop "some mechanism" (for example, growth
of certain  enzymes)  which  leads to enhanced biodegradation.
When this happens, the values  of the kinetic parameters might
change. The engineers could successfully make such changes work
to their advantage by controlling the HRTs/SRTs.
  The methods for determining the values of the kinetic param-
 IUK    BIOTRBATMENT
-------
eters are not included in this paper but are easily available in text-
books on Environmental Engineering.9
  The engineers need to know the values of the kinetic param-
eters for effective design of biosystems. Solving equations (1) and
(2) for complete-mix, continuous systems at steady-state yields:
                      b  e)
S  =
X =
 where:
0
S
             (Yk  -  b)   -l

            (S0  -  S)
                                                        (3)
                                                        (4)
        1 +  b
         solids retention time (SRT), days
         hydraulic retention tune (HRT), days
         substrate (pollution) concentration in feed, mass
         per volume
  Equation 3 is useful to calculate the effluent substrate (pollu-
tion) concentration after biotreatment. It is important to note
that for complete-mix systems the substrate concentration inside
the bioreactor equals the effluent substrate concentration. It is
useful to be able to predict S, because when we measure soluble
BOD in the effluent, we get a measure of S. Equation 4 is also
useful because it gives the bacterial concentration, X, at steady
state. Hence,  from this equation and with known flowrates, one
can calculate the amount of sludge generated from the biotreat-
ment system.
  In Equations 3 and 4,  all the terms on the right hand sides are
constants except 6 c, & and So. Assuming no variation in the in-
fluent substrate concentration So, the only two parameters that
the engineers need to control are 8 and ff c. The HRT (or 6 ) is
easy to control by controlling the flowrate of the influent. The
SRT,  on the other hand, can  be  controlled by  selecting  the
amount of sludge to be wasted  from the complete-mix system.
As  discussed before, a successful innovative process is one which
minimizes the HRT and maximizes the SRT. A  short HRT will
facilitate the treatment of large volumes of wastewater; a long
SRT should help satisfy the effluent quality requirements.

LIMITATIONS OF BIOPROCESSES IN TREATING
HAZARDOUS WASTES
  Some of the organic and inorganic compounds present in  a
waste may be classified as hazardous. Both organics and inorgan-
ics  may cause inhibitions/toxicity  to bioprocesses. The  toxic
organics might also be biodegraded under favorable conditions.

Toxicity Kinetics
  To quantify toxicity, the following models are useful:
 For Noncompetitive Inhibition
                    ksx
  dt
                K
S   (1  +  TX/KZ)
For Competitive Inhibition

dJi  =    _       kSX
               Ks  1  +  (Tx/Kj)   +  S)
                                                        (5)
                                                        (6)
where:
Tx  = concentration of toxicant, mass per volume
KI  = inhibition coefficient, mass per volume
                                                                   The concepts of noncompetitive and competitive inhibition
                                                                 are based on biochemistry. More information on these models
                                                                 is available in the literature.6'7
                                                                   At steady-state (dS/dt  = 0, dX/dt  = 0),  the model equa-
                                                                 tions reduce to simple algebraic equations which can be solved
                                                                 to determine the effluent substrate concentration:
                                                                  Competitive:
                                                                                                                          (7)


                                                                                                                          (8)



                                                                                                                          (9)
                                         Noncompetitive:
                                         St =  [Ks(l+W)

                                         Equation 7 can be rewritten as follows:

                                         st =  s  + s (TX/KI)

                                         where:

                                         St = effluent substrate concentration under toxic conditions
                                         S  = effluent substrate concentrations without toxicants
                                                                   Equation 9 indicates that the effluent substrate concentration
                                                                 increases linearly with increasing toxicant concentration. Equa-
                                                                 tion 8 can be simplified further to indicated that, unlike competi-
                                                                 tive inhibition,  noncompetitive inhibition does not have a pro-
                                                                 portional effect on effluent substrate concentration. That means,
                                                                 when noncompetitive inhibition occurs, the effluent concentra-
                                                                 tion remains unaltered up to  a "limiting" toxicant concentra-
                                                                 tion. When this limiting concentration is exceeded, a total system
                                                                 failure is possible.7
                                                                   The inhibition coefficient, Kj, is a measure of the bacterial re-
                                                                 sistance to toxicity. The engineers cannot change this coefficient
                                                                 (i.e., if an organism  does  not have the ability to resist toxicity,
                                                                 no innovative process can help it). On the other hand, as  indi-
                                                                 cated earlier, it might be possible for the organisms to undergo
                                                                 mutation (which the engineers call acclimation) which might lead
                                                                 to an increase in resistance to toxicity,  i.e., increase in value of
                                                                 KI.
                                                                    If it were known how the organisms increase their resistance,
                                                                 it would be easier for the engineers to provide the favorable con-
                                                                 ditions  to enhance such acclimation.  Since the mechanism of
                                                                 acclimation is not  understood in most cases, the Environmental
                                                                 Engineer's general approach should be to provide maximum pos-
                                                                 sible SRT without  making the HRT unpractical. As discussed be-
                                                                 fore, a low HRT will facilitate treatment of sufficient volume of
                                                                 wastewater.
                                                                    A significant limitation of the application of the concept of tox-
                                                                 icity kinetics is that  more research is necessary to  develop data
                                                                 so that the environmental  professionals can find out which com-
                                                                 pounds cause which  type of inhibition. Researchers have shown
                                                                 that organics such as formaldehyde cause competitive inhibition
                                                                 whereas inorganics such as ammonia and nickel cause noncom-
                                                                 petive inhibition.8-  '• 10

                                                                 Are the Concentrations of the Hazardous Organics High Enough
                                                                 to Cause Toxicity to the Biotreatment Processes?
                                                                   The earlier discussion of toxicity kinetics is limited to scenarios
                                                                 where high concentrations of hazardous substances may end up in
                                                                 existing treatment plants designed for conventional, nonhazard-
                                                                 ous, domestic and/or industrial wastewaters. It is quite common
                                                                 to face a situation where the hazardous organic compounds are
                                                                 too low in concentration to cause any toxicity to the organisms in
                                                                 the treatment plant. But removal of these low concentrations of
                                                                 the organics could still be critical because these low concentra-
                                                                 tions which do not kill the bacteria might have a long-term effect
                                                                 on human health. Some organic compounds are potentially car-
                                                                 cinogenic even at very low concentrations.
                                                                                                          BIOTREATMENT    849
-------
Fate of Toxic Substances in Biotreatment Processes
  When the concentrations of the toxic organics are too low to
cause any adverse effects on the microorganisms in the treatment
system, the following factors will determine the fate of these haz-
ardous organic substances:

• Volatilization
• Adsorption
• Biodegradation

  When dealing with hazardous materials, the most desirable fate
is biodegradation (assuming that biodegradation will not lead to
any toxic intermediates).  Volatilization of organics might create
air pollution. In  conventional aerobic processes, volatilization is
difficult to prevent, indicating the need for closed systems such as
anaerobic processes. Adsorption of the hazardous substances in
the biological sludge will make the sludge hazardous. Hence, if an
innovative  process can control sludge efficiently, it will be of
value to the client.
  No innovation can change the amount  of sludge  that will be
generated because of bacterial growth as long as the same organ-
isms are used. However, by proper choice of bacteria, the amount
of sludge can be  minimized. For example, anaerobic bacteria will
generate almost  an order of magnitude lower amount of sludge
than aerobic processes.
  Biodegradation will also depend on the choice of bacteria. En-
gineers can do very little about biodegradation except to provide
the "proper conditions" for acclimation. The problem is that in
most cases the "proper conditions" are unknown.
  A unified model is very useful to simultaneously predict the ex-
tents of  volatilization,  adsorption and  biodegradation of haz-
ardous substances. Development of  such models is  not easy. A
General Fate Model has been proposed by Namkung and Ritt-
mann."  Their work showed that  for VOCs (toluene, benzene,
ethylbenzene and methylene chloride), biodegradation is the most
important mechanism of removal in an activated sludge plant.
Volatilization and adsorption are not significant compared to
biodegradation when the latter occurs. When  biodegradation is
not important (for example, for chloroform), volatilization is the
main removal mechanism. TheseTcoTtclusions were based on a
study of a wastewater treatment plant.''

Can the Organisms Biodegrade Very Low Concentrations of
Hazardous Organic Substances?

  We have seen  that organisms use organics as their carbon and
energy source. Up to what concentration levels can the organisms
use the organics  as their primary carbon source? This question is
very  important  for biotreatment of hazardous  organic  com-
pounds since many of these compounds could be carcinogenic at
ug/L levels. That means the concentrations of these compounds
might be too low for biodegradation but too high to cause toxic-
ity to humans.
  The limiting concentration at which the bacteria can use a sub-
stance as their primary  carbon source is denoted by Sniin which
is the limiting condition  when growth equals decay. Using the
Monod kinetics discussed earlier, it can be written:
Growth
Decay
bX


bKs  +
bKs

Yk -  b
                                                       (10)
of these parameters are characteristics of the organisms used for
biotreatment. The values cannot be changed by using innovative
processes, but engineers need to realize that depending  on the
type of organism, Smjn can vary considerably. The following ex-
amples will make this point clear.
Example 1
Assume:   b
           Ks
           Y
           k
Calculated Snun
Example 2
Assume:   b
           Ks
           Y
           k
Calculated
Example 3
Assume:   b
           Y
           k
Calculated
                                                                     0.01 day-'
                                                                     10 mg/L
                                                                     0.05
                                                                     0.3 day-'
                                                                     20 mg/L

                                                                     0.01 day-'
                                                                     Img/L
                                                                     0.03
                                                                     2.0 day"1
                                                                     0.2 mg/L

                                                                     0.01 day ,
                                                                     1 mg/L
                                                                     0.05
                                                                     2.5 mg/L
                                                                     0.087 mg/L
   Equation 10 shows thai the minimum substrate concentration
 depends on the four kinetic parameters k, Ks, Y and b. The values
  These examples show that with apparently small changes in the
values of the kinetic parameters, the Smin value can change sig-
nificantly. It should be noted that most volatile compounds gen-
erally are present in very low concentrations in the wastewaters.
These concentrations might be too low for biodegradation unless
cometabolism occurs as discussed in the following section.

Is Biodegradation Impossible with Concentrations Lower than
the Required Minimum Substrate Concentration?
  Biodegradation of organics  with concentrations  lower  than
^min is stiu possible if the organisms can  use the  organics as
secondary substrates or cometabolites. A primary carbon source
is required. In POTWs,  domestic wastewater is the primary car-
bon source. This means that if low concentrations of toxic organ-
ic substances were discharged to POTWs, the only way these sub-
stances could be biodegraded is the use of  these compounds as
secondary substrates by the existing organisms in the treatment
plant. However, acclimation and other fate  mechanisms such as
volatilization and adsorption need to be addressed.
  In a recent U.S. EPA pilot-scale project, the fates of several
RCRA and CERCLA compounds were studied.12 The results in-
dicate that stripping of volatile compounds, such as chlorinated
hydrocarbons, in the activated sludge process could be signifi-
cant. Some semivolatile compounds, on the other hand, could be
treated more efficiently using a conventional  activated sludge pro-
cess. The concentration of each compound spiked to the influent
domestic wastewater was 0.5 mg/L which is presumably below the
respective Snun. Even though no mechanism study was possible
in this pilot study, it might be assumed that secondary utilization
was the reason for biodegradation. n

SELECTED INNOVATIVE BIOPROCESSES

  Since it is difficult to list and  discuss  all innovative biopro-
cesses, the focus of this part of the paper will be to study how
some of the innovative bioprocesses satisfy the fundamental re-
quirements. The most important question to be addressed in this
section is: "If the fundamental requirements of bioprocesses were
satisfied, would a bioprocess work successfully or are there some
'other' requirements that we have overlooked so far?"
  The discussion thus far has shown that an ideal bioprocess for
treatment of hazardous substances should have a proper selection
of organisms and adequate SRT. Table 2 lists some bioprocesses
applicable to hazardous wastewater treatment.
       BIOTREATMENT
-------
                          Table 2
      Selected Bioprocesses for Treatment of Hazardous Wastes

1. Aerobic Attached Growth Processes
2. Sequencing Batch Reactors
3. Anaerobic Attached Growth Processes
4. Combined Aerobic, Anoxic and Anaerobic Processes
5. Composting of Hazardous Wastes
6. In situ Bioprocesses
 Aerobic Attached-Growth Processes
  All attached-growth processes are generally favored for bio-
 treatment of toxic organic compounds. One argument in favor
 of attached-growth systems is that since the organisms are not
 wasted from the systems, "the SRTs are very high." However,
 one should be very careful about using the concept of SRT in
 attached-growth systems. SRT is applicable to suspended growth
 systems only.  The  kinetics of  bioprocesses  discussed earlier
 (Equations 3 through 10) is good for complete-mix, suspended-
 growth systems only. It is true that organisms are attached to
 the media (plastic, stones or any innovative substance could be
 used), but that does not necessarily mean that a very high value
 of SRT can be substituted in  the Model Equation  discussed
 earlier. Such an approach would be misleading. The Models for
 attached-growth systems are not discussed in this paper, but the
 information if easily available in the literature."
  Examples of aerobic attached-growth processes are trickling
 filters, rotating biological filters and aerobic fluidized bed reac-
 tors. It is well established that fluidized bed  systems are more
 efficient than other fixed-film processes.

 Sequencing Batch Reactors
  A Sequencing Batch Reactor  (SBR) is a self-contained treat-
 ment system incorporating equalization, aeration and clarifica-
 tion by using a draw and fill approach. SBRs have been used to
 treat wastewater from two hazardous waste sites in Buffalo, New
 York and Chicago, Illinois." The SBR is not necessarily limited to
 aerobic organisms. This simple but efficient process satisfies the
 fundamental requirements and also is efficient for sludge hand-
 ling. More applications of SBRs are expected for hazardous waste
 treatment, especially small-scale processes.

 Anaerobic Attached-Growth Systems
  Anaerobic attached-growth processes, such as anaerobic filters,
 anaerobic fluidized bed  reactors and  upflow anaerobic sludge
 blanket (UASB) systems, have the same inherent advantages as
 those of aerobic attached-growth processes. For applications of
 anaerobic processes, however, attached growth systems are even
 more useful because anaerobic organisms have very low Y values
 compared to those for aerobic organisms. This means that when
 the same amounts of a waste are Independently treated aerobical-
 ly and anaerobically, the amount of sludge (i.e., new organisms)
 generated from the aerobic process is generally an order of magni-
 tude higher than that from the anaerobic process. It is important
 to note that the anaerobic organisms should not be called "slow-
 growers." Then: k values are hot low  in spite  of having low Y
 values. It is the value of k which determines how fast a waste can
 be biodegraded.

 Combined Bioprocesses

  Many Superfund sites have mixtures of organic compounds.
 Some of these organic compounds such as the aromatics are
 ettieiently degraded by the aerobic organisms. However, com-
 pounds such as volatile,  chlorinated hydrocarbons are not suit-
 able for aerobic processes. It has been well established that the
'latter group of compounds are efficiently degraded by methano-
gens. Researchers have started documenting the list of respective
compounds which are efficiently degradable by aerobic, anoxic
and anaerobic processes. When this information becomes easily
available, combined bioprocesses (involving any combination of
aerobic,  denitrifications, sulfate reduction and methanogenesis)
will become more common.
  Hazardous leachates contain a mixture of several organic com-
pounds and heavy metals. A U.S. EPA study showed that anaero-
bic treatment (using an upflow anaerobic filter with plastic pull
rings) followed by conventional activated sludge treatment is a
feasible process for treatment of hazardous leachate." More field
studies are necessary before this innovative process can be imple-
mented.  However, if  this process becomes successful, leachates
from  hazardous waste sites can be anaerobically pretreated in
POTWs  and can be safely discharged to the existing wastewater
treatment systems.
  Other  anaerobic processes such as anaerobic fluidized bed sys-
tems with or without activated carbon  could be more efficient
and effective for such pretreatment of hazardous leachate. Sev-
eral U.S. EPA pilot-scale research  projects are currently being
run to study these innovative processes." It can be safely pre-
dicted that many problems in Hazardous  Waste Treatment will
be solved by innovative combinations of several bioprocesses.
  One common question to be asked about combined processes
is which process, the aerobic or the anaerobic, should come first.
The general answer is the anaerobic process should be followed
by the aerobic process for at least two reasons. First, the anaero-
bic process is generally more suitable for treatment of volatile
compounds for both microbiological reasons and because of the
fact that these are closed systems which  minimize volatilization.
Second, aerobic processes are more suitable as polishing systems.
Effluents from anaerobic processes contain sulfide which contrib-
utes to COD. We  should expect to  see more anaerobic/aerobic
processes than  aerobic/anaerobic processes. In  some cases, an
aerobic/anaerobic/aerobic process could  be the best option.

Composting
  Even though composting is a rather "old" process, it has been
listed in Table 2. Composting has generally been used for stabiliz-
ing sewage sludge. Parameters such as pathogen removal and
BOD reduction were the focus of many  earlier studies. Current-
ly, there is renewed enthusiasm for composting, especially  for
treatment of explosive wastes. It appears that facultative systems
with anaerobic  pockets are more common in compost piles than
a strict aerobic environment. Oxygen transfer and  nutrient trans-
fer problems need to  be solved before complete success can be
achieved.

In situ Biotreatment

  At many Superfund sites, excavation and treatment of contam-
inated soils would  be cost-prohibitive even for biotreatment. An
in situ process could be  the only  solution. Bioprocesses need
significant innovation before these  processes can compete with
successful in situ or physical processes such as In Situ Vitrifica-
tion (ISV). The latter process is quick  and  reliable. Improved
mass transfer is the key to future success of in situ bioprocesses.
Properties of soil such as permeability could be the main issues to
address.

CONCLUSION

  The basis of evaluation of innovative bioprocesses should be
the fulfillment of  fundamental requirements of bioprocesses.
Practical problems, such as sludge  handling, need to be solved.
One should not try to  ignore the limitations of organisms. Proper
selection of organisms is critical. Combined processes apparently
are a good solution for Superfund sites  with mixtures of various
organics. However, combined processes do not necessarily "com-
bine the advantages only."  These  processes could create new
problems and  should be evaluated based  on pilot-scale data.
                                                                                                           BIOTREATMENT   851
-------
More  improvements are required for applications of bioprocesses
such as in situ remediation of contaminated soils.


REFERENCES

 1.  Roy, K.A.. Hazmat World, 2 (12), p. 27,1989.
 2.  Monod, J., Annals Institute Pasteur, 79, p. 390, 1950.
 3.  Lawrence,  A.W. and McCarty, P.L., J.  San. Eng. Div.,  ASCE,
    S/U,p.757, 1970.
 4.  Bhattacharya,  S.K., Ph.D.  Dissertation,  Drexel University,  Phil-
    adelphia, PA, 1986.
 J.  Metcalf & Eddy, Inc., Wastev/ater Engineering,  2nd ed., McGraw-
    Hill Book Company, New York, NY.
 6.  Parkin, O.F. and Speece,  R.E., /.  Env.  Eng.  Div., ASCE, 108,
    p. 515, 1982.
 7.  Bhatiacharya, S.K. and Parkin, G.F., "Modeling Toxicity Kinetics
    in Complete-Mix Anaerobic Systems," Proc. Natl.  Conf. on Envi-
    ronmental Engineering, Vancouver B.C., July 1988.
 8. Bhattacharya, S.K. and Parkin, G.D., "Toricity of Nickel in Meth-
    ane Fermentation Systems: Fate and Effect on  Process Kinetics,"
    Proc. International Conf.  on Innovative Biological Treatment of
    Toxic  Wastewaters, Eds. Scholze, R.J., et al.. U.S. EPA, NSF,
    Naval Civ. Eng. Lab., U.S. Army CERL, NJIT, p. 80, 1967.
 9. Bhattacharya, S.K. and Parkin, G.F., "Fate and Effect of Methy-
    lene Chloride and Formaldehyde in  Methane  Fermentation Sys-
    tems," JWPCF60, 531, 1988.
10. Bhattacharya, S.K. and Parkin, G.F.,  "The Effect of Ammonia on
    Methane Fermentation Processes,' JWPCF,  61, 55,1989.
11. Namkung, E. and Rittmann, B.E., JWPCF,  59, (7), p. 670,1987.
12. Bhattacharya, S.K. and Angara, R., Proc.  15th  Annual U.S. EPA
    Research Symposium, Cincinnati, OH, Apr. 1989.
13. Rittmann, B.E.  and McCarthy, P.L., Biotech. Bioeng. 22, p. 2343,
    1980.
14. Hauck, J.  and Masoomian, S., Pollut. Eng., 22, (5), p. 81,1990.
15. Bhattacharya, S.K., Angara, R.,  and Dobbs,  R.A.,  Proc.  16th
    Annual U.S. EPA Research Symposium, Cincinnati, OH, Apr. 1990.
      BIOTREATMENT
-------
                               Energy  Recovery  From  Waste Explosives
                                     and  Propellants  Through  Cofiring

                                                      Craig A. Myler
                                                    Janet L. Mahannah
                                  U.S. Army Toxic and Hazardous Materials Agency
                                          Aberdeen Proving Ground, Maryland
ABSTRACT
  The growing problem of environmentally safe disposal options for
waste explosives and propellants along with the knowledge that budget
reductions are the rule, not the exception, prompts the development
of clean, safe, economical processes for the elimination of these wastes.
While there are many potential processes for elimination of these wastes,
most do not consider the energy content of the materials. While alone
these materials  exhibit relatively poor  fuel properties, mixtures of
explosives with other fuels such as  oil provide suitable combustion
mixtures. Initial studies of explosives cofiring processes indicate an
economic advantage to explosives supplemented fuels. As supplemented
fuels can be handled safely, it remains to show that they can be utilized
in an environmentally sound manner. A background of  the use of
explosives as supplemental fuels will be presented as well as current
research in the use of explosives and propellants as fuel supplements.

INTRODUCTION
  Disposing of waste energetic compounds has become more difficult
as a result of the end of interim status for incinerators under the RCRA.
Open Burning/Open Detonation (OB/OD) of energetic wastes requires
a Subpart X permit. Subpart X operations remain under interim status
until Nov. 1992. OB/OD operations  are of significant environmental
concern and whether or not they will be allowed to continue in their
current form is unknown. Means of disposing of energetic wastes have
been under intense investigation since 1973. In fact, Brown1 is con-
vinced that sufficient knowledge has been amassed on disposing of these
wastes in his 1976 study on incineration of propellants, explosives and
pyrotechnics (PEP) that he felt he need only mention the following
options for disposal:
• Ocean Dumping
• Open Burning (OB)
• Open Detonation (OD)
• Disassembly and Recycle
• Controlled Incineration
  Brown points out that at the tune of his study ocean dumping was
banned, recycling was limited and OB/OD were severely restricted. The
energy consciousness of the country  was just emerging and the focus
on hazardous waste was in the future. Even so, Brown recognized the
potential for energy  recovery as a possibility.

INCINERATION
  While more exotic forms of elimination of waste explosives are being
developed, incineration under controlled conditions will be the prevalent
form of destruction. To safely incinerate a pound of TNT by currently
available methods requires mixing bulk explosive in water, often with
a size reduction step, followed by incineration using propane or fuel
oil to vaporize  the  water and allow controlled combustion of the
explosive. The water slurry typically consists of approximately 1 part
energetic to 3 parts water. The bulk of the energy supplied externally
is used to vaporize the water in the energetic slurry. Subsequently, in-
cineration of the explosives is costly, as energy must be supplied to
the system while no product is produced.

SUPPLEMENTAL  FUELS ECONOMICS
  Rather than destroying the explosives by incineration, some means
of utilizing them for the energy they contain was sought. In  1985,
Lackey2 described scenarios whereby energetic compounds might be
economically used to generate steam and/or electricity in industrial com-
bustors. To better define the costs of using energetic compounds in this
manner, he compared the costs associated with cofiring explosives in
fuel oil in a boiler to other waste energetic management options including
incineration and  continued storage. Lackey's findings provided a rough
indication of the economic competitiveness of cofiring.
  An alternative approach to determining the economics of energetics-
supplemented fuels is to compare them to the current manner in which
they would be used, namely industrial boilers.  The economic analysis
can be broken down into three areas; raw materials, capital costs and
labor costs.

Fuel Costs
  The raw materials for the production of steam in industrial boilers
are fuel and water.  In the current case of supplemental fuels, the water
requirements are assumed to be equal to those using nonsupplemented
fuels.  There are additional electrical costs for pumping and controls,
but these also will be assumed to be roughly  equal for this analysis.
The baseline  for comparison will be a 20 MM Btu/hr (5.86  MW)
industrial boiler operating 6570 hours/year fired with #2 fuel oil. The
boiler is assumed to be 80% efficient for both the nonsupplemented
fuel and the supplemented fuel cases. Table 1 lists the physical proper-
ties and costs used in subsequent analyses. The base line fuel cost is
$856,812/year from the following calculation:

 2xl07 Btu/hr x 6570  hr/yr x 1 Ib #2 fuel/18,947  Btu x 1  gal #2
fuel/7.31 Ib #2 fuel x $0.7225/gal #2 fuel x 1/0.8 (efficiency factor) =
856,812 $/year
  A fuel oil supplemented with TNT will be compared to the baseline.
Consider a fuel  comprised of 55%  #2 Fuel Oil, 15% TNT and 30%
toluene. The cost of one pound of this fuel is $0.09311 from the following
calculation:

 (0.55 x $0.7225/gal #2 fuel x 1 gal/7.31 Ib #2 fuel)
                                                                                        THERMAL TREATMENT / INCINERATION 853
-------
  + (0.30 x S0.93/gal toluene x  1 gal/7.2  Ib toluene )  =
  0.09311 $/lb supplemented fuel

The healing value of the supplemented fuel is also necessary and is
found to be 16,880 Btu/lb according to the following:

     #2 Fuel Oil          toluene                TNT
  [(0.55 x 18,947) +   (0.30 x 18,302) +   (0.15 x  6,454)] Btu/lb  =
                16,880 Btu/lb of supplemented fuel

The estimate above assumes heats of solution to be negligible. With
these estimates,  the yearly fuel cost for operating the same boiler as
in the baseline case can be determined. The following calculation yields
a yearly cost of $906,002/year.

  2xl07 Btu/hr x 6570 hr/yr x  1  Ib supplemented  fuel/16880
  Btu x $0.09311/lb supplemented fuel x U0.8 (efficiency
  factor) = 906,002 $/yr

The net cost of operating the baseline boiler using  the explosive sup-
plemented fuel is:

  (906,002   856,812) $/yr = 49,190 $/yr

This figure is based on current (Mar.  1990) fuel and toluene prices.
Figure 1 describes the particular sensitivity to fuel oil costs at constant
toluene cost. The break-even point for fuel cost occurs at a cost  for
#2  fuel oil of $  0.83/gallon at constant toluene cost of $0.93/gallon.
Should  fuel prices rise above this point, there would be a net profit
for burning the supplemented fuel (not counting capital and labor costs).


                            Table 1
         Physical Properties and Costs Used in Calculations
 12 Fuel Oil
 Heat of Combustion
 Formula (avg)
 Density
 Coat

 Toluene
 Heat of Combustion
 Formula (avg)
 Density
 Cost

 TNT

 Heat of Combustion
 Formula (avg)
 Density
 Cost

 RDX

 Heat of Combustion
 Formula (avg)
 Density
 Cost
                     REFERENCE
                                      ENGLISH
18,947 Btu/lb
C7.275H12.6
 7.31 Ib/gal
S 0.7225/gal
                                                   METRIC
44.04 KJ/gm

0.8759 gm/cm3
SO.1909/1
18,302 Btu/lb    42.54 KJ/gm
  C7H8
 7.2 Ib/gal     0.8669 gm/cm3
$ 0.93/gal       SO.2457/1
6,454 Btu/lb
C7H5N306
12.94 Ib/gal
15.00 KJ/gm

1.55 gm/cro3
 4,101 Btu/lb     9.53 KJ/gm
 C3H6N606
 15.08 Ib/gal     1.806 gm/cm3
Capital Cost
  Capital cost estimates will be based on the assumption that the existing
boiler will be used with the supplemented fuels without retrofit. This
yields a zero cost for the baseline case. The feed system is  the only
capital equipment  required to burn the supplemented fuel.  A daily
volume of supplemented fuel required for operating the baseline boiler
is 3500 gallons. A feed tank of 5000 gallons could be specified  for
operations. Other equipments and estimated costs are given  in Table
2. If the final capital cost is considered over a 20 year period at 0%
interest, the yearly capital  cost expenditure is $57,687.

Labor Cost Estimate
  Finally, a labor cost estimate is required.  It is assumed that a two-
man operation is sufficient  to prepare the supplemental fuel.  A super-
visor is included at one quarter of the work time. Table 3 details  the
lahor cosl estimate.
                                                                           	TKT Suppl«m«Ud Fu«l
                                                                                (B5X Fu«l OIL SOX Toliuni.lSXTNT)
                                             0.600    0.650   0.700   0.750   0.800    O.B60   0.900   O.S50   1.000  00

                                                        Cost of #2  Fuel Oil  ($/gal)
                                                                    Figure  1
                                                       Yearly Fuel Cost Required to Operate a
                                                  20 MM Btu/he Industrial Boiler (80% Efficiency)

                                                                    Table 2
                                                          Capital Cost Estimate for 5000
                                                               Gallon Feed  System
                                             ITEM
                                                         Major Equipment Costs

                                                                   CAPACITY
                                         Feed Tank
                                         Mix Tank
                                         Toluene Storage Tank
                                         Acetone Storage Tank
                                         Agitators  (4)
                                         Pumps  {5)
                                               5000 gal, SS
                                               2250 gal, SS
                                               7500 gal, CS
                                               7500 gal, CS
                                                15 hp, SS
                                                15 gpm, SS
                                              COST (S)

                                               64,200
                                               47,900
                                               22,800
                                               22,800
                                               16,400
                                               13,500
                                                                                                                 TOTAL   187,600
Langs factor for solid-fluid  processing plant fixed capital is
4.188

     Capital Cost Estimate  •=  5187,600 x 4.1 - S 769,160

     A factor of 1.5 is applied  to the capital cost as an
     estimate to account  for  explosives requirements not
     included in equipment  estimates

  Final Capital Cost Estimate »  1.5 x S 769,160 - $ 1,153,740
                           Table 3
                      Labor Cost Estimate
                           2 operators   (i  S25,000/year)
                           1 Supervisor (6  $40,000/year)  x 0.25
                                              $50,000
                                              510,000
                                                                                                               Subtotal  $60,000

                                                                               Overhead     (875 %  labor  rate)           S45,000

                                                                                                           Labor Total  S105,000/year
                                      Overall Cost Comparison
                                        The total cost to operate the supplemental fuel fired boiler is then
                                      the sum of the fuel cost differential, the capital cost and the labor cost.
                                      The total is $211,877/year. The amount of TNT consumed is 1,167,792
                                      pounds/year  which  results in  a total cost for TNT destruction of
                                      $0.1814/pound or $363/ton. This analysis was performed on a basis of
                                      a 20 MM Btu/hr boiler to provide a realistic implementation scenario.
                                      The 20 MM Btu/hr boiler is a median size expected to be available
                                      for use at all military industrial locations. A similar calculation for Com-
                                      position B  (nominal  60% TNT, 40% RDX) supplemented fuel results
                                      in a per ton cost of $376. Comparison to currently available treatment
                                      methods can be made using the above per ton costs. If incineration
                                      capital and labor costs are assumed equal (an extremely conservative
85J THERMAL TREATMENT   INCINERATION
-------
assumption), the cost to destroy a ton of TNT would be a minimum
of $609 using water per TNT slurry fed to a rotary kiln. The current
cost of OB/OD  operations is approximately $260/ton of explosive.9
The above costs  would indicate a median cost for elimination of TNT
using  supplemented  fuels. While the costs of incinerating or open
burning/open detonating of energetics are expected to rise, the cost
associated with utilizing them as fuel supplements may actually decrease.
As the price of  #2 fuel oil increases, the value of the supplemented
fuel increases. Figure 2 shows the resultant total costs associated with
burning a TNT-supplemented fuel at varying toluene concentrations with
change in fuel oil cost. Notethata 10% toluene, 75% #2 fuel oil, 15%
TNT fuel mixture would result in a TNT destruction cost TNT less
than current OB/OD  costs.

EXPERIMENTAL PROGRAM
  The economic estimates presented above are encouraging but need
further refinement. A well designed test program is currently under-
way to verify assumptions and to provide design data for implementa-
tion. Previous study of the stability, handling and safety aspects of
explosives-supplemented  fuel  mixtures has been conducted  with
promising results.10 It was demonstrated that these mixtures are stable
and can be handled without detonation propagation. More recently,
similar studies have been conducted with nitrocellulose." While these
mixtures are stable and can be safely handled, the mixtures themselves
                                                             become gelatinous in three-phase mixture. Further study will have to
                                                             be performed to utilize propellant mixes.
                                                                 500
                                                                                                 Note: Constant 15% TNT Concentration

                                                                                                     V Indicates Current OB/OD Cost
                                                                                                     A Estimate Level
                                                                 150
                                                                   0.500  0.550  0.600  0.650  0.700 0.750  0.800  O.B50  0.900  0.950  1.000

                                                                                Cost of #2 Fuel Oil  ($/gal)

                                                                                         Figure 2
                                                                             Cost Per Ton of TNT Destroyed in a
                                                                         20 MM Btu/hr with Change in Fuel Oil Cost
                                                                              Cat Varying Toluene Concentration
                   Fuel/explosives
                      blending
                        tank
                                                                                                                    Steam
                                                                                                                    exhaust
                                                                                                      Steam
                                                                                                       vent
                                                                                                      system
                      pump        —
                                 Combustion
                                 air fan
                                                                                                                        £T\
                                                                                                                     Condensate
                                                                                                                     to drain
   —— Temporary operation used during startup

    |    Temporary operation followi

   (r)   Temperature measurement
Temporary operation following test run

                                             (L)   Level indicator
(P)   Pressure measurement            (V)    Viscosity measurement

        Flow measurement               (®)    Density measurement
                                                               Figure 3
                                                         Schematic of Pilot-Scale
                                                       Supplemental Fuel System13
                                                                                        THERMAL TREATMENT / INCINERATION    855
-------
  A proof of principle test program conducted in 1987 determined that
it was "clearly feasible to cofire explosives and fuel oil."u The proof
of principle testing also identified operational requirements for cofiring
explosives which must be considered.

Current Program Synopsis
  With the background testing completed, a pilot program was initiated
in 1989. The objective of the pilot program is to conduct an evaluation
of the use of explosives as fuel oil supplements in army industrial boilers.
Equipment currently is being developed for this test program.  Upon
acceptance by the  Department  of Defense Explosives  Safety Board
(DDESB), TNT and Composition B will be  used to supplement fuel
fed to a 1.7 MM Btu/hr commercial boiler. The  feed system will allow
blending,  heating and feeding  of the fuel mixtures under complete
automatic control. Automatic data acquisition will allow material and
energy balances to be performed. A schematic of the pilot system is
shown in Figure 3.
  While the economics appear feasible, two items related to cofiring
supplemented fuels appear critical. First, the resultant destruction and
removal efficiency (DRE) from normal boiler operations should be above
99.99%  for the explosives.  Secondly, how much of NOx is formed is
a key concern. Data on these operational  peramaters will be obtained
during extensive stack testing.

CONCLUSIONS
  The concept of economically utilizing  the energy content of energetic
materials  is being  developed with the  expectation  of safely burning
energetics mixed with fuel oil. Solvents will be used to put the explosives
TNT and  RDX into  solution. This approach does  not  seem feasible
for propellants at this time, but it may be possible to economically burn
pure propellant slurries. Comparisons of this technology  with incinera-
tion and OB/OD were made. Supplemented fuels depend on costs of
the raw materials being used and may compete economically with open
burning/open detonation. A testing program is  currently underway to
obtain the necessary data to implement this technology.
REFERENCES
 1.  Brown, J.A., "The Incineration Properties of Surplus Military PEPs", Report
    No. N60921-76-M-E946, Final Report to Naval Surface Wsapons Center,
    Dahlgren Laboratory under Contract No. N60921-76-M-E946, Dec. 1976
 2.  Lackey, M.E., "Utilization of Energetic Materials in an Industrial Com-
    bustor", AMXTHE-TE-TR-85003, US, Army Toxic and Hazardous Materials
    Agency, Aberdeen, June 1985
 3.  R.H. Perry and Chilton, C.H., Eds., Chemical Engineers' Handbook, 5th
    Ed., McGraw-Hill, New York,  NY, pg. 9-10, 1973
 4.  Current market quote form local fuel oil vendor, price for 1000 gallon lot'
    fob local delivery, Jackson, MS, Mar.,  1990
 5.  Wfeast, R.C, Ed., Handbook of Chemistry and Physics, 55th Ed., CRC Press,
    Cleveland,  Ohio, pg. C-512,  1974

 6.  Chemical Marketing Reporter, Mar. 5,  1990
 7.  Military  Explosives, Department of the Army Technical Manual, TM
    9-1300-214, pg. 8-30 and 8-72,  Sept., 1984
 8.  Peters, M.S. and Timmerhaus, K.D., Plant Design and Economics for
    Chemical Engineers, McGraw-Hill, New York, NY, pg. 181, 1980
 9.  Personal communication with Mr.  MacDonald  Johnson,  U.S.  Army
    Armament and Chemical Command, Rock Island, IL, Feb.  1990
 10.  Lackey,  M.E.,  "Testing  to Determine  Chemical  Stability,  Handling
    Characteristics and Reactivity of Energetic-Fuel Mixtures", U.S. Army Toxic
    and Hazardous  Materials Agency,  Report No. AMXTH-TE-CR-87132,
    Aberdeen Proving Ground, MD, Apr. 1988
 11.  Norwood, V., "Laboratory Tests to Determine the Chemical and Physical
    Characteristics of Propellant-Solvent-Fuel Oil Mixtures", U.S. Army Toxic
    and Hazardous Materials Agency, Report No. CETHA-TE-CR-90043, Aber-
    deen Proving Ground,  MD, Apr. 1990
 12.  Bradshaw, W.M., "Pilot-Scale Testing of a Fuel Oil-Explosives Cofiring
    Process for Recovering Energy from Waste Explosives", US. Army Tbxic
    and Hazardous Materials Agency, Report No. AMXTH-TE-CR-88272, Aber-
    deen Proving Ground,  MD, May 1988
 D.  Final Test Plan, "Pilot Test to Determine the Feasibility of Using Explosives
    as Supplemental Fuel at Hawthorne Army Ammunition Plant (HWAAP)
    Hawthorne, Nevada", USATHAMA, Apr. 1989, UNPUBLISHED.
8.16    THERMAL  TREATMENT  INCINERATION
-------
            Incineration of Contaminated  Soil at a  Superfund  Site:
                                  From  Pilot  Test to Remediation

                                           Kathy K. DiAntonio,  Sr. Engr.
                                               David A. Tillman, Ph.D.
                                                 Ebasco Environmental
                                                 Lyndhurst, New Jersey
                                                  Bellevue,  Washington
 ABSTRACT
  Soil contaminants at the Bog Creek Farm Superfund site include a
 wide range of volatile and semivolatile organics and heavy metals. The
 site is currently being remediated by on-site incineration. The purpose
 of this paper is to discuss the results of activities leading up to this
 remedial action; namely, incineration pilot tests, remedial design,
 preparation of bid specifications and selection of the on-site  incinera-
 tion system.

 INTRODUCTION
  The Bog Creek Farm CERCLA site is located on a 12-acre tract in
 a rural section of Howell Township, New  Jersey. It is alleged that in
 1973 and 1974, paint manufacturing wastes in the form of bulk liquids
 and sludges, disinfectants and trash were disposed of on-site, on the
 ground and in trenches, by the site owners. During the period from
 1983 to 1985, NUS Corporation performed an RI/FS for the site which
 resulted in an ROD, issued by the U.S. EPA in 1985. The ROD called
 for a first operable unit which would require that waste deposits, pond
 and bog sediment and highly contaminated soil be incinerated either
 on-site in a temporary unit or off-site in a RCRA facility. The ROD
 then called for a further study of the residual soil and groundwater con-
 tamination to determine the need for further remedy.
  During 1987, Ebasco Environmental performed a supplemental RI
 to support the Remedial Design (RD) of the first operable unit and the
 second-phase FS. The RD involved characterizing the waste, soil and
 sediment to be incinerated, determining the volume of material to be
 incinerated,  performing incineration testing  and, finally, preparing
 technical bid specifications for the site cleanup to be issued by the US
 Army Corps of Engineers (USACOE).

 CONTAMINATION AT THE BOG CREEK FARM SITE
  The Bog Creek Farm Site is contaminated by a wide range of volatile
 and semivolatile organics and heavy metals as shown in Table 1. Soil
 contamination levels reported in the NUS RI ranged from 180,000 ppm
 for toluene, 26,000 ppm for methylene chloride, 14,000 ppm for xylenes,
 8,900 ppm for benzene and 19,000 ppm for lead. Based on these results,
 the ROD required that all waste deposits and soil with greater than 10,000
 ppm of total volatile organics (TVO) be excavated for incineration.
  Ebasco Environmental's 1987 supplemental RI indicated lesser levels
of organics in the waste deposits and soils and higher levels of con-
tamination in the sediment than the previous RI. Based on these results,
approximately 15,000 yd3 of soil and sediment should be excavated for
incineration which would result in residual soil contamination orders
of magnitude lower than 10,000 ppm TVO required by the  ROD.
  Ebasco Environmental's RI also included performing ultimate and
proximate analyses of the waste, soil and sediment as shown in Table
2, in order to characterize these materials for incineration. Treatabili-
ty tests were then designed and performed in order to provide infor-
mation on the residual or ash characteristics and to support a concep-
tual incineration design.


                           Table 1
            Chemical Analytical Results: Waste Samples
pp
No.
CAS
No.
Number of
Compound Occurrences
Concentration
Range (ppm)
Organics


44V
11V
87V
85V
10V
6V
Z3V
4V
86V

38V
65A
258
558
548

613
663
688
678
Inorg














Notes


~6"7-64-l
78-93-3
75-09-2
71-55-6
79-01-6
127-18-4
107-06-2
56-23-5
67-66-3
107-06-2
108-88-3
1330-20-7
100-41-4
108-95-2
95-50-1
91-20-3
78-59-1
91-57-6
86-30-6
117-87-7
84-74-2
85-68-7
anics














:„ ppm
PP No.
CAS No.
acetone
2-butanone
methylene chloride
1, 1,1-trichloroethane
trichloroethene
tetrachloroethene
1,2-dichloroethane
carbon tetrachloride
chloroform
benzene
toluene
total xylenes
ethylbenzene
phenol
1,2-dichlorobenzene
naphthalene
isophorone
2-methyl naphthalene
n-nitrosodiphenylamine
bis(2-ethylhexyl)phthalate
di-n-butylphthalate
butylbenzylphthalate

aluminum
barium
calcium
chromium
cobalt
copper
iron
lead
manganese
mercury
selenium
thallium
vanadium
zinc
(mg/kg)
Priority Pollutant Number
Chemical Abstracts Service Number
6
3
2
3
3
3
1
1
1
4
6
5
4
3
3
3
4
2
1
5
4
2

5
3
6
5
3
4
5
5
5
4
1
1
4
5



9 -
16 -
2 -
5,300 -
4,700 -
840 -



30 -
8
1
30
76
160
120 -
39
21

10 -
82
96 -

80 -
58 -
1,120 -
7
6 -
3
876
4.6
7
.27


4
6 -



2,100
5,200
26,000
8,800
5,500
6,800
6,800
570
550
8,900
180,000
14,000
4,700
760
450
380
890
88
210
1,400
1,400
260

2,610
430
36,400
718
27
174
5,160
19,060
78
2.2
6.4
(20)
13
364



TREATABILITY STUDIES
  The treatability studies were designed to provide information to the
suppliers of thermal destruction equipment to facilitate bidding for site
                                                                                   THERMAL TREATMENT / INCINERATION   857
-------
                              Table 2
               Ultimate Analysis of Soils and Sediments
                      at Bog Creek Farm Site
Parameter
Ultimate Analysis
Carbon (not including carbonates)
Hydrogen
0
-------
                             Table3
            Summary of Bog Creek Incinerability Testing
Feed
Material
Waste
V
U
U
U
W
W
Soil
Sed.
(Bog)
Batch
Size
libs)
4
4
4
10
10
10
10
10
10
Tkiln
1,800
1,460
1,000
1,800
1,460
1,000
1,460
1,460
1,460
Feed Solids Analysis
Analysis 5 (rain)
u
u
u
u,vo
svo.m
u,vo u
svo,m
u,vo u
svo.m
u,vo u
svo.m
u,vo u
svo,m
u.vo u
svo.m
15 30 60
u u
u u
u u
u u.vo
svo, in
u u.vo u,vo
svo svo.m
u u,vo u.vo
svo svo, in
u u , vo u , vo
svo svo,m
u u,vo u.vo
svo svo.m
u u.vo u,m
Exhaust
Gas
Analysis



svo.vo
m
svo.vo
n
svo.vo
m
svo.vo
m
svo.vo
m
svo.vo
m
  u - ultimate analysis
 vo = volatile organics
 svo = seraivolatile organic
  m = netals
                                                  O 1800°F

                                               A O 1<60°F

                                                  O 1°00°F
                  10
                                                   60
                        20     30     40
                           Time, Minutes

                            Figure 2
        Influence of Time and Temperature on Carbon Content
         of Residuals from Heat Treatment of Waste Samples
depressed, indicating  consumption of the organic carbon over a
20-minute period. This impact of temperature points out a key issue
with rotary kiln incinerators. Rapid thermal decomposition of the waste
can result in a "puff,"  and consumption of local oxygen. In practice,
this phenomenon is seen as an excursion in CO in the flue gas just after
a charge of material is put into the kiln. These results suggest that
moderate kiln temperatures may be desirable for the Bog Creek Farm
incinerator.
                                                                          500 r
                                                                          400
                                                                          300
                                                                          200
  100
                                                                              -   - 12
                                                                                  20
                                                                                  16
                                                                                                                                  T - 1800°F
                               5        10       15
                                  Time, Minutes

                             Figure 3
              Exhaust Gas as a Function of Time at  1800°F
                          Kiln Temperature
                                                                                                                                20
                                                                             500 r    20 r
                                                                             400-    16 -   £ 16 -
                                                                                                                             T • 1000°F
                                                                          i  300
                                                                                      -   §12
                                                                                          04-
                                    10     15     20
                                      Time, Minutes

                              Figure 4
              Exhaust Gas as a Function of Time at 1000 °F
                          Kiln Temperature
                                                                                                                               25     30
  The continuous emission monitors also demonstrated the impact of
temperature on the thermal destruction processes. Figures 3 and 4
illustrate the behavior of gas phase CO, CO2 and O2 as a function of
time after the kiln was charged for two different operating temperatures.
At high temperatures, the evolution of carbon is apparently fast enough
to consume all available oxygen in the first 4 minutes after charging.
There is a pronounced peak of CO in this initial period. After 5 minutes,
the rapid reaction has ceased and emissions return to normal. For the
low temperature run (1,000 °F), the level of 02 in the exhaust gas, is
The Fate of Organic Compounds
  The volatile and semivolatile trace organics measured in the solid
before and  after thermal treatment for one  hour and at different
temperatures are shown in  Figures  5  and 6.  The open bars in the
diagrams represent the samples before treatment. After thermal treat-
ment for 60 minutes, all organics were removed from the samples to
below the detection limit of approximately 600 ppb as shown as black
bars. This removal occurred even at temperatures as low as 1,000°F.
  The results of the  gas phase organic analysis as a function of kiln
                                                                                           THERMAL TREATMENT / INCINERATION   859
-------
                              WASTC UATEmAl COUPOlmQN. f
                              Figure 5
             Trace Hazardous Volatile Organics in the Waste
            Samples Before and After Treatment for 60 Minutes
                       at Different Temperatures
                                                                          or partial reactions of the compound present in the waste sample. These
                                                                          species, sometimes referred to as products of incomplete combustion
                                                                          (PICs),  are  generally  polyaromatic  hydrocarbons such  as pyrene,
                                                                          phenamhrene and chrysene. Thus, the afterburner design must be chosen
                                                                          to destroy  these types of organic species as will be discussed in the
                                                                          next section.
                                                                           Z-IHthyl-
                                                                           njphlhilent
                                                                           phthilite
                                                                                                                              1«00°F
                                                                                                                              1«60°F
                                                                                                                              IOM°F
                                                                                                                          IOOO°F
                                                                                                                                     """"IHdoOr
                                                                                                                                     J   Kto'F
                                                                                                                                         IOOO°F
                                                         ieoo°F
                                                      D  1««0°F
                                                         IOOO°F
                                                           1«00°F
                                                           1«SO°F
                                                           1000"F
                                                                                                                       j • Be1o« Detection Hill


                                                                                                                      1       1        1
                                                                                                             10"
                                                                                                                     10"
                                                                                                                      "'
                                                                                                                             1
                                                                                                         [Bitted Organic*, M9/9 Feed
                               Figure 7
              Organics Measured in the Kiln Off-gas that are
              Originally in the Waste Stream as a Function
                          of Kiln  Temperature
                                                                                                                                     10
001 001 01 1 10 100 1C
rfrn it"V-t






I,,,,,,,,,,,,,,,,,,!,,*,*

< \ I I I
IX
ieniolc Acid
fyrtnt
Benio(i}pyrene
PKcninthrene
Fluonnthrtne
Bemo{b)
enio(M
luorinthrene
enio(t)
Fluerene
Chrysene
Acenoniphthtlene




	 1 — - •-[ 	 	 1 	
°°° i«n°f „
1 	 	 1 ii™»r
1000°F 1->HCr ,itn0r
	 1 1«00°F
I 1460°F
'"n ' i iooo°r
1 1JW1aF
1 i
-------
 removal of certain metals than lower term parameters. The metal enrich-
 ment in the participates relative to the untreated waste stream is shown
 in Figure 9 for two different temperatures. At low temperatures, enrich-
 ment was slight and was within the bounds of the variability of metals
 in the waste stream.  At high temperature (1,800 °F), the participates
 were highly  enriched  in  most metals except chromium. Arsenic,
 cadmium and lead were more concentrated in the fly ash particles. At
 the intermediate temperature (1,460° F), arsenic and cadmium were
 still highly enriched in the fly  ash. Lead  enrichment was  less
 pronounced. Antimony, copper and zinc were no longer enriched relative
 to the untreated waste sample.
                            Table 4
             Metals Content of the Feed and Residuals
                      for Selected Samples
Metal (ppm)
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Zinc
FEED (WASTE)
1800'F 1460'F
6.7
1.56
0.17
11.7
135
18.4
683
0.995
5.98
<0.219
86.8
180
2.33
<0.139
20.7
942
209
3800
3.70
9.47
0.822
263
ASH
1800°F 1460°F
1.2
0.287
<0.098
0.142
12.9
6.36
234
<0.047
<1.96
<0.196
31.6
11.0
0.302
<0.097
0.896
107
36.5
2160
<0.048
4.36
<0.194
59.6
   Ash leaching results as a function of temperature are summarized
 in Figure 10. As  shown, the results are generally favorable although
 for two samples, lead and cadmium exceeded the EP Tox standards (5
 mg/L and 1 /g/L, respectively) at lower temperatures.
   In summary, the kiln temperature performs two important roles in
 the thermal cleaning of the waste material from the Bog Creek site.
 In order to remove all organic carbon and hydrogen, longer times will
 be required at  lower temperature; however,  after 30 minutes even at
 low temperatures (1,000 °F), all organic material will be removed from
 the treated waste. For target hazardous organics originally in the waste,
 removal was complete even for low temperatures and short times.  Metal
 vaporization and enrichment of toxic metals in fly ash was found to
 be a problem at higher operating temperatures, particularly for arsenic,
 cadmium, lead and antimony.

 Influence of Material Type
   In this study,  four different materials wastes  were tested for their ther-
 mal treatability behavior. These waste samples were taken from dif-
 ferent locations on the Bog Creek site and were designated as  waste
 (Sample No. 1), waste (Sample No.  2), soil and bog sediment.
   The very different nature of  the material  and  their behavior upon
 heat treatment are shown in Figure 11. Upon heat treatment of 1,460 °F,
 the waste samples and soil lose carbon very rapidly. In the first 5 minutes
 the carbon content for these materials was reduced to less than 1%.
 At 30 minutes the carbon level is below 0.1%. However, the bog sedi-
 ment carbon content apparently increased (as-received basis) over the
 first 15 minutes of heat treatment as a function of drying and subse-
 quently fell. The lowest level of carbon content achieved for the sedi-
 ment after 60 minutes was 0.6%.
  The delay in  the release of organic matter  from the sediment is at-
tributable to the high moisture content of this  material. The high water
content of the sediment suppresses the material temperature in the bed
until the moisture evaporates. For these conditions, the evaporation time
can be substantial (approximately 30 minutes). Over this time period
          35
          30
                                                                                 25
                                                                                20
                                                                                15
                                                                           I   10
                                                                               1.0
        1
      15.0
°08
                                                                                                                 cPtfcbLtgrtC
                     1000°F
    1800°F
                   1000°F
     1800°F
                             Figure 9
          Metals Enrichment Relative to Waste Composition of
           Paniculate Catch from Kiln Off-gas After Thermal
                  Treatment at Different Temperature
there is little carbon evolution; consequently, the as-received carbon
content increases due to the loss of moisture. Thus, for the high moisture
material from the bog sediment, there are two apparent time scales:
drying time and devolatilization time.

CONVERSION OF TREATABILITY TESTS INTO A CONCEP-
TUAL DESIGN
  The treatability test results demonstrated  that:
• Primary  reactor temperatures  of 1,400 °F and  2,200 °F  (bed
  temperatures of 1,000°F to 1,800°F) with residence times of 30 to
  40 minutes are  adequate for devolatilization of Bog Creek  Farm
  materials
• Moderate primary reactor temperatures will minimize the potential
                                                                                          THERMAL TREATMENT / INCINERATION   861
-------
5  2.0
ec
o
o
   1.0
             Pb
                            Zn             Cd
                                 ELEMENT
                                                          Cu
                            Figure 10
            Influence of Treatment Temperature on Leaching
                    of Metals from Residual Ash
                            Figure 11
         As Received Carbon Contents of Solids as a Function of
        Time in the Rotary Kiln Simulator for Different Materials
                     (T"= 1460°  10 Ib Charges)
  for "puffs.'  and consequent overloading of the afterburner
• Afterburner temperatures in excess of 1.650°F are adequate for final
  destruction of contaminants
  On this basis, the conceptual design was developed by Ebasco En-
> imnmenial as nonbinding guidance for bidders and as a basis for cost
estimation. Critical elements in the conceptual design included selec-
tion of the basic system, selection of the incineration regime, develop-
ment of process flowsheets and heat and material balances, determina-
tion of post-combustion air quality and solid residue treatment systems
and then the development of equipment lists.

THE  BASIC INCINERATION SYSTEM
  The conceptual design focused upon a transportable rotary kiln based
thermal destruction unit.  The basic elements of this system included
the kiln, secondary combustion chamber or afterburner, quench tower,
air quality control system  and ash quench system. The kiln installation
for this site does not require its own wastewater treatment system due
to the presence of a larger wastewater system for remediation of other
site groundwater.  A rotary kiln  was chosen as the basis for thermal
destruction unit conceptual design, while recognizing that vendors of
all incinerator types could bid to performance specifications.

PROCESS FLOW  DIAGRAMS AND HEAT BALANCES
  Once the basic incineration  process was  selected,  process flow
diagrams were developed highlighting the thermal destruction unit itself,
the air quality control system and the interfaces between the incinerator
and the other site remediation activities. The development of a process
flowsheet led to the calculation of heat and material balances around
the thermal destruction unit and about  the air quality control system.
The heat and material balance about the incinerator was based upon
the following assumptions:
•  No. 2 distillate oil would be  used as fuel for the incinerator
•  Air atomization would  be  used rather than  steam atomization
•  Soil and sediments would  be  fed separately
•  Unit capacity would be 5 tons/hour
  The heat balance  was used to assist  in determining an appropriate
incineration regime.  As shown previously,  the  treatability  tests
demonstrated that any bed temperature greater than l.OOOT will
volatilize the organics in the Bog Creek  Farm materials. Consequently,
kiln and afterburner heat balances were constructed for bed temperatures
ranging from 1,000°F to  1,600°F and with afterburner temperatures
ranging from 1,600°F to 2,000°F. Finally, the calculations were based
upon  50% excess  air for  combustion in the kiln and 25% excess air
for combustion in the secondary combustion chamber.
  The results of preliminary heat balance calculations showed that the
optimum fuel consumption (Btu/ton) occurs with a kiln bed temperature
of 1,200° F,  a kiln gas temperature of 1,600°F and an afterburner
temperature of 1,800° F. Since the treatability studies demonstrated that
such temperatures are adequate for thermal treatment of the Bog Creek
Farm soils and sediments with  significant "insurance" margin, they
were chosen for the conceptual design.  The final heat balances for the
conceptual design are shown in Figures 12 and 13. Post-combustion
controls for the facility were selected  based upon the mobile  nature
of the installation, the low concentration of acid gases expected in the
                                                                                     :.'	TZ1
                                                                               PUEL            t
                            Figure 12
                1 Hour Heat and Material Balance: Soil
86:    THERMAL TREATMENT  INCINERATION
-------
                                                 ENTHALPY  HEAT FLOW (BTU)
                                                  (BTUflb)
                                                   Lay
                            Figure 13
             1 Hour Heat and Material Balance: Sediment
kUkiUn
AahOuinch
MA* Up
12.MS bft"
50°F
-0.2fl*10'BTU/hr

GASEOUS PRODUCTS
15,414 bfhr
1600 °F


Evtpottltan
647 Mu
0.64 x 10 BTU*f
t
|
1











.S62K
4-i
s
9
m













Twl SO°F .
-O^SxIO BTLVh
•*









Quench -
Facd



Sciubbe




RAW WATER
STOI1AGE TANK

Jr
s<
§|
3)
r








Scrubbtr













Aba
E

r~


fcj RECYCLE TANK
	 ( 	
t Qkmdovn
Aih .
MOO b*r M ASH O1IFMTH PT
«M«F 1
;.Gi10»8TUftr

1





Wei Ash 05S
26.M2 Mir
WW'F


10* BTLWu


ji
™s
O o
SP

T[
nrhpf
lucnl











e.
s
S
? AIR POLLUT
J> CONTROL S




Ciuillc
	 	 =?SH
	 70°F [
scrv



                                                          23.M1 Wtw
                                                           207 "f
                                                         8.2 x 10s BTLWv
       '—[
SOUOOTCATION
                          - 5ofdaic31ion/SI3bli»l«nMalc(iall
                            Figure 14
        Soil Incineration: Simplified Material and Heat Balance
        for Air Pollution Control and Ash Handling Operations
                           liable 5
            Technical Specification Standard Section

Section No.                        Description

                       DIVISION 1 - GENERAL REQUIREMENTS

  01000           Definitions, Codes and Abbreviations
  01005           Specification  Outline
  01010           Summary of Work
  01011           Site Description
  01025           Measurement and Payment
  01050           Field Engineering
  01060           Regulatory Requirements
  01065           Health and Safety Requirements
  01201           Pre-Construction and Pre-Work Conferences
  01202           Project Progress Meetings
  01300           Submittals
  01305           Letters of Commitment
  01400           Site-Specific Quality Management Plan
  01410           Construction Quality Control
  01420           Material Laboratory Services
  01430           Chemical Quality Control
  01440           Chemical Testing Laboratory Services
  01450           Spill Control
  01505           Mobilization/Demobilization
  01510           Temporary Site Utilities
  01540           Security
  01560           Temporary Controls/Environmental Protection
  01563           Erosion and Sediment Control
  01600           Equipment and Material Handling
  01720           Project Record Documents
  01725           As-Built drawings
  01735           Project Closeout

                            DIVISION 2   SITE WORK

  02040           Dust  and Vapor Control
  02090           Off-Site Transportation and Disposal
  02095           Drum  Removal  and Handling
  02100           Site  Preparation
  02140           Aqueous Waste Handling
  02200           Earthwork
  02360           Steel Sheet Piling
  02830           Fences  and Gates
  02900           Landscaping

                     DIVISION  13   SPECIAL  CONSTRUCTION

  13180           Incineration
  13350           Aqueous Waste Treatment System
 products of combustion and the behavior of metals as shown in the
 treatability studies and discussed previously. This system is shown in
 Figure 14.
  The system, as configured for advisory purposes, is a relatively simple
 process. Based upon the test burn/treatability studies, this incinerator
 should achieve the objectives of the site remediation program. Further,
 it should be readily  integrated into the overall site remediation effort.

 TECHNICAL BID SPECIFICATIONS
  Ebasco Environmental's RD effort resulted in a complete bid docu-
 ment which was  issued by the USACOE in early 1988. The entire
 remediation program  requires  that incineration be integrated  with
 numerous other on-site activities.  The technical  bid  specifications
 therefore covered  not only incineration, but also all aspects of the site
 remediation including soil  and  sediment  excavation,  dewatering,
 dewatered groundwater treatment, site restoration, health and safety
 and quality assurance.
  A complete list of  the  standard  sections of the bid  specification
 package prepared by Ebasco Environmental according to USACOE for-
 mat  is shown  hi Table 5.   Section  13180—Incineration contained
 performance-type specifications for either on-site or off-site incinera-
 tion. The treatability test results and  conceptual design report were
 appended to the  specification package for informational purposes only.
  Performance requirements and bid information for both the on-site
and off-site incineration options  were provided  in the following
categories:
• General requirements
                                                           •  Applicable regulations
                                                           •  Construction submittals which included a system backup report and
                                                              emergency response manual
                                                           •  Waste,  soil and sediment characteristics
                                                           •  Equipment requirements specifics for the waste feed, ash handling
                                                              and air quality control subsystems
                                                           •  Process development and demonstrated performance
                                                           •  Erection/installation for on-site incineration
                                                           •  Disposal/treatment of residuals
                                                           •  Incineration performance requirements
                                                           •  Procedures to verify performance
                                                           •  System rectification
                                                           •  System operation and maintenance
                                                              Of particular interest is the issue of disposal/treatment of residuals,
                                                           particularly the on-site treated soil/sediment or ash. Since the treatability
                                                           tests indicated that the ash could possibly be suitable as backfill without
                                                           further treatment, such as stabilization,  the specifications cited on-site
                                                           backfilling as the preferred disposal method for on-site incineration but
                                                           did not require ash treatment prior to backfilling on-site. Rather, Ash
                                                           Acceptance  Criteria, shown in Table 6, were developed to set accep-
                                                           table ash contaminant levels, and the TCLP limits were cited as the
                                                           compliance  levels that must be  demonstrated prior  to backfill.
                                                              The specifications also provided considerations relating to on-site
                                                           trial burning after installation in order to verify performance, including
                                                           selection  of POHCs based on  the  site contamination; specifically,
                                                           benzene and tetrachloroethylene were suggested as the volatile POHCs
                                                           and di-n-butyl phthalate was included as the semivolatile POHC. Also,
                                                                                            THERMAL TREATMENT / INCINERATION    863
-------
                             Table 6
                      Ash Acceptance Criteria
                                          WET ASHOUEMCH


                                   - FEEDER-COKOfllONER
       Constituent
       Arsenic

       Barium

       Beryllium

       Cadmium

       Chromium

       Copper

       Lead

       Mercury

       Nickel

       Petroleum Hydrocarbons

       Polychlorinated biphenyls

       Selenium

       Silver

       Total  Base Neutrals

       Total  Cyanides

       Total  Volatile Organics

       Zinc
Concentration fppm)


         20

        400

          1

          3

        100

        170

        100

          1

        100

        100

          1

          4

          5

         10

         12

          1

        350
suggestions were made with regard to spiking the feed with a surrogate,
such as carbon tetrachloride or hexachlorobenzene, to demonstrate DRE
(Destruction and Removal efficiency).

ON-SITE INCINERATION
  As a result  of the bidding process, a remediation  contractor was
selected by the USACOE and construction was initiated in 1989. An
on-site, temporary incinerator was installed and successfully operated.
Remediation of the on-site waste, soil and sediment was essentially com-
pleted at the time of the writing of this paper (in August of 1990).
  A schematic diagram of the on-site incineration system is shown in
Figure 15, and some operating parameters are given in Table 7. The
selected incinerator was a rotary kiln system which included a cyclone
prior to the afterburner  to remove solids from the off-gas, a quench
tower, baghouse and acid gas scrubber and a wet ash quench system.
This system was modified during construction to include oxygen enrich-
ment in order to meet the New Jersey paniculate emission requirement
of 0.03 gr/dscf (N.J.A.C. 7:26-10.7).
  During operation,  ash was stockpiled until test results confirmed
acceptability for backfilling.  At the time of writing this paper, all the
tested ash had  passed the acceptance criteria although some data were
still  outstanding. Treated groundwater obtained from the dewatering
operation during soil and sediment operation, was used for off-gas and
ash quenching and scrubber water was recycled back to the ground-
water treatment system. This process eliminated the need for any treated
effluent  discharge.  Approximately 15,500 yd3 of waste/soil and sedi-
ment were  incinerated in approximately 3 months of operation.

CONCLUSION
  Ebasco Environmental^ remedial design effort, which culminated
in the on-site incineration of contaminated soil and sediment at the Bog
Creek Farm site, included thermal characterization, treatability testing
and conceptual design. These activities were proven useful in the subse-
quent preparation of bid specifications as well as providing site-specific
information to potential remediation system selection  and on-site
operation.
                                         — SECONDARY
                                          COMBUSTION
                                          CHAUUR
                                                                                                                              ,- OUENCN TOWER
      AC10 GAS ABSORBER
              Figure 15
       Thermal Destruction Unit
               Table?
On-site Incinerator Process Specifications
                                       Waste soil rate, TPH
                                         wet basis @ 15% moisture

                                       Solid residence time, minutes

                                       Kiln size, dia x Length, feed

                                       Kiln outlet gas temperature, F

                                       Secondary combustion chamber
                                         outlet temperaturet F

                                       Secondary combustion chamber
                                         outlet oxygen concentration,
                                         measured in stack, % dry

                                       Secondary combustion chamber
                                         res.  time @1700 F, sec

                                       Fuel for burners

                                       Burner  rated cap.,  MM Btu/hr

                                       Baghouse inlet temp.
                                         measured at quench tower
                                         exit,  F

                                       Particulate loading after
                                         baghouse, gr/dscf

                                       HC1  removal efficiency,
                                         if >  U Ib/hr
                                     Value


                                     15-20

                                     >35

                                     7.5  x 45

                                     1450


                                     1700
                                     >2

                                     propane

                                     82



                                     350


                                     <0.03


                                     >99X
                              ACKNOWLEDGEMENTS
                                The authors would like to acknowledge the following people for their
                              contributions to this paper: Dr. W. Randolph Seeker, EER Corpora-
                              tion and Eugene R. Urbanik, Project Engineer-USACOE. The work
                              performed by Ebasco as described in this paper was funded by the U.S.
                              EPA under U.S.  EPA Contract No. 68-01-7250 with Ebasco Services
                              Incorporated. The contents do not necessarily reflect the views and
                              policies of the U.S. EPA.
       THERMAL TREATMENT  INCINERATION
-------
              Remediation  of  Gasoline-Contaminated  Groundwater:
                    Spray  Aeration/Internal  Combustion Oxidation

                                                   Mark L. Rippberger
                                                Harding Lawson Associates
                                                 Newbury  Park,  California
 ABSTRACT
  The use of a heated vacuum chamber for spray aeration enhances
 the rate of evaporation of gasoline from contaminated groundwater. The
 gasoline vapors are thermally oxidized by feeding them to the intake
 of an internal combustion engine, where (hey are burned as part of the
 combustion process.
  A vacuum will increase the rate at which the gasoline evaporates,
 as does the addition of heat. Separating gasoline from the groundwater
 is the first obstacle; the gasoline vapors in the air stream must also
 be treated before release to the atmosphere. Both problems can be solved
 by thermal oxidation. The vapors hi the air stream are below the flam-
 mability level, thus it is not possible merely to burn them. However,
 by feeding the vapors to an internal combustion engine which is powering
 the system pump and creating the vacuum, the vapors are consumed
 as part of the combustion process. The emission exhaust levels of the
 engine are unchanged because the vapors become part of the fuel. Thus,
 this system efficiently treats the effluent stream from the spray aera-
 tion unit.
  This system is  a fully self-contained remediation system that  uses
 thermal vacuum spray aeration and compressive thermal oxidation. It
 costs considerably less than conventional systems of air strippers  with
 carbon absorption or catalytic thermal oxidation.

 INTRODUCTION
  Gasoline-contaminated soil and groundwater have become major con-
 cerns in recent years as more and more leaking underground storage
 tanks have been discovered. Currently, two methods are typically  used
 to remediate  groundwater before it  is discharged to a reinfiltration
 gallery, sewers or storm drains: carbon filtration and air stripping.  Car-
 bon filtration is not desirable on highly contaminated sites, as the costs
 of carbon and its associated handling and disposal become prohibitive.
 With air stripping, if direct venting is allowed, the cost to replace fouled
 packing is the only major maintenance expense. However, in areas where
 emissions are controlled and risk assessments based on benzene  con-
 centrations are the governing factor, as is the case in the metropolitan
 areas of California, vapor phase carbon treatment for air polishing  after
 air stripping is required.  On highly contaminated sites, carbon costs
 again become prohibitive.
  A logical alternative for eliminating gasoline vapors is to burn them.
 On most sites the level of hydrocarbons present in the vapor stream
 is insufficient for combustion to be maintained by these vapors alone.
 Either additional fuel must be added to sustain combustion, or a catalyst
 must be used  to maintain combustion.  A system has been developed
 to utilize the energy of the heat of combustion of the vapors and sup-
plemental fuel. Part of the heat is converted to work to operate the pumps
of the system while the remaining heat is utilized to enhance the separa-
tion of hydrocarbons from the water.
  This system combines a thermal oxidation unit with a unique spray
aeration unit. Although the aeration unit operates on the same principle
as an air stripper, it has no packing, thereby eliminating efficiency
problems due to fouled packing. The spray aeration system sprays heated
water in a vacuum chamber. The engine develops a vacuum on the spray
aeration tank and also provides a vacuum on the well(s) for vapor
extraction.

PRINCIPLES OF OPERATION
  The entire system is self-contained and needs no additional power
source. The engine furnishes all power to drive the other components.
The technologies behind this system are spray aeration enhanced by
heat and vacuum and internal combustion of hydrocarbons in an engine.
Both of these are well proven concepts. Spray aeration has been proven
effective on both large and small scales to separate dissolved hydrocar-
bons and water. The technology for controlling internal combustion
engine emissions has been effectively demonstrated by the automotive
industry.
  This remediation system combines three separate methods of remedia-
tion and is  more efficient than any of the methods alone:
• Vapor extraction from soil
• Spray aeration
• Thermal oxidation using an engine for combusting hydrocarbon-laden
  vapors and a catalytic converter to control the exhaust

  The soil vapor extraction system uses a vacuum pump driven by the
internal combustion engine; alternatively, the vacuum may be developed
by the engine itself. The vacuum on the well causes the hydrocarbons
to volatilize and flow with the air into the well and up to the vacuum
pump.
  Water contamination is remediated using a spray  aerator. In this
system, water-hydrocarbon separation is enhanced by both vacuum and
heat; by lowering pressure, the temperature at which the hydrocarbons
vaporize decreases; increasing the temperature further increases the
potential for the hydrocarbons to vaporize. The spray aerator takes
advantage of both these principles by spraying heated water in a vacuum
(Fig. 1).
  Spray aeration works on the same principle as an air stripper. In an
air stripper, air is moved quickly over the surface of the hydrocarbon-
laden water to  volatilize  the hydrocarbons.  In  spray aeration,
hydrocarbon-laden water droplets move quickly through the air causing
the  hydrocarbons to volatilize; however, in the spray  aerator, there is
no packing to foul or replace. In the spray aerator, heated water is sprayed
in a vacuum. Lowering the pressure in the spray tank increases the rate
of evaporation of the hydrocarbons. Heat has the same effect. By adding
                                                                                     THERMAL TREATMENT / INCINERATION   865
-------
heat and lowering the pressure, the hydrocarbons are boiled or flash-
evaporated off the water droplet surface. A vacuum of 12 inches of mer-
cury is developed on the tank and the water is heated with waste heat
from the engine's cooling system. There are limits to the level of vacuum
on the tank  and the quantity of heat added to the water which must
be maintained to avoid evaporating a large quantity of water along with
hydrocarbons. As an example, at 110°F and 27 inches of mercury, all
the water would evaporate and be passed to the engine.  To ensure suf-
ficient hydrocarbon removal, the water is recirculated through a second
set of spray nozzles (Fig. 2).
                   DEMISTER
           xxxxxoo
                  VCLAT!L!ZED
                HYDROCARBONS
                                           TO ENGINE INTAKE
                                                  RECIRCULATING
                                                  PUMP
vapors. In the prototype test, water mixed with 1,700 ppm of hydrocai
bons was fed to the spray aeration unit at approximately 3 gpm. wcuui
on the tank was maintained at 12 in. of mercury and the recirculating
water was heated to  100 °F. The  vapor  flow  rate was 40 cfm.  The
discharge had an average total petroleum hydrocarbon (TPH) concen-
tration of 32 ppm, the cleanup efficiency was 98%. These results are
18% higher than spray  aeration without vacuum or heat.
                               COOLANT FROM ENGINE
                        Figure 1
                      Spray Aerator
                            Figure 2
                       Remediation System
  The vapors drawn by the vacuum are directed to the intake of the
engine where they are mixed with the primary fuel and then combusted
in the engine, thus consuming the total hydrocarbon mixture. The
engine's air: fuel ratio is adjusted to maintain efficient combustion when
the vapor from the wells and the spray aerator are combined with sup-
plemental air or fuel, thus resulting in minimum emissions from the
engine.  The  exhaust from the  engine is  passed through  a  small
automotive catalytic convener to ensure complete combustion (Fig. 3).
  Because the entire system is under vacuum until the vapors enter the
cylinders of the engine for combustion,  any possible leaks of seals or
connections are into the system, with no loss of hydrocarbons to the
atmosphere. If there is no combustion, the engine stops running. The
engine is the  power source for all other equipment; all systems stop
when the engine stops, thus preventing uncontrolled releases of hydrocar-
bons to  the atmosphere. The well pumps are pneumatically powered
from an air compressor driven by the engine; therefore, weU pumping
also ceases if the engine shuts off. In addition, the engine has shutoff
devices triggered by loss of vacuum, low oil pressure or engine overheat.

TEST RESULTS
  Currently there are more than 25 units permitted and operating on
the west coast.
  Initial test.-, were conducted on the prototype spray aeration system
and the  engine to determine the basic efficiency of the equipment in
remediating gasoline-contaminated water and thermally oxidizing the


AIR
~*~

CONTAMINATED
GROUNOWATEfl
FROM WELL
~*~
RECLAIMED


VGLATI
HYDROCARBONS
AND
WATER DROPLETS


| I

WATER

„ „ 	 , VAPORS

» VACUUM
PUMP
VAPORS
IFHOM WELL i
HEATED
WATER
-*— JL
S~\ WATER
\QJ PUMP
-^^—^
t






I/C
ENGINE

EXHAUST
CATALYTIC
CONVERTER

                            Figure 3
                 I/C Engine and Catalytic Converter

   The engine exhaust was analyzed for hydrocarbons using a continuous
 infrared meter and by  taking samples and analyzing them in a gas
 chromatograph. These  tests showed the emitted hydrocarbons to be,
 on the average, below 70 ppm in the exhaust stream. At this level, less
 than 1 Ib/day of hydrocarbons is emitted from the exhaust while more
 than 125 Ib of hydrocarbons are consumed by the engine during the
 same time period. The benzene concentration in the exhaust stream
       THERMAL TREATMENT  INCINERATION
-------
was near 1 ppm. By adjusting the air-fuel ratio, the benzene level was
lowered to less than 0.1 ppm, resulting in emissions of less than 0.003
Ib/day of benzene. This level is  low enough to pass risk assessment
criteria in the Los Angeles area. Current sites have hydrocarbon vapors
as high as 140,000 ppm going into the engine with  only 15 ppm TPH
being measured in the exhaust steam and benzene at less than 1 ppm.
  The following are the results from a typical site. The system was con-
nected to three wells. Free product was present in two of the wells;
the third well had no free product. A vacuum was placed on the first
well and the air:fuel ratio was adjusted.
  This first well produced enough vapors to run the engine with no
additional fuel; moreover the flowrate from the well had to be restricted
to avoid running in an over-rich state of combustion. The well, which
had been bailed  of free product before the system was started, had 1
foot of free product in it after 1.5 hrs. of operation. Prior  to the in-
troduction of a vacuum on this well, a 1 foot recovery of free product
would take 48 hrs. or longer. The well was restarted and the same results
occurred; free product flow to the well increased.
  No free product is pumped to the spray aerator. The free product
is evaporated in the well by the vacuum and this vapor is extracted by
the vacuum on the well and fed directly to the engine. Water out of
the well was tested and found to have 8.9 ppm TPH with benzene at
3.5 ppm. Initially, there was approximately 90%  reduction of con-
taminants. The discharge from the system was tested and found to be
below the detection limits of 0.1 ppm TPH and 0.7 ppb benzene. These
results are typical for the 25 sites at which the  systems are in opera-
tion. These particular units are designed for 8-10 gpm. This system has
shown itself to  be effective on  typical service station size lots for
remediating soils and groundwater. The system is capable of remediating
up to 150 Ib of hydrocarbons per day.

COSTS
  Currently this  system costs approximately $60,000.  It is ready to
operate when unloaded from the delivery truck and needs only to be
connected to the wells from which water and air are to be extracted
and supplied with supplemental fuel of propane or natural gas fuel.
  However, operating at the maximum combustion of the extracted
vapors,  the engine  needs no supplemental  fuel. Operations and
maintenance for the system costs are the costs of weekly oil and filter
changes, a monthly tuneup and an annual overhaul on an engine running
24 hours per day. These maintenance expenses require approximately
4 hours  of labor per week (at approximately $50  per hour) and ap-
proximately $50  in parts and supplies per week, resulting in a total
operations and maintenance cost of $250 per week.
  An equivalent system using carbon adsorption for vapor and  water
phase would require 1500 Ib of carbon per day. Comparable operations
and  maintenance costs for  a  carbon system would include carbon
replacement costs; the costs for electricity to operate three down well
pumps, a circulation pump and vapor extraction pump; and labor costs.
Carbon replacement costs would be approximately $21,000 per week;
625 kilowatt hours of electricity  would be used per week at $0.15 per
kilowatt  hour to run the pumps  in .the system;  and weekly labor (at
$50/hr) would be approximately  3 hours, including carbon changeout
time. This results in weekly costs of: $108 for electricity; replace 1500
Ibs of carbon per day at $2 per  Ib; and $150 for labor yields a total
cost  $21,258 a week for operations and maintenance of the carbon
system. Obviously there is a significant cost savings in using the com-
bustion system at a heavily contaminated site.
  Even at low vapor concentrations, this new system is more economical
than a carbon system. For a site for which only 1% of the fuel for the
engine is supplied by extracted vapors, the cost of supplemental fuel
(99% natural gas) is approximately $50 per week, resulting in a new
total operations and maintenance cost of $300 per week for the com-
bustion system.  Comparing this  system again to a carbon treatment
system for such a site, we find that the carbon usage rate would be ap-
proximately 15 Ibs per day, while all other costs for the carbon system
remain the same. At this carbon usage rate, the weekly cost of carbon
would be $210 per week, resulting in a total operations and maintenance
of $418 per week, over $100 more  than for the combustion system.
  Comparison of this system to an air stripper/vapor extraction unit
with a catalytic oxidation system for vapor control results in the following
operations and maintenance cost analysis. Assuming no supplemental
heat is needed to maintain the catalytic reaction, power requirements
are approximately 1 kw per hour for water pumping to the air stripper,
4 kw per hour for air and water pumping through the air stripper and
3 kw per hour for the vapor extraction pumps resulting hi 8 kw per
hour or 1340 kilowatt hours per week. At $0.15 per kilowatt hours, the
electrical costs would be $1,201 per week. Add three hours  of techni-
cian time and weekly operations and maintenance costs would be $1,351.
Again the spray aeration/internal combustion system is significantly
more cost-effective than an air stripper/vapor extraction system with
a catalytic oxidation unit.

CONCLUSIONS
  Vacuum enhanced spray aeration with thermal  oxidation has  been
demonstrated to be an effective method of removing hydrocarbons from
contaminated groundwater and oxidizing the contaminants so that they
are no longer a significant health hazard. The vacuum to die well ef-
fectively increases the flow  of free  product to the well as it extracts
vapors from the well for combustion. This system has been demonstrated
to be an  economical and practical alternative to carbon canisters and
their  associated costs.
  The vacuum spray aeration tank has been demonstrated to have an
effectiveness equivalent to a packed-tower air stripper, without the pro-
blems of packing fouling or the expense of packing replacement costs.
Savings are realized in both the initial cost of equipment and the
operating costs of a conventional system using vacuum extraction, a
packed-tower air  stripper and carbon polishing.
  While optimization of operating parameters is being further defined,
this system has been shown to be both practical and cost-effective for
remediation of gasoline-contaminated groundwater and contaminated
soil vapors.

SOURCES
1.  Blake, S.B. and Gates,  MM., Vacuum enhanced Hydrocarbon Recovery:
   A Case Study: Proceedings of Petroleum Hydrocarbon and Organic Chemicals
   in  Groundwater Prevention Detection and restoration Natural Well Water
   Association and American Petroleum Institute, Washington, DC, November
   1986.
2.  Kotuniak, D.L., "In-situ Air Stripping Cleans Contaminated Soil," Pollut.
   Eng., August 1986
3.  Kuhlmeier, P.D., "The Evaporation of Benzene, Toluene and O-Xylene from
   Contaminated Groundwater Proceedings of Petroleum Hydrocarbon and
   Organic Chemicals in Groundwater Prevention Detection" and  restoration
   Natural Well Water  Association and American  Petroleum Institute,
   Washington, DC, November 1986
4. Wood, PR., The Ins and Outs of Air Stripping Volatile  Chemicals from Waer,
   Applied Technologies Group.
                                                                                          THERMAL TREATMENT / INCINERATION    867
-------
       Hazardous Waste Minimization  and Control at  Army  Depots

                                                       Ronald  Jackson
                                  U.S. Army Toxic and Hazardous  Materials  Agency
                                          Aberdeen  Proving  Ground,  Maryland
                                                       Jeffrey S.  Davis
                                                    PEI Associates, Inc.
                                                       Cincinnati,  Ohio
ABSTRACT
  The  U.S.  Army  Toxic  and Hazardous  Materials  Agency
(USATHAMA) recently conducted visits to eight Army depots involved
in the maintenance of tactical equipment. The purpose of these visits
was to identify research needs related to hazardous waste minimiza-
tion in addition to control of volatile organic compounds VOCs emitted
during operations. The focus  of the information collected related to
methods of paint application and removal, degreasing operations, and
wastes generated from electroplating operations. The information was
used to identify several research projects that are currently being con-
ducted to address specific waste minimization issues at selected facilities.
  A total  of sixty-nine potential waste minimization and VOC  reduc-
tion/control projects were identified at the depots visited. Three of these
projects were selected for research/demonstration projects that will be
conducted and implemented at appropriate depots. The three projects
selected involve: (1) The evaluation of paint application systems to in-
crease transfer efficiency to reduce VOC emissions and paint waste
generation, (2) the extension of chromic acid bath lives  via electrodi-
alysis, and (3) the extension of the lives of alkaline paint-stripping baths
to reduce the amount of generated wastes.
  Findings of the depot visits and subsequent technical efforts described
in this paper.

INTRODUCTION
  U.S. Army depots are involved in the maintenance of tactical equip-
ment. Maintenance operations generate large amounts  of hazardous
waste and air pollutants as a result of paint application, paint removal,
degreasing and plating processes. Control, treatment and/or disposal
of air pollutants and hazardous waste are expensive.
  Preventing the generation of hazardous waste at the source reduces
the  amount of waste materials that must be tracked, treated  and/or
disposed of, and often results in significant cost savings for the depots.
Waste minimization also reduces the long-term liability associated with
the  generation of hazardous waste.
  U.S. Army Toxic and Hazardous Materials Agency (USATHAMA)
personnel are conducting research and development projects pertaining
to hazardous waste minimization (HAZMIN) at Army depots.  Hazar-
dous waste minimization is a  viable method for  solving some of the
problems created by the generation of hazardous waste. Additionally,
HAZMIN can  create a safer work environment.
  Anniston (Alabama),  Corpus  Christi (Texas), Letterkenny  (Penn-
sylvania). Red River (Texas). Sacramento (California), Sharpe (Califor-
nia). Tobyhanna (Pennsylvania) and Tcoele (Utah) Army Depots were
visited between April and July 1989. The purpose of these visits was
to identify research needs related to HAZMIN and/or control of volatile
organic compounds (VOCs) emitted during depot operations. The in-
formation was used to define several research projects that are currently
being conducted as part of USATHAMA's Pollution  Abatement and
Environmental Control Technology (PAECT) program.
  A total of sixty-nine potential waste minimization and VOC emis-
sions control projects were identified at the eight depots visited. Of
these, 24 were identified as short-term, high priority projects. The pro-
jects ranged widely in technical effort and scope of work required. Three
projects were  selected for demonstration testing based on the current
scope of work, interest of depot personnel,  applicability of the pro-
jects at several depots and potential for hazardous waste and/or VOC
reduction. Each of the three projects is currently being initiated at an
appropriate Army maintenance facility. Testing and evaluations will be
conducted during the fall of 1990.
  This paper presents the some of the findings of the depot visits and
describes subsequent technical efforts in hazardous waste minimiza-
tion and VOC control/reduction.

PAINT APPLICATION
  Paint application is a major source of hazardous waste generation
and VOC emissions at Army depots. Each waste generation problem
of this operation  is addressed separately.

Generation of Hazardous Waste
  Painting operations at Army depots produce large amounts of hazar-
dous waste. Waste results from excess paint, paint overspray, use of
cleaning solvents and the capture of paint particulates to prevent their
release into the atmosphere. Paint wastes are hazardous because com-
ponents of the paints are often toxic and/or flammable.
  All the depots visited used dry filters on some paint booths to cap-
ture the particulates from overspray during painting operations.  The
filters become clogged as the overspray accumulates and must be
replaced. Some of the depots dispose of all filters as hazardous waste,
whereas other depots have determined that some  of their filters are
nonhazardous waste.
  The water-wash paint booth is another type of control device used
by  the depots to remove paint particulates from overspray. In these
booths, water flows down a wall at the rear of the paint booth and over
an air vent through which the booth exhaust flows. The air containing
the paint overspray is vented through the water and the particulates are
captured. The resulting water and paint mixture (sludge) is collected
in a trough.
  Paint sludge from water-wash booths is a major hazardous waste pro-
blem at many of the installations. Some of the depots are attempting
to reduce the amount of sludge by separating the paint residue from
water through the use of cyclone separators combined with the addi-
tion of detackifying agents. Several facilities have expressed interest
     MILITARY ACTIVITIES
-------
in using filter presses to decrease the volume of collected sludge.
  Other methods of minimizing the generation of hazardous waste
during  depot painting  operations are being  implemented  by the
installations:
• Development of alternative methods for capturing particulates
• Recharacterization of waste materials
• Segregation of hazardous from nonhazardous waste
• Replacing paints which have hazardous characteristics
• Increasing transfer efficiencies of paint application systems

VOC Emissions
  Most depots are undertaking steps to reduce VOC emissions to levels
required by state or federal statutes. The depots located in California
and  Pennsylvania are under regulatory pressure to decrease  VOC
emissions. Even in states without stringent VOC regulations, depots
are expected to attempt  to reduce VOC emissions and to complete a
health and safety evaluation before regulatory authorities will permit
new  VOC sources.
  VOC control technology is very expensive and may not be practical
because the sources of VOC emissions often are located in different
sections of the installation. Most depots are focusing on reducing VOC
emissions by switching to paints with low VOC contents and improving
the transfer efficiencies  of paint application systems.
  Paint application operations at Army depots are production oriented.
Consequently, painting as rapidly as possible often is essential. Increased
rates of production often are achieved by increasing nozzle pressure
and/or using a wider paint gun nozzle angle. Overspray also increases
as a  result of these changes, resulting in higher VOC emissions and
lower transfer efficiency. The use of high efficiency painting equipment
will reduce the amount of overspray and VOC emissions. Consequently,
less hazardous waste in the form of spent  dry filters and sludge from
water-wall paint booths  will be generated.
  One of the USATHAMA HAZMTN projects presently being initiated
is the evaluation of transfer efficiencies of paint application systems
at Sacramento Army Depot (SAAD). Several high volume low pressure
(HVLP) spray guns will be purchased and tested to determine their
effectiveness in decreasing VOC emissions. The information obtained
from this project will  be used by depot personnel to identify and
implement high efficiency painting systems.
  The test equipment will be evaluated on an actual production line
at SAAD. The following  variables will be measured to  assess the
effectiveness of the paint application equipment:
• Transfer efficiency
• Speed of paint application to achieve a high quality coating
• Ability to meet coating specifications
A final report will be available in early 1991.

PAINT REMOVAL
  Paint stripping operations generate large amounts of hazardous waste
at Army depots. They are also a significant source of VOC emissions.
  The method of paint removal depends on the tactical equipment being
processed and often varies between depots. Chemical and mechanical
paint removal will be discussed separately.

Chemical Paint Removal
  Chemical stripping compounds commonly used during paint removal
are either methylene chloride- or alkaline-based formulations. Methylene
chloride-based strippers  are targeted for replacement because of health
and safety concerns. Many chemical strippers  also contain VOCs.
  Equipment parts to be stripped of paint usually are submerged in
a tank containing the stripping solution. This method of paint removal
generates large amounts of hazardous waste in the form of spent stripping
solutions and paint sludge. Paint removal  operations at Army depots
are also large generators of wastewater.
  Army depots are exploring several methods  for hazardous  waste
minimization during paint stripping operations:
• Replacement of strippers containing hazardous components
• Increasing the lives of stripping solutions
• Decreasing the volume of sludge via filter press
  The removal of paint residues generated during stripping operations
from paint stripping baths may be a viable method for extending the
useful life of chemical stripping solutions. The solid residue remains
in the bath after paint is removed from equipment parts and continues
to chemically react with the  stripping reagents. Eventually, these
reactions will deplete the stripper. Removal of the residues may result
in longer bath lives, fewer tank changes and a reduction in hazardous
waste generation.
  Another project selected for  USATHAMA demonstration testing is
to extend the life of a chemical stripping solution by removing solid
residues from the stripping bath.  The project will be conducted on an
alkaline paint stripping bath at  Letterkenny Army Depot. During this
project, the reduction in waste  generation will be quantified. Process
variables of the filtration system will be determined and factors that
may affect the life of the process bath will be studied. Data obtained
during this demonstration test will help implement the technology  at
other depots. A final report detailing the results of this task will be
available in early 1991.

Abrasive  Paint Stripping
  Many different abrasive blast media are used at Army depots. Types
of media used include walnut shells, steel shot, aluminum oxide, peridot,
sand, glass and plastic beads. Spent media usually are disposed of as
hazardous waste because of heavy metal contamination from paint
pigmentations and surface finishes removed  from equipment during
blasting operations.
  Several waste minimization efforts were identified during the visits
to the depots:
• Implementing or improving  recycling of blast media
• Use of media with longer usable lives
• Alternative blast methods
• Optimization of blast  parameters
  Some of the depots indicated a desire to replace methylene chloride-
based chemical strippers with  plastic media blasting (PMB). PMB
generates less hazardous waste than chemical strippers. Indications are
that plastic media do not damage sensitive  substrates and  are more
recyclable than many other types of blast media.

DECREASING OPERATIONS
  Army depots use various chemicals in degreasing and cleaning pro-
cesses. These compounds are sources of VOC emissions and hazar-
dous waste generation at the installations. The primary degreasing
solvent used at the depots 1,1,1-trichloroethane.
  Several depots have tried to recycle 1,1,1-trichloroethane.  However,
efforts to recover the spent solvent have been plagued by equipment
failure, acidification of the solvent and low recovery rates.
  Some of the installations are investigating the use of heated fluidized
beds to remove paint and degrease equipment. In the fluidized bed pro-
cess,  paints and grease are pyrolized  and the gaseous emissions from
the bed are destroyed in an afterburner. Fluidization of the bed medium
results in efficient heat  transfer.

PLATING AND SURFACE FINISHING  OPERATIONS
  Normal surface finishing operations at Army depots include cadmium
and chromium plating, anodizning and metal electrostripping processes.
Other metals such as brass, copper, gold, nickel,  silver, tin and zinc
also are plated.
  Several waste streams are generated during these operations at Army
depots. Process solutions, such as chromic acid and chromate conver-
sion coatings, are frequently replaced and disposed of as  hazardous
waste. Rinse water becomes contaminated due to carryover from the
process baths and must be treated as hazardous waste. Treatment of
the rinse water results in the generation of sludge. The plating baths
are rarely dumped and  are not a large source of hazardous waste.
  Hazardous waste minimization efforts can be targeted at the process
                                                                                                           MILITARY ACTIVITIES   869
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tank, at wastewater from rinse tanks, or at the sludge from wastewater
treatment. The HAZMIN target areas are discussed separately.

Hazardous Waste Minimization for Process Solutions
  Army depots are undertaking efforts to minimize waste from plating
and surface finishing operations at the source - the process solutions.
Several depots have eliminated cyanide-based cadmium electroplating
by using other types of process baths. Some installations have expressed
interest in replacing some cadmium plating operations with aluminum
ion vapor deposition (ATVD).
  Another method directed at the process tank is to increase the life
of the process solution. Contaminants that shorten the lives of the pro-
cess solutions generally consist of metals introduced by carryover. The
effectiveness of using an electrodialysis unit to remove metal con-
taminants from a chromic  acid  bath  will be demonstrated as  an
USATHAMA HAZMIN project. Chromic acid may be continuously
rejuvenated during the process by oxidizing trivalent chromium to its
hexavalent form. The electrodialysis unit will be installed and tested
on a process tank at Corpus Christi Army Depot (CCAD). A final report
will be available in 1991.

Reduction of Wastewater Generation
  The amount of  wastewater generated during plating and surface
finishing operations can be decreased by reducing dragout from pro-
cess tanks. Some depots use a spray rinse to remove and  return most
of the dragout to the process tank. The water from the spray rinse can
be used in the process tank to replace water lost through evaporation.
Other depots rinse parts directly over plating baths and use  drainage
boards between process and  rinse tanks.
  Army depot personnel have expressed interest in reclaiming metals
from the rinsewater. Metals can be efficiently recovered from wastewater
and returned to process tanks by such methods as ion exchange, evapora-
tion, reverse osmosis and electrodialysis. CCAD personnel, for exam-
ple, are presently  trying to implement a closed-loop process that will
use ion exchange  and electrodialysis to remove chromium' and other
metals from rinsewater. The rinsewater could be recycled and the
chromium converted to its useful form for reuse in a chromic acid bath.
This system, in conjunction with the USATHAMA test system, has the
potential for zero discharge of hazardous waste.

Reduction of Hazardous Sludge  Volume
  Wastewater from Army depot plating and surfacing operations requires
treatment before discharge to the environment. Generally, metals in the
wastewater are precipitated out as metal hydroxides at the installation's
industrial  wastewater treatment plant (IWTP). The resulting sludge
usually is disposed of as hazardous waste.  Consequently, HAZMIN
efforts can be applied to the  treatment  of wastewater once the water
reaches the IWTP.
  Several  methods have been, or are now being,  implemented to
minimize  hazardous  sludge generation.  Some  depots   combine
wastewater streams, and all sludge generated from wasterwater treat-
ment is considered hazardous. Segregation of hazardous  and nonhazar-
dous wastewater streams will reduce the amount of sludge classified
as hazardous waste. At some of the facilities, the heavy metal concen-
trations may be low enough that the sludge produced is not EP toxic.
The sludge is being recharacterized and may be delisted if it is not EP
toxic. Several depots have achieved sludge volume reductions through
the use of filter presses.

OTHER USATHAMA HAZARDOUS WASTE
MINIMIZATION EFFORTS
   Commercially available, state-of-the-art technology is being evaluated
in support of the Army depots' hazardous waste minimization efforts.
Three additional  USATHAMA demonstration projects are  outlined
below.

Alternative Chemical Paint Strippers
   The identification of commercially available chemical paint strippers
which may be viable alternatives to methylene chloride-based strippers
is presently being conducted.  The evaluation of the stripping perfor-
mance of one of the formulations identified is under way on an opera-
tional  paint stripping line at SAAD.
   The elimination of methylene chloride-based chemical paint stripping
solutions will aid in the reduction of total toxic organics (TTO) and
VOC emissions. The use of less hazardous strippers will also signifi-
cantly decrease the generation of hazardous waste at the depots.

Fluidized Bed  Paint Stripper/Degreaser
   The feasibility of using a heated bed of fluidized aluminum oxide
to remove grease and paint from tactical equipment parts is being
evaluated at Red River Army Depot. The results of this demonstration
test will be available in mid 1991.
   A  fluidized bed can directly replace chemical degreasers and paint
strippers for parts that can  tolerate temperatures up to 850° F. This
system can substantially reduce the generation of hazardous waste and
provide a  safer work environment.

Aluminum Ion Vapor Deposition
   The feasibility of using aluminum vapor plating in lieu of cadmium
plating is being evaluated at Anniston  Army Depot. Cadmium plating
is a large source of hazardous waste generation at most Army depots.
A report detailing the results of this project will be available in mid 1991.
   During aluminum vapor plating, the metal is deposited directly on
the part to be plated. Aluminum ion vapor deposition does not require
the use of hazardous materials and does not generate hazardous waste.
Aluminum also has been  shown to provide a superior corrosion
resistance compared to cadmium.

CONCLUSION
   U.S. Army depots are making progress  towards the Army's goal of
a 50% reduction of the total hazardous waste generated in fiscal year
1985 by the end of 1992. The technologies currently being evaluated
by USATHAMA may assist the depots in meeting the Army HAZMIN
goal. However, significant  obstacles  still remain, including  lack of
resources available to implement proven technology and lack of suffi-
cient technical  information  transfer among the installations.
      MILITARY ACTIVITIES
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 The Installation Restoration Program Information Management System
 (IRPIMS) and An Overview of Air Force Hazardous Waste Investigations
                                                Philip M.  Hunter, P.G.
                                            Air Force IRP Program Office
                                               Human  Systems Division
                                            Brooks  Air Force Base,  Texas
 ABSTRACT
  The Installation Restoration  Program Information Management
 System (IRPIMS) was developed by the Air Force Human Systems Divi-
 sion, IRP Program Office to support the data management needs of
 its Air Force hazardous waste program. The system was designed in
 1986 and was operational in 1987. Approximately 80% of the technical
 data stored consists of analytical sampling results. Data continue to be
 loaded into the system as IRP project data become available. More than
 600,000 analytical records have been entered into the system.
  The system stores information on more than 2000 hazardous waste
 sites that are distributed across 196 Air Force installations and 14 Major
 Commands. More than 7000 sampling locations (monitoring wells, soil
 borings, etc.) are identified from which analytical results can be retrieved
 and evaluated. In addition, the system stores and processes data related
 to general site and sampling location information, lithologic descrip-
 tions, monitoring well completion information, groundwater levels and
 sampling test methods.
  The intent of this paper is: (1) to provide an overview of the roles
 and capabilities of IRPIMS and (2) to describe the Air Force's Installa-
 tion Restoration Program in terms of the investigative effort performed,
 the types and concentrations of contamination found and the associa-
 tion of contaminants detected in groundwater at a variety of hazardous
 waste site types.

 INTRODUCTION
  The Air Force Human Systems Division Installation Restoration Pro-
 gram (IRP) Program Office (HSD/YAQ) is one of three service centers
 providing IRP technical and contract administration support to Air Force
 installations and Major Commands (e.g., Strategic Air Command, Tac-
 tical Air Command, etc.). IRP projects generate technical reports con-
 taining large volumes of hydrogeological and chemical data that  are
 difficult to manage with manually maintained systems. Mere storage
 and availability of these reports containing large amounts of hard-copy
 data does not represent information, in the modern sense,  without the
 ready access and computational  capability of a main frame computer
 equipped with the query tools of a relational data base. It was with
 these factors in mind that the Installation Restoration Program Infor-
 mation Management System (TRPIMS) was designed for use by the IRP
 Program Office and its customers.
  IRPIMS was designed by a multidisciplinary team of professionals
 consisting of hydrogeologists, chemists, applied statisticians, system
 analysts and IRP project managers. The major emphasis in designing
 the system in 1986 was to provide an application tool to assist technical,
contract-administrative and program managers. The design of the system
took approximately one year and  the first generation system was opera-
tional in 1987. Major changes in system architecture were made in 1988
and the second generation system was developed within a year. Since
1989 there have been relatively minor changes in the data structure and
more attention has been drawn to technical applications.
  IRPIMS hardware consists of a Digital Equipment Corporation VAX
8650 Computer. Data are entered into, stored and managed by Oracle,
a commercially-available relational data base. Other application soft-
ware, existing both in the VAX and personal computer (PC) environ-
ment, supports the system relative to data entry, graphics, statistics,
reporting and groundwater modeling.

Component Data Bases
  IRPIMS consists of three component databases: (1) the Technical In-
formation Management System (TIMS), (2) the Contract Administra-
tion Management System (CAMS) and (3) IRPTRACK, a Project Time-
line Management System. IRPTRACK is presently undergoing major
modifications and  will be replaced by a  second generation  full-
functioned program-management/program-control system. All three of
these existing data bases share data. TIMS and CAMS represent the
two most important data bases, both in terms of size and functional
capabilities. Figure 1 provides an overview of the IRPIMS database
and the relationship that exists between the two major data bases. The
TIMS data base, however and the technical information associated with
it will be the primary focus of this paper.
                          Figure 1
                     IRPIMS Data Archive
                                                                                                  MILITARY ACTIVITIES    871
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Technical Data
  The types of data stored can be broken down into major categories
as shown in Figure 2. These main data categories represent the foun-
dation of the data structure and are the keys by which data are queried
and retrieved from the system.
Operating
  UnR
UAJCOU
tASE
ore
LOCATION
         Subtunc*
           DM*
        ONJhPU
        APU
        LHAPU
Sampling
ktodlum
Location
 TypM
                               T.MB*.
                               •orinp
 Sit*
Typw
  Othar
Categories
                                                          rilcBJ method
                                                        Phyitckl pfttp*rtt*i
                            Figure 2
                   Major IRPIMS Data Categories
  When designing an  information  management  system,  it is the
forethought that is dedicated to developing the data structure (i.e., the
types of data captured and how the information will be categorized for
access) where most of the time and effort should be spent. Great flex-
ibility should be built into the data structure to accommodate a myriad
of "what if' queries and information requests from the user community.
Once the data structure has been defined and the system developed,
any changes to the data structure can pose major impacts and com-
plications to the management and operation of the system. Therefore,
great attention and detail should be paid to the principles of configura-
tion management when a change in  data structure is being considered.

Data Entry
  Data enter the system through two  mechanisms:  0) manual entry from
hard-copy reports ("keyed" data) and (2) batch entry from floppy disk
or magnetic tape (Fig. 4). Manually-entered data generally are associated
with historical IRP reports that were generated from completed hazar-
dous waste investigations. These data were  captured  originally from
Preliminary Assessment/Site Investigation (PA/SI)  and Remedial In-
vestigation/Feasibility Study (RI/FS) investigations. Data-entry staff key
the hard-copy data into terminals that are configured  with data entry
screens. The batch-entry system is designed for ongoing projects where
IRP contractors are tasked to prepare data submissions.  Data from these
submissions are uploaded into IRPIMS via  a series of batch-loading
software utilities.  Before data are uploaded, they undergo a series of
QA/QC checks  to verify data integrity and  format compliance.
  More than 125 different types of technical data (data fields) are stored
in TIMS. The bulk of this information, more than 80% of the total
data base, relates to analytical sampling results and data pertaining to
sampling events, analytical methods, or miscellaneous tests performed.
Hydrogeological data consist primarily of monitoring-well completion
information,  groundwater  level data, lithologic descriptions  and
hydraulic parameters.  Other data relate to general site and sampling
location information.  Figure 3 shows the relative size of the various
data tables stored in IRPIMS. A detailed discussion of the various types
of data stored in IRPIMS can be found in the IRPIMS Data Loading
Handbook.1
  Number of 390,000 -
  Records
           325,000
                    RES     TESTS    SAMP     LDI

                                    Data Table
                                                         GWD
L*gwtd: RES   Analytical RuuKl           LDI

       TESTS  Analytic*! MMhocte          GWD

       SAMP  Sampl* Typ» UK! Ev»nt Data
                                           Sampling Location InfomiMlon

                                           Groundwvttr Lftvvl Data
                            Figure 3
                            IRPIMS
                   Size at" Camponent D»ia Tables
                                                                                  Data Prom
                                                                                 ' Hard Copy IHP
                                                                                 Historical Reports
                                                                                                   Figure 4
                                                                                              IRPIMS Data Entry
                                                    As the data are entered into the system, they are inserted into a series
                                                  of 10 data tables where they are ultimately stored for access. One data
                                                  table, for example, may  consist of genera] site location information,
                                                  whereas another table may consist of the analytical results that are
                                                  associated with the site locations of interest. Many of the routine data
                                                  queries require that  tables be electronically  joined to  retrieve the
                                                  necessary information. This process is done through standard techniques
                                                  available to the query language in Oracle.

                                                  Capabilities
                                                    Aside from functioning as a data archive, IRPIMS was designed to
                                                  be used extensively for technical data analysis and information transfer.
                                                  Current capabilities involve QA/QC of analytical data, risk assessment
                                                  support and technical oversight of IRP contractors. The assistance that
                                                  IRPIMS provides to the Air Force IRP staff to oversee technical  inter-
                                                  pretations  made by contractors is especially  critical since the IRP
                                                  Program is heavily dependent  on contractors.
                                                    Several menu-driven reports exist to support routine technical data
                                                  queries. The information generated by these reports varies from general
                                                  program-wide inquiries (across all Air Force installations)  to reports
                                                  specific to a particular Air Force installation, site or sampling loca-
                                                  tion. Sampling results can be retrieved over a particular point in tune
                                                  as well as in space (both in the horizontal and vertical sense). Con-
       MILITARY ACTIVITIES
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taminant analysis reports are available to retrieve sampling data that
exceed a particular health-risk threshold such as a Maximum Contami-
nant Level (MCL). Menu-driven reports are developed after the user
community has expressed a need for accessing a routine data query.
  Ad hoc reports also are possible, and they are generated when special
information needs arise. Recently, ad hoc queries have been developed
to identify sites that would be suitable to certain remedial technologies
based on the types of contaminants present, constituent concentration
levels and the particular conditions posed by the hydrogeologic setting
(e.g., depth to groundwater).  This capability affords a particularly
powerful approach to identifying sites for remediation across the entire
Air Force IRP program.
  Other capabilities involve sophisticated three-dimensional graphics,
statistical data analysis and groundwater modeling.  These types of
applications have proven critical to supporting Air Force litigation pro-
ceedings in the past and have been responsible for rendering a favorable
legal decision that saved the government an estimated $10 million in
monitoring and remediation expenses.
  Statistical procedures are used to assess the precision and accuracy
of analytical data submitted by support laboratories. Statistical analysis
also is used to identify data outliers (anomalously high or low data
values) that may have  escaped other data validation checks.
  A Defense  Priority  Model (DPM) interface currently is being
developed. DPM is the hazard ranking model currently adopted by all
military services in the Department of Defense (DoD) for purposes of
prioritizing cleanup and remediation at hundreds of IRP sites.  This
interface will allow DPM scorers to access IRPIMS to retrieve the front-
end data necessary to run the hazard ranking model. This interface will
save the operators needless hours in preparing  raw data before running
the model, particularly since the data-preparation phase has been iden-
tified as the most time-consuming aspect of  running the model and
generating DPM scores.
  A Geographical Information System (GIS) supporting sophisticated
graphics for spatial analysis and volumetrics  is planned for the near
term. This system will support users who have the expertise to per-
form their own interpretations using the spatial data found in the IRPIMS
archive.
  Regarding the future of IRP in  the Long-Term Monitoring and the
Remedial Design/Remedial Action arenas, IRPIMS is designed to accept
data from these investigations as they become available. IRPIMS will
serve as the obvious technical tool to verify that remedial actions have
effectively improved the environment. This process will be accomplished
by analyzing trends in constituent levels detected in affected media prior
to,  during and after remediation.

User Community, Support and Access
  The IRPIMS' user community  consists of staff located at the IRP
Program Office, at individual Air Force installations and at Air Force
Headquarters  where program managers determine broad policy and
oversee the direction of IRP. Currently, information is transferred to
organizations outside the IRP Program Office via hard-copy; however,
direct remote access to the system is now being planned for the entire
Air Force community. This expanded access is due to recent decisions
that have identified IRPIMS as the central data repository for the Air
Force.
  Various scenarios for access have teen identified, and it is likely that
the level of access will vary depending on the needs of the user organiza-
tion. Some of the larger Air Force installations which have enormous
data management needs, for example, may require a replicated data base
installed on-site. This arrangement essentially clones IRPIMS for use
on an on-site computer at that particular installation. In other instances
at installations where IRP activities and technical staff are limited, hard-
copy access to the  system may suffice.
  Users are supported  by various  documents such as  user's manuals,
data loading manuals and, in the  near future, a quarterly newsletter.
On-site training will be provided  as the user  community expands to
other outside organizations. Government contractors will be trained on
data format requirements and on the use of software to assist data loading
and QA/QC of analytical data.
OVERVIEW OF AIR FORCE IRP INVESTIGATIONS
  The discussions that follow will provide an overview of Air Force
IRP investigations based on data that are currently stored in IRPIMS.
Emphasis will be placed on environmental data that are associated with
the groundwater media.  The discussions  that follow are qualified by
the fact that the data base is not entirely complete and, at this writing,
represents  a subset of data collected from  one of three  Air Force
technical service centers. The amount of data stored, however, is so
large that statistically significant conclusions can be drawn, particularly
in regards to quantitative estimates and summary information of con-
stituents detected in the environment. An ongoing program, nonetheless,
is in place to load IRP  data for the entire Air Force IRP program.
Funding for this effort has been approved for the 1991 fiscal year.

Data Base Size
  The data universe at this time (Table 1) represents information on
more than 2000 hazardous waste sites that are distributed within and
outside the contiguous United States across 196 Air Force installations
and 14 Major Commands. More than 7000 sampling locations have been
entered into the data base for which more than 630,000 sampling results
can be retrieved for analysis. More than 725 chemical substances com-
pounds are identified in the system and can be associated with analytical
results. As of this writing, 260 compounds have been detected in various
sampling media. Approximately  3500 monitoring wells  have been
installed and the borehole footage exceeds 231,000 feet.
                            Table 1
          Air Force IRP Data Universe and Sampling Effort
                     IRPIMS Data Summary
                     as of August 30,1990
                  Air Force Bases          196

                  Sites                   2245

                  Sampling Locations      7136

                  Analytical Results     632,123
The Air Force Base as an IRP Facility
  Based on the information in IRPIMS, the typical Air Force installa-
tion has an average of 12 sites. The largest number of sites that exists
on an Air Force facility is 132. The average number of monitoring wells
installed on an installation is 46, whereas the median number of wells
installed per base is  25. The maximum number of wells installed on
a particular base exceeds 460. A typical site has an average of 4.5 wells
installed with a median of 3 wells. The largest number of wells installed
on a given site is 60. The average depth of monitoring wells installed
across all Air Force bases is approximately 35 feet.

Sites and Site Types
  Information on  approximately 2250 sites has been  entered  into
IRPIMS.  Air  Force IRP  sites can  be grouped into  at  least  13  site
categories. Figure 5 illustrates the frequency of occurrence of these
various site categories. The site types that are found most frequently
are: (1) landfills, (2) waste disposal lagoons or waste pits, (3) spill sites,
(4) fire training areas and (5) underground storage tanks. By far the
most common sites are those that fall into the landfill category.

Sample Location Types
  IRPIMS stores information on 14  different sampling location types.
Figure 6 illustrates the frequency of occurrence of these sampling types
across the entire Air Force IRP program. Monitoring wells are the most
                                                                                                            MILITARY ACTIVITIES    873
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common type of sampling location as indicated by Figure 6. As noted
above, information on more than 3500 monitoring wells is available
at this time in  IRPIMS.

                                           IRP1MS Data Summary
                                           as of August 30,1990
             500 -/
                                                                                                         IRPIMS Data Summary
                                                                                                         as of August 30,1990
                  LF WP OT SS FT  LU DS RW WT MU DA US OW
                                   Site Type
Legend: LF

       WP

       OT

       SS

       FT

       LU
Landfill

Watte Disposal Lagoon/Pit

Other

Spill Site/Area

Fire Protection Training Area/Pit

Leaking Underground Storage
 Tank/Pipes
       DS    Drum Storage Area
RW

WT

MU

DA


US


OW
Radioactive Waste She

Waste Treatment Facility

Munition Disposal

Discharge Area or Surface
 Drainage

Underground Storage Tank or
 Pipeline

Oil/Water Separator
                              Figure 5
                        Air Force IRP Program
                        Frequency of Site Types
Common Organic Compounds Detected in Groundwater
  Figure 7 shows a ranked listing of the 10 most common compounds
detected in groundwater across the Air Force IRP Program. The con-
stituents are ranked based on a frequency analysis of the total number
of sampling locations where organics were detected. Not surprisingly,
the constituents that are detected most commonly on Air Force installa-
tions are those associated with solvents and fuels which  have been
released by  activities  related to  airplane maintenance  and  fuels
storage/handling. As Figure 7 indicates, Trichloroethylene (TCE) is cer-
tainly the most common contaminant detected. Other constituents such
as toluene and benzene also are commonly  detected in groundwater.
These compounds are found on Air Force installations are typical of
those compounds  found on other large industrial complexes.
  Table 2 shows representative concentration levels for the top 10 com-
pounds.  As commonly found  in environmental  data, the  frequency
distributions for these compounds  are typically  skewed towards the
higher concentration levels; hence, the mean or average concentrations
tend to be much higher than the median levels. This result is common
to frequency distributions that vary significantly from a normal distribu-
tion. The median is a better measure than the mean of central tendency
in the data and thus represents a concentration  that one could expect
to detect in the field in most instances. The mean concentrations tend
to exaggerate representathe constituent levels and thus are not recom-
mended tor this type of analysis.
  Because  of the  large  sample  size of data available  in IRPIMS,
statistical!) significant estimates of the median and other parameters
                                                                           4000-1
                                                                                      3000-
                                                                             Numberol
                                                                             Sampling  2000
                                                                             Locations
                                                                                      1000
                                                                                           WL BH SL RV CH TP LK CP TK  SP LH SE BR FW
                                                                                                             Type of Site
Legend: WL

      BH

      SL

      RV

      CH

      TP

      LK

      CP
Well

Borehole

Surface Location

River/Stream

Channel/Ditch

Test Pit

Lake/Pond

Composite from Several
Locations
TK

SP

LH

SE

BR

FW
Tanks & Containers

Spring

Leachate

Seep

Barrels

Faucet and Tap
                                                                                                       Figure 6
                                                                                                Sampling Location Types
                                                                                                    (Based on number of detects)
                                                                                                       IRPIMS Data Summary
                                                                                                        as of August 30,1990
                                                                          1500 •
                                                                   Number
                                                                     of    1000 -
                                                                   Detects
                                                                           500
                                                                                                   Compound
                                                                                             Figure 7
                                                                                 Most Common Organic Compounds
                                                                                      Detected in Groundwater
       MILITARY ACTIVITIES
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can be made. It is not likely, therefore, that the median levels for the
various constituents will vary significantly even as considerably more
data are added to the data base over time.
                            •Bible 2
          Ranked Listing of Common Organic Compounds
                    Detected in Groundwater
                      IRPIMS Data Summary
                      as of August 30,1990
Compound
TCE
Toluene
Benzene
Phenollcs
PCE
Ethylbenzene
1,1,1-TCA
trans-1,2-DCE
1,4-Dlchlorobenzene
1,1-DCA
Median
18
2
7
12
4
3
7
7
5
5
Mean
1971
1780
1758
2025
452
143
2394
509
197
137
Maximum
610,000
310,000
320,000
125,000
52,000
3,640
240,000
34,000
18,000
8,800
      (Note: All values In ng/L)
 Common Organic Compounds Detected at Selected Site Types
  When planning sampling protocols (choice of analytical method, etc.)
 for the common site types, it is of interest to assess the variety of com-
 pounds likely to be detected. Figure 8 illustrates the variety of organic
 compounds detected at selected site types, based on the number of
 distinct chemical substances encountered during sampling. As one might
 expect, landfills are the sites that demonstrate  the greatest variety in
 organic constituents detected; nearly 80 different compounds have been
 detected across the Air Force.
                                       IRPIMS Data Summary
                                        as of August 30,1990
               80 -/
               60 .
      Number of
       Different  40 .
      Constituents
       Detected
               20 .
Legend: LF  Landfill

      WP  Waste Lagoon, Weathering Pit

      FT  Fire Training Area
LU  Underground Storage Tank

SS  Spill Site
                               Table 3 lists the top 10 constituents most frequently detected at selected
                             site types. Of these compounds, TCE, toluene, benzene, ethylbenzene,
                             PCE,  trans-1,2-dichlorothene and  1,1,1-trichloroethane occur  in the
                             respective lists across all of the selected site types. Table 4 illustrates
                             median levels for these constituents as calculated separately for each
                             of the selected site types. One can  determine from this table that the
                             median concentrations at underground storage tanks for all constituents,
                             particularly for benzene, are significantly elevated above those levels
                             associated  with the other  sites. This analysis indicates that leaking
                             underground storage tanks/pipelines tend  to pose the greatest en-
                             vironmental threat based simply on the high concentrations  likely to
                             be detected.
                                                                                                     Table 3
                                                                                   Organic Constituents Most Frequently Detected
                                                                                       in Groundwater at Selected Site Types
                                                                                                    IRPIMS Drtn Summary
                                                                                                   in number ol witIB with (tol
                                                                                                    MOIAuouBt30,19BO
Landfills
Tricmorwthyl*n«(TCE)
Phenolic*
Toluam
Benzene
Ethylbenzeiw
Vinyl Chloride
1.1.1-Trlchlaroethafw
lrans-1 ,2-DlchlorMtham
1,1-DlchlorwhBna
Tclrachloroflthylene (PCE)
Wast* Lagoons/
Wvalhorlng Pits
Toluan*
Trtchtoioothylerw (TCE)
1,1,1-Trichloroethana
Totrachloroethylene (PCE)
Benzono
tran»-1,2-Dlchlon»therM
Chlorobanzana
Ethylbanzana
1,4-Dlchlorobenrene
1,2-Dlchloroathano
Fire Training
Areas
Toluane
Trlchloroelhylena (TCE)
Benzene
Ethylbenzene
trans-1 .S-Dlchloroeltwne
Teirachkirofllhylone (PCE)
1,1,1-Trlchloroetham
Trlchlofoduoromalhana
1 ,1 ,2,2'Tetrachloroethane
Vinyl Chlorlda
Underground
Storage Tanks
Trtchtorwthylene (TCE)
Banzan>
Elhylbanzem
Toluene
lrans-1 ,2-Dlchloroelhana
1,2-Dtehloroalhane
Tatrachloroalhylana (PCE)
Bromochloromathana
xylams
1,1,1-Trichloroathane
Spill Sites
Trlchloroathyleti* (TCE}
Toluune
Benzene
Ethylbenzene
Tetrachtoroethylene (PCE)
xy tones
lrans-1 ,2-Dlchloroalhena
1,1-Dlchloroetnene
1,1,1-Trlchloroathane
1,1-Dtehloroethane
                                                           Table 4
                                            Median Organic Concentrations Found in
                                               Groundwater at Selected Site Types

                                                       IRPIMS Data Summary
                                                       as of August 30,1990
Compound
TCE
Toluene
Benzene
Ethylbenzene
PCE
trans-1 ,2-DCE
1,1,1-TCA
Landfills
3.5
1.2
5.9
0.8
1.7
4.2
3.7
Waste Lagoons/
Weathering Pits
11.4
1.8
1.8
2.7
2.7
20.0
4.0
Spill
Sites
31.0
4.0
16.5
10.5
23.0
23.0
4.3
Fire
Training Areas
17.2
1.9
30.0
1.3
3.6
6.0
1.7
Underground
Storage Tanks
52.5
625.0
1806.0
23.0
109.0
4E.O
36.1
                             Figure 8
               Variety of Organic Constituents Detected
                 in Groundwater at Selected Site Types
                                                                            (Note: All values In |ig/L)
CONCLUSIONS
  The Human  Systems Division developed IRPIMS to support and
automate the data management needs of the IRP Program. The system
is designed around two principal data bases: (1) a technical informa-
tion management system and (2) a contract administration management
system. Both of these  systems share data.
  The major design and development phase of the system has largely
been accomplished. Large volumes of data are now available for mean-
ingful interpretation and analysis to support IRP decision-makers at
various levels within the Air Force.
  More than 80% of the data stored in IRPIMS consists of analytical
sampling results. Other technical data captured by the system relate to
general site location information, lithologic  descriptions, well comple-
tion information, groundwater level data and  the  like.
  Trichloroethylene (TCE), toluene and benzene are the most commonly
detected compounds in groundwater. These compounds are associated
with solvents and fuels handling and are common to large industrial
complexes. With the large sample size that is available in IRPIMS,  it
has been possible to estimate representative concentrations of consti-
tuents that would commonly be detected in the field across the Air Force
program. Occurrences of commonly detected compounds have also been
associated and identified with the important site types. Sampling pro-
tocols designed for routine site investigations have been derived based
on these constituent/site associations.
                                                                                                              MILITARY ACTIVITIES    875
-------
   Beyond the ongoing data loading process,  the current focus is to
 expand and further develop the various technical applications that are
 possible with IRPIMS. In addition, the system is soon to support the
 entire Air Force as the central data repository. This development will
 vastly increase the size of the data base and will pose a significant
 expansion  to the user community. Remote access to the system will
 be developed to improve the transfer of information to support various
 Air Force  customers.
   The current  IRPIMS data structure has future applications and is
 designed to accept other types of data as the RD/RA arid the Long Term
 Monitoring programs  respond to new data  demands. In addition,
IRPIMS will play an important role in verifying the effectiveness of
remediation as various remedial  alternatives are implemented and
sampling data becomes available for analysis.


