EPA/540/R-96/505
September 1997
SITE Emerging Technology Report
Innovative Methods for Bioslurry Treatment
by:
Kandi Brown
IT Corporation
San Bernardino, California 92408
EPA Assistance Agreement CR821186-01-0
IT Project No. 408250
Project Officer:
Brunilda Davila
National Risk Management Research Laboratory
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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TECHNICAL REPORT DATA
(Plane read Instructions on the mmt before completing]
1, REPORT NO.
EPA/S4Q/R-96/5Q5
3. RECIPIENT'S ACCESSION NO.
PB97-176820
4, TITLE ANOSUBTITUi
S, REFQRT DATE , ft-_
September 1997
SITE Emerging Technology Report:
Innovative Methods for Bioslurry Treatment
6, re,BF0«t«»NO ORGANIZATION CODE
7, AUTMOR(S)
Kandi Brown
S. PERFORMING ORGANIZATION REPORT NO,
9, PERFORMING ORGANIZATION NAMS AND AODWiSS
IT Corporation
1425 South Victoria, Suite A
San Bernadino, CA 92408-2923
1O. PROGRAM ELEMENT NO.
TD1Y1A
11. CONTRACT /GRANT NO,
CR821186-01-01
!~2. SPONSORING AGENCY NAME AND AOOBiSS
National Risk Management Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati^OH 45268 _ _ _
COVERED
14, SPONSORING AGENCY CODE
EPA/600/14
15, SUPPLEMENTARY NOTES
Project Officer: Brunilda Davila (513)569-7849
18. ABSTRACT
IT Corporation conducted a pilot-scale testing of biological and chemical oxidation of slurry-phase polycyclic
aromatic hydrocarbons (PAHs). The 7-month demonstration illustrated potential effectiveness of combined
biological and chemical oxidation for the treatment of PAH-contaminated soils. The 30 percent CPAH
destruction goal was achieved with CPAH transformation ranging up to 84 percent. A system hydraulic
residence time (HRT) of approximately 37 days increased system performance. Due to the increased
transformation of PAH in reactor I (Rl) and reactor 2 (R2) during optimal performance, transformation
in reactor 3 (R3) were significantly decreased. This result may indicate that R3 is not required for effective
treatment. It should be noted that greater than 80 percent CPAH removal was achieved during the last 2
weeks of operation following modifications to the treatment process made during the previous weeks. These
results are reflective of the effectiveness of the treatment system following achievement of'steady
operation. The modification to the treatment system included increasing the system HRT from 13.5 to 37
days. This change resulted in a HRT in Rl equal to the previous system HRT. As a result, PAH and CPAH
removal increased in Rl and 12, with a decreasing performance in R3. Overall, operation of Rl and 12 only
was adequate for effective treatment following in 'increase in HRT, Continued investigation under the process
set points maintained during the final month of system operation is recommended.
17.
KEY WORDS ANO DOCUMENT ANALYSIS
DESCRIPTORS
PAHs, CPAHs, biodegradation, Fenton's,
chemical, oxidation, bioslurry reactors
•.IDENTIFIERS/OPEN gNOED TERMS
c. COSATI Field/Croup
18, DISTRIBUTION STATEMENT
Release to Public
IS. SECURITY CLASS (This Report)
1. NO, OP ?AG
Unclassified
20. SECURITY CLASS (This pagtl
Unclassified
22. PRICE
6PA Form 2220-1 (R»*. 4-77) previous COITION is OBSOLETE
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Notice
The U.S. Environmental Protection Agency through its Office of Research and Development
partially funded and collaborated in the research described here under assistance agreement
CR821186-01-0 to IT Corporation. It has been subjected to the Agency's peer and administrative
review and has been approved for publication as an EPA document. Mention of trade names or
commercial products does not constitute endorsement or recommendation for use.
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Foreword
The U.S. Environmental Protection Agency is charged by Congress with protecting the Nation's
land, air, and water resources. Under a mandate of national environmental laws, the Agency
strives to formulate and implement actions leading to a compatible balance between human
activities and the ability of natural systems to support and nurture life. To meet this mandate,
EPA's research program is providing data and technical support for solving environmental
problems today and building a science knowledge base necessary to manage our ecological
resources wisely, understand how pollutants affect our health, and prevent or reduce
environmental risks in the future.