REFERENCE
1. Anderson, R., Vasil, J. and Hunter, P., Installation Restoration Program In-
  formation Management System (IRPIMS) Data Loading Handbook, \fersion
  2.1, Air Force Occupational and Environmental Health Laboratory Report
  89-119EQ0111JID, Human Systems Division,  Brooks Air Force Base, TX,
  September,  1989.
876    MILITARY ACTIVITIES
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             Optimal  Regulatory  Compliance  Strategy  for Multisite
     Investigations  Under the  Navy Installation Restoration Program
                        at the  Naval Air Station  (NAS) Pensacola
                                                   John Barksdale
                                           Ecology and Environment,  Inc.
                                                  Pensacola,  Florida
                                                Richard J. Rudy,  P.G.
                                           Ecology and Environment,  Inc.
                                                 Tallahassee, Florida
                                                David Criswell, RE.
                                       Southern Division NAVFACENGCOM
                                                  Pensacola,  Florida
 ABSTRACT
   The Naval Air Station (NAS) Pensacola, Florida, is an active naval
 flight training and aircraft rework facility located in the northwest Florida
 panhandle. It is also one of the oldest Naval facilities in the United
 States. The facility has recently been added to NPL and currently has
 37 sites on the Station which require investigations under the Naval In-
 stallation Restoration Program (IRP). The sites will be investigated in
 accordance with conditions and schedules outlined in a Federal Facilities
 Agreement between the Navy, the U.S. EPA and the State of Florida.
   All sites were classified as Solid  Waste Management Units in
 RCRA/HSWA permit for NAS Pensacola. Seventeen of the sites have
 been identified as requiring RCRA Facility Investigations, and all 37
 sites will be investigated under the CERCLA regulations.
   Given that all 37 sites need to be addressed under the Navy IRP, an
 approach has been developed to conduct a multimedia environmental
 investigation which incorporates the requirements of both RCRA/HSWA
 and CERCLA regulations. In addition, the 37 sites were combined into
 15 groups for maximum efficiency throughout the investigative process.
 Site groupings were principally based on: (1) similarity of documented
 or suspected contaminants; and (2) geographic proximity. Some of the
 sites have documented contamination, whereas other sites are only
 suspected of or have a low probability of contamination. As a result,
 a phased approach to conducting the contamination investigations is
 planned. This phased approach will allow efficient identification of sites
 where environmental contamination has actually occurred, and also will
 allow elimination of noncontaminated sites to be eliminated from the
 program in the most environmentally sound, cost-effective and timely
 manner possible. Sites identified as being contaminated will be further
 investigated through the completion of an RI/FS and, ultimately, design
 and remediation. This overall investigative approach and compliance
 strategy for NAS Pensacola will ensure the most optimal and streamlined
 procedure in meeting the objectives of the  multiple regulatory re-
 quirements of this Naval facility.

 INTRODUCTION
  In recent years, the United States Naval Air Station (NAS) Pensacola
 has taken an active role in evaluating past and present hazardous waste
 practices. As a result, the Navy, under its Installation Restoration Pro-
 gram (IRP), has implemented an investigation  and cleanup strategy
 designed to bring sites identified at NAS Pensacola into conformance
 with the RCRA, HSWA and CERCLA. The entire facility was added
 to the NPL in late 1989, providing further impetus for an extensive
 cleanup effort.
  NAS Pensacola is located on 5,874  acres  in southwest  Escambia
County,  Florida (Fig. 1). Two major industrial tenant commands are
located at NAS Pensacola: the Naval Aviation Depot and the Public
Works Center. These industrial facilities support all Naval training
activities which operate at the base. This support includes fuel storage
and transportation systems and maintenance and repair of aircraft.
Throughout the years, these support facilities have generated a variety
of materials, the majority of which have been disposed of on the base.
These materials include construction debris; municipal solid waste and
wastewater treatment plant sludge; and miscellaneous industrial wastes,
                                  0 KILOMETERS
                          Figure 1
                   Location of NAS Pensacola
                                                                                               MILITARY ACTIVITIES   877
-------
including waste oils, solvents, paints, electroplating liquids and spilled
fuels. The 37 potential sites of contamination identified at NAS Pen-
sacola (Fig.  2) are a result of the past generation and disposal prac-
tices of these materials.

HISTORY
  The NAS  Pensacola location has been associated with military ac-
tivities dating as far back as 1528, when the first European settlement
in North America was established at this site.' Until the early 19th cen-
tury, this location served as a fortification point for both the British
and the Spanish.
  In 1825, a naval yard was constructed by the U.S. Navy at the NAS
Pensacola site. Although activity at the yard was in turmoil throughout
the remainder of the 19th century and into the early 20th century, the
U.S. Navy kept the installation. Subsequently, in 1914, the Navy's first
permanent air station was  established at this site. Throughout World
War I and World War II, this base became the Navy's premier aviation
training facility. Along with the training facility, the Navy developed
all the required support systems for the various aviation activities which
occurred at  the site.
  In addition to the long time Naval Air Station command at Pensacola,
several  tenant commands  have been established at this  base. These
tenants include the Naval Education and Training Command, the Navy
Public Works Center (PWC) and the Naval Aviation Depot (NADEP).
The Education and Training  command manages  all  Naval training
activities. The PWC is responsible for all utilities and transportation
functions for the Navy's activities in this area. The NADEP serves as
a repair and maintenance  facility for various Naval aircraft.

ENVIRONMENTAL SETTING

Physiography
  NAS Pensacola is located in the Gulf Coastal Lowlands Subdivision
of the Coastal Plain Province physiographic division.2 The 5,800-acre
facility is located on a peninsula and is bounded on the east and south
by Pensacola Bay and Big Lagoon and on the north by Bayou Grande.
The most prominent topographic feature on the peninsula is an escarp-
ment or bluff which parallels the southern and eastern shorelines and
on which Fort Barrancas was built. Seaward of the  escarpment is a nearly
level marine terrace with surface elevations of approximately five feet
above mean sea level (MSL). The central part of the peninsula, located
landward of the escarpment, is a broad, gently rolling upland area with
surface elevations up to 40 feet above MSL.3-4

Hydrogeology
  There are three principal hydrogeologic units  of importance which
underlie the NAS Pensacola site. These are, in descending order, the
Sand-and-Gravel Aquifer, the Intermediate System and the Floridan
Aquifer System.
  The  Sand-and Gravel Aquifer occurs from land surface to a depth
of approximately 300 feet at  NAS Pensacola and is composed  of a
sequence of unconsolidated to poorly indurated clastic deposits.5* The
sediments making up this aquifer belong to all or part of the Pliocene
to Holocene Series, which, in this area, consist mainly of the Citronelle
Formation overlain by a thin cover of marine terrace deposits. In the
Pensacola area, the Sand-and-Gravel Aquifer is the primary source of
potable drinking water, and groundwater within the aquifer is classified
by FDER as G-l (sole source). Given that the Sand-and-Gravel Aquifer
is contiguous  with land surface and recharge occurs principally by the
direct infiltration of precipitation, the aquifer is particularly suscepti-
ble to contamination from surface  sources.
  The  lower limit of the Sand-and-Gravel Aquifer coincides with the
top of a regionally extensive and vertically persistent hydrogeologic unit
of much lower permeability. This unit is known as the Intermediate
System. In the  NAS Pensacola area, the Intermediate System is
approximately 1,100 feet thick and  is  composed  of the lower portion
of the Miocene Coarse  Clastics, the Upper Member of the Pensacola
                                                                 Figure 2
                                                       NAS Pensacola Sile Locations
       MILITARY ACTIVITIES
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Clay, the Escambia Sand Member of the Pensacola Clay and the Lower
Member of the Pensacola Clay; all of Miocene Age. In general, the
Intermediate System consists of fine-grained sediments and functions
as an effective confining unit which retards the exchange of water be-
tween  the overlying Sand-and-Gravel Aquifer and the underlying
Floridan Aquifer System.5
  Immediately underlying the Intermediate System and  occurring at
a depth of approximately  1,500 feet below land surface at NAS Pen-
sacola is the Floridan Aquifer  System. The Floridan Aquifer in this
area is composed of the Middle to Lower Miocene Chickasawhay
Limestone and undifferentiated Tampa Stage Limestone. Groundwater
within the Floridan Aquifer in this  area is highly mineralized and is
not used for water supply.5

Surface Water
  The NAS Pensacola facility is located on a coastal peninsula bounded
by Bayou Grande to the north, Pensacola Bay to the south and east and
Big Lagoon to the southwest. These surface water bodies have been
classified by FDER as Class HI (i.e., suitable for recreation and pro-
pagation offish and wildlife). Pensacola Bay and Big Lagoon are par-
tially separated from the Gulf of Mexico by Santa Rosa Island and
Perdido Key, both of which are barrier islands.
  There are no naturally occurring perennial streams on NAS Pensacola;
however, there are approximately 10 naturally occurring intermittent
streams and numerous manmade drainage pathways, which include many
stormwater outfalls. Discharge is mainly to the south into Pensacola
Bay; however, some small intermittent streams discharge into Bayou
Grande to the north from Sherman Field and Chevalier Field.3'4 The
southwestern and northern portions of NAS Pensacola contain areas
of freshwater wetlands.
  The discharge of surface waters into Pensacola Bay, Bayou Grande,
and the coastal wetland areas presents the potential for transport of con-
taminants into these systems. This system could have a significant impact
on seagrass and other sensitive plant communities as well as on shell
fishing, recreational  fishing and swimming in these coastal zones.
Discharges, either through the surface water or groundwater, into
wetland areas found on-site could also have a significant impact on the
biotic communities that are dependent on those habitats.

Biological Resources
  The NAS Pensacola facility encompasses approximately 15 terrestrial
and aquatic habitats.  The majority of the land on the eastern side of
the facility is developed for military use or is designated as a historical
or cultural resource. However, the NAS Pensacola installation has
approximately 3,500 acres in natural or seminatural (plantation) con-
dition,  primarily in the western portion of the facility.
  A number of threatened and endangered species have been identified
in the vicinity of the NAS Pensacola facility.7 Many rare, threatened
and endangered species are associated with the wetland or bog habitats.
Any site  remediation  and, more  importantly,  any assessment  of
environmental endangerment must consider the water level  requirements
of rare and endangered plant species and the foraging activities of birds
in the waters surrounding the NAS Pensacola facility, as well as nesting
and feeding animals on the facility grounds.

NAVY  INSTALLATION RESTORATION PROGRAM
  The Navy IRP was established in 1986 to direct the investigation and
remediation of uncontrolled hazardous waste disposal sites associated
with naval operations. Prior to 1986, these investigation/remediation
activities had been managed under the Navy Assessment and Control
of Installation  Pollutants  (NACIP) program.
  In accordance with the NCP, the Navy IRP currently  is being im-
plemented in  full compliance with the  statutory  requirements  of
CERCLA and  SARA. Furthermore, since CERCLA/SARA specifies
the inclusion of all applicable or relevant and appropriate requirements
(ARARs), the Navy IRP incorporates compliance with RCRA and the
HSWA of 1984, where applicable.
  The Navy IRP can be viewed as a five-step investigation and remedia-
tion process:
• Site discovery or notification
• Preliminary assessment (PA) and site investigation (SI)
• Establishment of priorities for remedial action (RA)
• Remedial Investigation/Feasibility Study (RI/FS)
• Remedial Design/Remedial Action (RD/RA)
Each of the above steps includes substeps or subdivisions.
  In order to supplement the IRP and in an effort to keep interested
parties abreast of activities at the NAS Pensacola facility during this
investigation, a Technical Review Committee (TRC) was formed. The
TRC for this project consists of the U.S. EPA, FDER, an Escambia
County official and a representative of private citizens. All documents
generated by the Navy for work conducted as part of this investigation
are submitted to the TRC  for review and comment.

PREVIOUS INVESTIGATIONS
  Three major investigation programs have been conducted at NAS Pen-
sacola under the NACIP/Navy IRP programs: Initial Assessment Study
(IAS);1 Verification Study (VS); and Confirmation Study (CS). The
IAS was conducted from 1982 to 1983 by the Naval Energy and Environ-
mental Support Activity (NEESA) to identify and assess NAS Pensacola
sites that could pose a potential threat to human health or the environ-
ment as a result of contamination derived from past naval operations.
The VS, conducted in 1984 and the CS, conducted from 1985 to 1986,
were carried out by a previous Navy contractor to confirm/ refute the
presence of contamination at specific sites identified in  the IAS.
  In addition to the above NACIP/Navy IRP programs, a RCRA Facility
Assessment  (RFA)  has  been completed  at NAS Pensacola and a
RCRA/HSWA permit was  issued to the installation by the U.S. EPA
on July 27, 1988. Seventeen of the sites were identified on the permit
as Solid Waste Management  Units (SWMUs) which required RCRA
Facility Investigations. A RCRA permit had previously been issued to
NAS Pensacola by the Florida Department of Environmental Regula-
tion (FDER) on September 29,  1987.
  Table 1 lists the 37 known and potential sites of environmental con-
                              Tablel
                  Navy IRP Sites at NAS Pensacola
            Site No.
                                 Site Name/Description
1*
2*
3*
4
5
6
7
B
9
10
11*
12
13
14
15*
16
17
18
19*
20
21*
22
23
24
25
26*
27*
28
29*
30*
31*
32*
33*
34*
35*
36*
37
Sanitary Landfill
Waterfront Sediments Area
Crash Crew Training Area
Army Rubble Disposal Area
Borrow Pit
Fort Redoubt Rubble Disposal Area
Firefighting School Area
Rifle Range Disposal Area
Navy Yard Disposal Area
Commodore's Pond
N. Chevalier Disposal Area
Scrap Bins
Magazine Point Rubble Disposal Area
Dredge Spoil Fill Area
Pesticide Rinsate Disposal Area
Brush Disposal Area
Transformer Storage Yard
PCS Spill Area
Fuel Farm Pipeline Leak Area
Pier Pipe Leak Area
Sludge at Fuel Tanks
Refueler Repair Shop
Chevalier Field Pipe Leak Area
DDT Mixing Area
Radium Spill Site
Supply Department Outside Storage Area
Radium Dial Shop Sewer
Transformer Accident Area
Soil South of Building 3460
Buildings 649 and 755
Soil North of Building 648
IWTP Sludge Drying Beds
Wastewater Treatment Plant (WVTP) Ponds
Solvent Area North of Building 3557
Miscellaneous IWTP SWMUs
Industrial Waste Sewer
Sherman Field Fuel Farm
                                                                       *Listed for  further  investigation under the 1988 RCRA/HSWA permit.


                                                                                                          MILITARY ACTIVITIES   879
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lamination thai have been identified on NAS Pensacola. Site locations
are shown in Figure 2.

FEDERAL  FACILITIES AGREEMENT
  The Federal Facility Agreement (FFA) is an interagency agreement
which exists  between the Navy, U.S. EPA and FDER. The FFA outlines
the conditions and schedules to be followed during the course of the
investigations at NAS Pensacola. The general purpose of the FFA is to:
• Ensure that the environmental impacts associated with past and pre-
  sent activities at NAS Pensacola are thoroughly investigated and
  appropriate  CERCLA response/RCRA corrective alternatives are
  developed and implemented as necessary to protect the public health,
  welfare and the environment;
• Establish  a procedural framework and schedule for developing, im-
  plementing and monitoring appropriate response action at NAS Pen-
  sacola in  accordance with CERCLA/SARA, RCRA, the NCP and
  U.S. EPA/state-issued guidance and policy relevant to remediation
  at NAS Pensacola;
• Facilitate  cooperation, exchange of information and participation of
  the Navy, U.S. EPA and FDER in such actions.

INVESTIGATIVE APPROACH
   As discussed previously, 17 of the sites are listed on the NAS Pen-
sacola RCRA/HSWA permit as SMWUs, and the investigations of these
sites are governed by RCRA requirements. The remaining  20 sites are
covered by CERCLA regulations. In an effort to avoid confusion and
duplication of effort in this multisite investigation, an integrated approach
was developed.  This approach complies with the intent and general
requirements of both regulatory programs, but is specifically neither.
As a result,  the investigation terminology has been modified somewhat
from the prevailing RFI for sites covered by RCRA and the Remedial
Investigation (RI) for sites covered by CERCLA. For simplicity, the
investigations of all NAS  Pensacola sites will be referred to as Con-
tamination Assessment/Remedial Activities Investigations.
   In order to provide for maximum efficiency in the generation of in-
vestigation work plans and  the implementation of fieldwork for the NAS
Pensacola program,  the 37 sites have been clustered into 15  groups,
as shown in Table 2. Several criteria were established to generate the
work plan groups, including:  (1) geographic proximity of sites; (2)
similarity of contaminant  types; (3) similarity of potential investiga-
tion methods; and (4) potential scope and complexity of the investigation.
  In addition, a phased approach has been developed for  performing
the  NAS Pensacola site investigations. Phase I (Field Screening) is
directed  toward identifying the  principal area(s)  and primary  con-
taminants of concern at a site,  thereby providing  a  mechanism for
focusing sampling and analytical efforts during  subsequent phases of
the  investigation. The field screening phase will employ a variety of
field investigation tasks, including surface  geophysics, habitat/biota
surveys,  soil gas surveys, hydrologic assessments and the collection of
surface water, soil, sediment and groundwater samples for laboratory
analysis. However, the analysis of these samples will be subject to less
rigorous QA/QC requirements, which reflect the "focusing" objective
of this phase rather than a formal contaminant quantification objec-
tive. Each field screening task will utilize all existing information from
preceding tasks, including aerial photograph analysis, to adjust the loca-
tions of the  various surveys and sampling locations,  thereby achieving
optimum results.
   Phase  n (Characterization) is directed toward the formal confirma-
tion and quantification of the full spectrum of site contaminants (if any),
thereby allowing determination  of whether further  investigation is
warranted. The primary objectives of the Phase n field investigation
are  as follows:

•  To characterize the nature and magnitude of the full spectrum of
   potential  site contaminants;
•  To confirm and validate the contaminant distributions indicated by
   the Phase 1  analytical screening results by collecting and analyzing
   samples under rigorous QA/QC requirements;
                              1W»le2
                W»rk Plan Groups for NAS Pensacola
   Work Plan
     Group
Site No.
                     Site Name
                       1*         Sanitary Landfill

                       11*        North Chevalier Disposal Area
                       12         Scrap Bins
                       26*        Supply Department Storage Area

                       2*         Vaterfront Sediments Area
                       13         Magazine Point Rubble Disposal Ar«t
                       14         Dredge Spoil Fill Area

                       15*        Pesticide Rinsate Disposal Area
                       24         DDT Mixing Area

                       30*        Buildings 649 and 755

                       9          Navy Yard Disposal Area
                       10         Commodore's Pond
                       23         Chevalier Field Pipe Leak Area
                       29*        Soil South of Building 3460
                       34*        Solvent North of Building 3557

                       25         Radium Spill Area
                       27*        Radium Dial Shop Sewer

                       8          Rifle Range Disposal Area
                       22         Refueler Repair Shop

                       17         Transformer Storage Yard
                       18         Polychlorinated Biphenyls (PCBs)
                                    Spill Area
                       28         Transformer Accident Area

                       3*         Crash Crew Training Area
                       19*        Fuel Farm Pipeline Leak Area
                       37         Sherman Field Fuel Farm Area

                       7          Firefighting School Area
                       20         Pier Pipe Leak Area
                       21*        Sludge at Fuel Tanks

                       4          Army Rubble Disposal Area
                       5          Borrow Pit
                       6          Fort Redoubt Rubble Disposal Area
                       16         Brush Disposal Area

                       31*        Soil North  of Building 648

                       36*        IVTP Sewer  Area

                       32*        IVTP Sludge Drying Beds
                       33*        WTP Ponds
                       35*        Miscellaneous IVTP SVHUs
 'Listed for further  investigation under 1988 RCRA/HSVA permit.


• To support the preliminary identification, screening and evaluation
  data requirements of potential remedial alternatives.
Phase n characterization will consist of limited soil sampling; biota
sampling; the installation,  development  and sampling  of shallow
monitoring wells and the sampling of existing wells; a continuation of
the hydrologic assessments; and air sampling, if necessary.
  The  necessity of implementing Phases in and IV (Extent Delinea-
tion) will depend on the results of Phases I and n. Phases III and W,
if required, will be directed not only toward fully identifying the horizon-
tal and vertical extents of contamination, but also toward providing the
quantitative data base necessary to support the screening and evalua-
tion of potential remedial alternatives.
  The main objectives/advantages of this phased approach are as follows:
• Efficient identification of those sites where environmental contamina-
  tion has actually occurred as a result of past and/or present opera-
  tions, thereby allowing noncontaminated sites to be eliminated from
  the program in the most environmentally sound, cost-effective and
  timely manner possible;
• Focused placement of sampling  locations and focused selection of
  analytical parameters in later phases of the investigation, thereby
  allowing full characterization of site  contamination in  the most
  environmentally sound, cost-effective and timely  manner possible;
 S80   MILITARY ACTIVITIES
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• Early screening of potential remedial alternatives, which, in turn,
  allows critical parameters necessary to the evaluation of these alter-
  natives to be incorporated into the analytical program in later phases
  of the investigation.
All sites at NAS Pensacola will be investigated through Phases I and
n. However, it is anticipated that some of the NAS Pensacola sites may
not require investigation beyond Phase n. On the other hand, sites which
have documented contamination will likely require the additional phases
of work and hence will comprise full-scale CERCLA/RCRA RFI/RI/FS-
type investigations. As discussed above, however, the investigations for
all NAS Pensacola sites will be referred to as Contamination Assess-
ment/Remedial Activities Investigations.  The final results of investiga-
tions at all sites will be incorporated into a Contamination Assessment
Report. Where appropriate, sites will be recommended for No Further
Action. The final results of site investigations that require work beyond
Phase n will be incorporated into a Remedial Investigation Report which
will provide all the information necessary for the development and com-
pletion of a Feasibility Study.
  Any  new sites discovered during the process of investigating known
sites will be incorporated into the established approach, depending on
regulatory provisions applicable to  the site.
  Included in the investigative process is the base line risk assessment
to characterize current  and potential risk to human health and the
environment posed by the site. The primary objectives of the base line
risk assessment are to identify the contaminants of concern, assess their
toxicity and identify the exposure pathways for both the public and the
environment. The base line risk assessment provides a preliminary in-
dication of risk before the FS is conducted to identify cleanup alter-
natives. If little or no threat to human health or the environment from
a site is identified, no further action, or only limited action, will be
required for cleanup and the FS will be scaled-down appropriately.
  As the RFI/RI process is completed, each particular site group will
be evaluated promptly for the need of  a feasibility study/corrective
measures study (FS/CMS) and  subsequent remedial design-remedial
action/corrective measures implementation (RD-RA/CMI). The strategy
for performing these remedial engineering/construction activities at NAS
Pensacola will be, in general, similar to that for the fieldwork. Essen-
tially, sites with contaminant similarity and close geographic proximi-
ty will  be remedially analyzed as  a  single entity or as a larger group
to whatever degree possible.

CONCLUSIONS
  NAS Pensacola, Florida, has recently  been added to the NPL. This
installation has 37 potentially contaminated sites, all of which will be
assessed and remediated under an integrated approach which combines
the requirements of RCRA and CERCLA. An FFA between the Navy,
U.S. EPA and FDER has been developed which details the procedure
by which remedial activity will occur at the facility, including the RCRA
and  CERCLA integration and  the  responsibilities of each party of
concern.
  Given that full-scale RI/RFI/FS/CMS investigations may be required
for most of the 37 sites,  an optimal technical and economic strategy
has been implemented to achieve all necessary regulatory requirements.
  This optimization strategy prioritizes the sites for investigation as well
as groups the 37 sites into 15 more manageable units for the purposes
of work plan  development,  fieldwork  implementation and remedial
selection and implementation. The strategy also identifies a phased in-
vestigative approach to allow noncontaminated sites to be eliminated
from the program while providing full characterization of sites where
contamination has occurred.  This overall approach will provide the
maximum great degree of efficiency, with respect to economics and
schedule,  to such an extensive  remedial program.


DISCLAIMER
  The views expressed in this paper are those of the authors and not
the Department of the Navy.


REFERENCES
1.  Naval Energy and Environmental Support Activity (NEESA), Initial Assess-
   ment Study of Naval Air Station,  Pensacola, Florida. NEESA  13-015, 1983.
2.  Brooks, H.K., Physiographic Divisions of Florida: Florida Cooperative Ex-
   tension Service, Institute of Food  and Agricultural Sciences, Gainesville, FL,
   1981.
3.  U.S.  Geological Survey,  7 1/2 Minute Topographic Map, Fort Barrancas,
   Florida Quadrangle, 1970.
4.  U.S.  Geological Survey,  7 1/2 Minute Topographic Map,  West Pensacola,
   Florida Quadrangle, Photorevised 1987.
5.  Wagner, J.R., Allen, T.W., Clemens, L.A. and Dalton, J.B. Ambient Ground
   Water Monitoring Program—Phase 1: Northwest Florida Water Management
   District, DER Contract Number WM65, 1984.
6.  SEGS, Florida Hydrogeohgic Units: Southeastern Geological Society Ad
   Hoc  Committee on Florida  Hydrostrategraphic Unit Definition  (SEGS),
   Florida Geologic Survey, Special Publication No.  28, 1986.
7.  Florida Natural Areas Inventory,  Survey of Pensacola Naval Air Station and
   Outlying Branson Field for Rare and Endangered Plants. Tallahassee, FL,
   1988.
                                                                                                            MILITARY ACTIVITIES   881
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                       Federal Facility  Agreement Implementation
                                    Oversight  at  a Superfund Site

                                               Arthur  W. Kleinrath, RE.
                                         U.S.  Environmental  Protection Agency
                                                          Region 5
                                                      Chicago,  Illinois
                                           Majid A. Chaudhry, Ph.D., RE.
                                                 William  H. Miner,  RE.
                                         PRC Environmental  Management, Inc.
                                                      Chicago,  Illinois
ABSTRACT
  Section 120 of SARA provides a mechanism for remediation of federal
facilities through federal facilities agreement (FFA). This paper discusses
implementation of the FFA for the New Brighton/Arden Hills Super-
fund site in Ramsey County, Minnesota. The site is owned by the U.S.
Army. It covers an area of approximately 25 mi2, which includes a
4-mi2 area of the Twin Cities Army Ammunition Plant (TCAAP) and
off-TCAAP areas contaminated by the migration of contaminants from
TCAAP. The soils and groundwater at the site are contaminated with
metals and VOCs. The groundwater contamination emanating from the
TCAAP site has  threatened water supplies  of several communities
downgradient of the site that use groundwater as a potable water supply.
  This FFA was the first agreement in the country pursuant to Section
120 of  SARA. The agreement was intended to ensure that the en-
vironmental impacts associated with the TCAAP site are thoroughly
investigated and that appropriate steps are taken to protect public health,
welfare and the environment. The agreement specifies a shared respon-
sibility  for conducting RI/FS at the site. The U.S. Army is responsible
for conducting Rls for on-TCAAP areas, the Minnesota Pollution Con-
trol Agency (MPCA) is lead agency for conducting Rls for off-TCAAP
areas (approximately  25   mi2)  and U.S. EPA is responsible for
preparing risk assessments (RA) of on-TCAAP and off-TCAAP areas.
Upon completion of the Rls and RAs, the U.S. Army will conduct an
FS to identify and evaluate feasible response actions for remediation
of contaminated soils and groundwater.
  Successful implementation of an agreement of this magnitude and
complexity  requires innovative management on the part of all  par-
ticipants. Meeting schedules, whether they are the Army's or the U.S.
EPA's, is critical to the credibility of the Section 120 process.
  This  paper highlights the oversight of the  RI/FS activities and the
resources and approaches needed to meet the rigorous review schedule
specified in the FFA. It discusses major features of the FFA, progress
made to date, resolutions of disputes among three organizations (U.S.
EPA, MPCA and U.S. Army) and schedules and workloads relevant
to the implementation of the FFA.

INTRODUCTION
  The New Brighton/Arden Hills Superfund  site consists of the Twin
Cities Army Ammunition Plant (TCAAP), located in Ramsey County,
Minnesota and all  other   areas contaminated by  the migration of
hazardous substances or contaminants from TCAAP. The U.S. Army
owns the TCAAP facility  and Federal  Cartridge Corporation (FCC)
has been operating the facility during most of its existence. TCAAP
has been used to manufacture, store and lest small arms ammunitions
and related materials since 1941. Presently, the plant is inactive, having
been on standby status since August 1976.  However, two major private
companies still use part of the facility for commercial and defense-related
operations. These companies are Minnesota Mining and Manufacturing
Company and Honeywell, Inc.
  Information from past studies indicates that between 1941 and 1981
waste material was disposed of at 14 disposal areas or sites within
TCAAP. The U.S. EPA and  the Minnesota Pollution Control Agency
(MPCA) have determined that there have been releases of hazardous
substances, pollutants, or contaminants into the environment. As a result
of these releases, the  New Brighton/Arden Hills site has been ranked
No. 43 on the NPL.
  The U.S. Army, U.S. EPA and MPCA entered into a federal facilities
agreement (FFA)  in  1987 to ensure that the  environmental impacts
associated with the TCAAP site are thoroughly investigated and that
appropriate steps are taken to protect the public health, welfare and
the environment. In accordance  with the FFA,  the U.S. Army initiated
remedial activities under the Department of Defense Installation Restora-
tion Program to remove and treat contaminated groundwater at several
locations, extract contaminated  vapors from soils at two source areas
(source areas D and G) and excavate and incinerate PCB-contaminated
soils at one source area (source area D) (part of the TCAAP site).
Argonne National Laboratory (ANL), a contractor to the U.S. Army,
has prepared a remedial investigation (RI) report on the contaminated
areas within the boundary of TCAAP.  Concurrently, Camp, Dresser
& McKee, Inc. (COM), a contractor to the MPCA, prepared  an RI
report of off-TCAAP areas to determine the extent of contaminant migra-
tion from TCAAP. PRC  Environmental Management, Inc. (PRC), over-
sight contractor to U.S.  EPA, performed a risk assessment of the New
Brighton/Arden Hills Superfund site.

SITE DESCRIPTION
  The New Brighton/Arden Hills Superfund site is located in the nor-
thern part of the Minneapolis-St.  Paul metropolitan area (Fig.  1). As
presently defined, the site covers much of the U.S. Geological Survey's
New Brighton, Minnesota, 7.5-minute quadrangle. For historical and
administrative reasons, the  site is divided into two areas. TCAAP is
the source area. As shown in Figure 2, TCAAP includes 14 individual
source areas plus the  remainder of the installation. The off-TCAAP por-
tion  of the site includes portions of several municipalities. The outer
boundaries of the site include all  areas affected by contamination
originating within TCAAP.
  Within the  New Brighton/Arden  Hills study area, groundwater is
found in both bedrock and glacial deposit aquifers. There are two major
bedrock aquifers in the area—the Prairie du Chein/Jordan Sandstone
and the Mt. Simon/Hinckley. There are also four minor bedrock aquifers
in the Twin Cities Basin—the Iromon/Galesville, the Reno Member
of the Franconia  Formation,  the St.  Peter  Sandstone and the
      MILIT^RI \CTIVITIES
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Platteville/Decorah. The St. Peter Sandstone and the Plattevffle/Decorah
units are in direct contact with the overlying glacial deposits in the New
Brighton/Arden Hills and Roseville areas, respectively.
                             -TWIN  CITIES ARMY
                              AMMUNITION PLANT
                           Figure 1
     General Location of New Brighton/Arden Hills Superfund Site
  „—.. ^* |—KNO*N AREAS OF
             CONTAMINATION
                            LEGEND
             MONTTORINO WEIL

             STE 80UNDRY
            GROUND-WA1ER
            EXPOSURE AREA
                                           QUADRANT IDENTIFIER
                                         •  QUADRANT IDENTIFIER
BOUNDARY OF SURFACE
WATER BODY
                          Figure 2
                      TCAAP Site Map
  On top of the irregular bedrock surface, a series of unconsolidated
glacial sediments has been deposited. Several of these units are water-
bearing and have been affected by the spread of contaminants  from
TCAAP. In general, there are four aquifer units at the site. Unit 1 is
composed of the  surficial lacustrine deposits that form the shallow
unconfined aquifer. Unit 2 is composed of glacial Twin Cities Till, which
acts as an aquitard, preventing hydraulic communication between the
surface and the underlying major glacial aquifer. Unit 3 is composed
of the Hillside and Arsenal Sands and is the major glacial aquifer in
the area. Unit 4 is the uppermost bedrock aquifer beneath the site. It
may  be hydraulically connected to the overlying Unit 3 aquifer.

SITE BACKGROUND
  In 1978, the U.S.  Army Toxic  and  Hazardous  Materials Agency
(USATHAMA) performed an assessment of TCAAP,  which identified
14 disposal areas at the site. These areas were used for the disposal
of waste solvents, acids, caustics,  heavy metals and other production
wastes. Approximate boundaries of the disposal areas are shown in
Figure 2.
  Subsequent groundwater sampling and analyses conducted by MPCA
and the Minnesota Department of Health (MDH) found VOCs in pro-
duction wells at TCAAP, the Arden Manor trailer park well in Arden
Hills and a number of residential wells in Arden Hills,  Shoreview, New
Brighton and St. Anthony.
  The following events occurred as a result of the identification of VOC-
contaminated groundwater:
• The City of New Brighton abandoned several municipal wells and
  either placed on standby or deepened several others.
• The Village of St. Anthony used U.S. EPA/MPCA funds to decom-
  mission one well and connected a portion of the village with Roseville
  water supplies for  an indefinite, but temporary period.
• A number of  New Brighton/Arden Hills residents drawing  con-
  taminated drinking water were provided municipal water through con-
  struction of U.S. EPA/MPCA-funded water main extension.
• Residents of the Arden Manor Trailer Park drawing contaminated
  drinking water were provided  with new wells finished in an aquifer
  with potable water.  The wells were provided by Arden Manor Trailer
  Park, which was later reimbursed by the Army.
• A New Brighton resident was provided MPCA Superfund money for
  reimbursement for connection to the New Brighton municipal water
  supply.
  Army reports of investigations and studies at TCAAP (Phases I, n
and III) in 1983 and  1984 identified major and minor disposal areas
on the facility that were sources of release or threatened release of
hazardous substances (mainly VOCs). In their review of these reports,
MPCA and the U.S. EPA noted inadequate investigations and studies,
the need to address the extent and magnitude of contaminated ground-
water and the need to complete an assessment of the disposal areas iden-
tified on TCAAP.
  In 1984 and 1985, Honeywell submitted (via the Army) investigative
reports addressing VOC contamination at Honeywell-leased TCAAP
Buildings  103 and 502 (Sites I and K). The reports indicated that the
buildings' operations were a source of VOC-contaminated groundwater
migrating toward Rice Creek from Building 103 and also to the west
or southwest from the Building 502 area. As a result of these findings,
Honeywell announced a three-phase off-TCAAP investigation on Ju-
ly 28,  1984, to supplement work being conducted by MPCA to iden-
tify off-TCAAP sources of release.
  On May 28,1985, MPCA released the Phase IRI report titled Phase I
Final Report, New Brighton/Arden Hills, Minnesota Multi-Point Source
Remedial Investigation. The report identified four potential source areas
of release of VOCs in the study area that had possibly contaminated
the area groundwater. The source areas included two  areas at TCAAP
and two areas adjacent to TCAAP. Phase LA RI activities were initiated
in July 1986. The purpose of the  Phase IA RI was to further define
the nature and extent of groundwater contamination in off-TCAAP areas.
  In the spring of 1985,  the U.S. EPA initiated an investigation of the
force mains off-TCAAP because a number of documented breaks had
                                                                                                           MILITARY ACTIVITIES    883
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occurred in the line in the study area and because VOCs and other
hazardous wastes and metals had been detected in the sewer sediments
on-TCAAP.
  On June 6, 1985, the Army announced a plan to begin addressing
groundwater contamination detected on-TCAAP. The plan included a
proposed  groundwater pump-and-treat  system to address  TCAAP
groundwater  contaminated  with VOCs. The  plan  also identified
Honeywell as the coordinator of the TCAAP groundwater cleanup effort.
In 1986, the Army activated an in situ volatilization system at Sites D
and G to  remove VOCs from the unsaturated zone.

THE AGREEMENT
  To facilitate cleanup of TCAAP, the Army entered into a federal facility
agreement (FFA) with the U.S. EPA and the State of Minnesota pursuant
to Section 120 of the SARA. The TCAAP FFA, which became effec-
tive on December 31, 1987, was the first agreement to be negotiated
between the U.S. EPA and any federal agency since the enactment of
SARA in  1986. The FFA calls for the on-TCAAP RI to be carried out
by the Army, while the off-TCAAP RI is to be done by the state and
the U.S. EPA. Following completion of both RIs, the Army will prepare
the FS to evaluate alternatives for  remediating  the  entire  area of
contamination.
  Section 120 (e)(2) and (e)(4) of SARA require the U.S. EPA and the
head of the responsible federal agency to enter into an interagency agree-
ment at the end of the RI/FS to specify the agreed-upon final remedial
action and to expedite its completion. In addition, Section  120 (e)(l)
provides that the state and  the U.S.  EPA administrator will publish
timetables and deadlines. The TCAAP agreement is an effort to com-
bine these requirements into an integrated and more efficient document
that involves U.S. EPA headquarters and  the state, as well as the Army
and the U.S. EPA regional office as participants and takes effect before
the Army has finished the TCAAP RI/FS process. Thus, this FFA is
an agreement "under Section 120" rather than strictly the interagency
agreement described  in SARA Section  120 (e).
  Prior to entering into the FFA,  the Army viewed the regulatory agen-
cies,  U.S. EPA and MPCA, in an advisory capacity only. Most often,
these agencies were notified of the Army's intended actions after these
actions were finalized and the agencies' abilities to influence or impact
the actions were inhibited.

Purposes of the Agreement
  The general purposes of this  agreement are to:
•  Ensure that the  environmental impacts associated  with past  and
   present activities at TCAAP  are  thoroughly  investigated  and  that
   appropriate remedial actions are taken to protect the public health,
   welfare and the environment
•  Establish a procedural framework and schedule for developing, im-
   plementing and monitoring appropriate response actions in accor-
   dance  with CERCLA/SARA, the National Oil and Hazardous
   Substances Pollution  Contingency Plan, Superfund guidance  and
   policy,  RCRA and RCRA guidance and policy
•  Ensure cooperation, exchange of information and participation of
   the parties in such  actions
  The specific purposes of the agreement are to:
•  Identify interim remedial action alternatives appropriate for preventing
   further migration of contaminated groundwater prior to the implemen-
   tation of final remedial action(s)  for  the site
•  Establish requirements for the performance of an on-TCAAP RI to
   determine fully the nature and extent of the threat to the public health,
   welfare, or the environment caused by the release and threatened
   release of hazardous substances, pollutants or contaminants at TCAAP
   and to establish requirements  for the performance of an FS for the
   site to identify, evaluate and select alternatives for the appropriate
   remedial action(s)  to  prevent, mitigate or abate the release or
   threatened release of hazardous substances, pollutants or contaminants
   at the site in accordance with CERCLA and SARA
•  IdemifS the nature, objective  and  schedule of response actions to
   he  taken at the site;  response actions at  the site shall attain that degree
  of cleanup of hazardous substances,  pollutants  or contaminants
  mandated by CERCLA and SARA
• Implement the selected interim and final remedial action(s)
• Assure compliance with federal and state hazardous waste laws and
  regulations for matters covered by the agreement

Major Features of the Agreement
  The TCAAP FFA contains 11  major features, which are presented
below:
• Point of Contact: It provided a point of contact to assume respon-
  sibility for the Army. This was important to the U.S. EPA because
  it often could not identify the correct individual to contact regarding
  issues relevant to TCAAP.
• Shared Responsibility: It specified a shared responsibility among the
  regulatory agencies and the Army for conducting RI/FSs for the site.
• Reimbursement of Oversight Cost: It provided means of reimburse-
  ment  to the U.S. EPA of past and future oversight costs as well as
  reimbursement of these costs to MPCA and the Minnesota Depart-
  ment  of Health.
• Specific Statement of Work: It provided a specific statement of work
  for RI/FS, remedial design (RD) and  implementation of remedial
  actions (RA) at the site.
• Implementation of Interim Remedial  Measures:  It provided for
  implementing interim remedial actions at the site, a device that the
  U.S. EPA has used extensively  for remediation of contamination at
  the site (see next section).
• Integration of RCRA, Section 3004(u) and (v): Currently, the  U.S.
  EPA is in the process of delegating RCRA 3004(u)  corrective action
  authority to states. Conforming with the terms of the FFA will satisfy
  the procedural requirements of Section 3004(u) and (v) and should
  accomplish the following:
  — Preserve cost-effectiveness as a criterion for selecting remedies
  — Bypass additional, needless and duplicative RCRA requirements,
     preventing increase of paperwork  burden, staff  time and ad-
     ministrative costs
  — Provide for unity of program management and  more efficient
     allocation of resources
• Dispute  Resolution  Process:  If,  after  proceeding  through  a
  multilayered dispute  resolution process,  the parties  are unable to
  unanimously agree on the resolution of any given issue, the U.S. EPA
  administrator will make the final decision, providing a national, rather
  than a regional,  perspective. Without  giving written notice to the
  Secretary of the Army, the U.S. EPA administrator may not delegate
  this decision-making authority.
• Exemption from Permits: This provision precludes the time-consuming
  permit application process.  The Army agrees to abide  by all ARARs
  which such permits would have included.
• Applicability of Citizens Suits: While the terms and conditions of
  the FFA are enforceable by citizen suits brought pursuant to Section
  310 of SARA, the actual effects of citizen suits are expected to be
  ameliorated by the provisions for Schedule Modifications and Ex-
  tension  of Schedules. The procedures for extending deadlines, if
  invoked in a timely manner, should revise schedules affected by delays
  due to circumstances that are beyond the  Army's  control (i.e.,
  mechanical breakdowns, equipment shortages, harsh or hazardous
  weather conditions, contractor strikes, etc.), thereby providing the
  Army with a measure of extra protection from baseless or frivolous
  complaints.
• Army to Reimburse the U.S. EPA and the State: The costs incurred
  for oversight, investigation,  new wells, etc., must be reasonable, con-
  sistent with the NCP under CERCLA (including the cost-effectiveness
  criterion) and subject to Army audit before being reimbursed.
• Applicability of Penalties: The  U.S. EPA  (not the  state)  may
  administratively  levy fines against the  Army for failure to comply
  with the  requirements of the FFA. The fines stipulated in the FFA
  are lower than the maximum stated in SARA and should be avoidable
  as long as the Army uses the provisions for schedule modification/ex-
  tension and dispute resolution. Moreover, if fines are imposed but
SS4    MILITARY ACTIVITIES
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are accepted by the courts  as constituting "diligent prosecution,"
citizen suits to enforce the  FFA will be effectively precluded.

PROGRESS TO DATE
  To date, significant progress has been made for remediation of con-
taminated soils and groundwater at the site. Some of the response actions
were implemented by the U.S. Army before signing the FFA and some
were implemented after the agreement. The response or cleanup actions
may be divided  into four groups:  (1) alternative  water supplies,
(2) unilateral removal authority actions by the U.S. Army, (3) actions
with U.S.  EPA and state concurrence and (4) other actions initiated
by the U.S. EPA and/or the U.S. Army.

Alternative  Water Supplies
  The alternative water supplies include a number of hookups  of in-
dividual well owners to city water supplies and construction of inter-
connecting pipelines between cities. For the city of St. Anthony, an
interconnect to the  neighboring city of Roseville  was made so that
St. Paul municipal water supply already used in Roseville could be
transported to St.  Anthony via Roseville. The State of Minnesota cur-
rently has a  cooperative agreement with the U.S. EPA to construct a
carbon treatment system to treat water from the contaminated St.
Anthony wells.
   Another alternative water supply  is a carbon treatment system for
the City of New Brighton. This system was formally operational hi June
 1990 and was funded by the U.S. Army as part of a litigation settle-
ment. While the U.S. Army signed a ROD for the New Brighton carbon
system, the U.S. EPA never concurred with the ROD, but viewed  it
as an acceptable [to U.S. EPA] means for settling the litigation  of the
U.S.  Army by the City  of New Brighton.

Unilateral Actions by the U.S.  Army
   Unilateral removal actions by the U.S. Army are actions taken by
the U.S. Army using its own delegated removal authorities  under
CERCLA Section 104. Most of these actions were  implemented prior
to the signing of the FFA. The two most successful actions in this  group
are the in situ soil vapor extraction (ISV) system  for remediation of
contaminated soils at Site D and Site G of TCAAP (Fig. 2). These ISV
systems were implemented in 1986 and since then, each system has
removed approximately 45  tons of VOCs per site. Their operational
status is continually reported to the U.S. EPA and the state, with all
modifications to the systems mutually agreed to by all three organiza-
tions. Other actions in  this group  are groundwater pump-and-treat
systems at sites A, I and K.
   The groundwater at Site A is contaminated with VOCs. To remove
and treat contaminated groundwater at the site,  an interim remedial
action was initiated by the Army hi 1988. This remedial action consists
of a groundwater extraction and treatment system  using liquid  phase
activated carbon. Sites I and K contain VOC-contaminated soils  under
buildings. Leaks from floor drains and sewer lines are identified as
the likely  source of contamination. Honeywell, an Army tenant, cur-
rently operates these buildings and  has performed remedial actions.
These actions were implemented in 1988 and include contaminated
groundwater extraction  and treatment by air stripping. The treated
groundwater from Site K is discharged to a sewer  under the NPDES
permit issued by the state. The treated groundwater from Site I is
discharged to the TCAAP groundwater  recovery system (TORS) for
further treatment.

Actions with U.S. EPA and State  Concurrence
  The most  significant action  under this group  includes the TORS,
which includes five source control (SC) wells downgradient  of Sites
D and G and a boundary groundwater recovery system  (BGRS)  along
the southwest side of TCAAP. The objective of the BGRS was to con-
tain and prevent continued migration of contaminants downgradient of
TCAAP. To  implement.BGRS, the U.S. EPA prepared an ROD in
September 1987. The ROD provided the specific criteria for the BGRS.
After extensive negotiations among the U.S. EPA, MPCA and the U.S.
Army, the BGRS was implemented in late 1987. This phase of the BGRS
included six Unit 3 extraction wells and three air stripping units for
treating extracted contaminated groundwater.
  A review of a 90-day performance report of the system by the U.S.
EPA and MPCA indicated that the BGRS was not in compliance with
the remediation  criteria  (full capture of the contaminated  plume)
established in the ROD. To comply with these criteria, the BGRS was
expanded in 1989 to include six additional wells (two in Unit 3 and
four in Unit 4) and one additional air stripping unit. The treated ground-
water must meet maximum contaminant levels (MCL) established under
the Safe Drinking Water Act before it may be discharged to a gravel
pit on-TCAAP. Except for some background metals, all other discharge
criteria are met. The capture criteria for the contaminants require the
capture of all contaminated groundwater plume migrating off-TCAAP
in excess of 10~6 cancer risk or a hazard index of one. It is up to the
U.S. Army to demonstrate adequate capture to the satisfaction of the
U.S. EPA  and MPCA.
  Other actions under this group include on-TCAAP RI, off-TCAAP
RI, risk assessment of on- and off-TCAAP areas,  FS,  remedial design
of appropriate response actions (RD) and implementations of these
actions  (RA). The on-TCAAP RI is prepared by the U.S. Army, the
off-TCAAP RI is prepared by the state, the risk assessment is performed
by the U.S. EPA and FS/RD/RA will be conducted by the U.S. Army.
In addition,  the U.S. Army  will prepare annual monitoring reports
covering more than 300 groundwater monitoring  wells and IRAs. All
documents prepared by the U.S. Army are  reviewed by the U.S. EPA
and the state for consistency and compliance with the requirements of
the FFA.
  The total mass of contaminants removed since implementation of the
above interim remedial actions is presented in Table 1. The ground-
water contamination plume for trichloroethene (TCE) in aquifer Units  3
and 4 are presented in  Figures 3  and 4.

                             Table 1
           Status of Interim Remedial Actions at TCAAP
    IRA
   Site A
   SileD
   Site G
   Site I
   Site K
   BGRS (6 wells)
   Expand BGRS (12 wells)
   SC Wells 2 to 5
Start Dale'
09/13/88
01/29/86
02/20/86
08/15/86
08/15/86
10/19/87
01/31/89
01/31/89
                                         Mass Conlaminant Removed fibs.)2
2.13
96,300*
90,000'
NA
NA
6,800s
87.0007
25.0007
by December 1989
by December 1989
by December 1989
NA
NA
by January 1989
by June 1989
by June 1989
        Interim remedial actions at these sites are ongoing with anticipated completion dates when
        final remedial actions are implemented.

   2    Cumulative mass or organic compounds removed by the dates indicated.

   3    Between the start date and December 1989, approximately 2.5 million gallons of ground
        water have been treated at the site. Information was obtained from monthly operations
        report, dated January 1, 1990.

   4    In the summer of 1989, approximately 1,400 cubic yards of PCB-contarninated soil were
        treated at the site using an infrared thermal treatment process. Information was obtained
        from ISV operation reports, dated January 2, 1990.

   5    Information was obtained from ISV operation reports, dated January 2, 1990.

   6    Estimated VOC removal based on BGRS Annual Monitoring Report, dated May 1989
        (4,800  Ibs, through October 21, 1988), and projected to be 6,800 Ibs. by January 1989.

   7    Estimated total VOC removal based on expanded BGRS (12 wells included Site I SC-1)
        and SC wells 2 to 5 (downgradient of Sites D and G) contaminant concentration data in
        the first and second quarterly monitoring report for 1989 by Army/Honeywell dated
        December 5, 1989; and ground-water extraction data in Table I of Draft ROD for PGRS
        by Honeywell dated May 15, 1989.

   NA - Information is not available.
Other Actions Initiated by the U.S. EPA and/or the U.S. Army
  Several other actions implemented at the site were initiated by either
the U.S. EPA or the U.S. Army. Some of these significant actions are
presented below:
• Thermal treatment of 1,400 yd3 of PCB-contaminated soils at Site
                                                                                                               MILITARY ACTIVITIES    885
-------
  D; the U.S. EPA prepared the ROD and risk assessment report
• Water management study to evaluate feasible alternatives for the
  disposal of treated groundwater anticipated from the future remedial
  measures;  Phase I of this study has been completed and Phase n
  is currently underway
• Force main RI   (Site  J)   and subsequent  cleanup  measures
  •  Investigation and remediation of 83 aboveground and below ground
  storage tanks

RESOLUTION OF DISPUTES
  The FFA set forth a procedure for resolution of disputes among the
three organizations, the U.S. EPA, the state and the U.S Army. The
disputes are resolved at the project manager's level. If project managers
cannot reach an agreement on any issue within 14 days, then any party
may elevates the dispute to the Dispute Resolution Committee (DRC)
for resolution. If none  of the parties elevate the dispute to the DRC
within this 14-day period, the position of the U.S. EPA's project manager
is final with respect to resolution of the dispute. The designated members
of DRC are the Waste Management Divisional Director of U.S. EPA
Region  5, the MPCA Executive Director and the Army's Deputy for
Environmental Safety and Occupational Health.
  Since the implementation of the FFA at TCAAP, no major disputes
have arisen. The primary issues have included schedule of deliverables,
hydrogeologic interpretations and technical aspects of the deliverables.
These issues have been resolved at a project manager's level in  a
cooperative manner. The schedule of deliverables has generally been
adjusted to ensure that  quality of the documents is not sacrificed by
the need to meet a deadline. The hydrogeologic interpretations and
technical issues have been resolved by calling special meetings, with
enough  lead time for each party to assemble his/her data and to pre-
sent his/her viewpoint. This process of resolving issues or disputes at
project manager and technical levels has resulted in good cooperation
among all parties.

SCHEDULES AND WORKLOAD
  A schedule of activities for the TCAAP site is shown in Figure 5.
As  shown in this schedule, several activities are currently underway,
including the operation and maintenance of several  interim remedial
actions. All documents submitted by the U.S. Army, including per-
formance evaluation of the interim remedial actions, are reviewed by
the U.S.  EPA and state for technical adequacy and  consistency with
the requirements of the agreement. The review time established in the
agreement is 40 calendar days. However, the complex documents, such
as on- and off-TCAAP RIs or other similar documents that require longer
review time.have been granted mutually agreeable extensions. This is
to ensure that quality of the documents is not compromised by the need
to meet the rigorous and stringent schedules.
  In general, considering the large magnitude and complexity of the
site, the number and length of delays have been similar to or better
than other Superfund sites in the region.  Individual  documents
sometimes appear to  take a long time to finalize (6 months for example),
but this is due to resolving any issues on the drafts and then delaying
the  final  issuance while  resources are focused on more time-critical
projects (e.g.,  the completion of the design of an IRA).

CONCLUSION
  This paper presents highlights of the first federal facilities agreement
in the country pursuant to Section 120 of CERCLA/SARA for remedia-
tion of soils and groundwater contamination at the New Brighton/Arden
Hills Superfund site in Ramsey County, Minnesota. It discusses the
      TWIN CITIES ARMY
      AMMUNITION PLANT
                                                               Figure 3
                                              TCE Groundwater Coniamination Plume in Unit 3
Si St.   MILITARY ACTIVITIES
-------
TWIN CITES ARMY
AMMUNITION PLANT
 1.  TCE Plum* OvIhMllon vu
   conducted by U.S. Armu,
   UPCA. and thtar conwItanU
   on February 6 and 6. 1080.
 2.  Th« 2.6ppb TCE contour Dn«
   can-Mponda to on «KC*U
   Cdnew risk of on* ti a
   mlDlon Aim to (nganitktn of
   contaminated ground watv.
                                                                Figure 4
                                            TCE Groundwater Contamination Plume in Unit 4
                                    1989
                                                       '!»0
                                                                   ill! 1 941ft Si 8
                                                                                                                                   '«*
                                                                           MOAM •

                                                                           BOAH •
         	t£££££Su-
                                                                Figure 5
                                                  Schedule of Activities for TCAAP Site
                                                                                                                MILITARY ACTIVITIES    887
-------
experiences gained and progress made through the implementation of       zations and their contractors. Tb meet this challenge and ensure high
the agreement at this very large and complex site.                        quality work has required  innovative  management procedures  and
  The agreement requires that all documents  submitted by the  U.S.        prompt allocation of resources on the part of all participants. The spirit
Army be reviewed by the  U.S. EPA and the state for technical  con-        of cooperation shown by all participants in resolving  technical  and
sistency within 40 calendar days. There are several activities concur-        schedule-related issues has been crucial in successfully  implementing
rently being conducted at the site. To perform consistency tests within        the agreement.
the specified schedule is and has been a challenge for the three organi-
      MILITARY ACTIVITIES
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                     Field  Detection  Kits  for TNT  and RDX  in  Soil

                                                      Kenneth T. Lang
                                   U.S.  Army  Toxic and Hazardous  Materials  Agency
                                                     Aberdeen, Maryland
                                                 Thomas  F. Jenkins, Ph.D.
                                                     Marianne £. Walsh
                           U.S. Army Cold Regions Research and Engineering Laboratory
                                                  Hanover, New Hampshire
 ABSTRACT
   The  U.S.  Army  Toxic  and  Hazardous  Materials  Agency
 (USATHAMA) and the Naval Weapons Center, China Lake, jointly
 developed an indicator tube in the mid-1980s for the detection of TNT
 in Army Ammunition Plant effluents. The tubes were later adapted for
 use in field detection of TNT in groundwater and soil. These tubes
 have been used extensively by the Army to assist in locating explosives-
 contaminated areas and in placing monitoring wells.
   Recently, the U.S.  Army Cold Regions Research and Engineering
 Laboratory (CRREL) and USATHAMA have developed a simpler, fester
 and more quantitative method for TNT determination in soil. Soils are
 extracted with acetone and quantitation is based on production of the
 highly colored Jackson-Meisenheimer anions with strong base. Measure-
 ment is obtained with a field-portable spectrophotometer at 540 nm.
   A similar method has also been developed for RDX. The soils are
 extracted with acetone and the extracts are passed through a disposable,
 strong anion exchange resin to remove any nitrate and  nitrite present.
 RDX is then reacted with zinc and acetic acid to produce nitrite, and
 the nitrite concentration is measured using the two-step Griess reac-
 tion.  Measurement is also obtained colorimetrically at 540 nm.


 INTRODUCTION
  One of the most serious environmental problems feeing the U.S. Army
 today  is the presence of soil contaminated with munitions residues at
 military installations throughout the United States. TNT and RDX are
 the two explosives most commonly observed in munitions-contaminated
 soils because of their widespread use and their long-term stability in
 the environment. Further, because of their mobility in the soil profile,
 TNT  and RDX  pose  an  immediate  problem  for groundwater
 contamination.
  Field screening methods can be rapid, inexpensive tools for locating
 explosives-contaminated surface soils. They can be useful in initial site
 surveys to locate zones of high contamination and select samples for
 more in-depth laboratory analysis. They also can be used during site
 cleanup to accurately locate the clean soil/contaminated soil interface.


 Background of TNT Test
  As early as 1891, Janovsky1 observed that colored reaction products
 were formed when polynitroaromatic compounds reacted with alkali
 such as potassium hydroxide. Meisenheimer2 and Jackson and Earle3
 independently proposed a  quinoidal  structure  to   explain this
phenomenon. Equation  1 shows the production of the Jackson-
Meisenheimer anion  from 2,4,6-trinitrotoluene (TNT). In general,
Jackson-Meisenheimer anions for dinitroaromatics are  blue to purple
in color, while those from trinitroaromatics are red.4
                                        CH3
                                 02N
NO2

OH
H
                                                          (1)
                                        NOP
  When sulfite ion is present along with hydroxide, addition of sulfite
to the aromatic ring also can occur.5 This anion is more stable than
the anion formed from hydroxide alone,6 with stabilities extended from
approximately  30 minutes for the hydroxide complex7 to at least six
hours.6
  When the base-catalyzed reaction takes place in a ketone solution
such as acetone (Janowsky reaction), addition of the carbanion (Equa-
tion 2) can also result.8
                                                          (2)
       NO,
  These reactions have been used analytically for a number of applica-
tions. Yinon and Zitrin9 show examples of  their use  for forensic
detection of TNT in post-blast debris. Heller et al.10 used the reaction
of strong base with TNT as the basis of a field  kit for detection of low
levels of TNT in water. The use of this kit was later extended to estima-
tion  of TNT in soil extracts.11 A discussion  of their procedure, its
method  of detection,  and an assessment of its utility are presented
elsewhere.12 In general, the kit provides a field method to detect the
presence of TNT in soil, but is less useful for estimating concentration.


Background of RDX Test
  Colorimetric chemical methods for RDX have been developed for
forensic application.9 These procedures generally rely on sequential
reactions where RDX is first converted  to nitrous acid using the
Franchimont reaction (Equation 3). The nitrous acid is used to nitrosate
an aniline derivative such as sulfenilic acid (Equation 4) and the resulting
diazo cation couples to a naphthylamine (Equation 5) to form a highly
colored azo dye (Griess Reaction). Several other pairs of reagents may
be used to produce azo dyes.13 A reagent containing procaine and N,N-
dimethyl-naphthylamine is used for the test described in this paper.
Wyant14  tested several reagents and found this  combination to be best
in terms of detection capability and shelf life. The authors are not aware
                                                                                                       MILITARY ACTIVITIES   889
-------
of a field method for RDX in soil based on this reaction sequence.

        NO2

                       Acetic Acid                           (3)
              NO2
       RDX
                   Zn  	*- 3 HNO2
                      Franchimonl Reaction (1897)
HNO2  +
                                                           (4)
                                                 NR',
                                                           (5)
              Griess Reaction (1864)
 OBJECTIVE
   The objective of the research described here is to develop simple,
 rapid field methods to estimate TNT and RDX concentrations in soil.
 The chemicals and equipment needed should be usable under field con-
 ditions by analysts with only minimal chemical expertise. The method
 should not require electrical power so that measurements can be made
 at the site of potential pollution.  It should be rapid enough to allow
 decision-makers on-site to utilize the results to make judgments regarding
 the need to take additional samples for laboratory analyses or,  under
 a  cleanup scenario, continue or halt soil excavation.

 EXPERIMENTAL

 Analytical Standards
   Analytical  standards  for 2,4,6-trinitrotoluene (TNT)   and
 hexahydro-l,3,5-trinitro-l,3,5-triazine  (RDX) were prepared  from
 Standard Analytical Reference Material (SARM) obtained from the U.S.
 Army Toxic and Hazardous Materials Agency (USATHAMA),  Aber-
 deen Proving Ground, Maryland. The SARMs were dried to constant
 weight in a vacuum desiccator in the dark, and standards were prepared
 in HPLC grade acetone.

 Soils
   Soils  used  for  laboratory extraction  studies  included  field-
 contaminated and uncontaminated soils from a number of present and
 former military installations  in 10 different states.  Interference tests
 utilized a commercial potting soil obtained locally that was rich in humus
 and  uncontaminated soils from a variety  of military installations.

 Soil Extraction
   Soils were extracted by manually shaking a 20-g sample for 3 minutes
 with  100 mL  of  acetone and filtering the extracts with  Millex-SR
 disposable syringe filters.

 Removal of Nitrate and Nitrite
   Nitrate and nitrite ions were removed from acetone soil extracts by
 passing 10 mL of the extract through a disposable strong anion exchanger
 (Supelco. Alumina-SAX) at 5 mL/min.22

 Generation of Jackson-Meisenheimer Anions for TNT Test
   A pellet of potassium hydroxide (KOH) and approximately 0.2  g of
 sodium sulfite were added to 20 to 25 mL of acetone soil extracts.
 Samples were  manually shaken for 3 minutes, then  filtered through a
 Millex-SR filter unit into a cuvette. Absorbance was read at 540  run.

 Production  of Azo Dye from RDX
   Acetone soil extracts were passed through an Alumina-A strong anion
 exchange cartridge at 5 mL/min to remove any nitrate and nitrite which
 could be present. A 5-mL aliquot was acidified with 0.5 mL glacial
 acetic acid and reacted with 0.3 g of zinc dust in the barrel of a syringe
 fitted with a disposable filter unit. This  solution was rapidly filtered
 into a vial containing 17 mL of a Griess color developing solution. The
 color developing solution was prepared by dissolving 0.35 g each of
 procaine and N,N-dimethylnaphthylamine in 100 mL of 1/1 glacial acetic
 acid-water. Prior to use, this solution was further diluted 5/12 v/v with
 water.

 Spectrophotometers
   Spectrophotometers  were used to measure absorbance at various
 wavelengths  in the visible region of  the spectrum. A Coleman Junior
 n (Model 6/20) was used for laboratory tests and either a Hach DR/2
 or DR/2000 was used in the field.

 DEVELOPMENT OF TNT METHOD

 Absorbance Spectra  of Analyte Anions in Acetone
   A 2.1-mg/L solution of TNT was prepared in 95% acetone—5% water
 and Jackson-Meisenheimer anions generated as described above. The
 absorbance spectrum was obtained from 400 to 600 nm (Fig. 1). Two
 Xmax were observed,  at 462  and 540 nm, the molar absorptivities
 being 2.70 x 104 and 1.77  x 104 L/cm  • mole, respectively. This solu-
 tion  was visually red.
   A number of other nitroaromatics, nitramines, nitrate esters and
 polynitrophenols were tested under  similar conditions and the visible
 spectrum of their anions obtained  (Table 1). Clearly, several other
  0.5
- 0.3
   O.I
                                                       TNT
    400                          500                         600
                                 X  (nm)
                             Figure 1
          Visible Absorbance Spectrum  of TNT Anion in Acetone
                              Table 1
          Colors and Xmax Obtained for Acetone Solutions
    of These Compounds Treated with KOH and Sodium Sulfite
Color observed
Compound
nitrobenzene
o-nitro oluene
m-nitro oluene
p-nitro oluene
1,3-dln trobenzene
2,4-dln trotoluene
2,6-dinitrotoluene
1,3,5-tr (nitrobenzene
Tetryl
2-Mlno-WT
4-talno-MT
nitroglycerine
P£TH
BOX
t#a
Picric Acid
2,4-dlnltrophenol
TUT
This study
Hone
None
Hone
None
Purple
Blue
Pinkish purple
Red
Or enoe
Pile ycllou
Hone
Hone
Hone
Hone
Hone


•«d
Boat and Hidiolson (4)
Hone
Hone
Hone
Hone
Purplish-blue
Blue
....
Red
...

...
...
...


Beddlsh-orir^e
rellauidi-orenoe
ted
Max (400-600 m)
(rail

...
...
...
570
570
550
460 , 540
460 , 550
MO
...
...



420
430
462 , 540
 8W   MILITARY ACTIVITIES
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polynitroafomatics and polynitrophenols also give colored anions under
these conditions that would be very difficult to distinguish from TNT.
During site cleanup activities, however, the ability to detect tetryl or
TNB as well as TNT may be quite useful.

Effects of Variable Concentrations of Wbter in Acetone Extracts
  Extraction of moist field soils with acetone will result in extracts con-
taining variable concentrations of water. A test was conducted to assess
the effect of variable water concentrations on the absorbance of TNT
anions in acetone.
  A series of 1.9-mg/L solutions of TNT in acetone was prepared with
water contents ranging from 0 to 53% by weight. Jackson-Meisenheimer
anions were generated and absorbances obtained at 540 nm (Table 2).
50 /*g/g (absorbances less than 0.9 AU). Thus for daily calibration a
replicated single point standard is  sufficient.

Background Absorbance of Blank Soils
  Experiments with a variety of blank soils indicated that the color of
acetone extracts will vary from colorless to yellow. An example of the
visible absorbance  spectrum of a commercial potting soil before and
after addition of the reagents is shown in Figure 2. The initial absor-
bance of the soil extract was considerably greater between 400 and 500
nm than between 500 and  600 nm. After the extract was allowed to
react with KOH and Na-jSOj,  the absorbance  approximately doubled
over the entire range of wavelengths,  with rather large absorbances
toward 400  nm.
                            Table 2
        Effect of Various "Water Contents on the Absorbance
                    of TNT Anions in Acetone
  Concentration of water   Corresponding* soil   Absorbance (540 nm)  for
      in acetone          moisture content     1.9 mg/L TNT solution
                        (X of wet weight)
                                                                         2.0
0.0
3.0
5.9
8.9
11.7
17.4
28.2
53.4
0.0
12.2
24.8
38.7
52.5
83.4
**
**
0.076
0.183
0.181
0.158
0.140
0.136
0.054
0.014
  *   Corresponding soil moisture contents on a wet weight of soil basis if 20
     g of soil is extracted with 100 nt of acetone.


  **  Exceeds possible water present in 20 a of wet soil.
  The results indicate that absorbance is dependent on the amount of
 water present in the acetone. At intermediate concentrations of water
 in acetone (1  to 17%), however, similar absorbances (+/— 15%) are
 obtained. If a 20-g sample of wet soil is extracted with 100 mL of
 acetone, the 1 to 17% range of water in acetone would correspond to
 soil moisture contents ranging from 5 to 83 % (on a wet weight of soil
 basis). This range of moisture content should include the large majority
 of surface soils from potentially contaminated sites.

 Reagent Contact Time
  Experiments  were  conducted  to  determine if  reagent  (KOH,
 Na^O^ contact time had an effect on measured absorbance.19 Con-
 tact time was  varied from 1  to 18 minutes, after which solutions were
 filtered and absorbances measured.  All experiments were conducted
 at laboratory  temperatures (22°  +/- 2°C).
  Maximum absorbance was obtained by 3 minutes in all cases.  Ex-
 posure to the reagents for longer periods resulted in reduced absor-
 bance at 540  nm. Thus, a 3-minute reaction time was selected.
  Field tests at Eagle River Flats, Alaska, indicated that at lower reac-
 tion temperatures, 3 minutes was not sufficient for full color develop-
 ment. An experiment  to relate proper  reaction  time  to ambient
 temperature is planned. Under field conditions, a standard solution can
 be used to select the time appropriate for a specific circumstance.
  Experiments were conducted to determine the stability of the color
 after filtering.15 The results indicate that color in filtered  solutions is
 stable for at least 2 hours.

 Instrument Calibration
  Experiments were conducted to determine whether this procedure
 results in linear  calibration curves.15 Using least-squares regression
 analysis at the 95% confidence level and lack-of-fit testing, linearity
and zero intercept were established for the concentration range 0.5 to
  1.6 —
                                                                          0.8
                                                                          0.4
                                          oBefore Added Reagents
                                          • After
                                                                                            o     •
                                                                                                           0 o o
                                                                            400
                                  500
                              Wavelength {nm)

                             Figure 2
            Visible Absorbance Spectrum of Acetone Extract
         of High-Humus Potting Soil, Before and After Addition
                       of KOH and :
                                                                                                                                        600
  The results of this test indicate that a blank absorbance measurement
must be made on acetone soil extracts prior to addition of KOH and
NajSOj to account for background absorbance of humic materials that
could be present in the extracts. To determine if the factor-of-two increase
in absorbance for the potting soil extract is typical of other soils, extracts
from a series of blank soils from eight different military sites were tested.
The ratio of the absorbance at 540 nm after reagent addition to that
before reagent addition ranged from 1.1 to 3.5  with a mean value of
2.1  (Table 3). Thus, to correct for background absorbance, the initial
blank reading should be doubled and subtracted from the absorbance
reading obtained  after addition of the  reagents.

Extraction Efficiency of Field Procedure
  For a field method to provide accurate estimates of TNT concentra-
tion in the soil, the extraction step must be rapid. Previous extraction
                             Table3
    Absorbance Measurements for Acetone Extracts of Blank Soils,
           Before and After Addition of KOH and Na2SO3
                                             Absorbance (540 nm)
Sample location
USATHAHA Standard Soil
Keystone Ordnance Works
Lake Ontario Ordnance Works
Susquehama Ordnance Depot
Ran" tan Arsenal
Hawthorne Army Anrnunition Plant
Hastings East Industrial Park
Fort Hancock
We I don Springs Training Area
Before
0.002
0.001
0.003
0.003
0.005
0.000
0.019
0.005
0.123
After
0.007
0.003
0.005
0.004
0.015
0.002
0.030
0.006
0.140
Ratio after/before
3.5
3.0
1.7
1.3
3.0
--
1.6
1.2
1.1
                                                       x = 2.1
                                                                                                               MILITARY ACTIVITIES    891
-------
studies  indicated  that  long  extraction times were  required when
acetonitrile or methanol were used as  the extraction solvent.16
  In order to determine how rapidly acetone will extract TNT from
soil, 16 field-contaminated soil samples from nine different sites were
extracted with acetone using 3 minutes  of manual shaking. An aliquot
of the extract was removed and the remaining soil/acetone slurries were
placed in an ultrasonic bath for 18 hours. Both sets of extracts (3 minutes
and 18 hours) were analyzed by RP-HPLC as described elsewhere;15-17
the  results are presented in Table 4. The average recovery after 3 minutes
of manual shaking with  acetone was 96.1% of that obtained with the
more exhaustive procedure,  indicating that acetone is an excellent
extraction solvent with respect to its extraction kinetics.
                            Table 4
       Comparison of Extraction Efficiency of Field Procedure
            and Standard Laboratory Procedure (TNT)
5**Dle Or loin
VI 90 Chealcal Pl«m
Ha-thome AAP
Netv-atta Ordnance Uork»
Nebraska Ordnance Uorfc»
Naitlnge E*it Industrie! Park
Ueldon Spring* Training Area
larvanan Ordnance Plant
Ueldon Sprlngi Training Area
Hawthorn* AAP
Nebraska Ordrwnc* Uorki
Bar 1 tan Arterial
Netoraika Ordnance Uorka
L*ifngton-Blu»gr«i Depot
Chickaaaw Ordnance Uorkj
Hawthorne AAP
Midori Springs Training Area
TKT cone
Field extraction
orocedure*
11.7
4.53
0.065
340
67.6
0.96
21.5
163
5.7V
63.5
71.7
0.59
5.90
0.21
0.79
0.075
:emration (no/g)
Laboratory extraction
procedure**
13.4
4.75
0.071
349
66.8
1.26
23.2
176
5.65
67.9
BO. 6
0.32
7.11
0.16
0.90
0.077
Recovery by
field extraction
aethodl
o7.3X
95.41
91. 5X
97.41
96.31
76.21
92. BX
9Z.6X
102. 5X
93.5*
89. OX
121.91
83. OX
131 -3X
87. flX
97.41
                                                         96.1
                                                         13.6
 •  20 g aoll •haken with acetone for 3 Minute*.
 " 20 e *oU extracted with acetone (or 16 hewn in conic bath.
 (  Relative to laboratory extraction Mthod.
Comparison of TNT Concentration Estimates for Soil Extracts
  The extracts obtained after manually shaking the soil with acetone,
as described above, were also analyzed by a colorimetric procedure
utilizing the Jackson-Meisenheimer anions. A 20-mL sample of the
extract was placed in a scintillation vial, KOH and sodium sulfite were
added and the vials were shaken manually for 3 minutes.  The vials
were allowed to stand for 5 minutes and the solution filtered into a clean
cuvette. The initial absorbance, before the reagents were added, was
doubled and subtracted from the absorbance obtained after reagent
addition, and the resulting difference was used to estimate TNT con-
                              Table 5
          Comparison of Colorimetfic and RP-HPLC Analysis
                      of Soil Extracts for TNT
*M
VI00 Ui
new! hor
uebratt
Met* ML
KHI ing
Mtidon
tartan
Meldon
uwlKw
tMxa*L
Untan
*t*r*tk
Leitr^E
Qtuu*
mMth»r
Wltt^
plo onoln
>wlcal Plant
rie AAP
• Ordnance wen*
j Ordnance yorti
4 fail Induttrial Part,
iprlrve, Training Are.
n Ordnance Plant
iprin^a Trainlno ATM
n« AA^
a Ordnance WO'it
ArMnil
• Ordnance Wfti
on-llurflfBtt D*pM
«• Ordnance ^»'i»
rie AAP lift!
*""" """'"• "~

13. S
5.49
i.je
572
».5
>.02
I.1 *
U5
5.6?
1^
as. 3
0.38
15 0
•£
l.W
0 !!
erhod 8P-IVIC itfthod
11.7
t.53
0.06S
5iO
67.6
0.96
Z1.5
163
5.JV
63.5
71.7
O.JV
5.«
0.21
0.79
0.075
RP-HPtc wrhod
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2.72
157
2.7
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-------
                           Table 6
           Comparison of Results of Field Samples from
        Umatilla Depot Using Field and Laboratory Methods
                  TNT concentration
             Field method     RP-HPLC  lab method
•-»""*r— — 	
lb
2a
3b
3a
4a
5a
6a
8a
9a
lla
12a
1060
3560
704
3180
4490
2530
84
102000 f
6610
716
109
2250
7430
1180
4030
8520
3990
131
38600 f
7690
1300
183
   Both laboratory  and  field method results are
   reported on a dry  weight of soil basis to
   allow direct  comparison.

   Results  for this sample  were  very  different
   than observed for  others and,  because  of very
   high values,  the results were not  included  in
   correlation analysis.
for this sample and the TNT concentration was an order of magnitude
higher than for any of the other samples. The correlation for the re-
maining 10 samples was excellent, with an R2 value of 0.865 which
was significant at the 99% confidence level. The slope of the best fit
relationship was 0.627, indicating the field procedure, on the average,
gave results only about 63% as high as the laboratory results.
  Two factors may  have contributed to the low results for the field
method. First, an excessively long reagent contact time prior to filtra-
tion was used. Thus, the absorbance would have been reduced relative
to its maximum value.  Second, the TNT concentrations in the Umatilla
soil were much higher than those in the other field-contaminated soils
tested, and the percentage extracted in the short extraction time used
by the field method could have been reduced compared to the 18-hour
extraction  with acetonitrile used in the laboratory  procedure. Never-
theless, the field results were encouraging for a first test.
  An additional field test was conducted at Eagle River Flats, Alaska.
All soils except  one were determined  to be free  of TNT and other
nitroaromatics by the field procedure, and these results were verified
by the standard laboratory method.17 One yellowish extract developed
     0.8
     0.6
     0.4
     0.2
      400
                      480             560
                          Wavelength (nm)

                          Figure 4
   Visible Absorbance Spectrum of the Azo Dye Produced from RDX
640
            a greenish color upon reaction with KOH and NajSOj and was found
            to contain 2,4-DNT at about  30 /tg/g. Reaction with 2,4-DNT stan-
            dards produces a bluish color which, when combined with the yellowish
            background, results in the observed greenish color. This color faded
            rather quickly,  however, unlike color produced by TNT.

            DEVELOPMENT OF RDX  METHOD

            Absorbance Spectra for Azo Dye Produced from RDX
             A 4.0-mg/L solution of RDX was prepared in 97% acetone-3% water
            and the azo dye produced as described above. This solution had a bright
            pink color. The absorbance spectrum shows a ^max at 535 nm (Fig.
            4), and the molar  absorptivity is 1.67 x 104 L/cm  mole. The same
            azo dye also is  produced when HMX, NG, NC or PETN are treated
            under similar conditions.

            Effects of Variable Concentrations of Water in Acetone Extracts
             In the field, soil extracts will be obtained by manually shaking 20
            g of soil with 100 mL of acetone. Since the soil will be moist in most
            cases, water will be a component of the soil extracts. An experiment
            was performed to see how variable amounts of water affect the produc-
            tion of the azo dye.
             To simulate the extracts obtained from soils with moisture contents
            ranging from 5  to 100% (wet weight basis), 10-mL aliquots of a solu-
            tion containing  2.3 mg/L of RDX were mixed with either 0.1, 0.2, 0.3,
            0.5, 1.0 or 2.0 mL of water. The azo dye was produced  as described
            previously. Absorbance was found to vary with the amount of water
            present (Table 7), with maximum absorbance for the case simulating
            a soil  with a moisture content of 25%  (wet weight basis).
                                       Table?
                   Effects of Various Water Contents on the Absorbance
                               Obtained from RDX Tests
Volume (mL) water
added to 10 mL
acetone
0.1
0.2
0.5
1.0
2.0
Corresponding soil
moisture content
It of wet weiohtl*
5.0
10
25
50
100
Absorbance (540 nm)
for 2.3-mg/L
RDX solution
0.150
0.3 0.3
0.425
0.421
0.399
             Corresponds to soil moisture content  if 20 g of wet soil is
             extracted with 100 mL of acetone.
Reagent Contact Time
  Development of the azo dye from RDX is a two-step procedure. First,
the RDX is reacted with zinc dust and acetic acid to produce nitrous
acid. The nitrous acid then reacts with a Griess color reagent to produce
the azo  dye.
  The amount of time the RDX is allowed to react with the zinc dust
and acetic acid is critical.22 Initial experiments with RDX dissolved
in acetone indicated that a 10-minute contact time was required to reduce
RDX. However, if a small amount of water was present in the acetone,
as will be the case with soil extracts, the reaction kinetics were much
faster. Contact times exceeding 30 seconds resulted in less nitrous acid
production, presumably because the nitrous acid was further reduced
to ammonia. Once the nitrous acid is produced, the solution must be
filtered to remove the zinc dust. Because of the fast kinetics, this filtra-
tion is conveniently performed by reducing the RDX in the barrel of
a syringe fitted with a disposable filter unit as described previously.
Once the filtered solution is added to the color developing solution,
full color development takes approximately 15 minutes (Fig. 5). The
color is stable for several hours.
Background Absorbance from Blank Soils
  The acetone extracts from soils high in humic material will be yellow.
However, once the acetone extract is acidified and mixed with the color
reagent, the humic material precipitates and may be removed by filtra-
tion. Experiments22 with a wide variety of blank soils showed that
background was  negligible in all cases.
                                                                                                       MILITARY ACTIVITIES   893
-------
     05
 ~  04|	
  o
  J3
  5  0.2
  i/i
  J3
  t
99.0
98.3
105
9B.5
95.5
99.7
92.6
X » 98.4
S = 3.8
 •   20 3 soil shaken with acetone for 3 minutes.
 **  20 g soil extracted with acetone for 18 hours in sonic bath.
 I   Relative to laboratory procedure.
Comparison of RDX Concentration Estimates for Soil Extracts
  Eleven field-contaminated soils were  used to compare the RDX
concentrations estimated by the field method with those obtained by
RP-HPLC analysis.17 The results using  the field method were cor-
related with those obtained by the HPLC method for both RDX alone
and the sum of RDX and HMX (Table 9). The correlation for RDX
resulted in a slope of 1.1 and an R- of 0.986 (Fig. 6). The correlation
with RDX plus HMX resulted in a slope of 1.2 and an R2 of 0.990.
Paired t-tests indicated that the estimates of RDX concentration obtained
by the field procedure were  not significantly different  from those
obtained by the HPLC procedure for RDX alone or for the sum of RDX
and HMX.

Effect of the Presence of TNT in  Soil Extracts
  For (he RDX field method, the presence of RDX is indicated by the
development of a  pink color. As shown in Table 9, some other colors
\vere produced from extracts  of field-coniaminated soils. Red  was
produced in those soils containing very high concentrations of RDX
(i.e..  greater than  1  mg/g).  Orange was produced in those  soils
containing high concentrations (i.e.. greater than 50 jig/g) of TNT or
                             Table 9
         Comparison of Colorimetric and RP-HPLC Analysis
                     of SoU Extracts for RDX
                                                                                           BOX concentratii
	 Sarole origin 	
Nebraska Ordnance Plant
Hawthorne AAP
Bari tan Arsenal
Nebraska Ordnance Plant
Nebraska Ordnance Plant
Nebraska ordnance Plant
Hawthorne AAP
Nebraska ordnance Plant
Nebraska ordnance Plant
Nebraska ordnance Plant
Nebraska Ordnance Plant
field
color (Metric
10M
za
10.5
2.66
not
10.0
5. 52
129
15.6
20.5
1.74
u>» ™™,tr.tlon (« Color
tP-KPt,C Method
1247
127
J.M
3.65
1143
19.0
2.6
104
13.6
59.9
-------
TNB, as determined by RP-HPLC. While standards of TNT or TNB
alone do not produce a color, standards containing RDX and TNT result
in the same orange observed in some soil extracts. Nitroaromatic com-
pounds, such as TNT and TNB, may be reduced to aminoaromatic com-
pounds in the presence of zinc and acid.  We speculate  that these
reduction products can be nitrosated by the nitrous acid produced from
RDX and, like sulfenilic acid or procaine, couple to the naphthylamine
in the color-developing reagent, producing another azo dye. Thus, in
the field, development of a pink to red color indicates that RDX is the
principal contaminant,  while development of an orange color is evidence
for both TNT and RDX together.
  One soil extract developed a brownish-yellow color. As determined
by RP-HPLC, this soil was also contaminated with TNT (> 745 /tg/g),
2,4-DNT (42.7 /
-------
   Three-Dimensional  Groundwater  Quality  Modeling  in  Support  of
         Risk Assessment at  the  Louisiana Army  Ammunition Plant
                                                   Grant Anderson
                                                  Donald Koch, RE.
                                                 Peter Mattejat, RE.
                                      Engineering Technologies Associates, Inc.
                                                Ellicott City, Maryland
                                                      Robin Stein
                                 U.S. Army Toxic  and Hazardous Materials Agency
                                                 Aberdeen, Maryland
ABSTRACT
  Regional, three-dimensional, groundwater flow and solute-transport
models were constructed at the Louisiana Army Ammunition Plant
(LAAP). This work was performed in support of a Feasibility Study/Risk
Assessment primarily  focused on the problems  of nitroaromatic
contamination of the shallow groundwater at the site.
  LAAP is located in the northwest portion of the State of Louisiana
on lands situated in Bossier and Webster parishes, 22 miles east of
Shreveport. Previous investigations have revealed groundwater problems
from several sources: (1) wastewater (pink water) leaching  pits, (2)
unlined ponds containing metals manufacturing wastes, (3) abandoned
landfills, (4) explosive loading areas and (5) burning ground areas.
  One of the primary waste products of an ammunitions plant is pink
water, the common name for wastewater contaminated with explosives
such as 2,4,6-TNT or RDX. Pink water was dumped in various lagoons
across the site for nearly forty years. Some of the explosive compounds
and their by-products are toxic. The objective of this modeling study
was to predict the future concentrations of these toxic compounds and
their location in groundwater as part of the feasibility  study risk
assessment.
  MODFLOW, a numerical model published by the U.S.  Geological
Survey, was used to simulate the regional groundwater flow at the site.
The flow system was represented as three aquifers. The top aquifer was
an unconfmed aquifer in the upper Pleistocene section. The second
aquifer included the lower Pleistocene and the upper Eocene Sparta
Sand. The third aquifer comprised the Paleocene/Eocene Wilcox-Carrizo
aquifer.
  The output from MODFLOW was used as input to a translation pro-
gram,  PREMOD3D,  to convert potentiometric  heads to three-
dimensional velocity vectors,  which  are in turn used as  input  to
RAND3D,  the solute-transport program.
  RAND3D is a three-dimensional solute transport model based on
the random walk algorithm. Several significant improvements were made
to the model for this study. The program allows the user to  simulate
the movement of contamination and includes the effects of advection,
dispersion, retardation and decay. The temporal progression of the plume
is graphically displayed on the computer screen during the simulation
at a scale selected by the user. RAND3D simulated the  fate of the
contamination at each of the six sites.

INTRODUCTION
  The objective of the study was to define the regional flow system
and the fate of the groundwater contamination at six areas within the
Louisiana Army Ammunition Plant (LAAP) in support of the feasibility
study/risk assessment being performed. The Louisiana Army Ammuni-
tion Plant is a government-owned  and contractor-operated facility in
northwestern Louisiana where munitions are loaded and packed. The
plant was constructed in 1942 and has been in continuous operation
since. Munition loading and waste disposal operations have contaminated
groundwater at this site in a number of specific locales: Area P, Burning
Ground No. 8, Burning Ground No. 5, Landfill No. 3, the Oily Waste
Landfarm and the M-4 Lagoon. Figure 1 shows the locations of these
areas and the general location of LAAP.
                         Figure 1
                      LAAP Study Sites
  The area of greatest concern is Area P. Pink water, the common name
for water containing dissolved nitroaromatic compounds, was dumped
into unlined lagoons at Area P for nearly forty years. Previous investiga-
tions have yielded conflicting information on the size of the plumes
and the direction of contaminant movement. Contamination has been
found off-site and in what were thought to be up-gradient monitoring
wells. Some of the more pressing questions included:

• Where is the contamination going? Previous studies suggest a west-
  southwest movement off the site toward the municipal well field of
  Doyline.
• Are any of the three municipal well fields located within a 3-mile
  radius of Area P going to be affected  and when?
• Is the LAAP well field itself drawing the contamination into deeper
  horizons?
• What will be the effect on the contaminant plumes if the LAAP is
  decommissioned and on-site pumping  stops?
8%   MILITARY ACTIVITIES
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  A regional, steady-state three-dimensional groundwater flow model
was developed and calibrated to both steady-state and transient condi-
tions. This flow model was used as  input to a random walk solute
transport model.

GEOLOGY
  The flow system at the LAAP was represented by three aquifers (Fig.
2) At the surface there are Pleistocene terrace deposits composed of
alternating beds of mixed sands, silts and clays typical of Mississippi
Coastal Plain sediments. For purposes of hydrogeologic modeling, the
Pleistocene  interval was divided  into  two aquifers. The aquifer
boundaries were defined by the water table surface on the top and a
semicontinuous clay layer on the bottom, and it is known as the Upper
Terrace. This clay was used as the boundary between the top and the
middle aquifer. However, the Upper Terrace is not continuous and
pinches  out in the southeast section of the model  area.
        LAAP X-SECTiON      A  -  A
     300
     200--
     -100
     -200
     -300-

     -400

     -500-

     -600
                              CANE RIVER CLAY
                          W1LCOX-CAHWZO AQUIFER
                                          12
                                                           18
                              (Thousands)
                           Figure 2
                  Regional Geographical Section
  Constant head nodes were used at the edges of all layers to simulate
 the continuation of the aquifers. The constant heads were based on
 historic water levels, topography and adjustments made during calibra-
 tion where data were sparse.
  The middle aquifer is comprised of the lower Pleistocene terraces
 and the Eocene Sparta sand below. The hydrogeologic characteristics
 of the lower Pleistocene are similar to the Sparta and the two units were
 combined into one aquifer known as the Lower Terrace/Sparta. The
 Sparta lies unconfonnably below the Pleistocene terraces and consists
 of nonmarine massive sands, silty sands'and silty shales, with occasional
 lignite and lignitic shales.
  Below the Sparta is the Cane River Formation, the middle member
 of the Eocene Claiborne  Group. It consists primarily of marine clay
 with abundant foraminifera, but also contains some silt and shale. The
 Cane River, where present, forms the confining layer between the second
 and third aquifers.
  The deep aquifer, though it is called the Wilcox-Carri/o, is actually
 composed of mostly Wilcox Group at the LAAP site. The Wilcox group
 sediments consist mainly of nonmarine,  white to grey, thin-bedded,
 micaceous sands and sandy shales with numerous thin lignites which
 lie on the Midway Group. The group is from upper Paleocene to lower
 Eocene in age. Regionally, the sequence varies in thickness from 350
 to 1000 feet;  however, thicknesses at LAAP only reach 550 feet.
  The Midway Group was formed during the stand of the early Tertiary
Sea and consists of the basal uniform marine black shale 500 to 600
feet thick. The clays are described as dense and are considered to be
an effective lower confining layer to the aquifer system.
FLOW MODEL
  The USGS MODFLOW model was used to simulate the regional
groundwater flow at the arsenal. The groundwater flow system was set
up as a three-layer model. The first layer was the Upper Terrace in
the unconfined top Pleistocene terrace interval. The second layer was
made up of the Lower Terrace/Sparta in the confined aquifer made up
of the bottom Pleistocene terrace interval plus the Sparta sand that lies
beneath. The bottom aquifer was the Wilcox-Carrizo located between
the Cane River Formation and Midway confining beds. The Cane River
Formation was modeled as  a  confining layer.
  A 54-column by 30-row model grid was developed (Fig. 3) to simulate
an area large enough to permit accurate simulation of well-field pumping
on the LAAP and local municipalities; the grid  also is spaced close
enough for contamination simulation. The minimum grid spacing was
900 feet. The model was calibrated at steady-state using the monitoring
well level data for all three aquifers. The average difference between
the model and actual data was 0.06 feet and the  root-mean-square
difference was 4.76 feet (73 wells in the Upper Terrace and Lower Ter-
race/Sparta aquifers). The calibrated water levels for the three layers
are shown in Figures 4  to 6.
                           Figure 3
                          Model Grid
                            Figure 4
            Calibrated Water Levels Upper Terrace Aquifer
SOLUTE TRANSPORT
  Solute transport was simulated at each site separately, as differen-
tiated from the regional flow model.  The program PREMOD3D
calculated the groundwater velocities at each contamination site based
on the calibrated water levels. The three-dimensional random walk
                                                                                                          MILITARY ACTIVITIES    897
-------
model RAND3D utilized these velocities to simulate the solute transport
at the six sites.
  The explosive compounds simulated were the compounds found in
the greatest concentrations and presented the greatest potential risks
based on their toxicity. The most common contaminant was RDX, but
other pollutants such as TNT, DNT and TNB also were simulated. Initial
conditions of the pollutants were taken from previous remedial investiga-
tions. Figure  7 shows the  initial RDX plume at Area P for the Upper
Terrace aquifer and Figure 8 shows the initial RDX plume for the Lower
Terrace/Sparta aquifer.
                         Figure 5
      Calibrated Water Levels Lower Terrace/Sparta Aquifer
                           Figure 6
           Calibrated Vtfcter Levels Wilcox-Carrizo Aquifer
  The RAND3D model simulated solute transport for a total of 100
years at time steps of five years. Figures 9 and 10 show the RDX plumes
after 50 years for the Upper Terrace and Lower Terrace/Sparta aquifers,
respectively. Figure 11 shows the corresponding screen graphics displays
of plan view and cross-sectional  view  generated by the RAND3D
program for the simulation of 50 years. Figures 12 to 14 show the results
after  100 years of simulation. Note that at this point RDX is shown
seeping into Boone  Creek via the Lower Terrace/Sparta aquifer.
  Similar simulations were undertaken at the other five sites. Like Area
P, four other sites. Burning Grounds No. 5  and 8, Landfill No. 3  and
the  Oily Waste Landfarm, showed contamination seepage into Boone
Creek during the 100 year transport simulation. The M-4 Lagoon in
comparison had  contamination seepage into Clarke Bayou.
                                                                                                  Figure 7
                                                                                        Area P Initial RDX Plume (ppb)
                                                                                            Upper Terrace Aquifer
                                                                                                  Figure 8
                                                                                        Area P Initial RDX Plume (ppb)
                                                                                            Lower Terrace Aquifer
          Figure 9
Area P RDX Plume after 50 Yrs
     Upper Terrace Aquifer
       MILITARY ACTIVITIES
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                           Figure 10
                 Area P RDX Plume after 50 Yrs
                     Lower Terrace Aquifer
                                                        9501
                                                       9581
                           Figure 11
                  Area P RDX Plume after 50 Yrs
                     RAND3D Screen Display

  Sensitivity analyses were performed because of the uncertainty in
the input parameters. The sensitivity of assumptions regarding adsorp-
tion, dispersivity, porosity, recharge at Area P and plant closure of the
LAAP was tested.

CONCLUSION
  A successful flow model of the LAAP groundwater was created with
three layers: the Upper Terrace aquifer, consisting of Pleistocene alluvial
terraces; the Lower Terrace/Sparta aquifer, consisting of Pleistocene
                                                                       alluvial terraces and the Eocene Sparta member of the Claiborne Group;
                                                                       and the Wilcox-Carrizo aquifer, consisting of the Eocene Carrizo Sand
                                                                       and Wilcox Group. The Lower Terrace/Sparta aquifer and the Wilcox-
                                                                       Carrizo aquifer are hydraulically separated by the Eocene Cane River
                                                                       Formation, a thick marine clay.
                                                                                                   Figure 12
                                                                                         Area P RDX Plume after 100 Yrs
                                                                                              Upper Terrace Aquifer
                           Figure 13
                 Area P RDX Plume after 100 Yrs
                      Lower Terrace Aquifer

  The groundwater flow in the shallow aquifers (Upper Terrace and
Lower Terrace/Sparta) at LAAP is dominated by the surface topography
and surface water system. The direction of groundwater flow is generally
towards the streams which bisect the LAAP. Boone Creek is the major
groundwater discharge area with five of the six sites showing contamina-
tion seepage into this stream.
  The Cane River Formation is a clay layer underlying  the Upper
Terrace and Lower Terrace/Sparta aquifers under most of the LAAP
(and all of the area known to be contaminated). It effectively stops con-
tamination in the shallow aquifers from migrating to the Wilcox-Carrizo
aquifer which is the source of drinking water for the LAAP and other
nearby towns. This conclusion is supported by the results of the intensive
water level monitoring  program.
  Area P was the major disposal area for pink water at the LAAP. It
is the area most heavily contaminated with explosive compounds. RDX,
TNT and total DNT were simulated for this site. The simulation results
                                                                                                           MILITARY ACTIVITIES    899
-------
indicate the existing groundwater contamination at Area P will travel
east through the Lower Terrace/Sparta aquifer to Boone Creek, which
is in the opposite direction of Doyline community. After 100 years, 2%
of the existing (1989 RDX concentrations in groundwater) RDX enters
Boone Creek or its tributaries. After 100 years, 3% of the existing (1989
TNT concentrations in groundwater) TNT enters Boone Creek or its
tributaries. After 100 years, 12% of the existing total DNT (1989 2,4
and 2,6 DNT concentrations in groundwater) reaches Boone Creek or
its tributaries.  Under the model setup  assumptions,  no explosive
contamination from Area P crosses the LAAP boundaries.
                                                       9371
                                                       3371
                            Figure 14
                  Area P RDX Plume after 100 Yrs
                      RAND3D Screen Display

  Burning Ground 5 (BG5) is an area used for the disposal (burning)
of explosives. Open  burning was practiced before 1986. RDX, TNT
and total DNT were simulated for this site. This site is adjacent to Boone
Creek and a tributary. The simulation results indicate the  existing
groundwater contamination at BG5 will travel to the adjacent streams
with most of the RDX, TNT and DNT contamination reaching surface
water within  twenty-five years.
  Burning Ground 8 (BG8) was an area used for the disposal (burning)
of explosives and as a  sanitary landfill. There  were  also pink water
lagoons at this site. RDX, TNT and TNB were simulated for this site.
The  simulation results  indicate the existing groundwater contamina-
tion  a(  BG8 will travel  east to  Boone Creek through the Lower
Terrace/Sparta  aquifer. After 100 years, approximately 80% of the
existing RDX.  TNT and  DNT contamination enters Boone Creek.
  Landfill 3 (LF3) was the site of pink  water lagoons and later a land-
fill for construction debris. RDX was simulated at this site. The simula-
tion results indicate the  existing groundwater contamination will travel
west  to  Boone  Creek  through  the Upper  Terrace  and  Lower
Terrace  Sparta aquifers  After 100 years. 98 <£ of the existing RDX enters
Boone Creek or its tributaries.
   The Oily Waste Landfarm (OWL) is an area where oily wastes and
 chlorinated solvents were disposed of by landfarming. TCE has been
 detected in groundwater at this site in small concentrations. A theoretical
 slug source of contamination representing a conservative pollutant was
 simulated. After 50 years, 99% of the contamination has entered Boone
 Creek and  its tributaries.
   The M-4 Lagoon was  used for the retention of wastewater from an
 electroplating operation until 1964.  No groundwater contamination was
 detected by monitoring wells at this site. A theoretical release of a con-
 servative pollutant was simulated at this site. The pollutant travels west
 to Clarke Bayou and after 100 years, 98 % of the contamination enters
 Clarke Bayou.
   The largest uncertainty in the above predictions is the travel time of
 contaminant movement.  The source of this uncertainty is the lack of
 knowledge  regarding the adsorption of the explosive chemicals onto
 the  aquifer sediments.  Adsorption retards the movement  of the
 chemicals. Sensitivity analysis was performed to quantify the magnitude
 of the uncertainty.  The following table shows the impact of different
 adsorption assumptions on the speed of contaminant travel. Data in Table
 1 report the number of years when 50% of the initial contamination
 seeps from the aquifer into surface water.

                             Table 1
           Retardation Sensitivity - Years for 50% Removal
Retardation Assumption
Site Contaminant Base Case None
Area P


BG5


BG8


LF3
OWL
M-4 Lagoon
RDX
TNT
DNT
RDX
TNT
DNT
RDX
TNT
TNB
RDX


> 100(98%)
>100(97%)
>100(88%)
7
7
6
11
5
7
24
23
60
48
50
48
5
4
3
5
3
4
7
23
60
High
> 100(100%)
> 100(100%)
> 100(100%)
60
37
30
> 100(55%)
13
21
99
> 100(64%)
>100(100%)
In the above table, where the time to 50% removal from the aquifers
is greater than 100 years, the percentage of the initial contamination
remaining in the aquifers after 100 years is in parentheses.
  Dispersion is another source of uncertainty in the model predictions.
Higher dispersion causes the initial plumes to spread out more, thus
lowering concentrations.  The mean travel  path of the plume is not
changed.
  Another source of uncertainty in the  model is effective porosity.
Porosity increases travel times for larger porosities. Thus the impact
is similar to that of adsorption.  Porosity varies over a much smaller
range than adsorption (retardation), however, so it is a much less
sensitive parameter.
  The impact on contaminant transport of shutting off the LAAP water
supply wells was simulated. Shutting off the water supply wells caused
water levels in the Wilcox-Carrizo aquifer to recover. The recovery was
virtually complete within five years. There were no changes in the water
table and potentiometric surface of the Upper Terrace and Lower Ter-
race/Sparta aquifers; thus, the shut-down of the water supply wells will
have negligible impact on the predictions of contamination fete and
transport.
  The impact of leakage from the Area P lagoons on groundwater flow
was simulated. The steady-state groundwater flow rerun was performed
with a significant mound in the water table at the Area P lagoons. This
mound in the water table changed groundwater velocities slightly. The
contamination in Area P spread out radially from its initial position
and after 100 years, the plume was distributed over a wider area to the
north, west and south than it was with the calibrated steady-state flow
model. The  fate of almost all of the contamination, however, was still
Boone Creek and its tributaries. A very small amount (< 1%) traveled
south and west in the Lower Terrace/Sparta aquifer at Area  P.
-------
         Arsenic-Contaminated  Groundwater  Treatment  Pilot  Study
                                                         Wayne Sisk
                                              Walter J. Wujcik, Ph.D.,  RE.
                                                         USATHAMA
                                          Aberdeen  Proving Ground, Maryland
                                              William  L. Lowe, Ph.D.,  P.E.
                                             Kilyur N. Panneerselvam, P.E.
                                                         Peter Marks
                                                     Roy F. Weston, Inc.
                                                West Chester, Pennsylvania
 ABSTRACT
  Groundwater treatment for the removal of contaminants may be needed
 at a number of U.S. Army installations, including Army depots. Treat-
 ability testing of potentially applicable technologies may be needed to
 facilitate design and operation of treatment systems. The study described
 here is a treatability test for the removal of arsenic from groundwater.
 The goal of the study was to evaluate the effectiveness of ion exchange
 (IE), granular activated carbon (GAC) and activated alumina (AA) for
 the removal of arsenic from groundwater.
  Laboratory IE, GAC and AA isotherms were conducted to select the
 two best performing carbon and resin types and the operating pH for
 the carbon and alumina media for further testing. Pilot-scale continuous
 flow column tests were conducted at Sharpe Army Depot in Lathrop,
 California, using the two carbons (Calgon Filtrasorb 400 and Hydro-
 darco 3000) and the two resins (Amberlite IRA 402  and lonac A-641)
 selected during the isotherm studies. Alcoa F-l AA was also used during
 the pilot-scale continuous flow column tests. The carbon and AA were
 tested at an adjusted pH of 4.0 and the resin was tested at natural pH.
 A pilot-scale, conventional packed column air stripper was  used to
 remove volatile organics (primarily trichloroethene)  from the ground-
 water prior to treatment by the pilot-scale columns. The data from the
 laboratory and pilot study were analyzed and a report was prepared
 to present the results and conclusions. The study concluded that arsenic
 can be removed to the U.S. EPA MCL for arsenic of 50 ug/L and that
 AA provided significantly longer runs (as measured by bed volumes
 of water treated) than either GAC or  IE resins.

 INTRODUCTION
  Groundwater treatment for the removal of contaminants may be needed
 at a number of U.S. Army installations, including Army depots. Treat-
 ability testing of potentially applicable technologies may be needed to
 facilitate design and operation of treatment systems. Sharpe Army Depot
 (SHAD), located in Lathrop, California, presently has a groundwater
 treatment  system for  the removal of trichloroethylene (TCE).  The
 groundwater also contains arsenic, possibly of natural origin, and there
 may be a  need to remove the arsenic prior to discharge.
  The goal of this study was to examine, via pilot-scale testing,  the
 possibility of arsenic removal from SHAD groundwater by ion exchange
 (IE), granular activated carbon (GAC) and activated alumina (AA)
 processes.

 BACKGROUND
  Arsenic (As) can occur in four oxidation states in water (+5,  +3,
 0 and -3), but generally is found in the trivalent and pentavalent states.
At low pH, pentavalent arsenic (As (5)) exists primarily as H3AsO4.
Between pH 3.0 and approximately pH 6.5, the predominant  form is
      ^, while from pH 6.5 through pH 12.5, HasO4"2 predominates.
Above pH 12.5, Aso4~3 is the predominant species. At all pH values
below approximately pH 9, trivalent arsenic (As (3)) exists primarily
as the undissociated weak acid H3AsO3. The distribution between As
(3) and As (5) species is determined by the redox condition of the water,
with As  (3) being stable under reducing conditions and As (5) under
oxidizing conditions.1 Thus, depending upon both pH and redox poten-
tial, various arsenic species may be present.
  Among the various treatment methods for arsenic removal, including
complexation with polyvalent metal species, coprecipitation with a metal
hydroxide, coagulation, lime softening, adsorption on activated carbon,
AA and IE, the literature suggests that the use of AA is the most
promising treatment alternative for treatment of low levels of arsenic
in groundwater. Much of the available literature on the AA treatment
method involves the use of AA for the removal of arsenic from drinking
water.
  The pH (as well as other anionic species) of feedwater, arsenic con-
centration, sulfate concentration, chloride concentration and fluoride
concentration play a major role in determining the AA capacity for
arsenic removal.2 The presence of other anions, such as sulfate and
fluoride, reduced the amount of arsenic removed by as much as 80%.
Substantial removals of As (5) by AA reportedly have occurred within
a pH range of 4 to 7.3
  AA has an equilibrium capacity for As (5) up to 10 times greater
than that for As (3). This capacity is  because at a pH of below 9, As
(3)  is present in a unionized form as H3AsO3.4 Oxidation of As (3)
to As (5) is necessary to achieve effective arsenic removal. Chlorine
has been successfully used to accomplish this oxidation.5 Results from
pilot tests on AA systems indicated that with an empty bed contact time
(EBCT) of 7.5 minutes, pH adjustment to 6.0 and oxidation of As (3)
to As (5), up to approximately 16,000  bed volumes could be processed
prior to  reaching a maximum contaminant level (MCL) of 50 ug/L in
the treated water, with a raw water As (5) concentration of approxi-
mately 100 ug/L.6
  When the adsorptive capacity of the AA is reached, it can be regener-
ated with a 4 to 5 % sodium hydroxide (NaOH) solution. The general
procedure for regeneration, which has been successfully used in pilot
tests, includes upflow treatment followed by downflow treatment with
NaOH,  raw water rinse  and neutralization with sulfuric acid. The
regeneration of an AA system would generate a concentrated waste con-
taining elevated levels of arsenic that may require disposal in an approved
hazardous waste landfill. It has been reported in the literature6 that the
volume of the waste products generated during the regeneration of the
AA system would be approximately 0.1% of the production of the system
(quantity of treated water).
  Limited information is available in the literature on activated carbon
                                                                                                     MILITARY ACTIVITIES    901
-------
treatment of arsenic-contaminated water and wastewater. In one study
involving arsenic removal from a potable water supply using activated
carbon adsorption, 70%  removal of As (5) was achieved with a raw
water arsenic concentration of 200 ug/L.7 Another study indicated that
the optimum pH for adsorption of As (5) on activated carbon is 4.O.3
A recent study in which activated carbon was used for treating a syn-
thetic solution of arsenic (prepared by dissolving As2O3 in distilled
water) indicated a GAC adsorption capacity of 2.5 Ibs As (5) per 100
Ibs of carbon.8  Batch adsorption experiments to evaluate GAC for
arsenic removal from the groundwater at SHAD indicated an ultimate
capacity for arsenic at an influent concentration of 734 ug/L, 0.05 Ib
As (5) per  100 Ibs carbon.9 This result is significantly lower than the
GAC adsorption capacity reported in the previously mentioned study.
The difference could have been due to the different sources of water
with different chemical compositions used in the studies.
   The IE process for arsenic removal involves the use of a strong-base
anion resin that  allows the exchange of chloride ions attached to the
resin with negatively charged arsenate ions (HjAsO4') in the raw water.
When the adsorptive capacity  of the resin is reached, the resin must
be regenerated using a concentrated sodium chloride (NaCl) solution
that replaces the HjAsO4"  with chloride ions.
   The results of pilot-plant testing of ion exchange treatment for removal
of arsenic from drinking water at the Fallon,  Nevada, Naval Air Sta-
tion indicated that with  a 5 minute EBCT, approximately 300  bed
volumes could be processed before  reaching the MCL of 50 ug/L in
the treated water with a  raw water arsenic concentration of approxi-
mately of 100 ug/L.10 The results further indicated that the efficiency
of treatment using a strong-base anion exchange resin is dependent on
the quantity of other anions in the water, particularly sulfate, which
are preferentially  removed before arsenic.  Successful treatment of
wastewater containing arsenate and arsenite with a strong-base resin,
at pH values ranging from 4 to  13, is  reported in the literature.7
   In an experimental study using the IE process, soluble As (5) at a
concentration of 500 ug/L was completely  removed from storm run-
off water." An EBCT of 3.6 minutes, hydraulic loading of 4.2 gpm/ft2
and bed depth of 2 ft were employed in the 1-in. diameter column used
in the study.
   One potential  benefit of using a strong-base ion exchange resin over
AA occurs during regeneration, where sodium chloride could be used
instead of caustic soda followed by an acid neutralization. The initial
cost of the resin probably will be higher than AA, but the lower cost
of NaCl and its easier handling may make an IE process less expen-
sive in the long run.4
   Precipitation of alkalinity (i.e., calcium carbonate) in the IE vessel
is a possible complication with an IE system.6 This process would
require the additional expense of removing the cations with a softener
(cation exchanger) prior to arsenic removal.

MATERIALS AND METHODS
   All tests performed during this project employed groundwater from
wells at SHAD as the test water. Wells MW-403A, 407A and 43LA were
used for the isotherm studies, and well MW-440A was used for the pilot-
scale tests. Contaminant concentrations in  these  wells varied during
the test period. Table 1 presents the analytical data obtained from initial
sampling of  wells 403A,  407A and 431A.

Isotherm Laboratory Tests
   Isotherm tests were performed for selected IE resins, activated car-
bon types and a single AA at Roy F. Weston, Inc.'s (WESTON's) En-
vironmental Technology Laboratory (ETL) in Lionville, Pennsylvania.
Groundwater was collected at  SHAD and shipped to ETL for testing.
   Since  treatment  for arsenic removal at  SHAD would  likely be
implemented following removal of TCE in the existing air stripper, the
contaminated groundwater from SHAD was pretreated for TCE removal
by batch aeration using spargers. For isotherms to be conducted at other
than  natural  pH.1-1 the pH of the groundwater was adjusted to the
desired value using sulfuric acid. Isotherm tests were then conducted
on the pretreated groundwater samples.
                            Ibbtel
          SHAD Pilot Study Groundwater Characteristics
                      (December 22, 1989)
Parameter
Volatile Oraanics
Trichloroethene, ,g/l
Hetals
Arsenic, total, ,g/l
Ca'dmium, total, .g/1
Cobalt, total, ,g/l
Chromium, total, .g/1
Copper, total, «g/l"
Iron, total, .g/1
Lead, total, »g/T
Selenium, total, ,g/l
Zinc, total, .g/1
Well 403A

5 u

143
10.0 u
50.0 u
18.0
8.1
7,070
9.6
6.3
172
Well 407A

34

214
10.0 u
50.0 u
10.0 u
6.8
4,020
16.8
9.5
71.2
Well 431A

5 u

11.7
10.0 u
SO.O u
10.0
15.1
18,000
15.9
5.0 u
196
     Ammonia nitrogen, tng/1     0.10 u         0.10 u
     Nitrate/nitrite as
       nitrogen, mg/1"         17.7          23.5
     Sulfate, mg/1            125 u         125 u
     Phosphate as
       phosphorous, mg/T      1.6           2.3

Other Parameters
     Temperature, -F          53.5          56.0
     Conductivity, .mhos       1,479         1,250
     pH	7.47	8.26
                                                         0.10 u
43.1
125 u
0.67 u
56
756
7.90
"Laboratory control  standards for copper and  lead were outside the  control
limits of 80-120*.
"Measured as nitrite nitrogen after reduction of nitrate; MCAWW Method 353.1.
'Samples analyzed beyond regulated holding time.
Note:  u  • Compound  was analyzed but not detected.  The associated
numerical value  is the  sample detection limit.

  Seven 250-mL aliquots were used for each isotherm. Tests were con-
ducted in polyethylene bottles. Preweighed quantities of adsorbent media
were added to the groundwater aliquots to provide the required dosages.
The bottles were sealed to preclude liquid and vapor losses during agi-
tation. Samples were agitated at room temperature on a rotating labora-
tory shaker for a period of 24 hours. Each isotherm test included one
blank, containing no adsorbent medium.
  Following agitation, each sample (including  the blank) was filtered
through a Whatman  0.45 micron GF/F filter into a clean filter flask
to remove the contaminant-laden adsorption medium.  Each filtrate sam-
ple was then analyzed for total arsenic concentration.
  From these data, the equilibrium concentration of arsenic in the so-
lution (Ce) and the arsenic loading on the adsorbent medium (qe) were
calculated. These data were plotted on log-log paper in accordance with
the Freundlich equation for adsorption:
    q^ = x/M = KCc'/n                                      (1)

where,

  qc  =  Adsorbent loading.
  X  =  C0-CC the amount of arsenic adsorbed for a given volume of
solution.
  M  =  Weight of adsorbent added.
  Co  =  Initial amount of arsenic.
  Cc  = Amount of arsenic remaining  in solution.
  K and 1/n are empirical constants.

  The results of these tests were used to select media to be testing in
the pilot-plant study phase of the  project.

Pilot-Plant Studies
  The objective of pilot-plant studies was to evaluate potential operating
characteristics of selected adsorbent types under actual  operating con-
ditions, with  respect to such  parameters as  adsorbent bed  depth,
hydraulic loading rate and EBCT. Pilot-scale testing of the media selected
from the isotherm data was conducted at SHAD using a skid-mounted
transportable activated carbon column pilot plant designed  and built
for USATHAMA. The system can  be used to evaluate treatment using
GAC, IE or AA technologies. The plant consists of three skids and
accessory tankage. One skid consists of the motor control center, feed
>>o:    MILITARY  ACTIVITIES
-------
pumps and utility pumps. Each of the other two skids contains four
plexiglas columns which hold the adsorption medium to be tested. This
pilot plant was designed to provide a high degree of operating flexi-
bility, using variable bed depths and waste-water flow arrangements.
Additional tanks and pumps are provided to allow for groundwater reten-
tion, pH adjustment and flow control as necessary.
  An air stripper 8 in.  hi diameter by 23 ft high with 15 ft of packing,
designed for a water flow rate of 5 gpm, was used to remove TCE in
the groundwater  prior to treatment for arsenic.
  In addition to  the treatment units described above,  the following
additional tankage was added to the GAC/IE/AA pilot treatment system:
• Two 3,000-gal influent holding tanks to receive and hold groundwater
  from the selected well
• One 2,000-gal equalization tank between the  air stripper and the
  GAC/IE/AA unit. When required by the Test Plan,12 pH adjustment
  was carried out in this tank
• Two 3,000-gal effluent holding tanks to retain the treatment effluent
  to be discharged after testing
  Figure 1  shows the  schematic configuration of the  combined air
stripping/GAC/IE/AA pilot system that was used in this study. As shown,
there were three GAC/IE/AA treatment trains. These three trains were
operated in parallel to allow for study under three different experimental
conditions at the same time.
  In order to evaluate  the need  for an arsenite oxidation step during
the pilot study, portions of samples from candidate wells were subjected
to arsenic speciation analysis. These specialized analytical services were
provided by the Benedict Research Laboratory of the Academy of Natur-
al Sciences.
 ANALYTICAL METHODS
   Samples were analyzed for total arsenic at WESTON's Stockton,
 California, laboratory by USATHAMA-certified Method SD01. Sam-
 ples were analyzed for TCE at WESTON's Lionville, Pennsylvania,
 and Stockton, California, laboratories by U.S. EPA Method 8010.

 EXPERIMENTAL RESULTS AND DISCUSSION

 Isotherm Testing
   A single round of isotherm testing was conducted for the purpose
 of examining equilibrium adsorption characteristics of the various ad-
 sorption media and to select media for use in pilot testing. Preliminary
 selection of media types for isotherm testing was based upon literature
 and vendor information.
   The isotherm tests performed during this study indicated that each
 of the major media types (IE resin, GAC and AA) may be capable of
 treating arsenic-bearing groundwater at SHAD to less than 50 ug/L.
 The lowest required dosages (weight of adsorbent per volume of con-
 taminated water) and highest qe values for equilibrium adsorption were
 observed with Alcoa Type Fl AA. In general, the selected IE resins
 appeared to perform better than activated carbon when compared on
 the basis of adsorbent dosages, with GAC achieving equilibrium arsenic
 concentrations less than 50 ug/L only at high carbon dosages. Table
 2  summarizes the results of isotherm testing  in terms of the media
 selected for pilot-scale evaluation.
Arsenic Speciation
  Arsenic speciation in the potential pilot study supply wells was evalu-
ated in order to determine the need for an oxidation step during the
                                                                                           GAC/IE/AA Columns
                          Legend
                          BS - Basket Strainer
                          Fl - Flow Indicator
                          PI - Pressure Indicator
                          TEM - Temperature
                          BW - Backwash Water
                                                                                    BW—»

                                                                                                            i
                                                                                                      BW.
                                          •M-
       Influent
       Holding
        Tank
                 Air Stripper
                   Blower
                                                               Figure 1
                                                    Pilot Treatment Unit Configuration
                                                                                          Sample 6
                                                                                                           Sample?
                                                                                                          MILITARY ACTIVITIES    903
-------
pilot study.  If the groundwater at SHAD contained predominantly
As^S, a pre-oxidation step using chlorine as the oxidant was planned.
  Sampling  for the initial characterization of arsenic speciation in
MW403A, 407A and 431A took place on February 28, 1990. Additional
sampling, from MW44QA  and at the actual pilot plant influent, took
place on May 23, 1990, during the pilot-plant phase of the study. Arsenic
speciation data from these samples are presented in Table 3. These data
demonstrate that arsenic in the sampled wells existed almost entirely
(2:99.5%) as the oxidized As+5 form.
  The finding that the arsenic to be treated existed in the oxidized form
obviated the need for a chlorine oxidation step in the pilot study. Since
As+3 concentrations were all well below the MCL of 50 /tg/L, effec-
tive removal of the pre-existing As+5 would likely permit attainment
of the discharge standard. The incremental increase in bed life (before
breakthrough at 50 /ig/L total arsenic) that might be achieved by oxi-
dation of the low levels of As+3 likely would be slight.
                           Table!
                  Summary of Media Selection
    Adsorbent
                       Adsorbents Screened
                          in Isotherms
                            Adsorbents Selected
                             for Pilot Testing
 Ion Exchange Resin
 Amber lite
Activated Carbon
Activated Alumina
Rohm and Haas Amber)ite IRA-402  Rohm and Haas
                           IRA-402

Rohm and Haas Amberlite 1RA-900  Sybron lonac A-641
Sybron lonac A-641
Sybron lonac ASB-1
Calgon Filtrasorb 200
Calgon Filtrasorb 300
Calgon Filtrasorb 400
Hydrodarco 3000
Hydrodarco 4000

Alcoa Type F-l, 28-48 Mesh
                                              Calgon Filtrasorb 400
                                              Hydrodarco 3000
                                              Alcoa Type F-l,  28-48
                                              Mesh
  Therefore, based upon the results of the initial arsenic speciation
analysis, as confirmed in subsequent resampling during the pilot-study
phase, chlorine oxidation of the influent groundwater was not employed
in this  study.

Pilot-Scale Testing
  The overall objective of the pilot scale test program was to evaluate
the potential performance of the selected media under continuous flow
conditions simulating those likely to be employed in a full-scale treat-
ment system. Specific objectives pertinent to this effort included:
• To determine the effectiveness of the medium in removing arsenic
  to the MCL (50 ug/L) under continuous flow conditions
• To determine the adsorption capacities of the medium
• To select the best performing medium
• To evaluate potential operating conditions for a treatment system,
  including hydraulic loading rate and EBCT
  These objectives were addressed in a test program conducted at SHAD
using USATHAMA's skid-mounted transportable pilot system described
earlier. The overall duration of the pilot test program (not including
mobilization and demobilization) was approximately 17 weeks. The test
program encompassed a total of seven experimental runs. Table 4
presents a summary of the test program.
  Each adsorbent bed rested upon a 1-ft thick base consisting of a layer
of stone sandwiched between two layers of borosilicate glass wool, speci-
fied as being free  from heavy metals, fluorine and alumina. Adsorp-
tion media were prepared as water slurries, allowed  to soak overnight
and then be added to the columns to provide a settled bed depth of 4
ft. The column was sealed, leak tested and backwashed prior to com-
mencing each test run. Once begun, each test ran continuously until
breakthrough with the  exception of  brief shutdowns for necessary
repairs. Breakthrough was defined as the MCL of 50 /tg/L.
  Each column was backwashed as needed during the run to remove
accumulated solids at the head of the column which interfered with
flow and contributed to excessive head  loss across the column. In
general, columns  were backwashed  when the  head loss across the
column exceeded 5 psi, as indicated by the pressure gauges mounted
on the inlet and outlet of each column. During  backwashing, the ad-
sorbent bed was also generally broken up, minimizing plugging or chan-
neling of flow through the bed. The duration of the backwashing
operation was approximately 15  minutes.
  This study evaluated the potential treatment of arsenic-contaminated
groundwater by three different technologies: IE, GAC adsorption and
AA. While the specific mechanism of arsenic removal may vary, the
implementation of each of these  technologies is similar,  each  likely
employing a series  of fixed bed down flow treatment columns (although
other configurations are possible) with  varying degrees of pretreatment
and/or post treatment. Therefore, the performance of the different media
can be compared in part on the basis of the quantity of contaminated
water, normally expressed in terms of bed volumes, which can be treated
prior to breakthrough.
  Table 5 summarizes the results of pilot tests conducted in this study
in terms of the quantity (bed volumes) of contaminated groundwater
treated under various operating conditions prior to breakthrough in the
primary column effluent, with breakthrough being defined as effluent
arsenic concentrations equal to or exceeding the Safe Drinking  Water
Act MCL of 50
                                                    DISCUSSION
                                                      These data indicate that both IE resins and AA can provide treat-
                                                    ment of SHAD groundwater to levels below the MCL. The longest bed
                                                    lives were achieved with AA at reduced pH, relatively low hydraulic
                                                    loading rates and contact times on the order of 9.8 to 14.7 min. Bed
                                                            SHAD Pilot Study
                                                   Groundwater Arsenic Speciation Data
Parameter
Arsenite,
(As0), ,9/L
Arsenate,
(As"). ,g/L
Total Arsenic
(Std. Dev.),
»g/i
MU 403A
28 February
1990
0.64
133
133 (i 4.6)
MW 407A
28 February
1990
0.77
240
241 (. 25.1)
MW 431A
28 February
1990
0.03
7.47
7.50 (» 0.34)
MW 440A
23 May
1990
0.91
224
225
Pilot Plant Influent
23 May
1990
0.84
193
194
       MILITARY ACTIVITIES
-------
                                                                    Iable4
                                                          Summary of Pilot Test Runs
•• —
Test
1a
1b
1<= ,
2a
2b
2c
3a

3b

3c

4a
4b
4c
5a:
5b
5c
6a
6b
7a
7c
7c
?EBCt
b-u „<
Adsorbent
(primary
1 column)
IRA 402
IRA 402
IRA 402
A-641
A-641
A-641
Hydrodarco
3000
Hydrodarco
3000
Hydrodarco
3000
Filtrasorb 400
Filtrasorb 400
Filtrasorb 400
Alcoa F-1
Alcoa F-1
Alcoa F-1
Filtrasorb 400
Filtrasorb 400
Alcoa F1
Alcoa F1
Alcoa F1
= Empty bed contact

Train
a
b
c
a
b
c
a

b

c

a
b
c
a
b
c
c
c
a
c
a
time.
Flow
rate
(gpm)
0.2
0.3
0.7
0.2
0.3
0.7
0.7

0.2

0.3

0.3
0.7
0.2
0.2
0.3
0.7
0.2
0.1
0.2
0.3
0.3

Hydraulic
loading
(gpm/ftz)
2
3
7
2
3
7
7

2

3

3
7
2
2
3
7
2
1
2
3
3
irt nU O
Bed
Depth
(ft)
4
4
4
4
4
4
4

4

4

4
4
4
4
4
4
4
4
4
4
4


EBCTa
(min)
14.7
9.8
4.2
14.7
9.8
4.2
4.2

14.7

9.8

9.8
4.2
14.7
14.7
9.8
4.2
14.7
29.
14.7
9.8
9.8


Influent
pH
natural
natural
natural
natural
natural
natural
±4

±4

±4

±4
±4
±4
4-6
4-6
4-6
natural
natural
natural
natural
natural


Dates
(all 1990)
19-26 March
19-24 March
19-23 March
29 March • 3 April
29 March 2 April
29 March - 1 April
28 April 29 April

28 April 29 April

28 April 29 April

1 May
1 May
1 May
5 May - 17 June
5 May 30 May
5 May 13 May
9 June
10 June 11 June
21 June - 28 June
21 June - 27 June
3 July 13 July


Notes


















distilled H^ slurry
distilled HjO slurry
with TCE spike
with TCE spike
with no TCE spike

                                                                   Tables
                                                         Summary of Pilot lest Results
Test
la
1b
1c
2a
2b
2c •.
3a
3b
3c
4a
4b
4c
5a
5b
5c
6a
6b
7a
7b
7c
Medium
IRA402
IRA402
IRA402
A-641
A-641
A-641
Hydrodarco 3000
Hydrodarco 3000
Hydrodarco 3000
Filtrasorb 400
Filtrasorb 400
Filtrasorb 400
Alcoa F-1
Alcoa F-1
Alcoa F-1
Filtrasorb 400
Filtrasorb 400
Alcoa F-1
Alcoa F-1
Alcoa F-1
Hydraulic
Loading Rate
(gpm/ft2)
2
3
7
2
3
7
7
2
3
3
7
2
2
3
7
2
1
2
3
3
EBCT
(min)
14.7
9.8
4.2
14.7
9.8
4.2
4.2
14.7
9.8
9.8
4.2
14.7
14.7
9.8
4.2
14.7
29.4
14.7
9.8
9.8
Influent"
Arsenic
(*tg/L)
227.8
227.1
200.5
238.7
252.8
225
-.
--
--
..
--
--
196.1
212.7
257.8
._
--
181.6
179.9
202.9
Influent
pH
Natural0
Natural
Natural
Natural
Natural
Natural
±4
±4
±4
±4
±4
±4
4-6
4-6
4-6
Natural
Natural
Natural
Natural
Natural
Bed Volumes of Water"
Treated (Approximate)
450
375
1,510
285
250
210
-.
--
--
..
--
--
3,700
3,475
2,100
_„
--
500
525
850
Delighted average concentration.
£Volumes treated prior  to breakthrough effluent arsenic  concentration >50 /tg/L.
 PH of  influent generally ranged between pH 8 and pH 9.
                                                                                                                 MILITARY ACTIVITIES    905
-------
lives on the order of 3,000 or more bed volumes of water treated appear
to be achievable in a single activated alumina column operating under
these conditions. Figure 2 is a plot of the arsenic breakthrough curve
for AA Run 5A. By contrast, ion exchange bed lives on the order of
200 to 500 bed volumes of water might be obtained.
       2*0 -j

       2?C 4
                             Figure 2
         Plot of the Arsenic Breakthrough Curve for AA Run 5A
  Granular activated carbon does not appear capable of meeting the
arsenic treatment requirements under the conditions used in this study,
as shown in Table 5.
  Definite selection between the two treatment technologies exhibiting
satisfactory performance in this study would depend upon analysis of
the relative treatments costs and the operating advantages/disadvantages
associated with each technology. This comparative analysis would con-
sider the  capital equipment requirements as dictated by such factors
as hydraulic loading and contact time, pre and posttreatment require-
ments, regeneration requirements and the attrition rate and replacement
costs of the media. For example,  although AA exhibited the longest
bed lives  in this study, the data indicate that a pH adjustment step is
required and that relatively  low hydraulic loading rates and long con-
tact times (corresponding to relatively large  adsorption  units) are
required.  By contrast, IE data suggest relatively little dependence on
loading rate and contact time over the  ranges evaluated; thus relatively
smaller adsorbers operating at higher loadings may prove suitable.

                             Thble6
                    Regeneration Requirements

 Ion Exchange
 Example:   IRA-W:
      1.    NaCl, 5-10% solution,  , 4 Ib. salt/ft' resin, at  0.25
           1.0 gpm/ft'
      2.    Rinse with water.
      Source:     Amberlite  1RA-402 Technical Literature
Activated Alumina
           Regeneration,  NaOH,  1% solution.  4 bed volumes.
           Rinse with water, 8  bed volumes oiniroutB.
           Acid rinse, 0.05 N H,SO,, 1  bed volume Biniraura.
           Final rinse, water,  1 bed volume.

                References 11, 12. and 13
  Regeneration of media was not addressed in this study. Since the ad-
sorption capacities of regenerated media may differ in some respects
from these of virgin media, this aspect should be addressed prior to
design of  a treatment system. Based upon previous  research  and
manufacturer's recommendations (summarized in Tkble 6), regenera-
tion of either IE resins or AA is a relatively straightforward operation
requiring conventional reagents, and attrition  of the media during
regeneration can be controlled.
  With respect to media  replacement, it should be noted that the IE
resins recommended by vendors for use  in this study were relatively
expensive as compared to, for example, conventional softening resins.
The recommended resins cost approximately SISO/ft3. By contrast, the
cost for the AA is relatively low, at approximately STl/ft3 ($1.65/lb).

CONCLUSIONS
  The following conclusions are drawn from the data obtained in this
study:
• Strong base anion exchange resins (specifically Rohm and Haas IRA
  402 and Sybron lonac A-641) and AA (specifically Alcoa Type F-l,
  24 to 48 mesh) are capable of treating arsenic-contaminated ground-
  water from well MW-440A at SHAD to effluent concentrations below
  the Safe Drinking Water Act MCL of 50 /tg/L (as total arsenic). The
  granular activated carbons tested were not capable of effective arsenic
  treatment under the conditions evaluated in this study.
• Of the successful media, AA provided the longest bed lives (in terms
  of bed volumes of water treated prior to breakthrough at the MCL
  level).
• The use of AA requires a pH reduction step. Hydraulic loading rates
  of 2 to 3 gpm/ft2 and EBCTs of 9.8 to 14.7 minutes provided the
  longest bed lives.
• IE resins exhibited less dependence on hydraulic loading rate or EBCT
  than did activated alumina. However, bed life at all loading rates was
  lower than with AA.13
• Analytical data from wells MW-403A, MW-407A, MW431A and
  MW-440 indicate that pentavalent arsenic (As+5) is the predominant
  arsenic species present in  SHAD groundwater and mat  trivalent
  arsenic (As+3) is  present only in small amounts. In fact, removal
  of As+5 alone would be sufficient to  achieve the SDWA MCL for
  total arsenic of 50 /ig/L. As a result, no oxidative pretreatment step
  was required or employed in this study and, as long as this situation
  prevails, oxidative pretreatment should not be required in a full-scale
  system.

REFERENCES
 1.  Ghosh, M.M and Yuan, J.R., Adsorption of inorganic arsenic and orgapoar-
    senicals on hydrous oxides, Environmental Progress, Vol. 6, No.  3, August
    1987.
 2.  Hathaway, S.W. and Rubel, F., "Removing arsenic from drinking water,"
    Journal American  Water  Works Association, August 1987.
 3.  Gupta, S.K. and Chen, K.Y., "Arsenic removal by adsorption," Journal Wner
    Pollution control Federation, March 1978.
 4.  Montgomery, James M.  Consulting Engineerings, Inc., Water Treatment
    Principles and Design, John Wiley  and Sons, Inc., New York, NY, 1985.
 5.  Shen, Y.S., "Study of arsenic removal from drinking water," Journal Ameri-
    can Water Works Association, August 1973.
 6.  Patten, T. P., Chan, R. L., and Misenhimer, G., "Evaluation of alternatives
    for treatment of arsenic in drinking water," American Hater Works Associ-
    ation Annual Conference, Los Angeles, California,  1989.
 7.  Patterson, J.W., Industrial Wastewater Treatment Technology, Second Ed.,
    Butterworths Publishers,  1985.
 8.  Equez, H.E. and Cho, E.H., "Adsorption of arsenic on activated charcoal,"
    Journal of Metals, July  1987.
 9.  O.H. Materials Corp., "Draft Laboratory Report—Removal of Arsenic from
    Ground Water at Sharpe Army Depot, Stockton, California," August 1986.
10.  Rubel and Hager, Inc., Pilot Study for Removal of Arsenic from Drinking
    Water at the Rulon. Nevada Naval Air Station, EPA Rept. No. 600/2-85/094,
    Washington, DC, July 1985.
11.  Wang,  L.K., Wu,  B.C.,  and Janus, J. Removal of Arsenic from  Wuerby
    Continuous Ion Exchange Process, Lenox Institute for Research Inc., MA,
    Report No. LIR/U-84, November 1984.
12.  Fleming, H.L., Application  of aluminas in water treatment  Chemical
    Process. 5, 3, 1986.
O.  U. S. EPA, Selenium Removal from Groundwater Using Activated Alumina,
    EPA Rept No 600/2-80-153, Washington, DC, 1980.
"Ot> MILITARY ACTIVITIES
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                        Selecting State-of-the-Art  Incinerators  for
                  Complex  Aqueous  Wastes:  The Rocky  Mountain
                       Arsenal  Basin F Liquids  Treatment  Action

                                                    JoAnn Tischler
                                             Woodward-Clyde Consultants
                                                    Denver, Colorado
                                                    Bruce  Huenefeld
                               Interim Response Division, Rocky Mountain Arsenal
                                               Commerce  City, Colorado
                                                    Gene H. Irrgang
                                                     T-Thermal, Inc.
                                             Conshohocken, Pennsylvania
 ABSTRACT
  The Rocky Mountain Arsenal (RMA) in Adams County, Colorado,
 has been identified as a priority site on the Superfund National Priority
 List. The Program Manager's Office of RMA announced in early 1990
 their intention to implement installation of a state-of-the-art incinera-
 tion plant to treat the most complex and controversial waste stream on
 the site.
  Established in 1942, the Arsenal served as an Army manufacturing
 center for chemical agents such as mustard gas, white phosphorus,
 napalm and GB nerve agent. Parts of the site were also leased to Shell
 Oil Company which manufactured pesticides and other agricultural
 chemicals at this  location between 1952 and 1982.
  To support these  activities, the  Army operated  a 93-acre surface
 impoundment called Basin F for collection and evaporation of chemical
 wastewaters. As a result of the wide variety of wastes received and con-
 centrated at Basin F, and early treatment attempts, its contents became
 a unique chemical cocktail. By the time that a formal interim response
 action for remediation was initiated in 1985, the Basin composition con-
 sisted of a multiphase fluid and sludge including supersaturated levels
 of inorganic salts; 30% or more organics such as pesticides, military
 agent byproducts, degradation products and solvents; high levels of
 ammonia compounds and bound nitrogen; and percent levels of copper,
 arsenic and other metals.
  Selection of a remedial alternative involved  12 years of characteri-
 zation studies and 11 years of treatability testing programs encompassing
 the universe of containment, encapsulation, stabilization, component
 separation, thermal, electrical, chemical and biological degradation
 technologies. The program resulted in the  selection of a state-of-the-
 art down-fired liquid incinerator for destruction of aqueous organic con-
 taminants in metallic salt matrices.
  The treatability  demonstration and technical justification for selec-
 ting the T-Thermal submerged quench incinerator for this application
 are the subject of this  paper.

 INTRODUCTION
  The Rocky Mountain Arsenal (RMA) was established in 1942 on rural
 property located in Adams County, Colorado, 10 miles from downtown
 Denver. The Arsenal  production  facilities have been used for the
 manufacture of materials such as mustard gas, white phosphorous, nerve
 agents and napalm;  filling  of munitions with  agents  and incendiary
 materials;  and the  destruction or "demilitarization"  of chemical
 weapons.
 Between 1952 and 1982, a series of private firms ending with Shell
Chemical Company (now Shell Oil Company) manufactured agricultural
chemicals, primarily pesticides, at the Arsenal.
 During the 1980s an extensive battery of characterization studies, con-
ceptual process studies and treatability tests were conducted to develop
potential remedial alternatives for the Basin F contents which had been
tentatively linked to groundwater contamination downgradient of the
Basin. Also during this period, the 8.5 million gallons of liquid con-
tents were removed from the Basin and placed in above ground storage.
In late 1988, Woodward-Clyde Consultants began a concentrated effort
to evaluate and interpret the prior studies, and identify and justify a
preferred alternative for destruction of the former Basin contents. This
selection of a preferred alternative has since been published and approved
by the Army, Shell Oil and all the responsible regulatory authorities.

BACKGROUND
  In 1956, Basin F,  a 243-million gallon evaporation pond was con-
structed in a natural depression by lining it with an approximately
1/2-inch catalytically blown asphalt surface, covered by a  1-foot
protective layer of earth. This Basin was the last in a series of linked
surface basins used for the evaporation of wastewaters from the Army
and industrial chemical activities at the site. From August 1957 until
its use was discontinued in early 1982, Basin F was the only evapora-
tion pond at the  Arsenal containing a liner.  Wastewaters entered  the
former Basin F for more than 20 years, directly or indirectly, from three
different manufacturing sources:  the Army North Plants, the Army
South Plants and Shell South Plants.

Army North Plants
  The North Plants complex operated  from 1953  to 1984 for  the
manufacture, munitions filling and later demilitarization of GB nerve
agent. During the period between 1953 and 1973 the plant produced
bulk GB agent and loaded GB into munitions. During that period the
plant also filled munitions with agents produced elsewhere, such as
VX-nerve agent,  and manufactured other devices such as microgravel
mines and button bombs. From 1973 to 1984 the North Plants served
as a "demilitarization" (demil) facility for destruction  of GB agent; VX
agent, Adamsite phosgene bombs and DDT-contaminated equipment.
  Wastewaters from these manufacturing and demil operations were
discharged indirectly to both Basin A and Basin F. Waters were caustic
neutralized in a disposal sump and then pumped to  these Basins for
evaporation.

Army South Plants
  The South Plants operated from 1942 through  1969,  producing
Lewisite, mustard gas and incendiary mixes, and filling munitions with
incendiary materials and phosgene. During World War II, the plant
produced Lewisite (a blister agent) and sulfur mustard. Phosgene was
not manufactured, but was purchased from private industry and used
to fill bombs in  the plant. The South Plants also produced or used
                                                                                            ROCKY MOUNTAIN ARSENAL    907
-------
napalm gel, cluster bomb incendiary mixtures, button bomb pyrotechnic
mixtures, white phosphorous and hydrazine preparation far missile fuels.
  The plant was used for destruction of bulk mustard from 1971 to 1974.
Wastes from the Army  processes and demilitarization were managed
in a variety of ways including incineration, neutralization and evapora-
tion in surface impoundments, including Basin F.

Shell  South Plants
  After WWII, portions of the South Plants area were leased to private
chemical manufacturers. The most significant lessees included Julius
Hyman and Co. and Shell Chemical Company, which manufactured
Chlordane, Aldrin, Dieldrin, Endrin, Vapona, Nemagon  and  other
organochlorine  and organophosphorus pesticides  and nematocides
between 1947 and 1982. Some wastewaters from these processes were
discharged to the evaporation basin system and ultimately to Basin F.

Other Sources and Factors
  Other factors contributed to the creation of the unique mixture of
components in the Basin as well. The most significant factor involved
early attempts at remediation of the contents. In the late 1950s it became
obvious that Basin F was not large enough to handle all the wastewaters
generated on-site. The  U.S. Army Chemical Corps considered deep
well disposal, and in 1960 the Corps of Engineers attempted to modify
Basin F for the purpose of pretreatment prior to disposal. A chemical
addition area was constructed at the Basin, and 100 tons of ammonium
phosphate were added to the Basin contents in an attempt to simulate
microbial activity and liquify some of the solids. Although injection
wells were drilled and injection was attempted in the early  1960s, the
pretreatment was never successful and ultimately the injection attempts
were abandoned.  However, the presence of the additional 200,000
pounds of ammonium salts had a significant long-term affect on the
behavior of the liquids.
  The final contributor to the Basin's properties was the very action
for which the Basin was designed. Years of warm-weather evaporation
at high altitude contributed to the creation of a supersaturated body
of liquid by the time characterization and remediation  studies began
in 1978. The residuals from the evaporation were so concentrated, in
fact, that during repeated Corps of Engineers attempts  to sample the
Basin in the 1980s the sample devices acted as seeds for precipitation
and caused instantaneous crystallization.

THE TECHNICAL PROBLEM
  As a result of the processes and actions described above, Basin F
liquids evolved into a mixture unique among chemical wastewaters. The
Basin F contents are generally an aqueous mixture consisting of ap-
proximately one-third water, one-third organics and one-third dissolved
solids, primarily salts and metals.
  Table 1 lists some of the organic components identified in Basin F,
primarily agent byproducts and pesticides and their intermediates and
byproducts. Most individual organic species reported have been iden-
tified as present at concentrations from 1 to 1000 ppb, with  the excep-
tion of two pesticides and three pesticide byproducts present at con-
centrations from 2000 to 100,000 ppb. However, no single organic com-
ponent is a significant  contributor to the liquid's  properties.
  The liquid's properties appear  to be driven by the high concentra-
tions of inorganic salts and metals. Table 2 shows the levels of selected
inorganic components. Table 3 describes some properties of the liquid
including those particularly affected by inorganic constituent levels such
as conductivity and density. In general, Basin F can be described as:
•  Supersaturated  with  salts (30 to 35%)
•  Unusually  high  in ammonia (5%)
•  Contaminated with environmentally significant levels of nerve agent
   byproducts, pesticide-related compounds  and arsenic
•  Prone  to off-gassing
•  Highly corrosive
  While the above items represent significant engineering handling and
treatment problems, three beneficial properties of the Liquid are that
it  is not: (1) radioactive, (2) flammable or (3) explosive.
                            Ikbiel
     Selected Organic Chemical Components Detected in Basin F
        Liquids During Characterization Studies 1978 to 1988
  Hexachlorocyclopentadiene
              Source

insecticide
insecticide intermediate
insecticide decomposition product

insecticide
mustard gas decomposition product

pesticide
pesticide
pesticide decomposition product
pesticide by-product
pesticide intermediate

herbicide
organophosphorus pesticide
organophosphorus pesticide
organophosphorus pesticide
organophosphorus pesticide
nerve agent by-product

nerve agent by-product	
                            Table 2
     Selected Inorganic Components Detected in Basin F Liquids
            During Characterization Studies 1978 to 1988
  Ammonia
  Urea
  Potassium
  Sodium
  Chloride
  Fluoride
  total phosphorus
  Copper
  Arsenic
         Values Reported  (pom)

             up to 61,000

             up to  143,000

             up to 2,900

             up to 65,000

             up to  159,000

                 170

             up to 16,200

             up to 5,860
                            Table3
      Selected Physical/Chemical Properties of Basin F Liquids
ParamEtsr
Specific gravity
Viscosity 25°c
viscosity 2'C
Conductivity
COD
Total Organic Halide
pH
Units

cp
cp
^mhos/cm
ppm
ppm
-
Value
1.24
5.0
2.]
110,000
up to 230,000
up to 570,000
5.B to 7.2
THE ADMINISTRATIVE PROBLEM
  Two administrative agreements which govern the RMA remedial
activities were signed in February 1989 by Shell Oil Company, the Army
and Federal Agencies responsible for  oversight of the cleanup. The
Federal Facility Agreement (FFA) and the Settlement Agreement (SA)
define the mechanisms for selection of remedial actions and the technical
and financial responsibilities for each party. The FFA also defines bow
the Interim Response Actions (IRAs) will be carried out. The Basin F
Action was identified as an IRA. The signed agreements required that
the liquids, which by this time had been removed from the Basin and
stored in three above ground  tanks and a lined surface pond, would
be permanently destroyed within  5 years of the date they were placed
in the tanks. The 5-year period was based on the assumed design life
       ROCKY MOUNTAIN ARSENAL
-------
of the tanks and implies that the liquids have to be destroyed by mid-1993.
This deadline complicated an already tough engineering problem by
requiring that a selected alternative must involve equipment that was
already proven for corrosive service on aqueous organic brines and
immediately commercially available.

THE APPROACH
  Characterization and treatment studies for remedial alternatives for
the liquid were  conducted by multiple organizations from 1978 to
December 1989. The technologies considered and tested during this
period spanned the entire spectrum of currently available treatment
approaches and included:
• Thermal destruction
• Electrical destruction
• Non^combustion thermal oxidation
• Chemical biological photolytic oxidation
• Separation and component recovery
• Stabilization and immobilization
  More than 40 different conventional and innovative technologies were
addressed. The technologies addressed included some as commonplace
as mechanical filtration and some as new and developmental as super-
critical water oxidation.  More than a dozen different bench-scale and
pilot-scale test programs were conducted. Based on the  governing
Federal Facilities Agreement, any technologies which were to be retained
from the foregoing studies for detailed evaluation needed to meet the
following criteria:
• The technology and equipment had to be suitable for the complex
  properties of Basin F liquids.
• It had to be generally capable of meeting Applicable or Relevant and
  Appropriate Requirements (ARARs).
• It must have been successfully demonstrated on actual Basin F liquids.
 - It had to be commercially available at full scale within the 5-year
  time frame.
  As a result, six technologies were retained for a detailed alternatives
evaluation conducted by Woodward-Clyde Consultants during 1988 and
 1989. They were:
• Electrical Melter Furnace (EMF)
• Solidification
• Submerged Quench Incineration (SQI)
• Wet Air Oxidation (WAO)
• Wet Air Oxidation with Powdered Activated Carbon Biotreatment
  (PACT)
• Off-site commercial incinerator
  The detailed evaluation consisted of two major components - a risk
evaluation and an engineering evaluation using quantitative scoring and
sensitivity studies to rank alternatives in the context  of the  CERCLA
evaluation criteria.
  Risk assessments considered short- and long-term risks from both
the operations and the materials transport (feed chemicals and residual
products) for each proposed alternative. In general, the transportation
risk from export of untreated liquids outweighed the risks arising from
on-site treatment.
  The engineering evaluation involved a numerical scoring of each alter-
native per each of seven of the nine standard CERCLA criteria. Two
criteria, community acceptance and State acceptance,  were not utilized
in the ranking study because they were evaluated explicitly through a
multistep community involvement program conducted after the study.
The ranking study, based on multiattribute utility theory, used a varia-
tion in weights on the CERCLA criteria to study the singular effects
of individual criteria and to model various viewpoints.  This process
resulted in the identification of on-site submerged quench incineration
as the technically preferred alternative. In general, however, despite
the extensive decision methods utilized, it was basically the properties
of the Basin F liquids that caused each of the other alternatives to be
ranked low or be ruled out altogether. That is, each other alternative
had a potential "fatal flaw" with respect to the liquid properties that
could ultimately  render  it unsuitable.
Electric Melter Furnace
  The electric melter furnace is a high temperature furnace used for
the production of glass from liquid or solid feeds with the addition of
silicates; no flame is present in the combustion chamber. Initially, this
equipment which is designed to handle fluids with high solids and high
metals content seemed like a strong candidate for a one-step process
to destroy Basin F's organics and stabilize its metals. But Basin F's two
other key components,  salts and ammonia, posed significant potential
problems for this process.
  The equipment is designed to run with a single-phase melt flowing
continuously along the bottom of the thermal chamber. Basin F, with
or without  addition of  glass formers, would create a two-phase melt
with salts lying above, and interfering with the purging of, the metals
stream.  More importantly, at the high temperatures of this process
(2500°F), the ammonia nitrogen in Basin F was expected to form NOX
compounds at rates that could not meet Denver air standards even after
selective catalytic reduction, thermal DeNOx or other NOX treatment
steps.
Solidification
  This process may have been suitable if Basin F's metallic aqueous
brine contained no organics or ammonia. While solidification of con-
taminated soils and sludges is frequently a straightforward one- or two-
step process, the process needed for material with Basin F's  composi-
tion would  have been extraordinarily complex. First, due to the high
content  of ammonia and the normally high pH of many solidification
additives, numerous ammonia sequestering additives were needed to
prevent  escape of large quantities of gas. Second, many of the organic
components were not only not amenable to stabilization themselves,
but also interfered with the inorganic matrix formation that was to bind
metals and inorganic ions. In total, this approach would have required
so much chemical addition it would have increased the treated volume
to a minimum of 3 to 5 times the untreated  waste volume.

Wet Air Oxidation
  This process represented a possible way to achieve primary destruc-
tion of organic components without the high temperatures common to
incineration processes that tend to create  NOX emissions.  High
pressure oxidation reactors have been utilized industrially on a variety
of rich and lean aqueous organic mixtures. However, Basin F's com-
position posed serious technical problems in the design of such equip-
ment. The manufacturers had difficulty identifying materials of con-
struction for high pressure, small diameter, high velocity reactor tubes
in corrosive and abrasive service which could be guaranteed to sur-
vive  for the life  of the project.

Wet Air Oxidation with PACT
  This approach was considered as a potential means of enhancing
WAO's overall destruction efficiency by utilizing microorganisms in a
polishing step on the WAO product. However, even though  the WAO
effluent  would have smaller, less toxic organic molecules than the Basin
F feed that may be suitable for biodegradation, the effluent still would
contain  two other Basin F components - ammonia and copper. While
microorganisms  utilize ammonia nitrogen as a nutrient, the copper
serves as a relatively potent biocide and must be removed.  The flow
sheet incorporating removal of copper-ammonium salts between WAO
and PACT became so complicated as to render the overall process poten-
tially  impossible to startup and bring to steady-state.

Off-site Incineration
  Most  commercial incinerators, whether  liquid injection type or kiln
type with liquid afterburners are capable of accepting waste with some
level of "ash content,"  that is, noncombustible inorganics.  However,
despite  a nationwide survey and several acceptance test trials,  no
commercial installation could be  identified that would guarantee
acceptance  of Basin F once they understood its chemical composition.
Two properties caused the most concern: (1) the "ash content," due
to the supersaturation of salts, was much higher than they felt they could
pump, purge from their equipment and stabilize with their product ash;
                                                                                                   ROCKY MOUNTAIN ARSENAL    909
-------
and (2) the ammonia content relative to the low Btu content was likely
to drive their operation above acceptable NOx emission levels.

THE SOLUTION - SUBMERGED  QUENCH INCINERATION
  The first and foremost requirement of the incinerator is the complete
destruction of the highly sensitive organics. However, the presence of
approximately 1,500  pounds per hour of salts and heavy metals dic-
tated an incinerator from which those materials could be continuously
removed. The high concentration of bound nitrogen and chlorides also
require that the incinerator be of a controlled atmosphere type to limit
NOt and other secondary pollution problems. The submerged quench
fits all of those parameters.
  The incinerator chamber of the SQI is a vertical cylinder instead of
horizontal as is common for most other incinerator designs. The burner
and  waste injectors are  located at the top of the chamber and are
downfired. This orientation allows the salts which are molten  liquids
at typical incineration temperature to flow down the chamber walls
carrying any  other inorganic metals with them. The outlet of the in-
cinerator chamber is the  submerged quench system. The submerged
quench  is a unique design which not only cools the gases, but also
provides for  excellent mass  transfer, lowering the  demands  on the
downstream pollution control system  to neutralize acids and remove
particulates. The hot corrosive gases and molten salts enter the quench
via a downcomer. The downcomer is a metal tube which extends into
the quench water bath. The bottom of the downcomer  is open, allowing
the salts to drop into the quench tank solution and redissolve. The quench
solution for the system is a concentrated salt solution to which caustic
is added to react with the acid gases.
  The gases exit the downcomer through holes in its side. These holes
are 24  inches below the solution level in  the quench  tank and are
designed with enough pressure drop to provide a jet sparging effect
of the gases into the water. As the gases exit the holes, they  rise as
millions of small bubbles providing extended surface  area for heat and
mass transfer. In the quench  tank, almost all of the acid gases are
neutralized and more than 99% of the particulates including heavy metals
above 2 microns are removed  from the gases before they enter the
downstream pollution control equipment.
  The destruction efficiency of the highly sensitive  organics present
in the waste has to meet U.S. EPA incinerator standards.  However, the
presence of the other inorganic compounds containing large concen-
trations of carbon monoxide,  chloride and nitrogen required an in-
cinerator system in which the atmosphere could be controlled and in
which the destruction could be achieved at temperatures at which those
compounds would not create secondary air pollution problems.
  The SQI combustion is carried out at approximately 1900°F and 3.5%
O2  with a 2 second retention time. These parameters were  derived
through pilot plant tests at the existing pilot facility at Conshohocken,
Pennsylvania, which were conducted both prior to and during the design.
At that set of parameters the destruction of organics exceeds 99.99%,
and the CO is less than 100 ppm corrected to 7% Or The low oxygen
concentrations ensured that the chlorine present forms as HC1 versus
free Clj,  therefore improving its  scrubbing efficiency. The SQI
accomplishes all of this because of the high turbulence in the chamber
providing excellent mixing of the vaporized waste, combustion air and
hot burner combustion products which initiates the waste oxidation reac-
tions. The high turbulence is derived from the Vortex  burner and
optimized design of the chamber, waste injectors and secondary com-
bustion air nozzles.
  The SQI system represents the state-of-the-art for handling this type
of waste today as well as it did almost  20 years ago when it was first
utilized. Therefore, not only can it be considered innovative, but it also
has been proven in over 125 installed systems around the world. The
operating experiences from those systems have resulted in improvements
to this system which will increase its reliability and safety.

CONCLUSIONS
  Basin F Liquid is a unique chemical mixture that poses a significant
treatment engineering problem due to its physical  and chemical
properties including:
• Supersaturation of salts
• High concentration  of complex organics
• Corrosivity
• Tendency to ammonia off-gassing
• Tendency to precipitate salts
  As a result, the selected alternative for permanent remediation of this
liquid required use of equipment that could not only destroy the organic
components, but could also simultaneously:
• Withstand the corrosive activity of the dissolved solids
• Continually purge itself to prevent accumulation of salts
• Process high rates of ammonium nitrogen throughput
  The singular  piece  of equipment  that was able to  meet both the
CERCLA criteria and  the demands of treating this problematic liquid
was the submerged quench incinerator.
      ROCKY MOl MAIN ARSENAL
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                              Abandoned Well  Closure  Program
                                  at a  Hazardous  Waste Facility
                      Rocky  Mountain  Arsenal Denver,  Colorado

                                               Karen  D. Holliway, P.G.
                                               Michael E.  Witt, Ph.D.
                                                  Roy  F.  Weston, Inc.
                                                  Lakewood, Colorado
                                                Mark A. Hutson, P.O.
                                                   Hydro-Search, Inc.
                                                   Golden,  Colorado
 ABSTRACT
   At the Rocky Mountain Arsenal in Denver, Colorado, more than 1500
 wells have been installed into various aquifers during the past 50 years.
 This concern over the integrity of these wells prompted the identifica-
 tion, examination and closure of wells which could contribute to aquifer
 cross-contamination.
   The well closure program at Rocky Mountain Arsenal was conducted
 using a three-phase approach. Phase 1 involved a records search and
 compilation of available data on wells; Phase 2 was a two-tiered field
 search for the wells, involving data review, visual inspection, geophysical
 survey and land survey; and Phase 3 involved the actual well closure.
   Of 493 wells identified and approved for closure at Rocky Mountain
 Arsenal, 352 have been located and closed. The various materials used
 in the construction of these wells included polyvinylchloride (PVC),
 steel of varying grades, concrete and brick. Wells ranged in size from
 two inches to six feet in diameter and were completed to depths up
 to 780 feet.  Drilling methods employed in the closure of the wells
 included auger, rotary, reverse circulation with cable tool or air hammer
 operations. Casings and obstructions  were removed or drilled out during
 the closure operations. Conventional  and unconventional "fishing" tools
 were used to remove casing. If casing could not be removed, men the
 casing was perforated. After the casing was removed or perforated, the
 sand zones and contacts within each of the wells were sealed following
 Colorado regulations on well closure/abandonment. The materials used
 to seal the wells included a grout mixture, bentonite, pea gravel and
 commercial concrete.

 INTRODUCTION
   The Rocky Mountain Arsenal (RM A) occupies more than 17,000 acres
 (27 mi2) northeast of Denver,  Colorado (Fig. 1).  The Arsenal was
 established in 1942 and has been used for the manufacture of chemical
 and incendiary munitions as well as the demilitarization of chemical
 munitions. Additionally, RMA lessees manufactured pesticides and
 herbicides from 1947 to 1982. RMA is currently an active Superfund
 site undergoing remediation. Part of the remediation involves the closure
 of unused or abandoned wells to prevent the vertical migration of con-
 taminants through these wells.
   More than 1,500 wells have been  identified at RMA, with as many
 as 250 of these water wells historically used for irrigation, stock watering
 and domestic use. Most of these wells were constructed prior to the
 establishment of RMA in 1942 and are hand-dug, ranging from 24 to
 60 inches in diameter with completion depths up to 100 feet and are
 constructed of brick or concrete. Since the establishment of RMA,
 hundreds of monitoring wells have been installed on the property. The
 concern over the potential for contaminant migration through unused
'or abandoned wells prompted the Program Manager for RMA to develop
a task to locate, examine and close wells that could contribute to cross-
aquifer contamination. Two hundred eighty-eight of these monitoring
wells had either poor construction or no potential future use and were
therefore targeted for closure. These wells varied from 2 to 10 inches
in diameter and ranged in depth from 6 feet to 250 feet. This initial
list was expanded to include 493 wells, of which 352 wells have been
                                  ROCKY MOUNTAIN
                                      ARSENAL  _.
                          Figure 1
              Rocky Mountain Arsenal—Site Location
                                                                                            ROCKY MOUNTAIN ARSENAL   911
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located and closed.
  The scope of work for the RMA well closure program included:
compilation of a well inventory and closure list, field location of wells,
cleaning and closure of all located wells and documentation of closure
activities.

WELL INVENTORY  AND CLOSURE LIST DEVELOPMENT
  The compilation of a well inventory and preparation of a data base
provided a means for evaluating and documenting historical well closure
information. Information sources utilized for the well inventory and
database included: existing databases, hand copy historical records and
field data collected during well search and closure activities.
  Well closure was evaluated on:
•  Past, current and future use of the well
•  Evaluation of well construction details
•  Subjective evaluation of reported well construction
•  Proximity or location to active/known contaminant plumes
•  Quality of groundwater (if known)
  After completing the evaluation, a list of wells targeted for closure
was compiled.

WELL CLOSURE PLAN
  Upon approval  of the well  closure list, well characteristics  were
evaluated and appropriate well closure techniques determined. These
decisions  were  based on the Well Closure Plan which  included the
following:
•  Well closure  specifications—in compliance with all Applicable or
   Relevant and Appropriate Requirements (ARARs)
•  Procedures for well cleaning and data collection—in compliance with
   Federal and State ARARs
•  Compilation of topographic and elevation survey data
•  Procedures for related support activities (i.e., waste management)
•  Procedures for field  drilling techniques
•  Procedures for data management and Quality Assurance (QA)

FIELD LOCATION OF WELLS
  All wells identified for potential closure were subjected to a two-
tiered search. The first level field search involved a historical data review
followed by a detailed visual inspection of the reported well  location
followed by  a detailed sweep of the suspected area with a hand-held
magnetic gradiometer. Any wells found visually during the first level
field search were surveyed and assessed for their physical characteristics
and current condition. Wells not visually located during the first level
field search were subjected to a second level field search. If necessary,
a detailed geophysical survey using a magnetometer was conducted in
the suspected area to further define the areas to be excavated.  If no
geophysical anomalies were detected, no further search efforts  were
conducted and the search was canceled. If an anomaly was identified,
then a visual field check was performed  and recommendations  were
made for a more detailed geophysical survey or an excavation to deter-
mine the source of the anomaly.

Geophysical Survey
  During the closure program, 90 suspected well locations were sub-
jected to gradiometer/magnetometer surveys. Approximately 35% of
the wellheads were located. Survey grids used at the site were 300 feet
on  a side with 25-foot spacings.  Additional fill-in  surveys were con-
ducted on 10-foot grid spacings over smaller areas to locate the source
of any detected anomaly.
  A SAGA Geophysics  GSM-19 gradiometer/magnetometer was used
lo conduct the surveys.  The SAGA GSM-19 permitted simultaneous
measurement of vertical magnetic gradient and total field readings  using
a dual sensor arrangement.'
  Data obtained in the  field were stored  in the SAGA GSM-19  com-
puter. These data  were  downloaded to a PC computer. A contouring
program was used to create contour maps of the total magnetic field
and vertical magnetic gradient. These contour maps allowed  a means
to evaluate anomalies and anomaly signatures.
Well Inspection and Cleaning
  Well closure and cleaning procedures are dependent on the actual
amount of debris or obstructions within wells and the type, construc-
tion, diameter and depth of each well. For this reason, the accurate
collection and field verification of well condition and construction details
are of critical importance. Well cleaning was conducted prior to closure
to verify that well depth information were accurate, ensuring effective
closure techniques were selected. Figure 2 illustrates recommended steps
involved in the well inspection and cleaning process. Well construc-
tion data generated during the field investigation was checked against
existing records to verify or reconstruct well  construction details. In
some cases, it was necessary to remove debris or redrill a well to clear
obstructions prior to closure/cleaning.
                             Figure 2
                    Well inspection and Cleaning


Geophysical Logging Techniques
  Borehole geophysical logging methods were utilized in wells deeper
than 200 feet to define downhole characteristics such as casing and
screen condition and  location, hole  condition  and stratigraphy.
Geophysical logging included casing collar locator (CCL), neutron and
gamma logging. The information compiled from caliper logs, CCL logs,
gamma logs and neutron logs helped in confirmation or identification
of well construction and stratigraphy. The stratigraphy of the borehole
was particularly important in the determination of zones to be perforated
       ROCKY MOl'NTAIN ARSENAL
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to properly seal the well bore.
  Caliper logging  (three-arm tool)  was conducted to determine the
diameter of the well or well bore and to identify washout zones, locate
swelling clay zones and detect holes in the casing material. The CCL
log! was conducted  to help determine the condition of the hole, casing
and screen.
  Gamma logging  consists of a measurement of naturally occurring
radiation emitted from materials encountered in and adjacent to the
borehole.2 The gamma log helped define the stratigraphy of the hole
and was run in association with a neutron log. Neutron logs employ
a neutron source with either a gamma-ray detector or neutron detector.
Combining the data gathered from the neutron log with the gamma log
helped to identify the stratigraphy and lithology of the well bore. This
process located permeable, sandy zones or contacts important in deter-
mining the best zones for casing perforation.

WELL CLOSURE  DRILLING TECHNIQUES
  The variety of wells encountered at RMA include PVC, steel, brick
and concrete,  ranging from 2 inches  to 72 inches in diameter, with
reported depths of up to 1,000 feet (Fig.  3). Due to the wide range of
well construction,  various conventional drilling techniques were used
for well closure (Fig. 4). Closure ideally included the removal of well
casing, screen and all well construction materials. Since wells  were
assessed on a case-by-case basis for closure, a variety of modifications
from conventional  methods were employed during well closure. Con-
ventional drilling  techniques included:  auger, direct rotary,  reverse
rotary, hammer and  modified use of cable tools.
Auger Drilling Method
  Continuous-flight hollow-stem augers (HSA)  cut a borehole using
excavation methods and carry cuttings up the hole along the flights
(Fig.  5). Hollow-stem augers were  used to overdrill PVC (and some
steel casing) 2 to 6 inches in diameter and up to 180 feet deep. The
CME-75 and CME-750 auger rigs were selected  for the work at RMA
due to capability of the rig.
  PVC wells,  2 inches to 6  inches in diameter, were measured with
tape or drill rod to verify depth within 104 of the historical record. If
         WELL   CONSTRUCTION
         TYPE      MATERIAL
      Domestic


      Domestic


      Monitoring
    Surface
     Casing

  PVC or Steel
  Well Casing

  Cement Seal
    In  Upper
     Aquifer
 Slotted Screen
        (PVC)
    Perforated
 Screen (Steel)
Concrete
Brick, Steel

Steel
Stovepipe

Steel PVC
SIZE  RANGE

 24"    72"


  3" -  20"


  3" -  10"
DEPTH RANGE

  20  ft.  - 90 ft.


  20  ft.  - 1000 ft.


   6  ft.  - 260 ft.
                                      alvanlzed
                                    ••Steel
                                     (Stovepipe)
                                                        WELL
                                                        DEPTH

                                                       6' -  150'


                                                     50' -  200'


                                                     20'    100'


                                                     150' -  1000'
                                                        WELL
                                                      DIAMETER

                                                       2" -  6"


                                                       6" -  24"


                                                      24" -  60"
                                                     CONSTRUCTION
                                                        MATERIAL
               RECOMMENDED
                   METHOD
                                                    PVC, GALVANIZED    HOLLOW STEM AUGER
                                                                       PERCUSSION  HAMMER

                                                    PVC, GALVANIZED,   MUD  ROTARY
                                                    BRICK              REVERSE CIRCULATION
                                                        3"  - 5"
                                                    GALVANIZED,
                                                    BRICK


                                                    GALVANIZED
             REVERSE  CIRCULATION
             ORANGE PEEL BUCKET


             MUD ROTARY
                                                                                 Figure 4
                                                                          Well Closure Techniques
                                                                                Rod  Inside  Hollow  Stem Auger
                                                                                   Auger  Flight
                                                                                      Hollow—stem  continuous  flight
                                                                                      augers cut u  borehole and
                                                                                      carry cuttings upward along
                                                                                      the flights.   Augers were
                                                                                      used  to drill  over PVC and
                                                                                      steel  casings 2"  to 8" In
                                                                                      diameter and  up to 150'
                                                                                      deep.  Casings  were  removed
                                                                                      or drilled  out with  a  center
                                                                                      bit inside  the  Hollow-Stem
                                                                                      Auger.
                                                                                                      Rod  Inside  Hollow  Stem  Auger
Auger Bit
                                                                                                      Center  Bit
                           Figure 3
            Wells Encounter at Rocky Mountain Arsenal
                                                                                                   Figure 5
                                                                                           Hollow Stem Auger Drilling
                                                     the well was open,  a center rod was inserted to help the HSA stay
                                                     centered on the well during overdrilling. If the hole was closed by grout,
                                                     the drilling speed was reduced and cuttings were observed for indica-
                                                     tions of drilling  across the well. If problems of staying on the well
                                                     occurred, the center bit was inserted in the HSA and the well casing
                                                     was removed by  drilling.
                                                       Drilling methods chosen for PVC wells with a diameter greater than
                                                     8 inches were considered on a case-by-case basis.  Some were drilled
                                                     out with a center  bit. In other cases, rotary drilling was used to remove
                                                     well debris. The auger rig and/or a rotary rig were used in some of
                                                     these cases.
                                                       Steel, galvanized, or ''stovepipe" wells generally ranged from 5 to
                                                     8 inches in diameter. Rotary drilling methods (with the auger rig) were
                                                     used to clean these wells of sediment and obstructions. Verification of
                                                     recorded depth was conducted by drilling through the bottom  of the
                                                     well into the formation below. Due to the size ranges of these types
                                                     of wells, methods of overdrilling and pulling casing were determined
                                                     on a case-by-case basis.
                                                                                                      ROCKY MOUNTAIN ARSENAL    913
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     ROTURT DRILL METHOD
     Drilling fluid !•  pumped down  through
     the drill pip. 1o the bit. to  lubricate
     and  cool  the bit, and |e1 material
     from  the  bottom of  the hole.
     The fluid  <« then displaced  upward
     In the annular  space between  the
     drill  rod and casing or borehole wall,
     carrying cutting! In  suspenilon.  At th«
     •urface th* drilling fluid Is  channeled
     Into  a mud pit  where cuttings
     •vttle out before fluid  reclrculates.

     Rotary drilling was ui*d to
     cloie  wellt exceeding 200'.
 Suction Strainer
Traveling
Block
                                                            Swivel
                                                  Table 1
                                  Fishing Tools, Operation and Application
                                                           Drill Bit
                               Figure 6
                        Rotary Drilling Method
   Once a well was successfully  overdrilled to remove construction
 materials, attempts were made to pull the casing by: sand  locking,
 plugging off the lead auger or using fishing tools. If PVC casing could
 not be  retrieved, the hole was redrilled with a center bit in the HSA.
 Cuttings were observed to verify that the well was drilled out. Generally,
 there were no problems in pulling the steel well casing in the shallow
 holes.
   Some problems that occurred with the auger method included:
 •  Wells not installed straight generally required the well to be drilled
   with a center rod in place, making it difficult to determine that the
   well  construction materials were removed.
 •  Wells not installed straight may have been drilled across during over-
   drilling, possibly pushing casing to the side wall of the closure boring.
 •  Difficulty was encountered in pulling the larger diameter steel casing.
 •  Crooked steel wells and twisted well casing caused augers to wedge
   in the  hole.

Direct  Rotary  Drilling  Method
   Direct  rotary drilling was used to circulate material out of a well to
clean the well of obstructions. In direct rotary drilling, the drill string
(Kelly,  drill pipe, collar and bit) advances by rotation that breaks the
formation or accumulated sediments. As the bit is rotated, drilling fluid
is  pumped down through the drill pipe to the bit to lubricate and cool
the bit and to jet material from the bottom of the hole to the surface.
The fluid is displaced upward in the annular space, between the drill
rod and well casing or borehole wall, carrying cuttings in suspension
to the surface.'  At  the surface, the drilling fluid is channeled to a mud
pit where cuttings settle  out before fluid recirculates down the hole.
Figure 6 contains a summary of the direct rotary drilling method. Mud
pits were generally excavated at the site; however, portable mud pits
were used on occasion. The bit generally used to clean the hole was
a roller bit or tricone bit.
   Direct  rotary drilling was used to clean out wells up to 1,000 feet
deep, ranging from 3 inches to 16 inches in diameter, including some
                   Olt collar (boa top)
                                                                              viral in* grab

                                                                              Magnet
constructed HIM flute* or ihreaos Iras I MMll end tapered to • lerfer dlea»ter M
that it rotated until it  internally engages.

C-Ktemelly engages over the top to drill pip*. well easing. or pu«p red by romlan.
the Inside at the collar Is threaded: guinea can be »«ed to engage over tfe tap a* *
objtct.

Internally catdiea drill pip* or Mil casing on rotation.  A grapple above the n«a
of tha spear graba onto the fish.

Slipa over tha top of the  I Ish and expands on circulation. Uaad to retrieve twist**
off drill plpa or PUBP root.

lelesse or engage on rotation over  tha top ol  tha Man.  mad to retrieve tvlste*
off drill pipa or pump rods.

sit with tungsten carbide  on tha grinding BurfMa to chaw (chip] up an object (flafc).
Malarial la circulated or a basket Is ufad to catch the Material (real the flah.

Harpoon- type apear Kith lagged edgea to engage  inarled/tNltted wireline.

Magnetic toola with  a controlled permanent aoonetic field, used to pick uj» Mil
object! (uauallr Irregular ahaped).
                   IV*M.on Hock


                  * Fro* UilBon Dotrtwlt S*rvtc«i riiMng Se.ilr.ir [5]
                                                                                                  Lead-filled cylinder uaad to atake an lapression of the top ol the fish to datenslm
                                                                                                  alia and shape.
                  shallow holes closed by the auger rig. After a hole was cleaned out,
                  total depth verification/determination was conducted by drilling through
                  the bottom of the well into the formation. Wells greater than 200 feet
                  deep were then subjected to borehole geophysical logging as described
                  earlier. Logs were then assessed to verify reported well construction
                  and stratigraphy and to aid  in determining the proper sealing method
                  for final closure. Wells deeper than 200 feet generally required per-
                  foration of the well  casing  to  achieve proper sealing.
                    Colorado  state regulations4  require that a minimum of 50 feet of
                  casing into the formation below the alluvium be removed. To help in
                  the removal of the casing, washover pipe was used to overdrill the casing
                  to a selected depth below the formation contact. As the washover pipe
                  was rotated and advanced, cuttings from the boring were circulated out
                  of the hole as previously described.  After the depth  was achieved,
                  attempts were made to  "fish" casing out of the hole using conventional
                  petroleum industry fishing tools. Fishing tools were also  used to remove
                  any solid obstructions encountered in the well during well cleaning ac-
                  tivities. The  fishing tool was attached to the drill string, lowered to the
                  obstruction and  rotated until the tool was firmly engaged. Table 1
                  summarizes  the  fishing tools and operation used during the Closure
                  Program.5
                    Problems encountered with the direct rotary drilling method included:
                  •  Crooked wells created problems of tools or drill pipe stuck in hole
                  •  Site accessibility was difficult  because of rig and equipment size
                  •  Large volume of water used for circulation created mud  pits that
                     required recontouring and reseeding of the site
                  Reverse Circulation Rotary Drilling Method
                    Reverse circulation rotary drilling was used to remove accumulated
                  sediment and debris from wells that were constructed of concrete,  brick
                  and, occasionally, steel or stovepipe. The wells closed with this method
                  ranged from 16  inches to 72 inches  in diameter to depths of 150 feet.
                  Some wells had  cased or screened  extensions below the concrete or
                  brick casing.
                    The reverse circulation rig utilizes large capacity centrifugal or jet
                  pumps to aid in the removal of cuttings from the borehole. Drill pipe
                  (threaded or flanged) is larger in diameter than direct rotary drill pipe
                  to accommodate  drill cutting removal and to drill larger  diameter  holes
                  up to 72 inches.  The drill string is rotated from a Kelly table instead
                  of a Kelly pipe (bar) due to the  higher torque required to rotate the
                  larger and heavier drill string. The formation or accumulated sediment
                  are cut by drag bits or reamer bits.
                    In reverse  circulation rotary  drilling, the flow  is reversed from the
                  direct rotary  method (Fig. 7). The  drilling fluid and suspended cuttings
                  move upward inside  the drill pipe (string) by a centrifugal pump and
                  are discharged into the mud pit. Cuttings are allowed to settle out in
                  the mud pit prior to the  drilling fluid returning to the borehole by gravity
                  flow. The fluid flows down the annular space, between the drill pipe
                  and well casing or borehole wall, to the bottom of the  hole,  picks up
<.M    ROCKY MOUNTAIN ARSENAL
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                                  REVERSE CIRCULATION ROTARY DRILLING
                                  The drilling fluid/water flows from
                                  the mud pit down fhe borehole  outside
                                  the drlllrods.  Fluid  Is then  pulled
                                  through the  bit Into  the  drlllrod  carrying
                                  cuttings.  Fluid Is pulled upward.
                                  flowing through the  swivel and mud
                                  pump and Into the mud pit, where the
                                  cuttings settle out.
                                                    notion  Strainer
                        / Traveling Block

                         Swivel

                                  Mud  (Piston)  Pump
                        ^Drilling  Mud
                      ^^Tand  Cuttings
    Drill Bit
Reverse Rotary Drilling was
utilized to close larger diameter
holes 24" - 72").
                            Figure 7
                Reverse Circulation Drilling Method
cuttings and re-enters the drill pipe through ports in the bit carrying
cuttings in suspension back up through the  drill pipe. Cobbles or
boulders that cannot pass through the drill pipe are removed with an
orange-peel bucket.
  The orange-peel bucket was used to excavate accumulated sediment
and/or debris in the wells. The heavy metal bucket, fitted with four
leaves that form a steel jaw, opens outward from the bottom. The bucket
is dropped into the well on a cable system with the bucket jaws open.
The weight of the  bucket digs the jaws into material at the bottom of
the hole. The jaws then close on a load of material, which is withdrawn
from the hole and  dumped at the surface.  Smith and Schneider6
describe the use of the orange-peel bucket for well installation. Large
diameter wells selected for closure at RMA were initially drilled with
the orange-peel bucket until no further advancement could be made.
Then reverse circulation drilling was employed to complete the closure.
  The bottom of a well was verified based on observation of cuttings
and drill rig reaction. Most wells closed with this method were con-
structed in the alluvium with screen set just above consolidated material.
Indications that the bottom of the well had been reached included: stiff
drilling, refusal, consolidated material, lack of well debris or lack of
accumulated sediment.
  Some problems encountered with the reverse circulation rotary drilling
method included:
• Limitation of accessibility at sites due to rig size
• Large amount of water supply for circulation also requires large mud
  pit
• Surface collapse problems caused by  the use of a large amount of
  water for circulation in unconsolidated (sandy) material
• Flowing sands and collapse of well casing
  Some of these problems were solved by using conductor casing set
inside the well casing to help keep the well open and allow circulation.

Percussion Hammer Drilling Method
  A percussion (casing) hammer drill drives a double-walled steel casing
into the ground with a diesel pile-driving hammer. The drilling method
can rapidly penetrate unconsolidated material including sand, gravels
and cobbles.
  Reverse-air circulation cools the bit and removes cuttings from the
boring. Air is forced down the drill pipe that escapes through ports
on the bit, lifting the cuttings back to the surface and into a cyclone
where the cuttings drop out of the circulated  air.3 The cuttings can then
be collected in a drop  box or drums to contain any contaminated
material.  Water-based drilling fluid can  also be used to help in the
removal of drill cuttings.  At RMA the dual walled drill pipe was driven
over PVC casings up to 6 inches in diameter and up to 100 feet deep.
Successful attempts were made to pull the well casing prior to drilling,
then the boring was redrilled to remove well construction matter. This
type of drilling helped alleviate the problems encountered with crooked
wells. The bottom of the well was determined based on cuttings and
drill rig reaction. The borings were cleaned with the reversed air cir-
culation and grouted.
  Problems encountered  with the Percussion Hammer Drilling method
included:
• Drilling across crooked PVC wells
• Limitations on site accessibility due to weight of the rig
• Material becoming lodged in return line (safety hazard due to potential
  breaking of return line)
• Drilling problems in flowing sands

WELL CLOSURE
  Recommended closure  methods employed during the program
included standard procedures commonly used in the water well and/or
petroleum industries. Modifications to these procedures were made on
a case-by-case basis. All closures were performed in compliance with
the requirements of the State of Colorado4  as well as  USATHAMA7
and  SDWA (UIC).
  Each well to be closed was evaluated individually, with careful con-
sideration given to the well construction characteristics and the geologic
setting. Closure techniques were then adapted for each  individual well
to accommodate well depth and the volume  of grout required to effec-
tively seal the well was calculated. If artesian conditions existed, the
sealing operation was designed to confine the water and prevent transfer
of groundwater between aquifers.4
  Standard closure practices included removal of all materials  which
would hinder the sealing operation, including screen and casing (Fig. 8).
If the casing was in good condition, an attempt was made to remove
it by fishing with cables, tools or sand-locking techniques. If the casing
was  in poor shape, an attempt was made to either  overdrill or wash
out the soil surrounding the casing to facilitate its removal. If the casing
could not be removed, it was cut, torn or perforated to  allow the grout
to completely seal the annular space. At a minimum, casing was removed
50 feet into the formation below the contact  with the alluvium (as
specified  by Colorado regulation). The targets for perforations were
                                               REVIEW AVAILABLE WELL DATA
                                                                     Figure 8
                                                               Standard Well Closure
                                                                                                        ROCKY MOUNTAIN ARSENAL    915
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zones of permeability, sand zones or contacts, where it is important
to have a good seal to prevent potential cross-aquifer contamination.

Large-Diameter Hand Dug Wells
   Wells at RMA with diameters of 24 to 60 inches and depths of 30
to 90 feet (hand dug or drilled) were typically constructed with cement,
stone, or brick liners. Prior to closure, debris was removed from these
wells by fishing tools with cables, reverse rotary drilling or cable tool
methods.  The bottom of each well was then inspected for drilled, cased
extensions. These types of wells were closed by filling the wells with
sand to within  10 feet of the surface, followed  by capping with
commercial concrete to three feet below grade. The remaining space
was allowed to collapse and fill with matrix  soil (Fig. 9). Those wells
found to have drilled, cased  extensions were closed as drilled wells by
grouting  in the extension portion, followed by closure of the upper
portion as described  above.

                                          Small  Diameter (<24")
                                             \ Wells
                                                    Closure Boring
                                                    Filled with Grout
                                                    From Bottom  to
                                                    Surfoce,
                                                            Boring
                                                    Casing/Screen
                                                    Removed
                             Figure 9
                       Well Closure Methods
Deep Drilled Wells
  Methods selected for the closure of deep (>200 feet) drilled wells
were based on available well construction information review. These
wells were effectively cleaned and closed using mud rotary methods.
Due to the depths of these wells, geophysical logs were run to deter-
mine the condition of the casing in the well and to aid in decision-making
on perforations and casing removal.
  Borehole  geophysical  logs were  evaluated for determination of
screened intervals and lithology of the borehole. The condition of the
casing and the location of casing and screen connection joints (CCL
log)  were taken  into consideration to help define zones that  needed
perforation to seal the well.
  Mechanical perforation methods were originally  proposed but deter-
mined to  be  unfeasible due to poor  well  conditions and  small well
diameters Class A explosives in shaped charges  were utilized to cut
holes in steel casing,  concrete and the formation behind the  casing.
  Follow ing perforation activities, the  well was grouted from the bottom
to a preselected interval. The grout was allowed to cure for 24 hours,
then well casing  overdrilling was used to remove the upper portion of
the well. Following remo\'al of the well casing, the boring was grouted
from the bottom  to the ground surface  (Fig. 9).

Shallow  Monitoring  Wells
  Shallow monitoring wells were usually constructed of PVC  or steel
casings with short screened intervals in unconsolidated alluvial materials
or water-bearing formations. Auger or hammer drilling methods were
normally used to close the wells following the procedure outlined in
the well cleaning and closure sections. If removal or perforation of the
casing was not possible, the  closure  technique was  modified and
included: backfilling the screened portion of the well with clean sand
and filling the remainder of the borehole with grout to the ground sur-
face, or drilling out the casing. If the depth of the well and the location
of the screened interval extended across more than one aquifer, the en-
tire casing and screened interval was required to be filled with grout
to the  ground surface  (Fig.  9).

Grout Placement in Small  Diameter Wells
  Following removal or perforation of the casing materials, grout was
mixed and placed in the borehole of small (< 24 inches) diameter wells.
A slurry of Type I-n  cement and approximately 3 to  5% bentonite
powder was prepared. This slurry was pumped under pressure through
a tremie  pipe to within one foot of the bottom of the borehole by the
Brandenhead method. With this method, mud channels are minimized.
  Grout  mixtures  of  this composition  are reported  to  attain an
approximate density of 14 lb/gal.9 This density is sufficient to displace
the  drilling fluid column. After allowing the grout column to cure, the
grout column was topped off to bring the grout level to within two feet
of the surface.

CONCLUSION
  Contamination of aquifers is a major environmental concern to PRPs,
industry and government. The closure of abandoned or unusable wells
is an important method for controlling this potential migration pathway
for  aquifer cross-contamination.
  If a well is unused, abandoned or of questionable integrity, the well
should be assessed  for  potential current or future use for monitoring,
dewatering, injection, etc. If the well does not comply with applicable
regulations, then closure should be recommended.
  Methods of well  closure are modified from those used in the well
drilling industry and vary depending upon the physical characteristics
of the well. The wells must be located,  if they have been damaged or
buried, and characterized by visual inspection or investigation  with
appropriate drilling and geophysical technologies. The actual closure
of the well and associated boring will be dependent upon local regula-
tions and conditions. Well closure programs are important in minimizing
or providing control to potential  aquifer cross-contamination.


REFERENCES
1. Gem Systems, Inc., 1989, GSM 19 Overhauser Memory Magnetometer In-
  struction Manual.
2. Pickett, G.R., "Resistivity, Radioactivity and Acoustic Logs," in Subsurface
  Geology, ed. L.W.  LeRoy and  LeRoy, D.O., Colorado School of Mines,
  Golden, CO, 1977.
3. Driscoll, EG., Groundwater and Wells, 2nd Edition, Johnson Division, St.
  Paul, MN, 1986.
4. State of Colorado,  Division of Water Resources, State Board of Examiners
  of Water Well Construction and Pump Installation Contractors, Revised and
  Amended Rules and Regulations for Water Well Construction and Pump In-
  stallation, 1987.
5. Wilson Downhole  Services,  Fishing  Seminar, Wilson Industries,  Inc.,
  Houston, TX.
6. Smith, R.O., Schneider, PA.  and Petri, L.R., "Groundwater Resources of
  the South Platte River Basin in Western Adams and Southwestern Weld Coun-
  ties, Colorado," U.S. Geological Survey Water-Supply Paper No. 1658,1964.
7. Department of the Army, "Geotechnical Requirements for Drilling, Monitor
  Wells,  Data  Acquisition and Reports," U.S. Army Toxic  and Hazardous
  Materials Agency (USATHAMA), Aberdeen Proving Ground, MD, 1987.
8. Colog, Inc., "Standard Operating Procedure for Use of Explosives for Well
  Perforation Activities," Colog, Inc., Golden, CO,  1988.
9 Moss.  R. and Moss, G.E , Handbook of Groundwater Development, John
  Wiley and Sons, New York,  NY,  1990.
       ROCKY MOUNTAIN ARSENAL
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                 Remediation  of a  Surface  Impoundment Basin F-
                                         Rocky Mountain Arsenal

                                                    Edwin W. Berry HI
                                              Office of the  Program Manager
                                                  Rocky  Mountain Arsenal
                                                 Commerce City, Colorado
 INTRODUCTION
  In Feb. 1989, the Department of the Army, Shell Chemical Com-
 pany, the U.S. EPA, the Department of Interior and the Agency for
 Toxic Substances and Disease Registry, entered into a Federal Facility
 Agreement (FFA) to establish a procedure through which the organiza-
 tions will cooperate in the implementation of response actions at Rocky
 Mountain Arsenal. One provision of the Agreement provides that
 specified Interim Response Actions which are compatible with long-
 range cleanup goals will be implemented in advance of a final Record
 of Decision, not planned until 1994. The remediation of Basin F is one
 of 13 IRAs identified in the FFA.
  Use of the Interim Response Action provisions of CERCLA at this
 NPL site significantly accelerated the time-frame for remediation as
 compared to the time that would be required for remediation after the
 Record of Decision. It is estimated that six years were saved by using
 this approach to a remedial action.
  This paper presents a case history of the remediation of "Basin F,"
 a 93-acre hazardous waste surface impoundment and as reported by
 other Superfund project site managers relates the challenges above and
 beyond typical construction project events and problems. Problems
 resulting from unusual weather conditions, community relations issues
 and reprogramming activities are highlighted rather than discussions
 of the normal construction and historical events.

 PROJECT OBJECTIVES
  Objectives of the Basin F interim action were: (1) eliminate future
 emissions of volatile chemicals from the basin; (2) to prevent infiltra-
 tion of Basin F contaminated liquids into underlying groundwater; and
 (3) to eliminate potential adverse impacts to wildlife that otherwise would
 come in contact with the contaminated liquids, sludges and solids. All
 of the objectives were achieved.

IMPOUNDMENT DESCRIPTION
  Basin F was constructed at Rocky Mountain Arsenal in 1956 for
disposal of contaminated liquid wastes from Army and lessee chemical
manufacturing operations. When constructed, Basin F was provided
a 3/8 inch thick catalytically blown asphalt membrane liner. This liner
was covered with a 12 inch protective soil/sand cover. Basin F covered
approximately 93 acres and had a capacity of 240 million gallons. Design
and construction of Basin F was a cooperative effort of the Bureau of
Reclamation and the Army Corps of Engineers (COE). In addition to
its life as a solar evaporation pond at RMA for 32 years, Basin F was
used as the settling basin for liquid waste prior to its treatment and
injection into the 12,000 foot deep well. The injection well has also
been closed.
Project Phrasing - Major Events
  After the contract for the remediation project was awarded, the COE
issued a notice to proceed in February 1988. Site preparation began
in March 1988. Initial work was designed to provide health, safety and
administrative facilities for the 180 personnel who would work at the
site for approximately one year. Special decontamination facilities were
constructed to accommodate the 110 workers who would enter the heavily
contaminated portion of the site. Initial activity included installation
of a 360° air monitoring network of high volume samplers and initia-
tion of a sampling program to characterize the surface characteristics.
Borings were placed on 50  foot centers to develop waste volume
estimates and to determine the extent of deposition of sludge material.
  Pumping of the liquid from the impoundment into 4,000,000-gallon
capacity storage tanks began in May 1988 with expectations that  this
storage capacity would be adequate. Stainless steel tanker trucks were
utilized to transport the liquid due to its extremely difficult material
handling properties.
  The first of several major weather complications to impact on the
project arrived in  May 1988 in the form of a 20-year rain event, yielding
3.5  inches of precipitation before it ended. The immediate effect  was
to increase the volume of chemically-contaminated liquid to 14,000,000
gallons, 10,000,000 million gallons in excess of tank capacity. This
increased volume of contaminated water also affected the site condi-
tion by expanding the shoreline to the point that it covered the planned
construction areas for a 16-acre waste pile. This waste pile was sup-
posed to contain the 480,000 cubic yards of dried waste that would be
generated by the  time the project ended.
  Immediate relief was achieved by constructing two double lined waste
ponds with 8,500,000 and 5,000,000 gallon capacities. The excess liquid
was transferred to these ponds, which then were covered. These ponds
also were used to collect leachate from the waste pile.
  The second major weather event occurred in June 1988, with a tornado
moving from west to east across the northern perimeter of the site. The
tornado caused damage to heavy equipment and, as we later discovered,
also placed contaminated soil particles between the layers of HOPE
liner as the ponds were being constructed. It was not until one  year
later that contaminated leachate was found in the collection systems.
This development gave rise to questions concerning the integrity of the
newly constructed ponds.
  Increasing volume estimates continued during later project phases.
At completion of the liquid pumping,  it was determined that bottom
elevations used to calculate waste volumes were incorrect and that
deposition of crystallized  waste into  a  hardened   solid  form had
dramatically misled  project  planners.  New exploratory excavation
revealed that another 4 feet of crystal waste and yet another 4,000,000
gallons of liquid waste remained entrenched in layers above the asphalt
                                                                                                 ROCKY MOUNTAIN ARSENAL    917
-------
liner.
  This discovery led the Army, the U.S. EPA and the COE to begin
a phase known as constructive suspension of the project to evaluate
engineering and cost alternatives. To the credit of the managers involved,
schedule and cost growths were authorized and a planned winter work
shutdown was canceled concurrent with a decision to move forward
through the winter of 1988 and to complete the project as nearly as
possible  to the original completion dates.

Odor Problems and Community Involvement
  In parallel with  increased volumes,  cost growth and expanded
schedules, odor problems developed in the community one mile from
the site; community concerns arose in August 1988. Prior to construc-
tion, numerous air monitoring studies had evaluated the potential for
VOCs  emissions; no potential off-site health hazard was identified.
Nonetheless, local citizens soon complained of odors causing symptoms
of nausea, headaches and choking. In retrospect, it is clear that these
odor problems caused decreased public confidence in the program,
which, in turn, necessitated major program modifications to:  evaluate
and implement odor control measures; reevaluate of acute and chronic
health effects (conducted concurrently by six health organizations); and
operate an odor control team which responded to a telephone hot-line
around-the-clock.
  Unique to this project was the delivery of 40 room air purifiers to
the residents to control odors in their homes. While odor problems have
been reported at other cleanup sites, this factor weighed heavily on com-
munity acceptance of the project even though Basin F had been known
in the community for 32 years at the time of remediation.
  A series of public site tours, public data exchange opportunities and
question and answer sessions was implemented to respond to community
concerns  regarding the odor problem. Ultimately,  legal action  was
initiated by citizens who considered themselves harmed by the odors.
All parties involved acknowledged that the Basin F project was being
conducted in  a commercial/industrial/residential mixed  area with
numerous odor sources. These factors will be considered well in advance
of future cleanup activity.
  Again, the sponsor and regulatory agencies had to evaluate alternatives
in order to proceed with the project with the potential of choose between
slowing down the cleanup and extending the schedule or proceeding
with controlled activity and finish as soon as possible, thereby shortening
the nuisance time. Assurances from senior health officials, based on
the air monitoring data and lexicological evaluation that air quality was
safe, provided the answer.

BASIN F - A SUCCESS STORY
  In evaluating the events at Basin F, in retrospect, one learns that  not
all  Superfund cleanups progress smoothly. Examples exist of sites
partially finished that remain on some federal court docket. Work was
never begun at other sites  after years of RI/FS  study and analysis.
Evaluation of remediated site conditions today shows that the area is
safely protected from the environment as stated in project objectives.
On  some projects, only persistence  will win the day.
       ROCKY MOUNTAIN ARSENAL
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              Evaluation  of Adsorption  Processes for  the  Removal
                    of  Residual Chemicals  from Water  Treated  by
                       an Ultraviolet/Chemical  Oxidation  System
                                                    Mark £. Zappi
                                        USAE Waterways Experiment Station
                                                Vicksburg, Mississippi
                                                   Michael D. Klein
                                              Harding Lawson Associates
                                                   Denver, Colorado
                                                   Kathryn R. Cain    ,
                                               Rocky Mountain Arsenal
                                              Commerce  City, Colorado
 ABSTRACT
  As one of several Interim Response Actions (IRAs) being conducted
 at Rocky Mountain Arsenal (RMA) under CERCLA, the Program
 Manager for Rocky Mountain Arsenal (PMRMA) chose ultraviolet
 (UV)/chemical oxidation as the best process for treatment of approx-
 imately 300,000 gallons of hydrazine-contaminated rinsewater at RMA.
 The rinsewater is contaminated with hydrazine and hydrazine-derivative
 compounds, such as unsymmetrical dimethylhydrazine or 1,1 dimethyl-
 hydrazine (UDMH) and monomethyl hydrazine (MMH), in concen-
 trations in excess of 1,000 mg/L, as well as N-nitrosodimethylamine
 (NDMA) and organic compounds such as organochlorine pesticides
 and chlorinated hydrocarbons.
  Because the project action level for NDMA  is  1.4 pg/L (ppt) and
 because the hydrazine fuels decompose before NDMA is destroyed to
 the action level, 1.4 pg/L of NDMA was targeted as the goal for treated
 effluent.  The UV/chemical oxidation process typically can treat
 hydrazine compounds in 16 hours, while 35 hours are required to
 decrease the NDMA concentration to approximately 1 to 2 ppb Otg/L),
 which does not meet the treatment goal of 1.4 pg/L.
  Investigating a possible secondary treatment that could reduce NDMA
 concentrations even further, RMA and the U.S. Army Engineer Water-
 ways Experiment Station (WES) attempted to achieve a lower effluent
 level without costly additional UV/chemical oxidation treatment. Three
 adsorption processes, granular activated carbon (GAC), organic-based
 ion exchange resins and activated  alumina, were evaluated by WES.
 None of the adsorbent manufacturers could provide any information
 on the NDMA removal  performance and adsorptive capacity of their
 products. Therefore, a bench-scale treatability study was initiated at
 WES to evaluate the three adsorption processes for removing trace
 amounts of NDMA from the UV/chemical oxidation system effluent.
  Results from the  study indicate that  GAC is the best adsorbent
 evaluated because of its ability to  reduce NDMA levels consistently
 below  2 ng/L. An economic analysis comparing GAC treatment to
 additional UV/chemical oxidation treatment was performed and  the
 results show that significant cost and time savings can be achieved by
 using GAC as a  secondary treatment process.

 INTRODUCTION
  The Hydrazine Blending and Storage Facility (HBSF) at Rocky Moun-
 tain Arsenal (RMA) in Denver, Colorado, is owned by the U.S. Air
 Porce (USAF) and was operated by RMA between 1962 and 1982 as
 a depot to receive, blend, store and distribute  hydrazine fuels. The
primary operation was the blending of anhydrous hydrazine and un-
symmetrical dimethyl hydrazine (UDMH) to produce Aerozine 50, a
rocket piopellant, in response to requests by the  USAF.  The materials
were manufactured elsewhere and shipped to RMA for blending. Other
operations performed at the HBSF included loading and unloading rail
cars and tank trucks carrying hydrazine fuels, destruction of off-
specification batches of Aerozine 50 and storage of Aerozine 50,
anhydrous hydrazine, monomethyl hydrazine (MMH), monopropellant
hydrazine, hydrazine 70,  UDMH and hydrazine.
  Hydrazine and UDMH are ignitable, corrosive and reactive, thus
meeting the  identification criteria for the characteristics of a hazardous
waste as defined by 40 CFR 261.' They are unstable in the natural
environment and rapidly decompose when exposed to the atmosphere.
One of the decomposition products of UDMH  is N-nitrosodimethy-
lamine (NDMA), a suspected carcinogen.2 The NDMA detected in
wastewater samples is an intermediate generated during the produc-
tion of  UDMH using  nitrosation  and the  catalytic reduction  of
dimethylamine.3
  When the OSHA inspected the HBSF in 19824 and found airborne
NDMA, RMA ceased operations and closed the HBSF to all but essen-
tial personnel. All blending materials were removed and the tanks and
piping were decontaminated. These activities resulted hi the genera-
tion of 300,000 gallons of rinsewater, which contains approximately
1,000 mg/L  of hydrazine, 160 mg/L of MMH, 1,100 mg/L of UDMH
and 180 /*g/L NDMA.
  In the Decision Document for the HBSF cleanup, the Army agreed
to attempt treatment of the NDMA in the wastewater to 1.4 pg/L, the
Ambient Water Quality Criterion for NDMA. Although not applicable,
the value is considered a relevant and appropriate requirement (ARAR),
thus serving as the ARAR governing the cleanup of the HBSF. The
1.4 pg/L level is well below the analytical detection limit for NDMA,
making verification of successful treatment very difficult.

SELECTION AND DESCRIPTION
OF A TREATMENT PROCESS
  After a thorough review of the possible treatment alternatives, an
ultraviolet (UV) light-catalyzed chemical oxidation process was selected
for the destruction of the hydrazine fuel compounds (hydrazine, UDMH
and MMH) and NDMA present in the wastewater. Three UV/chemical
oxidation systems were evaluated based on the results of bench-scale
treatability tests performed by each vendor on samples of wastewater
supplied by RMA.  The treatability tests were performed by each ven-
dor at their respective laboratories, while chemical analyses were per-
formed by an RMA contract laboratory.5'7 A UV/hydrogen peroxide
(Hf>2) system marketed as Perox-Pure by Peroxidation Systems, Inc.
(PSI), was selected based on the results of the treatability tests. The
Perox-Pure system utilizes medium-pressure  UV lamps with a pro-
prietary  UV spectrum and  injection of a 50% hydrogen peroxide
solution.
  Destruction of contaminants in  UV/HjOj treatment systems  is
                                                                                           ROCKY MOUNTAIN ARSENAL   919
-------
                                            Hydrogen
                                             Peroxide
                                                                Seal Water
                                                                  Recycle
     Hydrazine
   Waste Water
      Influent
                                                                                                           Post
                                                                                                   Treatment/Chemical
                                                                                                       Conditioning
                                                     Effluent
                                                 pH
                                             Adjstment
                                                                Figure 1
                                                          Process Flow Schematic
                                                   Hydrazine Wastewater Treatment Facility
                                                      Rocky Mountain Arsenal HBSF
 accomplished by: (1) photolysis via UV  irradiation,  (2) chemical
 oxidation by the hydrogen peroxide and hydroxyl radicals, which are
 strong oxidizers produced during photolysis of hydrogen peroxide and
 (3) the synergistic effects of both the chemical oxidizer species and the
 UV light.
   Based on the treatability results generated by PSI, a Model No.
 CW-180 was selected because of its ability to provide appropriate reactor
 volume and flexibility. The system is housed in  a newly constructed
 building at  RMA. A general process flow schematic  of the RMA
 Hydrazine Wastewater Treatment Facility (WWTF) constructed to treat
 the hydrazine wastewater  is presented in Figure 1. The total system batch
 capacity is 1,300 gallons.
   The wastewater treated by the WWTF is pumped from a steel tank
 located at the HBSF through a pretreatment system for the removal of
 iron and suspended solids and then is stored in  a feed tank.  Process
 chemicals, including  hydrogen peroxide,  caustic soda, catalyst and
 sulfuric acid, are fed into the wastewater at a chemical injection header
 upstream of the UV/HjO2 reactor. When required, these chemicals are
 dispersed through the wastewater by an in-line  static mixer located
 downstream of the inlet header. After passing through the static mixer,
 wastewater enters through a pressure vessel containing vertical tungsten
 rods arranged in  a bundle. The tungsten serves  as a catalyst for the
 hydrazine/chemical oxidizer species reaction.   Before  entering the
 UV/H2O, reactor, the wastewater passes through a bag filter located
 downstream of the catalyst pressure vessel. The bag filter removes iron
 floes carried over from  the feed tank.
   Treatment of the wastewater is accomplished in batch mode. A recycle
 module allows continuous recirculation of wastewater through the
 UV/H2O2 reactor and its associated recycle tank  during treatment. In
 the context of this report, batch time represents total system (\JV/H2O2
 reactor, chiller and recycle tank) hydraulic  retention time, but actual
 UV/H,O, reactor hydraulic retention time  is 25  % of the total  batch
 time for a 1,000-gallon batch. The recirculated wastewater is cooled
 via a chiller module, which circulates coolant through coils in the recycle
 module tank to remove excess heat generated during the UV/oxidation
 process. The temperature  of the wastewater is  maintained at 125 to 140 °F.
   The UV/H;O, process is operated at the initial pH of the wastewater
 brought in from the storage tank.  Because the wastewater is a  basic
 solution with a pH of 9.1 to 9.3, the hydrarine fuels act as a reducing
 agent. As the destruction  process takes place in the UV/H,O2 chamber,
 the favored  reaction  for hydrazine  is oxidation  to N,.- The rate  of
 hydrazine fuel destruction is measured by the decrease in pH and the
change in oxidation reduction potential (ORP) from a negative value
to a positive value. Once the pH levels off at approximately 7.0, the
destruction of hydrazine fuels is complete (Fig.  2).
  Following treatment in the UV/H2O2 reactor, the wastewater  is
pumped to one of two effluent holding tanks for analytical characteriza-
tion and pH adjustment,  if necessary, prior to disposal.

DESTRUCTION EFFICIENCIES
  Bench-scale studies performed by the Illinois Institute of Technology
Research Institute (IITRI) and PSI indicate that hydrazine fuel com-
pounds  are initially destroyed at a rapid  rate, but the rate decreases
as the concentration of hydrazine fuel compounds decreases. Based on
the experimental results, PSI5 and nTRI8  conclude that destruction of
hydrazine fuels and MDMA can be accompanied by the UV/HjO2 pro-
cess and that during the UV/HjOj process, hydrazine is decomposed
prior to NDMA destruction.
  Pilot testing was performed by Harding Lawson Associates (HLA)
under PMRMA contract using the full-scale UV/HjOj treatment
system to confirm the bench-scale treatability test results. The bench-
scale testing indicated that hydrazine and NDMA destruction could be
accomplished in 16 hours. The pilot-scale  testing verified that the
hydrazine fuels  are decomposed prior to  limited NDMA destruction
and determined that the time required for successful treatment of NDMA
and the  hydrazine fuels is dependent on the influent concentration of
NDMA. Further pilot testing indicated that treatment time of more than
50 hours may reduce the NDMA concentration below 1 jg/L, unfor-
tunately at a significant increase in treatment cost, but still may not
reach  the target effluent levels of  1.4 pg/L of NDMA.

ADSORPTION COLUMN  TESTING
  Because of the low target treatment levels and the extremely long
time required for the UV/HjOj process to reach those levels,  if they
could  indeed be reached (Fig. 3),  various adsorption processes were
evaluated for removal  of the residual NDMA  from the UV/Hj02
reactor effluent  after hydrazine compounds were destroyed (approxi-
mately 20 hours of treatment). This evaluation was performed in hope*
of meeting the  NDMA action level at an appreciable cost and time
savings over additional UV/HjOj treatment beyond the hydrazine com-
pound destruction end-point, which can be detected during system opera-
tion by  monitoring UV/H^Oj  reactor pH and  oxidation reduction
potential (ORP).
"20    R(K"KY MOUNTAIN ARSENAL
-------
900 -
800 -
700 -
Q.
g 600 ^
"S 500 -
~c -
u 400 -
O I
1 300 -
 0 -
-100 -
-200 -
-300 -
-400 -
13.0
12.0
11.0
X
^ 9.0
O
i_ 8.0
_4_f
s 7-°
a:
6.0
CM
o
CM 5.0
X
> 4.0
3.0
2.0
1.0
0.0
                                                                                    o  Total  Hz  Fuel  Cone.

                                                                                    *  pH

                                                                                      ORP
                                   10      15      20      25      30      35      40      45

                                             Reactor  Time (hrs)  Batch  No.  9

                                               Figure 2
                                  Total Hydrazine Fuel Destruction Utilizing
                                               UV/H202
                                                                                           50
                                                                                                  55
                                                                                                         60
   900



   800



   700
D_

o  600
O


^S  500  -
_c

<.  400


O  300
O
ce
   200
CM
o
CM  100


>    0


  -100


  -200


  -300


  -400
a
13.0



12.0



11.0



10.0



 9.0



 8.0   -
o;
    6.0
CM
O
CM  5.0
X

>  4.0


    3.0


    2.0


    1.0


    0.0
             100000 -g
                0.1
                        I  I I  I I I  I I  I I I  I I  I I  I I I  I I  I I I  I I  I I I I I  I I  I I I  I I  I I I  I I  I I I  I I  I I  I I I  I I  I I I  I 1

                            5      10     15     20     20     30     35     40     45     50     55      60

                                             Reactor Time  (hrs)  Batch  No.  9


                                               Figure 3
                                   NDMA Destruction Utilizing UV/H2O2
                                          Treatment Process
                                                                                 ROCKY MOUNTAIN ARSENAL    921
-------
  Adsorption column testing was performed at the U.S. Army Engineer
Waterways Experiment Station (WES). Test influent for this study was
collected from the UV/HjOj system effluent tank,  had a pH of 2.45,
had an NDMA concentration of 66 /ig/L and was shipped to WES in
two 55-gallon drums.
  The  adsorbents evaluated at WES were granular activated carbon
(GAC), activated alumina and two synthetic resins. Table  1 lists the
manufacturing source, trade name and vendor for each absorbent. The
columns were constructed of Plexiglas and measured 2.0 feet in length
and 0.17 feet in diameter. The columns were run in an upflow mode
using peristaltic pumps and flowmeters to control the influent flow rate
(Fig. 4). Stainless steel screens were placed over the  inflow and outflow
ports of the columns to prevent the adsorbents from exiting the columns.
                            Table 1
                  Adsorbent Types and Sources
                                            Adsorption Column Effluent NDMA Concentrations
    Adsorbent
                                    Brand
 Activated Carbon   Coconut Shell

 Activated Alumina  AluBinua Oxide

 Ion Ezchanffe      Polyaroaatlc

 Ion Exchange      -S03-H* Bated
CC 601

Celcxaon b CDO

XAD-4

Aaberlyat 15 WET
Manufacturer

Heitates

Alcoa

Roha and Haas

ROQB and Haal
        TEST COLUMN
                           Figure 4
                 Adsorption Column Test Apparatus
  The adsorbents were soaked for 24 hours in distilled, deionized (DDI)
water before they were loaded into the columns.  The columns were
filled with DDI water prior to loading them with the adsorbents so that
the adsorbents would stay wetted. As the adsorbents were added to the
column, DDI water was removed to prevent the columns from over-
flowing. Each column was completely filled  with the appropriate
adsorbent.
  All columns were run at a flow rate of 0.15 L/min,  which equates
to a hydraulic flux of 2.0 gpm/ft2. The empty bed contact time (EBCT)
for all columns was 8.25 minutes. NDMA samples were collected from
each column at 5, 10, 20, 40 and 70 bed volumes. A bed volume con-
stitutes an amount equal to the total volume  of the empty column.

COLUMN TESTING RESULTS
  The effluent NDMA concentrations from each column and the respec-
tive bed volumes at the time the samples were collected  are listed in
Table 2. Figure 5 is a plot of NDMA concentrations versus bed volumes
passed through each column.
  At 40 bed  volumes,  the effluents  from  all columns  experienced
increases of varying magnitudes in NDMA concentration (Fig. 5). The
reason for  this increase in effluent NDMA concentration is unknown.
The first of the two drums containing the test influent was emptied after
40 bed volumes had passed through each column, requiring that a sample
                                           5
                                           10
                                           20
                                   8.576
                                   8. 189
                                   8.078
                                   1.218
                                   9.828
                                         IAD-4
                                         Ippbl

                                         0. 755
                                         8.286
                                         8.585
                                         2. 518
                                         «. 117
                                                                                      Aabarlyit
                                                                                       IS NET
8.188
«. 167
8.265
1.678
1.668
from the second drum be used to complete the study. It is possible that
changing drums may have upset the adsorbent/adsorbate equilibrium,
due to slight differences in influent quality, causing desorption of NDMA
to occur until equilibrium was again reached with the new influent.
  Table 2 shows that the activated alumina column had the highest
effluent NDMA concentrations of the four adsorbents. However,
activated alumina did provide significant removal of NDMA from the
influent, except for bed volume No. 5 which had  a concentration of
201 fig/L and was not plotted because the high value would have distorted
the plot. The activated alumina bed volume No.  5 concentration is
approximately three  times higher than the influent NDMA concentra-
tion. The reason for this increase in NDMA concentration through the
column is not understood.  It is possible that sample  bottle or analytical
contamination  could have occurred, but the  QA/QC  procedures
associated with the NDMA analysis indicated no  such problems. A
second possibility is that the activated alumina initially contained NDMA
produced during the manufacturing process; however, the NDMA
removal achieved during subsequent bed volumes does not substantiate
this conjecture unless all of the NDMA was washed from the activated
alumina prior to sampling of bed volume No.  10.
  The two synthetic resins had appreciable NDMA removals throughout
the 70 bed volumes.  The Amberlyst 15 WET resin  performed slightly
better than the XAD-4 resin. Also, the  two resins did seem to have
more consistent NDMA effluent concentrations than the other two
adsorbents.
  In Table 2, it can be seen  that the activated carbon generally had
either the lowest (bed volumes 20, 40 and 70) or the  second lowest (bed
volumes 5 and 10) NDMA concentrations. All of the activated carbon
column effluents were less than 1.5 /tg/L, with only one sample (bed
volume 40) greater than 1.0 /ig/L. This result is surprising because some
activated carbons are actually used to purify amine compounds.
  Based on the results of the adsorption studies, GAC was considered
the best adsorption process because: (1) GAC generally had the lowest
NDMA effluent concentrations; (2) GAC seemed less sensitive to system
upset than the other adsorbents and (3)  resins traditionally, are very
sensitive to changes in influent quality, but GAC is much more flexible
in its ability to respond positively  to influent changes.

ECONOMIC ANALYSIS OF TREATMENT  ALTERNATIVES
  Because NDMA breakthrough was not detected in the effluent from
the activated carbon column after 70 bed volumes, for sake of economic
comparison it was assumed that the activated carbon column could treat
at least 70 more bed volumes before NDMA breakthrough. At this
loading, approximately 130 gallons of column influent could be treated
per pound of activated carbon.
  The cost of the activated carbon used in this study was $1.59/lb. Thus,
using  activated carbon to treat  all 300,000 gallons of the post-
UV/HjOj-treated water for an additional 30 hours would cost approx-
imately $13,000 and would take approximately 600 hours. This cost
estimate does not include labor or energy costs because they were con-
sidered minimal; the operation of small adsorber  systems is neither
labor-intensive nor energy-intensive. Labor associated with operating
a low-flow (<10 gpm)  GAC  canister system consists of turning the
system on and off daily and periodically changing the exhausted GAC
canister; operator supervision of this type of system usually  is  not
required. Energy costs associated with a low-flow GAC system consist
of the  operation of a small influent pump.
  Conversely, labor and energy associated with  the UV/HjOj system
costs are significant;  the additional 30 hours of treatment requires direct
operator system supervision  and the reactor uses  approximately  110
       ROCKY MOUNTAIN ARSENAL
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 \
 0)
 2
 Q
 Z
                                              20
                                            40
                                                60
                                                                     80
                       D
GAC
AA
Bed  Volumes
       A      XAD-4
A-15
                                                                 Figure 5
                                                          NDMA Adsorption Study
 kw/pperating  hour.  The  cost  of treating  1,000  gallons  with the
 UV/Hj02 reactor for an additional 30 hours is approximately $1,450.
 Therefore, the cost of treating all 300,000 gallons of wastewater for the
 additional 30 hours is $435,000 and the time involved is 9,000 hours.
  These estimated costs show that using the activated carbon system
 as a secondary treatment unit will result in a cost savings of approx-
 imately $423,000, which is significant compared to the overall cost of
 treating the 300,000 gallons of water. In addition,  the time saved by
 using activated carbon in the test configuration is approximately 8,400
 hours for all 300,000 gallons.

 ADDITIONAL RESEARCH EFFORTS
  Further testing will  be performed using the coconut shell-based
 activated carbon to determine whether increased EBCTs and/or pH
 adjustment would result in reduced NDMA effluent concentrations from
 the activated carbon column and to determine actual activated carbon
 NDMA-adsorption capacity.

 CONCLUSIONS
  AH adsorbents were able to remove NDMA from the test influents,
 except for activated alumina during the  initial bed volumes. The
 Amberlyst 15 WET resin performed slightly better than the XAD-4
resin. Activated carbon was considered the best of the four adsorbents
evaluated and will be further optimized in future  studies. Also, the
effluent from the GAC had consistently lower NDMA concentrations
than the effluent from the UV/HjOj system. It is believed that effluent
                                         NDMA concentrations less than 100 pg/L can be reached using GAC
                                         as a secondary treatment process. Economic analysis indicates that using
                                         GAC as a secondary  treatment system after 20 hours of UV/HjOj
                                         treatment would result in a net savings of $423,000 and 8,400 hours
                                         of treatment time.


                                         REFERENCES
                                         1. 40 CFR 261. Protection of the Environment, subpart b.
                                         2. 29 CFR 1990. Occupational Safety and Health Administration.
                                         3. Kirk-Othmer Encyclopedia of Chemical Technology. Hydrazine and its
                                           Derivatives, Wume 13, p. 734-771, John Wiley and Sons, New York, NY, 1981.
                                         4. AEHA (U.S. Army Environmental Hygiene Agency), Evaluation of Poten-
                                           tial Exposures, Hydrazine Blending Facility,  Rocky Mountain Arsenal,
                                           Colorado. Industrial Hygiene  Special Study No. 55-35-0125-83. 1982.
                                         5. Peroxidation Systems, Inc., Destruction of Hydrazines  and N-nitrosodi-
                                           methylamine in Rocky Mountain Arsenal Wastewater with  the Perox-Pure™
                                           Process. Confidential Testing Report, June 1989, Peroxidation Systems,
                                           Tuscon,  AZ.
                                         6. Solarchem  Environmental Systems, Destruction of Hydrazines and N-
                                           nitrosodimethylamine in  Rocky Mountain  Arsenal Wastewater with the
                                           Rayox™ Process. Confidential Testing Report, June  1989.
                                         7. ULTROX International,  Letter correspondence,  Results  of  Laboratory
                                           Treatability Study Conducted on Rocky Mountain Arsenal Wastewater. Con-
                                           fidential Testing Report, June 1989.
                                         8. Illinois Institute of Technology Research Institute, Neutralization of Hydrazine
                                           Fuels Using  Selected  Oxidation Processes,  Report No.  IITRI-
                                           C064567C004-TR, March 1986.
                                                                                                      ROCKY MOUNTAIN ARSENAL    923
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                 Hazardous Waste Incineration:  Remedy Selection
                           and Community Consensus Building at
                                      Rocky Mountain Arsenal
                                                  Steven E. James
                                                 Woodward-Clyde
                                                Oakland, California
ABSTRACT

  This paper discusses the selection of a technical solution to a
major  serious  hazardous waste problem and  development  of
widespread community support for that solution; it is a success
story. Rocky Mountain Arsenal is located in the Denver metro-
politan area and has frequently been called the "most contam-
inated  piece of ground in the United States," or the nation's
most serious hazardous waste site. The single most pressing and
urgent problem at  Rocky Mountain Arsenal is destruction  of
approximately 9 million gal of toxic liquid waste from Basin F,
an evaporative pond dating to the 1950s. In 1989 and 1990, a rem-
edy selection process was conducted under CERCLA, and a sub-
merged quench incinerator was  selected.  The remedy selection
process is of interest for several reasons:

• First, the waste is unique and has physical and chemical prop-
  erties that make it hard to treat in most conventional processes
  (therefore this was technically challenging)
• Second, the  work was  done under  a regulatory arrangement
  that made it necessary to accommodate the concerns and inter-
  ests of five federal agencies, a private company and the State
  of Colorado
• Third,  a 10-yr history  of (mostly  unsuccessful)  treatability
  studies and  the potential availability of promising (but un-
  tested)  new technologies presented an uneven set of technical
  data
• Fourth, for practical and legal reasons, the remedial decision
  had  to be made,  and the cleanup completed, within about a
  40-mo time frame
• Fifth, the selected  remedy called for installing a hazardous
  waste incinerator within the Denver metropolitan area, a tra-
  ditionally environmentally active area
• Sixth, a significant part of the remedy selection task was an in-
  novative community relations program that was aimed at build-
  ing consensus for a decision to avoid post-decision  opposition
  (the Army issues a "decision document" in lieu of ROD)

  The most interesting aspect of all was that no widespread public
opposition to this incineration proposal was experienced when the
decision was announced; on the  contrary, the U.S. EPA, State
of Colorado and several  local citizen  groups endorsed the de-
cision.  The incineration plant is being designed and will be built
and operated without formal permits, and the cleanup  is expected
to be completed on or ahead of schedule.  The  key elements of
ihis controversial and successful process are:

• A broad and  imaginative technology screening process
• Early and intensive use of quantitative risk analysis (as a tech-
  nology screening tool, for building public consensus for an on-
  site vs. off-site decision and for the detailed evaluation of re-
  medial alternatives)
• Use of formal decision analysis techniques (to clarify issues and
  tradeoffs, rank the alternatives, and predict/resolve concerns
  arising out of the points-of-view of the many public and pri-
  vate groups affected by the decision)
• Consensus building through direct public participation in the
  technical decision, in a community relations program

PROBLEM OVERVIEW
  For several years preceding 1988, remediation program man-
agers at Rocky Mountain Arsenal (RMA) had accumulated waste
treatability data that suggested that selection of an incineration
remedy seemed possible if not likely at this site. In mid-1988, the
Army agreed to a cleanup completion date for Basin F liquids that
meant  that  studies, design, construction, testing and operation
had to be completed in 5 yr, which is less than half of the normal-
ly required time for a hazardous waste incinerator,  if that was to
be the  chosen remedy.  Given this tight time  schedule, delays of
any length could not be tolerated; indeed, there was a pressing
need to accelerate the program. To meet this  challenge, a techni-
cal study was needed that not only addressed the subject matter
and  made a credible remedy selection, but also anticipated the
concerns and likely reactions of the public and regulators and re-
solved  these concerns prior to making a final decision. Further-
more, some type of community involvement program was needed
that  would give the public a role and a voice in the final decision,
thereby building consensus and reducing the possibility of delays
from local political pressure or litigation of local origin.

HISTORY OF BASIN F LIQUIDS
Rocky Mountain Arsenal
  Rocky Mountain Arsenal (RMA) is an installation of the U.S.
Army   Armament,   Munitions  and   Chemical  Command
(AMCCOM). RMA occupies more than 17,000 acres (approx-
imately 27 mi1) in Adams County, adjacent to and directly north-
east of metropolitan Denver, Colorado. RMA is bounded on the
south by industrial uses and Stapleton International Airport, on
the west and northwest by residential neighborhoods ranging
from medium to low density and on the north and east by agri-
cultural lands,  mostly rangeland. To the casual observer, RMA
appears to be wide open, gently rolling prairie with a few widely
dispersed concentrations of buildings  or  industrial  facilities.
<»:4    ROCKY MOLVTA1N ARSENAL
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Wildlife is abundant, including a few threatened and endangered
species such as bald eagles.
  RMA was established in 1942 and has been the site of manufac-
ture of chemical incendiary munitions and chemical munitions
demilitarization. Following World War II, Congress directed the
leasing of portions of RMA to private commercial interests; some
of the industrial production facilities at RMA were leased to
chemical companies. Agricultural chemicals including pesticides
and herbicides were manufactured at RMA from 1947 to 1982.
Present-day contamination  problems at  RMA result from both
the military and agricultural chemicals manufacturing activities.
All industrial activities at RMA ceased in 1982, and the Army's
attention focused on cleanup of the contaminated land and water
resources.  Initial  remedial  activities were planned  and imple-
mented by the Corps of Engineers; in recent years, the mission of
RMA has been redefined to be contamination cleanup, and the
remediation program is now managed directly by AMCCOM,
through the RMA Program Manager's Office.
  Disposal practices at RMA have included routine discharge of
industrial and munitions waste effluents to evaporation basins.
Spills of raw materials, process intermediates and final products
have occurred  within the manufacturing complexes at RMA.
Many of the compounds are mobile in groundwater.

History and Status of Basin F
  In 1956, an evaporation pond called Basin  F was constructed
in the northern part of RMA. Basin F had a surface area of 92.7
ac and a capacity of approximately 243 gal. The basin was created
by constructing a dike around a natural depression and lining it
with a 0.375-in. catalytically blown asphalt membrane.  An earth
blanket approximately 1-ft thick was placed on top of the mem-
brane to protect it. A vitrified clay pipe with chemically resis-
tant sealed joints was installed between Basin F and the faculties
where the wastes were generated. In 1962, a low dike was placed
across the southeast corner of the  basin to enclose an  area of
approximately 8 ac. From August 1957 until its use was discontin-
ued in December 1981, Basin F was the only evaporative disposal
facility in service at RMA. In 1982 the Army, Shell Oil Company,
the U.S. EPA and the Colorado Department of Health agreed to
start a cooperative development plan for a comprehensive remedy
for the environmental situation at RMA. In 1986, the Army,
Shell and the U.S. EPA, with input from the Colorado Depart-
ment of Health, agreed that an accelerated remediation be under-
taken pursuant to CERCLA to contain  the liquids and contam-
inated soils in and under Basin F.
  In the first part of Basin F remediation, Basin  F liquids were
transferred to three lined steel storage tanks and to one double-
lined covered pond. Transfer of Basin F liquids to tanks and the
surface pond for interim storage was initiated in  May 1988 and
completed in December 1988. Prior to this time, additional liquid
storage capacity in the form of a lined north surface pond had
been planned, since seasonal precipitation had increased the vol-
ume of liquid beyond the initial estimate. Presently, approximate-
ly 4 million gal of liquid are stored in the tank tank and 4.5
million gal in a portion of the north surface pond called Pond A.
  The present Interim Response Action (IRA) for Basin F liquids
addresses  treatment and disposal of the contents  of the  storage
tanks and Pond A. This IRA was initiated in September 1988. It
includes characterization of the stored Basin F liquids, selection
of a treatment alternative for the liquids, a community relations
program that was integrated with the remedy selection process,
pilot-scale demonstration of the selected treatment technology
and detailed engineering design  of  the remedial treatment  pro-
cess. The first steps of this work, characterization of the liquids
and selection of a preferred treatment alternative, were done in
accordance with the five-step process for remedy selection pre-
scribed generally by Section  121 of CERCLA and detailed in the
NCP (Sections 300.415  and 300.430 (e)). The community  rela-
tions program was in accordance with EPA guidance for com-
munity relations programs for NPL sites. The remaining steps,
pilot testing and detailed engineering design, are underway and
are planned to be completed by the end of 1990. This schedule will
lead to completion of construction and testing in late 1991 or
early 1992 and completion of the cleanup action (destruction of
Basin F liquids) by mid-1993.

Characteristics of Basin F Liquid

  In this study, characterization of the Basin F liquids consisted
of sampling and analyzing the wastes to determine their chemical
and physical properties in relation to engineering design and per-
formance requirements of potential treatment processes and to
provide the basic chemical parameters needed for a risk analysis
of alternatives selected for detailed evaluation.
  This testing confirmed that Basin F liquids are nearly saturated
with common salts  and ammonia gas. They also contain heavy
metals such as copper and arsenic. In addition, they contain low
levels of pesticides and byproducts of pesticide and chemical war-
fare agent manufacturing. The characteristics of Basin F liquids
constrain the choice of treatment and  disposal techniques and
may require special design of treatment alternatives. For example,
Basin F liquids may precipitate solid salts or release ammonia gas
when stirred or combined with certain chemicals. The amounts"of
heavy metals, particularly copper, in the Basin F liquids may rule
out certain treatments for the organic compounds also contained
in the liquids. The high salt content of the liquids is corrosive to
many kinds of treatment equipment.

REGULATORY FRAMEWORK
  The cleanup of Basin F liquids is subject to two principal regu-
latory  imperatives: CERCLA,  and the Federal Facility  Agree-
ment for RMA. In addition, a number of other regulations and
policies (ARARs) have been applied to the remedy selected for
Basin F liquids, and certain other regulatory positions were con-
sidered in forming the remedial decision.

Remedial Authority
  The  destruction of Basin F  liquid is an "interim response
action" planned to be completed prior to an Arsenal-wide clean-
up that is being defined in RI/FS studies. These RI/FS studies,
which will lead to "final response actions,"  are being conducted
under the Remedial Authority of CERCLA. The guidance for
these RI/FS studies exists'in a number of well-known U.S. EPA
guidance documents with titles like, Guidance for Conducting
Remedial Investigations Under CERCLA.
  The interim response actions, on the other hand, are conducted
under the Federal Facility Agreement and CERCLA. Guidance
for studies to select appropriate interim remedies CERCLA is less
well developed, occurring in sketchy form  in the NCP.  At the
time that the Basin F remedy selection studies were conducted, no
formal guidance documents existed for treatment assessment and
remedy selection, and only draft guidance existed for conduct of
community relations programs.
  In general, CERCLA encourages a practical and expedient ap-
proach to selecting and implementing a short-term remedy for
urgent contamination problems. In developing the final response
actions, a comprehensive remedial investigation and risk assess-
ment followed by a systematic feasibility study are required. For
an interim response action, no remedial investigation is required
and the surrogate for a feasibility study is a loosely defined "engi-
neering evaluation/cost analysis," where cost and technical per-
formance are the only factors that need to be considered in choos-
ing a remedy.
  The Basin F Liquids interim response action followed proced-
ures similar to a removal  under CERCLA, calling the Basin F
Liquids study a "Treatment Assessment" rather than a feasibility
study. The study was patterned after a CERCLA feasibility study
                                                                                              ROCKY MOUNTAIN ARSENAL   925
-------
and was accompanied by an extensive community relations pro-
gram. The treatment assessment and remedy selection were simi-
lar in appearance to a CERCLA feasibility study, but differed
notably in several ways:

• Detailed  engineering performance data on a number of treat-
  ment alternatives were considered at an early stage in the study,
  and the  detailed  evaluation of alternatives  was limited to a
  small set  of technical options.
• Quantitative risk  analysis was included in the comparison of
  alternatives.
• A community relations program was relied upon for technical
  input to the remedy selection.

  All of these measures were oriented to obtaining a practical and
widely-accepted decision that could be implemented in the short
5-yr time frame. The decision that was reached could be evaluated
and defended in terms of CERCLA. The process used to reach
the decision was streamlined by the implementation of CERCLA
at the site through the Federal Facility Agreement.

Federal Facility Agreement

  In 1989,  a Federal Facility Agreement (FFA) was signed by the
U.S. EPA, the Army and Shell; the State of Colorado, which is
given certain rights in this agreement, did not sign the Agreement,
but participates in the activities outlined in the FFA. In the FFA,
the Army and Shell  agreed to  share certain costs of the remedia-
tion, which was to be developed and performed under the over-
sight of the U.S. EPA, with opportunities for participation by the
State of Colorado. The long-term remediation is a complex task
that will take several years to complete.
  The Federal Facility Agreement specified 13  Interim Response
Actions determined  to be  necessary and appropriate to remove
active sources of contamination and to prevent the spread of con-
taminants.  Remediation  of Basin F liquids, sludges, and soils is
one of the 13 IRAs and is to be addressed in two parts. The first
part, now completed, was removal of the Liquids to secure storage
and removal and stockpiling of the soils and sludges to a double-
lined and capped temporary waste pile. The second part concerns
Basin F liquids disposal. The  time frame  for completion of the
second part is tied  to agreed-upon limits to interim storage of
Basin F liquids, and is set at 5 yr from May 1988.
  The FAA states that all studies and cleanup  done pursuant to
the FAA will be done in accordance with CERCLA, insofar as
practical, and the FFA calls for community relations programs to
be implemented in accordance with CERCLA. The FFA requires
that studies done under its authority conform to numerous review
and comment procedures involving all the parties to the FFA.

Other Regulatory Influences

  The State of Colorado has long maintained that at least a por-
tion of  the RMA  cleanups  are RCRA  closures  rather than
CERCLA actions, and that the State should have privacy in
directing these actions. (This disagreement  is the primary reason
why the State is not a signatory of the FFA.) The Army dismisses
this claim specifically, but generally follows the substantive re-
quirements of RCRA as  ARARs  to interim response actions
planned at RMA,  consistent with the expeditious implementation
of solutions to urgent contamination problems. In the case of the
Basin F Liquids interim response action, most of the substantive
technical requirements of a typical RCRA permitting process were
incorporated as ARARs, while many of the time-consuming ad-
ministrative requirements of RCRA were not.

REMEDY SELECTION  PROCESS

  The remedy selection process  consisted of three parts: a tech-
nical study, a regulatory  process and a community relations pro-
gram. These are discussed separately below.
Technical Study
  The technical study to identify feasible treatment or disposal
alternatives and select a preferred alternative consisted of five
steps:

  Waste characterization
  Screening of technologies and development of alternatives
  Treatability studies
  Detailed evaluation of alternatives
  Selection of a preferred alternative

Waste Characterization
  For the Basin F Liquids interim response action, characteriza-
tion of the Basin F liquids consisted of sampling and analyzing the
wastes to determine their chemical and physical properties in rela-
tion to engineering design and  performance  requirements of
potential treatment processes and to provide the basic chemical
parameters needed for a risk analysis of alternatives selected for
detailed evaluation.
  Two samples of the Basin F liquids were taken from Pond A.
These samples were submitted for chemical testing and the results
were compared to those  from other recent Basin F liquid samp-
ling efforts.

Screening of Technologies and Development of Alternatives
  Forty different treatment technologies were identified and eval-
uated for their ability to  tolerate the chemical and physical char-
acteristics of Basin F liquid and achieve the general cleanup objec-
tives of the IRA. The forty technologies encompassed all four of
the basic strategies known to treatment science:

• Thermal destruction
• Immobilization
• Separation
• Chemical/biological treatment
  Certain technical  objectives controlled the identification and
screening of alternative technologies:

• Ability to process the waste within the 5-yr time frame
• Demonstrated ability to treat the waste, based on bench-scale
  or pilot tests
• Ability to meet ARARs
• Orientation to the primary remedy selection  objective of
  CERCLA,  to achieve  overall protectiveness of human health
  and the environment
• Orientation to  the  CERCLA  guidance stressing permanent
  solutions that reduce toxicity, mobility or volume of hazardous
  substances

  Of the 40 technologies, only 12 were found to be potentially
feasible, given the physical and chemical properties of Basin F
liquids. No separation technology was found to  be feasible. The
12 potentially feasible technologies were studied  further in terms
of overall protectiveness, implementability within the stipulated
time frame and ability to meet Applicable or Relevant and Ap-
propriate Requirements  (ARARs). In the end, five technologies
were judged to be feasible, implementable within five years, pro-
tective of human  health and the environment and able to  meet
ARARs:
  Electric Melter furnace (thermal destruction process)
  Solidification (immobilization process)
  Submerged Quench Incineration (thermal destruction process)
  Wet Air Oxidation (chemical process)
  Wet  Air  Oxidation  with Biotreatment  (chemical-biological
  process)

  In developing remedial alternatives that would use  these  tech-
nologies, both on-site and off-site locations were considered. The
alternatives evaluated included the following:
       ROCK.Y MOl NTAJN ARSENAL
-------
• Off-Site Alternatives
    —Existing Off-Site Army Facilities
    —Existing Off-Site Commercial Facilities
        Deep Well Injection
        Hazardous Waste Incinerators
    —Associated Transport Facilities
        Pipeline
        Tank Trucks
        Rail Cars
• On-Site Alternatives
    —Existing Arsenal Facilities
    —Newly Constructed Arsenal Facilities
        Electric Melter Furnace
        Solidification
        Submerged Quench Incineration
        Wet Air Oxidation
        Wet Air Oxidation with PACT

  A brief summary  of the technical  characteristics and the
strengths and weaknesses of these treatment alternatives is given
below. All of the on-site, newly constructed treatment alterna-
tives were capable of being designed and implemented to be pro-
tective of the community and the workers and to meet ARARs to
the maximum extent practicable. Alternatives which reduce con-
taminant toxicity, mobility or volume  are more protective of
human health and the environment than alternatives that do not.
  The greatest differences between  the alternatives considered
were seen in the areas  of treatment efficiency (reduction of tox-
icity, mobility and volume) and implementability (feasibility, re-
liability and availability). The following  discussion focuses on
characteristics of the alternatives that make each alternative dis-
tinctive from the others.
  Because of the history of the Basin F Liquids Disposal Interim
Response Action, three types of alternatives which often are con-
sidered in the remedy selection process for CERCLA are not con-
sidered here. These types  of alternatives include the No Action,
Monitoring and Institutional Controls alternatives. Since the In-
terim Response Action discussed here directs the Army to choose
a strategy for treatment and disposal of Basin F liquids now  in
storage, the No Action, Monitoring and Institutional Controls
alternatives were, hi a peremptory .fashion, judged unacceptable
for application to Basin F liquids.
  Alternatives evaluated for treatment of Basin F liquids are dis-
cussed hi the following sections.

Off-Site Alternatives

Existing Off-Site Army Facilities
  Several U.S. Army installations operate or have operated haz-
ardous waste  incinerators for  the demilitarization of chemical
warfare agents or other military hazardous wastes. However, each
of these facilities was constructed to address specific wastes  from
its respective site and none has equipment  designed to operate on
the particular admixture of wastes found in Basin F liquids. Thus,
these incinerators are technically unsuitable. Moreover, construc-
tion of a new, technically  suitable incinerator for Basin F liquids
at these sites is contrary to the intent of CERCLA, which prefers
on-site waste remediation where possible.

Existing Off-Site Commercial Facilities (Deep Well Injection)

  With reference to off-site (or on-site) deep well injection, it was
concluded that direct disposal approaches which involve no treat-
ment are hi opposition to the objectives of the Federal Facility
Agreement.  Specifically, these approaches will not meet the re-
quirement of providing "permanent and  significant" reduction
of toxicity, mobility or volume. In addition, the deep well injec-
tion approach is irreversible and offers  no opportunity for later
treatment.
 The Federal Facility Agreement stipulates  that the  Basin  F
liquids remediation will attain ARARs to the  maximum extent
practicable. Primary guidance (U.S. EPA, 1988) defines reduc-
tion of toxicity, mobility or volume as "permanent and signifi-
cant reduction" through "destruction of toxic contaminants, re-
duction of the total mass of toxic contaminants, irreversible re-
duction in contaminant mobility, or reduction of total volume of
contaminated media" (Section 7.2.3.3, Draft Guidance for Con-
ducting Remedial Investigations and Feasibility  Studies Under
CERCLA, U.S. Environmental Protection Agency,  1988). Final-
ly, deep well injection of Basin F liquids was tried in the past at
RMA and failed due to the physical properties of the waste.

Existing Off-Site Commercial Facilities
(Hazardous Waste Incinerators)

  A survey of the capabilities  of existing commercial hazardous
waste incinerators showed that among  all of  the facilities in the
nation, only three sites with liquid injection incinerators were
equipped  to treat Basin F liquids. However, the actual technical
suitability of equipment at these  installations had not been
proven. In addition, each of these three commercial facilities has
indicated that they would require a treatment contract that would
allow the facility to refuse, at any time and at then: discretion, re-
ceipt of Basin F liquids for treatment. Thus, the commercial facil-
ities would not guarantee that Basin F liquids would be treated
within the agreed-upon time frame, nor would they guarantee
completion of treatment of all Basin F liquids.