The National Risk Management Research Laboratory is the Agency's center for investigation of
technological and management approaches for reducing risks from threats to human health and
the environment. The focus of the Laboratory's research program is on methods for the
prevention and control of pollution to air, land, water and subsurface resources; protection of
water quality in public water systems; remediation of contaminated sites and ground water; and
prevention and control of indoor air pollution. The goal of this research effort is to catalyze
development and implementation of innovative, cost-effective environmental technologies;
develop scientific and engineering information needed by EPA to support regulatory and policy
decisions; and provide technical support and information transfer to ensure effective
implementation of environmental regulations and strategies.
This publication has been produced as part of the Laboratory's strategic long-term research plan.
It is published and made available by EPA's Office of Research and Development to assist the
user community and to link researchers with their clients.
E. Timothy Oppelt, Director
National Risk Management Research Laboratory
m
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A bstract
IT Corporation (IT), Knoxville, Tennessee, in collaboration with U.S. Environmental protection
Agency (EPA), investigated the feasibility of combined biological and chemical oxidation of
polycyclic aromatic hydrocarbons (PAH). Bioslurry treatment of PAH-contaminated soils was
demonstrated under the Superfund Innovative Technology Evaluation - Emerging Technology
Program (SITE ETP) as an extension of research previously funded by IT Corporation (IT)
(Brown and Sanseverino 1993) and additional investigations supported by the U.S. EPA (Davila
et al. 1994). All testing was initiated in September, 1994.
During the demonstration, IT operated two 60-liter (L) TEKNO Associates bioslurry reactors
(Salt Lake City, Utah) and a 10-L reactor in series under semicontinuous, plug-flow mode for a 7-
month period. The first 60-L reactor received fresh feed daily and supplements of salicylate and
succinate to enhance PAH biodegradation.
Slurry from the first reactor was fed to the second 10-L reactor, where Fenton's reagent
(Fe+++H2O2)was added to accelerate chemical oxidation of 4 to 6-ring PAHs. The third reactor
in series was used to biologically oxidize contaminants remaining following addition of Fenton's
reagent. This reactor received no additions of salicylate and succinate and was aerated, nutrient
amended, and pH adjusted only.
During operation, the reactor system demonstrated total PAH and carcinogenic PAH (CPAH)
transformation up to 95 and 84 percent, respectively.
This report was submitted in fulfillment of assistance agreement CR821186-01-0 by IT
Corporation under the partial sponsorship of the United States Environmental Protection Agency.
This report covers a period from September 1994 to April 1995, and work was completed as of
December 1995.
IV
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Table of Contents.
Foreword iii
Abstract iv
List of Tables yii
List of Figures viii
List of Acronyms ix
Acknowledgment xi
1.0 Introduction 1
1.1 Site Description 1
1.2 Soil Characterization 1
1.3 Waste Stream Description 1
1.4 Remedial Technology Description 2
2.0 Conclusions and Recommendations 4
2.1 Conclusions 4
2.2 Recommendations 4
3.0 Treatability Study Approach 6
3.1 Test Objectives 6
3.2 Experimental Design and Procedures 6
3.3 Equipment and Materials 7
3.3.1 Soil Collection and Preparation 7
3.3.2 Reactor Description and Operation 9
3.4 Sampling and Analysis 10
3.4.1 Physical Analyses 11
3.4.2 PAH Analyses 11
3.4.3 Microbial Enumerations 12
3.4.4 14C Mineralization Assays 12
3.4.5 Toxicity Screening 12
3.4.6 Chemicals 12
3.5 Data Management 13
3.6 Deviations from the Test Plan and QAPP 13
4.0 Results and Discussion 14
4.1 Data Analysis and Interpretation 14
4.1.1 Reactor Operation 14
4.1.2 Physical Analyses 14
4.1.2.1 pH , 14
4.1.2.2 Dissolved Oxygen 15
4.1.2.3 Reactor Solids 15
4.1.2.4 Nutrients 16
4.1.2.5 Microbial Enumerations 16
4.1.2.6 Total Recoverable Petroleum Hydrocarbons 17
4.1.2.7 Total Organic Carbon Analyses 17
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Table of Contents (continued).
4.1.2.8 PAH and Mass Balance 18
4.1.2.9 14C-Mineralization Assays 20
4.1.2.10 Toxicity Screening 21
4.2 Quality Assurance/Quality Control 21
4.3 Costs/Schedule for Performing the Treatability Study 21
4.4 Key Contacts 21
5.0 References 22
Tables
Figures
Appendices - (Complete copies of all listed appendices may be received by contacting the U.S. EPA
Project Manger, Bruni Davila [513-569-7849].)