Newly Constructed Off-Site Facility

  A new treatment faculty for Basin F liquids could  be built off-
site in a location that the Army could purchase or lease.  Such a
facility could be located such that it would be  physically removed
from any populated area, and  thereby could presumably present
a lower operational risk to humans. A new off-site  facility,  like
any of the on-site options, could be designed and built to attain
ARARs and achieve cleanup objectives. The drawbacks of a new-
ly constructed off-site facility are the time required for permitting
and the requirement to transport the waste.
  On-site facilities would be constructed as a CERCLA action at
a CERCLA  site and would not require environmental permits
from Federal, State or local agencies. An off-site facility, on the
other hand, would not be considered  a CERCLA  facility,  but
rather would be viewed as a new waste  treatment, storage or  dis-
posal facility (TSD) and subject to permitting and regulation
under RCRA. The amount of time currently required to secure a
RCRA permit for a TSD in Colorado is 3 to 5  yr, due to the com-
plexity of application  data requirements and the number  and
duration of agency and public reviews. When  the permitting time
is added to the time required to design, test, build and operate the
treatment facility for Basin F liquids, the total time  required for
this off-site option exceeds the time available,  as agreed to by the
parties to the Federal Facility Agreement.

Associated Transport Facilities (Pipeline)

  Conveyance of Basin F liquids through a pipeline to an off-site
hazardous waste facility was considered. Although trans-state  and
interstate pipelines exist to convey fuel  products, such as natural
gas and guel oils, no pipeline suitable for liquid hazardous waste
presently exists. Therefore, a separate pipeline would have to be
built to transport Basin F liquids. The potential  for leakage of
Basin F liquids due to joint failure, corrosion failure and freeze
damage under Colorado weather conditions is substantial. Addi-
tionally,  since Basin F liquids  are a saturated or  supersaturated
brine solution, they could not be  piped long distances without
considerable  dilution to prevent salt precipitation and line plug-
gage. Thus,  the volume  of wastes would be  substantially in-
creased. The cost of constructing a suitable pipeline and  supply-
ing the power to pump the Basin F liquids long distances would
                                                                                               ROCKY MOUNTAIN ARSENAL    927
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be greater than the cost of either off-site bulk transport or con-
struction of an on-site treatment unit.

Associated Transport Facilities (Tank Trucks)

  Appropriate tank trucks exist that can safely transport Basin F
liquids over public highways. The scenario used here consisted of
tank trucks of approximately 5,000-gal capacity used to transport
Basin F  liquids off-site for treatment.  These  trucks would be
owned and furnished by a transportation contractor. To com-
plete treatment of Basin F liquids in 1.5 yr, approximately 500,000
gal would have to be transported per month. Depending on the
location  of the treatment facility, this could require using more
than 20 tank trucks per month (assuming five round trips each per
month) to transport Basin F liquids. Based on a survey of trans-
portation contractors,  we determined that this number of tank
trucks did not appear to be available from one company.
  Most available tank trucks are constructed of stainless steel ma-
terial, which may not be compatible with highly corrosive Basin F
liquids. There were only a few lined tank trucks available at the
time of the survey. The risk assessment reported in the Treatment
Assessment Report indicated that the risk of transporting Basin
F liquids off-site by truck was significantly higher than the risk of
transporting the liquids by rail car.

Associated Transport Facilities (Rail Cars)

  The use of rail cars, typically of 20,000-gal capacity, was also
evaluated.  The risk of transporting Basin F liquids off-site for
treatment by rail car was estimated to be low relative to any other
transportation mode. Specialized rolling stock exists in sufficient
numbers to accommodate shipments of Basin F liquid to an off-
site location. Some of the rolling stock is lined;  depending on the
supplier, some tank cars might need to be lined prior to receiving
Basin F liquid.

On-Site Alternatives

Existing A rsenal Facilities

  No treatment facilities exist at RMA that are technically appro-
priate, or can be modified to be technically appropriate, for Basin
F liquids.

Newly Constructed Arsenal Facilities

  This group of alternatives includes the five technologies iden-
tified in  the screening step of the Treatment Assessment Study.
They are presented here in alphabetical order.

Electric Melter Furnace

  The electric  melter furnace would  operate at high tempera-
tures—approximately 2300 ° F—to destroy organic compounds in
Basin F liquids. In the furnace (similar to a glass-making furn-
ace),  the organic compounds in Basin  F liquids would be de-
stroyed almost completely.  The metals would form  a molten
salt that  would float on top of the pool of  glass which lines the
bottom of the furnace. The molten salt would be removed from
the furnace periodically, poured into forms  and cooled in prepa-
ration for final disposal. The exhaust gases would include a mix-
ture of oxides of nitrogen and other gases. Exhaust gases released
to the atmosphere from this process would be passed through air
pollution control devices and would meet government standards;
these exhaust gases would be monitored to assure adherence both
to regulated conditions and nonregulated health risk-based oper-
ating goals.
  Operation  of the electric melter furnace would require the
transportation  of 8100 yd1 of pure liquid anhydrous ammonia
and 4400 yd' of sodium hydroxide into the Arsenal each year.
Both compounds would be used in the air pollution control pro-
cess. However, the risk assessment indicated that the amount and
concentration of ammonia transported to the site for this alterna-
tive could present a health hazard. The electric melter furnace
process would produce salts, containing metals, of about 10% of
the volume of the original Basin F liquids. These salts could be
disposed in a hazardous waste landfill. The form and chemistry of
produced salts are not suitable for subsequent metals recovery. Of
the  five  on-site  treatment alternatives evaluated, the electric
melter furnace ranked at the low end of the mid-range of costs,
with an estimated total project cost of $21.1 million. The electric
melter furnace has not been commercially demonstrated to be
feasible for destruction of wastes like Basin F liquid.

Solidification
  The solidification process would mix various chemicals with the
Basin F liquids to immobilize the metals and produce a solid. Or-
ganic compounds in Basin F liquids would be incorporated into
the solid  but would not be destroyed or immobilized and could be
leached from the solid material. Because Basin F liquids contain
large amounts of ammonia and nitrogen-containing compounds,
chemicals would be added to react with these compounds  and
prevent the release of ammonia during mixing and curing of the
solid. The Basin F liquids would be pumped into two batch  mix-
ing units  and mixed with Portland cement, fly ash, soil and agents
to reduce ammonia emissions. Mixing units would be sealed  dur-
ing operation. The moist mixture would be discharged into dis-
posable 50-gal drums and held in an adjacent building for IS days
to complete the curing process.
  Control measures will be used to reduce fugitive emissions from
the solidification process. Exhaust from the mixing and curing
areas would be treated by air pollution control equipment to con-
trol particulates and gases. The exact nature and concentrations
of emissions of organic chemicals as well as dust are not known or
readily estimated for the solidification process. Due to the quan-
tities of mixing materials handled, dust emissions could be  sub-
stantial.
  Solidification would require the transportation into the Arsen-
al of 17300 yd'/yr of phosphoric acid, plus comparably large
quantities of other compounds,  primarily used to reduce the
amount of ammonia released during mixing. Solidification would
produce solids of approximately three times the volume of Basin
F liquids, which would be disposed in a hazardous waste landfill.
  Solidification  is a  common  technology for many types of
wastes, but is not known to have been applied to saturated brine,
ammonia-bearing wastes like Basin F liquid in a commercial-scale
operation. The solidified  products of this process will meet pres-
ent hazardous waste landfill leachability requirements, but are
close to the acceptance threshold, and leachability testing prior to
disposal  may be required. Of the on-site treatment alternatives
evaluated, solidification ranked as the most costly, with an  esti-
mated project total cost of $71.8 million.

Submerged Quench Incineration

  The submerged quench incineration process would use a verti-
cal  downfired liquid  incinerator. The  liquid to be incinerated
would be injected at the top of the furnace along with a supple-
mentary  fuel.  Burning the liquid at high temperature (approxi-
mately 1900° F)  would destroy the organic compounds in Basin
F liquid  almost completely. After incineration,  the hot gases
would be forced downward and cooled in a liquid quench task to
aid in washing out particulates  and cleaning the exhaust gases.
The high temperatures would melt noncombustible components
of the Basin F liquids, producing molten salts which would  flow
down the walls of the incinerator and also be cooled in the quench
chamber. The brine from this process could be dried to produce a
salt. The exhaust gases, which would include a mixture of oxides
of nitrogen and other gases, would be passed through air pollu-
tion control devices. Exhaust gases released to the atmosphere
from this process would meet government standards and would
       ROCKY MOL NTAIN ARSENAL
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be monitored to assure adherence both to regulated conditions
and nonregulated health risk-based operating goals.
  Operation of the submerged quench incineration process would
require the transportation into the Arsenal of 26 rail cars (200,000-
lb capacity each) per year of sodium hydroxide, a caustic com-
pound used in the air pollution control process. The submerged
quench incineration process would produce salts, containing met-
als, of about 10% of the original volume of the Basin F liquids.
These salts could be disposed in a hazardous waste landfill. The
form and chemistry of the dried salts would permit a subsequent
metals recovery  step that would result in an innocuous residual
salt product. Compared to the other on-site treatment alternatives
evaluated, submerged quench incineration is the least costly, with
an estimated project total cost of $19.1 million. This process has
been demonstrated commercially on saturated brine wastes  like
Basin F liquid.

 Wet Air Oxidation

   In the  wet air oxidation  and spray drying process, Basin F
liquids  would be fed under pressure to an oxidation chamber
operating at approximately 500° F. In the chamber, organic com-
pounds in Basin F liquids would break down into  simpler,  less
toxic compounds. A minimum of 95% of the toxic organics
would be destroyed. The metals and many organic compounds
would remain in the liquid, although some gas also would be re-
leased by the reaction. The liquid from the oxidation chamber
would be treated to neutralize ammonia. Then the liquid and gas
from the  oxidation chamber would be  fed to a  spray dryer. The
dried salts containing metals would be separated and packaged
for shipment to a hazardous waste landfill.
   The gases, which would  contain some volatile organic com-
pounds and ammonia, would be passed through air pollution con-
trol devices. Exhaust gases released to  the atmosphere from  this
process would meet government standards and would be moni-
tored to assure adherence both to regulated conditions and non-
regulated health risk-based operating goals.
   Operation of  the wet air  oxidation process would require the
construction of  a large building to  house the process  and the
transportation into the Arsenal of 260  railroad  cars (100-ton ca-
pacity each) per year of highly concentrated sulfuric acid and 22
railroad cars of 50% sodium hydroxide. The sulfuric acid would
be used to neutralize ammonia, and the sodium hydroxide would
be used hi the air pollution control process. The wet air oxidation
and spray drying process would produce salts,  containing metals
and some simple organic compounds of approximately 10% of
the total original volume of  Basin F liquids. These salts could be
disposed in a hazardous waste landfill. The form of the dried salts
would permit a metals recovery step, but the organic content of
the salts could affect the purity of recovered metals and would re-
main in the salts to some degree anyway; hence, metals recovery
for this process is of questionable utility. Compared to the other
on-site alternatives evaluated, the wet air oxidation and spray dry-
ing process is in about the midrange of costs, with an estimated
project total cost of $48.2 million.

Wet Air Oxidation with Powdered Activated
Carbon Bio-Treatment (PACT)
  Wet air oxidation,  PACT and spray drying would destroy
organic compounds in Basin F liquids by subjecting them to high
pressure and moderately high temperatures in the presence of air.
After  passing   through the  pressurized  oxidation  chamber
(operating at approximately 500° F), the liquids would be further
treated by biological action to destroy organics. In the chamber,
organic compounds would break down to simpler, less toxic com-
pounds. The metals and many organic compounds would remain
in the liquid, although some gases would be released by the re-
action.
  Before liquid  from the oxidation  process was  treated in  the
PACT process, it would be pretreated to remove copper and
ammonia and diluted. The liquid then could be sent to enclosed
aeration basins for PACT biotreatment. The carbon would ad-
sorb and retain organic compounds in the aeration basins so that
microorganisms would have time to break them  down.  After
PACT treatment,  the liquid would be concentrated and spray-
dried in a dryer similar to that used in the wet air oxidation and
spray drying process.
  The exhaust gases from the dryer, which would contain some
VOCs and ammonia, would be passed through air pollution con-
trol devices. Exhaust gases released to the atmosphere from this
process would meet government standards and would be moni-
tored to assure adherence to both regulated conditions and non-
regulated health risk-based operating goals. Overall, the wet air
oxidation, PACT and spray drying process would destroy a min-
imum of 99% of the toxic organics in Basin F liquids.
  Operation of the process would require the construction of sev-
eral large buildings to house the process and the transportation
into the Arsenal of 260 railroad cars (100-ton capacity each) per
year of highly concentrated sulfuric acid and 22 railroad cars of
50% sodium hydroxide. The sulfuric acid would be used to neu-
tralize ammonia, and the  sodium hydroxide would be used hi the
air pollution control process. The process would produce dried
salts, containing some metals and simple organic compounds, of
approximately 20% of the volume of the original Basin F liquids.
These salts could be disposed in a hazardous waste landfill.
  The process includes a metals removal step and produces a
brine with very low levels of residual organics; no further metals
recovery or treatment of organics is feasible for the final residual
brine. Compared to the other on-site alternatives evaluated, wet
air oxidation, PACT and spray drying is in the top  of the mid-
range of costs, with an  estimated project total cost of $56.2
million.

Results of Screening
The  screening process concluded with the development of seven
remedial alternatives:

• On-site electric melter with solid residuals
• On-site solidification with solid residuals
• On-site submerged quench incineration with  solid residuals
  (spray drying of brine product)
• On-site submerged quench incineration, brine product, metals
  removal and PACT treatment of brine, no residuals
• On-site wet-air oxidation with spray drying, solid residuals
• On-site wet-air  oxidation, brine  product,  metals  removal,
  PACT treatment of brine, no residuals
• Off-site incineration at an existing commercial facility, with
  rail transportation of untreated Basin F liquid

Preliminary Risk Assessment
  In conjunction with the screening of technologies and develop-
ment of alternatives, a preliminary quantitative risk assessment
was  performed. Risks of  both on-site and  off-site treatment
alternatives were evaluated, and the results indicated that there
should be very low potential cancer risks and no significant non-
cancer health hazards from any of the treatment processes them-
selves. However, the risk assessment indicated that there may be
some potentially significant health hazards associated  with  the
transportation of Basin F liquids (to an off-site treatment facility)
or from the transportation of treatment chemicals (on-site for the
electric melter furnace, one of the treatment processes evaluated).
  The potential health hazard risks were associated with  possible
exposure to the ammonia content of Basin F liquids and  possible
exposure to the pure liquid anhydrous ammonia which would be
required for the electric melter furnace process.
  Based on this preliminary health risk assessment, off-site treat-
ment options were not considered further in the technical study.
                                                                                              ROCKY MOUNTAIN ARSENAL   929
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Treatability Studies

  Bench-scale or pilot plant tests were performed on Basin F
liquids using each  of the 12 technologies identified in the initial
screening step as potentially feasible. These  treatability  studies
were done  over  an 11-yr period from  1978 to  1989. Successful
bench-scale or pilot-test data exist for all of the  five technologies
retained in  screening and used in the development of remedial al-
ternatives, i.e., all  of the alternatives selected for detailed evalua-
tion had been demonstrated to be capable of  treating Basin F
liquid.

Detailed Evaluation of Alternatives

  Five alternatives remained for detailed evaluation (all  newly-
constructed on-site facilities). Each alternative was designed at a
conceptual level, and an assessment of probable performance was
made. This assessment included preparation of a detailed process
description; sizing of the treatment alternative to meet the waste
volume and schedule for this IRA; preparation of a materials bal-
ance to estimate volumes and  quantities of  feed,  process, dis-
charge and residuals streams;  assessment  of technical perfor-
mance in terms  of reduction of toxicity, mobility and volume;
evaluation  of the implementability of the process (technical ma-
turity, track record,  etc.);  estimates of capital and operating
costs; and  identification of regulatory issues. This information
was used in the selection of a preferred remedial alternative.
  Briefly stated, this is how the alternatives compared:

• Overall  Protectiveness. Of the  on-site options, the electric
  melter furnace and submerged quench incineration  have  the
  highest organic chemical  destruction efficiencies and are there-
  fore the most protective of human health and the environment.
  Wet air oxidation with PACT and wet air oxidation alone will
  destroy 90% or  more of the organic chemicals. Solidification
  does not provide any treatment to organics.
• Air Emissions. Of the on-site options, all processes but solid-
  ification will produce emissions that meet government stan-
  dards and will have monitoring to assure adherence to regu-
  lated conditions and negotiated operating goals. Solidification
  emissions, particularly fugitive dust, will be  difficult to esti-
  mate and will present monitoring and control problems.
• Use of hazardous chemicals.  All of the on-site options will re-
  quire importation of process  materials to RMA. The chem-
  icals required for the electric melter furnace present higher risks
  than chemicals required for any other process. The chemicals
  required for submerged quench incineration present lower risks
  than chemicals required for any other process.
• Residuals. The two incineration processes produce as residuals
  a metal-bearing  salt that  can be  landfilled.  The salts  from  the
  submerged quench process are suitable for a subsequent metals
  recovery step, while the salts from the electric melter furnace
  are not. The wet air oxidation processes produce as interim or
  final residuals a metal-bearing and organic  bearing salt that is
  not generally suitable for metals recovery, although removal of
  impure metals will permit subsequent organics  removal (PACT)
  and reduce the quantity of hazardous residuals. Solidification
  produces a hazardous waste that can be landfilled, but which is
  teachable for organics and to a lesser degree for metals. The re-
  sidual is not suitable for subsequent treatment  steps.
• Waste volume. The two incineration processes and wet air oxi-
  dation produce  a volume  of residuals that is approximately
  10% of the waste volume.  The wet air oxidation process with
  PACT produces a volume of residuals that is approximately
  20% of the waste volume. The solidification process produces
  a waste product that  is 300% to 500% of the original waste
  volume.
• Commercially demonstrated process. Of the  on-site options,
  the submerged quench incinerator and the wet air oxidation
  processes have been demonstrated commercially on saturated
  brine wastes like Basin F liquid. Solidification has been demon-
  strated  commercially on many types of wastes, but not on
  saturated brine, ammonia-bearing wastes like Basin F liquid.
  The electric melter furnace has not been commercially demon-
  strated for liquid hazardous wastes.
• Cost-effectiveness. Of the  on-site options, the electric melter
  furnace and submerged quench incinerator are the least expen-
  sive. The wet air oxidation processes are two to two and one
  half times as expensive as incineration, and solidification is
  three to three and one half times as expensive as incineration.

Selection of a Preferred Alternative
  A semiquantitative scoring  and ranking technique was used to
evaluate the five remedial options and select a preferred alterna-
tive. The technique derived from, and was based on, multiattribute
utility theory and applications of these techniques in similar de-
cision analysis exercises. CERCLA guidance (Section 121(b) and
NCP  Section 300.430(e)) identify seven evaluation criteria to be
used hi  selecting a preferred  remedial alternative.  These criteria
are:
  Overall protection of human health and the environment
  Compliance with Applicable or Relevant  and Appropriate Re-
  quirements (ARARs) to the  maximum extent practicable
  Reduction of toxicity, mobility and volume
  Short-term effectiveness
  Long-term effectiveness
  Implementability
  Cost

  The first step in the  evaluation procedure was to develop for-
mally correct quantitative evaluation criteria out of these seven
CERCLA remedy selection criteria. To do this, these seven cri-
teria were broken down into  more  specific technical factors re-
lated  to the set of alternatives under review (in accordance with
U.S. EPA guidance); a total of 19 technical factors was assessed
for each alternative. For example,  short-term effectiveness was
broken  down into worker safety, community protectiveness and
operational environmental impact factors.  A panel of chemical
and  environmental engineers and  a  risk  assessment  specialist
assigned technical scores to each factor for each alternative, using
discrete interval scales  developed in consultation with a decision
analyst.
  The next step was to  establish tradeoffs between evaluation cri-
teria, to provide for the correct handling of preferential informa-
tion in the evaluation procedure. Weights (importance values) for
each of the 19 factors were elicited from the technical panel by a
decision analyst,  using lottery and  consensus  techniques.  Using
the factor scores and the tradeoff values, an evaluation formula
was established; technical factor scores were  multiplied by the
weights to yield weighted factor scores, and  these scores were
summed to yield an overall score for each alternative. The alterna-
tives were then ranked in accordance with the scores. Controls in-
troduced by the decision analyst in the construction of the dis-
crete interval scales and the elicitation of weights kept this evalua-
tion procedure formally correct and logically rigorous, but the
written  record of the evaluation and the results were easily under-
stood by the lay public.
  Sensitivity studies were done on the ranking by varying the
weights (importance values)  for the 19 ranking factors.  These
studies showed how the rank  order would change if some factors
were considered to be more important and others less important.
This approach was used to model  many hypothetical points of
view, such as a point of view  that emphasized protection of near-
by residents over all other factors, or another  point of view that
emphasized all factors  related to short-term or  long-term risk and
deemphasized factors related to cost. More than a dozen hypo-
thetical points of view were modeled, including  some extreme
points of view (in which one or two  factors received all the weight
       ROCKY MOL'NTMN ARSENAL
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and all other factors were suppressed). In addition, several other
diagnostic sensitivity tests were run to understand better which
factors were most influential in ranking. The sensitivity studies
were used to identify a set of weights and a corresponding rank
order that was reasonable and realistic and could be shared by
many points of view. This rank order was recommended. The top
ranking alternative in this rank order is the preferred alternative.

Results

  In this analysis, the on-site submerged  quench incinerator was
consistently the highest ranking alternative, and only under ex-
treme and unrealistic points of view could the submerged quench
incinerator be made to rank second. The poorest performer in this
ranking analysis was solidification, and only under extreme points
of view could it be made to rank higher. The "middle" alterna-
tives of wet air oxidation and electric melter generally ranked far
below submerged quench. The recommended rank order was:
1. Submerged Quench Incinerator
2. Wet Air Oxidation
3. Wet Air Oxidation with PACT
4. Electric Melter Furnace
5. Solidification

Regulatory Process
  The treatment study proceeded from a carefully reviewed and
approved work plan to conduct of technical evaluations, review
of interim conclusions, preparation of a draft and final treatment
assessment report and then preparation of a proposed decision
document. Both the treatment assessment and proposed decision
document was presented in public hearings, and subsequently a
final decision document was issued. This  process assured that all
affected and interested agencies had ample opportunities to exert
an influence on the remedial decision.
  This process was  complicated  by the  number of entities in-
volved; in addition to  the Army,  Shell and the U.S. EPA, the
Departments of Justice, Health and Human Services and Interior
and the State of Colorado were participants. Each entity brought
different  interests to the process along with different styles of
dealing with other agencies and the public. To accommodate the
large number of interactions required by the participants in the
regulatory process, the Army arranged for numerous briefings,
progress meetings, special purpose committees and written ma-
terials to keep the parties up-to-date.

Community Relations Program
  To assure that the community at large also had opportunities
to exert an influence on the remedial decision, a community rela-
tions program was implemented. The program included informa-
tional elements, such as fact sheets and presentations, as well as
participatory (consensus  building) elements, such as workshops
and hearings. The community relations  program started at an
early point, and the public was made a participant in the evalua-
tion of technical material and the development of a remedial de-
cision. To give  the program more visibility and make it function
more  effectively, the Army  established  a  community relations
task force to plan and oversee all of the community relations ac-
tivities.

CONSENSUS BUILDING
  In 1988, the Army agreed to a 5-yr limit on temporary storage
of Basin  F liquid, yet any of the feasible remedial  alternatives
would take several years to implement. A delay in implementing
the selected remedy could not be tolerated if the 5-yr storage limi-
tation was to be observed. If there was general agreement in the
community on  the selection of a remedy, then the chances for a
program delay due to public opposition would be reduced. There-
fore, the Army set out to build consensus in the community for a
remedy selection, using the community relations program to dis-
seminate technical information and receive inputs from members
of the public. The main elements of this consensus-building in-
itiative are discussed below.

Frequent informational meetings

  The Army held several meetings to brief special interest groups
and the public at large on the progress of the technical studies.

Workshop
  The Army held a day-long public workshop on the technical
studies, and gave members of the public the opportunity to have
first-hand experience in evaluating the technical information. In
one exercise, the detailed evaluation and ranking of the seven re-
medial alternatives was opened up to the public, and the partici-
pants had the opportunity to alter  the ranking weights as they
wished and  see in real time the effect this had  on the ranking
scores and rank orders. This analysis showed the participants in
the public meeting that the Army's selection of a particular altern-
ative was the reasonable result of a logical process, and that under
a broad spectrum of points  of view, the same technology (sub-
merged quench incinerator) would rank first. This builds consen-
sus for the technical evaluation.

Well-planned media relations
  The Denver area press were invited to all public meetings and
were given special briefings.  Based on the high level of informa-
tion made available to the media, no single-issue special interest
groups were able to divert media attention.

Letting the public make part of the decision

  In the informational meetings and the workshop, numerous
concerns were expressed and repeated by the public, mostly con-
cerning the  operational safety of whatever remediation was se-
lected and the objectivity of the Army in monitoring the remedial
action. At the workshop, the Army committed to address these
concerns by converting these concerns into elements of the remed-
ial decision. Thus, for example, concerns over products of incom-
plete combustion (PICs) were addressed by a decision to conduct
a special predesign pilot test; concerns over operational safety
under severe weather or upset condition were addressed by a de-
cision to include operational controls in the design; concern over
the objectivity of monitoring was addressed by agreement to have
an independent third-party monitor on-site.  In all, 12 discrete de-
cision elements  were  added to the basic technological remedy
selection; all of these elements were shown in the decision docu-
ment to be directly derived from public concerns. While the Army
reserved the responsibility to select the remedial technology, the
public owned  a  significant part of the  decision concerning how
the selected technology would be operated.

Advance resolution of all sensitive issues

  The Army used an  "open-handed" approach, by bringing up
and resolving  sensitive public issues early in the process, before
they became points of contention. These issues included on-site
versus off-site remediation, health risk studies, the effects of in-
cineration, etc.

Establishment of standards-setting and
dispute resolution procedures

  The Army included standards-setting and dispute  resolution
procedures in the ARARs section of the decision document to
give form to the operating guidelines and lasting commitment to
safety and community interaction by the Army.

CONCLUSION

  When the Decision Document describing the selected remedy
was issued in March 1990, there was no widespread public oppo-
sition to the selection of a submerged quench incinerator for the
                                                                                              ROCKY MOUNTAIN ARSENAL   931
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Basin F Liquids at RMA. On the contrary, state officials com-
mended the Army on its selection process and lent their weight
to the decision. There has not  been any organized opposition
to this incinerator since the decision  was announced. The in-
cinerator is in the final stages  of design at the moment, and
construction is scheduled to begin in a  few months.  Some of the
principal lessons learned  in this remedy selection and consensus
building process are:

• Among the benefits of intensive planning is early identification
  and resolution of sensitive technical issues;
• Formal risk analysis is a cost-effective screening and evaluation
  tool because it addresses the top concerns of the public and
  most agencies;
• Sensitivity analysis of a formal ranking method  is  insightful
  and useful for planning consensus building activities;
• Early involvement of the public is key to building support for
  the decision;
• Direct use of public  input in the technical decision improves
  the quality of the decision and avoids downstream delays.
     RlHkY \1Ol\TM\ ARSHSA1
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 Interim  Response Actions:  An  Approach to Short-Term  Remediation
                                (Ahead of the Record  of  Decision)
                                                  Bruce M. Huenefeld
                                                     Kathryn R. Cain
                                                 Rocky Mountain Arsenal
                                                Commerce City, Colorado
 ABSTRACT
  The environmental restoration of Rocky Mountain Arsenal (RMA)
 in Denver, Colorado, is a nationally prominent CERCLA project. An
 outgrowth of the settlement between the Federal Government and Shell
 Oil Company is a unique Interim Response Action Program being
 implemented at the Arsenal by the U.S. Army with technical assistance
 from Shell under U.S. EPA oversight.
  Interim Response Actions (IRAs) were identified in the RMA Federal
 Facility Agreement as beneficial measures that could be taken prior
 to the final ROD for the entire Arsenal. A specially structured process
 was developed for the IRA program that simplifies the U.S.  EPA's
 standard RI/FS program guidance. The IRA process starts with the
 assumption of utilizing existing data which correlate with the  RI/FS
 site characterization. The next IRA process step, assessment, is the func-
 tional equivalent of the RI/FS steps of development and screening of
 alternatives, treatability studies and detailed evaluation of alternatives.
 The IRA decision document step corresponds to the RI/FS ROD. The
 IRA process also adds an implementation/design document step prior
 to remediation.
  The unique features of the IRA process include the range of measures
 possible, how the process is administered, the regulatory review in-
 volved and the community relations program intended to encourage
 public involvement. In addition to the organizations already mentioned,
 the Department of Interior, the U.S. Fish and Wildlife Service and the
 Colorado Department of Health are afforded a nearly  equal participa-
 tion in the IRA process.
  In  practice, the IRA process has  been  an  unqualified  success.
 Beneficial mitigation is being accomplished at 13 IRA sites. The IRAs
 range in scope from treating and disposing of 8.5 million gallons of
 liquid to groundwater treatment systems to in situ soils treatment. The
 most notable of the IRAs is the Basin F site — one example of how
 well the IRA process works. The Basin F IRA has involved two separate
 phases that entailed the removal and temporary storage of contaminated
 soils  and liquids, followed by final remediation of the liquids. Final
 remediation of the soils will be accomplished through the ROD. The
 first phase of the Basin F IRA has been completed and the second phase
 has just passed the Decision Document step.

 INTRODUCTION
  The environmental restoration of Rocky Mountain Arsenal (RMA)
 in Denver, Colorado, is a nationally prominent Superfund project. Out
 of the litigation between the Federal Government and Shell Oil Com-
 pany has risen a unique solution for accelerated remediation of certain
 sites at the Arsenal. The Interim Response Action  (IRA) program is
being implemented by the U.S. Army with technical  assistance from
Shell under U.S.  EPA oversight.
  Interim Response Actions were identified in the RMA Federal Facility
Agreement (FFA) as beneficial measures that could be taken prior to
the final ROD for the Arsenal. Because IRAs are near-term remediation
projects, they must be consistent, to the maximum extent practicable,
with the final remediation to be defined by the ROD. Through the FFA,
a specially structured process was developed for the IRA program that
simplifies the U.S. EPA's standard RI/FS program guidance.

HOW THE IRA PROCESS WORKS
  The IRA process is similar, but not identical, to the CERCLA RI/FS
process (Fig. 1). After utilizing existing data to characterize the site
of the IRA, the IRA process begins with the preparation of an alter-
natives assessment. The assessment step is equivalent to the RI/FS steps
of development and screening of alternatives, treatability studies and
detailed evaluation of alternatives.  The goal of the assessment is to
evaluate alternatives that can achieve the objectives of the IRA. The
evaluation of alternatives follows general CERCLA guidelines and may
include factors such as effectiveness, protection of human health and
the environment,  mitigation of the threat to human health, the
reasonableness of cost and timeliness. Concurrent with the assessment,
a proposed applicable or relevant and appropriate requirement (ARAR)
determination is developed and issued. The principal signatories of the
RMA Federal Facility Agreement (FFA)  (i.e.,  U.S. Army, U.S. EPA
Region VIII, U.S.  Department of Interior and Shell Oil Company),
referred to as the Organizations, are given 30 days in which to com-
ment on the draft assessment and proposed ARARs. Although not a
signatory of the FFA, the State of Colorado is allowed the same review
of and comment on IRA documents as the Organizations.
  Once the assessment and ARARs are finalized, based on comments
received,  a Proposed Decision Document is prepared to provide the
rationale for the selected alternative and the revised ARAR decision.
        BASIC CERCLA

    TECHNICAL STUDY (FS)

COMMUNITY  RELATIONS PROGRAM

    REMEDIAL ACTION PLAN

     RECORD  OF  DECISION.

    IMPLEMENTATION PLAN
              RMA
              JRA

    TREATMENT ASSESSMENT

 COMMUNITY  RELATIONS PROGRAM

•	 DECISION DOCUMENT
   IMPLEMENTATION DOCUMENT
                            Figure 1
             IRA vs. CERCLA Remedy Selection Process
                                                                                              ROCKY MOUNTAIN ARSENAL    933
-------
The Decision Document step is equivalent to the RI/FS ROD. The
Organizations and State (OAS) and the public are given 30 days to
comment on the Proposed Decision Document and ARARs. At least
one public meeting is held during the comment period to inform the
community in the vicinity of RMA.
  Following receipt of comments on the Proposed Decision Document
from the OAS and the public, a Draft Final Decision Document is
prepared. The Organizations then have 20 days to review the Draft Final
Decision Document and to raise any objections. If no dispute is raised,
the Draft Final Decision Document automatically becomes  the Final
Decision Document.
  The final step in the IRA process is the additional requirement of
an Implementation Document, which  includes the  final drawings,
specifications, design analysis, cost estimate for implementation and
deadlines  for  completion.  During design or implementation,   an
Organization may advise the others if it believes that the BRA is being
designed or implemented in a way that will not meet the ERA objec-
tives as set forth in the Final Decision Document.
  Disagreements that may arise between the Organizations are resolved
through a mechanism called dispute resolution. The dispute resolution
process consists of review of the issue at progressively higher  levels
of corresponding management authority among the Organizations. The
dispute  resolution process continues as necessary until it culminates
at the final review committee level, where the Administrator of the U.S.
EPA makes a binding decision for the Federal Government. Shell may
seek judicial review if still unsatisfied with the decision. To date, no
dispute  has been raised to the final review committee.
  At any time prior to the ROD, any Organization may request con-
sideration of the need for additional IRAs or modification of existing
IRAs. Additional IRAs have been considered and may be implemented
in the future at RMA.

SPECIFICS OF THE IRA PROGRAM
  In practice,  the  IRA  process  has  been an unqualified success.
Beneficial mitigation is being accomplished at 13 IRA sites (Fig. 2).
The IRAs range in scope from treating and disposing of 8.5 million
gallons  of liquid to groundwater treatment systems  to in  situ soils
treatment.
  The FFA identifies 13 cleanup areas for the IRA program:

• Groundwater Intercept and Treatment System North of the Arsenal
• Improvement of the North Boundary System and Evaluation of all
  Existing Boundary Systems
• Groundwater Intercept and Treatment System North of Basin F
• Closure of Abandoned Wells on the Arsenal
• Groundwater Intercept and Treatment System in the Basin A Neck
  Area
• Basin F Liquids, Sludge and Soils Remediation
• Building 1727 Sump Liquid
• Closure of the Hydrazine Facility
• Fugitive Dust Control
• Sewer Remediation
• Asbestos Removal
• Remediation of Other Contamination Sources
• Pretreatment of CERCLA Liquid Wastes

  When the IRA program was formulated in 1987, a combination of
proposed one-time and ongoing actions was considered. Thus, ongoing
projects such as application of dust suppressant and removal of asbestos
were exempted from the requirement of a Decision Document  and a
public meeting. Other projects such as the construction of recharge
trenches at the North Boundary System and the closure of abandoned
wells were exempted from the requirements of an assessment and public
meeting.
  The IRA program can be broken into two broad cleanup areas. For
example. IRAs A. B. C and E deal exclusively with the interception
and treatment of ground water contamination All other IRAs can  be
grouped a.s removal or treatment actions.
                                     @&(K)   Arsenal Wide

                                     (L)  Seven  Locations
                            Figure 2
                    Approximate IRA Locations
                                             Off Post Systems
  Alluvial
  Groundwat«r
  Contamlnatlo
                           Figure 3
             Groundwater Intercept and Treatment IRAs
GROUNDWATER INTERCEPT IRAS
  The IRA for Groundwater North of the Arsenal (IRA A) was initiated
to clean up the area just north of the Arsenal where contaminated
groundwater had migrated off the  Arsenal before the North Boundary
System was installed (Fig. 3). The groundwater presented a threat of
further migration and so was considered important enough to assess
the need to construct one or more  pump-and-treat systems in the area.
The design of two interconnected intercept systems has been completed
and the implementation document was issued in October 1990. Con-
struction is scheduled to begin in 1991.
  IRA B, Improvement of the North Boundary System and Evaluation
of all Existing Boundary Systems, consists of three parts: (1) assess-
ment of the need for improvements (such as  expansion) to the North
Boundary System and assessment,  selection and implementation of any
       ROCKY MOUNTAIN ARSENAL
-------
 necessary improvements to the system; (2) assessment of the other two
 boundary systems (Irondale and Northwest) and assessment, selection
 and implementation of any necessary improvements; and (3) implemen-
 tation of the groundwater recharge trenches to increase the rate of
 reinjection of treated groundwater at the North Boundary System. Cur-
 rently, construction of improvements to the North Boundary System
 is underway and is expected to be complete in December 1990. Assess-
 ment of the Northwest Boundary will be complete in December 1990,
 as well. The groundwater recharge trenches at the North Boundary are
 complete and have been operating since June 1990. The three boun-
 dary systems treat all contaminated groundwater approaching the boun-
 daries before  it leaves the Arsenal.
  The Groundwater Intercept and Treatment System North of Basin
 F (IRA C) and the Groundwater Intercept and Treatment System in
 the Basin A Neck Area (IRA E) were designed to intercept and treat
 contaminated groundwater flowing through small channels  the Basin
 F and Basin A. These systems are interior to the Arsenal and will treat
 water before it reaches the boundary systems. Treating contaminated
 water in this way will significantly speed up the final remediation after
 the ROD. These two IRAs are relatively close in location, so the Basin
 A Neck treatment system  of granular activated carbon (GAC), which
 was complete and online  in July 1990, will treat the North of Basin
 F groundwater after it is treated by an air stripper. The North of Basin
 F intercept system was complete in September 1990.

 OTHER IRAS
  From June 1988 until February 1990, 352 old and deteriorating farm
 wells and unused  Arsenal wells were located and closed under IRA
 D, Closure of Abandoned Wells. The success of this IRA in closing
 wells on the Arsenal that had the potential  to spread shallow ground-
 water contamination to deeper aquifers has prompted U.S.  EPA to
 suggest an expansion to areas off the Arsenal where Arsenal con-
 taminants exist in the groundwater.
  IRA G, Building 1727 Sump Liquid, was initiated in May  1987. The
 sump, which was a central collection sump for the North Plants manufac-
 turing complex, was filled to  capacity with contaminated run-off from
 the other buildings. A 5-gpm  treatment system was installed during the
 assessment portion of the IRA to begin liquid treatment and to alleviate
 the potential for overflow. More than 350,000  gallons of wastewater
 were treated by an activated  alumina (AA) and GAC process, which
 removed the principal contaminants of fluorine, arsenic and diisopropyl
 methylphosphonate  (DIMP).  Continued  operation of the small
 temporary system  was eventually determined to  be the preferred solu-
 tion and the  implementation has included  expansion of  treatment
 capacity to 7.5 gpm. IRA  G served to treat water that would have had
 to be stored until after the ROD was issued and that could have leaked
 into the groundwater.
  An assessment of the Closure of the Hydrazine Facility (IRA H) was
 already underway when the FFA was finalized.  The facility had been
 closed since  1982  when the blending  operations  ceased.  Fuels were
 removed from their holding tanks, which were triple-rinsed. The rinsate
 is unlike any other on the Arsenal and requires a unique treatment pro-
 cess. The preferred option for treating the remaining  300,000 gallons
 of hydrazine-contaminated rinsate is an ultraviolet (UV)/chemical
 oxidation system. In addition, the facility is to be dismantled once the
 wastewater has been treated and disposed. Implementation is scheduled
 to begin in early  1991.
  IRA I, Fugitive  Dust Control, consists of a periodic application of
 dust suppressant in Basin A. The application is necessary because Basin
 A no longer is filled with liquid and consists of highly contaminated
 soil. This situation  creates a risk of windblown dust contaminating other
 areas of RMA and possibly  locations beyond  the boundaries. One
 application has been made since the IRA was initiated in 1988 and a
 second is planned  for 1991.
  The sanitary sewer system at RMA was included as IRA J because
of its deteriorating condition in the area of the South Plants manufac-
turing complex and its location within saturated, contaminated alluvium
in the Basin A area during  seasonal high groundwater levels. The
preferred alternative was in-place abandonment of the sewer in the South
Plants and Basin A area. Most of the South Plants area will be aban-
doned, but remaining activities in the vicinity of South Plants will likely
be linked by a new line to the rest of the sewer system. The replace-
ment line will be constructed first, followed by in-place abandonment
as South Plants buildings are closed. This IRA is presently being
implemented.
  IRA K,  Asbestos Removal, was an outgrowth of ongoing Arsenal
programs to remove asbestos from occupied buildings. U.S. EPA has
decided that the IRA will eventually address all buildings at RMA prior
to demolition. Asbestos has been removed from 10 occupied structures.
More than 1,000 structures may eventually have asbestos removed prior
to demolition.
  "Hot Spots" is the title often used for IRA L, Remediation of Other
Contamination Sources. This IRA addresses as a group those sites of
suspected contamination that on their own might not warrant inclusion
as a separate IRA (Fig. 4). To date, seven sites have been assessed and
Final Decision Documents have been issued for six  of those. The
selected treatments range from in situ vapor extraction and in situ
vitrification to groundwater extraction and treatment to capping and/or
groundwater monitoring. This IRA is  unique in that it allows the in-
clusion of new  sites within its procedural mechanism upon approval
of the Organizations.
 /\
                            Figure 4
            Locations of Other Contamination Sources IRA
  The Pretreatment of CERCLA Liquid Wastes (IRA M) consists of
the design, construction and operation of a wastewater treatment system
to treat water generated by ongoing remedial investigation activities,
feasibility study testing, laboratory wastes and other IRAs. This IRA
is presently in design and completion of construction and startup will
occur in the fell of 1991. The constructed treatment facility will con-
tinue treating wastewater as the final remediations are being implemented
after the  ROD.

Basin F IRA
  Although the Basin F IRA is included in the "other'' category, its
extreme complexity and cost warrant a separate, detailed discussion.
Basin F was built as a state-of-the-art, asphalt-lined evaporation pond
in 1956 and was used as the primary disposal system for  Army and
Shell wastes until 1982. From its maximum capacity of 240 million
gallons, it was estimated that approximately 4 million gallons of con-
centrated brine and waste remained by the summer of 1987. As the only
remaining basin containing liquid, coupled with the wide variety of
wastes it received and its lengthy operating history, Basin F represented
one of the most complex cleanups at the Arsenal. It also represented
a potential threat to wildlife, groundwater quality and air quality.
                                                                                                     ROCKY MOUNTAIN ARSENAL   935
-------
   Two separate phases were recognized as necessary in remediating
 Basin F. In the first phase, conducted in 1988 and 1989. the liquid was
 removed from the  basin  and was stored and the most contaminated
 sludges and soils were consolidated into a double-lined, capped waste
 pile. Treatment of the liquid is to be earned out as a second phase within
 approximately 5 years from the time it was stored. The waste pile will
 be examined  in the ROD.
   Due to a heavy unexpected rainfaJl and the discovery of a false basin
 floor formed from crystalline condensate from the liquids stored there.
 a total of approximately 11 million gallons of liquid were removed from
 Basin F by September  1988. To accommodate this unexpected increase
 in liquid,  an 8 million-gallon pond was constructed in addition to the
 originally planned 4 million-gallon tank storage capacity. By the time
 the pond was covered  in May 1988. evaporation had reduced the total
 amount of stored liquid  to approximately  8.5 million gallons.  This
 amount has increased slightly over time due to the addition of leachate
 from the waste pile.
   Approximately 500,000 yd' of contaminated material were placed in
 the waste pile. The material consisted of the Basin F walls, the liner,
 approximately 6 inches of material below the liner and the overburden
 of sludges above the liner (Fig. 5).
   The second phase of  this IRA was initiated in  September  1988.
 Submerged Quench Incineration by the T-Thermal Sub-X Liquid Datur
 (TM) incinerator has been selected as the preferred treatment technology
 after an exhaustive review and assessment of treatment possibilities was
 conducted from  1979 through 1989. Design  will  be  completed in
 December 1990. and installation  on  the site will begin  in the spring
 of 1991. A trial burn has  tentatively been scheduled for January 1992.
 Operations are expected to take place from May 1992 through the fall
 of 1993. thus  completing liquid treatment within the 5-year limit.

 LONG-TERM BENEFITS
   By affording the Army and Shell an efficient regulatory process under
 which important actions  can be accomplished prior to  the  ROD, the
 IRA program has played a significant role in the initial  cleanup of RMA.
 Approximately $200 million in cleanup actions will have been completed
 by the time the ROD is issued (Fig. 6). Completion of the IRAs will
 simplify the eventual cleanup and, in the meantime, this approach will
 decrease the potential health threat of various sites on  the Arsenal.
 Significantly, the cleanup of Basin F is now a greatly reduced cleanup
 action under the ROD simply because of the IRA. Only the waste pile
 soil, possible limited underlying soils and empty liquid storage facilities
 will remain after the IRA is complete.
                                                                                            Assessment
                                                                                            Decision
                                                                                            Design
                                                                                            Construct/ Implement
                                                                                            Completed
                                                                                           OW INTERCEPT AND  TREATMENT N Or ARSENAL
                                                                                           IMPROV Or THE UBS - RECHARGE TRENCHES
                                                                                           IMPROV or THE NBS - PROCESS MODS
                                                                                           CVAL OF THE NWBS - SHORT TERM
                                                                                           EVAL OF THE NWBS - LONO TERM
                                                                                           CW INTERCEPT AND  TREATMENT N Or BASIN F
                                                                                           CLOSURE Or  ABANDONED  WELLS ON THE ARSENAL
                                                                                           OW INTERCEPT AND  TREATMENT AT BASIN A NECK
                                                                                           BASIN r -  PHASE I
                                                                                           BASIN r -  PHASE II
                                                                                           BUILDING  1727  SUMP LIQUID
                                                                                           CLOSURE Or  THE HYDRAZINE  FACILITY
                                                                                           FUGITIVE DUST  CONTROL
                                                                                           SEWER REMEDIATION
                                                                                           ASBESTOS  REMOVAL
                                                                                           OTHER  CONTAMINATION SOURCES
                                                                                           OTHER  CONTAMINATION SOURCES
                                                                                           OTHER  CONTAMINATION SOURCES
                                                                                           OTHCR  CONTAMINATION SOURCES
                                                                                           OTHER  CONTAMINATION SOURCES
                                                                                           OTHER  CONTAMINATION SOURCES
                                                                                           OTHCR  CONTAMINATION SOURCES
                                                                                            PRETREATMENT OF CERCLA LIQUID WASTE
                                                  LIME BASINS
                                                  Ml  PONDS
                                                  MOTORPOOL
                                                  RAILYARD
                                                  SHELL TRENCHES
                                                  ARMT TRENCHES
                                                  STF PLUMC
                              Figure 5
                      Basin F IRA - Phase One
                                                                                                    Figure 6
                                                                                         Summary of IRA Program Status
ACKNOWLEDGEMENTS
  The authors would like to acknowledge the Army's Office of The
Judge Advocate General, whose attorneys help make the IRA program
work  and the Department of Justice, whose attorneys negotiated the
settlement with Shell and continue in their efforts to negotiate a settle-
ment  with the State of Colorado.
936    ROCKY MOUNTAIN ARSENAL
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                      Selecting  a Chemical  Oxidation/Ultraviolet
                  Treatment System  and  Successful  Treatment  of
              Hydrazine  Wastewater  at  Rocky Mountain  Arsenal
                                              Robert T. Jelinek, RE.
                                              Arthur C. Riese, Ph.D.
                                            Harding Lawson Associates
                                                 Denver, Colorado
                                                 Kathryn R.  Cain
                                        Office of the Program Manager for
                                              Rocky Mountain Arsenal
                                             Commerce City,  Colorado
 ABSTRACT
  The unique quality  of wastewater  and  the stringent  treatment
 requirements imposed by regulatory agencies can drastically impact
 the type of treatment selected for any site. Remediation options for treat-
 ment of 300,000 gallons of hydrazine-contaminated wastewater at Rocky
 Mountain Arsenal (RMA) in Denver, Colorado, are affected by the
 presence of hydrazine fuel compounds and n-nitrosodimethylamine
 (NDMA), a decomposition byproduct, as well as part per trillion (ppt)
 limits on NDMA in the effluent from the treatment system. Although
 ultraviolet (UV)/chemical oxidation treatment is a fairly common pro-
 cess for destruction of organic constituents in water, the treatment
 method has only recently been used to destroy more exotic chemicals
 such as the hydrazine fuel compounds  and their by-products.
  Steps taken in the development approach for the treatment system
 include a rigorous treatability testing and equipment selection program,
 the analytical method development and certification process for the
 hydrazine fuel compounds and NDMA, and development of the optimal
 treatment equipment configuration and operating  parameters during
 design, construction and full-scale startup testing, all within significant
 time constraints set forth in the RMA Federal Facility Agreement (FFA).

 INTRODUCTION
  The Hydrazine Blending and Storage Facility  (HBSF) at Rocky
 Mountain Arsenal (RMA) northwest of Denver, Colorado, was con-
 structed in 1959 and operated for 23 years from 1959 to 1982. The
 10-acre site (Figure 1) consists of two  tank yards and a connecting
 pipeline and was used as a depot to receive, blend, store and distribute
 hydrazine fuel compounds.  The primary operation was blending
 anhydrous hydrazine and unsymmetrical dimethyl hydrazine (UDMH)
 to produce Aerozine 50, a  rocket propellant. The materials were
 manufactured elsewhere and were shipped to RMA for  blending.
 Blending operations were not continuous and occurred in response to
 U.S. Air Force requests. Other operations at the HBSF included loading
 arid unloading rail cars and tanker trucks, destroying off-specification
Aerozine 50 and storing Aerozine 50, anhydrous hydrazine, monomethyl
hydrazine (MMH), monopropellent hydrazine,  hydrazine 70, UDMH
and hydrazine.
  Hydrazine and UDMH are unstable in the natural environment and
 rapidly decompose when exposed to the atmosphere. One decomposi-
 tion byproduct of UDMH is NDMA, a suspected human carcinogen.
 In 1982, the U.S. Occupational Safety and Health Administration
 (OSHA) surveyed the HBSF and detected the presence of airborne
NDMA within the facility. In May 1982, RMA ceased operations and
closed the HBSF  to all but safety-essential or emergency-response
entries. In the process of closing the HBSF, piping and tanks were
cleaned, and 300,000 gallons of decontamination water from these
cleaning operations were generated. This wastewater is currently stored
in three tanks (Figure 2). Each tank was sampled at four depths, and
the ranges of concentrations of analytes found in the wastewater are
summarized in Table 1. Analytes showing the highest concentrations
include the hydrazine fuel compounds, NDMA, aniline and iron.
                           Figure 1
                         Location Map
  In February 1989, a Federal Facility Agreement (FFA) was signed
for cleanup of RMA, and a number of Interim Response Actions (IRAs)
were initiated to alleviate certain concerns prior to the final remedial
action. Before implementation of an IRA, the IRA process requires
                                                                                         ROCKY MOUNTAIN ARSENAL    937
-------
                              Table 1
            Range of Concentrations of Analytes Found in
                   Hydrazine Wbstewater at RMA
   Hvdran
            I Compoundi/Nilrotammc
   H>draz,ne
   Monomethy! hydrazjne
   Unsymmelrical dimelhyl hydrazine
   N-Nitrovodime Ihylamme
   Volatile Oreanics

   Ace lone
   Benzene
   Chlorobenzene
   Chloroethane
   Chloroform
   Chloromelhane
   1,2-Dichlorocthane
   I.I -Dichloroelhane
   I.l-Dichloroelhene
   1,2-Dichloropropane
   Dimelhyl lulfide
   Melhylelhyl kelone/^-buianone
   Methylene chloride
   O. P-iylene
   Telrachloroethene
   Toluene
   Trichloroethene
   Vinyl acetate
   Vinyl chloride
    Sgmivolalilei

    Aniline
    Alrazine
    Benzolhiazole
    4-Chloroaniline
    Malathion
    4-Melhylphenol
    Naphthalene
    Paralhion
    Phcnanlhrenc
    Phenol
    Vapona
    bis(2-Elhylhe»yl)phthalaie
    Milali

    Arsenic
    Cadmium

    Copper
    Iron
    Mercury
    Silver
    Zinc
                               200,000 gallon
                                  Tank
11,000 - 85.000
14,000 - 18.000
11.000- 79.000
  53 - 60
 23 8 - 32-0
 2-25 - 2.66
 96,6 - 106
 7.25 - 25.6
 1.61 - 1.67
 3 66 - 3.89
 1500 - 6400
 4 52 - 5 50
 2.97 - 14.9
 2.88 - 2.94
  16 I - 20.4

  6.62 - 761
            50.000 gallon
              Tank
22.000 - 60,000
50.000 - 36.000
11 000 - 82.000
  470 - 790
    507
  53-112
    41 6
    2000
 3000 - 4750
    45 3
  66 - 143
  96 - 570
    13 I
 26.0 - 89.1
 4.87 - 14.2

 2600 - 13.000
    I 84
    260
    5.09
    5.16
  134 - 186
    783
 1200- 1460
 33.1 - 440
 2.47 - 2 92
               19 I
               2.00
             43 I - 66.3
              In-ground
               Sump
85 - 1600
1.4 - 5.8
                           0.574
                         45.5 - 320
                           378

                         4.12 - 4.52
             5.22 - 6.87
               748
6330 - 12,100    48 - 81,000
0.241 - 0.658   0738 - 0868
   0.224         0 462
  12.4 - 228     122 - 28.9
              220 - 288
             0601 - I 88
              5.8 - 107

              700 • 1080


              24.6 - 55 4
        micrograms per liter
    10001,030 10

    OmOMTM
completion of an Assessment Document, a Decision Document that
includes applicable or relevant and appropriate requirements (ARARs),
and a draft  Implementation Document that includes design specifi-
cations. The Decision Document also specifies that the UV/chemical
oxidation process is to be used to treat the hydrazine wastewater that
currently is stored at the HBSF. The action levels for the contaminants
of concern are shown in Table 2. NDMA's action level, also an ARAR,
was derived from an overriding health-based goal of a 10* lifetime ex-
cess cancer risk. In an extremely conservative approach, discharge to
ambient water immediately following treatment was assumed. Therefore,
treating NDMA to the ultra-low level in the reactor was examined.
  The decommissioning of the HBSF is to occur in two phases: (1) treat-
ment of hydrazine wastewater and subsequent discharge of the wastewater
to the RMA sanitary sewer system, and (2) decontamination of tanks
and piping  and demolition of all  aboveground structures such  as
buildings, concrete, piping and support systems and storage tanks.
  The objectives of the hydrazine wastewater treatment portion of the
IRA include:  (1) developing analytical methods and certifying  the
methods and laboratories that  will perform the analyses under  the
Program Manager for  Rocky Mountain Arsenal's (PMRMA) analytical
certification program, (2) conducting a treatability test to determine
whether  qualified manufacturers can reduce the  concentrations  of
hydrazine fuel compounds present in the wastewater stored at the HBSF
to concentrations near the action levels identified in the Decision
Document, (3) selecting an appropriate UV/chemical oxidation treat-
ment system and designing and constructing a full-scale treatment system
to include one UV/chemical oxidation reactor, (4) conducting full-scale
startup testing of the treatment system using approximately 10,000 gallons
of hydrazine wastewater stored at the HBSF, (5) gathering sufficient
process information from the full-scale testing to more specifically define
operational treatment requirements, including kinetic data to predict
treatment time necessary to achieve action levels identified in the Deci-
sion Document and (6) preparing an Implementation Document defining
the step-by-step procedures for installation of a second treatment unit
and  treatment of the remaining hydrazine  wastewater at the HBSF.

ANALYTICAL PROGRAM
  Before any testing could  be accurately conducted, methods for
analyzing the hydrazine fuel  compounds and NDMA had to  be
developed and certified in order to ensure that the ultra-low levels
specified in the action levels could be reached in treatment. An analytical
method for NDMA was previously certified under the U.S. Army Toxic
and Hazardous Materials Agency (USATHAMA) certification program
at a level of 200 ppt. Hydrazine, UDMH and MMH  were not previously
certified under the USATHAMA certification process because methods
of analysis for  these compounds had  been shown to be unstable.
Extensive research was conducted during the method development
stages, and methods for NDMA and MMH were certified. The method
for analysis of UDMH still is not certified because it remains unstable.
Certified reporting limits are shown in Table 3.
  One difficulty encountered in implementing this IRA is that analytical
certification was not achieved at or below  the action levels specified
for this IRA. This can be seen by comparing the action levels in Table 2
with the reporting limits in Table 3.

TREATABILITY TESTING PROGRAM
  Neither a literature review nor the manufacturers of UV/chemical
oxidation equipment could provide much information regarding the treat-
ment of hydrazine fuel compounds and  NDMA by UV/chemical
oxidation. Thus, the primary objectives of the treatability testing were
to: (1) determine whether qualified manufacturers could reduce the con-
centrations of hydrazine fuel compounds and NDMA present in the
wastewater stored at the HBSF to concentrations near the action levels;
and (2) generate design and operational information for the full-scale
treatment system. Bench-scale and pilot-scale testing were performed
at the manufacturing facilities of three qualified vendors of UV/chemical
oxidation equipment using representative wastewater collected from the
largest tank in which hydrazine wastewater is stored at the HBSF. Peroxi-
dation Systems, Inc., and ULTROX International performed bench-scale
testing, while SolarChem Environmental Systems performed pilot-scale
testing of their respective UV/chemical oxidation equipment. Analytical
testing  was  performed by  an independent  laboratory.  Hydrazine
wastewater was collected, sampled and shipped in stainless steel drums
to the three vendors. A sample of influent wastewater was analyzed
for the hydrazine fuel compounds, NDMA, purgeable halocarbons and
metals, and the results served as the  influent baseline  for all  three
vendors.
  Visits were made to each vendor's manufacturing facility  during the
treatability testing to witness the testing and to assess the capabilities
of each manufacturer. Effluent wastewater samples from the treatability
testing were analyzed for NDMA and the hydrazine fuel compounds
by  developmental analytical methods  not yet certified  under the
PMRMA program. Purgeable halocarbons and metals were analyzed
using standard U.S. Environmental Protection Agency (EPA) methods.
  Performance results  from the treatability testing (Table 4) indicate
that  the hydrazine fuel  compounds and NDMA were reduced by all
three vendors to the respective detection limits of the developmental
methods used for analysis. Purgeable halocarbons also were reduced
to below detection limit levels. Thus, all three vendors met the objec-
tive of reducing the influent concentrations to action levels for the com-
pounds of concern. Recommendations from the treatability testing for
"38    ROCKY MOUNTAIN ARSENAL
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                 In-Ground Sump
                 Storage Tank
                            Hydrazine Wastewater
                            Treatment Facility
                                    200,000
                                    Gallon Tank
                                                                 Figure 2
                                              Location of Storage Tanks and Wastewater Treatment
                                                              Facility at HBSF
                             Table!
             Action Levels for Contaminants of Concern
                                               Action Level
                                            From IRA Decision
    Parameter                                   Document
    NDMA

    Hydrazine

    UDMH

    MMH
1.4 ppt

2.5 ppb

25 ppb

20 ppb
    ppb = parts per billion
    ppt = parts per trillion
                                                  Table 3
                            Certified Reporting Limits for Contaminants of Concern
 Parameter

NDMA

Hydrazine

UDMH

MMH
Certified Reporting
	Limit (CRL)

          42 ppt

          9.9 ppb

          25 ppb*

          7.4 ppb
                         * Action level only. UDMH was not certified.

                         ppb = parts per billion
                         ppt = parts per trillion
    20003,930.10
    0827090790
                         20003,930.10
                         0827090790
full-scale operation were similar for all three vendors and included:
(1) treatment in batch mode,  (2) treatment time of between 8 and
16 hours using an ozone and/or hydrogen peroxide chemical oxidant
concentration greater than the stoichiometric concentration, (3) main-
taining a solution pH of between 3 and 5 throughout treatment and (4)
use of a metal-based catalyst.
  The  selection  of  Peroxidation  Systems, Inc.,  to provide  the
UV/chemical oxidation equipment was based in part on the analytical
results from the bench- and pilot-scale testing program. Other evalua-
tion criteria that were considered included capital and operating costs,
potential for generation of off-gas, ease of installation and operation,
experience, delivery time and anticipated response and support services.
These other criteria were evaluated based upon information contained
in the treatability testing reports and gained from visits to the vendor
facilities during treatability testing.

DESIGN/CONSTRUCTION
  Full-scale design criteria resulting from the treatability testing pro-
                    gram included: (1) UV-enhanced oxidation of the high-strength hydrazine
                    wastewater should be performed in the batch treatment mode in order
                    to maintain a reasonable  reactor size;  (2) the temperature  of the
                    wastewater should be maintained at 140 °F or less; and (3) the pH of
                    the wastewater should be maintained between 3 and 5 for the most
                    effective reduction of NDMA. Based on these and other criteria, a full-
                    scale treatment system, incorporating the unit processes indicated in
                    Figure 3, was designed and constructed within a 4-month period. The
                    heart of the system includes the UV/chemical oxidation reactor, recycle
                    tank and pump, and chiller (Figure 4). Other appurtenant unit processes
                    include influent and effluent transfer and storage systems, bag filtra-
                    tion of the influent, hydrogen peroxide, concentrated sulfuric acid, liquid
                    catalyst, caustic chemical storage and feed systems, a tank and reactor
                    off-gas collection system, a hydropneumatic potable water system, air
                    monitoring and safety subsystems. The  off-gas collection system was
                    included to collect and treat air displaced in the headspace of tanks
                    and to treat any gases that might be generated in the reactor.
                      The treatment system is housed in  a  40- by  60-foot insulated
                                                                                                      ROCKY MOUNTAIN ARSENAL    939
-------
                                                                           Table 4
                                                          Analytical Results from Treatability Tests
                                                      Vendor A
               Anajytcs
                                                                                                                                  Vendor C
           Hydrazine Fuel  Compounds
               Kydrazine
               HUH
               UDHH
            1,100,000
            62,000
            960,000
<20
<990
<20
1,500,000
580,000
1,800,000
<250
610,000
99,000
540,000
43
•0,000
56
            HDHA

            Purqeable Kalocarbons
                                            120
                                                               0.02
                                                                                  72
                                                                                                     0.07
                                                                                                                        37
                                                                                                                                           0.20
                ChLoroethane
                Chloroform
                Chloromethane
                Methylene chloride
                Tetrachloroethane
            60
            31
            <5
<0.5
32
<5.0
8.8
                                                  44

                                                  18
                   <0.5

                   1.2
                   160

                   200
                   <5

                   12
                Total  arsenic
                Total  chromium
                Total  copper
                Total  mercury
                Total  molybdenum
                Total  nickel
                Total  thallium
                Total  zinc
                Total  iron
                               11
                               300
                               75
                               0.5
                               200
                               220
                               100
                               60
                               2,900
                                                                                  18
                   <25
                   0.2
                   <20
                   5,600
                   19
                   260
                   70
                   1.9

                   170

                   280
                   14,000
                                                                            16
                                                                            50
                                                                            0.6

                                                                            260
                                      90
                                      220
            NA = Not  applicable; sample  not received or analysis not required.
            < indicates not detected at  or below specified  reporting limit.
            /ig/l « micrograms per liter
            20003,930.10
            0829090790
                                                                                                 Chiller
                        Hydrogen
                        Peroxide    Polymer
                           Sludge •<- -
        Hydrazine
       Wastewater
         Storage
Iron Removal
Pretreatment
(il Necessary)
                                                    Recycle
                                                      Tank
                                                                                                                                              UV Lamps
                                                                                                                                               Stainless
                                                                                                                                                Steel
                                                                                                                                               Reactor
                                                                          Bag
                                                                        Filtration
                                                                                                    Catalyst
                                                                                                    Reactor
                                                                                       UV/Chemical
                                                                                         Oxidation
                                                                                          Reactor
                                                                            Figure 3
                                                        Schematic of the UV/Chemical Oxidation Process
                                                            for Destruction of Hydrazine Wastewater
-------
preengineered metal building.  All  tanks and equipment are located
within a secondary containment curbing; lined sumps are included
to collect and remove any spilled liquids; and the floor of the facility
is protected with a nonslip, chemical-compatible, protective coating
system.

FULL-SCALE  STARTUP TESTING
  Once the treatment building was complete, full-scale startup testing
of the hydrazine wastewater treatment  system was  conducted  from
January to May 1990, using nine batches of wastewater ranging in volume
from 700 to  1,300  gallons.  The purposes for startup testing were to:
(1) address equipment and  related startup concerns,  (2) perform any
necessary physical and operational modifications to the system and (3)
gather process and analytical data to define the operational requirements
for treatment of the approximately  300,000  gallons  of hydrazine
wastewater.
  Wastewater was pumped  via a submersible pump  suspended  at an
intermediate depth in the largest tank, which the characterization data
indicated has the highest concentration of the hydrazine fuel compounds
and NDMA. During treatment of each batch, the operating parameters
included pH,   oxidation/reduction  potential   (ORP),  temperature,
hydrogen peroxide concentration, catalyst type, recycle rate, total  treat-
ment time and wastewater volume (Table 5). For those parameters that
varied during treatment, both initial  and final  values are presented.
  Pretreatment  of all batches  consisted  of filtration  through 50- and
5-micron pore-size bag filters arranged  in series. Iron fouling of the
quartz sheaths that surround the UV bulbs in the reactor during Batches
1 and 2 resulted in  modifications  to the system including adding a
1-micron pore-size bag filter in-line with the reactor and recycle  tank,
replacing the liquid ferrous sulfate catalyst with an in-line solid tungsten
                                                                                 Figure 4
                                                          UV/Chemical Oxidation Reactor, Recycle Tank and Chiller
                                                 rod reactor and attempting to oxidize and remove iron using hydrogen
                                                 peroxide  and polymer chemical addition, slow mixing and settling.
                                                 Because the influent concentration of NDMA varied greatly between
                                                 batches, the attempt to remove iron seemed to be oxidizing the UDMH
                                                 and creating NDMA. Thus, pre-oxidation and polymer addition were
                                                 discontinued for pretreatment of Batches 8 and 9.
                                                   Batch 1 was treated  using the recommended operating  parameters
      Parameter

   pH (units)
   (initial/final)
Batch 1

2 • 5
Batch 2

9/3
                                                                    Table 5
                                                  Summary of Full-Scale Startup Testing results
Batch 3

7/1.3
Batch 5       Batch  6        Batch 7       Batch 8        Batch 9

1.6/1.6       1.5/1.5        1.4/1.4       9.3/2          9/2
   Catalyst
emulative treatment
time for batch
(hours)

Total volume
treated (gallons)

Recycle Rate
Range (gpm)

ORP Range (mv)
(initial/final)

Maximum Operating
Temperature (°F)

Hydrazine (ppb)
Influent/lowest
Level achieved

UDMH
       (/ig/l)
                          Ferrous
                          sulfate
                          solution

                          43
                          700
                          65 - 147
                          301 - 684
                          130
                          1,000.0007
                          < 2.5
810,OOO/
< 2.5
320,OOO/
< 2.5

106/
0.228
                                       None
                                       60
                                       1300
                                       65 -  151
                                       -138 - 692
                                       122
              NA/
              <  2.5
NA/
< 2.5
NA/
< 2.5

NA/
0.255
                           Tungsten
                           rods
                                                     76  - 134
                                                     -43 - 667
                                                     136
              1.200.000/
              <  0.25
                           Tungsten
                           rods
                                                                  46
                                                                  68 -  76
                                                                   •21 - 625
                                                                   130
              250,OOO/
              <  0.25
                           Tungsten
                           rods
                                                                                48
                                                                                1300
                                                                                130
96,OOO/
< 0.25
             Tungsten
             rods
                                                                                             50
             Tungsten
             rods
                                                                                             552 -  631
                                                                                              122
51,OOO/
< 0.25
                                                                                                           590 - 610
490,OOO/
< 0.25
             Tungsten
             rods
                                                                                                                        33.5
65,OOO/
< 0.25
             Tungsten
             rods
                                                                                                                                      53
130/
< 0.25
5, 300, OOO/
< 0.25
89, OOO/
< 0.25
2B5/
0.062
380, OOO/
< 0.25
120, OOO/
< 0.25
23.500/
0.467
250, OOO/
< 0.25
20, OOO/
< 0.75
59.200/
0.679
56, OOO/
< 0.25
64, OOO/
< 0.25
40, OOO/
25.8
940, OOO/
< 0.25
180, OOO/
< 0.25
28.300/
1.39
2, 000, OOO/
< 0.25
110, OOO/
< 0.25
3.880/
5.00
100/
< 0.25
2.600/
< 0.25
66,000
0.107
   < indicates parameter not detected at or above specified  reporting limit
   MA    = parameter not analyzed
   mv    = millivolts
   /ig/l   = micrograms per liter
                                                                                                           ROCKY MOUNTAIN ARSENAL    941
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from  the  bench-scale  testing program.  The literature suggests that
hydrazine fuel compounds are destroyed best via an oxidation process
at a pH above neutral, while destruction of NDMA is enhanced at a
pH  less than 4. Thus, for Batches 2, 3, 4, 8 and 9, the influent pH
of between 7 and 9 was maintained at the beginning of each batch in
an attempt to enhance the destruction of the hydrazine fuel compounds.
The pH was later reduced in these runs to promote NDMA reduction.
In an attempt to avoid the formation of NDMA by oxidation of UDMH,
Batches 5, 6 and 7 were run at a pH of less than 2 units for the entire
run time.
  Three types of wastewater samples were collected during each batch:
influent, process stream and effluent. Influent samples were collected
after the pretreatment steps to obtain baseline water quality data. Pro-
cess stream and effluent samples were collected from the same loca-
tion downstream of the reactor. Process stream samples were collected
at planned intervals throughout each batch and were analyzed to deter-
mine: (1) the concentration of NDMA and the hydrazine fuel compounds
as a function of time, (2) reaction rate kinetics and  (3) the time re-
quired to reach the lowest effluent NDMA and hydrazine fuel  com-
pound concentrations. Process stream samples were collected at 2-hour
intervals during Batches 3 and 9  to develop reaction kinetics data.
  Results from  the nine batches treated during the full-scale startup
testing period are shown in Tables 5 and 6 and in Figures 5 and 6. The
results indicate  the following:
• The UV/chemical oxidation process very successfully in reduced the
  levels of hydrazine fuel compounds,  NDMA and other organics
  present in die hydrazine wastewater at RMA. In particular, the removal
  of the suspected carcinogen, NDMA, ranged from 99.785 to 99.999%.
  The hydrazine fuel compounds  were consistently reduced to below
  detection limits in all batches. Where data are available, it appears
  that the hydrazine fuel compounds are destroyed in the initial 10 hours
  of treatment time. Other organic compounds also were reduced or
  destroyed  in the process.
• Analytical method limitations do not allow measurement of NDMA
  to the ARAR  (1.4 ppt) required for this IRA. Nevertheless, the detec-
  tion limit  for NDMA was not reached in any process stream or
  effluent sample through the full-scale testing program. It is therefore
  assumed that the  limits of the  UV/chemical oxidation technology,
  with  respect to NDMA, were  established during this testing.
• Iron fouling of the quartz sheaths that surround the UV bulbs occurred
  during Batches 1 and 2 and appeared to inhibit the treatment capability
  of the reactor.
• Pretreatment  of hydrazine wastewater to remove  iron appeared to
  enhance the formation of NDMA.
• A treatment scenario involving treatment at the initial pH of between
  7 and 9 until the  hydrazine fuel compounds are reduced to below
  detection limits, followed by reducing the pH to less than 4, appeared
  to provide the lowest effluent NDMA concentrations in the shortest
  treatment time. The data from Batch 9 suggest that effective reduc-
  tion of the compounds of concern may be achieved in approximately
  16 hours. Using this treatment scenario, it appears that the hydrazine
  fuel compounds may be reduced to below detection limits, while
  NDMA reduction to less than 2 ppb may be  consistently achieved.
• Influent concentrations for the hydrazine fuel compounds and NDMA
  appear to vary significantly throughout Batches 1 through 9.
• Influent concentrations  of NDMA and the  hydrazine  fuel  com-
  pounds can vary greatly, even when taken from the same depth in
  the same tank.

RECOMMENDATION FOR FULL-SCALE TESTING
  Based  on the results from the full-scale startup testing, the following recom-
mendations are made for treatment of the approximately 300,000 gallons of
hydrazine wastewaler stored at the HBSF:
• Each batch should be treated by not adjusting initial pH and by adding hydrogen
  peroxide in  an amount exceeding the stoichiometric requirement. After the
  hydrazine fuel compounds are destroyed, which is indicated by a drop and
  subsequent leveling off of pH. the pH of the waste stream should be reduced
  to 2 for destruction of NDMA Verification testing will be conducted during
  treatment of retches in the next phase of the IRA to determine whether the
                             Table 6
              Full-Scale Testing Treatment Results for
                   Other Parameters of Concern
                               Batch I
                               Influent
                               Concentration
Analvte

Volatile Organics

Acetone
Chloroform
Chloromethane
Methylene chloride
Semivolatiles

Dieldrin
Benzothiazole
Dimethyl disulfide

Metals

Arsenic
Cadmium
Chromium
Copper
Mercury
Silver
Zinc
32.0
106
< 10.0
110.0
0.0601
14.9
53.0
16.1
<0.2
< 22.4
< 10.0
0.658
0.224
<20
                         Batch 1
                         Effluent
                         Concentration
32.5 - 52.3
<5
36 - 37.5
18.8 - 23.2
< 0.0539
< 1.14
< 1.16
6.32 - 6.58
3.0 - 3.2
641  -645
15 - 16.6
0.962 - 1.100
0.968 - 1.130
114  - 118
< indicates parameter not detected at or above specified reporting limit
/jg/l = micrograms per liter
20003.930.10
0829090790
          - - pH
         ——— NDMA
             • Total Hydrarine Fuel Compounds
                    Cumulative Treatment Time (Hours)
                             Figure 5
                     Operating Results—Batch 3
              pH
             > NDMA
             • Total Hydrazine  Fuel Compounds
                                                                pH
                   Cumulative Treatment Time (Hours)

                              Figure 6
                     Operating Results—Batch 9
       ROCKY MOl STAIN  ARSENAL
-------
  recommended treatment scenario is effective.
• The treatment system should be modified to eliminate "dead spots" in the
  reactor, recycle tank and interconnecting piping.
• The reactor and associated steel piping should be modified such that all con-
  necting parts are made of 316 stainless steel in order to reduce the "battery"
  effect caused by the high concentrations of acid in the reactor.
• Treatment time should  be approximately 16 hours, but actual time should
  depend on the concentrations of hydrazine fuel compounds and NDMA in
  the influent.

CONCLUSION
  The results of the treatability testing and the startup testing suggest
that the UV/chemical  oxidation reactor  can successfully  treat the
wastewater; however, the limits of the reactor have been reached when
treating the hydrazine-contaminated wastewater at the HBSF. Additional
treatment time does not significantly reduce the concentration of NDMA
below 1 to 2 ppb. Therefore, the exposure pathways must be examined
to determine whether NDMA levels of 1  to 2 ppb may still achieve
the overriding  health-based goal of 10 ~6  lifetime excess cancer risk
rate. If the health-based risk goal cannot be achieved, additional treat-
ment with adsorption media or a solar evaporation pond must be per-
formed.  A risk assessment is being conducted, and the methods of
additional treatment are currently being tested.
                                                                                                         ROCKY MOUNTAIN ARSENAL    943
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        A  Systematic  Approach  to  Analytical Method Development
                          to Meet  Ultra-Low-Level-Based ARARs,
                      Rocky Mountain  Arsenal,  Denver,  Colorado

                                                   Robert  A. Howe
                                              Harding Lawson Associates
                                                   Denver,  Colorado
                                                  Michael  J. Malley
                                              Harding Lawson Associates
                                                   Denver,  Colorado
                                                Gregory B.  Mohrman
                           Office of the Program  Manager for Rocky Mountain Arsenal
                                               Commerce City,  Colorado
ABSTRACT
  In many cases, health-based action levels or applicable or relevant
and appropriate requirements (ARARs) are established that require treat-
ment of chemicals in environmental media to ultra-low levels that are
often below currently available method analytical detection limits. For
this reason, analytical method development must be undertaken to
achieve the lowest level of detection possible to demonstrate that ultra-
low-level ARARs can be met. Two approaches to method development
include: (1) modification of currently available analytical methods to
improve performance while not restricting the flexibility of the overall
analytical approach and (2) methods development when published
methods are not available for contaminants that are stipulated for regula-
tion under a recently developed technology or health-based ARARs.
  Modifying the current U.S. Environmental Protection Agency (EPA)
Method 607 became necessary  at Rocky Mountain Arsenal (RMA) for
the analysis of N-nitrosodimethylamine (MDMA) in treated wastewater
to evaluate the practicality of achieving an  Ambient Water Quality
Criteria (AWQC)-based ARAR of 0.0014 parts per billion (ppb) for
NDMA. In conjunction with method modification  for analysis  of
NDMA, method development for analyses of hydrazine (HYDZ),
monomethylhydrazine (MMH) and unsymmetrical dimethylhydrazine
or 1,1-dimethylhydrazine (UDMH) also was necessary because published
methods were neither available nor adequate to meet program-stipulated
ARARs. Methods are  evaluated using a systematic approach and a
rigorous quality assurance/quality control (QA/QC) program developed
by  the  U.S.  Army  Toxic  and  Hazardous  Materials  Agency
(USATHAMA) and adopted by  the Program Manager for Rocky Moun-
tain Arsenal (PMRMA). The PMRMA QA/QC program substantiates
that modified method results or results generated using newly developed
methods meet or exceed U.S.  EPA or state agency requirements for
analytical precision, accuracy, representativeness, completeness and
comparability.
  Conservative risk assessment-based ARARs may  be analytically
unachieveable, considering the current state of technology, and must
be evaluated before signing the  record of decision (ROD) to ensure the
action levels selected are practicable and protective of human health.
Well-documented  method  development programs  will improve  the
understanding of the analytical constraints that must be considered when
selecting final treatment levels.

INTRODUCTION
  During  1989, the U.S.  Army, U.S. EPA  Region  VHI, Shell  Oil
Company (Shell) and  the Department of Interior (DOI) agreed on a
plan for safe disposal of hsdrazine-contaminated wastewater and for
decommissioning of facilities previously used for blending of hydrazine
rocket pre>pellants at the Rocky Mountain Arsenal (RMA).  The plan
was defined by a Decision Document in which a preferred remedial
alternative was recommended. Action levels were established for four
compounds in the wastewater at the Hydrazine Blending and Storage
Facility (HBSF): (1) NDMA at 0.0014 ppt, (2) HYDZ at 2.5 parts per
billion (ppb), (3) MMH at 15 ppb and (4) UDMH at 25 ppb. The Interim
Response Action (IRA) program for RMA defined by the Federal
Facility Agreement (FFA) provides that "IRAs shall, to the maximum
extent practicable, attain ARARs."
  Development of the ARAR established for NDMA was based on a
health-based standard because NDMA is not directly governed under
any state or federal regulatory laws. At the time of signing the HBSF
IRA Decision Document, the Ambient Water Quality Criteria (AWQC)
was selected as the ARAR for NDMA. Because no health-based criteria
are currently available, the action levels selected for the hydrazine fuel
compounds (i.e., HYDZ, MMH and NDMH) were based on unpublish-
ed analytical method  detection limits.
  The AWQC for NDMA of 0.0014 ppb was developed pursuant to
Section 304(a)(l) of the Clean Water Act, 33 U.S.C.  13M(a)(l). Under
this section of the Clean Water Act, the U.S.  EPA must periodically
review and publish criteria for water quality that accurately reflect the
latest scientific health and welfare knowledge. The NDMA ARAR of
0.0014 ppb represents a  IxlO"6 cancer risk factor for an average per-
son who consumes a total of 2 liters of NDMA-contaminated water per
day during 70 years and an average 6.5 grams of NDMA-contaminated
fish per day during the same 73-year lifetime. This AWQC was developed
and published by the U.S.  EPA  during 1980 as  guidance  when
establishing ARARs  for site remediation.  The ultimate utility of any
such site-defined ARAR depends on two essential elements under the
Superfund Amendments and Reauthorization Act (SARA). A new level
of treatment can be redefined after an ARAR has been agreed upon
only if: (1) the new level of treatment can be shown to be protective
of human health or  (2)  the established ARAR can be shown to be
unpracticable.
  To show the levels to which ARARs are set  are practical  and
achievable, two elements of any pilot-scale or bench-scale treatment
program must be carefully examined: (1)  efficiency of the treatment
system to meet program ARARs and (2) the reliability of the analytical
method when evaluating the treatment system efficiency.
  Many methods currently are  available for evaluating the efficiency
of analytical methods. The U.S. EPA uses a  statistical approach for
calibration standards that evaluates method accuracy based on seven
replicate analyses run during a single day. The approach  is designed
to evaluate instrument sensitivity and accuracy. However, this method
of determining  method detection  limits  does not consider sample
preparation and extraction efficiencies,  which generally control and
dictate analytical method reliability.
-------
  During the early 1980s, USATHAMA introduced a statistical method
to evaluate method detection limits that was designed to account for
sample preparation and extraction efficiencies. This program requires
that a series  of calibration standards and investigative samples be
prepared and analyzed  over the entire estimated range of method
performance. Four consecutive days of extraction and analysis  are
required to be evaluated using a series of standard statistical tests. The
U.S. EPA method startup protocols, which prepare and analyze samples
in quadruplicate during a single day and compare results to a national
data base, are most comparable to the USATHAMA method design
plan; however, the investigative samples prepared and analyzed under
the U.S. EPA method startup protocol are run only  at a single level
of concentration and are analyzed during a single day.
  Under a prime contract to perform several different studies at RMA,
Harding Lawson Associates (HLA) designed and tested an ultraviolet
(UV)/chemical  oxidation treatment system for the HBSF wastewater.
Tb accomplish  this  task, HLA researched and developed analytical
methods to attempt to satisfy the program-stipulated ARARs set forth
in the HBSF Decision Document.

CHEMICAL PROFILE OF NDMA
  The major uses, sources and regulatory constraints on human exposure
to NDMA are  very  important  for  understanding  the  nation-wide
significance of  the analytical technology  available for analyzing the
presence of NDMA.
  Before April  1976, NDMA  was  used  as  an  intermediate in  the
production of UDMH, a liquid rocket propellant believed to have con-
tained up to 0.1% NDMA as an impurity. NDMA also forms from the
chemical breakdown of UDMH. NDMA has been used as an industrial
solvent; as an antioxidant; in lubricants and condensers to increase the
dielectric constant; as a nematocide; as a softener for copolymers; as
an inhibitor of nitrification in soil; and in active metal anode-electrolyte
systems.4
  Nitrosamines, including NDMA, are present in a wide variety of food
as reported by Fine5 and Scanlan.6 Nitrosamines  are  found  most
commonly in cured meats (particularly cooked bacon); beer; Scotch
whiskey; some cheeses (especially Gouda and Edam types); nonfat dry
milk and buttermilk; and sometimes fish.4  Levels  of total volatile
nitrosamines are generally less than 5 /tg/kg in these foods. The average
daily intake of volatile nitrosamines  from food is  estimated to be
approximately 1  /g per person. NDMA is also found in rubber pacifiers,
baby-bottle nipples and occasionally in cosmetics. Smokers are exposed
to an estimated 6.5  nanograms  (ng) of NDMA per cigarette  from
mainstream smoke; undiluted sidestream smoke may contain 20 to 100
times as much  NDMA as mainstream smoke.3
  NDMA does  not appear to be common in drinking water or ambient
air. Brodzinsky and Singh7  compiled  all  available  atmospheric
monitoring data for a number of organic compounds, including NDMA,
for 404 locations. In rural and remote areas the median concentration
of NDMA was  0.018 /ig/m3; the median concentration  in urban and
suburban areas was 0.028 ^g/m3 and in source-dominated areas, 0.042
/tg/m3.  Indoor levels of NDMA measured in restaurants and other
public places have been between 0.01 and 0.24 /tg/m3 and are attributed
primarily to tobacco smoke.

REGULATORY STATUS OF NDMA
  The following is a brief summary of the March 1, 1989, nationwide
regulatory status of NDMA. This summary is provided to inform the
reader of manufacturing and other industrial situations that may result
in the release of chemicals discussed in  this  paper. The regulatory
environment is rapidly changing in relationship to NDMA and HYDZ,
MMH and NHMH. A clear understanding of the state of current regula-
tions governing these  chemicals will provide the  reader  a  better
understanding of the potential effect that method development, such
as lhat described in this paper, will have  on the ultimate success or
failure of any remedial action. Not only can the following discussion
help to clarify the regulatory constraints  currently applicable to the
specific chemicals discussed in this paper, but it also can provide insight
into how method development will  affect remediation programs for
chemical compounds, other than those discussed in this study, for which
legal constraints are not yet clearly defined.

Federal Programs

Clean Water Act (CWA)
  NDMA is listed as a toxic pollutant, subject to general pretreatment
regulations for new and existing sources and to effluent standards and
guidelines. Effluent limitations specific to NDMA have been set in the
following point source categories: electroplating, steam electric power
generating and metal finishing. Limitations vary depending on the type
of plant and industry.

Resource Conservation and Recovery Act (RCRA)
  NDMA is listed as an acute hazardous waste and a hazardous waste
constituent. This chemical  is subject to land-disposal restrictions when
its concentration as a hazardous constituent of certain wastewaters
exceeds site-specified designated levels. NDMA is included on the U.S.
EPA's groundwater monitoring list. The U.S. EPA requires that all hazar-
dous waste treatment, storage and disposal facilities monitor  their
groundwater for chemicals on this list when suspected contamination
is  first detected and annually thereafter.

Comprehensive Environmental  Response
Compensation and Liability Act (CERCLA)
  NDMA is designated a hazardous substance under CERCLA. It has
a reportable quantity (RQ) limit of 0.454 kg. NDMA is designated an
extremely hazardous substance under SARA Title HI Section 302. Any
facility at which this  chemical is present in excess of its threshold
planning quantity of 10 pounds must notify state  and local emergency
planning officials. If NDMA is released from a facility in excess of
its RQ, local emergency planning officials must be notified.

Marine Protection Research and Sanctuaries Act (MPRSA)
  Ocean dumping of organohalogen  compounds as well as the dumping
of known or suspected carcinogens, mutagens or teratogens is prohibited
except when they are present as trace contaminants. Permit applicants
are exempt from these regulations  if they can demonstrate mat such
chemical constituents are nontoxic and nonbioaccumulative in the marine
environment or are rapidly rendered harmless by physical, chemical
or biological processes in the sea.

Occupational Safety and Health Act (OSHA)
  Employee exposure to NDMA should be avoided. This chemical is
designated an Occupational Safety and Health Administration (OSHA)
carcinogen. Detailed regulations exist in 29 CFR 1910.1016 for areas
where NDMA is manufactured, processed, used, packaged, released,
handled or stored. These include requirements for reporting maintenance
and decontamination.
Hazardous Materials Transportation Act (HMTA)
  The U.S. Department of Transportation (DOT) has designated NDMA
as  a hazardous substance with an RQ  of 0.454 kg, subject to requirements
for packaging, labeling and transportation.

State Water Programs
  All states have adopted the AWQC criteria as their promulgated state
regulations, either by narrative reference or by relisting specific numeric
criteria. The following states have promulgated additional or  more
stringent criteria:
•  Kansas - Kansas has an action level of 0.0014 ng/L for NDMA in
   groundwater.
•  New York - New York has a maximum contaminant level (MCL) of
   50 /tg/1 in drinking water.
•  Oklahoma - Oklahoma has set an enforceable Toxic Substance Goal
   of 0.8 ng/L for nitrosamines in surface waters classed for public and
   private water supplies.

Proposed Regulations
•  Federal Programs - No proposed regulations  are pending.
                                                                                                    ROCKY MOUNTAIN ARSENAL    945
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• State Water Programs
       Most States - Most states are in the process of revising their water
       programs and proposing changes in their regulations that will
       follow the U.S. EPA's changes when they become final. Changes
       are projected for 1989-90.
       Minnesota - Minnesota has proposed a Recommended Allowable
       Limit (RAL) of 0.007 /^/L for drinking water.

CHEMICAL PROFILE OF HYDRAZINE/HYDRAZINE FUELS
  For the purpose of demonstrating the significance of the hydrazine
fuel compounds to programs nationwide and in an attempt to not provide
an exhaustive narrative, hydrazine is  presented as an example of the
industrial uses and regulatory environment surrounding hydrazine fuel
compounds. Hydrazine is similar in chemical composition and in many
of its industrial applications to UDMH and MMH. However, distinctly
different industrial and regulatory constraints govern each of these
compounds. For a more detailed discussion of these topics, the reader
should contact a local regulatory agency  for further guidance and
reference materials.
  Hydrazine is used  in industry  as  a chemical intermediate in the
manufacture of Pharmaceuticals and plastic blowing agents and is used
as an oxygen scavenger in boiler feed-water treatment and in fuel cells.
It also is used as a  missile propellant and in auxiliary power units of
the space shuttle orbiter and solid rocket boosters. Each F-16 aircraft
carries 6.5 gallons of a 70% hydrazine/30% water solution used in an
emergency  power unit to supply electrical  and hydraulic  power.
  Information on sources of exposure to hydrazine  is limited. The
primary source of human exposure appears to be smoking, because
hydrazine is a component of mainstream cigarette smoke. No data were
found by HLA on its presence in the ambient environment. However,
UDMH is a common breakdown product for the plant growth regulator
Alar,  applied to many fruits such as  peaches and apples.
  The following is  a summary of the regulatory status  for hydrazine
as of  March 1, 1989:

Federal Programs

Safe Drinking Water Act (SDWA)
  In states with an approved Underground Injection Control program,
a permit is required for the injection of hydrazine-containing wastes
designated  as hazardous under RCRA.

RCRA
  Hydrazine is identified as a reactive, toxic hazardous waste and listed
as a hazardous waste constituent.

CERCLA
  Hydrazine is designated a hazardous substance under CERCLA. It
has an RQ limit of 0.454 kg. Reportable quantities have also been issued
for RCRA  hazardous waste streams containing hydrazine, but these
depend on  the concentrations  of the  chemicals in the waste stream.
Hydrazine is designated an extremely hazardous substance under SARA
Title in Section 302. Any facility at which hydrazine is present in excess
of its threshold planning quantity of 1000 pounds must notify state and
local emergency planning officials annually. If hydrazine is released
from the facility in excess of its RQ, local emergency planning officials
must be notified. Under SARA Title ID Section 313, manufacturers,
processors, importers and users of hydrazine must report  annually to
the U.S. EPA and state officials their releases of this chemical to the
environment.

MPRSA
  Ocean dumping of organohalogen compounds as well as the dumping
of known or suspected carcinogens, mutagens, or teratogens is prohibited
except when they are present as trace contaminants.

Occupational Safety and Health Act
  Employee exposure to hydrazine shall not exceed an 8-hour time-
weighied  average (TWA)  of 0.1 ppm. Employee  skin exposure to
hydrazine shall be prevented/reduced through the use of protective
clothing and work practices.

HMTA
  The DOT has designated hydrazine as a hazardous substance with
an RQ of 0.454 kg, subject to requirements for packaging, labeling and
transportation.

Food, Drug and Cosmetic Act (FDCA)
  Hydrazine may not be used as a boiler-water additive in any amount
in the preparation  of steam that will contact food.

State Water Programs
  All states have adopted U.S. EPA AWQC and National Discharge
Permit Water Restrictions (NDPWRs) as their promulgated state regula-
tions, either by narrative reference or by  relisting the specific numeric
criteria. The U.S.  EPA has not currently published any AWQC for
hydrazine. Only New "fork has promulgated additional or more stringent
criteria:
  New York has an ambient water quality standard for hydrazine of
5 /tg/L at less than 50 ppm hardness and 10 /tg/L at greater than or
equal to 50 ppm hardness for Class A, A-S, AA, AA-S, B, and C surface
waters. New York also has an ambient water quality standard for
hydrazine of 50 /tg/L at less than 50 ppm hardness and  100 jig/L at
greater than or equal to 50 ppm hardness for Class D surface waters.

Proposed Regulation
• Federal Programs - No proposed regulations are pending.
• State Water Programs - No proposed regulations are pending. Most
  states are in the process of revising their water programs and
  proposing changes in their regulations that will follow the U.S. EPA's
  changes when they become final.
After review of the current state of regulations for compounds such
as NDMA or hydrazine fuels, it is apparent that regulatory constraints
will  most likely be based, at least in part,  on the level of detection
achievable.

METHOD DEVELOPMENT FOR THE ANALYSIS
OF NDMA IN WATER
  U.S. EPA-approved methods for analysis of NDMA  in  aqueous
samples include U.S. EPA Methods 607, 625 and 1625. The method
detection limits published for these methods are 0.150 ppb or ug/1
(Method 607) and 50 ppb (Method 1625). No detection limit for Method
625 is published. Because the AWQC-based ARAR for NDMA under
the HBSF IRA program is 0.0014 ppb, none of these U.S.  EPA methods,
in their current  state of development, were adequate to  meet required
objectives.
  Some potentially applicable analytical work on the analysis of ultra-
low  levels of NDMA was  reported by Jody8 and others  from the
Illinois Institute of Technology Research Institute. In Jody's paper,
"Ozonation of Hydrazine Fuels and Their Associated Impurities," he
reported that levels of NDMA detection using a rotary-evaporation
sample concentration technique coupled with a gas chromatograph and
nitrogen phosphorus detection  (GC/NPD) system were approximately
0.010 ppb. The  DTRI method was essentially  a  modified U.S. EPA
Method 607.
  HLA  contacted  nTRI  and  requested they  repeat their  previous
analytical work and subject it to the statistical programs utilized by
PMRMA. The PMRMA certification  program for  systematically
evaluating method performance involves  a two-step process that
ultimately yields a  certified reporting limit  (CRL) for the analyte(s).
The  initial step, or precertification, is  used to  evaluate instrument
stability and linearity over the proposed testing range of concentration.
The program involves preparing two separate sets of calibration standards
and  analyzing them in the  sequence that will be used during daily
calibration. DTRTs analytical results were found to satisfy all linearity
and instrument sensitivity requirements. Table 1 shows that instrument
sensitivity and reproducibility  were acceptable down to the 0.020 ppb
level of concentration. Instrument response  to NDMA was evidenced
*4*    ROCKY MOUNTAIN ARSENAL
-------
at the 0.0075 ppb level, but reproducibility was poor. Linearity of calibra-
tion checks was acceptable, as shown in Figure  1.
  During the second step of method certification using the systematic
approach used by PMRMA, four consecutive days of instrument calibra-
tion and spiked-sample extraction analysis were performed and subjected
to statistical analysis. Table 2 shows the results  for spiked  samples
analyzed using the HTRI, U.S. EPA Method 607 modification during
4 days of analysis. Recovery values were found to be erratic. Figure
2 shows the data were not linear and failed to meet linearity  criteria.
Thus, it became apparent that investigation into the development of better
sample extraction procedures was required to analyze for the presence
of NDMA at ppt levels.
                                                                         Table!
                                                       IITRI Certification Sample Results for NDMA
                             Table 1
                   IITRI Precertification Results
  Target Value
 (in fjg/1 or ppb)

      0.0075

       0.020

       0.050

       0.100

       0.250
Instrument Values in Area Units
  Standard G       Standard  H
     0.0161

     0.0306

     0.0749

     0.1451

     0.3190
0.0098

0.0353

0.0656

0.1265

0.3590
  Spiked
Concentration
 fug/1 or ppbl

    2.000

    1.000

    0.400

    0.200

    0.100

    0.040

    0.020

    0.010

Method Blank



  Spiked
Concentration
 fue/l or ppbl

    2.000

    1.000

    0.400

    0.200

    0.100

    0.040

    0.020

    0.010

Method Blank
                                                              Reported
                                                            Concentration

                                                                 0.045

                                                                 0.040

                                                                 0.085

                                                                 0.035

                                                                 0.031

                                                                 0.000

                                                                 0.002

                                                                 0.000

                                                                 0.000
                                                     Percent
                                                     Recovery

                                                        2.26

                                                        4.00

                                                       21.40

                                                       17.70

                                                       30.90

                                                        0.00

                                                       11.SO

                                                        0.00
 Reported
Concentration

     0.216

     0.102

     0.033

     0.046

     0.038

     0.023

     0.020

     0.014

     0.000
Percent
Recovery

   10.80

   10.20

   8.20

   22.90

   37.50

   57.50

  102.00

  140.00
Reported
Concentration
0.192
0.070
0.060
0.035
0.020
0.009
0.019
0.020
0.000
Day No.
Reported
0.448
0.256
0.106
0.067
0.038
0.039
0.023
0.031
0.000
Percent
9.60
7.05
15.00
17.60
20.60
22.20
93.50
195.00
4
Percent
Recovery
22.40
25.60
26.50
33.40
37.50
98.20
114.00
308.00

                0.050
                         0.100     0.150     0.200

                         Target Concentration (ppb)
                                                     0.250     0.300
                              Figure 1
              Found Concentration vs. Target Concentration
                HTRI Precertification Results for NDMA
            0.250 0.500  0.750  1.00  1.25   1.50  1.75   2.00  2.25  2.50
                Spiked Sample Target Concentration In (ppb)
                             Figure 2
            Found Concentration vs. Target Concentration
            DTRI Certification Sample Results for NDMA
                                             Published QC acceptance criteria listed in U.S. EPA Method 607 for
                                           NDMA-spiked samples at 20 ppb in water are 13 to 109 percent recovery.
                                           The reported  method detection limit based on the analysis of seven
                                           replicate calibration standards is 0.150 ppb. This indicates that a sample
                                           with an NDMA concentration as high as 1.15 ppb could potentially be
                                           reported as not detected at the U.S.  EPA Method 607 detection limit
                                           of 150 ppt if sample recovery were  only  13%. This level of method
                                           performance was not acceptable using the PMRMA two-step certifica-
                                           tion process.
                                             DataChem Laboratories in Salt Lake City, Utah, had previously suc-
                                           cessfully certified a method for the analysis of NDMA at 0.200 ppb.
                                           Precertification was rerun by Datachem for the analysis of NDMA using
                                           instrument conditions  similar to those used by IITRI; the data were
                                           found to be comparable. In an attempt to improve spiked sample results,
                                           the florisil column cleanup recommended in U.S. EPA Method 607 was
                                           eliminated from the extraction procedure because it drastically reduced
                                           NDMA extraction efficiency. Separatory funnel extraction, used in U.S.
                                           EPA Method 607, was substituted with the use of liquid-liquid continuous
                                           extraction at a pH between 5 and 9.
                                             After an 8-hour liquid-liquid continuous extraction using the extrac-
                                           tion solvent methylene chloride (MECL2), sample concentration was
                                           found to be most efficient by adding 15 mLs of methanol (MeOH) to
                                           the 300 mLs of MECL2 extract and then concentrating the extract in
                                           a cool-water bath at 65 °C, using a Kuderna-Danish.  When the extract
                                           reached a volume of 100 mLs, a hot-bath concentration step at 90 °C
                                           was used to reduce the sample to a volume of 5 to 8 mLs. A nitrogen
                                           blowdown step was then used in a cold-water  bath at or below 30 °C.
                                           Numerous types of concentration methods were examined, such as con-
                                           densers, turbo-evaporators and micro-snyder columns. In all cases, the
                                           preferred method  that  yielded at least 40% NDMA recovery was the
                                           one that utilized the Kuderna-Danish coupled with a nitrogen blowdown.
                                             Table 3 shows the results of 4 days of spiked-sample extraction and
                                           analysis using the described modifications to U.S. EPA Method 607.
                                           The range of concentrations tested is a subset  of the actual range over
                                           which the method was tested.  The method was tested initially over a
                                           range of concentration from 0.010 ppb to 2 ppb. However, over this range
                                           the method was found to be not linear, so higher levels tested were
                                           eliminated and a selected low-end subset of the analytical results that
                                                                                                       ROCKY MOUNTAIN ARSENAL    947
-------
provided the lowest CRL possible was presented. From the analytical
results in Table 3 and the graphical display of these data in Figure 3,
it is obvious that some analytical variability exists even at the reported
levels  of spiked-sample concentrations  listed.  This resulted  in  a
statistically determined  CRL of 0.042 ppb and a working range that
extended only to 0.150 ppb. Because the program objective was to obtain
a CRL as close to 0.0014 ppb as possible, this limited range did not
cause problems.

                             Table3
          DalaChem Certification Sample Results for NDMA
Spiked
Concentration
fuZ/1 Or ODD)
0.020
0.050
0.100
0.200
Method Blank
Day No.
Reported
Concentration
0.014
0.035
0.064
0.136
0.000
1
Percent
Recovery
68
69
64
68

DavNo.
Reported
0.009
0.030
0.052
0.058
0.000
2
Percent
Recovery
47
60
52
29

Spiked
Concentration
(up/I or Dob)
0.020
0.050
0 100
0.200
Method Blank
Dav No.
Reported
0.013
0.030
0.043
0.140
0.000
3
Percent
Recovery
67
61
43
70

Day No.
Reported
0.004
0.028
0044
0.084
0.000
4
Percent
Recovery
21
56
44
42

               0.028  0.050   0.075   0.100  0.12S   0.150   0.175   0.200
                   Splktd Simple Target Concentration In (ppb)

                             Figure 3
             Found Concentration vs. Target Concentration
           DataChem Certification Sample Results of NDMA
   However, in addition to strict analytical considerations of precision,
 accuracy, completeness and comparability, the representativeness of
 analytical results was also considered when attempting to evaluate the
 practicality of ultra-low-level- based ARARs such as that for NDMA
 in the HBSF IRA program. Table 4 shows a list of method blank results
 obtained during some of the analyses performed during Phase I of the
 HBSF IRA program. Table 4 shows that when attempting to analyze
 high-level  samples, special considerations needed to be added to the
 method to eliminate cross-contamination. After analysis of method blank
 samples shown in Table 4, individual ventilation units were placed over
 each sample extraction vessel and concentration  steps for low- and high-
 level samples were segregated. This, along with adopting additional
 cleaning procedures and eliminating a step using a pipetting apparatus,
 eliminated the previously observed cross-contamination.

 METHOD DEVELOPMENT FOR THE ANALYSIS OF
 HYDRAZINE FUEL COMPOUNDS IN WATER
   The hydrazine fuel compounds are not included among the U.S. EPA-
 designated priority pollutants, and a U.S. EPA-approved procedure for
                             Table 4
              Hydrazine Blending and Storage Facility
     Method Blank Summary for N-Nitrosodimethylamine, Phase I
                     Commerce City, Colorado
   Blank ID

 JDR001
                  Related
                Investigative
                  Sample
                rRAH-11-I
                IRAH-2I-KB
                IRAH-23-KB
                IRAH-25-1CB
                IRAH-16-ICA
                IRAH-19-KA
                IRAH-20-KA
                IRAH-22-KA
                IRAH-24-KA
                IRAH27KAMS
                IRAH-27-K.A
                IRAH-12-I
                IRAH-17-KA
                IRAH-18-KA
                IRAH-25-K.A
                IRAH-26-KA
   Blank
   Sample
 Concentration
(in ue/1 or ppb)

     .123
                                                                         JKC001
                                                                                                               .263
                                                                                        IRAH-
                                                                                        [RAH
                                                                                        IRAH-
                                                                                        IRAH-
                                                                                        IRAH-
                                                                                        IRAH-
                                                                                        [RAH-
                                                                                        IRAH-
                                                                                        IRAH-
                                                                                        IRAH-
                                                                                        1RAH-
                                                                                        IRAH-
                                                                                        IRAH-
                     17-1
                     27-KB
                     28-KB
                     29-KB
                     30-KB
                     31-KB
                     32-KB
                     45-KB
                     48-KA
                     33-KB
                     47-KA
                     18-1
                     46-KA
   Sample
 Concentration
(in uB/1 or ppbl
                      23400
                      13000
                       9190
                       5910
                        147
                       47.7
                       8.79
                       4.32
                       2.34
                       1.82
                       1.50
                       .302
                       .174
                      <.020
                      <.020
                      <.020
                      66000
                      17200
                       4390
                       1090
                       25.0
                       22.0
                       18.5
                       8.30
                       5.70
                       5.21
                       3.59
                       3.37
                       1.07
the analysis of hydrazine fuel compounds is not currently available.
However, one analytical method recommended for the analysis of azo
compounds, hydrazines and derivatives  involves derivatization  and
analysis by GC/NPD, mass spectrometer (MS) or a flame ionization
detector. Numerous other methods for the analysis of hydrazine in air
and soil have been published and were investigated during the method
development process.
  The only directly applicable method for analyzing hydrazines in water
was developed by Environmental Science (ES) for the Facilities Manage-
ment Division (ASD/PMDA), Headquarters Aeronautical Systems Divi-
sion, Wright-Patterson Air Force Base, Ohio, and several other Air Force
bases, and was published in February 1988. In this experimental method,
derivitization using 2-furaldehyde,  benzaldehyde, 2,4-pentanedione,
methylethyl ketone and cinnamaldehyde was evaluated. The reaction
of the target compounds with 2-furaldehyde produced the most suc-
cessful results using an internal standard, nitrobenzene, for quantita-
tion.  No work was performed by ES concerning absolute recovery
efficiencies. This method utilizes procedural standards whereby calibra-
tion standards and analytical samples are derivatized before analysis.
Using such procedural standards,  and standard U.S. EPA-type statistical
methods for determination of method detection limits, the 2-furaldehyde
method detection limit for hydrazine was 21 ppb, for MMH was IS ppb,
and for UDMH was 18 ppb.
   Based on the QC results published by ES  on their 2-furaldehyde
method, Vista Laboratories, Wheat Ridge, Colorado, was asked to
conduct method development and evaluation of the ES method utilizing
the systematic program used by PMRMA.
   The method development effort began  with a review of the existing
method developed by ES as well as other methods  developed by NIOSH
for monitoring hydrazine fuels in air. The existing  methods did not meet
the project objectives of obtaining a CRL of 2.5 ppb for hydrazine and
20 ppb for UDMH; however, the existing methods showed the promise
of improvement to  attain these goals.
 •MS    ROCKY MOUNTAIN ARSENAL
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  The laboratory study began with the reaction of 2-furaldehyde
(furfural) with the hydrazines to create hydrazone derivatives that would
be of sufficient molecular weight to extract and of sufficient stability
to chromatograph. Following the evaluation of the derivatives of their
detector response, optimal GC conditions were developed for all three
derivatives on the primary DB-1 and confirmatory DB-608 columns.
Phenylhydrazine was investigated as a potential surrogate for the method
and the phenylhydrazine derivative was successfully chromatographed.
Two compounds, 2-picoline and nitrobenzene, were evaluated as poten-
tial internal standards for the method. Nitrobenzene was chosen because
of retention time considerations.
  Hydrazine  derivatives were synthesized in ethyl acetate solutions.
Because of the insolubility of furfural in hexane, the sample  extract
solvent of choice for nitrogen phosphorus detectors was ethyl acetate.
Calibration standards were prepared in hexane.  "Micro-extraction"
techniques were  evaluated for extraction of the derivatives from water
samples. Sample aliquots of 100 mLs were extracted with 2 mLs of
hexane, yielding recoveries of  1 to 10% for the hydrazones. MECL2
was evaluated as an extraction solvent followed by a solvent exchange
with hexane.  Initial tests of the concentration and solvent exchange
revealed the hydrazine derivatives were stable through these steps, with
recoveries ranging from 75 to 100%. One-liter samples were extracted
with MECL2 and the extracts were concentrated and exchanged to
hexane.  Excess  2-furaldehyde  was  co-extracted and  formed  a
nonmiscible layer with MECL2 during concentration. Recoveries of
the hydrazones ranged from  10 to 40%; thus, it was decided to seek
another extraction solvent.
  Hexane extraction was again attempted on a "macro-extraction" scale.
Aliquots of 100 mLs of hexane were concentrated to see if the hydrazones
would survive the higher water-bath temperatures required to concen-
trate hexane versus MECL2. Recoveries from  the concentration step
ranged from 83 to 95%. One-liter samples were extracted with hexane,
and the extracts were concentrated to 1 mL. Recoveries of the hydrazones
ranged from 7 to 40%, indicating no improvement in using hexane over
using MECL2.
  Because ethyl acetate had been used in some of the existing methods,
it was decided to evaluate it as an extraction solvent. Samples 100 mL
in size were  extracted with ethyl acetate and  extracts concentrated.
Recoveries ranged from 40 to 94%. Samples were prepared covering
a range from 2.5 to 250 ppb, and recoveries ranged from 65 to 100%
for hydrazine, 45 to 75% for UDMH and 2 to 10% for MMH. The
2-furaldehyde derivative of MMH yielded such a low response it was
decided to use another derivatizing agent for this compound. A method
using 2,4-pentanedione to derivatize MMH was evaluated with success.
  The sensitivity of the GC system to the derivatives was then evaluated.
Solutions of the  hydrazones were prepared to place 10 ng (absolute)
of the hydrazine fuel derivatives  on column.  Sufficient  instrument
response was  observed to estimate that a 100-mL sample volume would
be adequate to meet the target reporting limit  concentrations.
  The two methods were again evaluated over the previously established
testing range. Sample aliquots of  100  mLs  were derivatized  with
2-furaldehyde for hydrazine and UDMH and 2,4-pentanedione for MMH
and then extracted with ethyl  acetate.  Nitrobenzene  proved to  be a
suitable internal standard; however, the hydrazone of UDMH either was
not recovered or disappeared from the extract. The methods performed
favorably for  hydrazine and MMH.
  The methods were then redrafted to include "preparatory" procedural
standards rather than the "externally derivatized" standards used to this
point. It was  believed that any  inefficiency in synthesis or extraction
of the derivatives would be accounted for by preparing standards in
a manner identical to sample preparation.
  Precertification  of  the  method for  MMH  was  successful.
Phenylhydrazine  recoveries  were  very erratic;   subsequently,  this
compound as  a surrogate standard was abandoned. Precertification of
the method for hydrazine and UDMH was attempted with very poor
results. Very  poor chromatography was observed for the hydrazine
derivative at lower concentrations. The DB-608 column was replaced
with a newer version of the DB-608 column and NPD detector perfor-
mance improved. A DB-17 column was installed and adopted as the
confirmatory column.
  Because of the variability and introduction of chromatographic
interference from the ethyl acetate, it was decided to evaluate a different
extraction solvent.  Diethyl ether was chosen because of its similar
polarity properties.
  Diethyl ether was found to be a suitable extraction solvent. Precer-
tification was attempted using ethyl acetate in addition to diethyl ether
as a keeper during solvent concentration; however, retention time shifts
were noted during GC analysis, which invalidated the precertification.
Precertification was again attempted, and successful, using hexane as
a keeper to remove the previously observed retention time shifts. Precer-
tification for MMH was also attempted, and successful, using the diethyl
ether/hexane solvents.
  After precertification, approval was given to attempt certification of
the methods. Certification was successful for MMH, yielding a CRL
of 7.5 ppb, which was sufficiently below the program ARAR of 20 ppb.
During the certification attempts it was revealed that the concept of
initial calibration checks and daily single-point calibrations for hydrazine
and UDMH would not be successful. Although any single calibration
curve was reasonably linear, the slope of the curve varied from prepara-
tion to preparation. A scheme of daily five-point calibrations was,
therefore, drafted and included in the method.
  The second certification attempt proceeded and yielded CRLs of 9.9
ppb for hydrazine and 30 ppb for UDMH.  Because these CRLs  did
not meet the ARAR targets of 2.5 ppb and 25 ppb respectively, a third
certification attempt was scheduled.
  During   the  third  certification  attempt,  a problem  with  the
disappearance of the UDMH derivative was observed, as it had been
during previous  analyses. The derivative appeared to be synthesized,
but would rapidly disappear, from the derivatized extracts. Analyses
of a single extract performed one-half hour apart indicated a loss of
50% or more of the UDMH hydrazone.
  After experiencing the problems with UDMH disappearance, it was
determined that the method would be recertified as a qualitative method
at the level required by the ARAR. Recent developments have pointed
to the possibility that the antioxidant L- ascorbic acid may provide some
relief from the observed UDMH disappearance problem.

SELECTION OF  PROTECTIVE AND TECHNOLOGICALLY
FEASIBLE REGULATORY LIMITS
  When establishing ARARs or cleanup goals at any hazardous waste
site, careful consideration of the analytical constraints that govern the
reliability of analytical data must be reviewed and compared to proposed
health-based criteria.  Analytical  method  development,  using  an
exhaustive QA procedure similar to that used by PMRMA, is essential
before establishing final cleanup  goals for unregulated  chemical
constituents for  which methods are not available.
  Table 5 compares the  oral carcinogenic potency factor, the MO"6
calculated cancer risk factor  for two commonly known human car-
cinogens,  benzene and vinyl chloride, to the SDWA-stipulated MCLs.
The 10"6 cancer risk factor can be directly related to the cancer potency
factor, provided the route of exposure is the same. Comparing the  10~6
cancer risk factor to the SDWA MCL, it is obvious that the MCLs for
both benzene and vinyl chloride are significantly above the 10~6 cancer
risk level of concentration. The IxlO"4 cancer risk factors  (i.e.,  the
generally accepted level of protectiveness by  most regulatory agencies)
for benzene and vinyl  chloride (Table 5) are  100  and  1.5 ppb,
respectively.  The U.S.  EPA has chosen the MCL for these two com-
pounds by rounding the vinyl chloride 10"4 risk factor of 1.5 to 2.0 ppb
(which is the generally accepted practical quantitation limit (PQL) for
the U.S. EPA-accepted method for analysis of vinyl chloride) and has
set the MCL for benzene on the U.S.  EPA Method PQL alone.
  The rationale used to establish cleanup goals is similar to that used
to establish ARARs: (1) the selected cleanup goal should be protective
of human health, or between the 10"4 and 10"6 estimated  cancer  risk
level, and (2) the selected cleanup goal should be practically achievable
given the current state of available analytical technology. Based on this
                                                                                                     ROCKY MOUNTAIN ARSENAL    949
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                  Comparison of Health Risk versus
                    Analytical Quantitation Limits
              EPA
            Clasiificalion

                 B2
              Probable
               Human
              Carcinogen

                 A
               Human
              Carcinogen
  Oral
Carcinogenic
  Potency
  Faclor
(me/kB/davr
    51
One-in-one-Million
   Drinking
  Water Risk
  Concentration
	(pobl	

   I 4 x 10'1
SDWA
 MCL
iDDbl
 Vinyl chloride
line of reasoning,  the  analytical  constraints on  the detection of
unregulated chemical compounds should play a critical  role in the
selection of final treatment objectives at any hazardous waste site.

SUMMARY AND CONCLUSIONS
  In the case studies reviewed, it is apparent that a target treatment
level of 0.0014 ppb for NDMA is  realistically unachievable given the
current state of analytical technology. However, the technology currently
available can yield reliable data in the KT* to 10"* cancer risk factor
range between 0.140 ppb and 0.0014 ppb. In the case of hydrazine fuel
compounds,  it was  discovered that currently available methods of
analysis can verify treatment to higher levels of protection for the com-
pound MMH, but the method for analysis of hydrazine is insufficiently
reliable at the levels currently stipulated in the HBSF IRA  Decision
Document.
  For UDMH significant analytical problems still exist that must be
overcome before the reliable quantitation of UDMH can be performed,
but program objectives can be satisfied through the use of a qualitative
approach until further method improvements can be implemented.
  The role of analytical chemistry in the conscientious selection of
ARARs and final treatment objectives is often over-shadowed by the
desire to obtain a solely health-based protective solution to chemical
contamination problems at hazardous waste sites. Provided that a level
of cleanup is protective, it is critical that the analytical methods reliably
portray the level of contamination or remediation that may be required
by a program ARAR. Therefore, a careful selection and QA review
of health-based and technology-based criteria must be performed before
selecting final treatment or  regulatory limits.

REFERENCES
1.  U.S. Army Program Manager's Office for Rocky Mountain Arsenal, ruial
  Decision Document far the Interim Response Action at the Rocky Mountain
  Arsenal Hydrazine Blending and Storage facility, October 1988.
2. U.S. Army Program Manager's Office for Rocky Mountain Arsenal, Chemical
  Quality Assurance Plan Vsrsion 1.0,  July  1988.
3. U.S. Environmental Protection Agency (U.S. EPA), Ambient Water Quality
  Criteria for Nitrosamines, US. EPA Report No. 44015-80-064.: Criteria and
  Standards Division, Office of Water Regulations and Standards, Washington,
  DC, 1980.
4. U.S. Department of Energy (DOE),  The Installation  Restoration Program
  Toxicology Guide, Volume 1-4, Biomedical and Environmental Information
  Analysis Health and Safety Research Division Oak Ridge National Laboratory,
  Oak Ridge, TN, 1989.
5. Fine, D.H., "Nitrosamine in the General Environment and Food," in Ban-
  bury Reports: Nitrosamines and Human Cancer, Cold Spring Harbor, New
  York, NY, pp.  199-210,  1982.
6. Scanlan,  R.A.,  "Formation and Occurrence of Nitrosamines in Food," in
  Cancer Research, 43: pp. 2435s - 2440s, 1983.
7. Brodzinsky,  R.  and Singh,  H.B., "Volatile Organic Chemicals in the
  Atmosphere: An Assessment  of Available Data," Stanford Research Institute
  for Office of Research and Development, U.S. EPA, Washington, DC, 1983.
8. Jody, B.J. et al., "Ozonation of Hydrazine Fuels and Their Associated
  Impurities," Proc. Environmental Fate of Hydrazine Fliels in Aqueous and
  Soil Environments, pp. 202-215, 1983.
       ROCKY MOUNTAIN ARSENAL
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                     Timing—The  Critical  Element  in  a Successful
     Community Relations  Program  at  the  Rocky  Mountain Arsenal
                                      The Basin  F Liquids  Story

                                                    Ann C. Marshall
                                                Advanced Sciences, Inc.,
                                                  Lakewood, Colorado
                            William R.  Thomas                        Steven £. James
                            RMA Public Affairs,                 Woodward-Clyde Consultants,
                         Commerce  City, Colorado                    Oakland, California
 ABSTRACT
  Early community relations planning and implementation at controver-
 sial Superfund sites can enhance the quality of decisions made and help
 keep projects on schedule. A case study at the Rocky Mountain Arsenal
 in Denver, Colorado, demonstrates that at a site with complex technical
 issues and regulatory framework, where incineration is a likely decision
 and where the local populace is opposed  to incineration, an aggressive
 community relations program can be a technical tool for achieving
 technical objectives. The project worked within a framework of a com-
 munity relations task force, briefed a wide range of interested parties
 (including the governor's staff), offered a community workshop and
 responded to community concerns in the decision document or with
 written responses.

 PREMISE:
 COMMUNITY RELATIONS ENHANCES DECISIONS,
 SUPPORTS SCHEDULES
  During confirmation hearings for U.S. EPA administrator William
 K. Reilly, the U.S.  Senate asked for an evaluation of the Superfund
 program and how it could be improved. Reilly returned with a manage-
 ment review hi 90 days with A Management Review of the Superfund
 Program, known internally as the "90-day Study." In the study, the U.S.
 EPA announced a new long-term strategy for the Superfund program.
 One element is to encourage full participation by communities in cleanup
 decisions. The 90-day Study made 50 recommendations for improving
 the Superfund program. Of the 50 recommendations, 10 deal with com-
 munity involvement. One key recommendation was: "Strongly support
 increased public involvement in Superfund  decisions  and  accept
 occasional delays as the  result of greater public involvement."
  While we applaud the increased emphasis on public involvement,
 it has been our experience that an active community relations program
 initiated early in the process actually helps  avoid delays, rather than
 causing them. The case study that follows shows not only that citizen
 involvement can help us stay on schedule, but  that it can improve the
 quality of Superfund decisions.

 CASE STUDY:
 THE ROCKY MOUNTAIN ARSENAL
  In March 1990, the U.S. Army at Rocky Mountain Arsenal (RMA)
 announced it would act quickly to use on-site incineration to handle
 its most complex and controversial waste problem. This decision was
 endorsed and supported by the U.S. EPA, the State of Colorado, officials
of the local affected community and several citizen interest groups.
 The nature of this decision bears examination, because it was so
widely accepted and yet it contains so many elements of controversy.
Citizen involvement was not by  itself  the critical element in this
widespread acceptance. As this case study will show, it was the timing
of that involvement that made a difference. In a nutshell, our challenge
was to:
   "Site  a moderately-sized hazardous waste incinerator near
   Denver, a large, environmentally conscious city, to treat 8,500,000
   gallons of toxic liquid waste at the nation's worst military hazar-
   dous waste site under a tight, legally mandated deadline."
  At first glance, these conditions might seem to define a hopeless situa-
tion. To reach a remedial decision, the Army required some relatively
complicated technical studies. It also needed to build enough comprehen-
sion and confidence in the community to ensure citizens could comment
knowledgeably and the U. S. Army would have time to respond. We
believed if we could do this, the solution finally selected could be put
in place on time without fostering opposition or creating discomfort
among the people affected by the cleanup. How the Army faced this
challenge is the  subject of this paper.

HISTORY:
MUNITIONS AND  CHEMICAL HANDLING AT RMA
  The Rocky Mountain Arsenal was established in 1942 on more than
17,000  acres (27 mi2) adjacent to  Adams County, Colorado. The
installation is located  approximately 10 miles from downtown Denver
just north of Stapleton International Airport. The Arsenal has been the
site of the manufacture of chemical materials such as mustard gas, white
phosphorous and napalm. In the 1950s, the Army produced GB nerve
agent and continued munitions-filling operations until 1969. Later, the
Army initiated a program to destroy chemical munitions, which con-
tinued until the 1970s. To offset operating costs at the  end of World
War n, Congress directed the Army to lease selected facilities, including
the  Arsenal, to private industrial chemical manufacturers. Shell
Chemical Company (now Shell Oil Company), a major lessee, manufac-
tured agricultural chemicals at the Arsenal from 1952 to 1982.
  In  1956, Basin F, a state-of-the-art evaporation pond, was constructed
by building a dike around a natural depression and lining it with a
0.75-inch asphalt membrane. A one-foot layer of earth was placed on
top of the asphalt to protect it. The pond could hold approximately
243,000,000 gallons of wastewater. From August 1957 until its use was
discontinued in early 1982, Basin F was the only  lined evaporative
disposal facility  in service at the Arsenal.
  In  February 1989,  two administrative agreements were signed to
ensure the Rocky Mountain Arsenal cleanup program was carried out
in a smooth and responsible manner. The Federal Facility Agreement
(FFA) and the Settlement Agreement (SA) define how appropriate
remedial  actions will be determined and the technical and financial
responsibilities for each party. The FFA also defines how the interim
                                                                                            ROCKY MOUNTAIN ARSENAL   951
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response actions (IRAs) will be carried out, consistent with the NCR
The IRAs are designed to support and be consistent with the final ROD
on how the Arsenal will be cleaned up. When this decision is made
in late 1993, the IRAs will either be completed or be incorporated into
the final cleanup actions.

STRATEGY AND ISSUES:
AGGRESSIVE COMMUNICATIONS IN
A NEGATIVE ATMOSPHERE
  The remedial objective of the Basin F Liquids IRA is to destroy Basin
F liquids or render them harmless by June 1993. For a number of reasons
discussed below, this schedule is exceedingly restrictive. To help achieve
this objective on time, the Army needed a community relations pro-
gram that would do more than simply inform the public of a decision
after all the technical assessment had already been  completed, with
hopes the public would support the decision—or, at  a minimum, not
be so opposed that there would be delays in the schedule. The Army
needed the public's help and participation in framing a decision that
responded to citizen  concerns even as it was developed. The key to
the Army's approach was designing the community relations program
to be a technical tool that helped to shape the remedial decision and
thereby built consensus.  The design of the community relations pro-
gram was,  therefore, based on the  following premises:
• It  should accommodate the full range of issues and community con-
  cerns generated  by the technologies under consideration for Basin
  F  (as well as those technologies that were excluded).
• It  should provide a means of active public participation in technical
  issues that would have impact on significant portions of the remedial
  decision (i.e., response to public concerns should form a part of the
  decision and thereby build consensus and active  support for the
  decision);
• It  should have a substantial outreach component to ensure that all
  appropriate constituencies and affected parties are informed  and
  involved;
• It  should strive to achieve a "win-win" result. Early citizen involve-
  ment should improve the quality of the decision  and help the Army
  stay  on schedule.
  Within the framework of this approach, the community relations
program was influenced by several issues that were either peculiar to
RMA or inherent in the nature of the Basin F liquids problem and its
potential solutions. These issues were:

Complex Technical Issues
  Basin F  liquids are unique and unusual and cannot be handled by
most conventional treatment methods. The waste is corrosive to most
treatment equipment, has high concentrations of  ammonia and con-
tains significant concentrations of metals and organic chemicals (as many
as 80 species). Scores of experimental treatability tests have been done
over a 10-year period and a number of commercial  hazardous waste
facilities have tried without success to treat Basin F liquids. A few
innovative technologies still in developmental stages  seemed to be poten-
tially promising, but the limit on temporary storage of the wastes ruled
out all  but proven approaches, none of which had been tried on wastes
exactly  like Basin  F liquid.

Generalized Aversion to Incineration
  This issue is not local, but rather reflects a national fear and mistrust
of hazardous waste incineration. The Army evaluated 40 different treat-
ment technologies, but the final set of five feasible technologies included
two  incineration techniques and two quasi-incineration techniques.
Hence,  from an early point in the study, it  was apparent that incinera-
tion  was the major technology under active consideration. All the design
and risk studies subsequently showed incineration  to be the safest and
most reliable alternative. Nevertheless, the public in general and some
groups in particular, were predisposed against incineration and expressed
fears about  explosive hazards and deleterious health effects of
incinerators thai were taken to be common knowledge.
The Superiority of One Incineration Technology
Over All Other Alternatives
  Perversely, the problem of dealing with the widespread aversion to
incineration was made "worse" by the results of our remedy selection
study; they showed that one type of incinerator was so much better in
nearly every way  than the other alternatives, that  it was  almost
impossible  to define a set of decision-making priorities where this
incinerator  would not be the preferred solution. Thus, not only did we
think that incineration was the best solution while the public was
predisposed to think it was the worst solution, but also our technical
case for incineration was so strong that the public was likely to think
that we  had manipulated  the data.

Local Aversion to Incineration
  Colorado—and Denver  in particular—is environmentally conscious
and has a history of objecting to any type of disposal practices that
might result in air emissions into the already polluted atmosphere. As
a consequence, we knew the cumulative impact of any IRA alternative
on air quality would be carefully scrutinized by the public. Incinera-
tion, often referred to by  citizen activist groups as a "landfill in the
sky,"  would undoubtedly  be a target of Denver's concern if it were
proposed as a preferred alternative.

Complex Regulatory Framework
  The cleanup of RMA is a Superfund action, but a history of litiga-
tion, unapproved consent decrees and settlement agreements has shaped
the content and procedures of the cleanup program. In 1989, a Federal
Facility Agreement (FFA) was signed that defined the roles and respon-
sibilities of the participating organizations, who are: (1) the U.S. Army;
(2) the U.S. Environmental Protection Agency; (3) Shell Oil Company;
(4) the State of Colorado (not a  signatory); (5) the U. S. Department
of Justice; (6) the U. S. Department of Interior; and (7) the Agency
for Toxic Substances and Disease Registry.
  Two committees have an active role in remedial oversight. The RMA
Committee, which consists of representatives of all of the agencies listed
above, oversees  most investigation and remediation  programs. The
Technical Review Committee (TRC), which consists of representatives
of a number of local health and utility agencies, at-large citizen represen-
tatives,  local government and  representatives  of  the  Army,  was
established  by the FFA. In addition, day-to-day decisions on the com-
munity relations program are subject to the guidance of the Community
Relations Task Force, which includes representatives of the Army, U.S.
EPA, Shell and their contractors.
  The FFA states that community relations at RMA will be done in
accordance with U.S. EPA regulations. Interim Response Actions, such
as the Basin F Liquids IRA, are performed under the Superfund removal
authority, for which the community relations requirements are not well
defined and for which there is no formal guidance aside from the public
hearing  and comment period requirements. At RMA, the Community
Relations Task Force can recommend to the RMA Committee, which
approves the action, on the direction and content of community relations
programs for IRAs.
  The overall regulatory  picture,  then, consists of a complex legal
history, a complicated interagency agreement, seven major players with
widely differing agendas, committees making decisions and committees
making  committees and  reliance  on a law that  gives  no clear-cut
directions for community  relations programs for large-scale, removal-
authority actions like the Basin F Liquids IRA.

Multiple Conflicting Interests
   All parties to the FFA and the State of Colorado shared a common
interest: destruction of Basin F liquids by mid-1993. Each party, however,
had  other interests that had to be considered in the planning and
implementation of the community relations program.
   For example, the Army  and U.S. EPA, racing a multidecade cleanup
program, are individually concerned about establishing precedents for
the future and the adequacy of the public  participation and decision-
making  process as well as the effectiveness of the selected IRA alter-
952    ROCKY  MOt STAIN ARSENAL
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native. Shell urges caution in all matters that it believes might have
a bearing on present or future litigation. DOJ is concerned that con-
cepts and commitments are correctly presented and consistent with other
declarations of the federal government. The State maintains that it should
manage the Basin F cleanup as a RCRA action. The State usually takes
the position that the Army is not in compliance with RCRA and is
therefore in willful breach of the law. The State is concerned that its
official position should be correctly stated as final approval authority
on the project. The Department of Interior is charged with protecting
Arsenal wildlife, including the endangered bald eagles and the threatened
ferruginous hawks. All this is to say that, in addition to overcoming
the complexity of technical and community issues in working with the
public, we had to devote substantial energy to overcoming the com-
plexity of the RMA  Committee members' interests.

Community Sensitivities
  In 1988, Basin F liquids were removed from the basin and the soils
and sludges were scraped up and placed in secure storage. The process
of moving these soils and  sludges unexpectedly  released  strong
ammonia-like  odors to  the atmosphere.  The  odors drifted  into
neighborhoods adjacent  to  the Arsenal and  residents  complained
strenuously. Some neighbors said that the odors caused serious health
problems, but the Army, the U.S. EPA and the Colorado Department
of Health (CDH) were unable  to document any problems or detect
harmful concentrations of contaminants with ambient air monitors.
  Nevertheless, the odor problem was covered closely in the press and
lasted for several months. The memory of this problem, reinforced by
periodic mention in the press, lingered. Many residents perceived that
the Army and its contractors had not taken adequate precautions  to
prevent this hazard, that the hazard had adverse health effects and that
the Army either failed  to own up to its actions or had tried to cover
up a serious community health problem. Thus, a general climate  of
bitter memories and mistrust of the Army prevailed as the Basin F
Liquids IRA study began.
  In short, this was a tough technical problem with many of unusual
conditions. In spite of this situation, or perhaps because of it, we wanted
residents to understand these  technical issues  so  that they could
participate effectively in the critical elements of our decision: selec-
tion of one remedy from a small group of feasible technologies and
determination of how that technology would be operated to ensure that
it would both be safe and achieve  cleanup objectives.
  Based on the nature of these issues and the tight schedule for
implementation of a Basin F liquids remedy, Community Relations Task
Force members recommended to the management of their respective
organizations that an innovative approach be taken to informing the
public of incineration's probable preferred alternative status. Instead
of waiting for the Draft Decision Document to be released and then
holding a public meeting to hear from the citizens, the Community Rela-
tions Task  Force recommended that a public education and involve-
ment process start earlier than required in the FFA. The Task Force
recommended that the Army hold a series of briefings for elected of-
ficials, special interest groups, the media and the general public to inform
them of what technologies were being investigated and the pros and
cons of each technology.
  The Army approved this approach and within a week after the Draft
Treatment Assessment  Report was  released, more than 200  people
received background information on the technologies being considered.
During these briefings, the Army made it clear that incineration was
the leading candidate. The approach was significant because it was the
first time the Army had "gone public" with a Draft Treatment Assess-
ment Report. This departure from the norm was not only a first, but
as was demonstrated, was key to the Army's success in gaining com-
munity support for its  eventual decision.
 In addition to the briefings, the Army hosted an informal workshop
and invited interested citizens to attend. The workshop was designed
not only to provide more in-depth technical information to the public
on all  the technologies being studied, but more importantly, to also
provide the Army with in-depth knowledge of the public's questions
and concerns. Having learned of the public's concerns and questions,
the Army was then in a position to demonstrate its sensitivity to the
community by addressing its concerns orally at the workshop, at the
formal public meeting held at the start of the comment period two
months later and in the Army's Final Decision Document.
  The effectiveness of the Task Force's community relations efforts can
be measured by the overwhelming lack of negative reaction to the Army's
decision. The community relations program and individual techniques
that were employed are described below.

THE PROGRAM:
BUILDING CONSENSUS THROUGH INTERACTION
  The two basic building blocks of our community relations program
were the development of a community relations plan and strategy and
the implementation of aggressive community relations activities. These
activities were undertaken under the combined guidance and review
of the Community Relations Task Force.

The Community Relations Task Force
  The Task  Force represented the diverse interests of the Army, the
U.S. EPA and Shell Oil Company. The group met frequently and at-
tendance at any given meeting included some or all of the following:
the Army's  technical,  community  relations  and legal  staff  and
consultants;  Department of Justice  attorneys; Shell's public relations
and technical staff and consultants; and U.S. EPA's community rela-
tions coordinators. The purpose of this group was to discuss, coordinate
and agree on community relations activities planned for the Arsenal.

The Community Relations Plan and  Strategy
  To provide a useful framework for understanding and responding to
community concerns, Superfund guidance required development of a
Community Relations Plan (CRP) tailored to the community that sur-
rounds and is potentially affected by, the Arsenal. Using documents
and information previously developed by Shell and the U.S. EPA as
a basis, the  Army conducted a community assessment that included
telephone interviews with Arsenal neighbors and other interested parties.
All of this information was then distilled into  a CRP that provided
background  and guidance not only  for the Basin F Liquids IRA, but
also for the  program as a whole.
  Further, the Task Force developed a Communication Strategy targeted
specifically to the vigorous public information effort launched in con-
junction with release of the Draft Treatment Assessment Report. The
document identified messages, audiences and a briefing schedule. Out
of this overall planning process, we identified several categories of
interested individuals, each with its own unique set of interests and con-
cerns. While it might be natural to assume that we could take a single
approach to the information needs of a particular group, we discovered
through  the community assessment that we had to differentiate the
information needs and concerns even within categories. For example,
in the case of key federal officials, members of Congress not only had"
different concerns from the U.S. EPA, but different concerns from one
another.  These varied audiences are  described below:
•  Federal officials, including both regulatory agencies and Members
   of  Congress who have expressed continued  and active interest in
   cleanup plans for the Arsenal. Members of Congress have most often
   expressed concern about the cleanup schedule and the long-term uses
   of Arsenal land. The U.S. EPA sought the highly technical informa-
   tion in our Treatment Assessment Report and was very sensitive to
   state and  community acceptance of our alternative.
•  State officials, including four different groups: the Governor's office,
   the Colorado Department of Health, the Attorney General and state
   legislators, who at any given time had divergent agendas for the
   Arsenal.  For example, the Attorney General's office sought and
   reviewed information on the Basin F Liquids IRA with litigation issues
   as the foremost concern, while the Colorado Department of Health
   wanted detailed information about cleanup technologies and eventual
   uses of the land.
•  Local government, including the affected counties, cities and water
                                                                                                    ROCKY MOUNTAIN ARSENAL   953
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   district were most concerned about immediate and long-term health
   effects, long-term operation and maintenance costs and negative
   impacts on their communities and property values.
 •  Arsenal neighbors, including citizen groups such as Citizens Against
   Contamination that had organized to address Arsenal issues and had
   concrete, specific concerns and information needs about where, when
   and how cleanup technologies would be implemented.
 •  Special interest groups, such as Citizens' Intelligence Network, the
   National Toxics Campaign, the League of Women Voters, the Sierra
   Club and the Audubon Society,  whose interests spanned the  range
   of environmental issues.
 •  The media, including the major metropolitan print and electronic
   media, national media and two Commerce City newspapers,  all of
   which covered Arsenal activities with great interest, cast doubt on
   the Army's credibility and commitment to cleanup and often sensa-
   tionalized  new developments at the Arsenal.
   Even when everyone agreed on the  importance of a specific issue,
 individual information  needs were different.  For example, almost
 everyone  was concerned about cleanup standards, i.e., how clean is
 clean? For some audiences, this meant we had to speak in concentra-
 tion units ppb; for others, in precedents set at other locations; and for
 others, in terms of the long-term uses of the land that the standards
 would allow. As a result, we  knew not only that a single community
 relations technique would not suffice, but  also that even individual
 techniques, such as briefings, would have to be tailored to individual
 audiences.

 Community Relations  Activities
   Taking  into account the varied audiences and the aforementioned
 issues that were impacting the Basin F Liquids IRA alternative selec-
 tion process, we  embarked  on the community relations activities
 described below.

 Official briefings
   Over a  period of a week after the release of the  Draft Treatment
 Assessment Report, the Army presented tailored briefings to key target
 audiences described above. We devoted considerable effort to the
 briefings through the  preparation of the following materials:
 •  A slide show to provide background for the Basin F Liquids Interim
   Response  Action,  the alternatives  evaluated and  the  preferred
   alternative.
 •  Information kits that included the following information:
   — Five feet sheets  describing the five alternatives we evaluated;
   — Fact sheets on the Federal Facility Agreement, Risk Assessment,
     Notes on Chemicals in Basin F Liquids and the Remedy Selec-
     tion  Process
   — A U.S.  EPA fact sheet on Public Involvement in the Superfund
     Program
  — A Brief History  of the Rocky Mountain Arsenal
  — A Background Paper on the Basin F Liquids Interim Response
     Action,  including a detailed description of alternatives

 Media briefings
   After briefing key officials, we briefed the media, drawing upon and
 tailoring our repertoire of information and  support materials.

 Workshop
   To help interested citizens understand the complex technologies and
 evaluation process, we invited them to  a half-day workshop so that we
 could begin  to address  their  questions and  concerns  in detail. The
 workshop was designed to accomplish the following objectives: (1) help
 residents understand the  alternatives evaluated for Basin F liquids; (2)
 respond to concerns that had been expressed up to that point regarding
 the alternatives; (3) help  residents understand the selection process and
 provide the opportunity to manipulate weighting of the selection criteria;
 and (4) prcvide responses to new questions that the workshop generated.
 Activities  associated with each of these activities are described below.
Basin F liquids alternatives
  For this presentation, we drew upon key portions of the basic slide
show that had been used for the briefings and tailored the presentation
to a lay audience of neighbors.

Response to previously expressed concerns
  To make sense out of the high-tech information related to Basin F
liquids, we took a low-tech, down-to-earth approach to answering
persistent questions that had been generated previous to the workshop.
For example, to help people understand the physical properties of Basin
F liquids, we presented a one-liter graduated cylinder of simulated Basin
F liquids (made  with water, food coloring and coarse kosher salt) to
demonstrate how a supersaturated brine (like that from Basin F) looks
and  behaves. We used this demonstration to show how difficult it is
to pass the liquid through a normal pipe and to call attention to the
corrosive nature  of the liquid, both of which severely constrained the
alternatives that  could be considered.
  Then we used half-pint (250 Ml) jars to demonstrate the quantity
of waste that would remain after treatment with the various technologies
we had evaluated: from one liter of actual Basin F  liquid (the same
volume as our demonstration model), we demonstrated, that either of
the two incineration alternatives would leave 250 Ml (one jar) of residue.
Either of the two quasi-incineration alternatives would leave 750 Ml
(three jars) of residue and solidification, the fifth alternative,  would
leave 2,250 Ml  (nine jars). To demonstrate the quantity of residual
pesticides remaining in the off-gas production from incinerating the
entire 8,500,000 gallons of Basin F liquid during the  18-month opera-
tion  of the  incinerator,  we used a 0.5 oz vial, which could  fit in the
palm of our presenter's hand.

The  selection process
  For this discussion, we changed gears and brought the power of the
computer to the workshop. We set up the raw technical scores against
the selection criteria and  then projected this  matrix from a computer
screen onto an overhead  screen.  After explaining and  demonstrating
how the selection process worked, we changed the weightings of any
of the selection  criteria to meet the preferences of members  of the
audience—live and on-screen.
  It  is worth noting  that  in preparing for the workshop, this portion
of the agenda caused the most discussion and consternation. Some
members of our  Task Force said that putting this kind of information
in the hands of ordinary people was similar to "handing them a gun."
Others said that  allowing people to manipulate the values themselves
was  essential in order to persuade people that the Army had not skewed
the results  to favor its own preferred alternative. Alternate proposals
were set forth to provide hard copies  of different scenarios  or to
demonstrate the selection technology on the overhead computer screen
without  allowing citizens  to manipulate the  values.  Our  Program
Manager decided to  use  the full information approach that included
manipulation of weightings.

New questions
  To maximize opportunities for participants  to ask  questions,  we
divided into small, interactive groups moderated by neutral facilitators.
While we committed ourselves to a flexible format for these  meetings
to allow group dynamics to drive the way they operated (which turned
out to be rather differently from one another), in general we structured
them to be moderated by a neutral, non-Army employee, with a resource
person assigned to each group to assure that the group did not go off
on a tangent based on factually inaccurate information. In general, the
resource persons spoke only when spoken to;  they also synthesized the
public concerns  and  comments to feed  back to the Army's  technical
policy  staff for response  by the end of  the workshop.  The questions
generated also were recorded on large flip-charts. The U.S.  EPA had
an observer in each small group; but all Army and Shell staff left the
room,  in order to encourage the free flow of questions.
  At the end of this  part  of the agenda, the groups categorized their
questions and identified a representative to report to the full group.
•J.M
       ROCKY MOUNTAIN ARSENAL
-------
When the group questions and concerns were reported, the Program
Manager and his technical staff responded to questions that could be
answered at that time. Other questions were deferred until more infor-
mation was available. Some concerns were incorporated into the design
of the final decision.

Public comment period and public meeting
  We held a 30-day public comment period, during which we held a
public meeting to receive comment.

Information repositories and information center
  1b make the  full range of technical information  available to the
interested public, copies of the full technical documents were placed
in the Arsenal's Joint Administrative Record and Document Facility
(JARDF) and five  libraries in the Denver area.

Tours
  •fours of the Arsenal are an ongoing feature of the community relations
program.

Mailing List
  We compiled a mailing list from our own and the U.S. EPA's sources
to create a combined list oflcey contacts to whom we could send infor-
mation. We also used this list and a professional calling service to call
interested citizens to invite them to the workshop and the public meeting.

THE IRA DECISION:
THE PUBLIC MAKES A DIFFERENCE

Effects on Implementation and Operation Objectives

  One of the comments the public most commonly make regarding the
public involvement process for hazardous waste remediation is,  "You,
(the Army) say that you want public input to your decision. But I am
sure that if we come to the end and you favor one remedy and the com-
munity favors another remedy, you are going to go with your preferred
alternative."
  Our experience at the Rocky Mountain Arsenal  clearly demonstrated
that, as public involvement experts, we must recast the "them-us"
perception and the "thumbs up/thumbs down" approach to decision-
making. Involving the community early in the process allows us to work
together to develop a solution to the contamination. At the end of the
studies, we should share some common understandings about the nature
of the problems and the attendant complexities.
  In the case of the Arsenal, we were able to refocus the  discussion
from "incineration/not-incineration" to consideration of the best ways
to protect the public both from negative health effects and from worry
about the technology that was most appropriate for the overall manage-
ment of Basin F liquids.
  We did this in one of two ways: (1) we incorporated public concerns
into the decision document itself, and (2) we responded in writing to
public concerns about  incineration  and other issues related to final
disposal of Basin  F liquids.  Thirteen supplemental  provisions for
implementation and operation of a Submerged Quench Incineration treat-
ment facility were added to the decision document as a result of public
involvement. These supplemental provisions concern how the treatment
system will be developed and operated, to assure that government agency
and private citizen concerns for safety  and environmental  protection
are  met.
  The concerns fel into seven general categories with one  to six sub-
topics in each category. Each subtopic was addressed in one of the two
ways mentioned above.  To document how the Army addressed each
of the concerns, the decision document included a matrix with a bullet-
list  of the concerns and how the  Army responded to them (Table 1),
The matrix was followed by a description of the decision elements listed
in fc matrix.
  For example, under general concerns about incineration, the Army
incorporated specific provisions in the decision document  to respond
to four of the six specific subtopical concerns. One of these, the con-
cern about other uses  of the incinerator after  the  Basin F IRA is
completed, resulted in this commitment in the decision document:
"Following completion of the Basin F Liquids IRA, the incinerator will
be shut down, decontaminated, decommissioned and disassembled under
the closure provisions described in Section 9.0." The other two  con-
cerns that were subtopics under the general category of incineration
received written responses.
                              Table 1
              Expressed Concerns and Form Response1
   MAJOR TOPIC
                          SPECIFIC CONCERN
                                                      FORM OF RESPONSE*
Trutmcnl Process In General
Trusl/Crcdibiuly



Ranking


Public [nvolveircnl


Regulatory Process
                    Odor
                    Operational controls re: weilhcr, unset conditions
                    Location of facility
                    Off-site disposal of residuals or wanes
                    How Iho process works
                    Chanclerislics of submerged quench incinerator
                    Operational controls re: weather, upset conditions
                    Products of incomplete combustion (PICs)
                    Safely of SQI technology
                    Use of incinerator after Basin P IRA
                    Screening and selection of incinerators
   Transportation risks
   Treatment process risk]


   Long-term effects

   Objectivity and quality of monitoring
   Existence and enibreeability of standards for many
   eirdadon corr^nunds of concent
   Army's comrnjtmcnt to safely
   Details on ranking
   Constraints to study

   Expand opportunities for interaction
   Permanent hotline and response log

•  Scope of IRA in relation to other cleanup activities
                                  Writu
                                  Decision Element (4,5)

                                  Decision Element (I)
                                  Written Response
                                  Written Response

                                  Written Response

                                  Decision Elements (4,5,8)

                                  Derision Elements (2.8,11)
                                  Decision Elements (3,6)
                                  Decision Element (13)
                                  Written R
                                                    Decision Element (7)
                                                    Decuion Elements (43.8.9.11)
                                                    Written Response
Decision Elements (8.9.10)
        is (2,8.11)
Dedrion Element! (3,4,5,7.8,9)
Wrinen Ro-pontc
Wrilien Response


Written Response
Decision Element (12)
• Written response to expressed concerns occurs in Appendix A to the Treatment Assessment Report Concerns fiom the public workshop arc
grouped separately from other concerns and comments submitted by government agencies and parties to the federal facility agreement.

-Decision Element- means that the Army's response to the expressed concern has been made a pan of the proposed decision described in Secticc
6.0 of this decision document. The decision element numbers On parentheses) shown here correspond to the numbesed "Impkmentation and
Operating Objectives' presented in Section 6.2 of this document. (See below]
Public and State Response
  Response to our approach  was very  positive. At the end of the
workshop, for example, one person commented that for the first time,
he understood what the problems at the Arsenal are and how the
technology will help solve the problems. Another person said, "The
workshop was important to communicating to the citizens of this area
the concern of the Army."
  There has been no groundswell of opposition to the final decision.
In fact, when the National Toxics Campaign criticized the Army for
its decision, the Colorado Attorney General's Office came to the Army's
defense, noting that the Army had made extraordinary efforts to involve
and  respond to  citizens regarding the Basin F Liquids IRA.

LESSONS LEARNED:
BENEFITS OF PUBLIC INVOLVEMENT
  In many Superfund programs,  the community relations program is
tangential to the more central attractions of the RI/FS. The common
model is to use technical studies to reach decisions and the community
relations program to inform the public of these decisions and answer
any  questions about  the  decisions. For the Basin F Liquids IRA,
however, we moved the community relations effort to center stage and
gave the program a substantive role in shaping the technical decision.
The effectiveness of this approach provides us with several lessons for
the future on how similar technical decisions can be made in a fair and
timely  fashion.

Involve the Public Early
  Citizens expect to have a role in environmental decision-making and
laws such as those that gave us the Superfund program guarantee them
that right.  Superfund requirements, however, do not compel the Army
to provide for public  input  until  the official comment period, which
is held after the Army  has developed a preferred alternative. Being asked
to comment under these circumstances, however, invariably perturbs
                                                                                                           ROCKY MOUNTAIN ARSENAL    955
-------
the public and often results in opposition to a project based not so much
on its merits, but rather on how the initial decision was  made, i.e.,
with the public excluded.  For the Basin F Liquids IRA, it was evident
that involving the public at a predecisional stage met with wide approval
amongst  not only the public, but also the various  state and federal
agencies with oversight responsibilities. In other words, no one opposed
the Army's decision on procedural grounds. Tuning on this project was
absolutely key.

Incorporate the Public's Input Into the Decision-making Process
  It  is not enough simply to listen and record the public's questions
and concerns. These concerns must be addressed and considered in
a meaningful way. Timing of the community relations program for the
Basin F Liquids IRA demonstrated that it was possible to get the public's
input early enough in the process that the remedial alternatives  could
be crafted to enhance adherence to Superfund provisions that require
consideration of state and community  acceptance.

Document Your Response to the Public's Input
  Too often a federal agency gets no credit for the portion of the public's
input that it does incorporate, only criticism for the input it apparently
discounts. In its Final Decision Document for the Basin F Liquids IRA,
however, the Army went  to great lengths to document its full under-
standing of the community's concerns and addressed them in concrete
terms through the addition of more than a dozen supplemental provi-
sions. By developing the matrix of community concerns and Army
responses (Table 1), the Army got credit for  being responsive to the
community and  the  community  could clearly  see  that  it had been
included in the decision-making process.

Include Community Relations as a Technical Tool
to Achieve Technical Objectives
  Incorporating citizens' input was not designed simply to make them
feel better about the  process;  it improved the quality of the decision
itself. It is all too easy to be condescending in our attitudes toward public
input, believing that because we are the experts, we have all the answers
and could not possibly  have overlooked anything. The addition of 13
supplemental technical provisions to the decision document based on
public comments demonstrated that educating the public early helps
residents contribute constructively to the decision-making process. The
result  is a technical  solution that better addresses the  safety and
environmental protection objectives of the IRA.
  For example, the Army responded to citizen concerns about products
of incomplete combustion by agreeing to ".. .conduct a special predesign
pilot test of the incinerator, planned specifically to collect and analyze
data on products of incomplete combustion or PICs. Information from
this test will be used both  in design and hi planning of operational
controls... [and] will be presented to the Organizations  and the State
in a design review."

An Aggressive Community Relations Effort  Speeds,
Rather Than Delays, the Decision-making Process.
  Working under the tight  time frame  that  the Army had for
implementing the Basin F Liquids IRA, it would have been easy to con-
clude that there "wasn't time" for up-front community relations. The
experience for this IRA demonstrates clearly that the real potential for
delays  was not in involving  the public, but in making a  decision that
would be challenged by the community and oversight agencies. Given
the issues involved in the Basin F liquids problem, the Army knew that
such challenges  were not just possible, but probable. Timing of the
Army's up-front  community relations effort clearly demonstrated the
potential  for building consensus out of controversy.

If You Have a Pattern That Works, Use It Again.
  As the Army embarks on evaluation of remaining IRAs, we expect
to include community  relations planning as an integral part of our
technical work. In this process, we expect to identify community issues
and concerns, respond to those concerns as we go and thereby work
within our time constraints. 'Wfe expect to foster the free flow of technical
information and community concerns between the Army and the com-
munity and to build a decision tree that includes public  input. Thus,
we feel that by anticipating and responding to issues, we  can not only
stay on schedule, but also end up with better solutions to the Arsenal's
contamination problems.
     ROCKY MOUNTAIN ARSENAL
-------
          Remediation of  a  115,000-Gallon  Petroleum  Pipeline  Leak
                                                      Michael R. Noel
                                                    Kendrick A. Ebbott
                                                      Hydro-Search, Inc.
                                                    Brookfield, Wisconsin
 ABSTRACT
  A rupture in a buried petroleum pipeline released 115,000 gallons
 of diesel fuel, contaminating soil and groundwater at a site in Milwaukee,
 Wisconsin. Emergency and interim response actions resulted in the
 recovery of more than 70,000 gallons of product from the ground sur-
 face, a nearby creek and recovery trenches. Based on the results of a
 contamination assessment, an evaluation of remedial alternatives in-
 dicated that the most cost-effective and technically feasible remedial
 method included low temperature thermal desorption for treating the
 impacted soils and discharge of impacted groundwater via an automated
 interception trench to a sanitary sewer. The implementation of the
 thermal desorption process was the first application of its type in the
 State of Wisconsin.
  Approximately 10,000 cubic yards of soil,  with a total petroleum
 hydrocarbon (TPH) concentration of up to 24,000 parts per million
 (ppm), were treated at the site using the thermal desorption system.
 Using a feed rate of between 15 and 30 tons per hour, the impacted
 unconsolidated materials, varying in composition from gravelly sand
 to silty clay, were heated to between 400 and 500 °F in a propane-fired
 rotary kiln. The petroleum vaporized from the soils and was completely
 oxidized in an afterburner operating at 1450 °F. After processing, the
 soil was replaced in the excavation with a TPH concentration of less
 than 10 ppm.
  Groundwater remediation continues at the site. Impacted groundwater
 is intercepted  by a 225-foot long collection  trench. An  automated
 pumping system recovers impacted groundwater which is subsequently
 discharged to a sanitary sewer. Dissolved organic compounds total less
 than 5 ppm, therefore, no treatment is required prior to discharge to
 the sewer.

 INTRODUCTION
  On June 4, 1988, approximately 115,000-gallons of No. 2 diesel fuel
 leaked from a ruptured underground pipeline. The pipeline rupture
 occurred in a county park in a residential area of Wauwatosa, Wisconsin.
 Some of the product from the pipeline rupture gushed to the surface
 where  it flowed downhill and into an adjacent creek. The leak was
 immediately discovered by pipeline pressure monitoring at which time
 the pipeline was shut down. All relevant authorities were immediately
 notified including the local police and fire departments, the Wisconsin
 Department of Natural  Resources (WDNR)  and the Department of
 Transportation (DOT).
  Emergency response actions included controlling access to the site,
excavation and replacement of the  ruptured pipeline segment, and
recovery of free product. Free product was recovered from the pipeline
repair excavation and from the ground surface using vacuum trucks.
Absorbent booms and pads were placed in the creek to contain and
collect product from the surface water. During the week after the leak,
additional back-hoe pits were dug in the vicinity of the release to recover
subsurface free product with vacuum trucks. These immediate response
actions recovered approximately 70,000 gallons of free product.1

SITE INVESTIGATIONS
  Site investigations were required to define the nature and extent of
impacts to soil and groundwater. The investigations Hydro-Search, Inc.
conducted included the installation of soil borings  with soil sampling
to characterize the geology and determine the lateral and vertical extent
of impacted soils, and the installation and sampling of observation wells
to characterize the rate and direction of groundwater flow and the extent
of impacted groundwater. In  addition, a site survey was performed
locating all sampling locations as well as site features and utilities in-
cluding  overhead power lines, storm sewers, sanitary  sewers,  gas
pipelines and petroleum pipelines.

Geology
  Regional information regarding the geology at the spill site  was
obtained from 41 private well  logs located within one-half mile of the
site. Site-specific geologic information was obtained from more than
40 soil borings constructed during the site investigation.
  Geologic materials at the site consist of unconsolidated glacial deposits
underlain by dolomite bedrock. The thickness of the unconsolidated
deposits vary regionally from less than 10 feet to several hundred feet.2
The unconsolidated materials consist of intermixed silty clay, sand and
gravel. Figure  1 shows an east-west regional geologic cross-section
through the spill area. The cross-section information is based on private
well logs located in the area.  At the site, the thickness of the uncon-
solidated deposits is at least 30 feet. The unconsolidated material con-
sists of approximately 0.5 to  1.0 feet of clayey silt topsoil, between
1 and 4 feet of silty sand and  gravel fill material, occasionally a 1 to
2-foot thick buried black clayey silt soil horizon, and intermixed glacial
silty sand, clay, and gravel.3 Figure 2 presents a northeast to southwest
geologic cross-section across the  site.
  Underlying  the unconsolidated glacial deposits is the Niagara
dolomite, a white to gray, fine to coarsely crystalline dolomite.  The
Niagara dolomite dips gently to the northeast into the Michigan Basin.

Hydrogeology
  The water table at the site occurs in the unconsolidated glacial deposits
approximately  5 to 7.5 feet below ground level. Based on water level
measurements  obtained on several occasions from seven monitoring
wells and Underwood Creek, local groundwater flow across the spill
site is west towards the local discharge point, Underwood Creek.
Figure 3 shows a water table map which indicates the local flow direc-
tion. '  Regional groundwater flow deeper within the bedrock aquifer
is to the east towards Lake Michigan.2
                                                                                           SPILLS AND EMERGENCY RESPONSE   957
-------
  co
  E
      700-
  Z
  O

  1
  LU
  _1
  LU
       650-
       640-1
                        o    EXPLANATION
                        CM  	
                         I
                        £—	PRIVATE WELL LOCATION AND DESIGNATION

                               GROUND SURFACE


                               GEOLOGIC CONTACT. DASHED WHERE INFERRED


                              - WELL CASING


                      56 •*--	TOTAL DEPTH (II)

NOTE  All geologic and private well information Irom borelogs on Hie with the Wisconsin DNR.
                                                                                            HORIZONTAL SCALE

                                                                                           0        	     500

                                                                                                    FEET
                                                                                         Vertical Exaggeration: 10x
                                                                Figure 1
                                                    Regional Geologic Cross-Section A-A'
  The  site  hydraulic  gradient  is  relatively  gentle,  averaging
approximately 0.035 feet per foot. The hydraulic conductivity at the
site  ranges from  approximately  IxlO"3  cm/sec to  LxlO~5  cm/sec.
Assuming a porosity of 25 %, the calculated range of flow velocities
across the site varies depending upon the hydraulic conductivity from
0.4 ft/day (146 ft/year) to 0.004 ft/day (1.46 ft/year).

Local Groundwater Use
  All homes in the vicinity of the site have a municipal water supply
available for use.  Records indicate 41  private wells are located near
the site.  With the exception of five deep wells, all the private wells were
constructed prior to  1963. Because these homes are supplied with a
source of municipal  water, the private wells  are no longer used for
potable water. Therefore, the risk to local residential water users is low.
Some of the private wells may be used  for watering lawns. All the private
wells are cased from the ground surface into the bedrock.3

Soil Impacts
  The horizontal and vertical extent of soil impacted  by the diesel fuel
leak was investigated by installing 36 soil borings at the site. The
boreholes were advanced using  the continuous split spoon sampling
technique.
  Ail soil samples were screened for volatiles in the field during drilling
                                                                     using an HNu Model PI-101 photoionization detector (PID) with an 11.7
                                                                     eV probe. Soil samples with elevated PID readings were submitted for
                                                                     laboratory analysis of total petroleum hydrocarbon (TPH). Two samples
                                                                     were submitted from several boreholes to determine the vertical extent
                                                                     of the petroleum impacts. In general, soil impacts ranged from  non-
                                                                     detectible levels of less than 10 parts per million (ppm) TPH to 24,000
                                                                     ppm TPH.1
                                                                       In Wisconsin, there are no regulations governing the concentration
                                                                     of petroleum products in soils. However, the Wisconsin DNR uses a
                                                                     guideline of  10 ppm TPH as its cleanup standard.4 Based on this  stan-
                                                                     dard, the lateral extent of impacted soil is shown in Figure 4.  The im-
                                                                     pacted soils generally form a 25- to 50-foot halo around the surficially
                                                                     stained area  where  the spilled product initially pooled. The impacted
                                                                     soil area extends approximately 300 feet long by 100 to 260 feet  wide
                                                                     and covers an area from east of the pipeline rupture to the edge of Under-
                                                                     wood Creek. The lateral wicking of the product into the unsaturated
                                                                     soils was enhanced by the extremely dry condition of the soils at the
                                                                     time of the release due to drought conditions occurring in the area during
                                                                     the  summer  of  1988.
                                                                       The vertical extent of soil impacts indicated elevated TPH concen-
                                                                     trations  to depths of 12 feet.'  The impacts below the water table are
                                                                     attributed to the forced migration associated with the pressure of the
                                                                     release.  Figure 2 shows the lateral and vertical extent of soil impacts
       SPILLS AND EMERGENCY RESPONSE
-------
   *     B
    SOUTHWEST
                                                      B1
                                              NORTHEAST
   725-1
   720-
   I 715-
 UJ

 UJ
    710-
    705 J
                                                                                                                        BLACK SILT:
                                                                                                                      SOIL HORIZON
                         - WELL/BOREHOLE LOCATION AND DESIGNATION

                         - WELL CASING

                          WATER LEVELI8/3/89)

                         - LABORATORY RESULTS: TOTAL PETROLEUM HYDROCARBONS (ppm)

                          EXTENT OF IMPACTED SOIL AND SEDIMENT (TOTAL PETROLEUM
                          HYDROCARBONS 10 ppm OR GREATER)

                  __11J	GEOLOGIC CONTACT. DASHED WHERE INFERRED

                    [ |-	COMPLETION INTERVAL

              NOTE'Borehole projected onto cross section.
                               HORIZONTAL SCALE
                               0                  50

                                       FEET
                             Vertical Exaggeration: 8x
                                                               Figure 2
                                                    Local Geologic Cross-Section B-B'
                                                      with Extent of Impacted Soils
 at the site along a southwest to northeast cross-section.

 Groundwater Impacts
  Groundwater quality was monitored by sampling groundwater obser-
 vation wells which were installed around the perimeter of the impacted
 soil area. These wells were sampled on several occasions and analyzed
 for either benzene, ethylbenzene, toluene and xylene (BETX), or volatile
 organic compounds (VOCs) and base neutral/acid extractable com-
 pounds (BNAs). The laboratory results from all sampling events in-
 dicate no detections of any compounds in any of the monitoring wells.5
 Monitoring wells were not installed within the impacted area since they
 likely would be destroyed during soil remediation.

 INTERIM ACTION
  Based on the results of the site investigations, two recovery trenches
 were installed to prevent off-site migration of hydrocarbon compounds
 and to facilitate additional product recovery. In July 1988, two 150-foot
 long  recovery trenches  were installed  across  the impacted  area
 (Figure 4). Each trench was excavated to a depth of 2 to 5 feet below
 the water table, backfilled with pea gravel, and capped with site soils.
 A 36-inch diameter steel slotted culvert was installed vertically in each
bench to act as a sump for recovery of groundwater and free product.
Groundwater was pumped from the base of each sump and discharged
under permit into the sanitary sewer system. The groundwater pumping
removed impacted water and depressed the water table to expedite free
nroduct recovery. Free product was recovered using an oil skimmer
aim/or oil absorbent pads.
  During the past 2 years of operation of this recovery system, approxi-
mately 7,300 gallons of free product have been recovered with approxi-
mately 85 % of this total coming from Trench 2 which is located closest
to the pipeline leak. During this period, approximately 2,000,000 gallons
of water were discharged to the sanitary sewer. Monthly monitoring
of this effluent indicates the water contains an average of less than
500  ppb of total organics consisting predominantly of benzene,
ethylbenzene, toluene,   xylene,  naphthalene,  hexachloroethane,
bis(2-ethylhexyl)  phthalate,   fluorene,   acenaphthene  and
2,4-dinitrotoluene.'

EVALUATION OF SOIL REMEDIATION ALTERNATIVES
  Due to the large amount of unrecovered product contained within
the soils, the WDNR required remediation to the 10 ppm TPH level.4
Several methods  for remediation of impacted soils were evaluated by
Hydro-Search, Inc. and included:
• Passive Remediation
• Excavation and Landfilling
                                                                                            SPILLS AND EMERGENCY RESPONSE   959
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   OW-1
   (710.81)
           8         ?'        ?

             EXPLANATION
"•^ WATER TABLE CONTOUR (tL msl). DASHED WHERE INFERRED
•  MONITOR WELL LOCATION. DESIGNATION. AND WATER TABLE ELEVATION (tL msl)
     ss_-, •  STREAM STATION LOCATION AND DESIGNATION
    r.:.'••!::; ;i  GROUND WATER COLLECTION TRENCH

   NOTE Water level data trom 8/3/89  Data Irom OW-7 anomalous, not used tor contouring.
                                                                 Figure 3
                                                            Water Table Surface
• Landspreading
• Vapor Extraction
• Bioremediation
• Enhanced In Situ Bioremediation
• Thermal Evaporation
  These alternatives were evaluated for technical implementability and
environmental effectiveness; permitting and monitoring requirements;
and cost and duration of project.
  In order to evaluate various cleanup methods, the following assump-
tions were employed:
• The volume of impacted soils requiring remediation is 10,000 cubic
  yards.  The approximate dimensions  of the impacted area, as deter-
  mined by laboratory TPH analysis of less than 10 ppm, are 200 feet
  by 250 feet by 7 feet deep.
• The worst case average TPH concentration in the impacted soils is
  5,000 ppm. This conservative value is more than double the average
  laboratory TPH concentration detected in the impacted soil samples.
• Remedial  alternatives involving excavation would not be required to
  excavate beneath the high tension electrical towers, behind or beneath
  the concrete panels lining the creek or below the water table which
  occurs at  a depth of between 5 and 7.5 feet.
  In August 1988,  Hydro-Search, Inc.  submitted the feasibility study
to the WDNR.  A summary of the evaluation of these alternatives is
                                                             presented in Table 1. The WDNR review of the feasibility study con-
                                                             cluded the following:
                                                             •  Passive Remediation: determined to be inappropriate and rejected
                                                                in favor of more environmentally responsible options.
                                                             •  Excavation and Landfilling: determined to be an acceptable means
                                                                for cleaning up the site because it provides for source removal, thus
                                                                eliminating many long-term site management concerns.
                                                             •  Landspreading:  determined to present  a number  of permitting,
                                                                operating and monitoring obstacles which limit the applicability of
                                                                the method. In addition, landspreading was not  recommended for
                                                                diesel fuel contaminated soils.
                                                             •  Vapor Extraction: determined to be not appropriate based on the low
                                                                volatility of diesel fuel.
                                                             •  Bioremediation: determined to be not acceptable because operational
                                                                requirements for space preclude the use of the immediate vicinity
                                                                of the spill site.
                                                             •  Enhanced In Situ Bioremediation: determined to be unacceptable
                                                                based on lack of approval by the Water Supply Section for a waiver
                                                                for the use of injection wells.
                                                             •  Thermal Evaporation: determined to be the most acceptable means
                                                                of remediating the site because it contains a number of desirable
                                                                aspects such as:
                                                                —  It eliminates the  source of soil, air, surface water and ground-
•J60    SPILLS AND EMERGENCY RESPONSE
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                         EXPLANATION
       OW-10   MONITOR WELL LOCATION, DESIGNATION. AND TPH CONCENTRATION (ppm)

       B-39-$-   SOIL BOREHOLE LOCATION. DESIGNATION. AND TPH CONCENTRATION (ppm)
       	  LATERAL EXTENT OF SURFICIAL SOIL STAIN

       _-10 —  LATERAL EXTENT OF IMPACTED SUBSURFACE SOIL. DASHED WHERE INFERRED.
               LABORATORY RESULTS TPH 10 ppm OR GREATER
      \wmm>sA  GROUND WATER COLLECTION TRENCH
                                                                                  NOTE (NA) indicates not analyzed.
                                                                Figure 4
                                                      Lateral Extent of Impacted Soil
     water contamination.
  — It does not require a source of clean fill.
  — It does not take up valuable landfill space.
  — It does not generate a high volume of truck traffic to and from
     the site.
  — It does not involve the use of injection wells for supplying nutrients
     to microbial populations.4
  Based on these comments, the comparable costs of landfilling and
thermal evaporation, and the potential for continued liability with land-
filling, it was decided to remediate the soils using the thermal evapora-
tion process,  which was the first application of that technology in the
State of Wisconsin.
SOIL REMEDIATION

Contracting  and Permitting
  Bid specifications were prepared by Hydro-Search, Inc. in July 1989,
and submitted to several contractors who provide thermal evaporation
process services. The contractor selected for the job was Clean Soils,
Inc. of Minneapolis, Minnesota. Clean Soils was selected based on their
experience, cost and the iact that they already had the required permits
from the Air Management Section of the WDNR.
  A soil remedial action plan was prepared by Hydro-Search, Inc. and
submitted  for WDNR approval in December 1989.w The plan con-
sisted of five general elements which included:

  soil excavation
  confirmational testing of excavation
  soil treatment and stockpiling
  confirmational testing of treated soils
  backfilling and restoration

  The sequencing of these elements is presented schematically in the
flow chart shown in Figure 5.
  Prior to startup, arrangements had to be made and permits obtained
from county and local officials regarding operational procedures and
site restrictions. These included:
• Milwaukee County Parks and Recreation Board: permit specifying
  hours of operation, fencing restrictions, security arrangements, noise
  and  dust restrictions,  restoration  requirements,  and  insurance
  requirements
• City of Wauwatosa: temporary occupancy permit specifying hours
  of  operation, fencing  restrictions, and emergency  response
  arrangements
• Wauwatosa Fire Department: approved use of 18,000-gallon propane
  tank for treatment unit as well as fencing and signage requirements
• City of Wauwatosa Water Department: approved use of fire hydrant
  for dust control
                                                                                             SPILLS AND EMERGENCY RESPONSE    961
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                                                                 Table 1
                                                   Comparison of Remedial Alternatives
REMEDIAL
ALTERNATIVE
Passive
Remediation
Excavation/
Landf illing/
Refilling
Landsprcading
Thermal
Vapor
Extract Ion
Bioremediat ion
Enhanced
In-situ
Bio-
remedi at ion
TIME
4-10 years
20 days
3-6 months
75 days
6-12 months
6-8 months
9 months
2 years
COST ESTIMATE
Site Characterization J 25,000 - t 50,000
and Risk Assessment
Soil Sampling and J 40,000 - * 100,000
Ground-Water
Monitoring
TOTAL: S 65,000 - » 150,000
Landfilling S 120,000
Excavation/Fill S 250,000
Continuous Field t 15,000
Screening and
Supervision
TOTAL: t 385,000
S38.50/cu.yd
Excavation/Fill S 250,000
Tilting and Field S 20,000
Screening
TOTAL: t 270,000
127.00/cu.yd
Excavation and Treatment S 560,000
Ueekly Field Screening S 15,000
and Project Management
TOTAL: * 575,000
t57.50/cu.yd
Set-up and Operation 1400,000 - S 600,000
Project Manager S 20,000
TOTAL: W20.000 - I 620,000
«2-S62/cu.yd
Excavation S 200,000
Set-up and Operation 1500,000 I 800,000
Project Manager t 15,000
TOTAL: 1715,000 - 11.015, 000
»7l.50-»101.50/cu.yd
Set-up and Operation J 500,000
Project Management t 20,000
TOTAL: t 520,000
152/cu.yd
REGULATORY REOUIREHEMTS
Subject to DNR Approval
Landfill Acceptance Forms
Potential Noise Restrictions
Potential Air Emission Permit
•
90-120 days start-up delay
Potential Noise Restrictions
Potential Air Emission Permit:
90-120 days start-up delay
Potential Noise Restrictions
wells
Potential air Emission Permit:
90-120 days start-up delay
Requires DNR waiver of
injection well restriction
CONTINUING
LIABILITY
Yes
Yes
No
No
No
No
No
COMMENTS
Potential ground-water iapacts.
Excavate
Omega Hills Landfill
Contractor costs may vary
substantial ly
Excavate
Hove impacted soils to another site.
Excavate
In-situ
Cost dependent on final clean-up
criteria and number of required
Excavate
Cost dependent on final clean-up
criteria and bacteria,
nutritional requirements
In-situ
Provides soil and water treatment.
Cost dependent on final clean-up
criteria, bacteria, nutritional
requirements and number of
required wel Is.
Mote: All cost and item estimates arc approximate based upon 10,000 cubic yards of Impacted sotls.
LandMlting and thermal remediation costs are more fully determined than the other methods
due to the nature of the respective methods.
                             Figure 5
                      Soil Remedial Action Plan
• Wisconsin Electric Power Co.: approved set-back requirements to
  excavate around electric power towers and poles
• Metropolitan Milwaukee Sewage District: approved set-back require-
  ment to excavate near concrete lined creek
• Digger's Hotline:  clearance of on-site utilities
SOIL REMEDIATION PROCESS
  The treatment of the soils was accomplished using the Clean Soils
Thermal Desorber which was mobilized to the site in January 1990.
A schematic of the system is shown in Figure 6.
  Soils were excavated and transported to the processing unit using a
back-hoe and front-end loader. The soils were first screened through
two grates to remove rocks and debris larger than 2 inches in diameter
and then fed by conveyor to the treatment unit.  As the  soils entered
the treatment unit, they were cascaded by a 5-foot diameter rotating
drum towards the main burner. Within the chamber, the soils were heated
to approximately 450°F to vaporize the hydrocarbons. The resultant
vapors were  pulled  through a baghouse to  remove all dust-sized
paniculate matter. Combustion of the vapors occurred inside a propane-
fired afterburner  where the vapors were completely  consumed by
burning at temperatures of 1400 to 1470°F.
  The treated  soils exited the unit via a conveyor where they  were
stockpiled until confirmational analysis documented cleanup. Upon
receipt of the laboratory analysis verifying that cleanup standards were
met, the soils were backfilled into the excavation. Once the soil remedia-
tion was completed, the area was graded, covered with topsoil, seeded,
landscaped and the bike path restored.
  The soils were  processed at a rate of between 15 and 30 tons per
       SPILLS AND EMERGENCY RESPONSE
-------
 DISCHARGE AUGER/
 REHYDRATION SYSTEM
              LARGE DEBRIS
                                          CONTAMINATED SOILS
                                         FROM FRONT END LOADER
                          HOPPER AND
                          6" SCflEEN
                            Figure 6
              Thermal Desorption Treatment Unit Layout


hour. Processing rates were influenced by soil moisture content, diesel
fuel concentration and soil type. Fine-grained soils with a high silt and/or
clay content were processed at a slower rate than sandy or gravelly soils.
Wet and highly impacted soils were also processed slowly to maintain
the proper fuel/oxygen mixture in the afterburner for the combustion
of the vapors. Weather,  site  ground conditions and  equipment
breakdowns also affected  the rate of soil processing.
  Soil processing was carried out from January through May of 1990.
Over the total project duration of  132 days,  actual soil processing was
performed on 93 days. Complete system shutdown related to equip-
ment failure, maintenance or inclement weather occurred on 39 days.
Over the life of the project, daily soil processing rates varied from less
than 20 tons to more than 400 tons per day. A total of 13,989 tons of
soil were processed (10,000 cubic  yards) hi 93 days of actual  soil pro-
cessing for a daily average of 150 tons.
  Over the last 6 weeks of the project, most of the mechanical dif-
ficulties associated with the equipment had been corrected, and the ther-
mal desorption unit processed an average of more than 200 tons of soil
per day.

GROUNDWATER REMEDIATION
  A groundwater remediation plan was prepared by Hydro-Search, Inc.
and submitted to the WDNR in July 1990  for approval.5 The objec-
tives of the remediation plan were to clean up groundwater to meet
NR140 (Wisconsin Administrative Code) preventive action limits and
to prevent off-site migration of impacted groundwater. The plan5 called
for:
• The recovery of groundwater from Trench 1 along Underwood Creek
  (Trench  2 was destroyed during soil remediation)
• Discharge of groundwater to the MMSD sanitary sewer
• Free product recovery from the sump in Trench 1 as necessary
• Performance monitoring of the system
• Periodic reporting on the system progress
  Continued use of Trench 1 to capture on-site impacted groundwater
was proposed based on its successful performance over the past 2 years.
Although the trench  has only been pumped on a part-time basis (8 to
10 hours a day) for the past 2 years, impacted groundwater has not
migrated off-site. Automation of the system will provide full-time opera-
tion. Discharge of groundwater to the sanitary sewer is the most cost-
effective and least disruptive alternative for treating impacted ground-
water at the site.
  To implement the plan requires modifications to the existing trench
system which are anticipated to take place in fall of 1990, and which
include extending the trench 75  feet to the south to ensure adequate
capture, deepening the  sump construction, automating the pumping
system to reduce the manpower requirements and winterizing the system
to allow year-round operation. A plan and schematic of the  proposed
system are shown in Figures 7 and 8.
  Operation of the system will be controlled by float-activated switches
to maintain a 1.5-foot drawdown in the trench. Groundwater will be
discharged to a sanitary sewer with the volume monitored by an in-line
totalizing  flow-meter.
  Free product that collects in the sump will be pumped out with an
oil skimmer or oil absorbent pads on an as-needed basis. Manual opera-
tion was chosen because the diminishing product recovery in the trench
over the last 2 years indicates not much additional product will be
recovered. Automated product recovery and  containment would have
included construction of a building to house the recovered product.
Therefore, providing automated product recovery was not considered
cost-effective.
  Performance of the system will be monitored by the observation wells
shown in Figure 7. These wells will monitor both the hydraulic capture
of the system and water quality to ensure  impacts do not migrate off-
site. The system will operate until the hydrocarbon  compounds in the
groundwater are below  the NR140 preventive action limits.

CONCLUSIONS
  Within 24 months of the 115,000-gallon release, nearly all free product
has been recovered, impacted groundwater has been controlled to prevent
off-site migration and impacted soils have been remediated.  Ground-
water remediation is expected to continue  for another 2 to 4  years, or
until hydrocarbon compounds meet WDNR water  quality criteria.
  The cleanup's  success  is attributed to the emergency response efforts
that resulted in the recovery of approximately 70,000 gallons of product,
the  interim action of installing trenches to intercept  impacted ground-
water and recover an additional 7,300 gallons of free product and the
application of new thermal desorption technology which was mobilized
to the site during a harsh Wisconsin winter and used to remediate 10,000
cubic yards of impacted soil in less than 5 months.
  These accomplishments would not have been possible without the
environmental consciousness of the pipeline owner/operator, the dedica-
tion of the response crews and contractors, the cooperation of the local
agencies and officials, the understanding of the surrounding  residents
and the progressive attitude of the WDNR to allow the use of new and
innovative technologies.
REFERENCES
1. Hydro-Search, Inc. (HSI), Investigation and Analysis of Remedial Alternatives,
  HSI, Brookfield, WI, August, 1988.
2. Ketelle, M. J., Hydrogeologic Considerations in Liquid Waste Disposal, with
  a Case Study in Southeastern Wisconsin, Southeastern Wisconsin Regional
  Planning Commission  (SEWRPC),  3, (3), SEWRPC, Waukesha,  WI,
  September, 1971.
3. Hydro-Search, Inc. (HSI), Addendum: Investigation and Analysis of Remedial
  Alternatives,  HSI, Brookfield, WI, November, 1988.
4. Wisconsin Department of Natural Resources (WDNR), Proposed Remedial
  Actions, letter,  WDNR, Milwaukee, WI, May, 1989.
5. Hydro-Search, Inc. (HSI), Ground-Water Remediation Plan, HSI, Brookfield,
  WI, July,  1990.
6. Hydro-Search, Inc. (HSI)Soi7 Excavation Treatment and Sampling Plan, HSI,
  Brookfield, WI, December, 1989.
7. Wisconsin Department of Natural Resources (WDNR), Proposed Thermal
  Remediation of Contaminated Soils, letter, WDNR, Milwaukee, WI, January,
  1990.
                                                                                              SPILLS AND EMERGENCY RESPONSE   963
-------
                 EXPLANATION
          LATERAL EXTENT OF REMEDIATED SOILS
 OW-1 6   EXISTING MONITOR WELL LOCATION AND DESIGNATION
 OW-1R O   PROPOSED MONITOR WELL LOCATION AND DESIGNATION
 OW-3 •   PROPOSED ABANDONED MONITOR WELL LOCATION AND DESIGNATION
          GROUND WATER COLLECTION TRENCH
	GROUND WATER DISCHARGE LINE
                                                       Figure 7
                                             Groundwater Remediation Layout
 SPILLS AND EMERGENCY RESPONSE
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       — WISCONSIN
         ELECTRIC
        POWER POLE
36" DIAMETER STEEL SUMP
          FLOWMETEfi
     PUMPeLECTRtCUNB
            PLATFQRM
      2'PVC DISCHARGE UNE.
           ;  v  , RUMP ON
       EXISTING SUMPSASfi
      EXISTING TRENCM SASE-'
PROPOSED TRENCH DEEPENING
   PRQPOSEO SUMP 8ASE
                                 • PROPOSED PRIVATE ELECTRIC POLE
                                 . LOCKABLE, WATERPROOF STORAGE BOX WITH
                                  ON/OFF CONTROLS AND ELECTRIC OUTLETS
                                                         NATIVE  SOILS
             'SUBMERSIBLE RIMR
                                                Figure 8
                                     Groundwater Remediation Pump Detail
                                                                         SPILLS AND EMERGENCY RESPONSE   965
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                Assessment  of  the  Emergency Response  Actions  and
                      Environmental  Impact  of the January  2,  1988
                        Diesel  Oil  Spill  Into  the Monongahela River

                                                    Roger L. Price, RE.
                                                    Edgar Berkey, Ph.D.
                                        Center For Hazardous Materials  Research
                                            The University of Pittsburgh  Trust
                                                   Pittsburgh, Pennsylvania
 INTRODUCTION
  This paper presents an assessment of the overall adequacy of the
 emergency response to the January 2, 1988, Ashland Oil spill into the
 Monongahela River near Pittsburgh, Pennsylvania.  Additionally, we
 present an assessment of the environmental impacts of the spill. Infor-
 mation for the assessment has been gathered from meetings with public
 and private emergency response officials, public hearing records and
 government reports. Many of the recommendations made by emergency
 response officials involved in the Ashland incident have been included
 in this paper.
  The assessment of the overall adequacy of the emergency response
 portion of this paper was adapted from a chapter of a report entitled
 "Economic and Policy Implications of the January 1988 Ashland Oil
 Tank Collapse in Allegheny County, Pennsylvania,"  which was a col-
 laborative effort involving the staffs of both the Center for Social and
 Urban Research and the Center for Hazardous Materials Research at
 the University of Pittsburgh. The report was prepared  for the Allegheny
 County Planning Department and funded through a grant provided to
 Allegheny County from the Pennsylvania Department of Commerce.

 DESCRIPTION OF EMERGENCY RESPONSE ACTIVITIES
  Successful protection of the public health throughout the emergency
 resulted from the outstanding efforts and cooperation of hundreds of
 response personnel, including individuals from Ashland Oil Inc. and
 its contractors, 17 regional offices of seven federal agencies, 11  state
 agencies from four states and numerous local emergency response
 agencies, fire departments and water suppliers.
  The Center for Hazardous Materials Research (CHMR) has  iden-
 tified a number of events that are key to understanding and assessing
 the on-site emergency response. A detailed minute-by-minute summary
 of these events and a map of the accident site are provided in the full
 report on  the economic and policy implications of  this incident.
  Initial response efforts focused on the terminal site in order to: (1)
 establish access control; (2) stop the flow of diesel fuel on-site; (3)
 .pjug leaks 'found  In a damaged  tank holding 1.0UO,UUJ aallOiis~oT~
 gasoline: and (4) conduct a tnorouehassessment of the extent of the spill.
' «HFrie-mitiaTo"n-!ilu; as>s>esslllt!nl was "severely hampered by cold weather,''
 darkness and concern over the potentially volatile mixture of gasoline
 and diesel fuel. Dangerous conditions on the river (rapid currents, cold
 weather and  darkness), moreover, severely restricted any possible
 response action on the water.
  Asjyesult, estimates of the large volume of fuel released and the
 severity'of the impact of the spill on the river system and downstream
 water suppliers was  not fully realized until early the next morning,
 January 3. Preliminary reports suggested that water  intakes were low
 enough to avoid the oil or that river water could be adequately treated
( se
by the water plants. The dispersion of oil throughout the water column
was not recognized until at least 12 to 18 hours after the release.
  On January 3, 1988, approximately 14 hours  after the release, the
U.S. EPA On-Scene Coordinator arrived on-site and advised Ashland
that the U.S. EPA determined that the response actions taken by Ashland
were appropriate and that federal supervision of Ashland Oil's cleanup
was equivalent in every respect to what the federal government would
have done under the same circumstances.
  Considering the initially rapid rate of release, standard response time
for off-site emergency responders and  circumstances common to
incidents of this type, it is unlikely that the quantity of release could
have been substantially reduced in the crucial first 2 hours.
  It is important to note that the on-site company personnel responded
within  minutes of the  accident by closing a valve controlling the
discharge of oil from the facility API separator. This action effectively
stopped the discharge of oil from this source and  contained millions
of gallons  of oil within the facility's spill containment system.
  On January 2, 1988, the flowrate and velocity of the Monongahela
River were high. As river water moved over each dam, it dropped many
feet in height — a circumstance  which adversely affected oil recovery
efforts  because it caused the oil, water and  suspended sediment to
become increasingly mixed as each dam was passed. This mixing action
caused the oil to contact and coat sediment particles  suspended
throughout the water column, which prevented much of the oil from
floating back to the surface.
  Approximately 205,000 gallons of diesel fuel (29% of the total 705,000
gallons released to the river) were recovered through skimming opera-
tions. The oil which remained in the river became completely mixed
and emulsified in the water by the time the spill passed the Dashields
Lock and Dam, approximately 38 miles downstream from Floreffe on
the Ohio River. No substantial recovery occurred below this point. The
cleanup operations, which ultimately spanned 38 miles, were severely
hampered  by extremely cold weather conditions.  The risk of hypo-
thermia for cleanup crews led to the decision  to remove all personnel
from working on the river on the  fourth day after the spill.
  The  morning following the accident, state and local  authorities
directed their efforts toward concerns over water quality and drinking
water supplies. By noon on January 3rd, these  efforts began  to con-
stitute a separate, significant response activity, which the state and county
authorities managed.
  A disaster emergency was declared for Allegheny, Beaver and Butler
Counties by the governor. Temporary interconnects were installed to
link the City of Pittsburgh and  West Penn Water systems. Work was
started on numerous new permanent  interconnects and other, older inter-
connects were opened. Substantial efforts were made to bring in equip-
ment in order to distribute drinking water to affected communities.
 966   SPILLS AND EMERGENCY RESPONSE
-------
  West Penn Water Company, with assistance from the Pennsylvania
Department of Environmental Resources (PADER), developed and pilot-
tested a treatment that successfully removed oil from water supplies.
This process was used by downriver water suppliers, making it possible
for them to open river intakes days before they otherwise would have
been able to do so. Water supplies in four states — Pennsylvania, Ohio,
West Virginia and Kentucky —  were affected as the  spill flowed
downriver. By the time the spill passed Cincinnati, oil concentrations
in the Ohio River had decreased to the point where immediate concern
with regard to drinking water had subsided.
  Over the short-term, the diesel oil spill produced a few  small to
moderate impacts on organisms dependent on the river system in limited
regions of the first 185 miles down-river. Natural processes associated
with the spill and river system combined to mitigate and significantly
restrict the impacts, except in a few localized areas. Significant long-
term effects on the river system  as  a whole from the spill are not
expected.

CONCLUSIONS AND RECOMMENDATIONS
  The oil spill incident had a significant impact on the water companies
which depend on the Monongahela and OhjoRjjieisJbr their source
of supply. The spill created water suppry~snortages  in  some areas
requiring customers to conserve water; the spill actually led to the loss
of water supply in one service  area. In  spite of these hardships, the
outstanding efforts of all responding agencies, groups, individuals and
Ashland Oil Company resulted in the successful protection of the public
health throughout the emergency. Extensive emergency response actions
prevented any contamination of operating  public water systems.
  The goal of the following recommendations is to improve preparedness
among emergency responders in confronting incidents similar to the
Ashland Oil spill.  The recommendations  benefit from CHMR's ex-
perience in emergency management and preparedness as well as from
observations and suggestions offered by emergency response officials
in public hearing records and government reports on the Ashland Oil
spill.

Organization and Speed of the Response
  The following list provides a summary of CHMR's conclusions and
recommendations regarding the overall organization and speed of the
response. Five key findings can be highlighted.
• Ashland took appropriate initial response actions, which included
  notifying the National Response Center and  calling the necessary
  emergency response contractors.
• Although downstream water users were quickly notified of the inci-
  dent, the severity of the potential impact on the river system and
  downstream water supplies was not fully realized until 12 to 18 hours
  after the spill.
• The fact that the severity of the potential off-site impact was not
  realized, combined with concern over volatile conditions  on-site, cold
  weather, darkness and dangerous conditions on the river, hampered
  initial response actions and caused the initial priority of the response
  to be directed on-site.
• Although initial problems with the overall  organization of the response
  caused some operational difficulties for response personnel during
  the first 24 to 36 hours, it is unlikely that these difficulties adversely
  affected the overall adequacy of the emergency response for mini-
  mizing losses to property,  businesses and individuals.
• It  is  also unlikely that any other organization of the emergency
  response would have resulted in more effective protection  of the public
  health or further minimized losses caused by the accident.
  The overall organization and  speed of the  response thus were ade-
quate to fully protect public health and minimize losses  to property,
businesses and individuals under the circumstances of this incident.
However, some lessons can be  learned which may improve the effi-
ciency of future responses.
•  In the future,  the On-Scene Coordinator should  initiate coordina-
  tion activities earlier and start assigning responsibilities sooner. The
  RRT team should be activated as  soon as possible and a decision
   made as to whether its members should be brought together on-site.
   An "RRT Coordinator" should be designated to assist the OSC by
   facilitating communications among responding agencies.
•  A responsible party representative (in  this case,  someone from
   Ashland Oil) in RRT conferences should directly provide the RRT
   with factual details regarding the responsible party's activities and
   ability to comply with RRT recommendations to the OSC.
•  Important environmental data were not collected during the first few
   hours of the incident because emergency response personnel were
   preoccupied with responding to the  emergency at hand. Facility
   Preparedness  Prevention Contingency plans  should  identify  in-
   dividuals of the responsible party or its contractors whose sole respon-
   sibility is the  collection of environmental data.
•  In the initial days of the spill, the coordination and communications
   of river monitoring data suffered because no lead agency was assigned
   to oversee these activities. A lead agency should be designated to
   focus the coordination and communication of monitoring data and
   to assure standardization in the analysis of these data.

Adequacy of Equipment & Materials
  The lack of immediately available containment and monitoring equip-
ment hindered the emergency response. The need to locate and transport
essential equipment caused delays.
  However, as a result of the unique circumstances of this incident (e.g.,
the rapid release and discharge of most of the oil into the river with
the first two hours, darkness, cold weather, rapid river currents and
dispersion of oil throughout the water column), it is unlikely that another
response could have been any more effective in significantly reducing
the total quantity of oil discharged to the river or increasing the total
quantity of oil recovered from the river.
  Nevertheless,  additional lessons can be learned. The following 11
points summarize CHMR's conclusions  and recommendations regar-
ding the adequacy of available equipment and materials as well as the
preparedness of  personnel for future contingencies.
• Containment dikes are an essential  first line of defense to prevent
  the release of  oil and hazardous substances  from leaking tanks. It
  is unlikely, however, that dikes can be constructed to provide com-
  plete containment of all possible incidents such as sudden massive
  tank ruptures.
• Facility Preparedness Prevention Contingency plans should "look
  beyond the dike" and be prepared to install a "second line of defense"
  in the event a spill escapes the containment area. All drainage ways
  near containment dikes should be identified in PPC plans, a strategy
  should be developed for intercepting releases in the drainage ways
  and secondary structures should be maintained.
• A computerized geographic information system with the capability
  for displaying maps of the physical infrastructure of Allegheny County
  should be implemented to provide emergency responders as quickly
  as possible with necessary information for rapid responses.
• Facility PPC plans should be current and include information on loca-
  tions of hazardous and environmentally sensitive materials stored on-
  site. PPC plans should be provided or made readily available to local
  emergency responders. Consideration should be given to keeping a
  current copy of this plan in a highly visible  "lock box" located on
  the perimeter  of the site.
• Inventories of locally available equipment should be prepared to assist
  emergency responders in quickly locating necessary items. Such in-
  ventories could be developed and augmented where necessary through
  a cooperative arrangement between local industries and government.
• Methods to monitor the dispersion and concentration of airborne con-
  taminants which could emanate from a spill should be considered
  in local contingency plans. The availability of air-monitoring equip-
  ment (local stationary installations and mobile units) capable of pro-
  viding real-time data needed to estimate community exposures should
  be assured and included in inventory lists.
• State or local  contingency plans should maintain  a  list of local
  laboratories certified to perform necessary testing in an emergency.
  Development of a mobile laboratory capability by the responding
  agencies should be considered.
                                                                                               SPILLS AND EMERGENCY RESPONSE    967
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• The Ashland incident could have been far more devastating if public
  water supplies had been contaminated or water shortages had become
  more severe. Emergency planning agencies and water suppliers should
  work toward improving the availability of contingency water supplies
  with consideration given to the installation of permanent intercon-
  nect grids among neighboring water suppliers and expanded storage
  capacities for both raw and treated water.
• The ability of facilities such as hospitals, nursing homes, medical
  clinics and schools to respond to and maintain operations should be
  strengthened.
• Emergency planning  agencies should maintain  a current list of
  available bulk water haulers, facilities with tankers that can be used
  in refill operations and sources of plumbing expertise and supplies
  for distribution  hookups.
• Each water supplier should maintain a list of service and equipment
  companies that can provide replacement pumps, chlorination equip-
  ment and chemical feed equipment to add water treatment chemicals
  in the event of an emergency.

Adequacy of Communication  Among Emergency Responders
  Problems were encountered due to insufficient communications equip-
ment at  the command post to support the large number of response
agencies. Problems  were encountered contacting RRT  members dur-
ing off-duty hours, and numbers  to installed or rented phones were not
available in a timely manner.
• A list of 24-hour  telephone numbers for RRT members should be
  regularly updated and made available.  Electronic  mail  systems
  operated by various agencies can be efficient mechanisms for com-
  munication among RRT members. An RRT E-mail distribution system
  should be established, and each RRT member should be assigned
  an electronic  mailbox.
• Adequate telephone lines must be immediately installed at command
  posts in addition to having ample numbers of cellular phones available.
  Telephone numbers of newly-installed or rented portable phones must
  be gathered early and disseminated more aggressively during an
  emergency.
• The Ohio River Valley Water Sanitation Commission's electronic
  bulletin board  was  widely used and  worked well for distributing river
  monitoring  data.  Procedures  could be developed to  use  such a
  resource even more effectively.

Adequacy of Communications Between Responders and the Public
  The water suppliers' public communications activities were generally
excellent during the Ashland emergency, but some lessons nonetheless
can be learned from the experience. The following conclusions and
recommendations regarding proper procedures for communicating with
the  public during emergencies are offered for consideration based on
the  lessons learned from how information was  provided to the public
during the Ashland episode.
• At one point, prior to receiving official notice from the state, a local
  agency suggested that the need for water conservation  was lessening.
  Criteria and authority for lifting water conservation  orders should
  be made clear by  the party establishing such an order, so there is
  advance agreement on when conservation can be  discontinued.
• Information should be given to the media consistently and on a regular
  basis during emergencies,  preferably through one  spokesperson at
  the facility.
• Special attention must be paid to ensure that the media continually
  notify the public if the problem is one of quantity and not  of con-
  tamination.  Suppliers must communicate to  the public that the use
  of interconnections, changes  in water flow  patterns and varying
  pressures may lead to taste  and odor problems that can be misinter-
  preted as contamination.
• The need for predetermined health advisory threshold levels for
  releases of a wide variety of hazardous substances to surface waters
  and the atmosphere and a system to warn the public about health-
  threatening conditions continues to be a  concern.

Educational Training and Information Resources
  Although the response to the Ashland Oil  spill was effective in pro-
tecting public  health,  it is evident that more  timely health effects data
on spilled hazardous substances were needed along with assistance in
interpreting their significance.
  Recent federal requirements under the SARA are generating signifi-
cant new information  on the specific locations of hazardous materials
produced  or used  by particular industries. Firefighters and  other
emergency responders should be properly equipped to respond to any
emergency which could occur in their respective service areas.
  CHMR's conclusions and recommendations regarding training and
information resources, based on lessons learned from the Ashland Oil
spill, include the following items.
• The federal Agency for Toxic  Substances  and Disease  Registry
  (ATSDR) as well  as state health departments could be better utilized
  to provide more timely health effects data and data interpretation.
• More training for  fire fighters and other responders is recommended.
  The training programs need to emphasize rapid identification of hazar-
  dous substances involved in an emergency. The significant volumes
  of new SARA information on specific locations of hazardous materials
  used by particular industries must be assimilated into training up-
  dates for local emergency responders.
• Consideration should be given to the creation of computerized data
  base capabilities  for local emergency  responders. An appropriate
  mobile command vehicle might have access to this system.
• Sampling and analysis protocols for emergency responders should
  be developed.

SOURCES
1. Trauth, J. M., et al., Economic and Policy Implications of the January 1988
  Ashland Oil Tank Collapse in Allegheny County, Pennsylvania, prepared for
  the Allegheny County  Planning Department, prepared by the Center for Social
  & Urban Research and the Center for Hazardous Materials Research, Univer-
  sity of Pittsburgh,  Pittsburgh. PA, July, 1989
2. U.S. EPA Region in Emergency Response Team, Evaluation of the Response
  to the Major Oil Spill at the Ashland Terminal,  Floreffe, PA by the Incident-
  Specific Regional Response Team, October, 1988
3. Laskowski, S.L., and Voltaggio,  T.C., The Ashland Oil Spill of January
  1988—An EPA Perspective; U.S. EPA Region  IH; October, 1988
4. University Center for Social and Urban Research, An Evaluation of the Public's
  Perceptions of the Health and Environmental Risks Associated with the January
  2, 1988 Ashland Oil Spill (University of Pittsburgh, Pittsburgh, PA, December
  1988)
5. Center For Hazardous Materials Research, Assessment of Environmental
  Effects from the January 2,1988 Diesel Oil Spill into the Monongahela River,
  Final Report on A Two-Year Study Effort (University of Pittsburgh, Pittsburgh,
  PA, July 1990)
6. Individual interviews with  emergency response personnel representing the
  U.S. Coast Guard Pittsburgh  Marine  Safety Office. Allegheny County
  Emergency Management Agency and Allegheny County Health Department
  Bureau of Environmental Health,  PA
7. Testimony before the Pennsylvania Senate Environmental  Resources and
  Energy  Committee Public Hearing held  Thursday,  January  21, 1988,
  Pittsburgh, PA
8. Testimony before Subcommittee on Transportation, Tourism and Hazardous
  Materials, U.S. House of Representatives,  Washington, DC, Jan. 26, 1988
9. Testimony before The Subcommittee on Environmental Protection, Committee
  on Environment and Public Works, United States Senate, Washington, DC,
  Feb. 4,  1988
       SPILLS *\D EMERGENCY  RESPONSE
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The  "Petroleum Exclusion"  Under CERCLA:  A  Defense To Liability
                                                    Lloyd W.  Landreth
                                         PRC  Environmental Management,  Inc.
                                                      Denver,  Colorado
 ABSTRACT
  When CERCLA was originally passed in 1980, the petroleum industry
 lobbied successfully to exclude the term "petroleum" from the defini-
 tion of a CERCLA §101 (14) hazardous substance. Under CERCLA
 § 101 (33), petroleum is also excluded from the definition of a "pollu-
 tant or contaminant." Exclusion from the designation as a defined hazar-
 dous substance has provided a defense to liability under CERCLA §
 107 when the release of petroleum occurs.
  The scope of the petroleum exclusion under CERCLA has been a
 critical and recurring issue arising in the context of Superfund response
 activities. Specifically, oil that is contaminated by hazardous substances
 during the refining process is considered "petroleum" under CERCLA
 and thus excluded from CERCLA response authority and liability unless
 specifically listed under RCRA or some other statute. The U.S. EPA
 position is that contaminants present in used oil, or any other petroleum
 substance, do not fall within the petroleum exclusion. "Contaminants,"
 as discussed  here,  are  substances  not normally  found  in refined
 petroleum fractions or present at levels which exceed those normally
 found in such fractions. If these contaminants are CERCLA hazardous
 substances, they are subject to CERCLA response authority and liability.
  This paper  discusses the parameters of the CERCLA "Petroleum
 Exclusion." It briefly examines selected state laws, RCRA, the Clean
 Water Act (CWA) and the Safe Drinking Water Act (SDWA) for treat-
 ment of petroleum and petroleum products. And, finally,  this paper
 discusses  new  legislation  regarding oil pollution  liability and
 compensation.

 INTRODUCTION
  Crude oil, and the commercially derived fractions therefrom, repre-
 sent by quantity the  largest volume of hazardous substances in our
 environment today. However, the CERCLA  as amended  by SARA
 specifically excludes oil  and its  fractions  as defined  hazardous
 substances. This exclusion limits Superfund expenditures on sites con-
 taminated by such substances and denies claims based on the strong
 liability scheme of CERCLA/SARA.
  The following sections discuss the current environmental legislation
 on oil, the liability scheme within this legislation and new  legislation
 related to releases of oil in the environment.

 RELEASE OF CRUDE OIL AND DERIVATIVES
 UNDER  CERCLA/SARA
  When the release1  of a hazardous substance occurs in the environ-
ment, statutory authority to address such a release can be found in
CERCLA/SARA and analogous state laws. In establishing liability under
CERCLA/SARA, a key factual element is classification of the substance
released as "hazardous." The term hazardous  substance is defined in
CERCLA § 101 (14), 42 U.S.C. §9601(14)(1990) to mean:
   (A) any substance designated pursuant to section 311(b)(2)(A) of the
   Federal Water Pollution Control Act, (B) any element, compound,
   mixture, solution, or substance designated pursuant to section 102
   of this Act, (C) any hazardous waste having the characteristics iden-
   tified under or listed pursuant to section  3001  of the Solid Waste
   Disposal Act (but not including any waste the regulation of which
   under the Solid Waste Disposal Act has been suspended by Act of
   Congress), (D) any toxic pollutant listed under section 307(a) of the
   Federal Water Pollution Control Act, (E) any hazardous air pollu-
   tant listed under section 112 of the Clean Air Act, and (F)  any
   imminently hazardous chemical substance or mixture with respect
   to which the Administrator has taken action pursuant to section 7
   of the Toxic Substances Control Act. The term does  not include
   petroleum, including crude oil or any fraction thereof which is not
   otherwise specifically listed or designated as a hazardous substance
   under subparagraphs (A) through (F) of this paragraph, and the term
   does not include natural gas, natural gas liquids, liquefied natural
   gas, or synthetic gas usable for fuel (or mixtures of natural gas and
   such synthetic  gas).
  Liability can also be established under CERCLA/SARA to include
release of those substances described as pollutants or contaminants under
CERCLA §101(33), 42 +wS.C. §9601(33) and defined as follows:
   .. .any element, substance, compound, or mixture, including
   disease-causing agents, which after release into the environment and
   upon  exposure, ingestion, inhalation, or assimilation into  any
   organism, either directly from the environment or indirectly by in-
   gestion through food chains, will or may reasonably be anticipated
   to cause death, disease, behavioral abnormalities, cancer, genetic
   mutation, physiological malfunctions (including malfunctions in
   reproduction) or physical deformations, in such organisms or their
   offspring; except that the term "pollutant or contaminant" shall not
   include petroleum, including crude oil or any fraction thereof which
   is not otherwise specifically listed or designated as a hazardous
   substance under subparagraphs (A) through (F) of paragraph  (14)
   and shall not include natural gas, liquefied natural gas, or synthetic
   gas of pipeline quality (or mixtures of natural gas and such synthetic
   gas).
  If the substance  being released into the environment does not come
under the definition of "hazardous" or pollutant  or contaminant, then
CERCLA/SARA is not applicable. Note the last portion of each defini-
tion specifically excludes crude oil and derivatives therefrom as a defined
hazardous substance pollutant or contaminant. With a few words, the
U.S.  Congress denied CERCLA liability to the most voluminous class
of substances released in the  environment today. And  it did so with
                                                                                         SPILLS AND EMERGENCY RESPONSE   969
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poorly worked definitions which have resulted in a variety of attempts
to describe the congressional "intent" of its exclusatory language.
  In 1982, the U.S. EPA Office  of General Counsel described the
liability  under CERCLA for diesel oil contamination of groundwater.2
This memorandum discussion regarded classifying diesel oil as a hazar-
dous substance due to the presence of hazardous substances such as
benzene and toluene. General Counsel concluded that diesel oil and
its hazardous constituents fall within the CERCLA petroleum exclusion,
unless the constituents were found in elevated levels or added after the
product was issued as diesel oil. This early memorandum helped define
the question  which recurs to  this day, "When are crude oil and
derivatives therefrom not subject to the CERCLA petroleum exclusion?"
  In 1983, the General Counsel again issued an interpretive memoran-
dum on  the CERCLA  petroleum exclusion.3 This memorandum con-
cerned releases of gasoline, which in its  refined state always contains
defined  hazardous substances, pollutants or contaminants. The inter-
pretation posed to the General  Counsel  was that only raw  gasoline,
without  any  additives, comes under the petroleum exclusion. The
General  Counsel determined that such an  interpretation would enervate
the intent of  CERCLA. As with  diesel  oil, the conclusion was that
blended gasoline, as it is issued in a refined state, comes within the
petroleum exclusion.  Again, the  addition  of hazardous substances,
pollutants or contaminants to blended gasoline after refining may nullify
the applicability of the petroleum exclusion.
  Subsequent case law upheld the interpretation offered by the U.S.
EPA General  Counsel  in the 1982 and 1983 memoranda. In the  1984
case  U.S. v  Wade* the  court  held that fuel  oil came within the
petroleum exclusion, regardless of the hazardous components found
to normally occur therein. A 1986 case, Mormon Group, Inc. v. Rexnord,
Inc. ,' came to a similar conclusion. In that case the substance at issue
was "cutting oil." Based on the  facts, the court  held that this specific
cutting oil came within the petroleum exclusion.
   As an apparent result of receiving numerous interpretive inquiries
on the petroleum exclusion from the U.S. EPA Regional  Counsel, the
General Counsel in  1987 issued yet another memorandum on the sub-
ject.6 In this memorandum, the General  Counsel gave a history of the
U.S. EPA's position  regarding the CERCLA petroleum exclusion.  At
issue was the applicability of the exclusion to "used oil." The General
Counsel's conclusion was that oil,  having  been used and combined with
hazardous substances,  pollutants and contaminants, did not come under
the  petroleum exclusion.7 The General  Counsel further noted,
"moreover, under this interpretation not all releases of  used oil will
be subject to CERCLA since used oil does not necessarily contain non-
indigenous hazardous  substances  or hazardous  substances in elevated
levels. Although used oil is generally "contaminated" by definition,
see e.g., RCRA Section 1005 (36), the impurities added by use may
not be CERCLA hazardous substances."
   The 1987 the U.S. EPA memorandum was followed by  a case whose
facts were similar to the memorandum discussion. In State of \\bshington
v. Time  Oil Co. * the defendant was held liable for the release of hazar-
dous substances which contaminated groundwater supplies.  In this
opinion, the  court discussed used oil that was present and stated,
    ". . .some of the contaminants found on the Time Oil property were
    found in amounts in excess of the amounts that would have occurred
    in petroleum during the oil refining process. Other substances found
   on the property would not have occurred due  to the refining process.
   The  "petroleum exclusion."  CERCLA §104(a)(2), will not operate
   to exclude Time Oil from liability."

Time Oil at  687 F. Supp. 532.
   The Time Oil case was followed by the most recent definitive opinion
on the petroleum exclusion. In  Wilshire  Westwood. Assoc. v. Atlantic
Richfield.10 the Ninth Circuit court was asked to  interpret the  CERCLA
petroleum exclusion as it applies to unrefined and refined gasoline. The
facts of this case were  similar in form to the 1983 U.S. EPA memoran-
dum discussed above." In this case, a number of CERCLA hazardous
substances were found to exist in the gasoline that had been released
into the  environment. These hazardous substances were those normal-
l\ occurring  or added to gasoline in the refining process. In finding
that gasoline comes within the petroleum exclusion, the court concluded,
"the petroleum exclusion in CERCLA does not apply to unrefined and
refined gasoline even though certain of its indigenous components and
certain additives during the refining process have themselves been
designated  as  hazardous substances  within  the  meaning  of
CERCLA."12 The court, in this opinion, relied in part on the 1987 U.S.
EPA memorandum discussed above.13 It is unclear how the U.S. EPA
interpretation could carry such great weight when the word "petroleum"
is not defined in CERCLA.14

STATE CERCLA-TYPE STATUTES
AND THE PETROLEUM EXCLUSION
  Under the federal CERCLA statute, the petroleum exclusion covers
not only crude oil, but also a large number of crude oil derivatives.
While CERCLA is  expansive in jurisdiction, this  statute does not
preclude several states from developing legislation wherein the release
of petroleum and  its derivatives is actionable. °
  A list of states with CERCLA-type legislation where petroleum and
its derivatives are classified as hazardous substances is beyond the scope
of this  paper.  However,  CERCLA-type  statutes of Montana16 and
Washington17 provide  examples of  state laws  where petroleum is
defined  as an actionable substance.

PETROLEUM PRODUCTS SUBJECT
TO REGULATION UNDER RCRA
  While CERCLA may exclude  petroleum products from the defini-
tion  of hazardous substances,  a recourse to  liability for release of
petroleum may be available under RCRA. As with CERCLA hazar-
dous substances, petroleum or crude oil is not defined as a RCRA hazar-
dous waste.18
  If the constituents of the petroleum or oil product are considered a
hazardous waste, then a release may be actionable under RCRA. And
a finding that various components of petroleum may be considered a
RCRA hazardous waste when combined with soil is more likely under
the  new Toxicity Leaching Characteristic Procedure.19 For cleanup
liability to be established under RCRA, the release must occur  from
a transportation, treatment, storage or disposal facility. The release is
actionable both within and outside of the facility boundaries.20
  Perhaps the greatest source of petroleum contamination comes from
leaking underground storage tanks (USTs). In response to this obvious
problem, Congress added Subtitle I to RCRA.21 This subtitle provides
requirements for new USTs, testing of in place  USTs, and remedies
for  releases from USTs. To ensure that releases from USTs  were
remedied, Congress provided funds under SARA  to assist in the
financing of cleanup costs.22 The scope of the term UST is defined in
Subtitle I, as is the  word "petroleum."23
  RCRA UST legislation provides an avenue for cleanup liability when
a release of petroleum or crude oil occurs from a regulated tank. While
this legislation is a positive step in the direction of remediating all land-
based releases of crude oil and petroleum, it is not as far reaching as
CERCLA in its liability scheme.

PETROLEUM PRODUCTS  SUBJECT TO
REGULATION UNDER FWPCA
  Should a release of crude oil  or derivatives therefrom occur upon
the navigable waters of the United States, then said release is actionable
under  the  Federal Water  Pollution Control Act (FWPCA).24 The
FWPCA has a  specific section that  details the scope of liability tor
releases of oil.25

PETROLEUM PRODUCTS SUBJECT TO
REGULATION UNDER SDWA
  The Safe Water Drinking Act (SDWA) has as its primary purpose
the protection of public  drinking water supplies from contamination.26
For a substance to be actionable under the SDWA, it must exceed the
Maximum Contaminant Level (MCL) for that substance. The SDWA
does not identify an MCL for crude oil  or petroleum. However,
hazardous substances found in petroleum such as benzene or xylenc
have established MCLs.
       SPILLS AND EMERGENCY RESPONSE
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  The SDWA also established a permit program for the underground
injection of wastes. The Underground Injection Control (UIC) Permit
Program regulates those persons utilizing underground injection wells
for waste disposal.27 It appears injection  of oil or petroleum wastes
would be regulated or prohibited if such injection would endanger
drinking water resources.

PETROLEUM PRODUCTS SUBJECT TO REGULATION
UNDER THE OIL POLLUTION ACT OF 1990
  At the time of submittal of this  paper, proposed legislation entitled
the "Oil Pollution Act of 1990"  (OPA) had not become law. The most
recent information available on this legislation was the conference com-
mittee report on the bill.28 OPA  concerns and coverage focuses on
costal and marine environments. This legislation is obviously a reply
to the recent oil spills in  Alaska, the Gulf of Mexico, and along the
east coast of the United States  The term  oil is defined as  follows:29
   "... "oil" means oil of any kind or in any form including, but not
   limited to, petroleum, fuel oil, sludge, oil refuse, and oil mixed with
   wastes other than dredged spoil, but does not  include petroleum,
   including crude oil or any fraction thereof, which is  specifically
   listed or designated as a hazardous substance under subparagraphs
   (A)  through (F) of section 101(14)  of the [CERCLA] (42 U.S.C.
   §9601(1990)) and which is subject to the provisions of that  Act."
  Liability for discharge of oil into the costal and marine environments
covered by the OPA is the same  as in the CWA.30 One of the main
distinctions of the OPA is the establishment of a fund for the removal
costs incurred to cleanup the discharge.31 The OPA appears in  many
ways to be a combination of CERCLA and the CWA. It does provide
a true liability scheme for discharge of oil and derivatives therefrom.
However, this liability is limited to those environs described by the OPA.

CONCLUSION
  The petroleum exclusion is alive and well under CERCLA. When
a defined hazardous substance exists within crude  oil or petroleum in
levels exceeding the  norm,  CERCLA's  strong liability  scheme is
unavailable. There are a number  of valid public policy arguments to
support the petroleum exclusion,  but public policy should not be allowed
to interfere with our need for great care in exploration, transportation,
use and disposal of crude oil and its derivatives.  These substances are
truly hazardous and any release should be immediately addressed and
remediated by the person responsible parties.
  It appears that petroleum and oil will be treated as other hazardous
substances when discharged in  our costal  and marine environments.
And under the new Toxic Characteristic Leaching Procedures (TCLP),
RCRA corrective authority may be available for  cleanup of a wider
variety of oil and petroleum wastes. But there remain a number of land-
based sites in the United States where releases of crude oil and petroleum
are not actionable under federal law. On a number of these sites the
responsible party will initiate cleanup. On those sites without a iden-
tifiable or financially viable responsible party, the Hazardous Substance
Trust Fund is unavailable unless the release of a hazardous substance
can be identified.
  Public policy intends to represent the collective good of the popula-
tion at large. It is incongruous that the public and private industry
support the Hazardous Substance Trust Fund and yet a burdensome
exclusion stands in the way of using this fund for its intended purpose:
the cleanup of "hazardous substances" in our environment.

REFERENCES
 1. Release is defined in CERCLA §101(22), 42 U.S.C. §9601(22) as:
    ...  any spilling, leaking, pumping, pouring, emitting, emptying, discharging,
    injecting, escaping, leaching, dumping, or disposing into the environment
    (including the abandonment or discarding of barrels, containers, and other
    closed receptacles containing any hazardous substance or pollutant or con-
    taminant), but excludes (A) any release which results in exposure to per-
    sons solely within a workplace with respect to a claim which such persons
    may assert against the employer of such persons, (B) emissions from the
    engine exhaust of a motor vehicle, rolling stock, aircraft, vessel, or pipeline
    pumping station engine, (C) release of source, byproduct, or special nuclear
    material from a nuclear incident, as those terms are defined in the Atomic
    Energy Act of 1954, if such release is subject to requirements with respect
    to financial protection established by the Nuclear Regulatory Commission
    under section 170 of such Act, or, for the purposes of section 104 of this
    title or any other response action, any release of source byproduct, or special
    nuclear material from any processing site designated under section 102(a)(l)
    or 302(a) of the Uranium Mill Tailings Radiation Control Act of 1978, and
    (D)  the normal application of fertilizer.
 2. Perry, R.M.,  Applicability of CERCLA to Contamination of Groundwater
    by Diesel Oil, U.S. EPA Memorandum, Washington, DC, December 2,  1982.
 3. Barnes, A.J., Applicability of the  CERCLA Petroleum  Exemption to
    Gasoline Spills, U.S. EPA Memorandum, Washington, DQAugust 12,  1983.
 4. United States v. Wade, 14 E.L.R. 20440 (April 1984)
 5. The Mormon Group, Inc., v. Rexnordlnc., No. 85C 7838 (N.D. 111. June
    16, 1986) rev'd on other grounds, 822 F.2d 31 (7th Cir. 1987).
 6. Blake, F.S., Scope of the CERCLA Petroleum Exclusion Under Sections
    101(14) and 104(a)(2), U.S. U.S. EPA Memorandum No. 9838.1, July-31, 1987.
 7. Note that the response to a release of such used oil can only address the
    cleanup of those hazardous substances  found within the used oil, and not
    the originally constituted oil.
 8. State of Washington v. Time Oil Co., 687 F. Supp 529 (W.D. Wash. 1988).
 9. Id. at pg. 532.
10. Wilshire Westwood Assoc.  v. Atlantic Richfield Corp., 881 F. 2nd 801 (9th
    Cir. 1989). For an excellent article on  this decision see, Bailer, J. " The
    Petroleum Exclusion-Stronger Than Ever  After  Wilshire Westwood"
    Southwestern Law J.  915 (1990).
11.  See footnote  5 supra.
12. Wilshire Westwood, 881 F.2d at 810.
13. See U. S. U.S. EPA Memorandum cited  in footnote 6 supra.
14. Further, the adulteration of naturally occurring crude oil with hazardous
    substances, pollutants and contaminants and yet excluding the end product
    from CERCLA is incongruous. The level of authority given to the U.S. EPA
    General Counsel memoranda may be questionable in light of U.S. v.  Zim-
    mer Paper Products,  Inc., 20 ELR 20556 (December 1989)
15. Newsweek, "E pluribus, plures," pgs. 70-72, November 13,  1989. And see
    generally  Landreth, L.W. and K.M. Ward, "Natural Resource Damages:
    Recovery  Under State Law Compared with Federal Laws" 20 ELR 10134,
    10137 (April 1990).
16. Mont. Code Ann. tit 75, Ch. 10, pt. 701(6), (a)-(d). (1989)
17.  Wash. Rev. Code  Ann, tit. 70, Ch. 70.105 D (1989)
18. 40 CFR Part 261
19. 55 Fed. Reg. 11798 (March 29, 1990).
20. 42 U.S.C. §§3004(v) and 7003. Note that 3004(v) only applies to owners
    and operators of a facility.
21. 42  U.S.C. subchapter IX.
22. 26 U.S.C. §9508
23. 42  U.S.C. §9001.  The definition of petroleum is  stated in §9001(8) as:
    .. .petroleum, including crude oil or any fraction thereof which is liquid
    at standard conditions of temperature and pressure  (60°F and 14.7 psia).
24. 33 U.S.C.  §1251 et. seq. Note that §1321 details areas in addition to navigable
    waters where a release is actionable.
25. 33 U.S.C. §1321
26. 42 U.S.C. §300f et.  seq.
27.  42 U.S.C. §300h
28. Conference Report on H.R. 1465. Congressional Record - House H6232
    August 1, 1990.
29. Id. at H6234, §1001(23).
30. Id. at H6234, §1001(17).
31. Id. at H6238, §1013.
                                                                                                   SPILLS AND EMERGENCY RESPONSE    971
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                    The Development  and  Status of the U.S.  EPA's
                         Emergency Response Notification  System

                                                    David Ouderkirk
                                        U.S. Environmental Protection Agency
                                             Emergency Response Division
                                                     Washington,  DC
                                                      Robert Walter
                                          U.S. Department of Transportation
                                             Transportation System Center
                                               Cambridge,  Massachusetts
                                                      Debra M. Lee
                                             Booz, Allen & Hamilton  Inc.
                                                   Bethesda, Maryland
ABSTRACT
  A major objective of the U.S. EPA's Emergency Response Program
is to evaluate and, if necessary, respond to releases of oil and hazar-
dous substances that pose a threat or potential threat to public health
and/or the environment. To manage this function appropriately, the U.S.
EPA in coordination with other members of the emergency response
community including the National Response Center (NRC) and the U.S.
Coast Guard (USCG), developed a nationwide system to receive and
process notifications of releases.
  This nationwide system consists of notification data collection and
reporting processes that meet the legislative and regulatory requirements
of the Clean Water Act (CWA), section 311; CERCLA of 1980, sections
103 and 104; SARA; and the National Oil and Hazardous Substances
Pollution  Contingency Plan (NCP), sections 300.125, 300.300 and
300.405.
  Central to collecting, processing and reporting release notifications
among the NRC, U.S.  EPA and USCG is a national computer data base
called, the Emergency Response Notification System (ERNS). The data
base is maintained by  the Department of Transportation's Transporta-
tion Systems Center (TSC) through an interagency agreement with the
U.S. EPA. The data base contains release notification data reported each
time a call is made to the NRC, U.S. EPA or USCG.
  This paper focuses on the process used  in the  development and
advancement of ERNS and on the trends of oil and hazardous substance
releases collected by  ERNS for the past three years.

INTRODUCTION
  The Emergency Response Notification System (ERNS) supports two
U.S. EPA Emergency Response Program processes: release notifica-
tion and release verification. The notification process involves receiving
and capturing data on all reported notifications of a release. The verifica-
tion process involves making an initial release assessment, a response
evaluation and then, if necessary, planning  a removal action for the
release.
  The U.S. EPA portion of ERNS represents release notification reports
collected by each of the 10 U.S. EPA Regions using a Regional ERNS
data base. The Regional ERNS is a stand-alone Personal Computer (PC)-
or Local Area Network (LAN)-based system which standardizes the
process of collecting,  documenting and analyzing data on releases of
oil and hazardous substances specific to each Region.
  Each time a call  is  made to the U.S. EPA to report a release of oil
or a hazardous substance, the data are put into the Regional ERNS data
base as shown in Figure 1. Regional notification and verification data
are sent electronically to the National ERNS data base on a weekly
basis. At the same time, NRC notification reports, that are referred to
the U.S. EPA via phone for verification and response evaluation, are
also sent electronically to the respective Regional ERNS data base.
  By standardizing the collection, processing and reporting of oil and
hazardous substance release notifications through the use of ERNS,
the emergency response community has achieved consistent data col-
lection,  reduced operational differences among entities receiving
notifications and streamlined data sharing among the numerous and
widely dispersed members of the response community. The objective
of this paper is to describe the process used to develop ERNS and some
of the factors that led to its successful implementation.
                        National ERNS
                EPA ERNS - Regional Process
     Initial
   Spill Phone
   Notification
Initial Notification
   Forms
EPA Regional
ERNS Database
                        fa-.
 Batch Upload
Electronic Data
  Transfer
(Regional Data)
 oomsc
National ERNS
 Database
                                     Batch Download
                                     Electronic Data
                                       Transfer
                                      (NRC Data)
                           Figure 1
              Emergency Response Notification System
ERNS DEVELOPMENTS
YESTERDAY, TODAY and TOMORROW
  ERNS development began in 1986. The objective was to meet the
functional and regulatory requirements for recording and maintaining
data collected from the notifications of oil and hazardous substances.
Since then, ERNS has expanded its objective to include the assessment
of notification data for incident and  program management analyses.
  ERNS was developed and implemented in two phases as shown in
972   SPILLS AND EMERGENCY RESPONSE
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Figure 2: Phase I documented initial release notification information
and Phase n expanded the focus of information flow to assessment and
 PHASE I
 Documented Initial release
 notfflcatlon data for:
 • Initial Incident evaluation
 . Transmission to national ERNS
 . Responding to Information
 requests
                    PHASE II
                     Enhancing ERNS
                     Capabilities To
                     Support Release
                     Verification
                   Focus Information flow to
                   assessment and response:
                   • Verifies Initial Information
                   • Characterizes Incident sources/causes
                   . Documents Incident disposition
                                            PHASE II
                                            Developing ERNS
                                            Into An Incident
                                            Analyses and
                                            Program
                                            Management Tool
                                            Target Initiatives on:
                                            • Establishing program definitions
                                             for ERNS data
                                            • Improving data quality through
                                             training and audit reports
                                            • Expanding data access and
                                             usage
     1986                   1988                   1990s

                           Figure 2
                  ERNS Developments by Phase
  A phased systems development approach was taken in order to: (1)
 provide ERNS users sufficient time to understand and test how ERNS
 capabilities would or would not meet specific data and work needs and
 (2) permit the ERNS development team to gain a thorough understanding
 of removal program data and operational requirements and produce
 results within a short time frame. The following paragraphs describe
 ERNS developments by phase.

 Phase I: Building ERNS Notification
 Data Collection Capabilities in 1986
  Prior to ERNS development, collection of notification data was a
 manual and paper-intensive process.  At an April 1986 meeting  with
 federal emergency response personnel including the NRG, USCG, TSC,
 U.S. EPA Emergency Response Division (ERD)  Headquarters  (HQ)
 personnel and U.S. EPA Regional On-Scene Coordinators (OSCs), 85
 critical notification data elements were defined as the national data set.
 The U.S. EPA and TSC participants later became the U.S. EPA ERNS
 Work Group. The Work Group concept provided and continues to pro-
 vide, a core team that ensures that ERNS user needs are addressed on
 all current and new system initiatives  and that continual improvement
 is built into the operation and maintenance of the  system.
  To obtain the national data set for  each notification, report forms
 were developed and completed by U.S. EPA Regions manually. A copy
 of the forms was sent to TSC for data entry into a National ERNS data
 base. While the pre-ERNS process met legislative and regulatory data
 collection requirements, data handling and processing problems were
 encountered. They included: (1) notification forms being  completed and
copied illegibly; (2) form contents varying by Region, thereby hampering
data entry speed and causing inconsistent data collection  and interpreta-
tion; (3) use of different abbreviations and acronyms which hampered
data retrieval; and (4) poor notification reporting accountability for
program planning and management.
  Tb address several of these problems, ERNS Phase I development
was initiated to automate the processes of capturing Regional notifica-
tion data and sending the forms to TSC. The ERNS  role in Phase I
was to document notifications at the Regional level on standard notifica-
tion report forms. Regional staff would then either mail a copy of the
form to TSC or enter the data into ERNS which would transmit the
data electronically to the National data base. In addition, Regions were
requested to list Region-specific data elements. These data typically
included data for response  tracking and referral.
  ERNS Phase I was developed for stand-alone PCs using dBASEm
and was pilot tested in U.S. EPA Regions n and VI. The pilot program
served as a test for monitoring real-world performance  of ERNS.
Regional piloting also  allowed  direct system support by the ERNS
development team. The ERNS development team concentrated on the
two pilot Regions' systems  to ensure  smooth change  integration and
full system operability before implementation in the remaining Regions.
ERNS Phase I became operational in October 1986.

Phase U: Enhancing ERNS Capabilities to Support
Release Verification in 1988 and Developing ERNS Into
An Incident Analyses and Program Management Tool in the 1990s

  ERNS Phase n has focused and continues to focus, on improving
the Emergency Response Program's ability to characterize actual in-
cidents by providing information on the nature of the release for response
evaluation. While basic notification data collected by  ERNS Phase I
helps an OSC decide whether a U.S. EPA response is warranted, Regions
follow up on most, if not all, notifications to obtain more detailed in-
formation. This information is obtained by calling State/local contacts
at the scene or by an OSC or an authorized contractor visiting the site.
It is the information collected from these activities that provides the
key data gaps during response determination.
  In collecting after-the-fact or verification data,  the  emphasis is on
collecting as much data as possible on the release and to ensure that
the data are accurate and reliable enough to make a sound response
determination. After-the-fact  data provide a clearer,  more complete
picture of the accidental release. It provides key data that substantiate,
verify or revise data collected during the initial release notification.
It is this level of detail, accuracy and completeness that the U.S. EPA
management needs in order to make sound planning and  budgeting deci-
sions and to report program activities accurately to Congress and the
public.
  ERNS Phase n focuses on enhancing system capabilities by collecting
and modifying detailed after-the-fact data on a release and streamlining
the NRC data transfer process. ERNS  Phase n provides the capability
to:  (1)  record additional data  elements specific to verified incidents,
along with the original notification data; (2) continually update the status
of a verified incident; (3) receive notifications, originally received by
the NRC, automatically  through electronic transmissions from the
National ERNS data base;  (4) integrate user aids, such as chemical
and location tables, in the data capture process; and (5) expand Regional
access to ERNS by upgrading to a multiuser LAN environment.
  Additional features such as password security, variable fiscal year
data, cursor movements,  restricted input fields, on-line help, popup
screens, screen colors, archived spill records, free-form notepad, backup
procedures and NRC data transfer are also included in ERNS. To ensure
that ERNS Phase n features are appropriate for Regional ERNS opera-
tions,  they  are demonstrated at National ERNS conferences  for
maximum user suggestions and are tested  in a pilot Region  for real-
world performance.
  ERNS Phase n telecommunications  enhancements and user  aids
reduce the data input workload in the  U.S. EPA Regions significantly.
The telecommunications enhancements enable each Region to keep then*
individual notification data base current with the National notification
data base. ERNS Phase n ensures that the 10 distinct Regional systems
operate in a parallel fashion with one another and merge effectively
                                                                                              SPILLS AND EMERGENCY RESPONSE   973
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with NRC and USCG data to create the centralized National ERNS
data base. This merging of data bases saves resources and improves
the completeness and quality of the data.
  ERNS today encompasses all of these data capture and telecom-
munications capabilities. As ERNS users become increasingly skilled
in using ERNS as a notification data collection tool, they also  identify
ways of applying ERNS data to response activities. ERNS' function
is evolving from strictly an initial  notification data collection  system.
ERNS is used increasingly to support incident and program manage-
ment analysis,  emergency preparedness and  planning,  U.S. EPA
enforcement and responses to public and private information requests.
To meet these dynamic needs, the U.S. EPA's ERD has begun several
initiatives in fiscal year 1990 including: (1) establishing program defini-
tions for ERNS data to ensure consistent interpretation and usage; (2)
improving data quality for response determination; and (3) expanding
data access for information queries and public use.

KEYS TO ERNS SUCCESS
  ERNS success is attributed largely to the frequent and dynamic com-
munication among the ERNS Work  Group members and the close
working relationships among the  U.S. EPA, TSC, NRC and  USCG.
Regional communications cover topics  such as assistance on ERNS
operations and ad hoc reports; data quality assurance and data control
issues; input and feedback on HQ activities; and working through and
testing  planned  system enhancements  and  training  activities.
Communications with other federal  agencies cover topics  such as
National ERNS data base integrity and data quality issues; informa-
tion distribution to Congress and the public; and implications  of other
federal emergency response initiatives, such as the July 1990 promulga-
tion of the final rule on "Reporting Continuous Release of Hazardous
Substances."
  This section describes the key factors that contributed  to the suc-
cessful development and implementation of ERNS. These factors include
extensive user participation from the inception of ERNS; keeping ERNS
simple and flexible; proactive development and implementation  in-
itiatives; and maintaining ERNS visibility to management and visibility
to the emergency response community.

Extensive User Participation From The Inception Of ERNS
  The ERNS  Work Group established in 1986 has been and continues
to be the round table discussion forum for addressing ERNS program
requirements  and user needs on all current and new initiatives. The
Work Group consists of ERD HQ personnel. Regional OSCs and pro-
gram staff who represent U.S. EPA  Emergency Response Program users
and the TSC and U.S. EPA ERNS  development team who  support the
National and Regional ERNS data bases respectively. As illustrated in
Figure 3, the  ERNS Work Group is central to system management in
addressing programmatic and system issues and coordinating and com-
municating ERNS  activities within the U.S.  EPA, with its federal
counterparts,  NRC and USCG and with the public.
  A participatory development and implementation approach is used
to ensure that ERNS contains usable and practical features for U.S.
EPA Regional users. The overall  approach consists of:
•  Identifying requirements or improvement areas for ERNS
•  Demonstrating a system improvement concept to the entire Work
   Group usually at the National ERNS conference
•  Incorporating the new capability  into ERNS  if the feedback is
   favorable
•  Conducting a Regional pilot test for  real-world performance
•  Refining the capability based on Regional  pilot results
•  Implementing the enhancements or improvements in the remaining
   Regions
•  Operating,  maintaining and monitoring the system.
  All or parts  of this approach have been used successfully for a variety
of  ERNS  initiatives—from implementing   system changes  and
improvements to developing training courses and procedural guidance.

keeping ERNS Simple and Flexible
  Mam of ERNS users were and are first  time PC users. The way ERNS
  'looks and feels' is, therefore, important to its initial and continued use.
  With this in mind, ERNS was developed as a menu-driven system with
  tables which lead users through its operations. Additionally, the phased
  development approach and Regional pilot tests helped pace and tailor
  the introduction of new ERNS features and capabilities with users'
  knowledge and comfort with PCs and the system. The human/machine
  interactions also contributed to ERNS success. Human/machine inter-
  actions took into account how ERNS needed to 'look and feel' in order
  to ease any  user discomforts with using a computer for the first time.
   Requirements
Opcral!
    Implementation
     Extensive User
 Participation from the Start
                        Development
                     Pilot Test and
                       Refine
 Proactive Development
  and Implementation
      Initiatives
  ERNS Strategic Plan
                                                  Keeping ERNS
                                                Simple and Flexible
Maintaining Visibility to
 Management and the
 Emergency Response
    Community
                                ERNS National
                                Conferences
                              Figure 3
                        Keys to ERNS Success
    Not only does ERNS need to be easy to use, but it also needs to be
  flexible to support evolving program and user needs and changes in
  PC technology. As users became more knowledgeable and confident
  in the system, ERNS usage began to grow and change.  ERNS users
  grew to need more system capabilities as evidenced by the number of
  features added to ERNS in Phase n. ERNS maintains its simplicity
  to accommodate new users while providing expanded capabilities for
  more sophisticated users. In keeping with the Agency's direction in the
  use of PC LAN technology, ERNS was also upgraded from a single
  user system on a stand-alone PC to  a multiuser system operating on
  a LAN. Today, ERNS initiatives include addressing an evolving and
  growing need by the Emergency Response Program and  the public to
  use ERNS data for  incident  analysis in addition to the notification
  analysis performed today.

  Proactive ERNS Development and Implementation Initiatives
    Throughout development and implementation, ERNS  Work Group
  members defined what ERNS should do and what ERNS needs to do.
  The ERNS development team designed and developed how ERNS would
  operate and worked closely with Regional OSCs and program staff in
  testing and refining ERNS operations and user interface.
      SPILLS AND EMERGENCY  RESPONSE
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   Following ERNS Phase I implementation, the ERNS development
 team began providing technical support to ERNS Regional users. The
 Team provides user assistance more than the telephone; uses software
 which allows remote ERNS diagnostics, repair and assistance; and
 obtains user suggestions and feedback on ERNS operations and uses
 regularly. By having continual contact with Regional users, the ERNS
 development team has tracked recurring questions and problems and
 has suggested ERNS improvements based on first-hand knowledge of
 how ERNS is being used. This close working relationship keeps ERNS
 aligned with the emergency response support needed by the Regions.

 Maintaining ERNS Visibility  to Management and
 Visibility to the Emergency Response Community
   Management support and ERNS visibility to the emergency response
 community were obtained through the U.S. EPA's Emergency Response
 Program management briefings, environmental conference presenta-
 tions and public relations brochures. Fundamental to ERNS success
 is its well-established reputation and use by federal agencies and an
 increasing number of state and local agencies and commercial firms.

 NOTIFICATION TRENDS IN OIL
 AND HAZARDOUS RELEASES
   ERNS captures data on the initial notification of a release and on
 verified releases. With the 85 notification data elements, the following
 data are collected: the notification caller, the discharger and the released
 substance; the release location, date and time; the release source,
 medium and cause; the potential human health risks or imminent danger;
 and actions already underway to mitigate the reported release or release
 threat.
   Since October 1986, more than 95,000 release notifications have been
 collected by ERNS,  including 49,000 release notifications  for  oil
 releases. In the past two years, the total number of notifications has
 increased slightly with 29,874 reports in 1988 and 34,089 reports in
 1989. Figure 4 shows the distribution of notifications received since 1987.
                1987            1988             1989
                                YEAR
                            Figure 4
            ERNS Trends: Total Oil, CERCLA, and Other
                        1986 Through 1989
  As seen in Figure 4, the number of oil soil notifications in the last
three years has remained stable, showing only an increase of 571 reports
more than  the three-year period. In contrast,  reports of CERCLA
substance releases have increased steadily with 2000 more reports in
1989 than in 1987. The increase in CERCLA substances release reports
may be attributed to an actual increase in the number  of releases, an
increase in awareness of reporting requirements and/or compliance with
 spill reporting  requirements, as well as  an improvement in data
 recording and record-keeping used by the federal government.
   Since 1987, there have been more than  16,000 CERCLA release
 notifications. More than 75% of these reports identified the source of
 the reported release as a fixed facility-related incident.  Highway and
 rail incidents comprise another 15% of the reported sources of CERCLA
 notifications. Figure 5 provides the complete distribution of reported
 release sources  resulting in CERCLA notifications for  the last three
 years.
     FIXED FACILITY 76.6*
                                                UST 1*
                                                MARINE 1.34%
                                                PIPELINE 2.88%

                                               MISSING 3.66%
                                            RAIL B.69%


                                     HIGHWW 9.03%
                             Figure 5
             CERCLA Release Notifications by Source From
                           1987 to 1989
  The five CERCLA substances most frequently reported released, for
each of the last three years are shown in Figure 6. These most released
chemicals include PCBs, chlorine, sulfuric acid, sodium hydroxide and
anhydrous ammonia. PCBs have remained the most frequently reported
CERCLA hazardous substance for all three years. Figure 6 shows an
increase  of more than  100% in the number of anhydrous ammonia
                                                                      1000
                                                                          NUMBER OF NOTIFICATIONS
                                                                                  1987
                                                                                                     1988
                                                                                                                        1989
      §•  PCB            ^ SULFURIC ACID   ED ANHYDROUS AMMONIA
      E1H  CHLORINE       HID SODIUM HYDROXIDE
                            Figure 6
                         "ERNS Top 5"
                  CERCLA Hazardous Substances


release notifications in 1988 more than 1987. Although there was a slight
decrease  in the number of anhydrous ammonia reports  in  1989,
anhydrous ammonia remained the second  most frequently reported
CERCLA substance for that year.
  More than 47,000 oil release notifications have been received since
1987. Incidents related to fixed facilities, such as refineries and oil wells,
account for 49% of the  oil reports; 25% have been marine related.
Figure 7 provides the complete distribution of CERCLA notifications
since 1987.
  The most frequent oil substances released in  1987, 1988 and 1989
are shown in Figure 8. As the graph shows, crude oil reports increased
                                                                                           SPILLS AND EMERGENCY RESPONSE   975
-------
more than 40% from 1988 to 1989 and surpassed the number of diesel
oil reports. These data reverse the trend established in 1987 and  1988
                                FIXED FACILITY 4fi 1%
          MARINE 2* 7%
                                              IGHWAY 10 2%
                                     PIPELINE 12%
                             Figure 7
                  Oil Release Notifications by Source
                        From 1987 to 1989
when diesel oil releases were the most reported oil releases. The graph
also shows a significant drop in the number of waste oil reports from
approximately 1,100 in 1987 and 1988 to 670 in 1989.