Appendix A Geotechnical Reports
Appendix B Site Data
Appendix C PAH Data and Mass Balance Spreadsheets
VI
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List of Tables
Table Title
1-1 Physical/Chemical Properties of CPAH Constituents
1-2 General Influent Feed Characteristics for Bioslurry Treatment
3-1 Initial Operational Setpoints
3-2 Sampling and Analytical Schedule for Rl, R2, and R3 Slurry Phase
3-3 Summary of Analytical Methods
3-4 Summary of Chemicals
3-5 List of Technical Changes
3-6 List of Nonconformances
4-1 Summary of Reactor Upsets and Operational Modifications
4-2 Summary of Total Recoverable Petroleum Hydrocarbons (TRPH), PAH,
and CPAH for March 16 Samples
4-3 PAH Removal Efficiencies (Percent)
4-4 CPAH Removal Efficiencies (Percent)
4-5 PAH Mass Removal (Grams/Day)
4-6 CPAH Mass Removal (Grams/Day)
4-7 16-Hour Toxicity Determination Using Tetrahymena
vn
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List of Figures^
3-1
3-2
4-1
4-2
4-3
4-4
4-5
4-6
4-7
4-8
4-9
4-10
4-11
4-12
4-13
4-14
4-15
4-16
4-17
4-18
4-19
4-20
Title
Process Flow Diagram
Eimco Biolift™ Reactor
Reactor pH Data
Dissolved Oxygen Concentrations
Reactor Total Solids
Reactor Volatile Solids
Ratio of Volatile Solids to Total Solids
Solids Distribution in Reactor 1
Solids Distribution in Reactor 3
Reactor Ammonia Concentrations
Reactor Phosphate Concentrations
Reactor Total Heterotrophic Bacterial Populations
Solid Phase Total Carbon
Aqueous Phase Total Organic Carbon
Percent Reduction - Rl
Percent Reduction - R2
Percent Reduction - R3
Percent Reduction - Overall
Fluorene Concentrations
Benzo(a)Pyrene Concentrations
PAH Concentrations
CPAH Concentrations
Vlll
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List of Acronyms,
Biotechnology Applications Center
Benzo(a)pyrene
colony forming units per milliliter
Chemical Hygiene plan
carcinogenic polycyclic aromatic hydrocarbons
dichloromethane
diatomaceous earth
U.S. Environmental Protection Agency
Emerging Technologies Program
gas chromatography/mass spectrography
sulfuric acid
high performance liquid chromatography
hydraulic retention time
IT Corporation
liter
lethal dose
molar
milligrams per liter
milligrams per kilogram
manufactured gas plant
milliliters
millimolar
millimeter
Normal
nanometer
polycyclic aromatic hydrocarbons
pentachlorophenol
process flow diagram
quality assurance project plan
Reactor 1
Reactor 2
Reactor 3
IX
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List of Acronyms (continued).
rpm revolutions per minute
SITE Superfundlnnovative Technology Evaluation
SOP standard operating procedure
TC total carbon
TOC total organic carbon
TRPH total recoverable petroleum hydrocarbon
TS total solids
TSDF treatment, storage, and disposal facility
UV ultraviolet
VS volatile solids
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A cknowledgment
IT and U.S. EPA would like to acknowledge the contribution of Gunter Brox, TEKNO
Associates, during the execution of this work.
XI
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1.0 Introduction
IT Corporation (IT) was contracted by the U.S. Environmental Protection Agency (EPA)
under a cost sharing contract (CR821186-01-01) in October 1993 to conduct pilot-scale testing
of the biological and chemical oxidation of slurry-phase poly cyclic aromatic hydrocarbons
(PAH). Bioslurry treatment of PAH-impacted soils was demonstrated under the Superfund
Innovative Technologies Evaluation - Emerging Technologies Program (SITE ETP) as an
extension of research previously funded by IT (Brown and Sanseverino 1993) and additional
investigations supported by the EPA (Davila et al. 1994).
All testing was initiated in September, 1994. Testing was conducted by IT personnel at IT's
Biotechnology Applications Center (BAG) located in Knoxville, Tennessee.