CONCLUSIONS
  ERNS is a critical tool in streamlining and standardizing the collec-
tion and dissemination of information  on notifications  of oil and
hazardous substance releases.  Its success is largely a result of the
frequent and dynamic communications among members of the emer-
gency response community including the U.S. EPA, NRC and USCG.
                                                                           NUMBER OF NOTIFICATIONS
             1987
         CRUDE OIL

         VWSTE OIL
                                1988
VSl DIESEL FUEL

(HUD HEATING OIL
                                                   1989
                                           CD GASOLINE
                             FigureS
                 ERNS Top 5" Oil 1987 Through 1989

With a solid data base of release notification information, ERNS is now
being developed to support incident and program management analysis,
emergency preparedness and planning,  U.S.  EPA enforcement and
responses to public and private information requests.
      SPILLS  AND EMERGENCY RESPONSE
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             The  NLM/ATSDR  ANSWER™  Work  Station  with  the
                    TOMES Plus™ CD-ROM Information  System
                               for  HAZMAT Incident Response
            Alan H.  Hall,  M.D., FACEP
               Department of Pediatrics
   University of Colorado  Health Sciences Center
      Rocky  Mountain Poison and Drug Center
                   Denver, Colorado
                 Drs.  Hall & Dabney
          TOMES Plus Information System
                   Micromedex, Inc.
                   Denver, Colorado
                  Betty J. Dabney,  Ph.D.
           Department of Environmental Health
College of Veterinary Medicine and Biomedical Sciences
                 Colorado State University
                   Fort Collins, Colorado
                     Dalton C. Tidwell
              Specialized Information Services
               National Library of Medicine
                     Bethesda,  Maryland
 ABSTRACT
  The time-critical nature of emergencies involving hazardous materials
 demands a means of retrieving needed emergency response, medical,
 and lexicological information rapidly. Transportation-related hazardous
 materials emergencies often occur in locations where access to a
 telephone connection for on-line searching is unavailable and where
 surrounding terrain may complicate or preclude radio contact for
 dispatch-based information transfer.
  The ANSWER™ Workstation was produced by the National Library
 of Medicine (NLM) in conjunction with the Agency for Toxic Substances
 and Disease Registry (ATSDR) to address these issues. This work station
 is based on an IBM-compatible portable computer with a compact disc
 drive and internal modem. If telephone access is available, a gateway
 program called MICRO-CSIN allows for simplified on-line access to
 a wide variety of remote data bases. Pro-Corn provides access to real-
 time weather information from the National Weather Service. A hard-
 disk data base contains information collected during previous emergency
 response situations. Other ANSWER Workstation features are an air
 dispersion plume modeling  package, word-processing and  FAX
 transmission capabilities. The ANSWER Software will also run on a
 desktop IBM-AT or compatible PC.
  The TOMES Plus™ Information System (Toxicology,  Occupational
 Medicine and Environmental Series) is the CD-ROM (Compact Disc-
 Read Only Memory) portion of the ANSWER Workstation, allowing
 over 500 megabytes of information to be provided on-site on a single
 compact disc only 4-3/4 inches in diameter and weighing only 1/2 ounce.
 A menu-driven search software allows even novice users to quickly
 retrieve  required information on over 100,000 individual chemicals,
 accessed by chemical name, synonym, CAS number, NIOSH/RTECS
 number, UN/NA number, STCC number, RCRA Hazardous Waste
 Number, etc.
  The TOMES Plus system currently contains the following data bases
 of particular interest to hazardous materials incident responders:
 HAZARDTEXT™, DOT Emergency Response Guides, HSDB (the
 Hazardous Substances Data Bank produced by  NLM), CHRIS (the
 Chemical Hazards Response Information System produced by the US
 Coast Guard), OHM/TADS (the Oil and Hazardous Materials/Technical
 Assistance Data System produced by the U.S. EPA) and RTECS (the
 Registry of Toxic Effects of Chemical Substances produced by NIOSH).
 Additional data bases on the TOMES Plus disc provide information
 on medical evaluation and treatment, risk assessment, toxicology and
 reproductive hazards. Under development in 1990 are SARATEXT™
 for SARA Title HI Extremely Hazardous Substances medical evaluation
 and treatment  reporting and REPROTEXT™ with rating scales and
 monographs on  the chronic  toxicity  and reproductive hazards of
chemicals.
       The ANSWER Workstation is currently being used by several State
     health departments and hazardous materials response agencies.

     INTRODUCTION
       Emergencies involving hazardous materials may occur anywhere and
     any time. Some crucial aspects of successful HAZMAT  incident
     response involve rapid procurement of adequate data on hazards, tox-
     icity and proper response actions; plotting the anticipated spread of
     released airborne contaminants to determine possible areas for evacua-
     tion; transmission of data and current incident status to other agencies
     or facilities that may become involved in the response; and collection
     of incident-specific data for later evaluation and utilization when similar
     situations occur in the future.
       Because radio or telephone line communications may be difficult to
     achieve, particularly during the initial response phase, as much infor-
     mation as possible should be moved directly to the incident site. The
     concept of a portable work station, able to be carried on airplanes as
     hand baggage (fitting in overhead compartments or under a seat) and
     weighing less than 30 pounds, has been developed by the National
     Library of Medicine (NLM) in conjunction with the Agency for Toxic
     Substances and Disease Registry (ATSDR). The prototype product, the
     ANSWER™ Work station (ATSDR/NLM's Work station for Emer-
     gency Response), encompassing a variety of features required for HAZ-
     MAT incident response and including a CD-ROM data base (the
     TOMES Plus™  Information System from Micromedex, Inc.) is cur-
     rently being beta-tested by a number of state health and HAZMAT
     response agencies.
     ANSWER WORKSTATION FEATURES
       The Event Description File (EOF) is a hard-disk data base enabling
     emergency response personnel to maintain and query  a wide  range of
     information on  previous HAZMAT response events.   HAZMAT
     responders can retrieve actual experience and results from either their
     own or a nationally collated and snared data base of the results of similar
     incident responses. Each individual HAZMAT  response incident and
     the results of various interventions can be recorded in the EOF, retrieved
     by the responding organization and may also be shared nationally with
     other similar agencies. The EOF can also be used to prepare reports
     required for local, state or national agencies, or the National Fire Pro-
     tection Association (NFPA).
       Should information regarding a particular incident need to be shared
     on an urgent basis with other response agencies,  the FAX feature of
     the ANSWER Workstation can be used to transmit hard copy and files
     to fire departments, hospitals, other governmental agencies, etc. Both
     transmission of information and review of FAX files received from
     remote sites can be accomplished. Hard copy can be printed on-site
     as required.
                                                                                   SPILLS AND EMERGENCY RESPONSE   977
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  The Health/Hazard module of the ANSWER Workstation is the
CD-ROM-based TOMES Plus™ Information System developed and
provided by Micromedex, Inc. of Denver, Colorado. CD-ROM data
bases which can be accessed through the ANSWER Workstation are
described below. Any portion of the TOMES Plus Information System
can be printed out in hard copy or sent to the hard disk for local editing
or remote transmission with the ANSWER Workstation FAXing feature.
After telephone line connection is established,  the MICRO-CSIN feature
of the ANSWER Workstation allows simple access to a very wide range
of on-line data bases for retrieval of further  information about hazar-
dous substances. MICRO-CSIN is a gateway program which minimizes
the training required to successfully query remote on-line data bases
for retrieval of feet, numeric and chemical identification data from eight
component vendor systems. TYMENET and Telenet can be used with
MICRO-CSIN through the Communication Parameters feature. The
menu-driven software package Grateful Med, which greatly simplifies
searching NLM's MEDLARS data base, can  also be used  with the
ANSWER Workstation.
  The ANSWER Workstation WEATHER feature uses Pro-Corn to ob-
tain the most recent weather observations from 1,000 National Weather
System reporting stations throughout the United States and Canada from
the Weather Information System developed by the WSI Corporation.
The most applicable plume modeling program for ANSWER Worksta-
tion  users is currently being studied. As soon as a plume model is
available, data such as current  wind direction and  speed, relative
humidity, dew point, etc. can be retrieved with the WEATHER feature
and used in the plume modeling program.
  The ANSWER Workstation also incorporates word processing and
management functions to allow information editing, development of local
"call lists" of crucial personnel, inter- and intraagency locally-defined
communications functions and more. ANSWER Workstation Project
Information is available from Specialized Information Services at the
National Library of Medicine, Bethesda, Maryland. User Support Staff
are available at the Training & Management Systems Division of the
Oak  Ridge Associated Universities, Oak Ridge, Tennessee.

TOMES PLUS CD-ROM  DATA BASES
   The TOMES Plus™ Information System (Toxicology, Occupational
Medicine  and Environmental  Series)  developed and produced by
Micromedex, Inc. of Denver, Colorado, is the CD-ROM (Compact Disc-
Read Only Memory)  portion  of the ANSWER Workstation. The
TOMES Plus system provides more than 500 megabytes of  informa-
tion  available on-site on a single compact disc only 4-3/4 inches in
diameter and weighing only 1/2, ounce and is accessible  with either
a half-height CD-ROM disc drive which  can be internally mounted in
certain portable personal computers, or an external CD-ROM disc drive
connected to a desktop PC. The unique TOMES Plus system menu-
driven search software allows even novice users to quickly  retrieve re-
quired information on more than 100,000 individual chemicals, accessed
by a  wide variety of identifiers, including: chemical name, synonyms,
CAS number, NIOSH/RTECS number, UN/NA number, STCC number,
RCRA Hazardous Waste Number, etc. After initial query, a resident
function allows  retrieval of all  NIOSH/RTECS (and other source)
synonyms and identifiers to confirm that  the  correct chemical is being
researched.
   The TOMES Plus system currently contains a wide  variety of data
bases which are of particular utility for hazardous materials incident
responders:
•  HAZARDTEXT™ (produced by Micromedex, Inc.) containing a
   review of EMT-paramedic level clinical effects, patient evaluation
  and treatment data, range of toxicity including pertinent workplace
  and  environmental exposure standards and recommendations, a
  thorough review of common handbooks and other primary and secon-
  dary sources of information for fire control, hazards of combustion
  products, environmental hazards, chemical reactivities, physical and
  chemical properties and recommendations for the choice of chemical
  protective equipment
• Frequently-consulted DOT Emergency Response Guides (from the
  Department of Transportation); the entire HSDB (the Hazardous
  Substances Data Bank produced by NLM)  with detailed informa-
  tion  on  the  production,  common  uses,  manufacturing,
  physical/chemical properties and hazard, environmental and poten-
  tial health effects of more than 4,200 individual chemical substances
• CHRIS (the Chemical Hazards Response Information System pro-
  duced by the US Coast Guard) with fire, health, environmental and
  other hazard data on over 1,200 chemicals
• OHM/TADS (the Oil and Hazardous Materials/Technical Assistance
  Data System produced by the U.S. EPA) with information on the en-
  vironmental and health hazards of over 1,000 chemical substances
  and recommendations for cleanup or amelioration of spills or other
  releases
• RTECS (the Registry of Toxic Effects of Chemical Substances pro-
  duced by NIOSH) containing information on the irritant, acute tox-
  icity, genotoxicity, tumorigenicity and reproductive hazards of over
  100,000 individual chemical substances
  Additional data bases on the TOMES Plus disc:
• MEDITEXT™ (produced by Micromedex, Inc.), which provides
  physician-level detailed information on the medical evaluation and
  treatment of patients exposed to hazardous chemicals for use by both
  emergency responders and emergency department or other hospital-
  based medical personnel
• U.S.  EPA's IRIS (Integrated Rjsfc Information System) data base for
  performing risk assessments following releases into air or drinking
  water
• REPRORISK™ series of data bases for the assessment of potential
  chronic exposure and reproductive hazards of hazardous chemical
  exposure
  New TOMES Plus data bases being developed by Micromedex, Inc.
during 1990 are SARATEXT™ for SARA Title m Extremely Hazar-
dous Substances  medical  evaluation and treatment reporting and
REPROTEXT™ with rating scales  and monographs on the chronic
toxicity and reproductive hazards of chemicals.

BETA-TEST  SITES
  The  ANSWER  Workstation with the  TOMES Plus Information
System is currently undergoing beta-testing. Fifteen initial installation
sites have been chosen, including five State health agencies, a city-county
health department, three poison control centers, a county fire depart-
ment, three locations of the ATSDR, the National Library of Medicine
and the Oak Ridge Associated Universities (where training develop-
ment is in progress).

CONCLUSION
  Continuing development of both the informatics and utilities content
and features of the ANSWER Workstation and the TOMES  Plus  Infor-
mation System have promise to make this combination portable/remote
HAZMAT incident response tool an indispensable information and com-
munications resource for  HAZMAT incident response, community
planning and risk assessment.
       SPILLS AND EMERGENCY RESPONSE
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                                                     1990 Exhibitors
 3M Environmental
 Protection Products               0905-0907
 3M Center, Building 223-6S-04
 St. Paul, MN 55144-1000
 612/736-5335

 3M Company - Environmental Protection Prod-
 ucts - 3M Foams. 3M Foams have proven their
 suppression effectiveness during hazardous ma-
 terial clean-up that involves release of volatile
 organic compounds (VOCs), air toxics, odors, and
 dust. These water-based foams conform to the
 terrain and last hours, days, and even weeks, de-
 pending on the site requirements.

 A.E.T.C.                         2411/2413
 Gold Mine Rd.
 Flanders, NJ 07836
 201/347-7111

 A.E.T.C. has been providing fully integrated haz-
 ardous and chemical waste management services
 since 1976. A.E.T.C. specializes in the manage-
 ment of reactives and package laboratory chemi-
 cals, as well as production wastes, PCB destruc-
 tion, household hazardous waste, and a full range
 of site remediation services from our thirteen
 locations.

 A.O. Smith Harvestore
 Products, Inc.                          1903
 345 Harvestore Dr.
 DeKakLIL 60115
 815/756-1551

 A.O. Smith Harvestore Products,  Inc. will be
 exhibiting  its Aquastore®  Tank products line.
 These tanks, with capacities up to 2 million gal-
 lons, are factory coated with fused silica glass on
 the inside and outside for corrosion control. The
 tank is field-erected by bolting and the joints are
 sealed.

ABB Environmental Services Inc.       0223
261 Commercial St.
Portland, ME 04112
207/775-5401

Environmental   Consulting,  monitoring. and
chemical analysis; hazardous waste site investiga-
tions, remedial design, construction and clean-up;
thermal and non-thermal  waste  treatment sys-
tems.

AIM USA                             0218
P.O. Box 720540
Houston, TX 77272-0540
713/240-5020

AIM develops and manufactures microcomputer-
ized portable toxic/combustible/oxygen air moni-
toring instruments. AIM is able to quickly develop
hardware and software solutions for many special
gas detection needs. AIM instruments are used by
over 70 USA military installations, environmental
remediation firms,  all types of  industries and
many major hazardous material response teams.
ALCOA SEPARATIONS
TECHNOLOGY, INC.            2008/2010
Subsidiary of Aluminum Company
of America
181 Thorn Hill Rd.
Warrendale, PA 15086-7527
412/772-0086

Innovative  technologies for the recovery/treat-
ment of groundwater and the treatment of sanitary
and hazardous landfill leachates are on display by
Alcoa Separations Technology, Inc., Subsidiary
of Aluminum Company of America. Comprehen-
sive treatment/recovery equipment, services and
technologies are highlighted  and  information
regarding the various treatment approaches are
available.
ALL-PAK, INC.                       1608
2260 Roswell Dr.
Pittsburgh, PA 15205
412/922-7525

U.N. Performance Tested/DOT Exempt Packag-
ing, EPA Pre-cleaned Sample Bottles, Overpack
Drums - metal/plastic, Lab Packs, Teflon-lined
Caps, Safety Coated Bottles, Complete Line of
Glass, Plastic and Metal Containers.
ARAMSCO                           0320
1655 Imperial Way
Thorofare, NJ 08086
609/848-5330

ARAMSCO specializes in safety products for the
hazardous environment, introducing the Blastrac
- a portable shotblast cleaning system for emoving
contaminants such as PCB, asbestos, radiation
from concrete or metal floors.

AYS Video Productions                 0613
8548 N. Dale Mabry, 2nd Floor
Tampa, FL 33614-1600
813/935-1898

Turnkey video  production   scripting through
duplication of finished programs; OSHA certified
camera crews shoot broadcast quality footage of
remedial investigations,  Superfund  cleanups,
SITE demonstrations and experimental facilities;
post production  capabilities include state-of-the-
art 3D animation to illustrate the operation of
innovative equipment and chemical processes.

AWD Technologies, Inc.                2119
15200 Omega Dr.
Rockville, MD 20850
301/869-4800

AWD Technologies, Inc., a wholly owned sub-
sidiary of The Dow Chemical Company, provides
full-service groundwater,  soil, and site remedia-
tion. Services include site  investigation, planning
and engineering design, construction, operation
and maintenance,  and overall project manage-
ment.

Acres International Corporation        0501
140 John James Audubon Pkwy.
Amherst, NY 14228-1180
716/689-3737

Acres provides waste management expertise to a
wide variety of industrial firms, utilities, and
government agencies (federal, state and local).
Site  investigations,  permitting  and regulatory
compliance evaluations, remedial investigations
and feasibility studies, conceptual and detail de-
                                                                                                                                          979
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     sign, and construction supervision are among the
     comprehensive services offered. Acres offers a
     mullidi&ciplined and experienced team of geolo-
     gists, hydrogologists, chemists,  biologists, ge-
     otechnical, chemical, civil and hydraulic engi-
     neers and support staff to successfully complete a
     variety of waste management projects.

     Agency for Toxic  Substances
     and Disease Registry                   2407
     1600 Clifton Rd., N.E. (MS F-38)
     Atlanta, GA 30333
     404/639-0708

     The Agency  for Toxic Substances and Disease
     Registry (ATSDR) is part of the Public Health
     Service and is based in Atlanta, Georgia. It was
     created by Congress to  implement the health-
     related sections of laws that protect the public
     from hazardous substances.

     Alliance Technologies
     Corporation                           0301
     213 Burlington Rd.
     Bedford, MA 01730
     617/275-9000

     Alliance specializes on the investigative, diagnos-
     tic phases of environmental projects. The services
     we offer include:  emission source characteriza-
     tion and quantification, health and ecological risk
     assessments, pollution control technology evalu-
     ation and design, site assessments and subsurface
     investigations, environmental audits for facilities,
     permitting and  advanced modeling, health and
     safety plans, database design and management,
     and waste minimization and pollution prevention.

     Alternative Systems, Inc.               2009
     225 S. Cabrillo Hwy., Suite 124-C
     Half Moon Bay, CA 94019
     415/726-5700
     TTN1A  is the  most comprehensive hazardous
     materials liability management software designed
     for industry, State and Local, and Federal govern-
     ment. TINIA   is written in a fourth generation
     language  utilizing state  of  the art technology,
     integrated imaging, telephony, geographic infor-
     mation mapping, and systems integration. TTNIA
     is platform independent. TINIA is a commitment
     to the environment.

     American Colloid Company            2021
     1500 West Shure Dr.
     Arlington Heights, IL 60004
     708/392-4600

     American Colloid Company is the world's largest
     producer of bentonite clay and related  products.
     ACC's Environmental  Division manufactures
     Volclay bentonite  for landfill  lining,  Bentomat
     seepage control liner and Sorbond waste solidifi-
     cation/fixation  agents. The Water/Mineral Divi-
     sion will be showing the PureGold product line of
     Groundwaler Monitoring products, which in elude
     environmentally safe bentonite  grout, drilling
     fluid and tablets.

     American Health  & Safety, Inc.         0309
     6250 Nesbitl Rd.
     Madison, WI53719
     608/273-4000
     American Health & Safely. Inc. is a nationwide
industrial safety supply house featuring a full line
of on-the-job safety products. We have over 5,000
line items which are distributed throughout the
safety industry, including asbestos, laboratory
and food industries. American Health &  Safety
specializes in the hazardous materials and toxic
waste disposal  fields. We will be displaying
gloves,  respirators,  coveralls,  boots,  safety
glasses, tape, shovels, instrumentation  and first
aid used heavily in the hazardous materials indus-
try-
American Industrial Marine
Services                               0224
1550 E. Patapsco Ave.
Baltimore, MD 21226
201/756-4200

American Industrial Marine
Services                               LDC
1550 E. Patapsco Ave.
Baltimore, MD 21226
301/355-7600

American Industrial Marine Services specializes
in Hazardous Waste Transportation, Tank Clean-
ing and Removal; Remedial Services; Emergency
Spill Response; Decontamination Services; In-
dustrial Maintenance, and Equipment and Materi-
als Sales. Offices are located in NJ, MD, PA and
NY. Call 1/800/762-4201 for more information.

American International
Companies                            0317
2005 Market St., Suite 2800
Philadelphia, PA 19103
215/981-7117

Meeting the insurance needs of industry by pro-
viding  Environmental   Impairment  Liability,
General Liability, Business Automobile Cover-
age, and Property Insurance, for companies in the
environmental field, through experienced under-
writing, comprehensive risk management, and
dedicated claims handling.

American Laboratories
& Research                           0409
P.O. Box 15609
Hattiesburg, MS 39404
601/264-9320

Amoco Fabrics and Fibers
Company                              1710
900 Circle 75 Pkwy., Suite 300
Atlanta, GA 30339
404/956-9025

Amoco Fabrics and Fiber Company is the only
manufacturer of both woven and nonwoven ge-
otextiles. Nonwoven polypropylene fabrics rang-
ing in weight from 3 to 20 ounces per  square yard.
Applications  for geotextiles include geomem-
brane cushion, filtration, stabilization, erosion
control, separation and reinforcement. Call (404)
984-4433 for information.

AnalytlKEM, Inc.                      1008
28 Springdale Rd.
Cherry Hill, NJ 08003
609/751-1122

AnalytiKEM is a full services analytical labora-
tory network with facilities located in Cherry Hill,
NJ, Rock Hill, SC, Houston, TX, and Wilmington,
MA. AnalytiKEM's expertise includes  environ-
mental analysis for NJ/ECRA and other real estate
assessments, cleanup, Full RCRA characteriza-
tion, NPDES permit  compliance, groundwatcr
monitoring  and  compatibility  testing.  Ana-
lytiKEM utilizes state-of-the-art instrumentation
including GC/MS and provides field sampling
Andco Environmental
Processes, Inc.                         0401
595 Commerce Dr.
Amherst, NY 14228
716/691-2100
Wastewater treatment systems to remove heavy
metals, fluorides, phenol, and other organics from
industrial wastewater, contaminated groundwa-
ter, and leachate. Also a portable heavy metal pilot
unit.

Andersen Instruments, Inc.             0712
4801 Fulton Industrial Blvd.
Atlanta, GA 30336
404/691-1910
Andersen Instruments, Inc., is one of the world's
foremost manufacturers of environmental moni-
toring and occupational health diagnostic instru-
mentation. Andersen equipment is known for
protocol compliance, ease of use, and accuracy.
Specifically featured will be EPA-approved re-
mote air samplers, participate impactors and am-
bient toxic gas analyzers. Call (800) 241-6898 for
more information.

Aqua Tech Environmental
Consultants, Inc.                 2017/2019
181 South Main St., P.O. Box 436
Marion, OH 43302
800/783-5991
Aqua Tech  Environmental  Consultants, Inc.
proves accurate and precise analytical data on a
timely basis, at competitive prices, to industrial,
governmental and private clients. Aqua Tech's
services include complete capabilities for organic
and inorganic analysis,  bioassay/biomonilorlng,
sampling,  and mobile laboratory analysis. Call
(614) 382-5991 for more information.

Aqna-Chem, Inc.                       LDC
210 W. Capitol Dr., Box 421
Milwaukee, WI53201
414/962-0100

Aquastream                            LDC
1115 North First St.
Garland, TX 75040
214/276-5690
Aquastream has recently expanded its innovative
water well equipment product line to include a lab-
certified  pre-packed  "Gravelwall   Monitor
Screen." The unique environmental well screen
(available in stainless, PVC or Teflon), features a
silica gravel-pack which is bonded directly to the
screen itself, thus insuring uniform filtration with
reduced drilling costs.

Art's Manufacturing & Supply          1112
105 Harrison at Oregon trail
American  Falls, ID 83211
800/635-7330
AMS will be exhibiting  their full line of toil
180
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sampling equipment. AMS will be displaying foi
the fust time, the new "PAT" dual valve liquid
sampler. AMS will also be showing a video of the
new AMS dual reel portable boom system for
groundwater monitoring wells.
Associated Design &
Manufacturing Co.                     1114
814 N.Henry St.
Alexandria, VA 22314
703/549-5999

Associated Design provides suitable laboratory
equipment for TCLP and liquid relase testing
ofsolid waste. Featured products include the zero
headspace extractor (ZHE) for collection of vola-
tile contaminants, two bench-top filtration units,
the new liquid relase test device, and large-capac-
ity rotary agitators which hold bottles separatory
runnels or ZHEs. Design and fabrication services
are available. New products will be introduced at
this conference.
 ATLANTIC RESEARCH
 -ARC/ARCTECH                     0110
 1375PiccardDr.
 Rockville, MD 20850
 301/670-2000

 ATLANTIC RESEACRH    ARC/ARCTECH
 provides remedial technologies and consulting/
 engineering services including: LARC   Light
 Activated Reduction of Chemicals for PCS and
 Pesticide Destruction; OZO-DETOX - Ozonation
 for Destruction of Coal Tars and PAHs; COM-
 POSTING - Bioremediation of Organic  Com-
 pounds and Explosives; INFORMATION/DATA
 MANAGEMENT; MONITORING/MODEL-
 ING;  SITE  ASSESSMENT/SAFETY  and
 TRAINING/EDUCATION.

 B&V Waste Science and
 Technology Corp.                     1505
 4370 W. 109th St., Box 7960
 Overland Park, KS 66211
 913/339-2900
 A Black & Veatch Company, BVWST provides
 complete hazardous waste management services,
 including RI/FS, design plans and specs, implem-
 entation oversight, RCRA services, regulatory
 and permit support, and  litigation assistance.
 Other specialties include waste treatment, PCS
 transformer replacement,  public health evalu-
 ations, facility closure services, environmental
 audits, and community  right-to-know planning.


 BAKER/TSA, Inc.                     0808
 420 Rouser Rd.,  Airport Office Dr., Bldg.3
 Coraopolis, PA 15108
 412/269-6000
 Performance of:  remedial investigation/feasibil-
 ity  studies;  site  assessments; risk assessments,
 remedial/closure design and management; RCRA
 permitting and compliance programs; industrial
 hygiene  and asbestos  management;  economic
 analyses, waste  utilization and market  studies;
tank management; waste minimization programs;
water and wastewater treatment; environmental
auditing; and air  quality services.
BCM Engineers                       2100
One Plymouth Meeting
Plymouth Meeting, PA 19462
215/825-3800

Quality engineering since 1890. Services include
hazardous  waste  management  and  control;
groundwater studies, geophysical surveys, reme-
dial design engineering, Superfund site investiga-
tions, facility permitting, closure plans, real estate
contamination assessments, asbestos surveys, and
full-service laboratory.
BGI Incorporated                     1811
58 Guinan St.
Waltham, MA 02154
617/891-9380

Manufacturer/distributor of air sampling equip-
ment, negative air pressure monitors, and calibra-
tion equipment. Also available is a complete line
of personal gas monitors, Draeger grab sampling/
dosimeter  tubes and respiratory  equipment. In
addition, gas sampling bags of tedlar and teflon
and gas bag filling pumps.
BNA Communications Inc.              LDC
9439 Key West Ave.
Rockville, MD 20850
301/948-0540

BNA Communications Inc. will display bro-
chures on our new eight-module safety training
program, WORKING IN THE HAZARD ZONE,
plus brochures on our  HANDLING HAZARD-
OUS WASTE program, and our safety catalog in
the Literature Distribution Center.
BNA, INC.                       2218/2220
1231 25th St., N.W.
Washington, DC 20037
202/452-4200
BNA Publishes regulatory, legal and working
guides providing the latest information concern-
ing the manufacture, transportation, safe handling
and disposal of hazardous materials.
BOOZ, ALLEN &
HAMILTON Inc.                      1109
4330 East West Hwy.
Bethesda, MD 20814
301/951-2200

Booz, Allen & Hamilton Inc. is a leading technol-
ogy and  management  consulting firm that has
earned an outstanding reputation  in  environ-
mental services through years of direct involve-
ment developing and implementing key programs
for government and industry world-wide. The
firm has worked with the Superfund and RCRA
programs since their inception and offers compre-
hensive mission and program-related expertise.
Technology and management services include:
risk management; audits and  technical evalu-
ations; regulatory enforcement and policy sup-
port; records management; information system
development; and program planning, implemen-
tation, and evaluation.
Barnebey & Sutcliffe
Corporation                          0903
835 N. Cassady Ave.
Columbus, OH 43219
614/258-9501

We manufacture activated carbons made from
coconut shell, coal and wood. Granular, pelletized
and powder forms available. Carbon regeneration
service is offered by our factory in Columbus,
Ohio. We offer custom package systems for sol-
vent recovery, VOC emission control and waste-
water treatment applications.

Beazer Environmental
Services, Inc.                          LDC
436 Seventh Ave.
Pittsburgh, PA 15219
412/227-2198
Beazer Environmental Services, Inc., offers a full
range of environmental construction and reme-
diation services to customers on a world-wide
basis. We can provide complete engineering and
design, project  management and construction
services for groundwater and wastewater treat-
ment plants, RCRA/CERCLA closures, and bi-
oremediation projects.

Bergen Barrel & Drum
Company                       1815/1915
43-45 O'Brien St.
Kearny, NJ 07032
201/998-3500
An innovative line of polyethylene drums, both
open and closed head, tanks and environmental
products specifically designed for the hazardous
waste industry. Various sized drums and tanks
along with pallets, overpacks and other products
will be displayed.
Betz Laboratories                     1913
9669 Grogans Mill Rd.
The Woodlands, TX 77380
713/367-6201
Betz Analytical Services offers complete environ-
mental testing. We provide accurate timely data
using the latest, automated instrumentation. Our
facilities located in Houston and Philadelphia fol-
low strict QA/QC programs to meet your testing
needs. We participate in the EPA Contract Labo-
ratory Program (CLP).
Bioscience Management, Inc.            0319
1530 Valley Center Pkwy.
Bethlehem, PA 18017
215/974-9693
Your best single stop for bioremedial supplies and
services for cleaning up soil, sludge, groundwater
and wastewater.  We  manufacture and market
automated laboratory treatability and waste char-
acterization  instruments,  microbial  cultures,
packaged groundwater biotreatment units and bi-
ostimulation chemicals. We furnish treatability
studies, process engineering, site monitoring and
trouble shooting, and turnkey  bioremedial pro-
grams.

Biospherics Incorporated              1512
12051 Indian Creek Ct.
Beltsville, MD 20705
301/369-3878

Biospherics Incorporated has serviced asbestos
                                                                                                                                          981
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related and industrial hygiene needs for years,
therefore, knowledgeable of technical and opera-
tional requirements of such programs. Compre-
hensive services are provided including consult-
ing, visual and physical inspections, bulk sam-
pling, analysis, training, program management/
development, risk assessment and abatement pri-
oritization, lead paint and PCB investigation and
remediation.
Brown and CaldweU Consultants       1124
3480 Buskirk Ave.
Pleasant Hill, CA 94523-4342
415/937-9010

Brown and CaldweU Consultants is a nationwide
mullidisciplinary environmental consulting firm,
providing complete project services for hazard-
ous waste, water, wastewater, and solid waste.
Services  include RI/FS, regulatory compliance,
permitting, design, engineering, remediation, air
and water quality, laboratory services, project and
construction management.

Burlington Northern Railroad          LDC
3700 Continental Plaza, 777 Main St.
Fort Worth, TX 76102
817/878-2168

Burlington Northern Railroad Company operates
the largest railroad system in the United States. Its
main lines runs through 25 states and 2 Canadian
Provinces. It moves raw materials and finished
products  to over 4,000 communities  nationwide.
In addition, it serves ports in the Pacific Northwest
and the Gulf of Mexico.

CALGON CARBON
CORPORATION                     1105
P.O. Box 717
Pittsburgh, PA 15230
412/787-6700

Calgon Carbon  Corporation supplies activated
carbon products,  systems  and  services,  and
airstrippers to remove soluble and volatile organic
chemical compounds from contaminated ground-
water, surface water or wastewater.

CDM/Federal Programs
Corporation                          2016
13135 Lee Jackson Memorial Hwy.
Suite 200
Fairfax, VA 22033
703/968-0900

CDM  Federal  Programs  Corporation provides
environmental consulting services to the federal
government, including:  environmental assess-
ments, site investigations, sampling and analysis,
feasibility studies, risk  assessments, environ-
mental impact statements, groundwater model-
ing,  CIS  and CADD computer modeling, health
and safety plans, community relations planning,
operations/maintenance and underground storage
tank remediation services.

CEA Instruments, Inc.                 0306
16 Chestnut St.
Emerson, NJ 07630
201/967-5660

CEA Instruments, a leading supplier of hazardous
gas detection instrumentation since 1972, will be
exhibiting a new portable Landfill Gas Analyzer
for CO2 and CH4, portable and wall mounted CO2
analyzers, and other units for monitoring toxic
gases, combustible gases and oxygen levels in
portable, single and multichannel fixed systems.

CEIMIC
CORPORATION           2215/2217/2219
100 Dean Knauss Dr.
Narragansett, RI02882
401/782-8900

Ceimic, an employee-owned full-service environ-
mental laboratory, provides analytical support
nationwide to both  industry and government.
Ceimic specializes in rapid turnaround services
and our ability to produce quality  data is evi-
denced by participation in EPA's Contract Labo-
ratory Program (CLP), DOD's HAZWRAP and
NEESA programs, and multi-state certifications.
The laboratory facility and instrumentation are
state-of-the-art and they are complemented by a
staff of over 60 environmental professionals.

CH2M HILL, INC.                0510/0512
P.O. Box 4400
Reston, VA 22090
703/471-1441
CH2M HILL provides waste management serv-
ices - including  design, construction, investiga-
tion, and planning - to industry and government.
We are  the  largest  environmental  engineering
firm in the United States, with 4,500 employees in
60 offices worldwide. Over a third of our business
is managing hazardous, radioactive, and solid
waste.

The CHEMTOX* System               2117
P.O. Box 1848
Brentwood, TN 37024-1848
615/373-5040

The CHEMTOX* System provides software (The
CHEMTOX Database,  MSDS ACCESS", and
DocuWaste™ for Hazardous Waste) for retrieval
and documentation of chemical data needed for
safety and health environmental, emergency re-
sponse, and transportation decisions. It will pro-
duce needed management reports, record inven-
tories, employee exposures, create material safely
data sheets,  departmental reports,  and  track
chemical processes and waste through disposal.
Updated quarterly, users are provided the most
current chemical and physical data. All records
are variable length and accept any alphanumeric
character combination. CHEMTOX and MSDS
ACCESS are registered in the U.S. Trademark &
Patent Office. Docu Waste is a trademark of Re-
source Consultants, Inc.

COMPUCHEM
LABORATORIES,  INC.          2110/2112
3308 Chapel HilVNelson Hwy.
Research Triangle Park, NC 27709
919/549-8263

CompuChem Laboratories, Inc., a  full  service
organic and inorganic laboratory, specializes in
CERCLA, RCRA, DIOXIN, PRIORITY  POL-
LUTANT and WASTE CHARACTERIZATION
ANALYSES following the new TCLP  regula-
tions.  In  1990 CompuChem has expanded its
analytical services to include low level RADIO-
LOGICAL and MIXED WASTE ANALYSES.
CompuChem's Environmental Site Profile (ESP),
a proprietary data management system, provides
on-line access to test results which can be down-
loaded to your personal computer. For forensic
quality data and expedited turn-around times, visit
the staff of CompuChem Laboratories at booths
2110 and 2112.

Camp Dresser & McKee, Inc.           2014
One  Cambridge Center
Cambridge, MA 02142
617/621-8181
Camp Dresser & McKee, Inc., (CDM) provides
environmental engineering  and consulting serv-
ices to government and industry for the manage-
ment of hazardous and solid wastes, wastewater,
and water resources. Waste management services
include remedial design, site assessments, envi-
ronmental audits, RCRA compliance, treatment
facility design  and operation, and  groundwater
modeling and restoration.

Canadian Hazardous Materials Mgmt  LDC
12 Salem Ave., Suite 200
Toronto, Ontario, Canada M6H 3C2
416/536-5974

Canonle Environmental
Services Corp.                         1017
800 Canonie Dr.
Porter, IN 46304
219/926-8651
Comprehensive design and construction services
for the remediation of sites contaminated by haz-
ardous wastes. Principal services include, but are
not limited to, soil remediation (thermal treatment
and in situ), groundwater restoration, landfill and
lagoon closure, removal actions, slurry walls and
facility decommissioning. Complmenlary  serv-
ices  include engineering design  and analytical
services.

Carbonalr Services, Inc.                2419
8530 35th St., South
Minneapolis, MN 55343
612/935-1844
Carbonair Services, Inc. provides technology and
treatment plants for the decontamination of water,
soil and air. Services provided include carbon
adsorption, airstripping, inorganic and biological
pretreatment, soil venting, and other decontami-
nation technologies. Carbonair can provide what-
ever  level of assistance needed to complete the
project. Systems may be purchased or rented

Caswell, Elchler and Hill, Inc.           LDC
One  Harbour PI., Suite 300
Portsmouth, NH 03801
603/431-4899
CEH is a full-service hydrogeological consulting
firm  with extensive experience and capability in
contaminated industrial site characterization and
remediation and water supply development. We
are a firm of professionals specializing in geology,
hydrology, geophysics and remediation engineer-
ing,  who provide expert consulting service* lo
private industry, governmental agencies and large
contractors. Our services focus on solving the
complex problems associated with  the use, pro-
tection, management and cleanup of ground and
surface water resources.
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 ChemCycIe Corporation                1311
 129 South St.
 Boston, MA 02111
 617/451-0922

 ChemCycIe Corporation is an engineering and
 design consulting firm that specializes in solving
 industrial  hazardous waste and  environmental
 problems. We offer services in process engineer-
 ing, environmental controls, waste minimization,
 site assessments, compliance audits, permitting,
 site remediation and construction  management.

 Chemfix Environmental Services        0106
 2424 Edenborn Ave., Suite 620
 Metairie, LA 70001
 504/831-3600

 Chemfix Environmental Services offers the pat-
 ented Chemfix" process for treatment of sludges
 and high solids wastes. Complete mobile services
 are offered, as well as fixed plant facilities. CES
 services include site assessment, waste stream
 characterization and permitting support.

 Chemical Waste                  2207/2209
 Management, Inc.                 2211/2213
 3001 Butterfield Rd.
 Oak Brook, IL 60521
 708/218-1500

 Chemical Waste Management, Inc., is America's
 complete  Hazardous Waste Manager. Our full
 range of services includes: Water Reduction Serv-
 ices,  Resource  Recovery, Site  Remediation,
 Treatment, Transportation, Disposal,  Incinera-
 tion, Secure Landfill, Asbestos Abatement and
 Advanced Technologies for On-Site Soil Reme-
 diation and Wastewater Treatment and Recovery.
 Call Toll-free: 1-800-843-3604 for more informa-
 tion.

 Clark Boardman Company, Ltd.        LDC
 375 Hudson St.
 New York, NY 10014
 212/929-7500

 Clark Boardman Company is proud to offer its
 acclaimed Environmental Law Library. Designed
 to save hours of research time for busy practitio-
 ners and industry professionals, the library pro-
 vides detailed analysis of the law - and expert
 guidance. We understand that ensuring compli-
 ance with today's environmental laws is your first
 priority.

 Clayton Environmental
 Consultants, Inc.                       0101
 1252 Quarry Ln., P.O. Box 9019
 Pleasanton, CA 94566
 415/426-2600

 Since 1954, a recognized leader  in the field of
 environmental consulting with broad-based capa-
 bilities in the areas of environmental engineering,
 industrial hygiene, asbestos management, indoor
 air  quality, and laboratory analysis.  Clayton has
 11  offices and  six laboratories throughout the
 U.S.,  Canada  and the United Kingdom. The
 Michigan facility is an EPA CLP laboratory.
 Clean Air Engineering Inc.         1616-1617
 500 West Wood St.
Palatine, IL 60067
708/991-3300
Clean Air Engineering: Clean Air  Engineering is
a full service environmental consulting firm, of-
fering its industrial and municipal clients a wide
range of services. These include air quality moni-
toring (EPA Methods 1-25, Multi-metals, VOST/
MM5),  trial bum assistance, mobile analytical
laboratory services, environmental audits, flow
modeling, environmental software design, tem-
porary environmental professionals, design engi-
neering, instrumentation rental and training semi-
nars. CAE Instrument Rental: The leader in port-
able HazMat instrumentation,  including PIDs,
FIDs, Oj/LELs, Sample Pumps, Aerosol  Moni-
tors, Met Equipment, PUFs, etc. All available for
short  or long term rental featuring our "10 Day
Week."  Introducing a new product this year, the
ADC LFG 10 for landfill gas analysis. Those of
you who know who you are, stop by  and say hi.
Those of you who don't, come on by and  get
acquainted.

Clean Sites, Inc.                        0910
1199 North Fairfax St., #400
Alexandria, VA 22314
703/739-1209

Clean Sites is a non-profit organization founded in
1984 to accelerate hazardous waste cleanup. We
help parties at sites with: cost allocation; dispute
resolution;  technical assistance; quality assur-
ance; and managing site studies and cleanups. We
also work with government agencies to develop
effective hazardous waste programs and conduct
independent policy analyses.

Clem Corporation
(James Clem Corp.)                    0216
444 North Michigan Ave., Suite 1619
Chicago, IL 60611
312/321-6255

The  James Clem  Corporation  manufactures
CLAYMAX®, an impermeable clay  liner made
with the world's highest quality sodium bentonite.
It combines the durability of a woven geotextile
fabric with the  impermeability of a  pound per
square foot of sodium bentonite. The liner can be
used as a primary or secondary liner  in landfills
and landfill caps, tank farm secondary spill con-
tainment and various applications in  the mining
industry.

Consolidated Rail Corporation          2513
Room 919 - One Liberty Place
Philadelphia, PA 19103-7399
215/851-7281

Conrail  is one of the largest freight railroad sys-
tems  in the Northeast-Midwest quarter of  the
United States, operating over a network of ap-
proximately  13,100 route miles. Conrail is a li-
censed  and registered transporter of hazardous
waste and sixty percent of all Superfund sites are
located within its territory. Conrail works closely
with connecting rail carriers, trucking, and equip-
ment companies to offer reliable transportation
services.
Corroon & Black Env'l
Insurance Svs.
6510 Grand Teton Place, #102
Madison, WI53719
608/833-2887
2221
Cousins Environmental Services        0414
1800 Matzinger Rd.
Toledo, OH 43612
419/726-1500

A complete environmental contractor. Specializ-
ing in contaminated site  remediation,  we have
extensive  experience in bioremediation of soil
contaminated with both hazardous and  non-haz-
ardous materials. In addition, we have  designed
and operated biological systems for pretreatment
of industrial waste. Cousins' staff of over 100 are
experienced in UST removal, site assessments,
and specialized waste treatment and removal.

Curtis & Tompkins, Ltd.                0710
2323 Fifth St.
Berkeley,  CA 94710
415/486-0900
Curtis & Tompkins Laboratories. Analytical serv-
ices  since 1878. Environmental,  Industrial Hy-
giene and  Air Analyses. For analytical  services,
look to Curtis & Tomkins - the complete labora-
tory  offering customized reports, data  manage-
ment, and  electronic data transfer to ensure com-
plete, accurate and timely results for your projects.

DartAmerica                          1212
61 Railroad St.
P.O. Box 89
Canfield, OH 44406
216/533-9841

A group of companies dedicated to the transporta-
tion of hazardous waste and general commodities
in 48  states  utilizing dumps, roll-offs, vans,
flatbeds, pneumatic  and liquid tank equipment,
and LTL van service.

DataChem Laboratories               2214
960WestLeVoyDr.
Salt Lake City, UT 84123
801/266-7700

Serving the analytical chemistry support sectors
since 1971, DataChem Laboratories is now one of
North America's largest and most experienced
providers of laboratory services. The highly spe-
cialized tests performed by DataChem Laborato-
ries are designed to assist clients in the evaluation
of industrial hygiene and environmental issues.

Davy Environmental                  0503
2430 Camino Ramon
San Ramon, CA 94583
415/866-1166

Davy Environmental draws upon Davy's world-
wide technologies and project execution  capabili-
ties to provide comprehensive consulting, engi-
neering, design and construction management
services. These services include: remedial inves-
tigations/feasibility  studies; treatment  systems
design; remediation of contaminated soils, water
and air; waste encapsulation, isolation and incin-
eration; and facility closure monitoring.

Dexsil Corporation                     0102
1 Hamden Park Dr.
Hamden,CT06517
203/288-3509

Dexsil Corporation provides environmental field
                                                                                                                                             983
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     testing kits thai delect environmental contami-
     nants. Dexsil's field lest kits are quick, easy to use,
     and afford the user an economical advantage over
     costly and time-consuming laboratory services.
     Dexsil's lest kits detect total halogens (chlorine) in
     wasle oils, total  organic  halogens in oil/water
     mixtures, and PCBs in transformer oil and soil.

     Donohue & Associates, Inc.             1513
     4738 North 40th St.
     Sheboygan, WI 53083
     414/458-8711x2222

     Donohue is an ARCS contractor with a nation-
     wide staff of over 1,000 and a 1990 ENR ranking
     of 72. Our environmental scientists and engineers
     are specialists in waste management, disposal and
     cleanup. Donohue's hazardous waste services in-
     clude  RCRA investigations  and  compliance
     monitoring,  RI/FS studies, and engineering of
     remedial  cleanup actions.

     Ou Pont  Company                2104/2106
     1007 Market St., EA, NA-228
     Wilmington, DE 19898
     302/774-7248

     Du Pont Safety and Environmental Resources will
     exhibit its Environmental Remediation Service
     which provides the treatment of contaminated soil
     and groundwaler. In addition, the Du Pont Waste
     Management offering will be exhibited, providing
     state-of-the-art, in-compliance treatment and dis-
     posal services and environmental consulting to
     industry.

     Dunn Geosclence Corporation          1415
     12  Metro Park Rd.
     Albany, NY 12205
     518/458-1313

     Full Service Environmental Consultants: Com-
     plete  staff of hydrogeologists,  geologists, envi-
     ronmental specialists and engineers, lexicolo-
     gists, and regulatory experts provides a range of
     services including RI/FS and RCRA Corrective
     Actions, Remedial Design and Construction Man-
     agement,  Toxicology/Public  Health  Assess-
     ments, Hazardous Waste Planning and Manage-
     ment, Hydrogeologic Investigatory Services and
     Property  Transfer Environmental Site Assess-
     ments.

     Dynamac Corporation                 0812
     Dynamac #2 Bldg.
     11140 Rockville Pike, Third Floor
     Rockville, MD 20852
     301/230-6117

     Dynamac is a full service environmental firm. We
     are  specialists in integrating expertise in environ-
     mental regulations and technology with the latest
     in information management techniques. Our serv-
     ices include preliminary site and risk assessments,
     RI/FS and remedial  design activities, manage-
     ment of removal and remedial action efforts, pro-
     gram  management, as well as community rela-
     tions and public outreach activities.

     Dynamic Graphics                     1501
     7201 Wisconsin Ave., Suile 640
     Bethcsda, MD20814
     301/656-3060

     Dynamic  Graphics provides advanced software
tools for the modeling, analysis and display of 2-
dimensional and 3-dimensional phenomena in the
earth, water and air. Applications include plume
modeling and monitoring, particle dispersion, site
characterization and remedial evaluations. Geos-
cience disciplinary fields include geology, hy-
drology, geochemistry and meteorology.
EA Engineering, Science &
Technology, Inc.                       0612
11019McCormickRd.
Hunt Valley, MD 21031
301/584-7000

EA is a nationwide, multidisciplinary professional
services consulting firm providing a wide range of
engineering, scientific, analytical and remedia-
tion capabilities to address existing and potential
threats to the environment and to human health
and safety. EA develops solutions for waste man-
agement, energy  conservation and  emissions
control, and indoor air quality.
                       0504/0506/0603/0605
EBASCO
Environmental
160 Chubb Ave.
Lyndhurst, NJ 07071
212/839-2744

Ebasco Environmental, a division of Ebasco Serv-
ices Incorporated, provides a wide range of envi-
ronmental and waste remediation services (o in-
dustry and government clients. Services include
remedial  assessments/investigations, feasibility
studies, remedial designs and corrective actions; a
broad range of environmental and risk assessment
and remediation consulting services; design and
construction of quality management and control
systems;  and comprehensive licensing and per-
mitting services.
ECOFLO, Inc.                        2208
8520-M Corridor Rd.
Savage, MD 20763
301/498-4550

ECOFLO  provides  answers to client-specific
waste management needs from our extensive of-
fering of services, including: Waste Characteriza-
tion; Collection, Transportation and Treatment/
Disposal of  Most Wastes; Lab Pack Services;
Remediation and Cleanup Services; Waste Mini-
mization Advice. ECOFLO serves the Mid-Allan-
tic region  from offices in Maryland  and North
Carolina.

ECOVA Corporation                  2310
3820 159th Ave., N.E.
Redmond, WA 98052
206/883-1900

ECOVA solves hazardous waste problems with
technologies for on-site remediation: Bioreme-
diation, In Situ Treatment, Soil Washing, Incin-
eration. ECOVA  has cleaned up  more  than
800,000 cubic yards of soil and millions of gallons
of water using bioremedialion. Integrated science,
technology, and engineering expertise provides
successful  technology dvelopment and field re-
mediation.
EIMCO Process
Equipment Co.          1804/180671808/1810
P.O. Box 300
Salt Lake City, UT 84110
801/526-2000
EIMCO supplies a complete line of liquid-solids
separation and dewalering equipment, including
cost-effective bioremediation for treating hazard-
ous wastes. Bioremediation offers lower energy
costs than conventional systems, and is able to bi-
odegrade organic slurries of 30-50 WT. % solids
concentration.

EMPIRE SOILS
INVESTIGATIONS, INC.             101S
140 Telegraph Rd., P.O. Box 250
Middleport, NY 14105
716/735-3502
Empire Soils Investigations, Inc., along with its
laboratory division, Huntington Analytical Serv-
ices, and its wholly owned subsidiary, Asteco,
Inc., provides  the following services:  contract
drilling and installation of groundwater monitor-
ing wells, geotechnical testing including contami-
nated soils, geotechnical engineering, chemical
analytical testing, asbestos inspection and testing,
and materials engineering and testing.
ENCYCLE/TEXAS, INC.         0802/0804
5500 Up River Rd.
Corpus Chrisli, TX 78407
512/289-0035
Encycle/Texas  is a Part B permitted waste recy-
cling facility with the capabilities of processing as
well as recovering heavy metals from solids, liq-
uids, sludges, waste streams. Also, we process
acids, bases, sulfides and hexavalent chromium.

ENRECO.Inc.                   1611-1613
P.O. Box 9838
Amarillo, TX 79105
806/379-6424
ENRECO, Inc. uses a combination of basic chem-
istry and specialized  equipment to stabilize the
hazardous constituents within  a  waste matrix.
ENRECO consists of four operating groups;
Laboratories, Engineering,  Technologies,  and
Operations. The four groups provide a wealth of
experience which is used to design innovative, yet
economical, remedial plans, navigate through the
regulatory maze, and complete the construction in
a timely and proficient manner.

ENSCO.Inc.          0410-0412,0509-0511
333 Executive Ct.
Little Rock, AR 72205
813/289-5600
ENSCO provides Jntcgraled  hazardous  wasle
management services to private industry, public
utilities, and government entities. These services
include chemical analysis, collection, transporta-
tion, processing,  and incineration of hazardous
waste.
ENTROPY
Environmentalists, Inc.                 1125
P.O. Box 12291
Research Triangle Park, NC 27709
919/781-3550
ENTROPY Environmentalists, Inc., provides (he
984
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most comprehensive air emissions testing serv-
ices nation-wide. In business since 1972, EN-
TROPY is the specialist for Trial Bums, VOCs,
RCRA/TSCA,  SARA,   CEM,  Particulates,
POHCs, and Criteria Pollutant testing. Call Pete
Watsonforfurther information at (919) 781-3550.

ENVIROCARE OF UTAH,  INC.       LDC
215 South State, Suite 1160
Salt Lake City, UT 84111
801/532-1330

ENVIROCARE is  the country's first licensed
disposal facility for naturally  occurring radioac-
tive material (NORM). ENVIROCARE  has re-
cently received a permit to dispose of hazardous
(RCRA) radioactive waste. Our facility location
and design are the  result of long-term environ-
mental planning. Transportation options for ship-
ment to ENVIROCARE include rail and highway.

ENVIRONMENT TODAY             0113
1905 Powers Ferry Rd. #120
Marietta, GA 30067
404/988-9558

ENVIRONMENT TODAY - the  Newsmagazine
of Environmental and Pollution Control.

Environmental Audit, Inc.              0701
717 Constitution Dr.
Hankin Bldg., Ste. 101
Exton, PA 19341
215/458-1122

Environmental Audit, Inc. is an environmental
information and education company. EAI pro-
vides parties to real estate transactions and their
consultants with EPA and state environmental
agency records organized on  a database for use
with real estate assessments and audits. EAI also
provides education  and training for use of these
records.

ENVIRONMENTAL
PROTECTION Magazine              1809
225 N. New Rd.
Waco, TX 76710
817/776-9000

ENVIRONMENTAL PROTECTION magazine
reaches  more than 90,000 buyers of environ-
mental and pollution control products and serv-
ices. OCCUPATIONAL HEALTH & SAFETY
reaches more than 80,000 buyers of occupational
health, safety and hygiene products and services.

ENVIRONMENTAL
PROTECTION SYSTEMS             1812
3800 Concorde Pkwy., Suite 2100
Chantilly, VA 22021
703/631-2411
Environmental Protection Systems (EPS) is  a
rapidly growing engineering,  industrial hygiene
and analytical firm that has been providing envi-
ronmental consulting services  to government and
industry for over 17 years. With eight  offices
nationwide, EPA has developed  an outstanding
reputation for providing quality  engineering in
hazardous waste assessments  and site investiga-
tions; RI/FS development; spill response planning
and mitigation; real  estate audits;  facility permit-
ting and design; asbestos management and abate-
ment supervision and analytical services.
ERCE                                1813
3211 Jermantown Rd.
Fairfax, VA 22030
703/246-0440
ERCE is a professional and technical services
company that offers environmental, infrastructure
and energy consulting and engineering services to
industrial  and  commercial companies, electric
utilities and governmental agencies. Engineering,
design and environmental science services are
supported  by  four  EPA-accredited analytical
laboratories strategically located throughout the
U.S.

ERM Group, The                 2018-2020
855 Springdale Dr.
Exton, PA 19341
215/524-3500

The  ERM Group,  a full-serviceenvironmental
consulting firm with more than 50 offices world-
wide, provides the following services: site reme-
diation; hydrogeology; hazardous/solid waste
management; management consulting; industrial/
municipal water and wastewater treatment; under-
ground tank management;  environmental sci-
ence; air pollution  control;  computer sciences;
construction management; and health, safety and
toxicology.

Eagle-Picher/Environmental Services    1119
36 B.J. Tunnell Blvd. East
Miami, OK 74354
918/540-1507
Precleaned and certified, glass and plastic sample
containers to EPA specifications. Documentation
of quality control and chain of custody with each
container.  Complete line of clear or amber glass
and high density polyethylene in a variety of styles
and sizes. Also offering various ampule preserva-
tives. Free sample reference guide. For more infor-
mation, call our toll-free number: 800-331-7425.

Earth Resources Consultants, Inc.       2417
1227 Marshall Farms Rd.
Ocoee,FL 34761
407/877-0877
Earth Resourses Consultants (ERC) is a full-serv-
ice hazardous materials management firm spe-
cializing in the containment, treatment, and re-
moval of all types of hazardous materials. ERC
has a highly trained professional and technical
staff experienced in the design and implementa-
tion of innovative solutions to today's waste prob-
lems. ERC's capabilities include but are not lim-
ited to soil, groundwater, facilities, containerized
wastes and pressurized gas cylinders.

Earth Technology
Corporation, The                 1605/1607
100 W. Broadway, Ste. 5000
Long Beach, CA 90802
213/495-4449

As one of the nation's leading environmental,
earth sciences and geotechnical consulting firms,
The  Earth Technology Corporation's primary
business activities include: Waste Management
and Environmental Services, Critical Facilities
Siting, Related Advanced Technology and Test-
ing Services, and Asbestos and Air Quality Man-
agement. Founded in 1970, our staff of 500 expert
hydrogeologists, geologists,  engineers, environ-
mental scientists, chemists and managers in 15
offices nationwide work to deliver superior tech-
nical solutions for government and private indus-
try. Visit booths 1605 and 1607 for more specific
capability information.

EcoTekLSI                           2114
3342 International Park Dr.
Atlanta, GA 30316
404/244-0827

Full service  environmental  laboratory with
multiple state certifications. EPA CLP participant.
8,000 ft2 chemical laboratory, 16,000 ft2 radio-
logical laboratory. EcoTek LSI provides analyses
of full organics and inorganics, and some  R & D.
EcoTek LSI's radiological laboratory provides
analyses  on hazardous wastes,  mixed wastes,
drinking water, solid wastes, and other toxic ma-
terials.
Ecology and                      2103/2105
Environment, Inc.                2107/2109
Buffalo Corporate Center
368 Pleasantview Dr.
Lancaster, NY 14086
716/684-8060

Ecology  and  Environment, Inc., provides  the
complete range of  scientific and engineering
consulting services required by generators, stor-
ers, transporters, and disposers  of hazardous,
toxic, infectious, radioactive and solid wastes.
The firm has  offices from coast-to-coast and is
represented around the globe. A broad spectrum
of environmental assessment and pollution con-
trol services are also provided including emer-
gency spill response, asbestos removal manage-
ment, hazards and risks analysis, and analytical
laboratory and testing services.

Ejector Systems, Inc.   0902/0904/0906/0908
910 National Ave.
Addision, IL 60101
708/543-2214

Ejector Systems, Inc., manufactures pumping and
treatment systems for contaminated groundwater
and leachate.

Engineering News-Record (ENR)        1711
1221 Avenue  of the Americas
New York, NY 10020
212/512-3132

Engineering  News-Record  (ENR),  McGraw-
Hill's building  and construction newsweekly,
reports on every segment of the marketplace:
buildings, transportation projects,  water  and
power, the environment, and more. Over 416,000
decision-makers rely on ENR for the business and
technical news  they need to compete  in  the
world's largest industry.

Engineering-Science              2204/2206
75 North Fair Oaks Ave.
Pasadena, CA 91103
818/440-6101

Engineering-Science (ES) is  a full service,  na-
tional and international environmental engineer-
ing firm providing complete services in hazardous
waste management. With offices in 27 domestic
locations, ES is active in supporting industrial and
military clients in all phases of site/remedial in-
vestigations, feasibility studies, remedial action
                                                                                                                                            985
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plan preparation, sile cleanup/closure and post-
closure activities.
Enviro-Tech Management
Consulting
7120 Wyoming N.E.
Albuquerque, NM 87109
        1713

505/828-9885
Enviro-Tech is a full service management con-
sulting firm that specializes in acquisitions, merg-
ers, source funding, certified business valuation
and search & recruitment primarily for the envi-
ronmental industry. Give us your requirements for
a corporate candidate and let us put our highly
qualified personnel to work. (Offices nationwide)
For information call 1-800-873-4280.

The EnvlroMed Companies, Inc.        0602
414 West California Ave.
Ruston, LA 71270
318/255-0060

The  EnviroMed Companies, Inc.  (EMC),  is a
multidisciplinary   environmental  engineering,
consulting and testing firm founded in 1974. EMC
Personnel include  engineers, geologists, chem-
ists, biologists, lexicologists and industrial hy-
gienists who provide turnkey solutions to ground-
water, hazardous waste, effluent discharge and
industrial hygiene problems. EMS routinely de-
signs and installs hazardous waste/ground water
remediation systems. EMC owns three full-serv-
ice laboratories operating GC/MS, GC, ICP, AA,
HPLC and other stale-of-lhe-art instrumentation.
Call NATIONWIDE 1-800-256-4362.

Environmental Careers                0311
760 Whalers Way, Suite 100-A
Fort Collins, CO 80525
303/229-0029

ENVIRONMENTAL  CAREERS  magazine  is
dedicated to the human resources needs of the
environmental industry. Each issue features ad-
vert ising for environmental employment opportu-
nities and training programs, a professional edu-
cation calendar, and timely career and training
articles written by industry experts. Also on dis-
play are ENVIRONMENTAL LAB and ASBES-
TOS ISSUES magazines.

Environmental Chemical
Associates, Inc.                        0226
5118 Highway 33 & 34
Farmingdale, NJ 07727
201/938-3010
Waste Management Services: Waste Characteri-
zation, Laboratory Analysis, Facility Approval,
Transportation, Documentation, Disposal. Tech-
nologies available  include  Recycling,  Fuels
Blending, Incineration, Treatment, Stabilization,
Secure Landfill. Services also include: Lab Pack-
ing, Site Remediation and Consulting.

Environmental
Company, Inc., The                   1606
P.O. Box 5127
1230 Cedars Court, Suite 100
Charloitesvillc. VA 22905
804/295-4446

The Environmental Company (TEC) is a multi-
disciplinary environmental consulting company
providing services to DOD, civilian agencies, and
private clients. TEC offers the full range of envi-
ronmental  disciplines:  engineering, environ-
mental, physical science, asbestos, health  and
safety, as well as construction management in
support of environmental projects.

Environmental Compliance
Services, Inc.                          0302
One East Uwchlan Ave., Suite 300
Exton, PA 19341
215/269-6731

ECS is an organization dedicated to assisting
environmental companies with their insurance,
safety, and compliance needs through the unique
combination of in-house  expertise in environ-
mental regulation, risk management, and insur-
ance underwriting. ECS is the only company in the
country to provide an exclusive program of insur-
ance for companies facing an environmental
exposure.

Environmental Directory, The          2415
60 E. Chestnut, Suite 415
Chicago, IL 60611
708/671-5853

The Environmental Directory is a nationwide
company  which publishes  Regional Environ-
mental Directories. The Environmental Directory
is a Single-source Directory of hundreds of com-
panies offering a variety of Environmental Prod-
ucts and Services ranging from Air Consultants to
Waste  Minimization. Directories are currently
available for the  Midwest,  Eastern  Seaboard,
Southern California, Northern California, South-
west, Pittsburgh, and the Pacific Northwest, with
more to come.

Environmental
Instruments, Inc.                 0313/0315
2170 Commerce Ave., Unit S
Concord, CA 94520
415/686-4474

Environmental Instruments  Co.  (El) sells  and
rents equipment specifically designed to meet the
needs of the environmental industry - specializing
in innovative equipment for water, soil and air
treatment, sampling and monitoring. We will be
demonstrating  our vapor extraction blower  and
vapor treatment system, a catalytic incinerator,
new photo-ionization detector and new flame-
ionization detector. For more information, call our
toll-free number: (800) 648-9355.

Environmental Science &
Engineering, Inc.                 2118/2120
P.O. Box 1703
Gainesville, FL 32602-1703
904/332-3318

ESE offers comprehensive in-house services in
Toxic and Hazardous Materials Control; Environ-
mental Engineering; Analytical Services; Indus-
trial Hygiene/Safety; Geosciences; Surface  and
Groundwater Monitoring; Air Resources; Asbes-
tos Management; Biosciences; Risk Assessment;
Underground Storage Tank Management; Envi-
ronmental Audits; Planning and Permitting;  and
Public/Community Relations.
Environmental Technology, Inc.        0608
3705 Saunders Ave.
Richmond, VA 23227
804/358-5400

HazWaste Industries Incorporated and its operat-
ing subsidies (Environmental Technology, Envi-
ronmental  Risk Sciences,  Bionomics  and
HazLabs) provide a full range of environmental
services:  Site Investigations,  Inspections  and
Audits; Risk Assessments; Feasibility and Trcala-
bility Studies; UST Closures; Facility Decontami-
nation and On-Site Treatment; Site Remediation,
Emergency Response and Removal; and Long-
Term Monitoring. HazWaste provides complete,
quality and cost-effective solutions to its clients'
environmental problems.

Envirosafe Services, Inc.          2122/2123
P.O. Box 167571
Oregon, OH 43616-7571
419/255-5100

Envirosafe Services, Inc. provides cost effective,
proven waste management services to generators
of hazardous and industrial waste materials. Fed-
eral Part B awarded waste management facilities
in Idaho and Ohio conveniently service the entire
nation via truck or rail transportation. Envirosafe
specializes in secure disposal, chemical stabiliza-
tion and PCB management services. Envirosafe
offers economical, environmentally sound waste
management for a wide  variety of hazardous and
industrial waste materials.
                                                                    Envlrotrol, Inc.
                                                                    P.O. Box 61,432 Green St.
                                                                    Oregon, OH 43616-7571
                                      0711
                                                                    Envirotrol is a nationwide full service activated
                                                                    carbon company. We provide carbon reactiva-
                                                                    tion,  and adsorption  systems  for  wastewater,
                                                                    groundwater, air purification, solvent recovery,
                                                                    and process applications. We also  offer virgin
                                                                    carbon, bulk transportation. We serve hazardous,
                                                                    non-hazardous, liquid, and vapor phase applica-
                                                                    tions.

                                                                    Exxon Chemical Company             1303
                                                                    P.O. Box 4321
                                                                    Houston, TX 77210-4321
                                                                    713/460-6826

                                                                    Exxon Chemical Company offers a complete line
                                                                    of products and application expertise specifically
                                                                    for waste-water treatment. Of particular interest
                                                                    are Diklor® chlorine dioxide products for organic
                                                                    contaminate destruction of phenols, mercaptans
                                                                    and sulfides.

                                                                    Fenn-Vac, Inc.                        2022
                                                                    P.O. Box 62679
                                                                    North Charleston, SC 29419-2679
                                                                    803/552-8306

                                                                    Fenn-Vac, Inc., offers Tank Cleaning and Decon-
                                                                    tamination; Tank Removal and Disposal; Lagoon
                                                                    Closure;  Filter Press Dewatering Systems; Trans-
                                                                    fer, Transport  and  Disposal of Bulk Liquids/
                                                                    Sludge; Excavation and Removal of Waste Solids;
                                                                    Surface and Subsurface Product Recovery; Treat-
                                                                    ment  of  Contaminated Groundwater, Permitted
-------
Hazardous Waste Transporter; Emergency Re-
sponse  Actions;  Remediation  of  Hazardous
Waste Sites; and Total Capability in Hazardous
and Non-Hazardous Environments.

First Environmental Laboratories         0111
#2 Stewart Ct.
Denville, NJ 07834
201/328-3900

First Environmental Laboratories - complete ana-
lytical  services for soil,  air,  water - NPDES,
RCRA, drinking water, Superfund TLC -19,000
square foot facility - state of the art instrumenta-
tion used by professional, experienced staff.

Fluor Daniel, Inc.                 1014/1016
3333MichelsonDr.
Irvine, CA 92730
714/975-6000

Fluor Daniel offers a broad range of environ-
mental services including new facility support
(permitting air emissions, wastewater treatment),
regulatory compliance (audits, UST), and reme-
diation services (RI/FS, Remedial Design, Reme-
dial Action), which is backed by full engineering,
construction,  project  management and mainte-
nance experience.

Forestry Suppliers, Inc.                 1315
P.O. Box 8397
Jackson, MS 39284-8397
601/354-3565

Environmental equipment catalog company dis-
playing soil recovery augers and probes, ground-
water/surface water sampling and testing equip-
ment, safety wear for workers exposed to hazard-
ous wastes, surveying/engineering instruments
and supplies - and more! Sign up for our free 420-
page catalog.

Foster Wheeler
Enviresponse, Inc.               2203-2205
8 Peach Tree Hill Rd.
Livingston, NJ 07039
201/535-2378

Foster Wheeler Enviresponse, Inc. is a full serv-
ices environmental engineering, consulting, and
remediation company. Principal services include
regulatory  compliance   know-how,   environ-
mental technical assistance, remedial design ca-
pabilities and remedial action. The company has
an outstanding and well-trained professional staff
experienced in site investigations, environmental
audits,  permitting, risk  assessments, remedial
investigations, feasibility  studies,  technology
evaluations, sampling, closure plans, wastewater
treatment, air pollution  control, and remedial
designs as well as site cleanups.

Four Seasons Industrial
Services, Inc.                     2509/2511
4920 Old Pineville Rd.
Charlotte, NC 28217
704/527-1293

Full service environmental construction company
with capabilities in industrial services, tank serv-
ices, on-site treatment systems, emergency  re-
sponse, remedial services and transport  tanker
cleaning. To offer these capabilities, the company
has  developed  the  following  technologies:
groundwater  treatment utilizing  air  strippers;
contaminated soil treatment using vacuum extrac-
tion; bio-remediation; stabilization; design and
construction of secondary tank containment sys-
tems and thermal volatilization and destruction of
VOC-contaminated non-hazardous soils.

The Foxboro Company           2404/2406
Foxboro, MA 02035
508/543-8750

Instrumentation for  providing  quantitative and
qualitative information on hazardous waste and
spill site contaminants. The Foxboro CENTURY
Organic Vapor Analyzer (OVA) can be used to
detect areas of high vapor concentration, identify
and determine concentration levels of various
organic compounds and provide  rapid, reliable
screening/analysis of volatile hydrocarbons in
groundwater samples. The newest Foxboro MI-
RAN portable Gas Analyzer, the MIRAN 203, is
an economical choice for applications where only
one gas is being detected and measured. This new
lightweight analyzer permits the user to measure
any number of gases by simply inserting a differ-
ent calibration set.

FRANKLIN MILLER INC.             LDC
60 Okner Pkwy.
Livingston, NJ 07039
201/535-9200

GREENHORNE&
O'MARA, INC.                        2500
9001 Edmonston Rd.
Greenbelt, MD 20770
301/982-2800 x442
Greenhome & O'Mara, Inc. provides hazardous
waste management services to industry and gov-
ernment. Our  experienced staff (most OSHA/
AHERA-certified)  know the requirements of
RCRA, CERCLA, SARA, TOSCA, NEPA, CWA,
and CAA. Services include site characterization,
property transfer assessments, asbestos  manage-
ment, groundwater assessments, facility audits,
RI/FSs, remedial design, waste minimization, and
surveying.

Galaher Settlements Company          1209
260 Franklin St., Ste. 1510
Boston, MA 02110
617/439-6260
Pioneering the use of structured  settlements in
environmental cases, Galaher Settlements rein-
forces its position as a leading national firm spe-
cializing in the development of creative periodic
payment programs individually tailored  to the
present and future needs of all parties. Contact our
specialists today - there is no charge for our serv-
ice.

Galson Remediation              0115-0117
6627 Joy Rd.
East Syracuse, NY 13057
315/463-5160
Gaslon Remediation Corporation (GRC) special-
izes in the development and application of chemi-
cal destruction of PCB's, dioxins, PCP, pesticides,
and other hazardous wastes in soils and sludges.
Processes for cleaning soils and sludges are now at
full scale commercial operation  levels. Gaslon
Laboratories offers complete and professional
analytical services for the full range of environ-
mental samples, including hazardous wastes, pri-
ority pollutants, toxic metals and organics in soil,
groundwater  and   wastewater, air  toxics,
leachates, drinking water, and emission samples.
Gaslon  Laboratories  has  extensive  analytical
experience under environmental regulations such
as RCRA, CERCLA, the Clean Air Act, and the
Clean Water Act. We perform all pertinent analy-
ses according to the EPA Contract Lab Program
(CLP) protocols as a standard service.

Gartner Lee, Inc.                      1302
105 Main St.
Niagara Falls, NY 14303
716/285-5448

Environmental consulting - offering services in
environmental  and  engineering geophysics,
packer testing and contaminant hydrogeology.
Geophysical services include high resolution EM,
magnetics, radar,  borehole geophysics, seismic
refraction and reflection. Hydrogeology services
include site investigations, geochemistry, model-
ing, monitoring and water supply. Perform RI/FS,
ECRA studies, Phase I and II surveys.

General Physics Corporation           0209
6700 Alexander Bell Dr.
Columbia, MD 21046
301/290-2300

General Physics Environmental Services offers
laboratory and pilot treatability testing for many
industrial waste and remediation technologies.
GP combines the resources of environmental
engineering with our in-house EPA CLP testing.
GP provides a full range of industrial hygiene
services. GP provides innovative, value-driven
services that accurately address the needs of our
customers.

Geo-Con, Inc.                    0204/0206
P.O. Box 17380
Pittsburgh, PA 15235
412/856-7700

Geo-Con, Inc. is a national remedial construction
company specializing in on-site hazardous waste
treatment. Capabilities of the company include:
Turn-key project execution; In-situ solidification
and stabilization;  Containment systems such as
vertical  barriers,  capping and  liners; RCRA
landfill construction and retrofit; Deep soil and
Shallow soil mixing; Groundwater collection and
treatment; VOC removal from soil; Bioremedia-
tion; Plant decontamination and Decommission-
ing and construction Management.

GeoGroup, Inc.                  1106-1108
9029 Shady Grove Ct.
Gaithersburg, MD 20877
301/258-7491

Geo Group, Inc. provides a range  of quality soil,
rock and environmental monitoring services. Part
of our range includes Water Level Indicators,
Bailer Samples and Temperature Meters. We also
provide innovative Data Logging Systems and
Portable Readout Units using infra red techniques
to monitor gas emissions from landfill sites.
                                                                                                                                              987
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Geophysical Survey Systems, Inc.       0601
13 Klein Dr.
P.O. Box 97
North Salem, NH 03073-0097
603/893-1109

Radar: Ground penetrating, subsurface interface
radar  (SIR)  systems used  to non-destructively
scan the subsurface for buried tanks, pipes, and
drums; locate and delineate landfills and trenches;
and identify water table, bedrock and other geo-
logical features.

Geoprobe Systems                     2420
607 Barney St.
Salina, KS 67401
913/825-1842

Geoprobe  Systems  manufactures  innovative
equipment  for soil gas, soil core, and shallow
groundwaler  sampling  using  small  diameter
driven probes. This equipment includes the hy-
draulically  powered Geoprobe  8-M probe ma-
chine  which has found extensive use in site inves-
tigation work.  Geoprobe manufactures a com-
plete line of probing tools.

Geosafe Corporation                  2102
303 Parkplace, Suite 126
Kirkland, WA 98033
206/822-4000
Geosafe  Corporation offers in situ vitrification
(ISV) services for remediation of contaminated
soil and sludge sites. The ISV process destroys
hazardous organics through pyrolysis and simul-
taneously immobilizes hazardous inorganics in a
delistable, vitrified residual. This cost-effective
process offers  significant advantages over con-
ventional soil treatment processes.

Geosclencc Consultants, Ltd.           1914
500 Copper N.W., Suite 200
Albuquerque, NM 87102
505/842-0001

Geoscience Consultants, Ltd. (GCL) is a minority-
owned small business (8(a) Certified) and is a full-
service environmental design and engineering
consulting firm. GCL provides the following serv-
ices: UST Management; Air Quality Assessment
or Permitting; Remedial Engineering, Investiga-
tions,   and  Actions; Waste Minimization and
Compliance Reviews; Groundwater  Remedia-
tion; Regulatory Negotiation; Risk Assessments;
and Health and Safety Training.

GILARDE ENVIRONMENTAL
OF FLORIDA, INC.                   LDC
1201 U.S. Hwy. One, Suite 435
North Palm Beach, FL 33408
407/624-9770

GILARDE ENVIRONMENTAL OF FLORIDA,
INC. offers full service  environmental manage-
ment lo private industry,  utilities and governmen-
tal entities. GILARDE specializes in: project man-
agement, remedial action, hazardous waste trans-
portation/disposal, biohazardous/medical  waste
removal/destruction, emergency response man-
agement and landfill construction/closure, uliliz-
ing its own Oeel of heavy equipment and trained
opcralors.
GoWer Associates, Inc.                 LDC
3730 Chamblee Tucker Rd.
Atlanta, GA 30340
404/496-1893

Colder Associates is an international group of
employee-owned consulting engineering compa-
nies providing regular support to clients in the
fields of hazardous, solid, nuclear and mixed
waste management,  transportation, power gen-
eration,  water  resources management,  mining,
and  commercial development. The  group of
companies currently maintains 37 offices in the
United States, Canada, the United Kingdom, Swe-
den, Australia, Germany and Italy. The worldwide
staff consists of over 950 personnel including
more than 600 professional engineers and geolo-
gists.

Griffin Remediation Services, Inc.       0610
500 Winding Brook Dr.
Glastonbury, CT 06033
203/657-4277
Griffin Remediation Services, Inc. (GRS) is a full-
service remediation company with specialty ex-
pertise in the design and implementation of com-
prehensive solutions to groundwater-oriented en-
vironmental problems. An affiliate of Griffin De-
watering  Corp., GRS utilizes over 50 years of
groundwater control experience. From Iheir 21
locations throughout North America,  Griffin
employs innovative technologies focused on the
containment, recovery, treatment and/or disposal
of hazardous and  nonhazardous  groundwater
pollutants. Services include: remedial dewater-
ing; trenching; slurry, bio-polymer, interceptor,
leachate collection; landfill gas vents; deepwells;
wellpoints; monitoring wells; soil vents; air strip-
ping; and pump sale/rentals.

Groundwater Technology Inc.          1001
220 Norwood Park South
Norwood, MA 02062
617/769-7600

A full service environmental company specializ-
ing in petroleum hydrocarbon site investigation
and remediation including in  situ and above-
ground bioremediation, vapor extraction, chemi-
cal neutralization,  soil gas surveys,  air quality
monitoring, well drilling, real estate audits, risk
assessments, GTEL Analytical Laboratories, and
ORS Environmental Equipment including Ther-
mal and Catalytic  Scavenger Vapor Abatement
Systems, product recovery pumps, bioreactors,
and airstripping towers.

GRUNDFOS PUMPS
CORPORATION                      0211
2555 Clovis Ave.
Clovis, CA 93612
209/292-8000

GRUNDFOS PUMPS CORPORATION is the
manufacturer  of the REDI-FLO ENVIRON-
MENTAL PUMP. The REDI-FLO is constructed
of stainless steel and Teflon and is designed lo
pump contaminated groundwaler from a 4-inch
well or larger. REDI-FLO pumps can provide flow
rales up to 32 gallons per minute and to beads of
680 feet. For more information, contact GRUND-
FOS at (209) 292-8000.
Gundle Lining Systems, Inc.            0505
19103 Gundle Rd.
Houston, TX 77073
713/443-S564
Gundle  Lining Systems, Inc. Houston, Texas, is
recognized as the world leader in the manufacture
and installation of high density polyethylene lin-
ing  systems.   Gundle  manufactures  HOPE
(Gundline HD) synthetic liner in over 34 ft. seam-
less widths from 30 to 140 mils thick. The com-
pany  offers  a full product range that can be
adapted to any  operational need. In  addition,
Gundle  illustrates its commitment to excellence
with innovations such as the patented  extrusion
welding machine and the new automatic wedge
welder.  Product innovations from Gundle in-
clude: Gundnet, drainage net; Gundline HOT, a
textured HOPE linen and Hyperlaslic, a very low
density polyethylene liner.

H2M Group                          1908
575 Broad Hollow Rd.
Melville, NY 11747
516/756-8000

H2M is a multi-disciplined consulting firm. With
over 57  years of experience, H2M specializes in
civil, environmental and structural engineering,
architecture, planning and environmental science.
The firm's full scope of professional services
encompasses wastewater pollution control, civil/
site engineering, community planning, water sup-
ply/resources management, solid and hazardous
waste management, environmental impact analy-
sis, as well as environmental laboratory services.

HARDING LAWSON
ASSOCIATES                   0413/0415
1155 Connecticut Ave., N.W., #500
Washington, DC 20036
202/429-6675
HARDING  LAWSON ASSOCIATES (HLA)
provides engineering,  environmental, and con-
struction services for hazardous and solid waste
management. Ranked 59th in top 500 design firms
and 12t h in hazardous waste by Engineering News
Record:  ranked one of nation's best small compa-
nies by Business Week and Forbes: and awarded
two national and one State engineering excellence
awards for innovative site remediation.

HAZCO
Services, Inc.         2303-2307 & 2304-2308
2006 Springboro West Rd.
Dayton,  OH 45439
513/293-2700
Personal protective equipment,  instrumentation
rental and repair services, sampling equipment,
decontamination  trailers and software  solutions
for the hazardous waste cleanup market.

HAZMAT Training, Information
and Services, Inc.                      1006
(Hazmat TISI)
6480 Dobbin Rd.
Columbia, MD 21045
301/964-0940

HAZMAT Training, Information and  Services,
Inc. (Hazmat TISI), is a training company whose
offerings include the development and delivery of
-------
 courses that meet the hazardous waste operations
 and emergency response training requiiments of
 29 CFR 1910.120 and/or NFPA Standard 472, etc.
 In addition to open-enrollment courses offered at
 their Columbia, Maryland, location, they deliver
 tailored, on-site programs. For more information,
 call our toll-free number: (800) 777-TISI (8474).

 HMCRI                               2011
 9300 Columbia Blvd.
 Silver Spring, MD 20910-1702
 301-587-9390

 Hazardous Materials  Control Research Institute
 (HMCRI) is a  public, nonprofit membership or-
 ganization. Its mission is to promote the establish-
 ment and maintenance of a reasonable balance
 between expanding industrial productivity and an
 acceptable environment. This major goal is being
 met by providing national and regional confer-
 ences, numerous publications and texts, seminars,
 advanced degree possibilities, exhibitions on a
 large scale showing equipment and products, and
 many  other informational  dissemination pro-
 grams. HMCRI's membership program, unique to
 the industry, now exceeds 5,000 active partici-
 pants.  A definite and distinctive forum is now
 available for these individuals and future mem-
 bers to exchange information  and experiences
 dealing with hazardous waste and the protection
 of the environment. JOIN HMCRI TODAY!
 Become  active in  the ONLY hazardous waste
 membership organization.

 HMM Associates, Inc.                  2201
 196 Baker Ave.
 Concord, MA 01742
 508/371-4000

 HMM Associates is an environmental engineer-
 ing, consulting and planning firm with headquar-
 ters in Concord, Massachusetts. HMM provides a
 full range of hazardous waste/materials services
 including: Superfund RI/FSs, remedial design and
 construction oversight; personnel protection and
 safety  training; and environmental compliance
 audits and management. HMM is a Summit Envi-
 ronmental Group company.

 HNU Systems, Inc.           2421/2422/2423
 160 Charlemont St.
 Newton Highlands, MA 02161
 617/964-6690

 Model HW101   Hazardous  Waste Analyzer;
 IS101 - Intrinsically Safe Analyzer; PI101 - Pho-
 toionization  Analyzer (and portables);  301DP -
 Dedicated Programmable Gas Chromatograph;
 311 - Portable Gas Chromatograph; 321 - Com-
 pact temperature programmed gc; 331 - Compact
 dedicated capillary gc; SEFA-P - Portable x-ray
 fluorescence analyzer; 75 Meter - Portable ph/mv
 temperature meter; 76 Meter - Microprocessor ph/
 ion meter; ISE - Ion Selective Electrodes.

 HWAC                               0514
 1015 Fifteenth St., N.W., #802
 Washington, D.C. 20005
 202/347-7474
 HWAC - An Association of Engineering and Sci-
 ence Firms Practicing in Hazardous Waste Man-
agement (formerly the Hazardous Waste Action
Coalition) is a national trade association repre-
senting engineering and science firms involved in
hazardous waste management. HWAC represents
more than 115 member firms who employ 60,000
people across the nation who are responsible for
approximately 90 percent of the available consult-
ing capacity of cleanup of hazardous waste sites in
the United States. Since its formation  in 1985,
HWAC has worked to improve business and pro-
fessional conditions for engineering and science
firms.

HYDRO-SEARCH, INC.               0615
175 N. Corporate Dr., Suite 100
Brookfield, WI53045
414/792-1282

Services in Hydrogeology, Engineering, and Proj-
ect Management for:  Remedial Investigations/
Feasibility Studies (RI/FS); Preparation of Work
Plans;  Managing On-Site Activities; Designing
and Implementing  Remedial Action Programs;
Technical Guidance  for  Responsible Parties;
Oversee EPA Contractors; Review Groundwater
Monitoring  Plans  and Reports; Underground
Storage Tank Management;  Landfill Siting and
Design; Water Resource Management; Mine Tail-
ings and Water Management.

Hanson Engineers Incorporated         1405
1525 S. 6th St.
Springfield, IL 62703
217/788-2450
Hanson Engineers,  Inc., provides a full range of
environmental-waste management services na-
tionally to industry, government and consultants.
Services include: site assessment; RI/FS; design/
oversight of remedial action; hydrogeologic/geo-
physical services; UST management; property au-
dits; RCRA permitting; site  characterization for
hazardous, mixed and LL nuclear waste; soil gas
surveys;  geotechnical  laboratory for contami-
nated soils.
Hart Crowser, Inc.                     LDC
1910 Fairview Ave., E.
Seattle, WA 98102
206/324-9530
Hayward Baker Inc.                    1021
1875 Mayfield Rd.
Odenton, MD 21113
301/566-6110
Hayward Baker Environmental, a national spe-
cialty contractor, provides a range  of solutions
including: Containment Barriers; Contaminated
Groundwater Collection;  Sludge Solidification
and Stabilization; Landfill Closures and Stabiliza-
tion; and other On Site Remediation Services.
With over 40 years of experience, we have the
resources to meet time, quality control and safety
constraints.

HazMat Environmental
Group, Inc.                            1401
60 Commerce Dr.
Buffalo, NY 14218
716/827-7200

HazMat Environmental Group,  Inc., is a firm
specializing in hazardous waste/hazardous mate-
rials management. Our  services   are offered
throughout the United States. The  services we
offer include transportation, technical consulting,
and personnel training. HazMat operates offices
in Buffalo, NY and Cincinnati, OH.
HazMat World Magazine               0411
800 Roosevelt Rd., Bldg. C, #206
Glenellyn,IL 60137
708/858-1888

A publication edited for individuals responsible
for specifying and purchasing products, systems,
equipment and services used for hazardous mate-
rials and waste management from  generation
through  packaging,  handling,  transportation,
processing or ultimate disposal. Information and
forms for tree subscriptions will be available for
qualified individuals.

Hazen Research, Inc.                   1004
4601 Indiana St.
Golden, CO 80403
303/279-4501

Hazen Research, Inc.  provides a full range of
waste treatment services including characteriza-
tion, reduction, remediation and  minimization,
treatability studies, leaching and extraction proc-
esses, soil washing, and thermal processes. Spe-
cializing in treatment of metal-bearing wastes,
Hazen's other services include custom engineer-
ing, pilot plant services, process development,
analytical services, and market/feasibility studies.

Heritage Environmental
Services Inc.                     2401/2402
2728 Colonial Ave., #100
Roanoke, VA 24015
703/344-1750
Heritage is a full-service environmental company
with national service. Some of the services pro-
vided include complete laboratory services, treat-
ment and disposal, transportation, remediation
and engineering, and lab pack.
Hewlett-Packard                 1011-1013
Route 41, Box 1100
Avondale, PA 19311-1100

Hewlett-Packard will display systems for EPA
environmental  analysis and methods. They in-
clude:  a GC/MS  system  for  hazardous  waste
analysis, an HPLC-based Pesticide Analysis Sys-
tem, and a Supercritical Fluid Extractor for sample
preparation. All feature automation and instru-
ment control.

Hill International, Inc.            2502/2504
One Levitt Parkway
Willingboro, NJ 08046
609/871-5800

Hill International, the world's leader in construc-
tion claims and construction consulting, will be
introducing the ENVIRONMENTAL CLAIMS
CENTER. The Center is a professional services
organization combining the skills of attorneys, en-
gineers, and environmental specialists along with
contracts and construction experts. The Center
assists clients with Superfund enforcement ac-
tions and cost recovery.

Howard Smith Screen Company         1709
P.O. Box 666
Houston, TX 77001
713/869-5771

Howard Smith Screen Company is a manufacturer
of well screens and accessories for the environ-
mental, water well and oil industries.
                                                                                                                                             989
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Hoyt Corporation                     0303
251 Forge Rd.
Westport, MA 02790
508/636-8811

Hoyt Corporation of Westport, MA will be dis-
playing their full line of Solvent Vapor Recovery/
Air Pollution Control  Equipment, Distillation
Equipment, Odor Control Equipment, and Liquid
Purification Equipment.

Hydro Group, Inc.                     1118
97 Chimney Rock Rd.
Bridgewater,  NJ 08807
201/563-1400

Hydro Group, Inc. is a unique full-service com-
pany that can  combine engineering and construc-
tion capabilities  for all phases of groundwater
remediation  from   groundwater  exploration
through well installation and treatment systems to
startup. Treatment equipment manufactured by
Hydro Group, Inc. includes air stripping towers,
clarifiers, pressure filters, aerators and GAC units.

Hygienetlcs,  Inc.                      0807
150 Causeway St.
Boston, MA 02114
617/723-4664

Hygienelics,  Inc. is an industrial hygiene and
environmental consulting firm specializing in as-
bestos management, hazardous materials man-
agement, and indoor air quality assessment. Our
worldwide offices - in Boston (Headquarters);
Hartford, New York City, Washington, D.C., Chi-
cago, Los Angeles, San Francisco, Honolulu and
Frankfurt, West Germany - assure quick and cost-
effective service.

I-Chem Research                1703-1705
23787-F  Eichler St.
Hayward, CA 94545
415/782-3905

A complete line of glass and polyethylene sample
bottles, jars and vials supplied with Teflon-lined
closures  attached and  available chemically pre-
cleaned and  laboratory-certified  to meet EPA
specifications. Also available are: custom cleaned
sample containers, protective shipping materials,
convenient sampling kits,  and preservatives in
ampules.

ICF Kaiser Engineers                  1214
1800 Harrison St.
Oakland, CA  94612
415/268-6000

ICF Kaiser Engineers provides engineering and
construction  services  to clients involved with
environmental,  transportation, industrial,   ad-
vanced technology, energy, and other infrastruc-
ture projects around the world. ICF Kaiser Engi-
neers'  1600 professionals work on hundreds of
projects including planning and  managing  the
cleanup of Boston Harbor. We are one  of  the
nation's top five  companies in hazardous waste
engineering.
ICM Laboratories                     0416
1152 Route 10
Randolph, NJ 07869
201/584-0330
Full service laboratory specializing in environ-
mental analysis.  Laboratory  services include
analysis for compliance  with ECRA,  RCRA,
N JDES, hazardous waste classification, CERCLA
and TCLP. Monitoring well sampling also avail-
able.
In-Situ, Inc.                           1002
P.O. Box 1,210 South 3rd St.
Laramie, WY 82070
307/742-8213

In-Situ's HERMIT Data Logging Systems pro-
vide reliable field instrumentation for water re-
source evaluations, including aquifer testing and
short- and long-term monitoring in many types of
water bodies. The instrumentation is widely re-
spected for its ability  to operate unattended in
extreme weather conditions over extended peri-
ods of time without compromising accuracy. In-
Situ also offers a number of Hydrologic Software
programs for both PC and mainframe computers.
In-Situ's Leak Detection Systems use a patented
sensing technology for monitoring underground
storage  tank installations that provides intrinsi-
cally safe and reliable leak detection. Three differ-
ent models are available.

Industrial & Environmental
Analysts, Inc.                         0310
3000WestonPkwy.
Gary, NC 27513
919/677-0090

LEA, Inc. is an environmental testing and sam-
pling corporation. IEA offers unparalleled per-
formance  under  the EPA  Contract  Laboratory
Program (CLP). Analytical services include TCL/
TAL, TPH by GC and IR, TCLP,  asbestos by
TEM, metals by AA, ICP and ICP/MS, SEM and
full wet chemistry. In addition, LEA offers sam-
pling services in groundwater, air, wastewater and
soils, adhering to strict EPA protocols.
Inqulp Associates                      0713
1300 Old Chainbridge Rd., #3
McLean, VA 22101
703/442-0142

Inquip Associates, Inc. is a geotechnical contrac-
tor whose history dates back to the 1950's. In-
quip's main activity has related to the installation
of soil-bentonite cutoff barriers and liners.  Re-
cently , it has expanded to include other geotech-
nical techniques, especially environmental proj-
ects, using the latest technical advances  in the
field.

Institute of Gas Technology       1706/1708
3424 South State St.
Chicago, IL 60616
312/567-3794

IGT is a not-for-profit educational, energy and
environmental research and development organi-
zation established in Chicago, Illinois in 1941.
IGT's environmental capabilities include waste
incineration and detoxification, and catalytic and
biological decontamination of hazardous and in-
dustrial waste, soils and sludges, and groundwa-
ter. IGT programs range from fundamental inves-
tigations  through bench-scale and pilot plant
process development to field testing.
Integrated Chemistries,
Incorporated                          1609
1970 Oakcrest Ave. Suite 215
St. Paul, MN 55113
612/636-2380
An environmental specialty chemical company
that develops and markets chemical processes that
create more effective ways to remediate and ana-
lyze hazardous waste. Our CAPSUR system his
effectively remediated nonporous surfaces con-
taminated with Polychlorinated Biphenyls and
Pentachlorophenol. The CAPSUR system is cost-
effective and offers significant advances over
conventional surface cleaning methods.

Intergraph Corporation                1123
2051 Mercator Dr.
Reston, VA 22091
703/264-5600
Intergraph Corporation is the largest CAD/CAM/
CAE systems vendor in North America and the
leading supplier of interactive computer graphics
systems to the federal government. A Fortune 500
company, Intergraph provides  UNIX worksta-
tions and servers as well  as fully integrated soft-
ware in environmentally oriented applications
such as mapping/CIS, AEC and facilities manage-
ment.

International Technology Corporation  0203
23456 Hawthorne Blvd.
Torrance, CA 90505
213/378-9933
International Technology Corporation (FT) is an
environmental management company with mul-
tiple technologies and human resources to solve a
wide variety of problems involving hazardous
chemical and nuclear materials. The Company
provides a comprehensive range of services and
products to industry and  governmental agencies
in four business areas: Environmental Engineer-
ing and Services, Analytical Services, Remedia-
tion  Projects and Services and Pollution Control
Systems.
Interox America                       0225
3333 Richmond Ave.
Houston, TX 77098
713/522-4155
Hydrogen peroxide and FB* Sodium Percarbon-
ate - the oxidants of choice for wastewater treat-
ment. Control odors and oxidize organic com-
pounds, cyanides, chlorine  and reduced sulfur
compounds without toxic by-products.
JJ. Keller & Associates, Inc.
8361 U.S. Highway 45
Neenah, WI 54957-0368
414/722-2848
2418/LDC
JJ. Keller & Associates, Inc. currently researches,
writes, edits, and prints over 60 technical publica-
tions serving the CPI and transportation industry.
Keller also offers chemical handling and regula-
tory training kits, videos, and handbooks as well
as hazardous materials  management  software.
Featured at Superfund '90 will be Keller's Haz-
ardous  Waste  Management Guide;  Chemical
Regulatory CrossReference; HAZWOPER Man-
ual and Training Kits; OSHA Compliance Mao-
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ual; Chemical Training Booklets; Hazardous Ma-
terials  Guide;  Chemical  Crisis  Management
Guide; Haz Mat II Software, and Reg-A-Dex Soft-
Jacobs Engineering Group Inc.           2108
251 South Lake Ave.
Pasadena, CA 91101
818/449-2171

Jacobs is one of the largest professional service
firms in the U.S. providing engineering, design
and consulting  services; construction and con-
struction management; and process plant mainte-
nance. The Company provides its services nation-
wide and internationally for selected industries in-
cluding environmental and hazardous waste; fa-
cilities for aerospace, high technology and other
applications; and process plants for chemical,
petrochemical and pharmaceutical industries, the
energy and refining industries, and the mineral
and fertilizer industries.

James T. Warring Sons, Inc.            2212
4545  S St.
Capitol Heights, MD 20743
301/322-5400

All types and sizes of containers - new and recon-
ditioned - fiber, steel, plastic. Our hazardous waste
containers are DOT approved and range in size
from  5 to 110 gallons. We accept orders from one
to truck loads and we ship anywhere. You order a
container - we don't have it - it's special - we will
get it for you. No order is too small for James T.
Warring Sons, Inc. Let us help you contain your
hazardous waste. Also provided is empty drum
removal with custom shredding  and  crushing
done  on your site.

KV Associates                         1414
281 Main St.
Falmouth, MA 02541-9811
508/540-0561

KV Associates is a manufacturer of investigation
products for soil, gas and water; and soil sampling
of remediation products for soil venting and vola-
tile destruction using shield screens and catalitic
converter systems and flowmeters for determin-
ing rate and direction of groundwater flow.

Kimmins Thermal Corporation          0806
256 Third St.
Niagara Falls, NY 14303
716/282-7252

Kimmins Thermal  Corporation, a Subsidiary of
Kimmins  Environmental Service Corporation
(NYSE:KVN),  provides full-service hazardous
waste remediation contracting. Services range
from  packaging,  transportation,  and  disposal
services to on-site incineration. Disposal services
include: radioactive and mixed wastes, gas cylin-
ders,  and  explosive/shock sensitive materials.
Services available nationally.

LTC  International, Inc.                 0912
101-G Executive Dr.
Sterling, VA 22170
800/822-2332
LTC International offers a full line of dust-free,
high production vacuum blasting machines. This
equipment is suitable for removal of many toxic
substances, such as lead paint, while reducing
waste generated by 95% over conventional open
blasting!
LWD, Inc.                             1010
P.O. Box 327
Calvert City, KY 42029
502/395-8313

LWD, Inc.  is a full service waste management
company specializing in the rotary kiln incinera-
tion of hazardous and non-hazardous materials.
We are a licensed transporter of such materials and
operate a HDPE non-hazardous industrial waste
"special" landfill. A field service division per-
forms site remediation and industrial cleaning to
customer specifications.
Laboratory Resources
363 Old Hook Rd.
Westwood, NJ 07675
        2416
201/666-6644
Laboratory Resources is a full service analytical
testing laboratory capable of analyzing air, water,
soil, hazardous waste, asbestos, industrial hygiene
and a host of other matrices. The distinguishing
nature of the company includes responsiveness to
the customer, fast turnaround and unparalleled
quality service. Call (800) 729-1397 for more
information.

Laborers-AGC Education
& Training Fund                      2116
P.O. Box 37, Rte. 97 & Murdock Rd.
Pomfret Center, CT 06259
203/974-0800

The Laborers-AGC Education and Training Fund
is a labor/management trusteed organization that
develops and implements training programs for
over 70 training centers located throughout the
United States and Canada (32). Courses offered
include: Line Foreman Safety Training, Pipe Lay-
ing, Blasting, Laser Beams, Asbestos Abatement,
and Hazardous Waste Worker Training.

Laidlaw Environmental            0215/0217
 Services, Inc.                     0219/0221
P.O. Box 210799
Columbia, SC 29221
803/798-2993

Laidlaw Environmental Services is the new name
for GSX Chemical Services, Tricil and their affili-
ated companies. From  more than 50 locations
throughout  the U.S.  and Canada, Laidlaw Envi-
ronmental Services offers a longstanding record
of performance, financial stability, and the organ-
izational flexibility to tailor service solutions to
your specific environmental concerns. Combined
strengths. Combined resources. Laidlaw Environ-
mental Services...the ONLY name you need to
know to manage your industrial and hazardous
wastes.
Lancaster Laboratories, Inc.           1005
2425 New Holland Pike
Lancaster, PA 17601
717/656-2301
An independently owned and operated testing
laboratory located in Lancaster,  Pennsylvania.
With a staff of more than 370 scientists, techni-
cians, and support personnel housed in a 78,000
sq. ft. facility, we provide a wide range of environ-
mental, industrial hygiene, food, and pharam-
aceutical testing services. We also provide Ex-
pressLAB and sample pickup services.

Law Environmental, Inc.           2503/2505
114 Town Park Dr.
Kennesaw, GA 30144
404/590-4605
With more than fifty years of experience in the
environmental consulting field, Law focuses on
giving you creative and proactive solutions to
environmental regulatory compliance issues. We
offer you services in the following areas: Under-
ground Storage Tanks;  RCRA    Hazardous
Wastes;  CERCLA/SARA    Superfund; Solid
Waste   Management;  Hydrology/Water   Re-
sources; Commercial Property Transfers; Indus-
trial Property Transfers; Air Quality; Wetlands.

Layne-Western
Company, Inc.                   2004/2006
1900 Shawnee Mission Pkwy.
Mission Woods, KS 66205
913/362-0510

Layne-Westem Company, Inc. brings technical
knowledge and practical experience to the spe-
cialized fields of investigative  drilling, remedial
action  and environmental monitoring. From of-
fices  located  coast-to-coast,  Layne  provides
clients  with a pool of talented professionals and a
high commitment to professionalism, safety and
quality.

Lockheed Analytical
Laboratory                      2517/2519
1050 E. Flamingo Rd.
Las Vegas, NV 89119
702/734-3303

Built to meet the environmental chemistry needs
of industry and government, Lockheed's world-
class laboratory in Las Vegas, Nevada, offers a
broad  range  of superior analytical chemistry
services—services that ensure the success of even
your most difficult environmental projects.

Lopat Enterprises Inc.                  2101
1750 Bloomsbury Ave.
Wanamassa, NJ 07712
908/922-6600

Lopat's K-20/LSC is used in the control and
remediation of all hazardous teachable toxic met-
als mandated by the USEPA, state and local au-
thorities in incinerator ash, soil, soil-like solids or
semi-solid wastes. K-20/LSC treated wastes will
meet TCLP, CAM WET, MEP or EP TOX require-
ments.  K-20/TCC is used in the control of PCB's
and other chlorinated and organic compounds in
soil-like particulate matter and on various cemen-
titious surfaces.

Los Alamos Technical
Associates, Inc.                       1507
6501 Americas Parkway NE, Suite 900
Albuquerque, NM 87110
505/884-3800

Los Alamos Technical Associates, Inc. (LATA),
provides engineering and scientific services to
government and industry in the areas of waste
                                                                                                                                             991
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management  (hazardous, radioactive, mixed-
waste); NEPA compliance planning and docu-
mentation; and nuclear process equipment and
facility design. Over 300 personnel representing
40 technical disciplines. Most staff hold DOE Q
clearances.

MAC Corporation/
Saturn Shredders                      1117
201 East Shady Grove Rd.
Grand Prairie, TX 75050
214/790-7800

Manufacturers, designers, and fabricators of re-
duction systems to address the needs of PCB, haz-
waste, low-rad waste, and steel-drummed chem-
waste processors. If incineration or other treat-
ment requires preparing the infeed through shred-
ding, opening, separating, disengaging or reduc-
ing the size of same, our expertise will positively
contribute to your decision-making process.

MICROMEDEX, Inc.                 1306
600 Grant St. 6lh Floor
Denver, CO 80203-3527
303/831-1400

Referenced source on medical and hazard infor-
mation regarding thousands of chemicals used in
the industrial setting; in-depth coverage of clinical
effects, range of toxicity, workplace standards,
and response to hazardous incidents. Designed for
use by health and safety directors, occupational
medicine professionals, and industrial hygienists.

MFC Environmental                  2015
8631 W.Jefferson
Detroit, MI 48209
313/849-2333

MPC Environmental is a full service Environ-
mental Contractor.  Services include: 24  hour
Emergency Response Capability, High Capacity
Portable  Pumping Systems  (3,000 GPM), Site
Cleanups,  PCB  Decontamination/Removal/
Transportation, Hazardous  Materials  Cleanup/
Transportation and  Groundwaler  Remediation
Services. GET TO KNOW  US BEFORE ALL
HELL BREAKS LOOSE!

MSA (Mine Safety
Appliances Co.)                        0304
P.O. Box 426
Pittsburgh, PA 15230
412/967-3000

MSA will display a full line of personal protective
equipmenl including  products for respiratory
protection and environmental monitoring.

MSP Technical Services, Inc.           1313
110 James Drive West, Suite 218
St. Rose, LA 70087
504/465-3300

To  provide  technically  advanced, innovative
products and services for the Waste Management
Industry,  while achieving the highest level of
customer-driven,  quality service at the lowest
possible cost with  an  organization  of highly
trained people committed to health, safety and the
environment  for its employees and the commu-
nity
MWR, Inc.                            2121
615 W. Shepherd St., POB 10
Charlotte, MI 48813
517/543-8155
Remedial services emphasizing a patented soil
vapor extraction process.

Map Express                          LDC
P.O. Box 280445
Lakewood, CO 80228
800/627-0039
Map Express provides the full-service link be-
tween you, the professional community, and the
resources of the U.S. Geological Survey and other
agencies, supplying the map products your com-
pany needs today. Overnight shipping, toll-free
24-hour order line, personalized customer serv-
ice, corporate deposit  accounts,  and a special
research department are among the services we
offer.

Marcel Dekker, Inc.                    LDC
270 Madison Ave.
New York, NY 10016
212/696-9000

Publishing firm of all types of Hazardous Waste
texts, reference books and manuals.

Maxwell Laboratories,
S-CUBED Division                    1402
P.O. Box 1620
La Jolla, CA 92038
619/453-0060

Chemical Analysis Services: CLP Organic Analy-
ses; RCRA Analyses; Methods 1618,1624,1625
Analyses for OWRS Samples; Inorganic Ana-
lytes. Quality Assurance Support - BOAT, SITE,
OPP Projects: QA Project Plan Reviews; Final
Report Reviews; Field Audits; QA Training. Ana-
lytical  Methods  Development  and  Research.
Environmental  Engineering: Site Investigation/
Field  Sampling  and  Monitoring;  Treatability
Studies; Solidification/Stabilization.

Medlab Environmental
Testing, Inc.                          0402
P.O. Box 2045
Wilmington,  DE 19899
302/655-5227

Medlab offers: full service environmental testing
laboratory; free  courier service;  sampling; and
analysis for hazardous waste, asbestos, wastewa-
ter and soils, drinking water and radon, and indus-
trial hygiene; multi-stale certifications. NVLAP
accredited, NIOSH PAT participant.

Metcalf&Eddy                  1126/1128
30 Harvard Mill Square
Wakefield, MA 01880
617/246-5200

Metcalf & Eddy protects the environment. Using
a complete range of environmental services and
capabilities,  we assure that the  nation's water
resources  and  waste-generating  activities are
properly managed. Unique in the  environmental
field, Metcalf & Eddy offers you a single source
for the development, design, construction man-
agement, and operation  of water,  wasiewalcr,
sludge, hazardous and solid waste management
systems. Few other firms offer their clients finan-
cial planning and management alternatives, such
as total project delivery, contract operations, and
program management. Industries, municipalities,
and governmental agencies  around  the world
have benefited  from Metcalf & Eddy's unique
blend of technical, operation, and management
expertise provided by a highly experienced staff
of 2,200 technical and management specialists.
Licensed, highly skilled personnel use a large and
specialized assembly of equipment to clean up
and transport hazardous waste.

Michigan  Waste Report, Inc.           LDC
400 Ann Street,  N.W., Suite 204
Grand Rapids, MI 49504-2054
616/363-3262

Publishers for: MICHIGAN WASTE REPORT -
Bi-weekly Newsletter, 21 Issues plus Directories,
$325/yr. 3 SPECIAL ANNUAL DIRECTORIES
REPORTS (sold separately)  Haz.  Waste, Env.
Mgt., Solid Waste, $43.60 each. ACT 64 LEGAL
MGT. SYSTEM MANUAL, MI Haz. Waste Laws
& Regulations, $395. RESOURCE EXCHANGE
& NEWS  MAGAZINE Waste Exchange & Re-
cycled Material Markets, 6 Issues, $48/yr. ENVI-
ROX  ON-LINE COMPUTER SERVICE Envi-
ronmental  Information & Waste Exchange List-
ings.

Mllllpore  Corporation                 0202
80 Ashby Rd.
Bedford, MA 01730
617/275-9200 x2337

Millipore will exhibit its line of products for the
analysis of hazardous materials including the Zero
Head Space Extractor  designed specifically for
evaluating waste according to the TLCP. Mil-
lipore also offers a Rotary Agitator, dispensing
pressure vessels and a complete line of membrane
filters.

Morrison  Knudsen Corporation         1101
P.O. Box 73
Boise, ID 83729
208/386-6172
"One Sea, One  Sky, One World  Environment,
One Company: MORRISON KNUDSEN" - serv-
ing private- and public-sector clients worldwide
through  site investigation,  feasibility  studies,
engineering, and construction for:  Industrial
waste treatment and pollution control; Municipal
waste management; High- and low-level radioac-
tive waste disposal; Waste treatment, storage, and
disposal (TSD) facilities.

NUS Corporation               2322-2323
Park West  2, Cliff Mine Rd.
Pittsburgh, PA 15275
412/788-1080

For 30 years, NUS Corporation has provided the
environmental and engineering expertise to solve
industry and government  waste problems with
cost-effective solutions. Our staff of 1950 mul-
tidisciplinary professionals offers a full range of
services including environmental assessment, en-
vironmental engineering, remedial design engi-
neering, hydrogcologic and geologic services,
-------
•risk assessment, regulatory assistance, environ-
mental health and safety and analytical services.
Nappi Trucking Corporation            1514
P.O. Box 510, Hwy. #34
Matawan, NJ 07747
201/566-3000

Transportation and storage of Hazardous and
Non-Hazardous Waste.

National Academy Press                LDC
2101 Constitution Ave., N.W.
Washington, DC 20418
202/334-3313

The National Academy Press was created by the
National Academy of  Sciences to publish the
reports issued by the Academy and by the Na-
 tional Academy of Engineering, the Institute of
 Medicine, and the National Research Council, all
 operating under the charter granted to the National
Academy of Sciences  by the Congress  of the
 United States.

 Nat'l Env'l Tech. Appl. Corp.
 (NETAC)                              0213
 615 William Pitt Way
 Pittsburgh,  Pa 15238
 412/826-5511

 The National Environmental Technology Appli-
 cations Corporation (NETAC) facilitates com-
 mercialization of promising environmental tech-
 nologies. NETAC services include technical and
 commercial assessments; technology  develop-
 ment assistance; testing and demonstration, mar-
 ket analysis and business development; permit-
 ting and regulatory assistance; identification of fi-
 nancial sources.  NETAC was created in 1988
 through cooperative between the U.S. Environ-
 mental Protection Agency and the University of
 Pittsburgh to help move environmental technol-
 ogy to the marketplace.

 National Draeger, Inc.                  2507
 101 Technology Dr.
 Pittsburgh,  PA 15275
412/787-8383

National Draeger offers a wide range of products
within the respiratory, instrumentation, and detec-
tor tube lines. The  Model 190 Datalogger is the
most advanced portable gas monitor available for
industrial hygiene  and safety professionals.  It
detects toxic gas and alarms independent of the
microprocessor function. National Draeger's air-
purifying respirators include cartridges for or-
ganic vapors, and gases and ammonia, as well as
high efficiency particulate filters for dust, fumes,
mists, radionuclides, and asbestos.

National Environmental Products       2521
Greenwood Ave., P.O. Box 38
Newfield, NJ 08344
609/697-1066

"Drum Stix" environmental sampling tools for
liquids, solids and sludge. Call out toll-free num-
ber for more information: 1-800-542-6816.

National Environmental
Testing, Inc.                      1312/1314
220 Lake Drive East
Cherry Hill, NJ 08002
609/779-3373
A growing nationwide network of environmental
testing laboratories, dedicated to providing high
quality analytical services backed by a compre-
hensive field services which include field sam-
pling, stack testing and industrial hygiene serv-
ices.

National Express
Laboratories, Inc.                      1712
6801 Press Dr., East Building
New Orleans, LA 70126
504/283-4223

NatEx is a network of environmental laboratories
located in strategic regions of the country serving
industry, engineering/consulting firms and gov-
ernmental agencies. Each network laboratory is a
participant in the EPA Contract Laboratory Pro-
gram and has expertise in analytical methodolo-
gies in support of  RCRA, CERCLA, SARA and
CAA regulations.  At NatEx, we emphasize re-
sponsive client services and meeting committed
turnaround times, in addition to high quality ana-
lytical services.

National Library of Medicine            1612
8600 Rockville Pike, Building 38A, 3S308
Bethesda, MD 20894
301/496-6531

The National Library of Medicine plans to exhibit
Environmental  Protection  Agency's  (EPA's)
Toxic  Chemical  Release  Inventory  (TRI87,
TRI88) databases on NLM's Toxicology Data
Network (TOXNET) System. TRI databases con-
tain information on the annual estimated releases
of toxic chemicals to the environment. It is man-
dated by Title III of the Superfund Amendments
and Reauthorization Act (SARA) of 1986. The
Inventory contains provisions for the reporting,
by  industry, on the releases of over 300 toxic
chemicals into the air, water and land. NLM also
will perform on-line demonstrations of searching
the other files of TOXNET System such as HSDB,
RTECS, CORK, IRIS, DART, ETICBACK, EM-
ICBACKandDBIR.

National Lime Association              2414
3601 North Fairfax Dr.
Arlington, VA 22201
703/243-5463
Lime - Calcium Magnesium Oxides and Calcium
Magnesium Hydroxides - Man's Oldest and Most
Versatile Chemical. Nature's gift for the steward-
ship of our planet. It almost does it all: neutraliza-
tion, chemical fixation, stabilization and solidifi-
cation of toxic and hazardous materials. Lime may
be  the natural,  cost-effective solution to your
hazardous waste problems.
National Seal Company                0318
1245 Corporate Blvd., #300
Aurora, IL 60504
708/898-1161

National Seal Company manufactures and installs
flexible membrane liners, drainage netting  and
geotextiles for landfills, hazardous waste storage,
leach pads and reservoirs. Computerized manu-
facturing system produces competitively priced
liners that are twice as good as industry standards.
NSC's unique seaming procedure enhances liner
strength and leakage resistance.
National Solid Wastes
Management Association               1714
1730 Rhode Island Ave., N.W., Suite 1000
Washington, DC 20036
202/659-4613

CWTI (Chemical Waste Transporters Institute),
ICWM (Hazardous Waste Treatment and Dis-
posal Institute) and RCI (Remedial Contractors
Institute)  are  components  of National Solid
Wastes Management Association to promote safe
transport and cleanup of hazardous waste sites.
NSWMA is the only association representing
these interests for Superfund and other state clean-
ups.

Normandeau Associates, Inc.           2005
25 Nashua Rd.
Bedford, NH 03102
603/472-5191

Normandeau Associates, Inc., has been providing
specialty environmental consulting services since
1970. These specialty services include ecological
risk assessment, aquatic  toxicology, analytical
laboratory services,  wetland mitigation, water
quality studies, and a full range of environmental
specialists at over 12 locations throughout the
eastern U.S.

Northeast Research
Institute, Inc.                          1121
309 Farmington Ave., Ste. A-100
Farmington, CT 06032
203/677-9666

NERI provides Petrex soil gas surveys, and Indus-
trial Hygiene and Analytical Lab Services. Tech-
nical representatives will discuss how the Petrex
soil gas  method is used  for site assessments,
LUSTs, property transfers, etc. Custom analyses
of Petrex samplers can now be achieved by GC/
MS to meet sophisticated survey objectives.

Northeastern Analytical
Corporation                      1307/1309
4 East Stow Road
Marlton, NJ 08053
609/985-8000
Environmental  Services: Complete  Environ-
mental Field Sampling, In-house Gas Chromatog-
raphy/Mass Spectrometry (GS/MS) Laboratory
Analysis, Hazardous  Site Training (40 Hours),
Asbestos Inspection & Management &  Abate-
ment Monitoring Services, Asbestos Analysis by
Transmission Electron & Optical Microscopy,
Underground Storage Tank Testing, Excavation,
Removal and Installation, Stack  Emission and
Ambient Air Testing.

OHM Corporation                0403/0405
16406 U.S. Route 224 East
Findlay, OH 45840
800/537-9540

OHM's subsidiaries provide the following envi-
ronmental services: Environmental Testing and
Certification Corp. (5 laboratories) - analysis and
management; OHM Remediation Services Corp.
(21 response centers) - assessment, engineering,
design, on-site remediation for soil, groundwater,
lagoons,  facilities, waste  sites; OHM Resource
                                                                                                                                             993
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Recovery Corp. (Part B facility): Waste treatment
and disposal.

OLDOVER CORPORATION          1909
P.O. Box 228
Ashland, VA 23005
804/798-7981

Oldover  Corporation  provides comprehensive
waste management services including transporta-
tion, fuel blending, thermal destruction, recycling
and drum recovery. State-of-the-art equipment
and multiple locations assure prompt, dependable
service. A 17-year no-lost-time accident record
demonstrates Oldover's commitment to the safe
handling of hazardous wastes.

OSCO Environmental
 Management                         0308
618 Grassmere Park Dr., #7
Nashville, TN 37211
615/832-0081

The new treatment facility in Nashville, Tennes-
see, processes all types of liquid and solid wastes
including waters,  oils, sludges, acids, bases and
cyanides. Solids stabilization is offered in bulk.
Waste is received in bulk and drums by truck or
rail. Transportation  is available  in 42 states.
Remediation and professional consulting services
are offered nationwide.

OCCUPATIONAL HAZARDS
Magazine                             1412
1100  Superior Ave.
Cleveland, OH 44114
216/696-7000
OCCUPATIONAL HAZARDS Magazine is ed-
ited for management  officials who are responsible
for workplace safety, health and environmental
compliance. Editorial material includes coverage
of major legislative, regulatory, scientific and
other  developments affecting the field, as well as
practical "how-to" articles.

Ogden Environmental
Services, Inc.                     1308/1310
3550  General Atomics Ct.
San Diego, CA 92121-1194
800/876-4336
Turnkey site remediation services and in-plant
destruction solutions. Ogden's transportable in-
cinerator provides cost effective, environmentally
safe, remediation alternatives.

On-Slte Instruments/
EnviroRENTAL            0704/0706/0708
689 North James Rd.
Columbus, OH 43219
1/800/766-7483

On-Sile Instruments/EnviroRENTAL sells, rents
and services a complete line of industrial hygiene,
laboratory and environmental monitoring instru-
ments and equipment. Rent-lo-own and leasing
options are also available. Our service department
provides technical and applications assistance,
while  our distribution cenler handles all accessor)1
orders. On-Sitc also offers training classes at our
Columbus, Ohio,  facility.  Call 1-800-7-On-Site
for more information.
P.E. LaMoreaox &
Associates, Inc. (PELA)                LDC
P.O. Box 2310
Tuscaloosa, AL 35403
205/752-5543
P.E. LaMoreaux  and Associates, Inc. (PELA),
consulting hydrologists, geologists,  engineers
and environmental scientists, offers hydrological,
geological, environmental and hazardous waste
consultation services. Other services provided
include sampling, laboratory analysis, develop-
ment of monitoring programs and installation of
wells, reclamation, permitting, court testimony,
and graphics and communications programs.

PACE Incorporated              0702-0801
1710 Douglas Dr. North
Minneapolis, MN 55422
612/544-5543
PACE is a national environmental laboratory and
consulting firm serving all regions of the United
States. Services are provided through a national
network of 10 facilities. Services offered include:
field sampling, organic and inorganic laboratory
analyses for water, soil, and air; bioassay toxicity
testing; and, asbestos, industrial hygiene, air pol-
lution and risk assessment consulting services.

POLLUTION EQUIPMENT NEWS/Rlmbach
Publishing Inc.                        1023
8650 Babcock Blvd.
Pittsburgh, PA 15237
412/364-5366
POLLUTION EQUIPMENT NEWS, published
bi-monthly, provides product information to the
person responsible for air, water, wastewater and
hazardous waste. An  annual  CATALOG  &
BUYER'S GUIDE provides buying source infor-
mation. INDUSTRIAL HYGIENE NEWS, pub-
lished bi-monthly, provides information on prod-
ucts and services for measuring and controlling
health hazards in the  work environment.
PRC Environmental
Management, Inc.                      1510
303 East Wacker Dr., Suite 500
Chicago, IL 60601
312/856-8700

PRC EMI provides environmental services to both
government and industry. Headquartered in Chi-
cago, Illinois, PRC EMI maintains major offices in
McLean, Virginia, San Francisco, and Denver as
well as 13 other offices throughout the country.
Specialties include remedial investigations/feasi-
bility studies, endangerment assessments, reme-
dial design and implementation, compliance au-
dits, permitting support, waste reduction audits,
risk management support, environmental and
systems engineering, policy and regulatory analy-
sis, economic analysis, and program management
support.
PacTec, Inc.
28701 Allen Rd.
Clinton, LA 70722
        0915
800/272-2832
PacTec, Inc., offers polyethylene liners utilized in
dump trucks, roll-off assemblies and rail gondolas
for transporting bulk solids and sludges. These
liners reduce the risk of leaking, help eliminate
washout costs and increase container longevity.
Pacific Analytical, Inc.                 1610
1989-B Palomar Oaks Way
Carlsbad, CA 92009
619/931-1766

Pacific Analytical (PA) is an innovative, high
technology environmental analysis  laboratory
oriented  toward work with unusually complex
samples.  PA specializes in providing high quality
analysis results for volatile and semivolatile or-
ganics, and pesticides using 500 series, 600 series,
1600 series and SW-846 methods; dioxins by
8280 (LRMS), 8290 and  1613 (HRMS); and
metals by 6020 and 200.8.

Pennsylvania Drilling Company        0214
500 Thompson Ave.
McKees Rocks, PA 15136
412/771-2110

Pennsylvania  Drilling Company will be demon-
strating  capabilities  for installing monitoring
wells on  a variety of sites under a  variety of
conditions. In  addition, they will be  displaying
drilling tools  and monitoring well equipment
made in their new shop in McKees Rocks near
Pittsburgh, Pennsylvania.
Peoria Disposal Company              2515
4700 N. Sterling Ave.
Peoria, IL 61615
309/688-0760
RCRA Treatment, Disposal Facility,  Analytical
Services,  Transportation, Remediation, Consult-
ing and Engineering Services.

PermAlert ESP, Inc.                   1912
7720 Lehigh Ave.
Niles, IL  60648
708/966-2190
Manufacturers of the Double-Pipe1*1  secondary
contained piping systems. PAL-AT™  cable type
leak  detection  and  location  system, and
TankWatch™ leak detection system. DOUBLE-
PIPE is a preengineered and prefabricated system
available  in steel, fiberglass and thermoplastics.
The PAL-AT leak detection system is micropro-
cessor based, UL listed and intrinsically safe for
Class 1, Groups C & D, Div. 1.

Peroxldatlon  Systems             0205/0207
4400 E. Broadway, Suite 602
Tucson, AZ 85711
602/327-0277

Peroxidalion  Systems  supplies  services and
equipment for UV/hydrogen peroxide chemical
oxidation of organic materials in water or waste-
water.

Photovac International
Incorporated                     2410/2412
25-B Jefryn Blvd. West
Deer Park, NY 11729
516/254-4199

Photovac will  display portable instruments for
environmental toxic monitoring in groundwater,
soil, and ambient air TIP™, a hand held Total Or-
ganics analyzer; the 10S Series Portable Gas
Chromaiographs; and MicroTIP™, a hand held
analyzer which incorporates advanced micropro-
cessor technology for real time digital or graphic
assessment of toxic gases and vapors.
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Poly-John Trailer Division    2514/2516/2518
P.O. Box 1037, Old U.S. 31 South
Rochester, IN 46975
219/223-6566

Poly-John Trailer Division's Decontamination
Units are state of the art design and construction.
Special attention is given to every detail insuring
users of comfort and safety with a functional and
practical floorplan. Any industry  dealing with
contaminated materials must take every precau-
tion possible for the safety of its employees and
the  environment.  Poly-John has created these
units to meet these strict requirements and to put
your mind at ease.

Polyfelt, Inc.                          0109
1000 Abernathy Rd., Suite 1520
Atlanta, GA 30328
404/668-2119

Polyfelt, Inc. is a worldwide manufacturer of
spunbonded,     continuous     filament,
needlepunched geotextiles with a major focus in
the  Waste Containment industry.  Our  product
lines range from 2.7 - 22 oz/sy. We provide tech-
nical support, geotechnical design guidelines and
data, QC/QA certifications, and a worldwide dis-
tributor network.

Princeton Testing
Laboratory, Inc.                       1116
P.O. Box 3108
Princeton, NJ 08543
609/452-9050
Environmental  Analysis;  Industrial Hygiene;
RCRA/ECRA; industrial wastewater;  NPDES;
groundwater; OSHA workplace surveys; asbestos
monitoring & evaluation; complete NIOSH labo-
ratory methodology; asbestos & HAZ-MAT train-
ing courses; Right to Know compliance; Microbi-
ology; Bioassay; Underground Storage Tank test-
ing; AHA  accredited.  Certified for:NJ DEP;
NYDOH; PA DER; CT; RI; & DE.
Project Time & Cost, Inc.              0810
3390 Peachtree St., NE, 16th Floor
Lenox Tower South
Atlanta, GA 30326-1108
404/239-0220

Skillful management of cost, time and quality is
essential to the successful completion of any proj-
ect  plan,  especially in  today's environmental
arena. Project Time & Cost, a full-service cost
engineering and project management consulting
firm, possesses the experience and resources re-
quired to provide these essentials to both govern-
mental and private sector clients.

QED Environmental Systems, Inc.  1025-1027
P.O. Box 3726
Ann Arbor, MI 48106
313/995-2547

Well  Wizard®  Dedicated Sampling Systems;
Sample Pro® Groundwater Sampling Supplies;
Pulse Pump® Recovery Pumping Systems; Hydro-
Punch® Groundwater Sampling Without Wells.

QUALTEC, Inc.                  0803-0805
11300 U.S. Highway One, Suite 600
Palm Beach Gardens, FL 33408
407/775-8395
QUALTEC, Inc., specializes in on-site remedia-
tion utilizing stabilization via fixation/solidifica-
tion. QUALTEC also provides construction/clo-
sure of landfills and RCRA caps; treatability stud-
ies; pilot studies; site restoration; groundwater
remediation; construction management; and fixa-
tion equipment and personnel leasing. QUAL-
TEC's state-of-the-art cementitious fixation proc-
ess has been utilized at Superfund sites across the
nation.

Quantum Analytics, Inc.               0201
363-D Vintage Park Dr.
Foster City, CA 94404
415/570-5656

Quantum Analytics rents state-of-the-art analyti-
cal instruments and portable GCs. Products in-
clude GC, LC, AA, IR, UV, FL, TOC, and TOX.

R&GSloane                         1907
7660 N. Clybourn Ave.
Sun Valley, CA 91352
818/767-4726

Containlt - secondary containment piping system
fits over virtually any piping system. It is available
with either split or solid pipe and split fittings,
making it ideal for both retrofit and new system
installations. The Containlt systems injection
bonding method allows it to be pressure rated up
to 75 psi.
R.E. Wright Associates, Inc.            1305
Environmental Restoration Systems
3240 Schoolhouse Rd.
Middletown, PA 17057

REWAI designs and manufactures groundwater
treatment  and  subsurface  towers, pneumatic
pumps and the Auto-Skimmer. REWAI provides
turnkey systems - pre- and/or post-treatment, off-
gas treatment and installation and maintenance
contracts.

RJ. Lee Group, Inc.                    1003
350 Hochberg Rd.
Monroeville, PA 15146
412/325-1776
RJ Lee Group provides analytical and consulting
services in  materials characterization. A wide
variety of analytical equipment is used with  em-
phasis on optical, scanning and electron micros-
copy. Materials investigated include metals, ce-
ramics, powders, air participates, semi-conduc-
tors and bio materials. Complete in-house chemi-
cal laboratory. Products include  Zeppelin  mi-
croimaging and MICROSURE® OPTICAL FI-
BER COUNTING COMPUTER systems.

RMC Environmental
 Services, Inc.                         1113
R.D. #1, Pricks Lock Rd.
Pottstown, PA 19464
215/326-9662

Environmental  Consulting,  Engineering  and
Analytical Services; including hazardous waste
site investigations, hydrogeological investiga-
tions,  aquatic and terrestrial ecological studies,
wetland studies, natural resource damage assess-
ments, regulatory compliance audits, hazardous
waste volume and toxicity reduction, permit assis-
tance, underground storage tank systems assis-
tance, waste treatment system engineering, and
environmental chemistry laboratory services.

Radian Corporation                    2403
8501 MoPac Blvd., P.O. 201088
Austin, TX 78720-1088
512/454-4797

RADIAN CORPORATION PROVIDES A FULL
RANGE OF PROCESS, SOLID, AND HAZ-
ARDOUS    WASTE     ENGINEERING
SERVICES...including site assessment to reme-
diation design and construction, waste minimiza-
tion to the design of waste treament or disposal
systems, and preparing  permit  applications to
responding to consent orders. In addition, the
company has three full-service laboratories pro-
viding complete characterization and classifica-
tion of soils, groundwater, run off, leachates, air
emissions, soil vapors, and virtually any  other
substance or material for which measurements are
required. RADIAN also has the unique ability to
perform remedial pilot studies on site. This is
accomplished through our transportable treat-
ment systems. The unit physical-chemical opera-
tions incorporated into these systems can be con-
figured to treat most contaminated waste streams.
These systems have sufficient capacity to provide
full-scale groundwater remediation.

Recra Environmental, Inc.              1410
10 Hazelwood Dr.
Amherst, NY 14228
716/691-2600

Recra Environmental,  Inc.  is an independently
owned and operated corporation providing a wide
range of organic and inorganic analyses on wa-
ters, soils and waste matrices. Recra is a U.S. EPA
CLP laboratory with laboratories in Amherst, NY,
Columbia, MD, Cleveland, OH and Detroit, MI.
Data management, electronic transfer, individual-
ized programs are provided with rapid, profes-
sional, high quality analytical services.

Remcor, Inc.                      1506/1508
701 Alpha Dr.
Pittsburgh, PA 15238
412/963-1106

Remcor, Inc., provides the full spectrum of haz-
ardous waste consulting and remediation serv-
ices. By uniquely integrating expertise in engi-
neering, construction,  and  environmental  field
services, Remcor performs projects ranging from
investigations and assessments through actual re-
mediation. As a turnkey contractor, Remcor has
completed numerous projects including building
decontaminations,  surface impoundment and
landfill closures,  storage tank management, as-
bestos removals, groundwater remediation and
mixed waste cleanups.

Remediation Technologies,
Inc. (ReTeC)                           0614
22419 - 72nd Avenue South
Kent, Washington, 98032
206/872-0247

Remediation Technologies, Inc. (ReTeC), is  a
field services and engineering company specializ-
ing in on-site remediation of contaminants associ-
ated with organic wastes at industrial sites. ReTeC
provides turnkey services  from investigation
                                                                                                                                             995
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through final remediation/closure.  ReTeC has
designed and implemented bioremediation pro-
grams, groundwaler treatment systems and ther-
mal treatment systems for numerous RCRA and
CERCLA sites.

Research Alternatives, Inc.              0105
966 Hungerford Dr., Suite #1
Rockville, MD 20850
301/424-2803

Research Alternatives, Inc., will be demonstrating
the Emergency Information System (EIS) soft-
ware used for environmental and emergency plan-
ning, response, and recovery for natural and tech-
nological disasters. This PC-based software com-
bines 19 emergency and regulatory compliance
databases with georelational digitized maps and
data communication capabilities to provide im-
mediate access to critical information.

Resource Analysts,
Incorporated                    0314/0316
P.O. Box 778, One Lafayette Rd.
Hampton, NH 03842
800/992-0724            603/926-7777 in NH

Resource Analysts, Inc., is dedicated to complete
customer satisfaction  in the  area of analytical
testing, field sampling, bioassay, bioaccumula-
tion, product registration, FIFRA, TSCA, RCRA,
CLP (ino/org) aquatic research organism supplier.
Maintains certifications/approval status in numer-
ous states, EPA regions, DOD, ACOE, and regu-
latory agencies.

Response Rentals                       0502
1460 Ridge Rd. East
Rochester, NY 14612
800/242-3910

Response Rentals provides rental instrumentation
for remedial investigation studies, compliance
surveys and substance emergencies. The instru-
mentation is easy to operate,  reliable and repre-
sents the best names in the industry. Broad product
line meets virtually every application need and
includes, X-Met, OVA's, CGI's, PID's Isothermal
GC's, ELF Radiation and more.

RJedel Environmental
Services, Inc.                           0307
461 IN. Channel Ave.
Portland, OR 97217
503/286-4656

Riedel Environmental Services, Inc., provides to
its governmental and private clients turnkey envi-
ronmental services  which include site investiga-
tions, real estate audits, environmental engineer-
ing and design, groundwaler assessment, design
and operation of vapor and liquid recovery sys-
tems,   remedial  cleanup  utilizing alternative
cleanup technologies, underground storage tank
management, 24 hour emergency  response to
hazardous material incidents  and operation of
treatment, storage and disposal facilities.

Robertson's Barrier Systems
Corporation                           0901
580 Hornby St., Suite 800
Vancouver, BC Canada V6C3B6

Robertson Barrier Systems - Testable, High Secu-
rity Geomcmbrane Liner Syslems. The Robertson
Barrier Liner is a unique patented liner geomem-
brane system specifically designed for the safe
containment of hazardous, toxic or valuable mate-
rials or wastes. Unique because it allows testing
for the presence of potential leaks at any  time
without letting any of the contained liquid escape.
It can be used for ponds and surface impound-
ments, landfills, underground storage tanks and as
secondary spill containment. You can: Test for
leaks both during  construction  and operation;
Detect the onset and location of leaks; Control and
isolate potential leaks. All this means reduced risk
and liability for the owner, operator and the public.

Rocky Mountain Arsenal                0707
Public Affairs Office
Commerce City, CO 80022-2180
303/289-0250
Rocky Mountain Arsenal is an inactive installa-
tion conducting environmental cleanup, a result of
past production practices. Environmental Reme-
diation costs are expected to meet or exceed $1
billion. Because of its complex hazardous waste
streams and contamination, RMA has been on the
leading edge of technology with innovative tech-
niques for sampling soil, groundwater and build-
ings.

Rollins Environmental
Services, Inc.                     0517-0518
P.O. Box 2349 One Rollins Plaza
Wilmington, DE 19899
302/479-3164

The Rollins Environmental Services family of
companies provides unparalleled liability protec-
tion in hazardous waste management and disposal
services which include multiple incineration fa-
cilities, laboratory analyses, small quantity waste
and lab pack services,  PCB removal, transporta-
tion, secure land disposal, encapsulation  and
deepwell injection. In Delaware, phone 302/479-
2968 for more information.

Rose-Tillmann Inc.                     1601
One Mark Twain Plaza
Suite 200
Edwardsville, IL 62025
800/228-3328

Rose-Tillmann Incorporated is a bonding and
insurance  brokerage specializing in providing
programs nationwide for all types of environ-
mental and pollution cleanup contractors. Spe-
cializes in providing hard-to-place programs for
hazardous waste, asbestos abatement,  under-
ground storage tank removal and toxic and haz-
ardous material transportation.

Rosemount Analytical/
Dohrmann Dlv.                        0312
3240 Scott Blvd.
Santa Clara, CA 95052
408/727-6000

Dohrmann designs and manufactures trace ele-
ment analyzers for water chemicals and petroleum
products; Total Organic Carbon Analyzers, Total
Organics HaJide Analyzers, and Organic Halide
Analyzers, plus analyzers for sulfur, chlorine and
nitrogen in oil. Primarily used in product quality
control and in pollution prevention and monitor-
ing.
 Roy F. Weston, Inc.               1102/1104
 Weston Way
 West Chester, PA 19380
 215/430-3025

 WESTON is a full-service environmental engi-
 neering firm specializing in analytical laboratory
 services, consulting and  engineering, remedia-
 tion, facility construction and operations, techni-
 cal information management and the manage-
 ment of major programs. WESTON  employs
 more than 2,500 people from various disciplines,
 wholly owns 8 subsidiaries and now has 42 offices
 nationwide.

 S.S. Papadopulos &
 Associates, Inc.                        LDC
 12250 Rockville Pike, Suite 290
 Rockville, MD 20852
 301/468-5760

 S.S. Papadopulos & Associates, Inc. (SSP&A), is
 an internationally recognized firm providing spe-
 cialized services in groundwater. SSP&A offers
 expert technical assistance in all areas involving
 water and contamination in the subsurface envi-
 ronment - including groundwater and soil con-
 tamination investigations and remediation, com-
 puter modeling of hydrogeologic  systems and
 hydrochemical investigations.

 SCS Engineers                        0611
 11260 Roger Bacon Dr.
Reston, VA 22090
703/471-6150

SCS,  founded in 1970, provides hazardous and
solid waste engineering to state and local govern-
ments, the federal government, industries, corpo-
 rations and developers. Hazardous waste services
include: Remedial Investigations, feasibility stud-
 ies, and remedial designs for CERCLA and RCRA
facilities; hazardous waste storage facility design;
real  estate contamination  assessments;  under-
ground storage tanks; and wetland studies.

 SENTEX SENSING
TECHNOLOGY, INC.                1509
553 Broad Ave.
 Ridgefield, NJ 07657
201/945-3694

Computerized, self-contained gas chromatogra-
phs to provide  laboratory  analysis, on-sile, for
emergency response,  site  evaluation, soil gas
analysis and  other applications. NEW  ITEMS
INCLUDE: A portable hand-held Flame loniza-
lion Detector featuring "Point and Shoot" opera-
tion for total  hydrocarbon  detection; a portable
Gas Chromatograph/Total  Hydrocarbon Ana-
lyzer; and a portable Purge and Trap Gas Chrorna-
tograph System designed for on-site analysis of
drinking, ground and waslewaler.

 SERROT CORPORATION             1012
5401 Argosy
 Huntington Beach,  CA 92648
 714/895-3010

Specializing in the fabrication and installation of
geomembrane liners and floating covers.  We can
provide backup engineering experience and sup-
port to ensure successful installations in  a broad
span of applications from hazardous waste linen,
sewer treatment plants, chemical cell liners and
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landfills. In addition we have a large prefabrica-
tion facility that makes liners for specialty applica-
tions.

SLT North America, Inc.               2506
16945 Northchase
Houston, TX 77060
713/874-2150

SLT the world's originator of High Density Poly-
ethylene Lining Systems; manufactures & installs
its own patented lining innovation FrictionFlex,
from 60-240 mils. SLT also manufactures & in-
stalls HyperFlex,  UltraFlex  &  PolyLock  for
landfills, tunnels, floating covers, primary & sec-
ondary containments, leach pads & potable water
containments.
 SMC Environmental
 Services Group                  2113-2115
 Box 859
 Valley Forge, PA 19482
 215/265-2700

 For more than 35 years, SMC Environmental
 Services Group's Scientists and Engineers have
 been providing environmental, engineering and
 consulting support to industry, bankers, lawyers,
 developers, and government agencies. Areas of
 expertise include:  solid and hazardous  waste,
 industrial hygiene  and occupational safety and
 health, water and wastewater treatment systems,
 land planning, environmental property and facil-
 ity audits, wetlands assessments/delineations, and
 a range of engineering specialties.

 SSI Shredding Systems                 1019
 28655 S.W. Boones Ferry Rd., P.O. 707
 Wilsonvffle, OR 97070
 503/682-3633

 SSI Shredding Systems provides on-site volume
 reduction and material processing of solid hazard-
 ous waste prior to material treatment. Specific
 services include pre-processing, feedstock prepa-
 ration and volume  reduction of solid hazardous
 waste utilizing mobile, low-speed rotary shear
 shredders. This low RPM equipment  is easy to
 trailer  mount  and  once on-site, is operational
 within hours. OSHA certified operators are  pro-
 vided. Other services include solvent recovery
 and volume reduction/blending for stabilization.

 SURETEK: Surety
 Teknicians, Inc.                       2512
 4830 W. Kennedy Blvd., Suite 600
 Tampa, FL 33609
 813/281-2550

 SURETEK is a National Bond-only agency  spe-
 cializing in all types of Environmental Bonds,
 including: Remedial Action; Superfund; Lining
 Systems; Landfill Closure; Contractors; Under-
 ground  Storage Tanks; Analytical/Laboratory;
 Monitoring & Detection; Transport; and Consult-
 ants/Engineers. We handle Contractors  of all
 sizes, from those needing Small Bonds to  Multi-
 National Public Companies.
Safety Storage, Inc.
2380 South Bascom Ave.
Campbell, CA 95008
408/559-3901
                                       LDC
Sanderson Equipment Inc.              1603
P.O. Box 1066
Princeton, NC 27569
919/936-2042

Sanderson Equipment, Inc., is the USA distributor
for the R-B VC Series of Long Reach Excavators.
Utilizing a moving counterweight, the VC reaches
up to 65' with a one cubic yard bucket which can
be placed precisely where needed for a high de-
gree of productivity and safety.

Science Applications
Internat'I Corp.                        0811
1710 Goodridge Dr.
McLean, VA 22102
703/734-4302

Scientific Specialties
Service, Inc.                           1107
4030 Benson Ave.
Baltimore, MD 21227
301/644-6200

Scientific Specialties Service, Inc., is showing its
line of environmental sampling supplies. Includ-
ing precleaned and regular vials, bottles, and jars
in both glass (which is also  available Safety-
Coated, if  desired) and plastic. They  are also
showing their Teflon® Capliners and Teflon®/Sili-
cone septa and their line of Teflon® Sealing tapes
and Teflon® tubing in an extensive range of sizes.
Sevenson Environmental
Services, Inc.                      1406/1408
2749 Lockport Rd.
Niagara Falls, NY 14302
716/284-0431

Sevenson Environmental Services, Inc., provides
remedial construction services to government and
industry in site restoration;  excavation, charac-
terization, transportation, and disposal of bulk and
drummed wastes; secure landfill and lagoon con-
struction/closure; slurry wall construction; sludge
solidification; recovery and treatment  systems
installations for groundwater, soils and  air;
leachate collection  and treatment systems con-
struction; on-site incineration; biological  reme-
diation; facilities decontamination and demoli-
tion; dewatering; and storage tank removal/reme-
diation.

Shields Manufacturing/
Unified Safety Corp.               0604-0606
624 Maulhardt Ave.
Oxnard, CA 93030
805/988-1055

Environmental Compliance Products,  HazMat
Storage Facilities, Secondary Containment Sys-
tems, Fire Rated and  Non-Fire Rated, First and
Only Non-combustible Fire  Rated, Factory Mu-
tual Approved Units in the U.S.A.

Shimadzu Scientific
Instruments, Inc.                      1707
7102 Riverwood Dr.
Columbia, MD 21046
301/381-1227

Shimadzu is among the three largest scientific
instrument  companies in the world.  The  broad
product line includes gas & liquid chromatogra-
phs, spectrophotometers, TOC and thermal ana-
lyzers, oil content meters, and balances, turn key
and/or special application instruments such as En-
vironmental GC, TOGAS, and Carbamate analyz-
ers are also available.

Site Reclamation Systems, Inc.          0516
P.O. Box 11
Howey-in-the-Hills, FL 34737
904/324-3651

Manufacturing, Remediation:  Mobile  Rotary
Kiln/Afterburner System designed to treat soils
contaminated by light petroleum products such as
gasoline, aviation gas and diesel fuel.

Skolnik Industries, Inc.                 2510
4900 South Kilbourn Ave.
Chicago, IL 60632
312/735-0700
New steel  containers  (carbon, composite and
stainless),  SALVAGE  DRUMS  and  OVER-
PACKS, drum tools and accessories, heavy-duty
dolly, utility carts, components and drum replace-
ment parts, drum liners and hoist paks.
Solarchem Environmental
Systems                               1814
40 West Wilmot St., Unit #5
Richmond Hill, Ontario L4B 1H8
416/764-9666

SOLARCHEM ENVIRONMENTAL SYSTEMS
is the manufacturer of RAYOX®, a second genera-
tion enhanced oxidation process for the destruc-
tion of toxic and hazardous organic contaminants
in industrial process wastewater and contami-
nated groundwater. RAYOX® has also been ap-
plied to contaminated water from Superfund sites.

Soils Magazine                        LDC
10229 E. Independence Ave.
Independence, MO 64053
816/254-8735

Solinst Canada Ltd.                    2400
The Williams Mill, 515 Main St.
Glen Williams, Ontario, Canada L7G 3S9
416/873-2255

Manufacturers of high quality groundwater moni-
toring instrumentation, known for the Waterloo
Multilevel System and reliable water level indica-
tors. New this year are: a Water Level Meter tape
marked each 1/50 ft. and improved environmental
probe. Also an Interface Meter which measures
the level and thickness of both floating and sink-
ing hydrocarbons.

Solmar Corporation                    0813
625 West Katella Ave. Suite 5
Orange, CA 92667
714/538-0881

Advanced Bio Cultures - Formulated bacterial
products for the remediation of hazardous waste,
containment soils and groundwater, and industrial
and municipal wastewater. Solmar is a customer-
oriented service company providing excellent
support for our products, with years of experience
in bioreraediation.

Southdown Environmental              1206
Systems, Inc.                     1208/1210
1200 Smith St., Suite 2400
Houston, TX 77002
713/653-8043

Advanced Organics-Processing Technologies.
                                                                                                                                            997
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Southern Bonding and
Insurance Brokers, Inc.                 2321
2540 Professional Rd., Suite 8
Richmond, VA 23235
804/320-8390

Southern Bonding  and Insurance Brokers is an
agency established to service the needs of contrac-
tors and consultants working in the environmental
field.  Unique experience and knowledge of the
specialized area  of environmental liability and
risk management, provide our clients the opportu-
nity to choose the product best suited to their
needs. Call (703) 525-8060 for more information.


Southwest Laboratory
of Oklahoma                          0417
1700 West Albany  - Ste. C
Broken Arrow, OK 74012
918/251-2858

Quality and service oriented laboratory offering:
CERCLA,  SARA,  RCRA, Priority  Pollutants,
Dioxins/Furnas,  Appendix  IX, Explosives and
TCLP. SWLO is a full participant, in good stand-
ing, in the CLP program with contracts for organ-
ics, inorganics, and high concentration organics.
Also, certified by Corps of Engineers  for explo-
sives and DERA PROJECTS.
Southwest Research Institute            1615
6220 Culebra Rd.
San Antonio, TX 78228-0510
512/522-2687

Southwest Research Institute provides commer-
cial leak location surveys of geomembrane liners
for landfills, impoundments, and lined tanks to
accurately locale leaks in the material and seams.
Analytical laboratory systems and techniques will
be presented for both the sampling and analysis of
environmental pollutants. Bio-degradation tech-
niques will also be discussed.


Specialized Environmental
Equipment, Inc.                        0809
311 Three & Twenty School Rd.
Easley, SC 29642
803/859-8277

Mobile Laboratories: Chemical Analysis Units,
Water Pollution Analysis Units, Decontamination
Units. Special Service Units: Emergency Prepar-
edness Trailers. Row-Thru Proportional Bioassay
Dilulor Systems;  Dual Purpose Pumps; Water
Baths; Reactors; and Oxygen Demand Apparatus.


Staff Liners Industries                  1417
240 Chene St.
Detroit, MI 48207
313/259-1818

Liners  and Caps fabricated and installed world-
wide for hazardous  and non-hazardous sites.
RCRA and all Agency compliance. Forty (40)
hour OSHA trained and medical'd crews wilh
immediate response capability. 1910.120,134 All
materials - PVC, CPE, CSPE (Hypalon®, BA(XR-
5®l LDPEand HDPE. References.Call (800)526-
13wv ur (303)  251-1820 for more information.
Our FAX number is (313) 259-0631.
Stearns and Wheler                    1407
1 Remington Park Dr.
Cazenovia, NY 13035
315/655-8161
Steams & Wheler is an environmental engineer-
ing and scientific consulting firm. With nearly 200
professionals and support personnel, the firm
offers services in property audits, petroleum engi-
neering, hydrogeologic investigations, remedial
investigation/feasibility studies,  remedial de-
signs, industrial hygiene,  and risk assessments.
Headquartered in Cazenovia,  New  York, the
branches are in Tampa, Florida, Darien, Connecti-
cut, and Bedford, New  Hampshire.

Stout Environmental, Inc.         1120/1122
101 Jessup Rd.
Thorofare, NJ 08086
609/384-8000
Stout Environmental, Inc., is a full service envi-
ronmental management company providing treat-
ment and  disposal of hazardous, industrial, and
municipal wastes, along with a broad range of
specialized support services. Our 15 service divi-
sions enable us to offer a turnkey approach to
environmental  problems  providing timely and
cost-effective solutions.

Sverdrup Corporation                  LDC
801 North Eleventh
St. Louis, MO 63101
314/436-7600

With over 60 years of providing total project man-
agement,  Sverdrup  Corporation  continues to
maintain its status as one of the most diversified
companies in the industry. Our Environmental
Divisions  continue to provide a growing list of
clientele with engineering  services in the areas of
hazardous waste, wastewater treatment, ultrapure
water, and air quality control.

Sybron Chemicals,  Inc./
Biochemical Dlv.                       2007
P.O. Box 66
Birmingham Rd.
Birmingham, NJ 08011
609/893-1100

Leaders in the application of Augmented Biore-
clamation (ABR) for the  treatment of contami-
nated soil  and groundwater. Capabilities  include
biosystems engineering services and supply of
selectively adapted organisms for specific con-
tainments.  Technology useful for cleanup of
chemicals from leaking storage tanks, pipeline
spills, train derailments, etc. Advantages are ulti-
mate disposal technology and low  cost.

TCT-SLLouis                          2408
1908 Innerbelt Business Center Dr.
St. Louis, MO 63114
314/426-0880

TCT-St. Louis (formerly Envirodyne Engineers,
Inc.) is a consulting engineering firm and  an ana-
lytical laboratory. Our certified laboratory offers
full service capabilities including: radioactive
waste analyses, dioxins/furans, explosives. Ap-
pendix VI11/IX, EP Toxicity, TCLP, Priority Pol-
lutants, herbicides, and all conventional inorganic
parameters in waslewater, potable water, soil, air,
and biological matrices. Our engineering services
include site assessments, UST, treatability studies,
groundwater monitoring, RI/FS, design and con-
struction oversight.

TEBKA VAC                          LDC
P.O. Box 2199
Princeton, NJ 08543-2199
609/530-0003

Terra Vac is a subsurface remediation company
providing the full range of technologies, technical
expertise and construction services required for
the resolution of soil and groundwater contamina-
tion problems. Terra Vac's services are focused
on the definition and implementation of remedial
programs which utilize on-site technologies to
address subsurface contamination in situ.

TETRA TECH, INC.                   1409
630 N. Rosemead Blvd.
Pasadena, CA 91107
818/449-6400

Tetra Tech is a consulting engineering firm with
expertise in designing and implementing environ-
mental engineering projects for private industry
and government. Lines of business include envi-
ronmental   contamination  assessment  and
cleanup, and innovative engineering solutions for
facilities  design, process automation, and waste
management. Current clients represent all sectors
of business and industry as well as federal, state,
and municipal government agencies.

TMS Analytical Services, Inc.           0104
7726 Moller Rd.
Indianapolis, IN 46268
317/875-5894

While specializing in Dioxin/Furan analysis, TMS
offers a full complement of environmental testing,
including those specified by EPA for drinking and
waste waters, air, and solid  waste. Slate of the art
instrumentation includes GC, GC/MS, GC/MS/
MS.  GC/HRMS, HPLC, AA, ICP, and IR with
computer interfaces.

TMS, Inc.
c/o U.S. Department of Energy          LDC
20201 Century Blvd.
Germantown, MD 20874
301/353-0102

TechLaw, Inc.                          1201
14500 Avion Parkway, Suite 300
Chantilly, VA 22021-1101
703/818-1000

TechLaw, an environmental consulting firm ex-
perienced in the application of legal and technical
principles to tasks in support of RCRA and CER-
CLA enforcement activities, provides services in-
cluding:  PRP searches, image based case man-
agement, computer  tracking systems, evidence
audits, documentary inventory systems, legal re-
search, full text databases, transactional data vali-
dation, environmental site assessments and com-
pliance audits.

Technical Minerals, Inc.                  1910
P.O. Drawer 23028
Jackson, MS 39225-3028
601/944-4758

Technical Minerals, Inc. (TMI) products are the
culmination of a technical  approach to problem
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 solving which involves a unique mixture of pro-
 prietary processes and  materials. Surface modi-
 fied minerals from TMI have been specially de-
 signed for a broad line of  environmental and
 industrial application.

 Tekmar Company                      1614
 P.O. Box 371856
 Cincinnati, OH 45222-1856
 513/761-0633

 (1) LSC 2000 Series of Purge and Trap/Dynamic
 Headspace Concentrator; (2) the Automatic Proc-
 ess Sampler samples up to six aqueous streams
 which may be monitored either sequentially or on
 a timed basis using an internal real time clock; and
 (3) Static Headspace System: the SHS 7000 offers
 an unprecedented approach to static headspace
 analysis  that significantly  increases throughput
 and  reproducibility;  whether  using static
 headspace for screening or direct analysis, sample
 integrity is assured by Tekmar's superior product
 performance.

 Thermo Analytical, Inc.                2003
 5635 Jefferson Blvd., N.E.
 Albuquerque, NM 87109
 505/345-9931

 Thermo  Analytical  Inc.'s  (TMA's)  network of
 laboratories provides a full range of analyses of
 environmental  contaminants  and  radioactive
 materials in soil, water, air, industrial waste and
 other matrices. TMA laboratories have analytical
 capabilities for the detection of pesticides, herbi-
 cides, industrial solvents, PCBs, dioxins, asbes-
 tos, trace metals, and over 200 radionuclides.

 Thermo Environmental
 Instruments, Inc.                       0609
 8 West Forge Parkway
 Franklin, MA 02038
 508/520-0430

 Thermo Environmental Instruments will display a
 complete line of portable instruments for the field
 measurement of toxic vapors and liquids, includ-
 ing the new Model 580B Portable Organic Vapor
 Meter (OVM).

 Tigg Corporation                 1205-1207
 P.O. Box 11661
 Pittsburgh, PA 15228
 412/563-4300

 Manufacturers of modular adsorbers designed for
 the remediation of vapor and water pollution. The
 combination of over 30 years of experience with
 adsorbents and systems provides unique capabili-
 ties of technical expertise and product availability
 to address specific remedial  problems with the
 most appropriate technology.

 Toney Drilling Supplies, Inc.             1301
 14060 NW 19 Ave.
 Miami, FL 33054
 305/685-2453
 Complete line of drilling equipment: New/used
 drill rigs, drill rods, subs and  bits. Diamond bits,
 core barrels, mud and additives;  augers, casing
 and plugs; stainless steel screens, PVC  screens,
points and pcaps; monitoring and sampling de-
vices; safety clothing, masks, gloves and boots.
Consultation and instruction are also available.
Tracer Research Corporation           1602
3855 North Business Center Dr.
Tucson, AZ 85705
602/888-9400

Tracer Research Corporation specializes in leak
detection for underground  storage tanks, bulk
storage, above ground tanks and pipelines; Tracer
technology for  groundwater monitoring  and
landfill liner tightness testing; on-site detection of
subsurface  volatile organic contaminants (Soil
Gas Analysis); full-service organic analysis labo-
ratory services.

TreaTek, Inc.                          1316
2801 Long Rd.
Grand Island, NY 14072
716/773-8661 or 800/833-3335

TreaTek is an environmental service subsidiary of
Occidental Chemical Corporation, and has as its
commercial objective the application of advanced
microbial and chemical treatment technologies to
the remediation of waste streams and containment
soil. TreaTek can provide remedial consultation,
laboratory treatability studies (biological, chemi-
cal & physical), analytical support, system design
& specifications and  turnkey project  manage-
ment.

Triangle Laboratories, Inc.             0212
801-10 Capitola Dr.
Research Triangle Park, NC 27713
919/544-5729

Triangle Laboratories, Inc. includes two  em-
ployee-owned contract laboratories specializing
in the analysis of organic compounds. Both labo-
ratories offer high quality environmental analysis
using EPA approved methods guaranteed by ex-
perienced scientists. The Research Triangle Park
(NC) facility is  nationally  recognized for low
detection analysis for polychlorinated dibenzo-p-
dioxins and dibenzofurans.

Trinity Environmental
Technologies, Inc.                      0103
6405 Metcalf, Suite 313
Overland Park, KS 66202
913/831-2290

EPA-approved destruction of PCBs in mineral oil
dielectric fluid less than  18,000 ppm;  EPA-ap-
proved destruction of PCBs in other oils less than
500 ppm (fuel, #2, and hydraulic oils); Disposal of
PCB-contaminated water;  Laboratory analysis for
PCBs in oil, water, solids, surface wipes and air
monitoring cartridges with fax reporting from our
laboratory within 48-hours  at no extra charge;
PCB sampler/mailer kits for oil, water, solids and
surface wipes.

Troxler Electronic
Laboratories, Inc.                      0709
P.O. Box 12057
Research Triangle Park, NC 27709
919/549-8661

Troxler, the World's leader in depth moisture,
surface moisture/density  and sediment density
technology, has developed a full line of gauges for
the hazardous materials industry. Introducing this
year, the Sentry 200.  A permanently installed,
non-nuclear moisture gauge with the accuracy of
our State-of-the-Art Neutron Probe.

U.S. Analytical Instruments             1416
1511 Industrial Rd.
San Carlos, CA 94070
415/595-8200

Available for rent and immediate delivery - HNU
model 101s, Foxboro OVA 128GCs, and Pho-
tovac MicroTips from U.S. Analytical Instru-
ments. In addition, USAI offers for rent or lease
GC, HPLC, Fluorescence, UV/VIS, AA and ICP,
IR and FTIR instrumentation from major manu-
facturers such as Hewlett-Packard, Perkin Elmer,
Varian, Foxboro, and Waters. We offer flexible
rental and purchase option plans designed to meet
your financial and instrumentation needs.

U.S. Army Corps of Engineers          0407
P.O. Box 103, Downtown Station
Omaha, NE 68101
402/691-4532

The U.S. Army Corps of Engineers and the U.S.
EPA have joined forces to clean up Federal lead
hazardous waste sites under the Superfund pro-
gram. The booth will be manned by Corps person-
nel to assist architect-engineer firms and construc-
tion contractors take advantage of work available
to them through the Corps of Engineers.

U.S. Army Toxic & Haz.
Mat Agency                          2202
Bldg. E4460, Attn: CETHA-PA
Aberdeen Proving Ground, MD 21010-5401
301/671-2556

U.S. Bureau of Mines             1026/1028
2401 E Street NW, MS 6201
Washington, DC 6201
202/634-1224

The U.S. Bureau of Mines  conducts research to
help managers, consultants, and engineers better
handle mining and minerals processing wastes. In
addition, experts at the Bureau analyze the impact
of existing and proposed regulations on sectors of
the industry. Results of these efforts will be avail-
able through free technical publications and the
Bureau's exhibit  at Superfund '90.

U.S. Bureau of Reclamation            1018
Mail Code D-3800
P.O. Box 25007
Denver, CO 80225
303/236-8646

The U.S. Bureau of  Reclamation provides Total
Project  Management in hazardous waste  site
cleanup-PA/SI, RI/FS, RD, RA, and O&M. Work
may be completed for other government agencies
in planning,  designs, construction, construction
oversight, reviews or research. Work has been
completed under RCRA, Superfund, and Federal
Facilities section of CERCLA.

U.S. DOE Five-Year Plan              2405
EM-2
1000 Independence Ave., S.W.
Washington, DC 20024
202/586-4373

This five-panel exhibit described the U.S. Depart-
ment of Energy's Office of Environmental Resto-
                                                                                                                                             999
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ration and Waste Management's Five Year Plan.
This plan was developed to set DOE's strategy and
activities for cleaning up and restoring its nuclear
research and production sites.
U.S. Environmental
Protection Agency
26 W. M.L. King Dr.
Cincinnati, OH 45268
513/569-7522
  2311-2320
  2311-2319
& 2312-2320
The U.S.  Environmental  Protection  Agency is
responsible for developing regulations, imple-
menting programs, and conducting research to
carry out its mandate established in the Compre-
hensive Environmental Response,  Compensa-
tion, and Liability Act (CERCLA/Superfund) and
other Hazardous Waste Management statutes.

U.S. Envlrosearch, Inc.                  LDC
445 Union Blvd., Suite 225
Lakewood, CO 80228
303/980-6600

A nationwide recruiting firm based in Denver,
Colorado, specializing in the recruitment of haz-
ardous waste,  environmental and incineration
personnel. U.S. Envirosearch represents client
companies in the areas of: hazardous waste dis-
posal, site remediation, environmental engineer-
ing, analytical laboratories, environmental law,
air quality, solvent recycling, PCB disposal, in-
dustrial cleaning and generators.

U.S. Geological Survey             1020-1024
12201 Sunrise Valley Dr.  MS 790
Reston, VA 22092
703/648-4377

Panels depicting research and products of the U.S.
Geological Survey dealing with earth sciences.

ULTROX INTERNATIONAL          2200
2435 S. Anne St.
Santa Ana, CA 92704
714/545-5557

The innovative ULTROX® process utilizes ultra-
violet light with ozone and/or hydrogen peroxide
to destroy toxic organic contaminants in ground-
water, surface waters, wastewaters and leachate,
on site. No sludges or wastes are generated requir-
ing regeneration, disposal or incineration. UN-
TROX® is used as a stand  alone treatment system
and with other technologies.

URS Consultants, Inc.                  1511
One Penn Plaza, Ste. 600
New York, NY 10119
212/736-4444

URS' multidisciplinary staff of engineers  and
scientists provides a full range of hazardous waste
management services  to governmental  and pri-
vate entities through  its  25 offices  nationally.
Services include remedial investigations, feasibil-
ity studies, design of remedial actions, treatment
system design,  implementation of remedial ac-
tions, RCRA services, regulatory and permit sup-
port and litigation assistance.

USPC1, Inc.                      0703/0705
515 West Greens Rd., Suite 500
Houston, TX 77067
713/775-7800

A  full-service  hazardous waste  managemeni
company.  Services include laboratory analysis,
transportation,  treatment,  remediation and dis-
posal.

Union Carbide Industrial
Gases, Inc.                            2216
39 Old Ridgebury Rd.
Danbury, CT 06817
203/794-5601

America's leading producer of industrial gases,
including  oxygen  and  nitrogen. The LJNDE
Oxygen Combustion System can safely double
the capacity of your incinerator reducing CO
excursions and auxiliary fuel consumption. See us
to leam about recent Superfund installations.

University of Findlay                   LDC
1000 N. Main
Findlay, OH 45840
419/424-4540

Training and education provided in the areas of
hazardous materials/waste, emergency response,
spill response, confined space entry, asbestos re-
moval, 40 hour OSHA, 8 hour OSHA and OSHA
site supervisor training. Hands-on training facil-
ity. On-site training available upon arrangement.

VFL Technology Corporation          1007
42 Lloyd Ave.
Malvem, PA 19355
215/296-2233

VFL Technology Corporation is a civil/geotech-
nical construction firm specializing in the design
and implementation of solutions to a variety of
waste management problems. Services include
soil/sludge solidification  and stabilization, la-
goon/landfill closures,  hazardous site remedia-
tion, groundwater recovery and treatment, on-site
treatment systems, excavation, treatment and dis-
posal of contaminated materials on-site or off-site.

Vapex Environmental
Technologies, Inc.                      1716
480 Neponse! St.
Canton, MA  02021
617/821-5560


Vapex designs, installs, and operates high tech-
nology remediation systems for the cleanup of soil
and groundwater. SOIL VAPOR EXTRACTION
SYSTEMS FOR VOC SOIL TREATMENT:
bench scale and field treatability testing; proprie-
tary 3-D air  flow modeling; chemical transport
modeling; AIR SPARGING:  for groundwater
treatment; BIOVENTING: for treatment of semi-
volatiles.
                  Versar Laboratories, Inc.              1213
                  6850 Versar Center, P.O. Box 1549
                  Springfield, VA 22151
                  703/750-3000

                  Versar Laboratories,  Inc. provides comprehen-
                  sive environmental analytical chemistry services.
                  Capabilities include  GC/MS,  GC,  AA,  ICP,
                  HPLC, Bioassay and various general chemistry
                  techniques. Certified  by USCOE-MRD, MMES
                  and seven slates.
Vesta Technology, Ltd.                 0112
1670 West McNab Rd.
Fort Lauderdale, FL 33309
305/978-1300

Mobile On-Site Incineration Service.

Vlar and Company, Inc.                1715
300 N. Lee St.
Alexandria, VA 22314
703/684-5678

Viar is an environmental sciences and systems
development  consulting firm of 250 providing
program  management and technical support to
federal clients. Our services include: QA design/
monitoring, data interpretation/validation; pro-
gram budget, administrative and technical analy-
ses; and  all aspects  of scientific, financial, and
management  information  systems technology
evaluations, design and development, and opera-
tional support services.

Vortec Corporation                    1807
3770 Ridge Pike
Collegeville, PA 19426
215/489-2255

Vortec brings to the  market a revolutionary new
approach to solving hazardous waste  disposal
problems with its Advanced Vitrification/Incin-
eration Process (AVIP). This system offers a new,
modern  alternative   to  standard  and costly
landfilling (in hazardous landfills) which is the
current solution for disposal of most solid hazard-
ous wastes.

WATERSAVER
COMPANY, INC.                      1211
P.O. Box 16465
Denver, CO 80216
303/289-1818

Watersavcr provides the world's most reliable
membrane lining systems. Meet all stale and fed-
eral regulations with  Watersavcr. Liners and clo-
sure caps for a wide variety of applications.  Cus-
tom fabrication and installation of CSPE, CPER,
PVC, XR-5, and others. Continuous service for
over 30 years.

WSOS Community  Action
Commission, Inc.                       LDC
P.O. Box 590, 109 South Front St.
Fremont, OH 43420
419/334-8911

WSOS provides head start programs, services for
senior  citizens, housing and energy programs,
food services, outreach services, economic and
community development, employment and train-
ing programs and environmenial programs.

Wadsworth/ALERT
Laboratories, Inc.                      1111
4101 Shuffel Dr. N.W.
North Canton, OH 44720
216/497-9396

Laboratory services for environmental and indus-
trial hygiene markets. Analysis of soil/sediment,
sludge/waste, and water and air, using slate of the
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art equipment, including GC/MS, GC, HPLC, AA,
ICP, TOX, TOC and IR. Facilities include fixed
location and mobile laboratories.

Waste Abatement
Technology, Inc. (WATEC)             0513
1300 Williams Dr.
Marietta, GA 30066
404/427-1947

Waste Abatement Technology,  Inc. (WATEC),
provides a full range  of remediation services in-
cluding: excavation of contaminated soils, waste
deposits and drums; drum handling, characteriza-
tion and removal;  industrial UST remediation;
surface impoundment closure-in-place stabiliza-
tion, sludge removal and dewatering; water treat-
ment (process, surface and groundwater); build-
ing decontamination;  on-site treatment - physical,
chemical, biological; transportation and disposal.
WATEC, in both the public and private sector, has
 consistently  demonstrated its ability to compete
 for and then carry projects to successful comple-
 tion.  This success is attributed to our staff of
professionals and technicians who are well re-
 spected hi the hazardous waste cleanup industry
 and our corporate commitment of placing senior
 level professionals in charge of site operations.
These individuals,  combined with our desire to
 excel in project execution, form the foundation for
 our record of innovative and successful  project
 completion.  WATEC's Marietta, Georgia, loca-
 tion can service sites nationwide. Additionally, we
 augment our capabilities through staff and serv-
 ices provided to us by our sister company, ATEC
Associates, Inc., and its 45 offices.
Waste-Tech Services, Inc.               2409
800 Jefferson County Pkwy.
 Golden, CO 80401
303/279-9712
Waste-Tech  Services, Inc. (WTS), an  affiliate of
Amoco Oil Company, is "Making a Difference" in
hazardous waste management through the appli-
cation of proven and innovative technologies in
the areas of thermal destruction and waste minimi-
zation. WTS offers services from design through
operations. Let WTS  make your difference!

Water Pollution Control Federation     LDC
601 Wythe St.
Alexandria, VA 22314-1994
703/684-2400
The Water Pollution Control Federation is a tech-
nical, professional organization of 36,000 mem-
bers from Member Associations and affiliated
associations  throughout the world. Dedicated to
"preserving and enhancing water quality  world-
wide," the WPCF offers more than 80 publica-
tions, 8 periodicals, educational  training materi-
als, a water curriculum program for schoolchil-
dren, public education materials, career informa-
tion, safety & health videos, and technical serv-
ices.

Wayne Associates, Inc.                  2001
2628 Barrett  St.
Virginia Beach, VA 23452
804/340-0555

We are one of the oldest and largest specialized
recruiting firms serving the hazardous waste in-
dustry (since 1978). Our services include both
retained contract and contingency search and our
expertise  covers all areas of the Hazwaste &
Environmental market. We effectively service a
nationwide client base. Stop by booth 2001 to
discuss to discuss  your company's needs or to
investigate career alternatives.

Well Safe, Inc.                    0913-0914
10223 FM 1464
Richmond, TX 77469
713/277-2530

Hazardous Waste,  Petro-Chemical Industry and
Oil &  Gas Drilling and Production Safety Serv-
ices. Specializing in on-site breathing air, breath-
ing  apparatus,  instrumentation, on-site  safety
supervisors and decontamination services.

Westates Carbon, Inc.                  0108
2130 Leo Ave.
Los Angeles, CA 90040
213/722-7500

Westates specializes in activated carbons, water
and air pollution control equipment, solvent re-
covery, odor and corrosion  control, precious
metal recovery and custom engineered systems.
Westates maintains a complete in-house labora-
tory for  quality assurance, carbon testing and
evaluation. Sales and service offices in Los Ange-
les, Oakland, Cincinnati, Houston and New York.

Westbay Instruments Inc.              0305
507 E. Third St.
North Vancouver, BC V7L 1G4
604/984-4215

Westbay manufactures and markets the MP Sys-
tem which allows multi-level groundwater moni-
toring  in a single drillhole. This system reduces
project costs and time related to drilling while im-
proving filed quality control. In addition, water
sampling with the MP System is achieved without
repeated  purging,  thereby reducing operating
costs. For more information, dial (800) 663-8770
(in U.S.).

Westinghouse Environmental
Systems and Services              1411/1413
875 Greentree Rd., Bldg. 5,1st Floor
Pittsburgh, PA 15220
412/937-4061

Westinghouse offers a full range of environmental
assessment and engineering approaches, environ-
mental remediation, and hazardous waste treat-
ment, storage and disposal services. Employing
the best available technologies at TSD facilities in
Minnesota, Kansas and Utah, Westinghouse helps
clients deal  effectively with stringent environ-
mental requirements for disposing of wastes regu-
lated under TSCA, RCRA and CERCLA.

Williams Environmental
Services, Inc.                          LDC
1530 Alabama St.
Auburn, AL 36830
205/821-9250

Williams Environmental Services, Inc., does on-
site remediation using mobile equipment, primar-
ily thermal processing, volume reduction  and
stabilization of hazardous waste.

Wilson Laboratories                   0208
525 N. 8th St.
Salina, KS 67401
913/825-7186

Wilson Laboratories provides accurate and timely
analytical  services to industry, governmental
agencies, municipalities and private consultants.
Our services include: groundwater,  waste water,
and drinking water analysis; toxic and hazardous
waste analysis for inorganics, organics and PCBs
in various matrices.

Woodward-Clyde Consultants          1911
4582 S. Ulster St., Ste. 600
Denver, CO 80237
303/740-2600

Woodward-Clyde Consultants is a  professional
services firm with over 30 years of experience in
geotechnical engineering, environmental, and
social sciences. In hazardous waste, we offer total
management solutions, from evaluation, permit-
ting and initial investigation through design, con-
struction, and remedial action. Our scientists and
engineers represent all disciplines necessary to
provide complete services - the earth, physical,
and natural sciences as well as environmental,
chemical  and geotechnical engineering.  With
offices in 45 cities, we are staffed and positioned
to offer nationwide management programs that
are both comprehensive and responsive.

Worne Biotechnology, Inc.              0107
1507 U.S. Route 206
Mt. Holly, NJ 08060
609/261-5550

Worne Biotechnology, Inc., is a biotechnology
company providing professional environmental
and biological consulting services to both govern-
ment and industry for the biological detoxification
of hazardous and toxic organic wastes throughout
North America, South America and Asia. WBI
uses laboratory remediation studies coupled with
environmental analysis, hydrology and feasibility
evaluation to define environmental projects and
integrates biotechnology with regulatory require-
ments to solve enviromental problems. WBI high
rate biological reactors for industrial wastewater
treatment and develops highly effective microbial
ecosystems for these reactors to remove recalci-
trant halogenated and non-halogenated organic
wastes from municipal, agricultural and industrial
waste streams.

Youngstown Barrel &
Drum Company                       LDC
1043 Marble St.
Youngstown, OH 44502
216/746-3277

Youngstown Barrel & Drum  Company is your
one-stop container source specializing in a  full
line of standard and specialty pails, drums, over-
packs, components and accessories made of steel,
stainless, plastic, fibre or composites, from 2 gal-
lon to 110 gallon capacity. In full compliance with
all applicable  DOT and/or U.N. specifications.
                                                                                                                                              1001
-------
  Containers are in slock and ready to ship in any
  combination of sizes, types, styles and quantities.
  There is no minimum. Reconditioned containers
  are also available. Call  1-800-359-DRUM  for
  more information.

  Ztapro/Passavant                2222/2223
  301 W. Military Rd.
  Rothschild, WI 54474
  715/359-7211

  Zimpro/Passavanl is the developer of the PACT*
  wastewaler treatment system, and wet air oxida-
  tion. Used in tandem, or singly, they are effective
  technologies for treating hazardous waslewalers
  and sludges, including process  discharges, con-
  taminated groundwater of surface runoff, landfill
  leachales.  Portable  units,  factory-built  skid-
  mounted plants, field-erected systems. Treatabil-
  ity studies and complete analytical laboratory
  capabilities.
100:
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                                                        Author Index
                                                            1980-1990
 Abbott, C. K., 89-23
 Abraham, John E., 88-524
 Abrishamian, Ramin, 90-549
 Absalon, J. R., 80-53
 Accardi, J., 85-48
 Aceto,F., 89-273
 Adamowski, S. J., 83-346
 Adams, R. B., 84-326
 Adams, W. M., 83-108
 Adams, W. R., Jr., 82-377, 83-352
 Adams, William J., 90-793
 Adaska, W. S., 84-126
 Adkins, L. C, 80-233
 Adrian, D. D., 89-519
 Aguwa, A. A., 86-220
 Ahlert, R. C, 82-203; 83-217; 84-
    393
 AhneU, C. P., Jr., 80-233
 Ainsworth, J. B., 83-185
 Alam, Abu M.Z., 87-111
 Albrecht, O.  W., 81-248, 393
 Aldis, H., 83-43
 Aldous, K., 80-212
 Alexander, W. J., 82-107
 Allcott, G. A., 81-263
 Allen, Douglas C, 88-329
 Allen, E. E., 89-485
 Allen, Harry L., 81-110; 88-424
 Allison, Jerry D., 90-498
 Allison, Terry L., 90-498
 Allred, P. M., 88-528
 Aim, R. R., 87-480
 Altevogt, A.  Charles, Jr., 90-42
 Alther, George R., 88-440; 89-543
 Alvi,M.S., 84-489
 Amdurer, M., 87-72
 Ammann, P., 84-330
 Ammon, D.,  84-62,498
 Amos, C. K., Jr., 84-525
 Arnster, M. B., 83-98
 Anastasi, Frank S., 90-85
 Anastos, G. J., 86-93, 322
 Anderson, A. W., 84-511
 Anderson, D. C., 81-223; 83-154;
   84-131,185; 85-80; 89-4,503
 Anderson, David W., 90-565
 Anderson, E. L., 86-193
Anderson, Grant, 90-896
Anderson, J. K., 84-363
Anderson, Kenneth E.,  89-600; 90-
   201
Anderson, M. C, 89-4
Anderson, T., 89-27
Andrews, J. S., Jr., 86-78
Andrews, John S., Jr., 90-169
Angelo, J. F., 89-374
Anglin, Robert J., 90-266
Antizzo, J., 87-515
Apgar, M., 84-176; 89-618
Applegate, J., 87-273
Appier, D. A., 82-363
Arland, F. J., 83-175
Arlotta, S. V., Jr., 83-191
Arnold, D. F., 84-45
Arthur, J., 84-59
Asante-Duah, Daniel Kofi, 90-226
Ashcom, D. W., 87-315
Asoian, M. J., 86-152
Assink, J. W., 82-442; 84-576
Astle, A. D., 82-326
Atimtay, A., 85-464
Atwell, J. S., 83-352
Aulenbach, S. M., 89-146
Aurelius, Marcus W., 88-495
Averett, Daniel E., 88-338, 347
Ayres, J. E., 81-359
Ayubcha, A., 84-1
Babcock, K. B., 87-97
Bad, Lisa A., 90-1
Back, David, 90-376
Badalamenti, S., 83-202,358; 84-
   489; 87-111
Baer, W. L., 84-6
Bagby, J. R., Jr., 86-78
Bailey, P. E., 82-464
Bailey, T. E., 82-428
Bailey, W. A., 83-449
Baker, Jan H., 90-4
Baker, Katherine H., 88-490
Baker, Sara B., 87-264
Balfour, W. D., 82-334; 84-77
Ball, Brandon R., 90-686
Ballif, J. D., 82-414
Banerjee, P., 87-126
Barbara, M. A., 83-237; 83-310
Barber, J. A., 89-443
Barboza, M. J., 86-152
Bareis, D. L., 83-280
Barich, John J., 87-172,198
Barich, J. T., 89-264
Barill, Terryn, 90-98
Barkdoll, Michael P., 88-164
Barker, L. J., 82-183
Barkley, Naomi P., 82-146; 85-164;
   88-419
Barksdale, John, 90-877
Barndt,J.T., 89-194, 618
Barnes, D. L., 89-91
Barnes, Joan K., 90-355
Barnett, B. S., 89-635
Barone, J., 84-176
Barrett, K. W., 81-14
Barry, Theresa A., 90-144
Barsotti, Deborah A., 88-537
Bartel, Thomas J., 88-287;  90-606
Bartel, Tom, 88-125
Barth, D. S., 84-94
Barth, Edwin, III, 90-730
Barth, Edwin B., 90-665
Barth, Edwin F., 86-224; 87-172
Bartley, R. W., 84-35
Bartolomeo, A. S., 82-156
Bascietto, J., 89-609
Bashor, M. M., 89-72
Bath, R. J., 89-41
Baughman,  K. J., 82-58
Baughman,  W. A., 86-126
Baumwoll, D., 86-22
Bausano, James, 89-306
Baxter, T. A., 84-341
Bayer, Hans, 88-219
Bayse, D. D., 84-253
Beam, P., 86-84
Beam, P.  M., 81-84; 83-71
Beck, W. W., Jr., 80-135; 82-94; 83-
   13
Becker, D. Scott, 88-323
Becker, J. C., 83-442
Beckert, W. F., 82-45
Beckett, M.  J., 82-431
Beekley, P., 86-97
Beers, R. H., 81-158
Begor, K. F., 89-468
Beilke, P. J., 82-424
Beling, Christine, 87-296
Bell, R. M.,  82-183,448; 84-588
Ben-Hur, D., 84-53
Bennett, Doug, 88-208
Benson, B. E., 80-91
Benson, J., 86-386
Benson, R. C., 80-59; 81-84; 82-17;
   83-71; 85-112; 86-465
Bentley, H. W., 90-557
Berdine, Scott P., 88-582
Berg, Marlene G., 87-337
Berger, I. S., 82-23
Berk, E., 83-386
Berkey, Edgar, 90-966
Berkowitz, J., 83-301
Berkowitz, Joan B., 87-471
Bernard, H., 80-220; 86-463
Bernardin, Frederick E., Jr., 90-768
Beraert, J. T., 84-253
Berning, W., 86-386
Berry, Edwin W., Ill, 90-917
Bertelsen, C. A., 90-553
Berzins, Nick, 88-158
Best, Jay Boyd, 90-280
Beukema, P., 89-497
Bhalla, S., 85-189
Bhattacharya, Sanjoy K., 90-847
Bhinge, Deepak, 88-440
Bianchini-Akbeg, Martina, 90-793
Biggs, Richard K., 87-37
Bigham, Gary, 87-444
Bilello, L. J., 83-248
Billets, S., 84-45
Bilyard, Gordon R., 88-323
Binder, S., 85-409
Bingham, Anne, 90-1
Bird, K. J., 86-126
Bird, Kenneth J., 88-594
Bissett, F., 89-190
Bissex, Donald A., 86-208; 88-429
Bisson, D. L., 89-413
Bitto, Ronald, 90-357
Bixler, Brint, 88-1
Bixler, D. B., 82-141; 84-493
Blackman, W. C., Jr., 80-91; 84-39;
   86-407
Blais, L., 86-441
Blasco, Marcello J., 87-367
Blasland, W. V., Jr., 81-215; 83-123
Blayney, E. K. H., 85-476
Blowers, Mark A., 88-287; 90-606
Boa, J. A., Jr., 82-220
Bode, B. D., 89-463
Bogue, R. W., 80-111
Bonazountas, M., 84-97
Bond, F. W., 82-118
Bond, Linda D., 88-125, 287
Bond, Rick, 87-198
Bonneau, W. F., 84-509
Boornazian, L. Y., 86-398
                                                                                                                                         1003
-------
      Bopp, F., Ill, 84-176
      Borden, W. C, 89-582
      Borgiannini, Stephen A-, 88-79
      Borisch, R. R., 87-405
      Borow, Harlan S., 89-325; 90-800,
         814
      Borsellino, R.  J., 85-299
      Bort, R. M., 85-152
      Boucher, Peler, 90-612
      Bouck, W. H., 81-215
      Bourquin, Al W., 88-395
      Bourwell, Scoll H., 83-135; 87-153
      Bove, L. J., 84-412
      Bowden, Brian K., 90-266
      Bowders, J. J., 81-165
      Bowlcn, Gene F., 88-451
      Boyd, J., 84-382
      Boyd, Keith A., 86-61; 88-65
      Bracken, Brian D., 82-284; 88-245
      Bradford, M. L., 82-299
      Bradley, Allen, 88-164
      Bradley, C. K., 86-120
      Bradshaw, A. D., 82-183
      Bramlelt, J. A., 86-237
      Brandwein, D. I., 80-262; 81-398
      Brandwcin, S.  S., 82-91
      Brannaka, L. K., 81-143
      Brass, Brian E., 90-257
      Braun, J. E, 84-449
      Brcnneman, D., 85-299
      Bridges, E. M., 84-553
      Bridges, Jack F., 88-498
      Bright, Donald B., 90-536
      Bright, Steven A., 90-536
      Brink, J. M., 84-445, 504
      Broadbent, Greg, 87-183
      Broadstreet, 90-117
      Brockbank, B. R., 84-371
      Brockhaus, R.  D., 87-409
      Brodd, A. R., 82-268
      Brokopp, C., 84-239
      Brown, K. W., 81-223; 84-94, 185;
         85-442; 87-66
      Brown, M. J., 82-363
      Brown, Patricia M., 90-589
      Brown, Richard A., 90-529
      Brown, Stuart M., 81-79; 83-135;
         88-259
      Browning, Scott, 88-409
      Bruck, J. M., 84-72; 85-452
      Bruehl, D. H.,  80-78
      Brugger, J. E.,  80-119, 208; 81-285;
         82-12; 87-390
      Brugger, John  E., 90-589
      Brunner, Dirk  R., 90-103
      Brunner, P. G., 85-43
      Brunner, Paul,  87-204
      Brunotts, V. A., 83-209
      Brunsing, T. P., 82-249; 84-135
      Bryson, H. C.,  80-202
      Buchanan, S., 90-164
      Buchert, James M., 90-56
      Buck, John W., 87-409
      Buckley, J. W., 89-6-45
      Buechler, T. J., 86-61
      Buecker, D. A., 82-299
      Buehlcr,  R., 86-208
      Buelt.J. L. 84-191
      Buhts, R. E, 85-456
      Bullcr, J., 83-395
      Bumh, A. C, 84-162
      Buniski, Deborah A., 88-490
      Burg, )e Anne  R., 90-161
      Buri;an. Karen, 88-32
      Burgess. A. S.,  83-331
      Burgher.  B. J..  82-357; 84-335
     Burmaslcr. David E., 87-138, 153;
    88-550; 89-82, 108; 90-215
 Bums, H,, 83-428
 Burns, Lawrence A., 90-133
 Burns, Robert B., 89-576; 90-632
 Bums, Janet A., 88-353
 Burruel, J. A^ 86-318
 Bumis, B. G., 82-274
 Burse, V. W, 84-243
 Burtan, R. C., 89-75
 Bush, B., 80-212
 Butchko, S., 90-474
 Butler, H. P., 82-418
 Butterfield, W. S., 82-52
 Buttich, J. S., 84-200
 Byers, W. D., 84-170; 89-479
 Byrd,J. F., 80-1
 Cadavid, Eva Marie, 90-753
 Cadwallader, M. W., 86-282; 89-534
 Cain, Kathyra R., 90-919, 933, 937
 Caldwell, Jack A., 87-449
 Caldwell, Steve, 81-14; 87-143
 Call, Hollis J., 88-44
 Campbell, D. L., 85-36
 Campbell, David C., 90-320
 Campbell, Ken W., 90-492
 Campbell, P. L., 84-145
 Cane, B. H., 82-474
 Cange, Jeffrey B., 90-348
 Cange, Susan M., 90-47
 Canter, Larry, 90-245
 Caplice, D. M., 89-447
 Caravanos, J., 84-68
 Carberry, Judith B., 90-826
 Cardenas, Porfirio, 90-760
 Carnow, B. W., 86-455; 87-532
 Caron, Denise, 90-386
 Carroll, John P., 90-748
 Carroll, Peter J., 88-287; 90-606
 Carson, L. P., 86-445
 Carter, J. L., 85-192
 Carter, Richard, 87-258
 Carter, T. D., 83-63
 Cartwright, R. T., 89-642
 Casteel, D., 80-275
 Castle, C., 85-452
 Cavalli, N. J., 84-126
 Cederberg,  Gail A., 90-415
 Celender, J. A.,  82-346
 Chaconas, J. T., 81-212
 Chadwick, P., 89-488
 Chaffee, J. B., Jr., 87-492
 Chan, R., 83-98
 Chang, Kou-Rouny, 90-439
 Chang, R., 85-97
 Chang, S. S., 81-14
 Chapin, Mark, 88-97
 Chapman, G. H., 86-120
 Chappell, R. W., 86-115; 88-261,
    393
 Chan, Desi M., 87-459
 Chamley, G., 86-193
 Chase, D. S., 83-79
 Coalman, S. D., 89-137
 Chatwin, Terrence D., 88-467
 Chaudhari,  R., 89-380
 Chaudhry, Majid A., 90-882
 Cheatham, R. A., 86-386
 Cheng, R-Y., 89-102
 Chiaramonle, Gerald R., 90-25
 Chieh, S-H, 84-1
 Childs, K. A., 82-437
 Chisholm, Kevin, 86-420;  87-362
 Cho, Y., 83-420
 Chorlog, John, 90-539
 Chouery-Curtis, Vicky, 90-474
Christofano, E. E, 80-107
Christopher, B. R., 86-247
Chrislopher, M. T., 80-233
 Chrostowski, Paul C, 86-242; 88-
    292; 89-547,552
 Chung, N. K., 80-78
 Ciavettieri, Frank J., 88-343
 Cibor.J.M., 89-512
 Cibulas, William, Jr., 86-467; 88-537
 Cibulskis, R. W., 82-36
 Cichon, Edward J., 87-204
 Cichowicz, N. L., 80-239
 Cioffj, John A., 90-800
 Cioffi, John C., 90-814
 Clark, Jef&eyS., 87-169
 Clark, R., 84-486
 Clarke, A. N., 89-562
 Clarke, J. H., 83-296; 89-562
 Clay, P. F., 81-45, 82-40; 83-100;
    86-120
 Cleary, Joseph G., 88-474
 Clem, Arthur G., 87-512
 Clemens, B., 84-49, 335; 85-419;
    86-445
 Clemens, R., 84-213
 demons, G. P., 84-404
 Cline, Patricia V., 84-217; 88-108;
    90-153
 Cline, S. P., 89-277
 Clinton, R. J., 86-4
 Glister,  William E., 90-646
 Cluxton, Phillip R., 90-542
 Coates, A. L., 86-365
 Cobb, William E., 87-436
 Cochran, S. R., 82-131; 84-498
 Cochran, S. R., Jr., 80-233; 85-275
 Cockcroft, B. F., 87-367, 496
 Cogliano,  V. J.,  86-182
 Cohen, S. A., 81-405
 Coia, Michael F., 86-322; 88-363
 Colangelo, Robert V., 90-308
 Coldeway, W. G., 84-584
 Cole, C.R., 81-306; 82-118
 Cole, Harold, 87-280
 Collins, G., 89-41
 Collins, J.  P., 81-2; 83-326
 Collins, L, O., 83-398
 Collison, Gary H., 90-446
 Colonna, R., 80-30
 Compeau, Geoffrey C., 90-780, 814
 Condon, Suzanne K., 90-144,182
 Conibear, Shirley A., 86-455; 87-
    532
 Connelt, A., 89-267
 Connolly,  John P., 88-359
 Connor, John A., 88-234
 Connor, Michael S.,  87-426
 Conway, Sheila  H., 90-17
 Cook, D. K., 81-63
 Cook, L. R., 83-280
 Cooney, J. A., 89-647
 Cooper, C, 81-185
 Cooper, D., 85-419;  86-457
 Cooper, E. W., 83-338
 Cooper, J. W., 82-244
 Cooper, L. M., 86-415
 Cooper, Lance R., 87-231
 Cooper, Stafford F., 90-297
 Cooper, William J., 90-753
 Coover, M. P., 89-331
 Copeland, L, G., 86-287
 Corbett, C. R-, 80-6; 81-5
 Corbin,  Michael H., 86-322; 87-380
 Corbo, P.,  82-203
 Cord-Dulhinh, Emily, 88-429
 Com, M. R., 81-70
 Comaby, B. W., 82-380
 Costa, S., 89-130
Cothron, T. K., 84-452
Cotton, Thomas A., 88-39
Courtney, Catherine  A., 90-137
H«u
 Coutre, P. E., 84-511
 Cox, G. V., 81-1
 Cox, R. D., 82-58, 334
 Crawford, R. B., 86-272
 Crawley, W. W., 84-131,185; 85-80
 Criswall, David, 90-877
 Cromwell, John E, 87-53
 Crosbie, J. R., 89-338
 Crosby, T. W., 86-258
 Crouch, Edmund A. C., 90-215
 Crutcher, Michael, 90-222
 Cudahy, J. J., 85-460
 Cullinane, M. John, Jr., 84-465; 88-
    435; 89-222
 Cunningham, John M., 87-337,515
 Curry, J., Jr., 84-103
 Curry, M. F. R., 86-297
 Curtis, M., 89-181
 Cuttino, Sandra, 90-386
 Czapor, J. V., 84-457
 Dabney, Betty J., 90-977
 Dahl, T. O., 81-329
 Daigler, J., 83-296
 Daily, P. L,, 85-383
 Dalton, D. S., 85-21
 Dalton, T. F., 81-371
 Danko, J. P., 89-479
 Dapore, J. L., 89-493
 Dappen, Paul, 90-230
 Darilek, G. T., 89-56
 Davey, J. R., 80-257
 Davidson, G. M., 89-631
 Davis, A. O., 86-115
 Davis, Andy, 89-145; 90-696
 Davis, B. D., 84-213
 Davis, Jeffrey S., 90-868
 Davis, L. R., 86-303
 Davis, N. O., Jr., 89-15
 Davis, S. L., 84-449
 Davol, Phebe, 87-66
 Dawson, G. W., 81-79; 82-386; 83-
   453; 86-173
 Day, A. R., 83-140
 Day, P. T., 89-417
 Day, Robin A., 90-29
 Day, S. R., 86-264
 Day, Stephen R., 88-462; 90-382
 De Percin, Paul R., 88-508
de Walle, F. P., 88-479
 DeCarlo, V. J., 85-29
 Deck, N., 86-38
 Decker, Jennifer A., 88-145
 DeGrood., T. J., 85-231
 Dehn, W. T., 83-313
 Deigan, G. J., 86-287
 Del Re, S., 86-110
 Delfino, Joseph J., 88-108
 DeLuca, R. J., 86-148
 Demaresl, H. E., 86-143
 Demeny, D. D., 86-247
 Demmy, R. H., 81-42
 Dempsey, J. G., 85-26
 Denbo, R. T., 86-56
 Denfeld, D. Colt, 88-202
 Dent, Marc J., 87-223; 89-313; 90-
   517
 Deraramelaere, Ron, 90-595
 DeRosa, C, 85-412
 Derrington, D., 84-382
 Desmarais, A. M. C., 84-226
 DeSmidt, Pamela D., 88-55
dcs Hosiers, J. Paul E, 90-575
 Desvousges, W. H., 87-517
 Dev, Harsh, 88-498
 Devary.J. L., 83-117
 Devinny, J. S., 89-345
Dey, Jeffrey C, 90-529
DeYong, Gregory D., 90-266
-------
Dhamotharan, D. S., 86-56
DiAntonio, Kathy K., 90-857
Dickens, Ward, 87-280
Dickinson, R. F., 84-306
Dickinson, R. Wayne, 86-258; 87-
    371
Dickinson, W., 86-258
Dickinson, Wade, 89-371
DiDomenico, D., 82-295
Diecidue, Anthony M., 82-354; 83-
    386; 86-22; 89-600; 90-254
Dienemann, E. A., 84-393
DiesLW.F., 80-78
DiGuilio, Dominic C., 88-132
Dikinis,J. A., 84-170
DiLoteto, John, 88-484
Dime, R. A., 83-301
Dimmick, Ross, 90-80
DiNapoli,J. I., 82-150
Ding, Maynaid G., 88-575
DiNitto, R. G., 82-111; 83-130
Dinkel, Mary E., 87-459
DiPuccio, A., 82-311
Dirgo,J. A., 86-213
Diugosz, E. S., 85-429
Dodge, Elizabeth E., 88-1
Dodge, L., 85-255
Dole, L.R., 89-476
Dombrowski, Lori A., 90-489
Donaloio, Bienda, 88-234
Donate, Michael J., 88-353
Donnelly, James R., 90-513
Donnelly, Kirby C., 87-66
Donovan, Kevin, 90-80
Dorau, David, 87-251
Dorrler,R.C, 84-107
Dosani, Majid A., 88-419
Dover, M.J., 89-609
Dowiak, M. J., 80-131; 82-187; 84-
    356
Downey, Douglas, 88-498
Downie, Andrew R., 88-103
Downing, Jane, 90-148
Doyle, D.F., 85-281
Doyle, Mary E., 90-21,765
Doyle, R. C, 82-209
Doyle, T.J., 80-152
Dragun,J., 86-453
Drake, B., 82-350
Drever.J. I., 84-162
DriscoU, K. H., 81-103
Droppo, James G., Jr., 87-409,465;
    88-539
Dryden, F. E., 89-558
Du Pont, A., 86-306
Duba, G., 89-190
Duff, B. M., 82-31
Duffala, D. S., 82-289; 88-65; 89-13
Duffee,R. A., 82-326
Duke, K. M., 82-380
Dunbar, David R., 90-748
Duncan, D., 81-21
Dunckel, J. R., 85-468; 86-361
Dunford, Richard W., 87-517
Du Pont, Andre, 88-398
Durrani, M., 90-618
Durst, C. M., 85-234
Duvel, W. A., 82-86
Dwight, D. M., 89-241
Dybevick, M. H., 83-248
Earp, R. F., 82-58
Eastman, K. W., 83-291
Eastwood, D., 86-370
Ebbott, Kendrick A., 90-957
Eberhardt, L. L., 84-85
Eckel, W. P., 84-49; 85-130; 88-282;
   89-86
Ecker, Richard M., 87-465
Edmonds, Brenda Kay, 90-173
Edson, Carol O., 90-471
Edwards, D. K., 89-286
Edwards, J.S., 85-393
Edwards, R. C, 89-309
Edwards, Sally, 87-254
Ehrlich, A. M., 86-167
Ehrman,J., 84-374
Eicher, A. R., 85-460
Eimutis, E. C, 81-123
Einerson, Julie H., 88-157
Eisenbeis, John J., 88-177
Eissler,A.W.,84-81
Eklund, B. M., 84-77
Eley, W. D., 84-341
Elkus, B., 82-366
Elliott, Gordon M., 90-197
Ellis, H. V., HI, 86-213
Ellis, R. A., 82-340
Eltgroth, M. W., 83-293
Hy, John, 87-5
Emerson, L. R., 83-209
Emig, D. K., 82-128
Emmett, C. H., 86-467
Emrich, G. H., 80-135; 86-412
Enfield, C, 89-501
Eng,J., 84-457
Engelbert, Bruce, 88-32
Engels, J. L., 84-45
Engler, D. R., 85-378
English, C. J., 83-453; 84-283; 86-
    173
Englund, E. J.,  86-217
Enneking, Patricia A., 88-521
Epperson, Charles R., 88-72
Erbaugh, M., 85-452
Erdogan, H., 85-189
Esmaili, Houshang, 88-245
Esposito, M. P., 84-486; 85-387
Ess, T. H., 81-230; 82-390, 408
Evangelista, Robert A., 88-424
Evans, G. B., 89-503
Evans, G. M., 89-425
Evans, J. C, 82-175; 85-249,357,
    369; 88-403,440; 89-292,543
Evans, Jeffrey C, 90-712
Evans, M. L., 84-407
Evans, R. B., 82-17; 83-28
Evans, R. G., 86-78
Evans, T. T., 84-213
Everett, L. G., 82-100
Exner, P. J., 84-226
Fagliano, J. A., 84-213
Fair, G. E., 89-558
Falcone, J. C., Jr., 82-237
Falk, C. D., 86-303
Fang, H-Y, 82-175; 85-369
Farrell, R. S., 83-140
Farro, A., 83-413
Fassbender, Alex G., 87-183
Fast, D. M., 84-243
Faulds, C. R., 84-544
Feeley, James A., 90-525
Feild, Robert W., 88-255
Feld, R. H., 83-68
Feldt, Lisa G., 87-1,28
Fell, G. M., 83-383
Fellman, Robert T., 87-492
Fellows, C. R.,  83-37
Fenn, A. H., 85-476
Fenstermacher, T.  Edward, 87-476
Ferenbaugh, R. W., 86-1
Fergus, R. Benson, 87-376
Ferguson, J., 84-248
Ferguson, Richard D., 90-601
Ferguson, T., 80-255
Fiedler, Linda, 90-726
Fields, S., 84-404
Figueroa, E. A., 81-313
Filardi, R. E., 89-137
Fine, R. J., 84-277
Finkbeiner, M. A., 85-116
Finkel, A. M., 81-341
Fischer, K. E., 80-91
Fisher, W. R., 86-124
Fisk,J.F., 85-130; 89-86
Fitzgerald, William M., 88-55
Fitzpatrick, V. F., 84-191; 86-325
Flathman, Paul E., 88-446
Flatman, G. T., 85-442; 86-132,217
Fleming, E., 89-222
Flood, Deborah, 90-35
Fogg, Andrea, 88-292
Fontenot, Martin M., 87-348
Ford, K. L., 84-210,230
Forney, D., 85-409
Forrester, R., 81-326
Fortin, R. L., 82-280
Foss, Alan, 88-455
Foster, Allan R., 87-78
Foster, R., 89-407
Foster, Sarah A., 88-292; 89-407,
   547
Foth, D. J., 86-176
Foumier, L., 89-273
Francingues, N. R., 82-220
Francingues, Norman R., 90-831
Francingues, Norman R., Jr., 88-338
Franconeri, P., 81-89
Frank, J., 84-532
Frank, J. F., 89-377
Frank, James F., 87-459
Frank, U., 80-165; 81-96,110
Fredericks, S., 86-36,120
Fredericks, Scott C, 87-14
Freed, J.R., 80-233
Freestone, F. J., 80-160,208; 81-285
French, Richard E., 90-525,681
Freudenthal, H.  G., 82-346
Friedman, P. H., 84-29,49
Friedrich, W., 83-169
Fries, Butch, 89-606; 90-254
Froelich, Emery M., 90-768
Frost, John D., 87-72
Fuller, P. R., 86-313
Fullerton, Susan, 88-598
Fullerton, Tod H., 88-409
Funderburk, R., 84-195
Furdyna, Stanley D., 90-336
Furlong, Eileen A., 90-128,144
Furman, C, 82-131
Furst, G. A., 85-93
Gabanski, Gilbert, 87-89
Gabry, Jon C., 87-104
Gaire, Roger, 90-760
Galbraith, R. M., 86-339
Galer, Linda D., 88-521
Gallagher, G. A., 80-85
Gallagher, John, 88-199
Galuzzi, P., 82-81
Gangadharan, A. C., 88-592
Garczynski, L., 84-521; 86-40
Garlauskas, A. B., 83-63
Gamas, R. L., 84-39
Garrahan, K. G., 84-478; 86-167
Gaskill, Bart, 87-439
Gay, F. T., ffl, 82-414
Gee, J.R., 89-207
Geil, M., 85-345
Geiselman, J. N., 83-266
Gemmill, D., 83-386; 84-371
Gensheimer, G. J., 84-306
Gentry, John K., 87-273
George, J. A., 86-186
George, L. C., 88-413
Geraghty, J. J., 80-49
Germann, Ray, 90-88
Gerst, Donna Lee, 87-5, 21
Gervasio, R., 89-15
Geuder, D., 84-29
Ghassemi, M., 80-160
Gherini, Steven A., 87-444
Ghuman, O. S., 84-90
Gianti, S. J., 84-200; 89-459
Gibbs, L. M., 83-392
Gibson, S. C, 81-269
Gift, J. S., 90-164
Giggy, Christopher L, 87-174
Gigliello, K., 84-457
Gilbert, J. M., 82-274
Gilbertson, M. A., 82-228
Gill, A., 84-131
Gillen, B. D., 82-27; 83-237
Gillespie, D. P., 80-125; 81-248
Gillis, Thomas, 87-41
Gilrein, S. A., 86-158
Ginn, Thomas C., 88-323
Giordano, Joanne M., 90-17
Gish, B. D., 84-122
Giti-Pour, Steve, 90-730
Givens, R. C, 86-31
Glaccum, R. A., 80-59; 81-84
Glass, J., 89-246, 501
Gleason, Patrick J., 88-125, 287; 90-
   606
Glynn, W. K., 86-345
Godoy, F.E., 89-555
Goggin, B., 81-411
Gold, J., 84-416
Gold, Jeffrey W., 88-183
Gold, M. E., 81-387
Goldberg, Steven C, 90-692
Goldman, L. M., 84-277
Goldman, Norma J., 88-273
Goldman, R. K., 81-215
Goldstein, P., 83-313
Golian, S. C, 86-8
Golian, Steven C, 88-1
Goliber, P., 80-71
Golob, R. S., 81-341
Golojuch, S. T., 85-423
Goltz, Mark N., 87-129
Goltz, R. D., 82-262; 83-202; 84-
   489; 85-299
Gomez, Gregory, 90-776
Goode, D. J., 83-161
Goodman, J., 85-419
Goodwin, B. E., 85-7
Gorton, J. C., Jr.,  81-10; 84-435
Goss, L. B., 82-380
Gossett, N. W., 89-306
Grabowski, Loretta V., 90-320
Grachek, Randall W., 90-484
Granger, Thomas, 88-474
Gratton, P. F., 89-13
Gray, E. K., 85-406
Gray, Robert H., 90-285
Graybill, L., 83-275
Grayson, Linda, 88-79
Greber, J. S. 84-486; 85-387
Greber, Jack S., 88-419
Green, Ermon L., 88-440
Green, J., 81-223
Greenburg, John, 87-502
Greene, Joseph, 87-198
Greenlaw, P. D., 89-41
Greenthal, John L., 88-60
Greiling, R. W., 84-535
Gridley, G. M., 88-467
Griffen, C. N., 85-53
                                                                                                                                           1005
-------
Grisham, George R., 90-745
Grissom, R. E, Jr., 90-164
Griswold, F. D., 89-463
Griswold, Roben M., 90-439
Grubbs, J. B. ("Jones"), 90-536
Grabc. W. E_ Jr., 82-191, 249; 89-
   413
Gruenfeld, M., 80-165; 81-96; 82-36
Gnininger, R M., 89-455
Grupp, D. J., 89-41
Guentzel, M. Neal, 90-776
Guerrero, P., 83-453
Gupta, Gopal D., 88-592
Gurba, P., 84-210, 230
Gurka, D. F., 82-45
Gushue, J. J.,  81-359; 85-261
Gushue, John J., 87-138
Gustafson, M. E., 86-448
Gulhrie, J., 86-386
Guttler, U., 89-537
Gulzmer, Michael P., 88-72
Haaker, Richard F., 90-503
Hadzi-Antich, T., 86-18
Hacberer, A. F., 82-45
Hafferty, Andrew J., 87-107
Hagarty, E. P., 89-455
Hagel, W. A., 86-186
Hager, Donald G., 82-259;  87-174
Hagger, C, 81-45; 84-321; 8S-7
Hahn, S. J., 86-448
Haiges, Lisa, 87-311
Haight, E. W., 89-652
Hajali, Paris, 87-238
Haji-Djafari, S., 83-231
Hale, David W., 87-223
Halc.F.D., 83-195
Halepaska, J. C., 84-162
Haley, Jennifer L., 88-19; 89-246,
    501; 90-575
Hall, Alan H., 90-977
Hall, D. W., 89-348
Hall, J.C., 84-313; 86-27
Hallahan, F. M., 85-14
Haller, P. H., 86-469
Hamm, Ben, 90-201
Hammond, J.  W., 80-250; 81-294
Hamper, M. J., 89-122
Hana, S. L., 89-4
Hanauska, Chris P., 87-480
Hanford, Richard W., 88-462
Hangeland, Erik B., 87-380
Hanley, G., 89-452
Hanley, M. M., 82-111
Hannink, G., 88-479
Hansel, M. J., 83-253
Hansen, Penelope, 90-66, 71, 77
Hanson, B., 82-141; 85-4; 86-224,
   462
Hanson, Bill, 88-5; 89-501; 90-575
Hanson, C. R., 84-189; 85-349
Hanson, J. B., 81-198; 84-493
Hanson, Sergius N., 90-585
Hardy, Mark J., 87-179
Hardy, U. Z., 80-91
Harl, Rodney S., 90-266
Harraan, H. D., Jr., 82-97
Harmon, G. R., 89-387
Harrington, W. H., 80-107
Harris, D. J., 81-322
Harris, John, 90-290
Harris, M. R.. 83-253
Harrily, Deborah A., 90-300
Hanman, Craig, 90-585
Hsnsficld, B., 82-295
H»ru, Kcnneih E, 88-295
HK&.H.. 83-169
Hstavama. H.  K_, 81-14'*. 84-363
Haich, Norm N., Jr., 85-285; 87-300
Hatheway, A. W., 85-331
Halhorn, John W., 90-270
Hatton, J. W., 89-298
Hauptmann, M., 90-557
Hauptmann, Michael G., 90-110,
   580
Hawkins, C., 83-395
Hawkins, Elizabeth T., 87-166
Hawley, K. A., 85-432
Hay, G. H., 89-392
Hayes, Douglas, 87-439
Hayes, E., 85-285
Hayes, Lisa C, 90-128
Hazaga, D., 84-404
Hazelwood, Douglas, 88-484
Head, H. N., 86-258
Heare, S., 83-395
Hebert, Richard !_, 88-113
Hedigcr, E. M., 86-164
Heeb, M., 81-7
Heffernan, A. Z., 86-8
Hefferman, Amelia, 87-515
Heglund, William, 87-5
Hein, James C, 88-174
Heinle, D., 89-130
Helgerson, Ron, 90-595
Helsing, Lyse D., 87-471
Hemker, D. L., 90-553
Hemsley, W. T., 80-141
Henderson, D. R., 86-380
Henderson, R. B., 84-135
Hendry, C. D., 85-314
Hennelly, Alyson A., 87-53
Hennington, J. C, 83-21;  85-374
Henry, Linda, 90-133
Hcrrington, Lisa, 88-19
Herson, Diane S., 88-490
Hess, Eric, 90-376
Hess, J. W., 83-108
Heyse, E., 85-234
Hickey, James C., 90-340
Hijazi, N., 83-98
Hilker, D., 80-212
Hill, H. David, 87-7
Hill, J. A., 86-292; 89-122
Hill, R., 82-233
Hill, R. D., 80-173; 86-356; 87-25;
   88-516
Hillery, Pamela A., 90-92
Hillenbrand, E., 82-357, 461
Hiltz, Ralph H., 90-589
Hina, C. E., 83-63
Hines, J. M., 81-70; 85-349
Hinrichs, R., 80-71
Hinzel, E.J., 86-313
Hirschhora, Joel S., 85-311; 87-251
Hitchcock, S., 82-97; 86-318
Hjersted, N. B., 80-255
Ho, Min-Da, 88-575
Hoag, R. B., Jr., 85-202
Hodge, V., 84-62, 498
Hoffman, Mike, 90-620
Hoffman, R. E., 86-78
Hoffmaster, Gary, 87-326
Hokanson, Sarah, 87-502; 88-484;
   90-730
Holberger, R. L., 82-451
Holland, J. Kent, Jr., 87-520
Holliway, Karen D., 90-911
Holm, L. A., 89-436
Holmes, David B., 90-492
Holmes, R. F., 84-592
Holmes, T., 89-222
Holacin. E. C. 84-251
Homer, David H., 86-213; 87-126
Hoogendoorn, D.. 84-569
Hooper, M. W, 83-266
Hopkins, F., 80-255
Home, A., 81-393
Homsby, Robert G., 90-363
Horton, K. A., 81-158
Hosfeld, R. K., 86-415
Hostage, Barbara, 88-37
Housman, J., 80-25
Housman, J. J., Jr., 81-398
Houston, R. C, 80-224
Howar, Michael, 87-439
Howe, R. W., 82-340
Howe, Robert A., 90-944
Hoylman, E W., 82-100
Hubbard, A. E, 86-186
Hubbard, Robert J., 86-186; 87-326
Hubner, R. P., 89-41
Hudson, Charles M., 87-158
Hudson, Joy, 90-776
Hudson, Kay K., 90-241
Hudson, T. B., 89-198
Huenefeld, Bruce, 90-907, 933
Huffman, G. L., 84-207
Huggins, Andrew, 88-277
Hughes, B. Mason, 90-793
Hughey, R. E, 85-58
Huizenga, H., 85-412
Hullinger, J. P., 85-136; 86-158
Hunt, G. E, 80-202
Hunt, R. A., 89-586
Hunter, J. H., 85-326
Hunter, Philip M., 90-871
Hupp, W. H., 81-30
Hushon, J. M., 89-99
Hutchison, C., 89-282
Hutson, K. A., 86-8; 87-515; 88-565;
   89-596
Hutson, Mark A., 90-911
Hutton, Daniel L, 88-557
Hwang, J.C., 81-317;84-1
Hwang, Seong T., 84-346; 87-149,
   485
Hyman, Jennifer A., 88-193
laccarino, T., 84-66
lanniello, Michael L, 88-251
lerardi, Mario, 87-204
Ikatainen, Allen J., 88-329
Ing, R., 84-239
Ingersoll, T. G., 81-405
taghara, A. T., 85-429
Ingra, Thomas S., 90-439
Irrgang, Gene H., 90-907
Isaacson, L., 81-158
Isaacson, P. J., 85-130
Isbistcr, J. D., 82-209
Isett, Jennifer, A., 90-336
Iskandar, I. K., 84-386
Islander, R. L., 89-345
Jackson, D. R., 89-413
Jackson, Ronald, 90-868
Jacob, T. A., 89-86
Jacobs,;. H., 82-165
Jacobson, C. Dale, 90-505
Jacobson, P. R., 86-233
Jacol, B. J., 83-76
James, S. C, 80-184; 81-171, 288;
   82-70, 131; 84-265; 85-234
James, Steven E, 90-924, 951
Janis, J. R., 81-405; 82-354
Janisz, A. J., 82-52
Jankauskas, J. A., 85-209
Janosik. Vic, 88-363
Jansen, David J., 88-335
Janssen, James A., 87-453
Jarvis, C. E, 84-469
Jelinek, Roben T., 90-937
Jenkins, Thomas F., 90-889
Jensen, Stephen L, 87-101
Jerger, Douglas E, 88-446; 90-807
Jerrick, N. J-, 83-389; 84-368
Jessbergw, H. U, 85-345; 89-537
Jessup, David J., 90-320
Jewett, J. J., m, 88-67; 89-1
Jhaveri, V., 83-242; 85-239
Job, Charles A., 87-89
Johannsen, Stephen D., 90-13
Johnson, D., 84-544
Johnson, D. W., 86-227
Johnson, E, 89-41
Johnson, G. M., 86-93,105
Johnson, Gregory, 90-484
Johnson, James T., Jr., 90-42
Johnson, K., 89-267
Johnson, Leonard C, 87-326
Johnson, M., 89-186
Johnson, M. G., 81-154
Johnson, Mark, 90-201
Johnson, Maik F., 86-52; 87-34; 88-
    23; 89-600,606; 90-254
Johnson, Steven B., 90-466
Johnson, Thomas L, 88-226
Johnson, W. J., 86-227
Johnson-Ballard, J., 81-30
Johnston, R. H., 83-145
Jones, A. K., 82-183,448
Jones, B., 84-300; 85-412, 419
Jones, K. H., 82-63
Jones, Philip L_, 87-18
Jones, R. D., 83-123, 346
Jones, S. G., 83-154
Jordan, B. H., 82-354
Jowett, James R., 84-339; 86-40; 87-
    14
Joyner, Sarah, 90-32,277
Jurbach, R., 84-66
Kabrick, R. M., 89-331
Kaczmar, S. W., 84-221
Kadish, J., 82-458
Kaelin, J. J., 85-362
Kaelin, Lawrence P., 90-257
Kaltreider, R., 86-14, 398
Kanehiro, B. Y., 89-259
Kaplan, M., 82-131
Karably, Louts S., 86-436; 87-97
Karas, Paul, 87-355
Karlsson, Haraldur, 90-357
Karmazinski,  Paul L, 87-213
Karon, J. M., 84-243
Kaschak, W. M., 82-124; 84-440;
    85-281; 86-393
Kastury, S., 85-189
Katz,S.,85-419
Kavanaugh, Michael C., 88-287,
    125; 90-606
Kay, R. L., Jr., 84-232
Kay, W., 85-409
KcaneJ., 89-318
Keffer, W., 84-273
Keim, M. A..  85-314
Keith, Slevan  M., 90-206
Keitz,EU, 82-214
KeUeher, Timothy E, 87-7
Kemerer, J. A., 84-427
Kemplin, Martin  G., 87-18
Kennedy, S. M., 81-248
Kenney, Patricia J., 88-429
Kerfoot, H. B., 84-45; 87-523
Kerfoot,W. B.,81-351
Kesari, Jaisimha, 87-380
Kester, Paul E, 87-457
Keulen, R, W., 88-479
Kcyes, J. Dennis, 90-681
Khan, A. Q., 80-226
Khara, B. H.,  86-220
-------
 Kiefer, Michael L., 88-188
 Kilpatrick, M. A., 80-30; 84-478
 Kim, C. S., 80-212
 Kimball, C. S., 83-68
 Kincare, K. A., 89-146
 Kinesella, J. V., 89-325
 King, J., 84-273; 85-243
 King, Wendell C., 88-152
 Kingscott, John, 90-716, 726
 Kirkpatrick, G. L., 89-277
 Kirner, Nancy P., 87-403
 Kissel, John C., 88-142; 89-67
 Klein, George, 87-111
 Klein, Michael D., 90-919
 Heinrath, Arthur W., 90-882
 Kling, Timothy L., 88-419
 Hinger, G. S., 85-128
 Knapp, Joan O'Neill, 88-429; 90-
    510,700
 Knorr, Robert S., 90-182
 Knowles, G. D., 83-346
 Knowles, Gilda A., 90-450
 Knox, J. N., 86-233; 89-186
 Knox, R. C, 83-179
 Knox, Robert, 87-311
 Koch, Donald, 89-152; 90-896
 Koemer, Robert M., 80-119; 81-165,
    317; 82-12; 83-175; 84-158; 86-
    272; 87-390
 Koesters, E. W., 84-72
 Kohn, Douglas W., 87-34
 Kolsky, K., 84-300
 Konz, James J., 87-143
 Kopsick, D. A., 82-7
 Kosin, Z., 85-221
 Koski, William A., 90-510
 Kosson, D. S., 83-217; 84-393; 88-
    451
 Roster, W.C., 80-141
 Koutsandreas, J. D., 83-449
 Kovalick, Walter W., Jr., 90-716,
    726
 Kovell, S. P., 86-46
 Kramer, Victoria H., 90-580
 Kraus, D. L., 85-314
 Krauss, E. V., 86-138
 Krishnan, P., 90-420
 Krohn, Russell B., 87-306
 Kruger, Joseph, 90-66,71
 Kuersteiner, J. D. Boone, 88-287;
    90-606
 Kurmer, Ann C, 90-807
 Kufc, Charles T., 80-30; 82-146; 86-
    110; 87-120
 Kugelman, I. J., 85-369
 Kumar, Ashok, 87-525
 Kunce, E. P., 86-345
 Kunze, M. E., 89-207
 Kuracz, Charles N., 90-753
 KuykendalL R. G., 83-459
 LaBar, D., 85-449
 LaBrecque, D., 83-28
 Labunski, Stanley, 90-425
 Lacy, Gregory D., 88-429
 Lacy, W. J., 84-592
 LaFaire, M. A. C, 89-447
 LaFornara, J. P., 81-110, 294; 85-
    128
 LaGrega, M. D., 81-42; 88-277,403
 Lahlou,  Mohammed, 90-245
 Laine, D. L., 89-35,56
 LaMarre, B. L,, 82-291
 Lamb, Robert H., 88-67
 Lambert, W. P., 84-412
 Lamont, A., 84-16
LaMori, Philip N., 87-396
Lampkins, M. J., 86-318
Landreth, Lloyd W., 88-605; 89-613;
    90-969
Lang, David J., 88-19
Lang, Kenneth T., 90-889
Lange, J. H., 89-78
Lange, R. M., 89-377
Langley, William D., 88-282
Langner, G., 82-141
Langseth, David, 90-398
Lanier, John H., 88-587
Lappala, E. G., 84-20
Larimore, D. R., 89-91
Larson, R. J., 80-180
Laskowski, Stanley L., 88-317
Laswell, B. H., 85-136
Lataille, M., 82-57
Laudon, Leslie S.,  88-261
Lavigne, Deborah, 90-273,329
Lavinder, S. R., 85-291
Lawrence, L, T., 84-481
Lawson, Frank D., 88-103
Lawson, J. T., 82-474
Leap, D. R., 87-405
LeClare, P. C, 83-398
Lederman,  P. B., 80-250; 81-294
Lee, C. C, 82-214; 84-207
Lee, Charles R., 88-435
Lee, Debra M., 90-972
Lee, G. W., Jr., 83-123,346
Lee, Kuantsai, 90-189
Lee, R. D., 85-157
Lee, Wen L., 90-189
LeGros, Susan P.,  88-277
Leighty, D. A., 83-79
Leis,W.M., 80-116
Lemmon, A. W., 89-380
Lennon, G. P., 85-357
Leo, J., 82-268
Leo, Margaret R., 90-628
Lepic, Kenneth A., 87-78
Leu, D. J., 86-303
Lewis, D. S., 84-382
Lewis, N., 89-407
Lewis, Ronald A.,  88-113
Lewis, W. E., 84-427
Li, Wen-Whai, 90-117
Lia, Paula M., 87-72
Librizzi, WUliam, 88-77
Lichtveld, Maureen, 88-524
Lidberg, R., 86-370
Liddle,J. A., 84-243
Lieber, Marc P., 87-72
Lieberman, Stephen H., 90-297
Liedel, J. M., 89-582
Lincoln, D. R., 85-449
Lincoln, David R., 88-259
Lindsey, W. B., 89-137
Linkenheil, R., 85-323
Linkenheil, Ronald J., 87-193,533
Lippe, J. C, 83-423
Lippitt, J. M., 82-311; 83-376
Lipsky, D.,  82-81
Litherland, Susan T., 90-565
Livolski,J.A.,Jr.,84-213
Lo, T. Y. Richard,  83-135; 87-228
Locke, P. W., 89-95
Lockerd, M. Joseph, 88-93
Loehr, R., 87-533
Logemann, Friedrich Peter, 90-658
Lombard, R. A., 85-50
Lominac, J. K., 89-309
Lonergan, Andrew J., 90-348
Longo, Thomas P., 88-39
Longstreth, J., 85-412
Lord, Arthur E., Jr., 80-119; 81-165;
   82-12; 83-175; 84-158; 86-272;
   87-390
Losche, R., 81-96
Lough, C. J., 82-228
Lounsbury, J., 84-498; 86-457
Loven, Carl G., 82-259; 87-174
Lovett, John T., 88-202
Lowe, G. W., 84-560
Lowe, William L., 90-901
Lowfance, S.  K.,  83-1
Lucas, R. A.,  82-187
Lucia, S. M., 89-298
Lueckel, E. B., 83-326
Lundy, D. A., 82-136
Lunney, P., 82-70
Lupo, M. J., 89-570
Lurk, Paul W., 90-297
Lybarger, J. A., 86-467
Lynch, D. R., 84-386
Lynch, E. R.,  81-215
Lynch, J. W., 80-42; 85-323
Lysyj, I., 81-114; 83-446
MacDonald, James R., 87-306
MacFarlane, Ian D., 90-42
Mack, J., 84-107
MacPhee, C.,  89-289
MacRoberts, P. B., 82-289
Madison, M. T., 89-95
Magee, A. D., 85-209
Magee, Brian, 87-166
Mahaffrey, William R., 90-780
Mahan, J. S., 82-136
Mahannah, Janet  L., 88-152; 90-853
Maher, Thomas F., 87-296
Makris, J., 86-11
Malhotra, C. C. J., 89-455
Malley,  Michael J., 90-944
Malone, P. G., 80-180; 82-220
Malone, Philip G., 90-297
Maloney, S. W., 85-456
Malot, James J., 87-273; 90-624
Mandel, R. M., 80-21
Mandel, Robert, 90-261
Mandel, Robert M., 88-424
Manderino, L. A., 89-600
Mangan, Chuck, 88-598
Manko, J. M., 81-387
Mann, M. J., 85-374
Mansoor, Yardena, 87-41
Manuel, E. M., 85-249
Marcotte, Barbara, 90-290
Margolis, S., 85-403
Mark, D. L., 89-436
Markey, Patricia,  87-300
Markowitz, Daniel V., 90-10
Marks, Peter, 90-901
Marley,  Michael C., 90-636
Marlowe, Christopher S. E., 88-546,
   567
Marquardt, George D., 87-284
Marsh, Deborah T., 88-251
Marshall, Ann C., 90-951
Marshall, T. C., 84-261
Marshall, T. R., 89-345
Marszalkowski, Robert A., 88-219
Marti, Tom, 90-513
Martin, Brad,  90-92
Martin, J. D., 89-512
Martin, Jeanne, 89-251
Martin, John, 90-425
Martin, W. F., 83-322; 84-248
Martin, W. J.,  82-198; 86-277
Martyn,  S., 89-430
Martz, M. K.,  86-1
Maser, K. R., 85-362
Mashni, C. I.,  86-237
Maslansky, S. P.,  82-319
Maslia, M. L., 83-145
Mason, B. J., 84-94
Mason, R., 86-52
Mason, Robert J., 84-339; 87-34,
    520; 88-23
Massey, T. I., 80-250
Masters, Hugh, 90-760
Mastrolonardo, Ray M., 90-304
Mateo, J., 86-14
Mateo, M., 83-413
Matey, Janet, 88-598
Mathamel, Martin S., 81-280; 86-
    472; 87-162; 88-162, 546,557,
    567
Matson, C., 89-273
Mattejat, Peter, 89-152; 90-896
Mattern, Charles, 87-268
Matthews, R. T., 83-362
Mauch, S. C., 89-157
Maughan, A. D., 84-239
Maughan, James, 90-148
Mavraganis, P. J., 83-449
May, I., 89-152
Mays,  M. K., 89-298
Maziarz, Thomas P., 88-395
Mazzacca, A. J., 83-242; 85-239
McAneny, C. C, 85-331
McArdle, J., 84-486
McAvoy, David R., 88-142
McBride, R. E., 89-348
McCabe, Mark, 90-549
McCartney, G. J., 89-392
McCartney, M. Carol, 90-13
McCloskey, M. H., 82-372
McClure, A. F., 84-452
McCord, A. T., 81-129
McCracken, W. E., 86-380
McDevitt, Nancy P., 87-453
McDonald, Ann M., 88-145
McDonald, S., 89-190
McElroy, William J., 90-433
McEnery, C. L., 82-306
McFarland, Wayne E., 90-529
McGarry, F. J., 82-291
McGinnis, J. T., 82-380
McGinnis, Roger N., 87-107
McGlew, P. J., 84-150; 85-142; 86-
   403
McGovem, D., 84-469
McGowan, T. F., 89-387
McGrath, Richard A., 87-420,426
McKee, C. R., 84-162
McKenzie, David E., 90-793
McKnight, Robert, 87-111
McKone, Thomas E., 90-215
McKown, G. L., 81-300, 306; 84-
   283
McLane, Gerald A., 90-300
McLaughlin, D. B., 80-66
McLaughlin, Michael W., 87-296
McLaughlin, Tom, 90-153
Mclelwain, T. A., 89-497
McLeod, D. S., 84-350
McLeod, R.S.,84-114
McMillan, K. S., 85-269
McMillion, L. G., 82-100
McNeill, J. D., 82-1
McNelly, Greg, 90-730
Meacham, David E., 90-753
Meade, J. P., 84-407
Meegoda, Namunu J., 87-385
Mehdiratta, G. R., 89-512
Mehran, M., 83-94
Meier,  E. P., 82-45
Meier,  Marina P., 88-413
Melchior, Daniel C., 87-502
Melvold, R. W., 81-269
Menke, J. L, 80-147
Mentzer, Dave, 90-10
                                                                                                                                         1007
-------
     Mcnzie, Charles A., 87-138; 90-215
     Mercer, J. W., 82-159
     Mercer, James W., 90-720
     Mercer, Mark l_, 87-143
     Merin, Ira S., 90-314
     Merlchofcr, MUey W., 89-39, 44
     Mcmilz,  S., 85-107
     Messick, J. V., 81-263
     Messing, Alan W., 90-176
     Messinger, D. J., 86-110
     Meyer, AJvin F., 90-772
     Meyer, J., 80-275
     Meyers,!. E., 80-180
     Michael, James I., 90-686
     Michaud, G. R., 89-377
     Michelsea, D. L, 84-398; 85-291
     Michelsen, Donald L., 88-455
     Miklas, M. P., 89-35
     Milbralh, L. W,, 81-415
     Mililana, L. M., 86-152; 89-157
     Miller, D. G., Jr., 82-107; 83-221
     Miller, Greg C, 90-517
      Miller, K.R., 85-136; 86-158
     Miller, Keith E., 88-103
     Miller, M. A., 89-468
      Miller, Michael S., 90-363
      Millison, Dan, 88-269;  90-290
      Mills, W. J., 89-497
      Mills, William B., 87-444
      Millspaugh, Mark P., 88-60
      Mindock, R. A., 86-105
      Mineo, T. O., 89-286
      Miner, William H., 90-882
      Minnich, Timothy R., 90-628
      Mischgofsky, F. H., 88-479
      Mitchell, F. L.,  84-259; 85-406
      Mitchell, Kenneth L., 90-56
      Mittleman, A. L., 84-213
      Moaycr, Masoud, 88-245
      Mohrman, Gregory B.,  90-944
      Mohsen, M. F. M., 90-415
      Mohsen, M. Famikh, 90-460
      Molton,  Peter M., 87-183
      Monsces, M., 85-88
      Monserrale, M., 86-14
      Montgomery, R. J., 86-292
     Montgomery, V. J., 83-8
     Montgomery, Verna, 88-32
     Moon, R. E., 89-137
     Mooney, G. A., 84-35
     Moore, James B., 87-28
     Moore, S. F., 80-66
     Morahan,T. J.,83-310
     Moran, B. V., 83-17
     Morey, R. M., 81-158
     Morgan, C. H., 80-202
     Morgan, R. C., 82-366; 84-213; 85-
         396
     Morgenstem, Karl A., 88-84; 90-35
     Morin, J. O., 85-97
     Momingstar, Mary P., 87-471
     Morson,  B. J., 84-535
     Mortensen, B. K., 86-74
     Morton, E S., 86-213
     Moscati, A. F., Jr., 86-164, 420
     Moslchi, J., 85-326
     Mole, Peter A.,  87-371
     Molt, H.  V., 89-526
     Moll, R.  M., 80-269; 83-433
     Motwani, J. N.,  86-105
     MousaJ.J., 83-86
     Moy.C.S., 89-19
     Mover, E E, 85-209
     Moylan,C. A., 85-71
     Mueller,  Susan L, 88-528
     Muller. B W.. 82-2(^
     Mullcr-Kurchcnbauer. H., 83-169
Mullins, J. W., 85-442
Mundy, P. A., 89-609
Munger, Robert, 87-453
Mungin-Davis, Queenie, 88-208
Munoz, H., 84-416
Murdoch, Lawrence C., 90-542
Murphy, Brian L., 82-331, 396; 83-
    13; 87-138, 153
Murphy, C. B., Jr., 83-195; 84-221
Murphy, J. R., 84-213
Murphy, J., 89-152
Murphy, Mark T., 90-453
Murphy, Melissa, 90-95
Murphy, Vincent P., 87-390
Murray, J. G., 85-464
Musser, D. T., 85-231
Mutch, R. D., Jr., 83-296; 89-562
Myers, F., 89-267
Myers, R. S., 89-459
Myers, V. B., 82-295; 83-354
Myler, Craig A., 90-853
Myrick, J., 84-253
Nadeau, P. F., 82-124; 83-313
Nadeau, Paul F., 88-15
Nadeau, R. J., 85-128
Nagle, E., 83-370
Nakata, (Catherine T., 90-4
Naleid, D. S., 89-555
Nangeroni, Peter E., 90-636
Narang, R., 80-212
Naugle, D. F., 85-26
Nazar, A., 82-187; 84-356
Needham, L. L, 84-253; 86-78
Neely, James M., 88-561
Neely, N. S., 80-125
Neithercut, Peter D., 87-169
Nelson, A. B., 81-52
Nelson, D. D., 85-32
Nelson, Jerome S., 87-371
Nelson, Michael J. K., 90-800
Neumann, C, 82-350
Newborn, J. Scott, 90-333
Newman, J. R., 84-350
Newton, C. E., 86-420
Newton, Jeffrey P., 87-187
Nichols, F. D., 84-504
Nickelsen, Michael G., 90-753
Nickens, Dan, 84-416; 87-268
Nielson, D. M., 86-460
Nielsen, J. Mark, 90-460
Nielson, M., 81-374
Niemele, V. E., 82-437
Nikmanesh, J., 89-190
Niland, Penelope L, 90-585
Nimmons, M. J., 83-94
Nisbet, I. C. T., 82-406
Noel, M. R., 83-71
Noel, Michael R., 90-957
Noel, T. E., 83-266
Noland, John W., 84-176,  203; 87-
    453
Norman, M., 86-318
Norman, Michael A., 88-313
Norman, W. R., 82-111; 85-261
North, B. E., 81-103
Nowell, Craig A., 87-179
Nunno, Thomas J., 88-199
Nyberg, P. C, 84-504
Nygaard, D. D., 83-79
O'Connor, Ralph C, Jr., 88-537
O'Dca, D., 83-331
O'Flaherty, P. M., 84-535
O'Hara, Patrick F., 86-126; 87-367,
    4%, 499; 88-594
O'Kccfe, P., 80-212
O'Malley, R., 85-58
0' Neil, L Jean, 88-435
O'Reffly, Kathlene, 87-355
OToole,M. M.,85-116
Obaseki, S., 84-598
Offutt, Carolyn K., 88-12, 429; 90-
   510, 700
Ogden, Palmer R., 90-123
Ogg, R.  N., 83-202, 358; 86-356
Ohonba, E., 84-598
Oi, A. W., 81-122
Okeke, A. C., 85-182
Oldenburg, Kirsten U., 87-251
Oldham, J., 89-306
Olmstead, Donald G., 90-839
Olsen, Roger L., 85-107; 86-115,
   313, 386; 88-261, 393; 89-145;
   90-696
Olson, Kathlene A., 87-480
Oma, K. H., 84-191
Openshaw,  L-A, 83-326
Opitz, B. E., 82-198; 86-277
Oravetz, Andrew W., Jr., 88-429
On, J. R., 85-349
Ortiz, M., 86-84
Osborn,  Craig G., 90-505
Osbom,  J., 83-43
Osheka,J.W., 80-184
Osier, J. G., 86-138
Otis, Mark J., 88-347
Ottinetti, Luca, 87-476
Ouderkirk, David, 90-972
Ounanian, D. W., 83-270
Owens, D. W., 80-212
Owens, Victor, 87-228
Owens, William, 87-300
Owens, William W., 88-164
Ozbilgen, Melih M., 88-125, 287;
   90-386, 606
Paczkowski, Michael T., 88-375
Padgett, Joseph,  90-748
Page, Norbert P., 87-132
Page, R. A., 84-594
Page, Roger H., 90-415
Paige, S. F., 80-30, 202
Paine, D., 89-586
Pajak, A. P., 80-184; 81-288
Palombo, D. A.,  82-165
Pancoski, S., 89-292
Pancoski, Stephen E., 88-403, 440
Pankanin, J., 89-216
Panneerselvam, Kilyur N., 90-901
Papesh,  Judy, 90-367
Paquette, J. Steven, 86-208, 393; 87-
   1
Parker, Frank L., 81-313; 87-231;
   88-119; 90-222
Parker, J. C., 84-213
Parker, W. R., 84-72
Parks, G. A., 83-280
Parratt, R. S., 83-195
Parris, George E., 88-602
Parrish, C. S., 85-1
Parry, G. D. R., 82-448; 84-588
Partridge, L, J., 84-290; 85-319; 86-
   65
Partymiller, K. G., 84-213; 89-413
Paschal, D., 85-409
Paschke, R. A., 85-147
Pasior, S., 89-635
Patarcity, Jane M., 87-326
Patchin,  P,  89-267
Patel, M. A., 89-455
Patelunas, G. M^ 89-78
Patnode, Thomas J., 85-323; 87-193
Patrick,  Cynthia D., 87-158
Patterson, D. G., Jr., 86-78
Paulson, Steven  E-, 88-413
Pearct, R. B., 81-255; 83-320
Pearsall, L. J., 86-242; 89-552
Pease, R. W., Jr., 80-147; 8M71,
    198
Pedersen, T. A^ 86-398
Pedersen, Tom A., 88-199
Pei, Phyllis C, 88-157
Pendurthi, Ravindra, 90-245
Pennington, D., 85-253
Perkins, L C., 89-137
Periis, Randy, 88-97
Peters, J. A, 81-123
Peters, N., U, 86-365
Peters, W. R., 82-31
Peterson, B., 89-50
Peterson, J. M., 85-199
Peterson, R. Michael, 90-624
Peterson, Sandy, 87-45
Pezzullo, Joseph A., 90-624
Pheiffer, Thomas, 88-193
Phelps, Donald K., 88-335
Phillips, C R., 89-198
Phillips, J. W., 81-206
Picket!, J. S., 86-424
Pierson, T., 84-176; 89-152
Pike, Myron T., 87-480
Pimentel, E. M., 88-35; 89-417
Pinlenich, J. L., 81-70
Plitnik, Marilyn A., 87-414
Plourd, K. P., 85-396
Plumb, R. H., 84-45
Plunkett, James B., 90-641
Pomeroy, John, 90-85
Ponder, T. C., 85-387
Popp, S. A., 86-105
Porter, Don C., 87-436
Porticr, R. J., 89-351
Possidento, M., 80-25
Possin, B. N., 83-114
Potter, Thomas, 88-108
Powell, D. H., 83-86
Prann,R.S.,89-lll
Prater, R. B., 89-91
Predpall, D. F., 84-16
Preston, J. E,, 84-39
Preston, Jerry S., 90-333
Preuss, P. W., 86-167
Previ, Caroline, 90-77
Price, D. E., 84-478
Price, D. R.,  82-94
Price, Roger L., 90-29,966
Prickett.T.,89-152
Pritchett, Thomas H., 90-257
Priznar, F. J., 85-1, 74; 86-84
Proko, K., 85-11
Prothero, T. G., 84-248
Prybyla, D. A., 85-468
Puglionesi, Peter S., 87-380
Pyles, D. G., 86-350
Quan, W., 81-380
Quimby, J. M., 82-36
Quinlivan, S., 80-160
Quinn,K.J.,84-170;8S-157
Quinn, R. D., 86-393
Quintrell, W. N., 85-36
Rademacher, J. M., 84-189; 85-349
Rams, J. M., 81-21
Ramsey, Robert H., 90-466
Ramsey, W. l_, 80-259; 81-212
Rand, John B., 90-103
Ranney, Colleen A., 88-103
Ransom, M., 80-275
Rappaport, A., 81-411
Ralnaweera, Pra&anna, 87-385
Ray, Michael C., 90-230
Raymond, Arthur, 88-403
Rea.K.H.,86-1
Read, John R. U 90-197
HI'S
-------
Rebis, E. N., 83-209
Redeker, Laurie A., 87-21
Redford, David, 87-465
Reed, Karen A., 90-17
Reeme,T.L., 89-638
Reifsnyder, R. H., 82-237
Reinert, Kevin H., 90-185
Reitei, G. A., 80-21
Remeta, D. P., 80-165; 81-96
Kendall, John D., 90-47
Repa, E., 82-146; 85-164
Repa,E.W., 86-237
Reverend, I. M, 84-162
Reyes, J.J., 89-72
Rhoades, Sara E., 87-358
Riccio, R., 89-41
Rice, Craig W., 87-63
Rice, E. D., 85-84
Rice, I. M., 85-182
Rice, R. G., 84-600
Richards, A., 80-212
Richardson, S., 84-1
Richardson, Thomas L., 90-230
Richardson, W. S., 89-198
Richardson, W. K., Jr., 89-277
Richey, Marine, 88-269
Rick, J., 84-469
Ridosh, M. H., 84-427; 85-243
Riese, Arthur C, 90-937
Rikleen, L. S., 82-470; 85-275
Riley, John, 88-37
Riner, S. D., 82-228
Ring, George T., 87-320
Riojas, Arturo, 88-382
Rios, Yeonn, 90-776
Rippberger, Mark L., 90-865
Rishel, H.  L., 81-248
Ritthaler,W.E., 82-254
Rizzo,J, 82-17
Rizzo,W.J., Jr., 85-209
Robbins,J.C, 83-431
Roberts, Andrew W., 88-313
Roberts, B. R., 83-135
Roberts, Bryan D., 90-646
Roberts, D. W., 86-78
Roberts, DarylW., 90-169
Roberts, Paul V., 87-129
Robertson, J. Martin, 88-435
Rockas, E., 85-11
Rodenbeck, Sven E., 88-532
Rodricks,J.V., 83-401
Roe, C, 89-246
Rogers, John, 88-503
Rogers, W., 84-16
Rogoshewski, P. J., 80-202; 82-131,
    146; 84-62
Romanow, S., 85-255
Ronk, R. M., 86-471
Rood, A. S., 89-117
Roos, K. S., 83-285
Rosasco, P. V., 84-103
Rosbury, K. D., 84-265
Rosebrook, D. D., 84-326
Rosenberg, M. S., 89-202
Rosenkranz, W., 81-7
Rosenthal, Seymour, 88-513
Ross, Derek, 84-239; 87-315; 88-
    395
Ross, W. O., 89-592
Rothman, D. W., 84-435
Rothman, t., 82-363
Roy, A J., 83-209
Roy, Mell  J.-Branch, 87-48
Royer, M.  D., 81-269
Rubenstein, P. L., 86-143
Rubin, Bernard, 90-760
Ruda, F. D., 84-393
Rudasill, Cinthia L., 90-371,765
Rudy, Richard J., 88-219; 89-163;
   90-877
Ruggaber, Gordon J., 90-498
Rulkens, W. H., 82-442; 84-576
Rumbaugh, James, 90-110
Rupp, G., 89-216
Rupp, M. J., 86-164
Ruta, Gwen S., 87-508
Ryan, C. R., 86-264
Ryan, Elizabeth A, 87-166; 88-353
Ryan, F. B., 81-10
Ryan, John, 87-533
Ryan, M.J., 85-29
Ryan, R. M., 85-125
Ryckman, M. D., 84-420
Sabadell, Gabriel P., 88-177
Sachdev, Dev R., 87-341; 90-739
Sackman, Annette R., 88-97
Sadat, M. M., 83-301,413
Sale, Thomas C., 87-320,358
Salhotra, Atul M., 90-157
Salisbury, Cynthia, 88-214
Salvesen, R. H., 84-11
Sanders, D. E., 82-461
Sanders, Thomas M., 87-218
Sandness, G. A., 81-300; 83-68
Sandrin, J. A, 89-348
Sandza,W.F., 85-255
Sanford,J. A, 84-435
Sanning, D. E., 81-201; 82-118,386
Santos, Susan L., 87-166,254; 88-
   353
Sanville, Cynthia Y., 90-788
Sappington, D., 85-452
Saracina, Rocco, 88-214
Samo, D. J., 85-234
Samo, Douglas J., 88-255; 90-52
Sather, Norman F., 90-788
Saunders, Gary L., 90-748
Saunders, M. J.F., 89-111
Sawyer, Stephen, 88-504,508
Schafer, P. E., 85-192
Schalla, R., 83-117; 84-283
Schanz, Robert W., 90-157
Schaper, L. T., 86-47
Schapker.D.R., 86-47
Schauf, F. J., 80-125
Scheinfeld, Raymond A, 88-363
Scheppers, D. L., 84-544
Schilling, R., 84-239
Schleck, Daniel S., 89-642; 90-677
Schlossnagle, G. W., 83-5,304
Schmidt, C. E., 82-334; 83-293
Schmierer, Kurt, 90-668
Schmierer, Kurt E., 88-226
Schnabel, G. A, 80-107
Schneider, P., 80-282
Schneider, R., 80-71
Schnobrich, D. M., 85-147
Schoenberger, R. J., 82-156
Schofield, W. R., 84-382
Scholze, R. J., Jr., 85-456
Schomaker, N. B., 80-173; 82-233
Schramm, Wayne F., 90-169
Schroeder, Brett R., 90-236
Schuller, R. M., 82-94
Schultz, D. W., 82-244
Schultz, H. Lee, 87-143,149
Schweitzer, G. E., 81-238; 82-399
Schweizer, J.W., 86-339
Scofield,P.A.,83-285
Scott, J. C, 81-255; 83-320
Scott, K. John, 88-335
Scott, M., 82-311; 83-376
Scott, Michael P., 90-117
Scotto, Robert L., 90-628
Scrudato, R. J., 80-71
Sczurko, Joseph J., 88-113,413
Seanor, A M., 81-143
Sebastian, C, 86-14
Sebba, F., 84-398
Segal, H. L., 85-50
Selig, E. L, 82-458; 83-437
Senior, Steven T., 90-17
Sepesi, J. A, 85-423, 438
Sergeant, Ann, 87-431
Sevee, J. E., 82-280
Sewell, G. H., 82-76
Seymour, R. A, 82-107
Shafer, R., 89-519
Shafer, R. A, 84-465
Shah, RameshJ., 87-414
Shangraw, R. F., Jr., 90-241
Shanks, Marti, 90-95
Shannon, Sanuel, 87-300
Shapiro, Melissa F., 88-269; 89-452
Shapot, R. M., 86-93
Sharkey, M. E., 84-525
Sharma, G. K., 81-185
Sharrow, D., 89-606
Shaw, E. A, 86-224
Shaw, Elizabeth A, 88-5
Shaw, L. G., 81-415
Sheedy, K. A, 80-116
Shen, Thomas T., 82-70,76; 84-68;
   87-471
Sheridan, D. B., 84-374
Sherman, Alan, 88-592
Sherman, J. S., 82-372
Sherman, Susan, 87-280
Sherwood, D. R., 82-198; 86-277
Shields, W., 89-130
Shih, C. S., 81-230; 82-390,408; 83-
   405; 89-12
Shih, Shia-Shun, 88-382
Shimmin, K. G., 86-143,463
Shiver, R. L., 85-80
Shoor, S. K, 86-4
Shore, Charles O., 90-176
Shroads, A. L., 83-86
Shuckrow, A J., 80-184; 81-288
Shugart, S. L., 86-436
Shultz, D. W., 82-31
Sibold, L. P., 85-74
Sibold, Lucy,  87-14
Siebenberg, S., 84-546
Siebers, D. L., 90-420
Sigler, w. B., 89-9
Sikora, L., 89-298
Silbermann, P. T., 80-192
Silcox, M. F., 83-8
Silka, L. R., 80-45; 82-159
Silka, Lyle R., 88-138
Sills, M. A., 80-192
Simanonok, S. H.,  86-97
Simcoe, B., 81-21
Simmons, M. A, 84-85
Simmons, Thomas P., 90-641
Sims, L. M., 89-582
Sims, R. C., 83-226
Sims, Ronald C., 90-820
Singer, G. L., 84-378
Singerman, Joel A., 87-341; 90-739
Singh, J., 84-81
Singh, R., 83-147
Sirota, E. B., 83-94
Siscanaw, R., 82-57
Sisk, W. E., 84-203,412
Sisk, Wayne, 90-901
Skach, Robert F., 88-188
Skalski, J. R., 84-85
Skilton, C, 90-164
Skipp, David C., 90-720
Skladany, George J., 87-208
Skoglund, T. W., 85-147
Slack, J., 80-212
Sladek, Susan J., 88-5
Slater, C. S., 82-203
Sloan, A, III, 85-438
Sloan, Richard L., 88-273
Slocumb, R. C, 86-247
Smart, David A., 88-67
Smart, R. F., 84-509
Smiley, D., 84-66
Smith, C., 84-546
Smith, Craig W., 88-188
Smith, E. T., 80-8
Smith, J. R., 89-331
Smith, J.S., 84-53
Smith, Jeffrey W., 88-455
Smith, John J., 87-492
Smith, John, 88-214
Smith, Lee A,  85-396; 87-158; 88-
   208
Smith, M. O., 86-430
Smith, Michael A, 82-431; 84-549;
   87-264
Smith, P., 86-313
Smith, Philip G., 87-101
Smith, R., 80-212
Smith, R. L., 85-231
Smith, Richard, 90-10
Smith, S., 86-462
Smith, Stephen M., 88-304
Smith, W., 86-333
Smith, William C, 87-367,496; 88-
   594
Snow, M., 85-67
Snyder, A. J., 81-359
Snyder, M., 80-255
Snyder, Mark G., 90-686
Sokal, D., 84-239
Solinski, Philip J., 90-MSS-628
Solyom, P., 83-342
Sonderman, DR-ING Wolfgang, 90-
   745
Sophianopoulos, Judy, 90-450
Sosebee. J. B._84;35P,_
Soundarajan, R., 90-665
Sovinee, B., 85-58
Spatarella, J. J., 84-440
Spear, R., 81-89
Spear, R. D., 89-41
Spencer, Elizabeth B., 90-542
Spencer, R. W., 82-237
Spinola, A. A,  90-839
Spinier, T. M., 81-122; 82-40,57;
   83-100,105; 85-93
Spooner, P. A, 80-30,202; 82-191;
   85-214, 234
Springer, C, 82-70
Springer, S. D., 86-350
Sresty, Guggilam C., 88-498
Srivastava, V. K., 83-231
St. Clair, A. E., 82-372
St. John, John P., 88-359
Stadler, Gerald J., 87-7
Staible, T., 85-107
Staley, L. J., 89-421
Stamatov, J. R., 89-443
Stammler, M., 83-68
Stanfill, D. F., Ill, 85-269
Stanford, R. L., 81-198; 84-498; 85-
   275
Stankunas, A. R., 82-326
Stanley, E. G.,  83-1
Starr, R. C, 80-53
Stattlemyre, James A, 90-453
Stecher, Eugene F., 87-334
Stecik, Robert E., Jr., 87-28
Steele, J. R., 84-269
                                                                                                                                           1009
-------
     Steelman, B. 1-, 85-432
     Steffen, Douglas E., 90-601
     Stehr, P. S, 84-287
     Slebr-Green, P. A^ 86-78
     Steimle, R. R-, 81-212
     Stein, G. F., 84-287
     Stein, Robin, 90-8%
     Steinberg, K. K., 84-253
     Steinhauer, William G., 87-420, 426
     Stephanotos, Basilis N.( 90-612
     Stephens, R. D., 80-15; 82-428; 85-
         102
     Sterling, Sherry, 87-61
     Stetz, Elizabeth, 88-269
     Steward, K., 89-430
     Stief, K., 82-434; 84-565
     Stinson, Mary 1C, 88-504
     Stirts, Hugh M., 88-300
     Sloclcinger, Siegfried L., 87-420; 88-
         343
     Stokely, P. M., 84-6
     Stoller, P. J., 80-239;  81-198
     Stoloff, S. W., 89-443
     Stone, J. E., 90-478
     Stone, K. J. L., 89-537
     Stone, Marilyn E., 88-8
     Stone, T., 85-128
     Stone, W. L., 81-188
     Stoner, R., 84-66
     Strandbergh, D., 84-81
     Strattan, L. W., 81-103
     Strauss, J. B., 81-136
     Slrenge, Dennis L., 85-432;  87-409;
         88-539
     Strickfaden, M. E., 85-7
     Strobel, G., 89-163
     Strong, T. M., 85-473
     Stroo, H. F., 89-331
     Stroud, F. B., 82-274
     Slrullmann, T., 89-27
     Struzziery, J. J., 80-192
     Suffett, Irwin H., 88-132
     Sukol, Roxanne B., 88-419;  90-730
     Sullivan, D. A., 81-136
     Sullivan, Daniel, 90-716
     Sullivan, J. H., 83-37
     Sullivan, J. M., Jr., 84-386
     Sullivan, Jeffrey A., 88-274
     Sullivan, Kevin M., 87-208
     Sunanda, Daniel K., 88-177
     Susten, AllanS., 90-173
     Sutch, R. W., 89-468
     Sutton, C., 89-41
     Sutlon, P. M., 86-253
     Swaroop, A, 84-90
     Swaroop, Ram, 87-258
     Swarthout, Brian, 90-367
     Swatek, M. A., 85-255
     Sweet, Carol, 90-21
     Swenson, G. A., Ill, 83-123
     Swibas, C. M., 84-39
     Swichkow, D., 89-592
     Sydow, W. U, 86-393, 398;  87-1
     Syvcrson, Timothy L., 88-84
     Tackett, K. M., 81-123
     Tafuri, A. N., 81-188; 82-169; 84-
         407; 89-202
     Tan, Chee-Kai, 90-776
     Tannka, John C., 87-330
     Taiuer, M.S., 81-10
     Tapscott, G., 82-420
     Tarhon. S. F.. 84-445; 87-355
     Tarllon, Sieve, 87-355
     Tasca, J. J., 89-111
     T«lc, C. U, Jr., 84-232
     Tiylor, Alison C. 87-153; 89-108
     Taylor. B., 83-.W
Taylor, Larry R., 88-158
Taylor, M. D, 86-88
Taylor, Michael L, 88-419
Teepen, Kristina L, 88-274
Teeter, Cynthia l_, 90-831
Teets, R. W., 83-310
Teller, J., 84-517
Testa, Stephen M., 88-375
Tetta, D., 89-130,259,301
Tewhey, J. D., 82-280; 84-452
Thibodeaux, L. J., 82-70
Thiesen, H. M^ 82-285
Thorn, J. E., 89-479
Thomas, A., 84-176
Thomas, C.M^ 85-112
Thomas, G. A., 80-226
Thomas, J. E., Jr., 84-150; 85-142
Thomas, J. M., 84-85
Thomas, S. R., 85-476
Thomas, William R., 90-951
Thompson, G. M., 84-20
Thompson, K. Michael, 90-25
Thompson, Kimberly  M., 90-215
Thompson, S. N., 83-331
Thompson, W. E., 84-469; 85-387
Thomsen, K. O., 86-138, 220
Thomson, Kurt O., 90-277,300, 304
Thome, D.J., 89-117
Thorsen, J. W, 81-42, 259; 82-156
Thorslund, T. W., 86-193
Threlrall, D., 80-131;  82-187
Tidwell, Dalton  C, 90-977
Tifft, E. C., Jr., 84-221
Tillinghast, V., 85-93
TiUman, David A., 90-857
Timmerman, C.  L., 84-191; 89-309
Tinto, T., 85-243
Tipple, Gregory L, 90-681
Tischler, JoAnn, 90-907
Titus, S. E,, 81-177
Tong, Peter, 87-149
Tope, Timothy J., 88-119
Topudurti, Kirankumar, 89-407; 90-
    425
Torpy, M. F., 89-331
Towarnicky, J., 89-380
Towers, D. S., 89-313
Townsend, R. W., 82-67
Traver, R. p., 89-202
Travis, Daniel S., 88-119
Trees, D. P., 84-49
Tremblay, J. W., 83-423
Trezek, G. J., 86-303
Trezek, George J., 90-673
Triegel, E. K., 83-270
Troasl, Richard, 90-510
Trojan, M., 89-503
Troxler, W. L., 85-460
Truen,J. B., 82-451
Truilt, Duane, 87-449
Tsai, TenLin S., 90-788
Tucker, W. A., 84-306
Tuor, N. R., 83-389; 84-368
Turkeltaub, Robert B., 88-569
Turner, J. R., 83-17
Tumham, B., 85-423
Turoff, B., 80-282
Turner, Robert J., 90-788
Turpin, R. D., 81-110, 277; 83-82;
    84-81, 273
Tusa, W. K., 81-2; 82-27
Twedell, A M., 80-233
Twedell, D. B., 80-30, 202
Tyagi, S., 82-12
Tyburski. T. E, 85-396
Ulirsch, Gregory, 90-182
Ulirsch, Gregory V., 88-532; 89-72;
   90-128
Unger, M, 89-503
Unites, D. F., 80-25; 81-398; 83-13
Unterberg, W., 81-188
Upadhyay, Hans D., 90-308
Urban, M. J., 84-53
Urban, N. W., 82-414; 83-5, 304
Vais, C, 84-427
Valentinetti, Richard A., 88-77; 89-
   404
Valines, Edward J., 90-793
Valkenburg, N., 90-557
Valkenburg, Nicholas, 90-110,580
Van Amam, David G., 87-223; 89-
   313
van de Velde, J. L., 88-479
van der Meer, J. P., 88-479
Van Ee, J. J., 83-28
van Epp, T. D., 86-361
Van Gemert, W. J. Th., 82-442
Van Hine, Lydia, 90-85
van Munster, Joan, 87-330
Van Slyke, D., 83-442
Van Tassel, Richard, 87-396
Vanderlaan, G. A., 81-348; 82-321;
   83-366; 86-407
Vandermark, Tracey L., 90-251
VanderVoort, J. D., 86-269
Vandervort, R., 81-263
Varuntanya, C. Peter, 90-839
Vasudevan, C., 89-623
Vega, Ivette, 88-37
Velaquez, Luis A., 87-453
Velez, V. G., 86-93
Vias, C, 84-273
Viellenave, James H., 90-340
Virgin, John J., 88-226
Viste, D. R., 84-217
Vitale, Joseph, 88-199
Vocke, R. W., 86-1
Vogel, Albert, 90-409
Vogel, G. A, 82-214
Volanski, James T., 90-839
Voltaggio, Thomas C., 88-317
von Braun, M. C., 86-200; 89-430
von Lindem, I., 86-31,200; 89-430
von Stackelberg, [Catherine, 88-550;
   89-82
Voorhees, M. L, 85-182
Vora, K. H., 84-81
Vrable, D. L., 85-378
Waddell, Richard, Jr., 90-668
Wagner, J., 84-97
Wagner, K., 82-169; 83-226; 84-62;
   85-221
Waite, Thomas D., 90-753
Walker, K. D., 84-321
Wall, Howard O., 88-513
Wallace, J. R., 83-358
Wallace, Kenneth A, 87-213
Wallace, L P., 83-322
Wallace, Robert C., 88-495
Wallace, William A, 88-259
Wallberg, Jeanne S., 90-210
Wallen, Douglas A, 88-138
Waller, M. J, 83-147
Wallis, D. A, 84-398; 85-291
Walsh, J., 82-311
Walsh, J. F., 82-63
Walsh, J. J., 80-125; 81-248; 83-376
Walsh, Marianne E, 90-889
Walsh, Matthew T., 90-636
Waller, Gary R^ 90-557
Waller, Martia B., 87-409
Waller, Robert, 90-972
Walters, Gary, 90-620
Walther, E G., 83-28
Wardell, J, 81-374
Warner, R. C, 86-365
Warren, S. D., 89-485
Wasser, M. B, 85-307
Watkin. Geoffiey W., 87-508
Watson, K. S., 85-307
Way, S. C, 84-162
Weathington, B. Chris, 87-93; 90-
    336
Weaver, R. E C, 85-464
Webb, K. B, 84-287; 86-78
Weber, D. D., 83-28; 86-132,217
Weber, W. J. Jr., 89-526
Wehner, D. E, 89-194
Weiner, P. H., 81-37
Weingart, M. D., 87-405
Weiss, C, 84-546
Weissman, Arthur B., 88-8
Weist, F. C, 83-175
Welks, K. E, 80-147
Wells, Suzanne, 88-269
Wentz, John A., 88-419
Werle, C. P., 89-596
Werner, J. D., 83-370; 86-69
Wessling, Elizabeth, 90-620
West, M. L, 89-586
Westhorp, Brenda J., 90-539
Weston, R. F., 89-99,157
Wetzel, R. S., 80-30, 202; 82-169,
    191; 85-234
Wheatcraft, S. W., 83-108
Whelan, Gene, 85-432; 87-409; 88-
    295,539; 90-820
White, D., 89-497
White, D. C, 86-356, 361
White, L. A, 85-281
While, M., 80-275
While, R. J., 89-41
White, R. M., 82-91
Whitlock, S. A, 83-86
Whitmyre, Gary K., 87-143
Whitney, H. T., 86-436
Whillaker, K. F., 82-262
Widmann, W., 89-163
Wiehl, Christopher D., 88-569
Wieland, Karen A., 88-274
Wiggans, K. E., 85-314
Wilboum,  R. G., 89-396
Wildeman, Thomas R., 88-261
Wilder, I., 80-173; 82-233
Wiley, J. B., 85-58
Wilkinson, R. R., 80-255
Williams, R. C., 86-467
Williams, R. J., 89-78
Williams-Johnson, M., 90-164
Williamson, J. A, 89-9
Williamson, S. J., 84-77
Willis, N.,  89-606
Willis, N. M., 86-35
Wilson, D. C., 80-8
Wilson, D. J., 89-562
Wilson, L.G., 82-100
Wilson, S. B., 89-227
Wine, J., 83-428
Winklehaus, C, 85-423
Wirth, P. K., 84-141
Wise, K. T., 84-330
Witherow, W. E, 84-122
Wilmer, K. A, 85-357
Wilt, Ann, 88-79
Witt, Michael E, 90-911
Win, Peter V., 90-35
Wilten, Alan J., 88-152
Wiltmann, S. G., 85-157
Woelfel, G. C., 85-192
Wohlford, W. P., 89-463
1010
-------
Wolbach, C. D., 83-54
Wolf, R, 83-43
Wolfe, S. P., 85-88
Wolff, Carl T., 90-371
Wolff, Scott K., 87-138
Wong, J., 81-374
Woo, Nancy, 88-145
Wood, D. K., 89-631
Wood, J. G., 89-198
Woodhouse, D., 85-374
Woodhull, Patrick M., 90-807
Woodson, L., 86-208
Woodward, Richard E., 88-273
Worden, M. H., 84-273
Worden, R., 89-41
Worobel, Roman, 88-424; 89-488
Worst, N.R., 84-374
Wotherspoon, J., 86-303
Wright, A. P., 80-42
Wright, Brad, 88-55
Wright, Stuart A., 90-101
Wu, B. C., 86-350
Wujcik, Walter J., 90-901
Wuslich, M. G., 82-224
Wyeth, R. K., 81-107
Wyman, J., 83-395
Yaffe, H. J., 80-239
Yancheski, Tad B., 88-265
Yang, E. J., 81-393; 83-370; 84-335;
   86-52
Yaniga, P. M., 86-333; 89-273
Yaohua, Z., 84-604
Yare, Bruce S., 87-315; 90-270
Yeh, Hsin H., 87-341; 90-739
Yemington, C., 90-478
Yerian, Tracy, 90-261
Yeskis, Douglas J., 87-213
Yezzi, J. J., Jr., 81-285
Yiannakakis, A., 90-557
Yim, Chan S., 90-460
Young, C. F., 89-638
Young, L., 80-275
Young, R. A., 81-52
Youzhi, G., 84-604
Yu, K., 80-160
Yuhr,L.B., 85-112; 86-465
Zachowski, Michael S., 87-85
Zaffiro, Alan D., 87-457
Zamuda, Craig D., 88-304
Zamuda, Craig, 85-412, 419; 86-
   457; 87-56, 61
Zanowick, Marie B., 90-471
Zappi, Mark E., 89-519; 90-831, 919
Zaragoza, Larry, 90-80
Zarlinski, Stephen, 89-543; 90-712
Zatezalo, Mark P., 87-499
Zeff, J. D., 89-264
Zhang, Jinrong, 88-467
Ziegenfus, L. M., 84-521
Ziegler, F. G., 81-70; 85-349
Zieraba, W. L., 89-436
Zilis, Kim, 90-620
Zimmerman, P. M., 84-326
Znoj, Edward W., 90-539
Zorato, Enzo, 90-513
Zumberge, J., 89-41
Zuras, A. D., 85-1
                                                                                                                                         1011
-------
                                                       Subject Index
                                                          1980-1990
Abandoned Well Closure, 90-911
Abiotic Immobilization, 90-820
Above Ground Closure, 83-275
Accuracy, 88-157
Acid
   Extractable Screening,87-107
   Extraction, 90-739
   Mine Drainage, 8J5-261
   Oil Sludges, 88-395
Acidic Waste Site, 85-326
Activated Alumina
   Arsenic Removal, 90-901
Activated Carbon, 81-374; §2-259,
        262; 83-209, 248,253,342;
   88-409; 89-479; 90-839
   Adsorption, 90-420

   Design, 90-686
   VOCs, 90-748
Administrative Order, 88-72
Adsorbent Traps, 87-459
Adsorption, 84-393
   After UV/Ozone, 90-919
   Clays, 89-543
   Gas Phase, 90-748
Advanced Technologies, 84-412
Aeration
   Gasoline Removal, 90-865
Aerosol, §§-546
Agency for Toxic Substances and
        Diseases Registry
        (ATSDR), 86-467; J8-524,
        528,532, 537; 90-128
Agricultural Fire Residue, 84-420
Air
   Dispersion, 89-570
      Modeling, 2Q-117
   Modeling, 82-331; 84-66
   Monitoring, 82-67,268, 299,
        306,331; 83-82, 85; 86-
        152; 88-335,557, 561,567;
        89-15; 90-117, 257,  489
      Ambient, 81-280; 83-293;
        85-125; 87-284
      Cleanup Site, M-72
      Design, 86-152
      Emissions, 82-70
      Nitrogen Compounds, 83-
        100
      Real-Time, 83-98; 90-270
       Sampling, 88-557
       Techniques, 82-334; 86-152
       Two-Stage Tube, 83-85; 84-
        81
    Photos, 8Q-116; §5-116
    Quality, 82-63
       Assessment, 82-76; 87-284
    Sampling, 88-567
       Pump (SP), 88-567
    Sparging, 90-636
    Stripper, 88-188,395; 89-479
    Stripping, 83-209,313,354; 84-
        170; §§-125, 446; §£-558;
          90-420,513,517, 529,
        606,624, 839
       Emissions Control, 84-176:
        90-748
       In Situ, 89-313
       Soils, 86-322
       Vinyl Chloride, 90-686
    Toxics
       Modeling, 89-157
Alara, 87-403
Allied Barrel & Container, 88-32
Alternative
    Concentration Limits, 86-173
    Financial Mechanisms, 89-600
    Hazardous Waste Management,
        §S-5
    Soil Treatment, 88-484
    Strategy, 88-214
    Treatment Technologies, 86-361
Alternative Remedial Contracts
        Strategy (ARCS), 88-15
Aluminum Reduction Faciity
    Cleanup, 90-320
Ambient, §§-282
    Air
       Quality, 89-157
       Sampling, 90-290
Ammunition Waste, 88-569
Anaerobic, 88-451
    Biodegradation, 88-495
Analysis, 82-45; 88-145
    Attributive Utility, §§-44
    Chromium, 90-266
    Dimethyl Mercury, gO-257
    Drum Samples, 84-39
    Environmental, 88-97
    Field, 88-251; 89-41; 90-261
       Screening, 90-333
    Geostatistical, 88-274
    Hydrocarbon, 90-620
    Low Concentration, 90-944
    Lower Detection Limits, §2-280
    Metals, 83-79
    Mobile, 86-120
    On-Site, 90-273
    Organic Halogens, 90-329
    PCBs, 87-420; 90-273
    Portable Instruments, 82-36,40,
        57
    Pyrographic, §1-114
    Quality Control, 84-29
    Risk Management, 90-251
    Screening, 83-86; §5-97
    Site Data Base, 84-49
    Soil, §8-251; 90-336
       Gas, 90-277, 340
    Spectrometer, 83-291
Analytical Methods
    Precision and Accuracy, 89-50
Annuity, 88-23
Antimony, §9-298
Aquatic Ecosystem, 88-119
Aquifer
    Alluvial, 87-444
    Bedrock, 86-403
    Gravel, §§-219
    Response Test, 87-213
    Restoration Program, 87-238
    Testing, 90-300
       RI, 90-580
ARARs, 87-436; 88-8,12, 35,241,
        295,304,435; §0-13
    Asbestos, 89-547
    Compliance, 88-12
    Rocky Mountain Arsenal
        (RMA), 90-944
Arizona
    TCE Contamination, 82-424
Arnold Air Force Base, Tennessee,
        89-309
Aromatics
    Biodegradation, 2Q-780
Arsenic
    Groundwater, 90-123,371, 901
    Removal, 90-601
    Waste, 84^469; 85-409
Arsine
   Health Assessment, 90-144
Asbestos, 85-21; 88-145; 89-547
ASCE, 81-2
Ashland Oil, 88-317
   Spill
      Monongahela River, 90-966
Assessment, 82-17,27; 83-37
   Areal Photography, 85-116
   Biological, 82-52
   Cold Weather, §2-254
   Endangerment, 84-213, 226; 88-
        295,539
   Environmental, 86-1
   Exposure, 86-69; 87-476; 88-
        300, 353
   Health, 88-528,532
      Effects, 84r253
      Risk, §4-230,261
   Management, §1-348, 351
   Mathematical Modeling, 81-306,
        313
   Mercury Contamination, 82-81
   Methods, 81-79
   Multiattributive Utility, 88-39
   Pesticide Plant, 82-7
   Petitioned Health, 88-528
   Public Health, 88-353
   Remedial Action, 88-338
   Risk, §6-69; §7-485; §8-35,241,
        277,287,295,304,353,
      382, 484,539, 550, 602; 89-
        78
      Public Health, 89-78
      Quantitative, 88-277; 89-78
   Site, §5-209; 88-60,152
   Technical Risk, 88-602
   Wetland, §2-431
Assessments, Type A & B, 88-605
Asset Liquidation, 89-600
Assignment of Obligations, 88-23
ASTSWMO, 88-77
ATSDR (see Agency for Toxic
        Substances and Diseases
        Registry)
Attapulgite Stabilization, 2Q-712
ATTIC Data Base, 90-716
Attributive Utility Analysis, 88-44
Audit, 81-398
   Environmental, 88-60
   Compliance Monitoring, 88-93
                                                                                                                                       1013
-------
     Austria, §§-219
     Automobile Shredder Fluff (Auto
             Fluff), §2-216

     Background, §§-282
     Baird & McGuire Site, §5-261; 87-
             138; 2&-371, 765
     Bankruptcy, §2-600
     Banks and Lending Institutions, §§-
             60
     Bar Code Inventory, §9-485
     Barrier(s), §2-249
        Bentonite, §2-191; §2-126, 519
        Cement, §4-126
        Gelatinous, §2-198
        Geomembrane, §£-282
        In Situ Vitrification (ISV), 90-
             453
        Leachate Compatability, §4-131
        Sorptive Admix, 86_-277
        Wall, 22-460
            Sheet Pile, 22-484
     Basic Extraction Sludge Treatment,
             §6-318
     Battery
        Casings, §9-301
        Plant
            Soil Cleanup, 22-498
     Bayesian Data Analysis, 22-189
     BOAT, §§-12
     Bedrock Aquifers, §5,-142
        Contaminant Movement, 82-111;
             §5-202
        Contamination, 89-468
        Fractured, §4-150; §2-213; §2-
             468
        Fracturing, §2-468
     Bench-Scale
        Study, §1-288
        Testing, §2-184; §§-329
     Beneficial Use, §4-560
     Beneficial ion, §§-413
     Benthic Organism, §§-323
     Bentonite, §£-543; 22-308
        Barrier, §2-519, 526
        -Cement Mixtures
            Durability, §5-345
        Slurry Wall, §2-313; 2Q-439
     Bentonite-Soil
        Mixture Resistance, 84-131
        Slurry Walls, 85-357, 369
     Benzene, §§-202, 451; §2-570
     Benzidine
        Health Assessment, 22-144
     Berlin & Farro, §1-205
     B.E.S.T., §2-348; 2Q-681
     Bid Protests, §4-520
     Bidding, 89-181
        Cleanup Contracts, 84-509
     Bikini Aloll
        Sunken Ships,  22-137
     Bioassay, 87-66; 88-323; §2-23
        Microfax, §§-323
        Sediment, §§-323
     Bioassessment, 88-72
     Bioaugmentation,  90-536
     Bioavailability, §§-142
     Biodecomposition, §8-265
     Biodegradalion, §2-203; §4-393; §5_-
             234; §§-444, 446,  467, 495;
        20-793
        Anaerobic, §§-495
        Aromalics,  22-780
        In situ, £§-495
        PCP. 22-826
        TCE, 22-826
     Bioindicalors. 81-185
Biological, §8-455
    Markers, 22-164
    Monitoring, §1-238; §2-75
    Technical Assistance Group, 89-
        613
    Treatment, 86-253; 87-208; 22-
        839
       Hazardous Waste, 22-847
Biopolymer Slurry
    Drain, §§-462
    Trench, £0-382
Biopolymerization, 22-820
Bioreclamation, §5-239; §7-193,
        315,533
Bioremediation, 88-273, 395, 429,
        446, 490; 89-10,325, 331,
        338;
    22-529, 536, 831
    Diesel Fuel, 20-776
    In Situ, 22-800
    Oil Refinery, 22-807
    Solid Phase, 90-814
    Treatability Study, 90-681
Biota, 88-72
Biotechnology, 88-273
Biotransformation, §§-138
Biotreatment
    Red Water, 22-788
Blasting, §2-468
Block Displacement Method, §2-249
Borehole
    Geophysics, §2-277
    Logging, §§-363
Bottom Barrier, §4-135
Bridgeport Rental and Oil Services
        Site, §5-299
Brio Refining, §7-315; 22-780
    Real-Time Air Monitoring, 20-
        270
Bromine
    Organic, §2-442
BTEX
    Bioremediation, 22-807
    State Criteria, 22-21
BTX, §2-642
Building Decontamination, 84-486
Bureau of Reclamation, §9-652
Burial
    Shorl-Term, §7-512
Buried
    Drums, 80-239
    Waste, 87-300; §9-27
       Location, 22-314

California
    Superfund Program, §2-428
   •Ranking System, §5-429
Callahan Site, §2-254
Canal Bottom Liner, 87-334
Cap(sX 22-474
    Clay, §9-181
Capacity Assurance Plan, §9-606
Capital Budget, §8-602
Capping, §2-123, 296; §§-245
    Cost, §2-370
Carbon
    Adsorption, 90-513
    Arsenic Removal, 22-901
    Recovery System, §9-558
    Sleam  Regeneration, 90-624
    Tetrachloridc, §§-188
       Irradiation, 22-753
       Soil Contamination, 22-277
Carcinogens, 84-11
    Reponable Quantities, §6-162
Case
    Histories, §§-395
    Management Strategy, §§-79
Cell Model, §5-182
Cement
    Asphalt Emulsion, §4-131
    Bentonite Slurry Wall, §6-264
    Kiln Dust (CKD), 88-398
       Stabilization, 22-712
Centrifuge Tests
    Clay Liners, §2-537
CERCLA (See Also Superfund), §§-
        295,537,539; §9-417
    Cleanup Cost Data Base System,
        89-186
    Defense Protection, 90-969
    Enforcement, 89-631
    EPA/State Relations, 86-22
    Facilities Settlements, 88-23
    Options and Liabilities, 86-18
    Program Objectives, 89-503
    RCRA Integration, §2-631; 22-
        25
    Remedies, §5-4
    Settlements
       Facilitating, 88-23
       Litigation, §§-55
       Policy, §9-600
Change Orders, 84-521
Characterization
    and Analysis, 88-567
    Population, 22-173
Chemfix Process, 22-739
Chemical(s), §§-539
    Analysis, Rapid, §0-165
    Concentration, §§-282
    Control, §1-341; §4-416
    Data Base, 22-977
    Emission Reporting, 90-56
    Fixation, §7-187; 22-739
    Hazardous Releases, §§-37
    Information, 22-977
    Leaching, §§-413
    Occurrence, §§-282
    Oxidation, §2-253; §7-174; 90-
        768
       UV Process, 22-937
    Plant
       Emergency Removal, §3-338
    Ranking Methods, §§-282
    Reagent, 88-419
    Release, 2Q-589
       Reporting, 90-56
    Specific Parameters, §5-412
Chemometric Profiling, §6-242
Children
    Arsenic Exposure, 85-409
China, §4-604
Chlorinated
    Hydrocarbons, §§-219, 395
       Groundwater, §2-519
          Monitoring, §2-1
    Phenols, §9-325
    Solvents
       DNAPL, 22-565
       Remediation, 22-696
    Volatile Organics, §§-164
Chlorobenzene, §2-570
Chloroform
    Irradiation, 22-753
Chromic Acid, §£-448
Chromium, §§-409, 413; §2-455
    Recovery, §§-413
    Sludge, §2-259
    Soil, 22-681
       Analysis, 22-266
Circulating Bed
    Combustion, §2-396
    Combustor, §5-378
Citizen Information Committees, §5_-
        473
Claims, §4-521; §2-647
Classification System
   Hazardous Waste, 2Q-222
Clay, §§-440
   Cap, §§-199; §2-181
   Leachate Interaction, §2-154
   Liners, §2-512,543
       Deformation, §2-537
   Organic Leachate Effect, §1-223
   Organically Modified, §§-440
   Plastic, §2-512
Clean Closure, 2Q-478
Cleanup, §2-147, 257; §§-317; §£-
        282, 286, 325; 22-254,529
   Activities, §§-313
   Air Monitoring, §4-72; 22-270
   Alternative Levels, §§-287
   Asbestos, §5-21
   Assessment, §2-389; §5-116
      Bioassay, 87-66
   BT-KEMI Dumpsite, §2-342
   Case Studies, §2-395; §4-440
   Coal Tar, §3-331
   Cold Weather, §2-254
   Community Relations, §5-468
   Contract Bids, §4-509; §2-496
   Cost(s), §2-186; 22-230, 241
      Allocation, §4-326
      Effectiveness, §£-193
      Estimate, 22-236
      PRP Ability to Pay, §2-600
      Recovery, 22-1
   Criteria, §2-301; §§-103
   Degree, §2-436
   Delays, §2-320
   Drum Site, §2-354
   Dual Purpose, §2-352
   Effectiveness
      Long-Term, §2-434
   Enforcement, §4-478
   Extent, §2-433
   Evaluation, §2-246
   Federal, §5-7; §7-296
      Slate Cooperation, §5-50
   Forced, §1-255
   Gasoline-Contaminated Soil, 22-
        636
   Generator, §5-7
   Gilson Site Proposal, §2-289
   Goals
      Petroleum, 22-21
   Groundwater, §§-19; §2-468; gQ-
        420, 433
   Hardin County Brickyard, §2-
        274
   In Situ, 90-677
   Innovative
      Techniques, 22-726
      Technology, 22-716
   Level, §2-398; §£-173; §§-241;
        22-157,612
      Alternatives, §§-287
      Risk Based, 22-185
      Soil, 22-498
   Liability, §2-442
   Management, §2-370
   Method Selection, 22-52
   Pacific Island, §4-427
   PCS, §2-156, 284; §2-104
   Picillo Farm, §2-268
   Public Information Needs, §4-
        368
   Radioactive Mine Tailings, 84-
        504
   Radium Processing Residue*, §4-
IOM
-------
        445
   Refinery Site, 90-536
   Requirements, 88-8
   Reserve Fund, 85-58
   Rocky Mountain Arsenal, 85-36
   Role of Liner, 89-534
   Sewer Line, 89-493
   Soil, 88-202, 495
      Lead, 90-505
      VOC(s), 90-641
   Staged Approach, 82-262
   Standards, 88-5, 304
   Superfund Site, 90-539
   Technology, 85-285
   Toxic Wastes, 85-311
   Under Superfund, 86-407
   Wildlife Habitat Improvement,
        90-10
Cleve Reber Site, 85-136
Closure, 81-259; 88-245; 89-345,
        642; 90-478
   Compaction, 90-618
   Copper Residue Disposal Site,
        81-70
   Cost Apportionment, 86-56
   Cover Design, 89-4
   Impoundment, 83-195
      Creosote, 85-323
   Industrial Site, 84-277
   In-Place, 84-185
   Lagoon, 90-466
   Landfill, 88-199
   Options, 87-337
   Post-Closure
      Illinois Perspective, 83-459
   Superfund Site, 90-539
   Vickery, Ohio, 86-297
   Well, 90-911
Clothing
   Chemical Protection, 22-489
CMA, 81-1,88-409,598
Coal
   Gasification Waste, 89-216
   Mine Groundwater Cleanup, 84-
        356
   Tar, 89-642
      Cleanup, 83-331; 84-11
Cofiring
   Fuel and Explosive, 90-853
COLIS Data Base, 90-716
Collection Media, 88-567
Colloidal Gas Aphron, 88-455
Column Tests, 88-467
Comeback Mine, 88-32
Communication, 88-524; 89-452
   Risk, 22-98
   Systems, 89-638
   Traps, 89-452
Community
   Activities, 84^371
   Assessment, 89-635
   Benefits, 86-31
   Concerns, 88-241
      Health, §2-321
   Consensus Building
      Rocky Mountain Arsenal, 90-
        924
   Coordinator, 81-411
   Health Assessment, 90-182
   Organizations), 90-95
   Participation, 90-92
   Program, §2-386, 389
      Rocky Mountain Arsenal, 90-
        951
   Reaction, 90-161
   Relations (See Also Public
        Participation), 81-405,415;
       82-354; 84-378; 87-254; 88-
        269,521; 89-447
       Plan, 89-635
       Program, 89-638
       PRPs, 22-88
Community Right-to-Know Act, 86-
        11; 88-516,565; 89-443
Compaction
   Dynamic, 22-618
Company-Internal Limits, 88-546
Compatibility Testing, §1-110
Compatible Materials, 89-488
Compensation, 89-194
Compliance, 90-668
   Federal, 89-631
   Title III, 89-443
Composting
   Soils, 82-209
   Treatability Study, 89-298
Comprehensive Environmental
        Assessment and Response
        Program, 86-1
Compressed Gas, 88-183
   Cylinder Management, 87-268
Computer
   -Assisted Evaluation, 22-542
   -Assisted Site Evaluation System,
        90-542
   Chemical
       Data Base, 90-977
       Data Series, 90-977
       Information, 22-977
   Cost Estimation, 90-236
   Expert Systems, 86-208
   Modeling, 87-111
       Site Assessment, 90-376
       Soil Cleanup, 90-498
   Risk Analysis, 84-300
Concrete, 88-419
Cone Penetration Test, gg-158
Confirmation Study, 88-208
Confined Disposal Facility, 88-338,
        343, 347
Connecticut
   Risk Evaluation, §2-25
Consent Decree, §2-592
Consistency, §8-79
Consultant
   Liability, 86-47
Contained Aquatic Disposal, 88-338,
        347
Container-Piles, 88-479
Containment
       Temporary Barrier Wall, 22-
        484
Contaminant, §§-245, 295
   System Design, §2-175
   Transport, 86-88; 88-539; 89-
        570
   Volatilization, §§-498
Contaminated
   Land, §4-549
   Sediment, 88-338
   Soil, §2-226, 231; §g-395, 409,
        424, 435; 89-396
       Cleanup, 83-354; 87-172
Contamination, 88-208, 300
   Explosives, §§-569
   Groundwater, 88-84,113
   Mapping, 83-71; §4-85
Contingency
   Fund, §2-21
   Plan
       Massachusetts, §3-420
   Remedial Sites, 84-489
Continuing Evaluation, §§-567
Contract, 88-214
   Administration, §2-647
   Laboratory
      Investigation, 22-355
      Program, §7-43; §§-282
Contractors)
   Indemnification, 86-52; 87-521;
        22-201
   Liability, 87-34,520
   Risk Management, 22-201
Contracts
   Bidding, 87-496
   Construction, §7-496
   Control, 87-492
   FIT, 86-36
   Remedial Planning, §6-35
   REM/FIT, 83-313
   Superfund, 86-40, 46
   Technical  Enforcement Support,
        86-35
Cooperative Agreement, 84-103; 85-
        53
Copper Smelter
   Arsenic Wastes, 85-409
Corporate Successor Liability, 87-48
Corrective Action, 22-25
   Process, §2-503
Correlation, 88-103
Cost, 80-202;  81-248; 82-289; 83-
        209;  §8-409, 598
   Above Ground Waste Storage,
        82-228
   Air Stripping, 83-313
   Analysis, §2-404
   Assessment Team, 22-241
   Benefit Analysis, 90-280
   CERCLA Financed, 83-395
   Cleanup, §2-262; 83-296,366,
        370;  84-341; 89-186, 282;
          22-230, 241
      Allocation Model, §4-326
      Level,  §3-398
   Closure Apportionment, 86-56
   Computer  Models, 83-362
   Cover, §2-187
   Discounting Techniques, 86-61
   Earned Value, §7-492
   Effective, §8-594
      Screening, §5-93
   Effectiveness, §2-404
      Evaluation, 82-372; 84-290;
        §6-193
   Estimates,  §2-202; §4-330, 335;
        88-594
      Cleanup, 22-230, 236
   Ground Freezing, 84-386
   Groundwater Treatment, §2-248,
        358
   Health and Safety Impact, 83-
        376
   Interest and Litigation, §§-55
   Lackawana Refuse Site, 87-307
   Leachate
      Collection,  83-237
      Monitoring, §2-97
   Management, 84-339
   Minimization, 81-84; 87-258,
        326
   Model, 87-376
   Recovery,  84-313; §§-605; §2-
        600
      Actions, §§-277
      Documentation, 82-366
      Massachusetts, 90-1
      Private, 88-67
   Reduction, 88-287
   Remedial,  §2-118; 92-398
      Action, 89-181
    Risk Benefit Analysis, 88-484
    Savings, 86-164,420
       Via Negotiation, 82-377
    Treatment System, §1-294
    Water Recovery System, §2-136
Counting Techniques, 88-145
Coventry, Rhode Island, 80-239
Covers (see Also Caps), 82-183,
        187,448; 84-588
    Design, §2-4
       and Construction, 85-331
    Landfill, 90-553
    Pesticide Disposal Site, 85-349
Credibility, 88-157
Creep Characteristics, 86-247
Creosote, 88-226; 89-642
    Biodegradation, 90-780
    Bioremediation, 87-193
    Contamination, 89-130
       Groundwater,  22-439
    DNAPL, 22-565
    Impoundment, 85-323
    Incineration, §2-387
Cresol, 88-424
Criticism, §4-532
Cutoff Wall, §3-123, 296
    Chemically Resistant, 83-169,
        179,191
    Cost, §3-362
    Materials, 22-439
Cyanides, §4-598, 600; §§-467
Cylinder, §8-183
    Management, §7-268

Damage
    Models, §§-15
    Recovery, §1-393
Data
    Bases, 83-304; §4-49,59, §§-282
      Problems, §6-213
    Gathering, §§-259
    Quality, 89-50
      Objectives, 88-35
    RI/FS, 86-398; §7-72
DC Resistivity, 86-227
De Minimis Settlement, §9-190
Debris, §8-12,419
Decay Theory, §2-208
Dechlorination, §8-429
Decision, 88-55
    Analysis, 88-44,55
    Making, 81-230
    Tree Analysis, §2-408
Decommissioning, 89-586
Decontamination, §2-226; §§-419,
        557; §2-421,586
    Buildings, 84-486
    Waterway, 83-21
Defense Environmental Restoration
        Program (DERP), 89-596
Defense Priority Model (DPM), §2-
        99
Deformation
    Clay Liner, §2-537
Degradation, 88-108,467
    TNT Sludge, 83-270
    VOCs, 84-217
Degreasing
    Waste Minimization, 90-868
Delaware Groundwater
        Management, §2-618
Demographics Analysis, 90-173
Demonstration, 88-521
    Test, 88-504, 508
Denitrification, 88-451
Denney Farm, §1-326
Denver Radium Superfund Site, 89-
                                                                                                                                         1015
-------
             652
     Depth-Specific Samples, §7-320
     Dermal Exposure, £7-166; §8-142
     DERP (See Defense Environmental
             Restoration Program)
     Design, §§-594
        GAC, 22-686
        Mathematical Modeling, §1-306
        Preliminary, §2-202
        Sample, §§-503
     Detection, §§-152
        Buried Drums, §4-158
        RDX, 20-889
        TNT, 22-889
     Detonation, §£200
     Detoxification, §0-192; §£382; 87-
             533
        Fire Residues, §£420
     Dichloroethene, §g-138
        1,1-dichloroethene, §§-108
     Diesel Fuel, §6-415; §§-317, 462
        Bioremediation, 2S-776
     Diffusion
        Effective Transport, §7-129
     Diligent Effort, 22-201
     Dimethyl Mercury
        Air Monitoring, 20-257
     DIMP, §1-374
     Dioxin, §1-322, 326; §2-405; §£
             287; §5-261; §£-78, 97; §7-
             306;
        §§-255, 292, 479, 513, 587; §2-
             117,286
        Destruction, §2-380
        Health, 22-169
            Assessment, 22-144
     Dipole Configurations, 88-84
     Direct Reading Instrument (DRI),
             §§-567
     Discovery
        Methods, §6-84
        Site, 22-35
     Dispersion, §§-455
        Coefficients, §2-135
        Modeling
            Chemical Release, §7-525
     Disposal, §1-329; §§-183, 335,343,
             575, 592
        Above Ground, §2-275
        Commercial Criteria, §2-224
        Computer Cost Model, §2-362
        Confined Facility, §§-347
        Contained Aquatic, §§-338, 347
        Demolition Debris, 22-585
        Fuel and Propellent, 22-853
        Liability, §2-431
        Mine, §5-387
        Pentachlorophenol, 22-446
        Salt Cavities, §2-266
        Shock Sensitive Chemicals, §£
             200
     DNAPL, 22-492,565, 624
        Oil, §2-497
     Documentation
        Cost Recovery, §2-366
     DOD (see U. S. Department of
             Defense)
     DOE (see U. S. Department of
             Energy)
     Dose-Response Assessment,  89-82
     Downhole Sensing, §2-108; §2-320
     Drain System, §2-237
     Drainage
        Acid Mine, §§-261
        Nets, §$-247
        Trench, §§-462
     DRASTIC, 22-35
Dredging, §§-335,338,343,347
   Disposal, 88-335,338
DRF, §8-587
Drilling
   Buried Drum Pit, 86-126
   Dual Wall Drilling, §7-355,358
   Horizontal, §6-258
   Techniques, 22-409
Drinking Water
   Contamination, §4-600
Drum(s), §2-254
   Analysis, §4-39
       Electric Method, 87-385
   Buried, §2-12; §4-158
   Disposal Pit, 86-126
   Handling, §2-169
   Site Cleanup, 83-354
   Tracking, §2-485
Dual Extraction, 22-624
Dust Control,  84-265
Dynamic Compaction, 90-618

Ebonite Casings, §2-301
Ecoassessment, 88-72
Ecological Assessment
   Wetland, 90-148
Economic
   Analysis
       TCLP, 22-280
   Aspects
       Hazardous Waste Sites, 87-
         264
ECRA,§9-9
Effluent,  §§-347
Electric Reactor, §4-382
Electric Utilities Site, §2-377
Electrical Leak Detection, §2-35,56
Electrochemical Oxidation, §7-183
Electromagnetic
   Conductivity, §2-27
   Induction, §2-28, 68; §£-132,
         227
   Resistivity, §2-1
   Survey, §0-59; §2-12; §§-84
   Waves, §2-119
Emergency
   Planning, §4-248; §§-565
       Community Right-to-Know
        Act, 89-443
   Removal, §2-338
   Response, §§-37,313
       Notification System, 22-972
       Oil Spill, 22-966
Emissions
   Monitoring, §2-293
   Rates, §£68
Encapsulation, §2-405
Endangered Species, §§-435
Endangerment, §8-72
   Assessments, §£213; §5-396,
        423,  438; §8-295, 539
Enforcement, §£544; §5-21; §9-600
   CERCLA
       U.S. EPA/State Relations, §£-
         18
   Cleanup, §£478
   Endangerment Assessments, §£
        213;  §5.-396
   Information Management, 85-11
Environmental
   Analysis, §§-97
   Assessment, 89-9
   Audit, §§-60, 65; §2-13
   Cleanup Responsibility Act
        (ECRA), §8_-60
   Compliance Monitoring, §§-93
   Concerns,  §£592; §2-635
   Evaluation
       Manual, §9-609
       Policy, §9-609
   Impact, §1-177; §8-435; §2-194,
        576
       Oa Spill, 2S-966
   Liability, §2-45, §8-60
   Modeling, §2-149
   Monitoring, 22-285
   Pathways, 88-532; 22-128
   Risk Analysis, §2-380
       Real Estate Transfer, §7-499
   Sensitive Areas, §7-341
   Torts, §7-48
EPCRA, 22-MSS-214
Epidemiologic Study, §£287; §2-
        532
   Dioxin, 86-78
Estuary
   PCB Analysis, §2-420
Ethylene Glycol, §9-298
Europe
   Leachate Treatment, 22-658
   Technology, §§-193
Evaluation, §§-329, 504
   Continuing, §8-567
   Groundwater, §8-19
   Public Health, 88-304
Evaporation, 88-424
Event Tree Modeling, 90-226
EXAMS Model, §§-119
Excavation, §2-331; 88-479;  §9-463
Executive Branch Dispute
        Resolution, §2-631
Exhumation, §2-150
Expanded Health Assessment, 90-
        182
Expedited Response Action (ERA),
        §£-393; §§-188, 226
Expert
   Judgment, 8§-44
   System, §§-93
Exploratory Drilling, §£-126
Explosives, 22-478
   -Contaminated Materials, §2-289
   Contaminated Soils Incineration,
        §£203
   Contamination, §§-569; §£-493
   Incineration, 22-853
   Waste Disposal Sites, §£141
Exposure, §§-119,142, 528
   Analysis Modeling System, 22-
        133,153
   Assessment, §6-69; §2-126, 153;
        §§-300, 353; §2-82
       Model, 22-157
   Children, §£239
   Limit, §§-546, 567
   Pathway, §§-300
   Response Analysis, §2-386
   Scenarios, §§-484
   Toxic Substances Registry, 90-
        161
Extraction, §£576; §2-479
   Groundwaler, §2-241
   Interception Trench, 22-382
   Metals, §2-380
   Soil(s), §2-348
       Metals, 22-739
       Vapor, 22-557, 646
       Vacuum, §2-273
       Wells,  §§-125

Fast-Tracked
   Design and Cleanup, §7-296,
        362
   Hydrogeological Study, §5-136
Fate, §§-119
    and Transport, §2-126; 22-128
Fault Tree Analysis, §§-382
Faunal Species, §2-576
Feasibility Study (FS), 82-113,295,
        338,435,484,490; §2-436
    Arsenic Waste, §£469
Federal
    Cleanup, §5-7
    Compliance Program, §2-631
    Facility
       Agreement, 22-882
          Rocky Mountain Arsenal,
        22-917
       Compliance, §§-516,565;
        §2-631
       Coordinator, §5-32
       Remediation, 22-882
    State and Local Jurisdiction, 8J-
        53
    State Cooperation, §2-420; §5-50
Fenton's Reagent
    Biodegradation, 22-826
Field
    Analysis, §§-251; 22-261
    Data Acquisition, §£-148
    Detection
       RDX, 22-889
       TNT, 22-889
    Identification, §5-88; §£-120
    Investigations, §2-251
    Operation Methods, §2-28
    Quality Assurance, §£-143
       Laboratory, §2-93
    Test Kit
       Organic Halogens, 22-329
    Sampling, §4-85, 94
    Screening, §£-105; §2-100,107;
        §§-174; §2-19,41; 22-333
       Organic Vapors, 22-632
    Validation, §§-323
Financial
    Ability to Pay, §2-600
    Assessment, §2-600
Fire, §1-341; §2-299
    Underground, §£-350
Fire Fighter
    Toxic Exposure, §£-152
First Rcsponder Training, §5-71
FIT
    Contracts, §2-313; §£-36
    Health and Safely, §2-85
Fixation, §2-413; 22-739
    Solidification, §£-297; §2-187,
        396
Flotation, §§-455
Floating Covers, §£406
Floreffe,§§-317
Florida, §g-287
    Remedial Activities, §2-295
Fluorescence, §£-370
    X-Ray (XRF) Spectroscopy, §§-
        97
Flushing
    Soil, §2-207
Flux Chamber, 22-290
Ry Ash
    Bentonile Barrier Improvement,
        §2-526
Foam(s)
    Scrubbing, 22-589
    Vapor Suppression, 8J-480
Food Chain, §§-359
Fort Miller, §1-215
Foundry Wastewater, §£598
FT/IR, §£-371
Fraud Investigation
1016
-------
   Laboratory, 90-355
Fuel Spill, §8-202
Fugacity, 88-142
Fugitive
   Dust Control, §£-265
   Hydrocarbon Emission
        Monitoring, §1-123
Fume Incineration, £2-765
Funding
   Mixed, §2-592
Fungus
   Biotreatment, 90-788

GAC (see Granulated Activated
        Carbon)
Galvanizing Operation, §§-245
Gas, 88-183
   Chromatograph, §2-57,58; 83-
        76
      Field Screening, 90-632
      PCB Analysis, 87-420
      Portable, 82-36; §3-105; §9-
        15
      Screening, 86-386
    Chromatography/Thermal
        Extraction, 89-41
    Collection, 90-513,553
      and Treatment, 86-380
    Cylinder Management, 87-268
    Migration, 88-265
    Plants, §6-93
    Soil Sampling, 90-277
    Subsurface, 89-251
    Unknown, §4^416
 Gasification Plant Site
        Contamination, 86-242
 Gasoline, 85-269
    Contamination, 90-433
    Extraction, 87-273
    Spill, 22-636
 Gaussian Puff Model, 87-465
 GC/MS, 82-57; 89-50
    PCB, 87-420
 Generator
    Cleanup, 85-7
    Liability, 90-245
 Geochemical
    Control, §2-267
   Modeling, §§-245
   Technique, 90-348
 Geographic Information Systems,
        §6-200; 89-430; 90-35
 Geogrid, 90-474
Geohydrology, §3-117; §9-259
Geologic Repositories, §7-502
Geomembranes, §6.-269; §£-56
   Barrier Technology, §6-282
   Liners
      Leak Detection, 89-35
   Seam Testing, §6-272
Geophysical, 83-68,71
   Diffraction Topography, 88-152
   Investigation, §4-481; 86-217
   Logging, §6-292; §2-320
   Methods, 82-17
   Modeling, 86-110
   Monitoring, §3-28
   Survey, 81-300
   Techniques, 83-130; 86-465; §9-
        27
Geophysics, §1-84; 82-91; 88-363;
        §2-277
   Characterizing Underground
        Wastes, 86-227; 87-300
   Horizontal Radials, §2-371
Geostatistical
   Decision-Making, §9-146
   Methods, §5-107; 86.-217; 88-
        274
Geotechnical Engineering, 89-436
Geotechnology
   Containment System, 82-175
   Property Testing, 85-249
   Techniques, §3-130
Germany, §1-565, 600
Gilson Road Site, 82-291
Glass Matrix, §2-309
Government
   Local, §2-645
   Relationships, §2-645
Granulated Activated Carbon (GAC)
   Design, 90-686
Ground
   Engineering Equipment, 87-187
   Freezing, §4-386
   Penetrating Radar, 80-59,116,
        239; §1-158, 300; 83-68;
       86-227; §7-300; 90-314
Groundwater, 88-108,138,164,219,
        234, 300,375,382; §2-122,
       241,246,251,259,267, 277,
        476,479,558; 90-720
   Activated Carbon Treatment, 86-
        361
   Applied Modeling, 86-430
   Arsenic, 90-123, 371,901
   Barrier, 90-453
   Bayesian Analysis, 90-189
   Bedrock Aquifers, §6-403
   Biological Treatment, §6-253,
        333
   Biodegradation, 85-234; 87-208
   Bioremediation, 89-273; 90-831
   Case Histories, 86-430
   Chemical Oxidation, 87-174
   Chrome Pollution, §6-448
   Cleanup, §2-118,159; §1-354;
        §4-176; 87-311, 348; 88-
        19;
       89-313,407,468,534
   Collection, 86-220
   Computer Modeling, §7-111
   Containment, §2-259; §3-169;
        90-460,484
       Movement, 22-111; §5_-147
   Contamination, §1-329,359; §2-
        280; 83-43,358; 84-103,
        141,
       145,162,170, 336; §5-43,
        157,261; §§-84,113; §2-
        648
       Creosote, 2S-439
       Cyanide, §4-600
       Detection, 84-20
       Liabilities, 83-437
       Mapping, 83-71
       Potential, §0-45
   Control, §2-436,468
   Diffusion
       Effect on Transport, §1-129
   Dioxin, §2-117
   Discharge to POTW, 89-137
   DNAPL(s), 2Q-492
   Evaluation, §8-19
       Hydrologic, of Landfill, §6-
        365
   Extraction
       and Treatment Model, 90-
        386
       System, §7-330; 22-415
   Field Screening, £2-632
   Flow
       Calculations, 90-103
       System, 83-114,117
Flushing, 86-220
Gasoline Contamination, 90-865
Geochemistry, 22-348
Halocarbon Removal, 85-456
Heavy Metals, 86-306
   Cleanup, §7-341
   Soil, 22-681, 730
   Transport, §7-444
HELP, §6-365
Horizontal Drilling, 86-258
Hydraulic
   Assessment, 87-348
   Evaluation, 83-123
   Investigation, §2-78,84-1,
     107; 86-158
Hydrocargon Contamination, 90-
     210
In Situ Biodegradation, 85-239
Interception Trench, 22-382
Lead, 90-371
Lime Treatment, 86-306
Management Zone, 89-618
Mathematical Modeling, §1-306
Metal Finishing Contamination,
     §3-346
Microbial Treatment, 83-242
Migration, §2-71; 84-150,210
   Control, 22-415
   Prevention, §3-179,191; 84-
     114; 86-277
Mobility, §4-210'§7-444
Modeling, 82-118; 83-135,140,
     145; 84-145; 86-88; 89-
     146,
      152,163; 22-110,376,
     386,606
   Exposure Assessment, §7_-
     153
   Three-Dimensional, 22-896
Monitoring, §2-53; §2-17,165;
     §§-363
   Bentonite, 22-308
   Evaluation, 85-84
   Interpretation, 82-86
   Long-Term, 85-112
   Post-Closure, §3-446
   Statistics, §4^346; §6-130
   Well Design and Installation,
     §6-460
Penetrometer, 22-297
Plume
   Definition, 85-128
   Location, 22-304
Pollutant Fluxes, §7-231
Pollution Source, §1-317
Post-Closure Monitoring, §2-446
Protection, §2-131, §4-565
Pump-and-Treat, 22-668,765
Pumping
   Uncertainty, 22-206
Recharge, 86-220
Recovery
   Cost, §2-136
   Design, §2-136
Remedial Plans, 83-130
Remediation, §6-220; 87-213;
     88-125, 446; §2-468; 92-
     433,
   517, 595
   VOC(s), 22-420
Research Needs, 83-449
Restoration, §2-94; §4-162; §6.-
     148; §7-204, 223
Sampling, 81-143,149; £0-367
Slurry Wall, 86-264
   Interaction, 89-519
Studies, 86-431
    Superfund Protection Goals, 86-
        224
    SUTRA, §7-231
    TCE Contamination, 82-424; §£-
        137
    Three-Dimensional Modeling,
        22-896
    Transport, 22-189
    Treatability, §1-288
    Treatment, §2-184; 82-259; §3-
        248,253; 86-220; §7-218;
        §8-188, 226,409; §2-246,
        436; 22-529
       Activated Carbon, 22-624
       Air Stripping, 90-624
       Granulated Activated Carbon
        (GAC), 22-686
       Heavy Metals, 22-425
    Trend-Surface Modeling, 87-120
    Ultra Clean Wells, §6-158
    VOqs), £0-304,492, 882
       Biodegradation, 84-217
       Removal, 22-748
    Well(s), 22-357
       Abandonment, §7-439
Grout, §3-169,175
    Chemistry, §2-220
Grouting, §2-451
    Silicates, 82-237
Guarantee Agreement, 88-23

Halby Chemical Site, 90-730
Halocarbon Removal, 85-456
Halogen
    Analysis
       Field Test Kit, 22-329
    Combustion  Thermodynamics,
        85-460
Hanford Site, §9-417; 22-25
    Monitoring, 22-285
Harbor Contamination, 89-130
HARM, §9-99
Harrisburg International Airport, 85-
        50
Hazard
    Degree, §1-1
    Potential, §2-30
    Ranking, §1-188
       Prioritizing, §1-52
       Scoring,  §5-74
       U.S. Navy Sites, §3-326
    Unknown, §1-371
    vs Risk, 84-221
Hazardous
    Materials, §§-119
       Control, 22-772
       Identification, 85-88
       Release,  87-525; 88-37
       Storage
          Spills, §2-357
       Technical Center, §2-363
    Ranking
       System (HRS), §1-14; §2-
        396; 22-80,153
          Revision, §§-269; 90-35,
        153
    Substances, §8-537
       and Petroleum Products, 88-
        60
       Health Monitoring, 90-144
    -Toxic-Waste, 88-202
    Waste, §§-295,446,539; §2-606
       Biological Treatment, 22-847
       Categorization, 89-488
       Classification, 90-222
       Collection Data Base, 90-716
       Disposal, 90-450
                                                                                                                                          1017
-------
            Emergencies
               Information Sources, 84-
             59
               In situ Vitrification, 86-
             325
            Expert Management System,
             86-463
            Land Treatment, §6-313
            Management
               Alternatives, §§-5
               Facility Siting, §4-517
            Minimization, 23-868
            Policies, §4-546
            Regulations, 22-32
            Screening, §£-370
            Short-Term Burial, §7-512
            Site, §§-39,532; 20-128
               Bioremediation, §7-533
               Exposure Assessment,
             §2-153
               Personal Safety, 20-489
               Ranking, §§-44
               Reuse, §4-363
               Risk Analysis, §7-471
               Safety, §7-162
               Social, Psychological and
             Economic Aspects,  87-264
             Treatment, §6.-303; §8-546;
             §2-298
      HAZRISK Data Base, 22-236, 241
      Health
         and Safety (See Also Safety), §9-
             282
            Assessments, §4-261, §5_-
             423; §8-528, 532; §£-72;
             20-128
               Expanded, 20-182
               Petitioned, §§-528; §2-72
               Public Health, §§-353
               Risk, 22-176
               Superfund  Site, 20-144
            Communication, 88-524
            Community Concerns, 82-
             321
            Concerns, §2-635
            Cost Impact, §2-376
            Evaluation
               Public Health, §§-304
            Exposure
               Potential Ranking Model,
             §7-158
               Significant Human
             Exposure Levels, §§-537
            Guidelines, §1-322
            Hazardous Waste Site, §7-
             162
            Hazards, §2-233
               Potential, §8-567
            Medical Surveillance, 87-532
            Plan, 83-285
            Program, §2-85, 91, 107
            Radiation Training, 22-503
            Recreational Exposure, 87-
             143
            Training, §§-473
         Physics Training, 22-503
         Risk Assessment, §4-230, 253;
             §7-143; §9-108, 582; 90-
             176
      Heart Stress Monitoring, 84-273
      Heal Stress Monitoring, §§-546
      Heavy
         Black Liquor. £§-313
         Metals, §§-12, 84,  261, 338, 343,
             353. 359, 398, 508; §9-78,
               222, 298
            Analysis, £§-97
      Cleanup, §7-341
      Fixation, 20-673
      Groundwater, 22-425
      Impoundment Closure, 83-
        195
      Soil, 22-185
          Remediation, 22-673
          Treatment, §7-380
      Treatment, §7-218
      X-Ray Fluorescence, 86-114
Helen Kramer Landfill, 22-513
HELP, 20-539
Herbicides), §9-325
   Dioxin, 89-117
   Field Analysis, 20-261
   Mixing, §6-97
Hexone  Oxidation, 87-183
High Energy Electron Beam
        Irradiation, §0-753
High Pressure Jet Grouting, 90-745
High-Pressure Liquid Chromatogra-
        phy,§3-86
Highly Permeable Aquifers, 2Q-300
Highway
   Superfund Site Proximity, 22-42
Horizontal
   Drilling, §6-258; §7-371
   Well, 22-398
   Wellbore System, 22-357
Hospital Waste
   Site  Remediation, 22-513
Hot Gas Process, §2-289
How Clean is Clean?, 22-157, 612
HRS (see Hazardous Ranking Sys-
        tem)
Human  Exposure
   Potential Ranking Model, §7-158
   Significant Levels, §§-537
Human  Health Evaluation Manual,
        §2-609
Hyde Park, §5-307; §§-479
Hydraulic
   Barrier, §2-259, 468
      Deformation Effects, §2-537
   Conductivity
      Estimating, 22-103

   Performance, 22-398
   Probe Sampling, 22-304
Hydrazine
   Chemical Oxidation, 90-937
Hydrocarbons, §5-269; §§-375; §9-
        392
   Analysis, 22-620
   Biodegradation, §6-333
   Chlorinated, §§-219, 395
   Contamination, §9-331
   Extraction, §2-348
   Field Screening, 87-174
   Groundwater, 22-210
   Leaks, 82-107
   Petroleum, §§-395
   Recovery, 86-339
   Soil, 22-210
Hydrogen  Peroxide, 89-264
   Biodegradation, 22-826
   UV Light, §7-174; §9-264; 22-
        768
Hydrogeologic(al)
   Assessment, 87-348
   Data, §4-6
   Evaluation, §2-49
   Fast-Track, 85.-136
   Investigation, §1-45, 359; §£-
        346; §£-148, 403;  22-103,
      300, 492, 580
   Landfill, §5.-182
   Monitoring, 22-896
Hydrogeology, §2-277
   Pump-and-Treat, 22-720
Hydropunch, 22-367
Hypothesis Tests, §8-503

Identification, §1-63; §§-329
   Hazardous Material, §5-88
   Reactivity, §2-54
Illinois
   Closure/Post Closure, 83-459
Immediate Removal
   Dioxin, §7-306
Immobilization, §2-220; 88-429,
        504;89-476
   Abiotic, 90-820
Impact
   Analysis, §§-409, 598
   Assessment, §1-70
Impoundment, 80-45
   Cleanup, 20-917
   Closure, §1-195; §4-185; 85-
        323; §6-318
   Leaks, §1-147
   Membrane Retrofit, 82-244
   Sampling, §5-80
   Surface, §1-245
In Situ, §8-455, 467,504
   Biodegradation, 85-234, 239,
        291; §§-495
   Bioremediation, 22-800
   Chemical Treatment, §5-253
   Decontamination, 88-498
   Permeability/Hydraulic
        Conductivity, §§-199
   Pesticide Treatment, §5-243
   Remediation, §2-338
   Soil
       Decontamination, §7-396
       Washing, 20-745
   Solidification/Fixation, §5-231
   Stabilization, §5_-152
   Steam Stripping, §7-390, 396
   Treatment, §4-398; §5-221; §§-
        446,490; 22-677
   Vapor Stripping, §2-562
   Vitrification (ISV), 84-195; §9-
        309; 22-453, 471
   Volatilization, 88-177
Incineration, 82-214; §5-378, 383;
        §§-255, 292, 413,513, 569,
          575; 89-286,374,377,
        387
   Air Pollution Control, §7-459
   Community Relations, 20-951
   Dioxin, §2-380
   Explosives
       and Propellants, 22-853
       Contaminated Soils, §4-203
   Fumes, 22-765
   Gaussian Puff Model, §7-465
   Halogens, §5-460
   Mobile, §0-208; §1-285; 87-453,
        459
   Ocean, §7-465
   On-Site, 22-525, 857
   Oxygen Technology, §§-575
   Performance Assessments, §5-
        464
   Pilot Test(s), 22-857
   Research, §4-207
   Rocky Mountain Arsenal, 22-
        907
   Safely, 86^4
   Sampling, 87-457
   Sea, §Q-224
   Soil, 20-857
   Hazardous Waste, 22-924
Incinerator, §§-582
   Infrared, §§-513,582
   Mobile, §§-582; §2-380
   Portable, §§-587
   Regulation, §§-592
   Rotary Kiln, §£-374
   Selection, 22-907
   Shirco, §§-513
   Transportable, §2-387
Indemnification, §§-52; §7-520
   U.S. EPA Guidelines, 22-201
Indian Land Waste Regulations, 22-
        32
Indigenous Microbial Consortium,
        22-793
Indirect Heating, §2-421
Inductive Coupled Plasma
        Spectrometer, §1-79
Industrial
   Hygiene, §§-546,561,567; §2-
        15,75
      Training, 22-503
   Property, §2-9
   Waste
      Biological Treatment, §1-208
      Lagoon Closure, 22-466
Infiltration Barrier, 22-618
Information
   Committees, §5-473
   Management, 85-11
      System, 22-871
   System
      Geographic, 22-35
   Transfer, 22-726
Infrared Incinerator, §5-383; §§-582
Innovative
   Technique, 22-726
   Technology, §§-35,193,241,
        516,521; 22-716
Inorganics, §§-282
Installation Restoration Program
        (IRP), §§-300,569; §£-309,
        596
   Information Management System
        (IRPIMS), 22-871
   McClellan AFB, §4-511; §5-26
Insurance, §2-464; §§-60, 602
   Pollution Liability, 22-201
Integration, §§-79
Integrity, §8-504
Interagency Management Plans, §Q-
        42
Interest/Discount Rales, §§-55
Interim Response Action Program,
        22-933
Interstate 70 Acid Spill, §§-32
Inventory Control, §2-485
Investigation
   Hydrogeologic, §2-280
   Remedial, §§-295,363,539
Ion Exchange
   Arsenic Removal, 22-901
IRIP, §§-569
IRP (see Installation Restoration
        Program)
IRPIMS (see Installation Restoration
        Program Information
   Management System)
Irradiation
   Toxics Destruction, 22-753
ISV (see In Situ Vitrification)

Kerr Hollow Quarry, 22-478
KPEG Process, §§-474
Kriging, §2-66;  §§-274; §2-146
   Probability, §§-274
1018
-------
Laboratory
   Data, 88-157
   Management, 81-96
   Mobile, 86-120; 89-19
   Quality Assurance, §7-93
   Regulated Access, §1-103
   Screening, 88-174
La Bounty Site, 82-118
La Salle Electric Site, §£-447
Lackawana Refuse Site, 87-367
   TAG, 22-85
Lagoon(s), 81-129; 82-262
   Closure, 89-642; 90-466
   Floating Cover, 84-406
Land
   Ban, §§-398; 22-450,510
      Effect on Mixed Waste, 90-
        692
      Treatability Issues, 90-700
   Disposal
      Restrictions, 88-12,429; 90-
        450
      Sites
          Numeric Evaluation, 87-
        508
   Treatment, 86-313
      Systems, 89-345
Landfarming, 88-490
Landfill, §§-164; 89-570
   Closure, 80-255; 88-199
   Covers, 86-365; 90-553
   Future Problems, 80-220
   Gas, 88-164
   Leachate, 89-122
      WeU, 90-363
   Life Cycle, 88-164
   Risk,§5_-393
   Test Cell, 88-199
Leach
   Field, SS-409
   Tests, 88-484
Leachate, 88-347
   Characterization, 86-237
   Qay Interaction, 83-154
   Collection, 83-237; 85-192
   Control, 84-114; 86-292
   Drainage Nets, 86-247
   Effects on Clay, §1-223
   Generation Minimization, 80-
        135,141
   Landfill, 89-122
   Migration, 82-437; 84-217
   Minimization, §1-201
   Modeling, 83-135; 84-97; 85-
        189
   Monitoring Cost, 82-97
   Plume Management, 85-164
   Synthetic, 86-237
   Treatment, 80-141; 82-203,437;
        83-202, 217;  84^393;
      85-192; 90-658
   Well Installation, 90-363
Leaching, 88-508; 89-222
   Chemical, §8-413
   Solid, §2-395
   Soil, §§-424
Lead, 84-239; §5-442; §6-164, 200,
        303; 89-413,  430
   Cleanup
      Soil, 90-498
   Contamination, 89-301
   Fixation
      Silicates, 90-505
   Groundwater, 90-371
   Immobilization, 90-665
   Recycling, 89-301
   Remediation, 90-505
    Soil, 90-681
Leak Detection, 83-94,147; 85-362;
        87-523; 89-56
Leaking Underground Fuel Tank
        Field Manual (LUFT
        Manual),
       9Q-210
Legal Aspects
    Extent of Cleanup, §1-433
Legislation
    Model Siting Law, §0-1
LEL, 88-265
Level of Protection, §§-546
Liability, §2-458,461, 464,474; §§-
        55, 65,67; 89-13
    Consultant, §6-47
    Contractor, 87-34,520
    Corporate, §2-262
       Successor, 87-48
    Defense
       Petroleum Extraction
        Exclusion, 92-969
    Disposal, 83-431
    Generator, 81-387
    Groundwater Contamination, 83-
        437
    Inactive Sites, 80-269
    Minimization, 90-245
    Reduction, 90-251
    Superfund
       Cleanup Failure, 83-442
       Minimization, 86-18
    Trust Fund, §3-453
Lime, 88-398
Liner, 89-543
    Breakthrough, §3-161
    Canal Bottom, §7-334
    Flexible, §4-122
    Leak
       Detection, §5.-362; §2-35
       Location, 82-31
    Membrane, §9-56
    Synthetic, §9-534
       Membrane, §3-185
    Testing, 86-237
Liquid
    Membrane, §9-318
    /Solids Contact Reactors (LSCs),
        §9-331
Litigation,
    Expected Monitary Value, 88-55
Lobsters, §8-359
Love Canal, 80-212, 220; 81-415;
        82-159, 399; §6-424
Low
    Concentration ANalysis, £0-944
    Level VOC Analysis, §7-85
    Occurrence Compounds, 85-130
    Temperature Thermal
        Desorption, §§-429;  90-730
LUST(s), 22-433

Macroinvertebrate, 88-72
Magnetrometry, §2-59,116; §1-300;
        8J-12; §3-68; 86-227; §7-
        300
Management, §8-15, 343
    Capacity, §9-606
    Plans
       New Jersey, §3-413
    Remedial Program, 88-15
    Review of the Superfund
        Program, 90-17
    Superfund, §8-15
    Systems Review, 90-25
Managing  Conflict, §4-374
Marine
    Environment
       Sunken Ships, 22-137
    Sediment, 87-485
Marsh Cleanups, §7-341
Mass Selective Detector, 85-102
Massachusetts
    Contingency Plan, §3-420; §5-
        67; §9-95
    Cost Recovery, 22-1
Mathematical Model, §8-119,359
MCL,8§-8
MCLG,8§-8
McClellan AFB, 85-43; §7-204
Medical, §§-546
    Radiological Exposure, §§-546
    Surveillance, §4-251,259; §6-
        455; 87-532; 89-75, 91
    Wells, §8-202
       Dual Wall Hammer Drilling
        Technique, §7-358
       Installation, §1-89
          In In-Place Wastes, 86-
        424
       Integrity Testing, 86-233
       Location, §1-63
       State Regulation, §7-89
Membrane-Like-Material, §2-318
MEPAS, §8-295
Mercury, §2-81; 22-336
    Dimethyl,
       Air Monitoring, 22-257
Metals, §2-183; §§-282; §9-476
    Analysis, 83-79
    Cleanup, 87-341
    Detection, §0-239
    Detector, §0-59; §1-300; §2-12
    Finishing, 83-346
    Screening, 85-93
    Washing, §2-207
Methane, §§-265
Methanogenisis, 88-265
Methylmercury, 22-336
Methylene Chloride, §8-446
Microbial Degradation, 83-217,  231,
        242
Microbubble, §§-455
Microcomputer, §2-108
Microdispersion, §4-398; §5-291
Microencapsulation, 87-380
Microfiltration
    Groundwater, 90-425
Microorganisms, 88-490
Microtox, 89-23
    Bioassay, §§-323
Migration, 84-588; 88-132
    Control
       Groundwater, 22-415
    Cutoff, 82-191
    Prevention, 82-448
    Sedimantary Channel Deposit,
        87-414
Mill
    Paper, §§-313
Mine
    Disposal, 85-387
    Drainage, 88-261
    Heavy Metal Mobilization, 87-
        444
    Mine/Mill Tailings, §5-107
    Sites, §3-13; §7-436
    Tailings Cleanup, §4-504
    Waste Neutralization and
        Attenuation, §6-277
Minimization, 92-868
Minimum
    Risk Levels, 90-164
    Technology Requirement, 88-
         234
Missouri
    Dioxin, 90-169
Mixed
    Funding, §9-592
    Waste, 87-403; §§-539; 89-417;
         90-25
       Regulations, 90-692
       Site, 22-553
          Cleanup, 22-601
Mobile
    Incinerator, §5-378,382; 87-453,
         459; §§-582; §2-380
    Laboratory, §0-165; §4-45; §6-
         120; §9-19
    MS/MS, §4-53
    Soil Washer, 90-760
    Thermal Destruction, §2-377
    Treatment, §6-345, §2-392
    Waste Oil Recovery, 87-179
Model, §§-108,142
    Vacuum Stripping, 89-562
Modeling, §§-132, 234; §9-267,570
    Air
       Quality, 90-117
       Toxics, §2-157
    Applied, §6-430
    Cell, §5-182
    Cost, 87-376
    Environmental, §7-149
    Event tree, 90-226
    Exposure Assessment, 87-153
    Geochemical, §§-245
    Geophysical Data, 86-110
    Groundwater, §2-152,241; 90-
         110,398,415,896
       Extraction and Treatment,
        90-386
       Treatment, 83-248; §7-11
       Zone, 22-539
    Human Exposure Potential
        Ranking Model, §7-158
    Leachate Migration, §2-437; §5-
        189
    Management Options, 83-362
    Plume, 89-146
    Random Walk, 89-163
    Remedial Action, §2-135
    Sediment Movement, 87-426
    Site Assessment, §1-306; 90-376
    Soil Cleanup, 90-498
    Surface Water, 90-133
    Three-Dimensional, §9-152
    Trend-Surface, 87-120
    Wetland, 90-148
MODFLOW, 22-398,460
    Cleanup
       Groundwater Modeling, 90-
        110
MODPATH, 90-398
Molten Baths, 89-421
Monitoring, §§-113,347
    Air, §§-335, 546,561,567
    Ambient Air, §1-122,136
    Wells
       Bentonite, 90-308
Monongahela River, §8-317
    Oil Spill, 90-966
Montana  Pole, §8-32
Monte Carlo Technique, §§-550; 90-
        215
MS/MS Mobile System, §4-53
Multi-Attribute Utility Analysis, §§-
        39
Multi-Media
    Exposure Assessment, 87-476
    PCB Cleanup, §7-362
                                                                                                                                          1019
-------
         Risk Analysis, £7-471, 485
     Multiple Burner System, §9-374
     Multi-Site/Multi-Activity
             Agreements, §5-53
     Municipal LandfUl(s), 89-251
         Cover, 22-553
         Gas Collection, 90-553
         RI, §7-72
         Site{s)
            Site Assessment, 90-376
            RI/FS, 90-47
     m-Xylene,§§-451

     NAPL
         Pump, 22-720
     Napthylamines
         Health Assessment, 2Q-144
     National
         Contingency Plan (NCP), 88-304
            Revisions, §6-27
         Contract Laboratory Program,
             §4^29
         Exposure Registry, 2Q-161
         Priority List (NPL),  85.-1; 88-
             537; §2-552
            Deletion, 86-8
            Mining Sites, §2-13
            Site Assessment, 2Q-71
         Resource Damage, 8J.-393
         Response, 81-5
            Center, 2Q-972
     NATO/CCMS Study, §4-549
     Natural
         Attenuation, §8-113
         Resources
            Damages, §2-517; §2-194
            Definition, §§-605
            Improvement, 90-10
            Injury, §2-613
            Restoration/Reclamation, 84-
             350
     Naval
         Air Station, Pensacola, £0-877
         Installation Restoration Program,
             2Q-877
     NCP (see National Contingency
             Plan)
     Negotiated Remedial Program, g4-
             525
     Negotiating, §2-377, 470
     Netherlands, §1-569
     Neutral Validation RJ/FS, §6-445
     Neutralization, §2-63
     New Bedford Harbor
         Site, §7-420, 426; §§-335, 338,
             343, 353, 359
         TAG, 22-85
     New Jersey, §§-77
         Cleanup Plans, 83-413
         DEP, §5-48
         Reserve Fund, §5_-58
     New York City, §4-546
     NIKE Missile, §§-202
         Sile, §§-208
            Investigation, §6^436
     Ninety-Day Superfund Study, 22"17
     NIOSH. §§-546
     Nitrale(s), §2-267
     Nilroaromatic Contamination
         Pink Water, 22-896
     N-nilrosodimclhylaminc Detection,
             22-944
     No-Action Alternative, §5_-449
     "No Migration" Demonstration, §§-
             234
     Nondestructive
         Assay Syslcm, §9-586
   Testing Methods, §2-12, 84-158;
        §6-272
Nontarget Compound Identification,
        §2-86
North Hollywood Site, §4-452
Notification
   Emergency Response, 90-972
   Mass, 87-7
NPL (National Priorities List, see
        National)
Numerical
   Evaluation System, §7-508
   Model, 88-55

Observational Method, §2-436, 459
Obsidian, §2-309
Occupational Health Programs, 84-
        251,259
Ocean Incineration, 87-465
Odor, §2-326; 83-98
Off-Gas VOC Removal, 22-765
Oil
   Analysis, 22-620
   Pond Pollution, §6-415
   Recovery, §5-374; 87-179
   Refinery
      Bioremediation, 22-807
   Retrieval, §9-318
   Sludge
      Best,  §6.-318
   Spill, §§-317
      Cleanup, §9-318
      Monongahela River, 22-966
   Sunken Ship Release, 22-137
Oily
   Sludges
      Thermal Treatment, 22-549
   Soils
      Thermal Treatment, 22-549
   Wastes, §2-318
Old Hardin County Brickyard, §2-
        274
Olmsted AFB, 85-50

OMC Site, §4-449
On-Site
   Analysis, 22-273
   Incineration, 22-525
   Laboratory, 22-261
   Leachate Renovation, §4-393
   Storage, §2-455
   Water Treatment, §7-169
Operation
   Treatment System, 22-517
Optimization of Soil Treatment, 87-
        172
Organic(s), §§-12,508
   Biooxidation, 90-839
   Chemical Oxidation, §7-174; 90-
        768
   Degradation, §9-338
   Emissions, §2-70,  84-176
   Field Screening, 90-632
   Halogen Analysis, 22-329
   Irradiation, 22-753
   Land Treatment, §£-313
   Sludge Stabilization, §4-189
   Solvents Permeability, §4-131
   Treatment, 22-820
   Vapor
      Analysis, §2-98
      Field  Screening, §2-76
      Leak  Detection, §2-94
      Personnel Protection, §1-277

   Wastes, 85-440
      Characterization, §4-35
       Fixation, 87-187
Organically Modified Clays, 58-440;
        89-292,543
Organism
   Benthic, 88-317
Organizations
   Community, 90-95
OSHA,8§-546
   Safety Requirements, 87-162
   Training Requirements, §7-18
On/Story, §1-288
Oxidation, §§-467; §9-264, 407
   Chemical, §7-174
   Electrochemical, 87-183
   Gasoline, 90-865
   Organics, 22-768
Oxygen
   Incineration Technology, 88-575
   Supply, §2-338
o-Xylene, §§-85
Ozone, §9-264
Pacific Island Removal, 84-427
PACT, 92-831
PAH (see Polynuclear Aromatic
        Hydrocarbon)
Paint Stripping Waste Minimization,
        22-868
Painting Waste Minimization, 90-
        868
Paper Mill, §§-313
Parametric Analysis, §1-313
Passive Treatment, §§-261
PCBs, §1-215; §2-156, 284; §3-21,
        326, 366, 370; 84-243, 277,
        449;
    §6-420; 87-89; §§-241, 251,
        329, 335, 338, 343,353,
        359, 419,     474,508,
        513,575,587; §2-67, 207,
        313,377, 396, 413,
         447, 476; 22-273
   Analysis, §7-420
       Oil, 22-273
       Soil, 90-273
   Biodegradation, 90-780
   Cleanup, §2-362; 22-575
   Field
       Screening, §9-19
       Measurement, §3-105
   Fractured Bedrock, §2-497
   Health Assessment, 22-144
   Land Disposal Site Evaluation,
        §7-508
   Modeling Movement, §2-426
   New Bedford Harbor, 92-85
   Screening, §6-370
   Soil
       Extraction, §7-104
       Treatment, §2-187
   Wetland, 22-148
Peer Review
   Superfund, 22-17
PEL (see Permissible Exposure
        Limit)
Penetrometer Development, 22-297
Pennsylvania Program, 81-42
Pentachlorophenol (PCP), §§-226
   Analysis, §§-274
   Biodegredation, £0-826
   Disposal, 22-446
Performance
   -Based Risk Assessment, £2-197
   Incentive, §§-15
       Incentive, §§-214
Periphyton, §8-72
Permanent Remediation, §£-309
Permanent Remedy, §2-623
Permeability Coefficient
        Measurement, §4-584
Permissible Exposure Limit (PEL),
        §8-546
Permitting, §§-582
Persistence, §§-119
    Factor, £Q-153
Personal Protection, §§-561; 9JJ-489
Personnel
    Protection
       Equipment (PPE), §5-546
       Levels, §1-277
    Safety Equipment, 56^471
Pesticides, §2-7; §5,-255,349; §$-
        386; §§-395; §£-325
    Contamination, §§-495
    In Situ Treatment, §5_-243
    Risk Assessment, §6-186
    Site Contamination, £2-585
PETREX Technique, £2-340
Petro Processors Site, §4-478
Petro-Chemical Systems Site, §£-
        282; £2-681
Petroleum
    Bioremediation, £2-814
    Cleanup Goals, £2-21
    -Contaminated Soil, §£-345
    Contamination, 84-600
       Bioremediation, 22-800
    Extraction Exclusion, 22-969
    Hydrocarbons, §§-395
    Pipeline Leak, 22-957
    Sludges, §§-395;  §2-292
       Stabilization,  22-712
    Soil Remediation, 22-957
Pharmacokinetic, §§-142
Phased Approach
    Remedial Investigation, §2-326
Phenol, §§-424
    Chlorinated, §£-325
    Polychlorinated, §§-347
    Soil, £0-745
    Treatment, §7-218
Photographic Interpretive Center,
        §1-6
Physical Chemical Data Use, §1-210
Physical/chemical Methods, §§-395
Picillo Farm Site, 82-268
Pilot Plant, 51-374
    Bioremediation, 82-315
Pilot Study, §§-347
Pink Water, §§-569
Pipeline Leak, £2-957
PIRS, 52-357
Pittson, Pennsylvania, §2-250
Plan Review, §6^143
Plant Bioindicalors, §1-185
Plasma Reactor, §£-421
PLM, §§-145
Plugging We!ls,§7-439
Plume
    Capture/Interception, §£-468
    Location, £Q-304
    Modeling, §£-146
Plutonium Fabrication Facility, §£•
        586
Policy, §£-609
Pollution
    Abatement Site, §1-435
    Prevention,
       Assistance, £Q-29
Polyaromalic Hydrocarbons, §1-11;
        §£-259
Polychlorinated
    Biphenyls, §5-504
1020
-------
    Phenols, 88-347
Polynuclear Aromatic Hydrocarbons
        (PAHs), 86-242; 89-23,
        130
    Biodegradation, 90-780
    Biopolymerization, 90-820
    Bioremediation, 87-193
    Risk Assessment, 90-176
Polysilicate Technology, 90-673
Polystyrene Waste Contaminated
        Soil, 90-793
Pond
    Cap, 90-474
    Closure, 88-245
Population Characterization, 90-173
Portable Incinerator, 88-587
Post-Closure
    Care, 8J.-259
    Failure, 83-453
    Groundwater Monitoring, 83-446
    Monitoring, 82-187
    Monitoring Research, 83-449
Potential Health Hazard, 88-567
Potentially Responsible Party (PRP),
        §5-275; 89-190,600
    Risk Premium, 8J7-41
    Search, 87-5; 89-600
       Methodologies, 87-21
POTW
    Groundwater Discharge To, 89-
        137
    Leachate Treatment, 83-202
Power Curves, 88-503
Pozzolans, 88-398; 89-413, 476
Preauthorization Decision
        Document, 89-592
Precipitation, 88-398
Preliminary Off-Site Evaluation, 88-
        567
Preremedial Programs, §2-14; 88-
        269
Pretreatment, 89-455
Price Landfill
    Groundwater Computer
        Modeling, 87-111
    Remedial Action, 83-358
Prioritization (see Also Hazard
        Ranking), §1-188; 87-409;
        88-79
Priorities, 88-32
    Removal, 88-32
Private
    Cleanups at Superfund Sites, 86-
        27
    Cost Recovery, 88-67
    Property Legal Issues, §
-------
           Cleanup Levels, 22-157
        In Situ, 2Q-677
        Innovative Approach, 85-307
        Lead, 20-505
        Short-Term, 20-933
        Soil, 22-696
        Technology, 2Q-716
        VOC, 20-606
        Western Processing, §7-78
     Remedy
        Selection, 20-88
           Process, 20-52
     Remote,
        Controlled Excavation, 89-463
        Sensing, gQ-59, 239; §1-84, 158,
             165, 171; §§-152
        Systems
           Operation, 20-478
     Removal
        Emergency, §§-32
        Priorities, §8-32
     Reportable Quantities, §6-182
     Reporting Requirements, 88-37
     Research
        Post-Closure Monitoring, §2-449
        U.S. EPA Program, §Q-173
     Reserve Fund, §5-58
     Residual, §§-108
     Resistivity, §Q-239; §1-158; 82-31;
             §1-28
     Resource
        Damage, §£-194
        Recovery, §1-380
     Respirator, 2Q-489
     Response
        Actions, 20-933
        Costs, §§-32
        Emergency, 88-13
        Model, §1-198
        Procedures, §Q-111
     Restoration
        Natural Resource, §£-613
        Swansea Valley, §4-553
     Resuspension, 88-347
     Retardation Factor, §§-245
     Retention Index, §2-86
     Reusing Hazardous Waste Sites, §3-
             363
     Reverse Osmosis (RO), §2-203
        Leachate, 2Q-658
     Reversionary Trust, §8-23
     Revised MRS, 2Q-35
     RI
        /FS, 88-15, 55, 343; §2-552
           Bridgeport Oil and Rental
             Services Site, §5-299
           Chromic Acid Leak, §6-448
           Computerized Expert
             Systems, 86-208
           Data Quality Objectives, 86-
             398
           Guidance, 88-1
           Municipal Landfill Site, 90-
             47
           Neutral Validation, §6-445
           New Bedford Site, 87-420
           NIKE Missile Site, §6-436
           Phased Approach, §7-326
           Project Performance
             Improvement, 87-1
           Site-Specific Values, §7-126
           Slate Cooperation, §§-15
           Uncertainty, 20-206
           Wood Treating Sile, §§-441
        Pcnctrometer, 20-297
     Right-of-Way
        Slate Liabilily, 9Q-4-
Right-to-Know, 86-4; 20-56
Risk, 88-142,145, 300
   Acceptability, §£405; 88-382
   Analysis, §1-230; §3-37; §7-471
       Computer, 84-300
       Environmental, 82-380
       Premium, 87-41
   Assessment, §1-238; §2-23, 386,
        390, 406, 408; §2-342; 84-
        283,
       321; 85-393,412,449; 86-
        69, 74,457; 87-61; §8-35,
        65,
       241, 277,287, 292, 295,304,
        353, 382,484, 539, 550,
       602; §2-67, 78,82, 95,102,
        108; 22-13,133,185, 215,
       226
       Air, 90-290
          Quality, 82-63
       -Based Cleanup Levels, 90-
        185
       Cleanup Criteria Setting, 20-
        612
       Communication, 87-254
       Comparative, §2-401
       Data Problem, 86-213
       Dermal Exposures, 87-166
       Dioxin,§2-117
       Environmental Modeling, 87-
        149
       Food Chain, §2-13
       Groundwater Modeling, 90-
        896
       Health, §4-230
       Manual, §5-419
       Modeling, §2-396
       Multi-Media, 87-485
       PAHs, 20-176
       Performance-Based, 2Q-197
       Prioritizing, 8JJ-433
       Properties, §7-45
       Public Health, §7-138
       Quantitative, §4-290; §§-65,
        186
       Radioactive Chemicals, §2-
        582
       Remedial Action
        Alternatives, §5-319
       Scoping Level,  87-143
       Uncertainty, 20-206
       Underground Tanks, §4-16
       U. S. EPA Guidelines, 86-
        167
   -Based Approach, 88-208
   Cleanup Level, §2-398
   Communication, 90-98
   Concepts
       Superfund Process, 87-251
   Decision Analysis Module, 86-
        463
   Design, 84-313
   Estimation, 88-382
   Evaluation, §0-25
   Financing, 20-201
   Management, 89-91; 90-201, 251
   Minimal Levels, 20-164
   Minimization, 81-84
   Perception, 86-74
   Superfund Sites, §7-56
RO (see Reverse Osmosis)
Roasting, §2-380
Rocky Mountain Arsenal, 81-374:
        §2-259; §5-36; 89-75;
   22-907, 917, 924, 933, 937, 944,
        951
   UV/Ozone, 2Q-919
   Wen Closure, 20-911
RODS Data Base, 90-716
Rotary Kiln Incinerator, §2-286, 374
Routes of Exposure, §2-67
RRT.88-317

Safety (See Also Health and Safety),
        82-299, 306; 85-406; §9-75
   Cost Impact, 82-311
   Equipment, 86-471
   Evaluation, 2Q-226
   Incineration, 86-4
   Information, §4-59
   Plans, 84-269
   Procedures, §1-269
   Remedial Construction,  §2-280
   Sampling and Analysis,  81-263
   Tank Investigation and Removal,
        §5-198
   Training, §2-319
Sample
   Design, §§-503
   Preparation, §§-145
   Size, 88-503
   Thief, §1-154
Sampling, §2-91
   Air, 88-546,567
      Pump (SP), §§-567
   Analysis
      Safety, §1-263
   Biological, §2-52
   Drums, §1-154
   Errors, 2Q-206
   Groundwater, 2Q-367
   Impoundments,  85-80
   Program, 2Q-320
   Screening, §1-103,107,  114
   Statistical-Based, 86-420
   Strategy,  §5-74
   Subsampling, §4.-90
   Techniques, §1-143,149
Sanitary Wastes, §§-164
SARA, §§-5, 269,295,409,537,
        539,598
   Title HI, §2-443; 20-56
Scoping Level Assessment,  87-107
Screening, §8-329; §2-41
   Acid Extractables, §2-107
   Analytical, §5-97
   Field, §6-105
   Mass Selective Detector, 85.-102
   Metals, §5-93
   PCB, §6-420
   Spectrometry, §3-291
   Statistical, 86-164
   X-Ray Fluorescence, 86-115
Sealed Double-Ring Infiltrometcr,
        88-199
Security, 83-310
Sediment, §8-353
   Bioassay, 88-323
   Contaminated, §8-338; §2-130
   Toxicity, §9-130
   Transport, §§-338
Sedimentary
   Channel Deposits, §2-414
   Movement, §7-426
   Multimedia Risk Assessment,
        §2-485
   PCB Analysis, §7-420
Seismic
   Boundary Waves, §5-362
   Refraction, §Q-239; §§-227
Semivolatile  Organics
      Soil Analysis, 22-340
Sensing
   Downholc, §2-108
Sensitivity Assessment, £0-133
Serum Reference Methods, §4-243
Settlement, §5-275; §2-190,592
    Agreements, §2-470
       Hyde Park, 85-307
    Authorities, §§-23
    CERCLA Facilitation, §§-23
    De Minimis, §2-190
    Financing Mechanism, §§-23
    Inflation Hedge, §§-23
    Offer, 88-55
    Structural, §§-23
      Specialist, §§-23
Sewer Line Decontamination, §2-
        493
Seymour Recycling Site, 22-110,
        557
Sheet Pile Barrier Wall(s), 20-484
Shenango, 80-233
Shirco Incinerator, §§-513
Shock Sensitive/Explosive Chemical
        Detonation, 84-200
Shope's Landfill Qeanup, §2-296
Short-Term Burial, §7-508
Shotblasting, §§-419
Significant Risk, §2-95
Sikes Superfund Site, 22-525
Silicates, §2-237; §§-303
    Grouts, §2-175
Silresim Site, §2-280
Simulation
      Barrier Wall, 2Q-460
SITE, §§-77,508,513,516,521; §£-
        264, 396,404,407, 421
    Microfiltration, 20-425
Site, §2-413
   Assessment, §0-59,91; §2-221;
        §4-221; §5-209; §§-60,
        152;
        £2-9; 20-66, 71, 77
      Computer Modeling, 2Q-376
   Characterization
      Geochemical, 22-348
   Discovery, §2-37; §§-84; 20-35
    Entry, §§-567
    Evaluation, §Q-25, 30
      Computer, 9Q-542
    First Year, §2-25
    Hazard Rating, §0-30,2Q-101
    Inspection, §§-269
       Sampling Strategy, §5-74
    Investigation, §5-48; 22-340
    Listing, §2-552
    Location, §0-116; §1-52
      Methodology, §0-275
    Problems
      Whales,  §4-594
    Program, §§-356
    Ranking, 89-99
    Remediation, §2-459
    Reuse, §4-363, 560
    Screening, §§-97
Siting, §0-1
    Hazardous Waste Management
        Facility, §4-517
    Public Information Needs, §£-
        368
Slagging, §§-193
Sludge, §8-413; §2-292
    B.E.S.T. Process, §§-318
    Pond Cap, 2Q-474
    Stabilization, §§-277
Slug Testing, 22-300
Slurry
    Cutoff WalL?JM39
    Trench, §2-191; §§-462
    WaU, §5-357, 374; §§-264; ftg-
102:
-------
        181, 519
Small Quantity Generator, 85-14
Smelter, 89-430
   Lead, §4-239; 85-442
      -Contaminated Soil, 90-505
   Site Remediation, 86-200
Social Aspects
   Hazardous Waste Site, 87-204
Soft Hammer, 22-450
Soil, 88-12,142,145, 282, 467,490,
        546
   Advanced Technologies, 84-412
   Aeration, 90-696
   Air Stripping, 86-322
   Analysis, 88-251
   -Bentonite
      Barrier, 89-526
      Slurry Wall, 85-357,369; 89-
        519
   Bioremediation, 87-533; §0-814
   Cap, 90-474
   Characterization
      Electric Method, 87-385
   Chemistry of Hazardous
        Materials, 86-453
   Chromium Analysis, 90-266
   Cleanup, 88-202,495; 90-636
      Levels, 90-157,185,498
      Sampling, 90-320
   Contamination, 82-399, 442; 83-
        43; 84-569,576; 88-395,
        409,
        424,435,569; 89-345
      Coal Tar, 89-642
      International Study, 82-431
      Lead, 90-505
      Pesticides, 85-243; 88-495
   Cover, 86-365
   Decontamination, 87-396; 88-
        498
   Diesel Fuel, 90-776
   Dioxin Contaminated, 88-292
   Extraction, 82-442; 89-348
   Hushing, 89-207
   Gas
      Analysis, 86-138; 90-290,
        340
      /Groundwater Survey, 88-
        158
      Sampling, 84-20; 90-277
      Survey, 87-97,523; 89-555
   Gasoline Extraction, 87-273
   Geotechnical Property Testing,
        85-249
   Heavy Metal Treatment, 87-380
   Hydrocarbons, 2Q-210
   Incineration, 89-387; 90-857
   Leaching, 88-424
   Lead
      Contamination, 90-505
      Immobilization, 90-665
   Liners, 89-512
      Construction, 89-512
   Mercury, £2-336
   Metal Contaminants, 92-739
   Oil Determination, £0-620
   PCB Analysis, 89-19
   PCP-Contaminated, 90-446
   Penetrometer, £0-297
   Petroleum
      Cleanup Goals, £0-21
      Contamination, £2-814
   Phenol Removal, £2-745
   Pile VOC venting, £0-641
   Polystyrene Waste
        Contamination, £2-793
   Radium-contaminated, 88-103
    RDX Detection, £2-889
    Remediation, 90-595, 696
       Heavy Metals, £0-673
    Stabilization, 87-198
       Solidification, §£-216
    Steam Stripping, 87-390
    Superfund, 88-429
    Thin Layer Chromatography
        (TLQ, £0-826
    TNT Detection, 90-889
    Treatability Study, §0-730
    Treatment, §8-429,474; §£-396;
        90-510, 700
       Alternatives,  88-484
       Optimization, §2-172
       Thermal, 84-404
    Vacuum Extraction, £2-624
    Vapor
       Extraction, 89-479; £0-460,
        557,646
       Measurement, 85-128
       Recovery, 90-529
       Stripping, §£-562
    Venting, §§-177
    VOC Cleanup, £0-641
    Washing, §5-452; 88-193,424;
        §£-198,207,318; 90-780
       In Situ, 90-745
       Mobile Unit,  £0-760
Solid Waste Management
    China, 84-604
Solidification, 81-206; §8-395,440,
        508; §£-216, 222,413
    Fixation, §6-247
    Lead, 90-665
    Organics, 86-361
    Silicates, 82-237
    Stabilization, £2-730
       Heavy Metals, £2-673
    TNT Sludge, §2-270
Soliditech, §9-413
Solubility, §§-108
Solute
    Migration Control, §9-526
    Transport, §£-152
Solvent
    Extraction, §8-429; §£-348
    Mining, §2-231
Sonic Coring, 90-409
Sorption, §§-132
Source
    Control, §8-188
    Emission Rate Estimate, 90-628
South Valley San Jose 6 Site, 87-355
Spatial Contouring, 85-442
Spectroscopy
    X-Ray Fluorescence (XRF), §§-
        97
Spent Solvents, §§-164
Spill(s), §§-313, 317
    Hazardous Materials Storage, 82-
        357
    Response
       Chemical Information, 90-
        977
Spray Aeration
    Gasoline REmoval, 90-865
Stabilization, §2-192; 88-440; §£-
        216,222, 292,476
    Lead, 90-665
    Petroleum Sludge, £2-712
    Solidification, §2-180; §5-214,
        231
       Organic Sludge, 84-189
       Quality Control, §6-287
       Soil, §7-198
   Viscoelastic Polymer Waste, 85-
        152
Starch Xanthate, £2-730
Startup
   Groundwater System, 87-223
State
   Cooperation, §§-15
   Criticism, 84-532
   Enforcement, 84-544
   Participation, 82-418; 84-53
   Petroleum Cleanup Levels, 90-21
   Plans
      New Jersey, §3-413
      Pennsylvania, 81-42
   Statute
      Natural Resource Injury, 8£-
        613
   Superfund
      Involvement, 90-4
      Program, §2-428; 85-67
Statistical
   Analysis
      Air Toxics Data, §£-157
   Methods, §4-243
      Groundwater Monitoring, 84-
        346; §6-132
      Sampling, 86-426
      Screening, 86-64
   Modeling
      Geophysical Data, §6-110
Statistics, §8-503
Steam Stripping, §2-289; §7-390,
        396; §9-558; 90-595
Storage Tank Leaks, §§-462
Strategic Planning, §§-79
Stratification, 90-492
Streamline, §9-488
Stringfellow Site, 80-15,21
Stripper
   Air, §8-395
Structure(s)
   Contaminated, 90-585
Structured Settlements), §9-600; 90-
        254
Subsampling, §4-90

Subsurface
   Barrier Wall, £2-460
   Geophysical Investigation, 84-
        481
Sunken Ships
   Bikini Atoll, £2-137
   Environmental Rish, 90-137
Superfund (See Also CERCLA), §8-
        108,113,145,214,338,
        409,
      419,435,503; §£-309
   California, §1-37
   Cleanup, 90-10
   Cleanup Failure Liability, 83-442
   Compliance, 88-12
   Contracts), §6-40,46
   Contractor
      Indemnification, §6-56; 87-
        520
      Liability, §7-34
   Drinking Water, §3-8
   Federal/State Cooperation, 81-
        21; 83-428
   Field Operations Methods, 87-28
   Groundwater Protection Goals,
        86-224
   Highway Right-of-Way, £2-42
   Impact on Remedial Action, 86-
        407
   Implementation, 83-1
   Improvement, 90-52
   Innovative Technology
         Programs, 86-356
    Management, §3-5; §§-15
    Natural Resources Damage, 87-
         517
    Peer Review, £Q-17
    Private
       Cleanup, 86-27
       Property Cleanup, 86-31
       Sector Concerns, §1-10
    Programs
       New Jersey, 83-413
       Texas, §3-423
    RCRA
       Closure Options, 87-337

       Interrelationship, 86-462
       Response Impact, 87-509
    Revisited, §6-412
    Right-to-Know, 86-11
    Risk
       Assessment, 87-61
       -Based Policy, §7-251
    Site
       Assessment, £0-77
       Closure, £0-539
       Health Assessment, £2-144
       Management, 86-14
       PCB Remediation, £0-575
       Risk, §7-56
    State
       Involvement, 90-4
       Perspective, 84-532
       Programs, §8-72
    Strategy for Dealing With, 86-
        469
    U.S. EPA Research, 81-7
Surface
    Geophysics, §7-300
    Impoundment, 88-245
       Cleanup, £0-917
    Sealing, 81-201
    Water
       Exposure, 87-143
       Management, 80-152
       Modeling, £0-133
SUTRA, §7-231
Swansea Valley, 84-553
Swedish Dump Site Cleanup, §3-342
Sweeney, 82-461
Sydney Mine Site, §5-285
Sylvester Site, 81-359
Synthetic
    Liner, §9-534
    Membrane Impoundment
        Retrofit, §2-244

TAG (see Technical Assistance
        Grant)
Tailings, §5-107
Tank Investigation and Removal, 85-
        198
Tar Creek Site, 87-439
TAT
    Health and Safety, §2-85
2,3,7,8-TCDD, 88-292
TCE (see Trichloroethylene)
TCLP
    Economic Analysis, 90-280
Technical Assistance
    Grant (TAG) Program, 90-85
    Waste Minimization, £0-29
Technical Enforcement Support
        Contract, §6-38
Technology
    Emerging, 88-516
    European, §§-193
    Evaluation, 82-233
                                                                                                                                         1023
-------
         Innovative, 88-193,516; 90-716
         Screening, 90-924
         Treatment, §§-329
     Tentatively Identified Compounds,
             89-86
     1,1,2,2-tetrachloroethane, §§-138
     Texas
         Ambient Air Sampling, 85-125
         Superfund Program, §3-423
     Thamesmead, §4-560
     Thermal
         Desorption, 22-549
            Diesel Fuel, 2Q-957
         Destruction, §8-429
         Extraction/Gas Chromatography,
             §2-41
         Treatment
            Soils, 84-404
         Volatilization System, 89-392
     Thermodynamics
         Halogen Combustion, 85-400
     Thin Layer Chromatography (TLC),
             §6-420; 2S-333
     Three-Dimensional Modeling, 90-
             896
     Time Varying Parameters, §2-108
     Times Beach, §§-255
     Title III, §8-516, 565
         Compliance, §2-443
         SARA, 22-56
     TLV, §§-546
     TNT, §2-209; §5-314; §§-569; §2-
             493
         Field Detection Kit, 20-889
     Toluene, §§-451
     TOMES Plus, 2Q-977
     Tomography, §§-152
     Tooele Army Depot
         Lagoon Closure, 90-466
     Top-Sealing, §2-135
     Total Quality Management (TQM),
             22-71
         Superfund, 22-17
     Town Gas, §4,-H;8£-93
     Toxaphene, §§-495
     Toxic Substances and Disease
             Registry Agency, 85-403
     Toxicity, §§-119
         Analysis, 22-788, 793
         Sediments, §2-130
     Toxicological
         Data, §6-193
         Profiles, §§-537
     Toxicology
         Environmental, 22-977
         Occupational Medicine, 22-977
     Toxin-Exposure, 89-91
     Trace Atmospheric Gas Analyzer,
             §2-98,100
     Training, §§-546
         Firsl Respondent, §5-71
         Health and Safety, 22-503
         OSHA Requirements, §7-18
         Resources, §2-304
     Transport, §§-132
         Contaminant, 8§-539
         Heavy Metals, §7-444
         Model, §8-125. 287
     Transportable Incinerator, 82-387
     Transuranic Waste, §2-586
     Treatability, §§-12
         Study, §8-1, 484; 22-831
           Biorcmedialion, 22-681
           Composting, §2-298
           Soil, 22-730
         Tests, §§-413
     Trcatmcnl, 8J-455. 521
   Effectiveness, 88-429
   Groundwater, §2-241
   In Situ, §2-451; §3-217,221,
        226,231
   Mobile, 86-345
   On-Site, 82-442
   Passive, 88-261
   Soil, 22-510, 700
   System
       Design, §1-294
       Operation, 90-517
   Technology, 88-329
Trench
   Biopolymer Slurry, 90-382
   Drainage, §§-462
   Extraction/Interception, 90-382
   Slurry, §8-462
Trend-Surface Modeling, 87-120
Trichlorobenzene, 89-497
1,1,1-trichloroethane, §8-108
Trichloroethene, §§-138
Trichloroethylene (TCE), §9-313,
        497
   Biodegradation, 22-826
   Bioremediation, 90-800
   Contamination, §2-424
       Groundwaler, 22-386
   Groundwater Contamination, 89-
        137
Tritium, §9-576
Twin Cities Army Ammunition
        Plant, 22-882
TSCA
   PCBs, 22-575
TSD
   Evaluation, 22-245
   Selection, 22-245

Ultraviolet Light (see also UV), §9-
        264
   /HjO2 oxidation, §7-174
UMTRA Project, §7-449
Uncertainty,  88-259
   Analysis, §2-82, 102; 22-206,
        215
   Engineering, 82-436, 459
Uncontrolled Hazardous Waste Site
   Population Demographics, 90-
        173
Underground Storage Tank, 88-202
   Fuel, 86-350
   Leak Detection, §7-523
   Spill Risk Assessment, §4-16;
        §6-176
   Trichloroethylene, §6-138, 430
   Waste Characterization, §6-227
United Kingdom, 80-8, 226
Unknown Gases, 84-416
Unsaturaled
   How, 88-234
   Zone, §§-132
U.S. Army
   Corps of Engineers, 82-414; 83-
        17;§8-15
   Installation Restoration Program,
        §4-511
   Waste Minimization, 22-868
U.S. Coast Guard (USCG), §2-6
U.S. Dept. of Defense (DOD), §9-99,
        596
   Environmental Restoration
        Program, §2-128; §7-7
   Hazardous Materials Technical
        Center, §2-363
   IRP, §5-26
   Site Cleanup, §3_-326
   TNT Cleanup, §5-314
U.S. DepL of Energy (DOE), §5-29;
        §8- 39; §9-582,586,652;
        22-241
    CEARP.86-1
    Cleanup Costs, 90-241
U.S. Environmental Protection
        Agency (EPA)
    Expedited Response Action
        Program, 86-393
    Mobile Incinerator, §1-285
    Reportable Quantities, 86-182
    Research, §1-7
    Risk Assessment Guidelines, 86-
        167
U.S. Navy, 85-48
    Air Station at Pensacola, 90-877
    Naval Installation Restoration
        Program, 90-877
    Pollution Control, 90-772
Uranium, §2-267
    Removal, 2Q-601
    Tailings, §7-449
UST(s)
    Leakage, 22-632
UV (see also Ultraviolet Light)
    /Chemical Oxidation, 22-937
    /Hydrogen Peroxide, §2-407; 22-
        768
    /Ozone, §2-264,407; 2Q-919
    Study §5-456

Vacuum
    Extraction, §7-273, 390; §§-193;
        22-624
    Stripping, §9-562; 22-595
Vados Zone, §§-158,164
    Monitoring, 82-100
Value Engineering, 88-594
Vapor
    Control, 22-589
    Detoxification, 22-589
    Emission, §2-326
    Entrapment, 22-589
    Extraction, 22-557,595, 636,
        641, 882
      System, §8-188
    Foam Suppression, 87-480
    -Phase Carbon Adsorption, 90-
        748
    Soils, §5-128,157
Variance, §§-234
Variogram, §§-274
Verification Sampling, 22-320
Verona Well Field, §2-330
Vienna Basin, 88-219
Vinyl Chloride, §§-138
Viscoelaslic Polymer Waste, §5-152
Vitrification, §7-405; 90-471
    In Situ, §4-191; §6-325; 2Q-453
VOC (Volatile Organic Compound),
        §§-125, 158,174, 219, 287,
      395, 409; §2-122, 277, 313,
        468,479,555, 558, 562,
        570
   Air
      Monitoring, 22-290
      Stripping, §2-313
    Carbon Adsorption, 22-748
    Collection, 22-765
   Contamination, §2-558
    Emission
      Rales, 22-628
      Reduction, 22-868
   Groundwater, §2-519; 22-304
      Cleanup, £2-420
   Purgeable, §§-174
   Remediation, 22-606
    Soil, 22-21,730
       Analysis, 22-340
       Vapor Extraction, 2Q-557
       Venting, 22-641
    Total, §8-174
Volatile
    Nitrogen Compounds
         Monitoring, §2-100
    Organics
       Analysis, §7-85; §9-15
       Chlorinated, §§-164
       Emissions, §1-129; §4-68,77
       Foam Suppression, §7-480
       Lower Detection Limits, §7-
         280
       Monitoring, §1-122; §4-72
       Removal, §7-218
       Sampling, §7-457
       Screening, §6-386
       Soil Gas Survey, §2-523
       Stripping From Soils, §6-322
Volatilization, §§-467
Volume
    Estimation, §8-274
    Reduction Unit
       Mobile, 22-760
VOST, §2-457

Wales, §4-594
Walls
    Design and Installation, 86-460
    Gelatinous, §2-198
    Slurry, 82-191
Washing, §2-198, 207
Waste
    Management Facilities
         Real Estate Transfer, §7-
        499
    Minimization, §2-13, 606
       Assistance, 22-29
    Oil Recovery, §7-179
    Radioactive, §8-193
    Storage
       Above Ground, §2-228
       Geologic Repositories, §7-
        502
Wastewater
    Disposal Ponds, §§-84
    Treatment, §2-160; §4-598
Water
    Oil Determination, 22-620
    Thin Layer Chromatography, 22-
        333
    Treatment
       Cost, 81-370
       On-Site, §2-169
Waterway Decontamination, §2-21
Weathering
    Stabilize Sludge, 22-712
Weldon Spring Site, 22-601
Well
    Abandonment, 82-439
    Bentonile, 22-308
    Closure, 22-911
    Contamination, §7-320
    Drilling, 22-357
    Horizontal, 2Q-398
       Wellbore System, 22-357
    Installation
       Leachate, 22-363
    Monitoring, §§-202
    -Point Systems Evaluation, §2-
        228
West Germany, §2-68
West Valley Demonstration Project,
        82-405
Western Processing Superfund
1024
-------
        Site,87-78,198; §2-645;          Treatment, 88-261                    PAH, §6-242                           Spectroscopy (XRF), §8-97
        20-668                     White Rot Fungus, 2Q-788                Plant Bioremediation, §7-193       Xylene
WET Procedure, 86-303              Wilsonville Exhumation, 82-156          RI/FS, 86-441                       m-Xylene, §§-451
Wetland, §8-435                     Winter Flounder, §§-359                                                    o-Xylene, 88-451
   Assessment, 90-148              Woburn, Massachusetts, §1-63,177     X-Ray                                 p-Xylene, §8-451
      Procedure, §7-431             Wood Treating, 88-226                  Analyzer, §5.-107
   Contamination, 85-261                Facility, §1-212                      Fluorescence, §5-93; 86-115        Zinc, 86.-200; §9-430
   Modeling, 90-148
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