1.1 Site Description
Among the types of contaminants present in Superfund soils, complex PAHs constitute the
more challenging class to treat. Sites that contain PAH contamination include manufactured
gas plants (MGP), wood-treating facilities, petrochemical facilities, and coke plants. Soils
employed during this investigation were collected from a wood-treating facility located in
Arkansas.
1.2 Soil Characterization
All soil collection and screening activities were conducted by IT personnel, with supervision
by the wood-treating site health and safety officer during the week of September 12, 1994.
For a complete review of soil screening activities see Section 3.3.1.
1.3 Waste Stream Description
PAH and carcinogenic PAH (CPAH)-impacted soils, primarily sand (30 percent) and clay (70
percent), were wet-sieved on site through a 30 mesh screen and submitted to IT's BAG, for
testing. All geotechnical analyses are presented in Appendix A. Oversized material was
disposed on site. Blended slurry PAH and CPAH concentrations ranged up to 6,120 and 434
milligrams per kilogram (mg/kg), respectively. Wet sieving the soils increased the uniformity
of the slurry, thereby, reducing the potential for sampling variability.
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1.4 Remedial Technology Description
PAHs are characterized by high organic partition coefficients, low aqueous solubility, and low
vapor pressures (Table 1-1). These characteristics result in the highly sorptive nature of PAHs
and their subsequent limited availability to microbial populations. IT's past experience with
PAH-contaminated soils indicated that contaminant desorption from soil is the rate limiting
factor in bioremediation. Manipulation of parameters such as pH, agitation, and temperature,
as well as the addition of surfactants or solvents, can be used to enhance the rate of desorption
and, thereby, increase in the rate of biodegradation.
The optimum method of manipulating these parameters is in bioslurry reactors. Bioslurry
reactors can provide rapid biodegradation of contaminants due to enhanced mass transfer rates
and increased contaminant to microorganism contact. These units are capable of treating high
concentrations of organic contaminants in soils and sludges, with demonstrated biodegradation
of selected contaminant concentrations ranging from 2,500 to 250,000 mg/kg. In general, the
percent removal of PAH in these systems ranges from 70 to 95 percent, with 30 to 80 percent
reduction of the CPAH fraction (EPA, 1990).
Bioslurry reactors can aerobically biodegrade aqueous slurries created through the mixing of
soils or sludges with water. Maximum contaminant reduction is accomplished in bioslurry
reactors primarily through proper feed preparation. Preparation of the influent waste stream
should produce the general characteristics presented in Table 1-2.
The most common mode of bioslurry treatment is batch; however, continuous-flow operation
can be achieved. Aeration is provided through floating or submerged aerators or compressors
and spargers. Mixing may be achieved through aeration alone or in conjunction with
mechanical mixers. Nutrient addition and pH adjustment are accomplished through metered
chemical addition to the reactor. Following aeration, the treated slurry is dewatered via
standard dewatering equipment, such as clarifiers or filter presses.
The residual streams created during bioslurry treatment include treated solids, process water,
and possible air emissions. The process water collected during the solids/liquid separation
phase is usually recycled for influent waste stream slurrying or discharged under permit. Air
emissions may be controlled through air pollution control devices.
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Full-scale commercial bioslurry units require approximately 0.5 to 1 acre per million gallons
of reactor volume (EPA, 1990). Reactor size is determined based on the hydraulic retention
time (HRT) required for treatment. Retention times are established based on the
biodegradability of the waste, level of treatment required, influent contaminant concentration,
and physical/chemical nature of the waste.
Major issues of concern during bioslurry treatment system design include reducing system
HRT and increasing the rate and extent of contaminant biodegradation. These factors were
addressed by IT during the SITE investigation. To reduce the operating HRT, thereby
decreasing the size of the system, IT operated bioslurry reactors in series (i.e., plug flow)
under semicontinuous mode and evaluated two HRT set points.
During the demonstration, IT operated two 60-liter (L) Tekno Associates bioslurry reactors
(Salt Lake City, Utah) and a 10-L fermentation unit in semicontinuous, plug-flow mode for a
7-month period. The first 60-L reactor received fresh feed daily and supplements of salicylate
and succinate to enhance PAH biodegradation.
Slurry from the first reactor was fed to the second 10-L reactor, where Fenton's reagent
(Fe+++H2C>2) was added to accelerate chemical oxidation of 4 to 6-ring PAHs. The third
reactor in series was used to biologically oxidize contaminants remaining following addition of
Fenton's reagent. This reactor received no additions of salicylate and succinate and was
aerated, nutrient amended, and pH adjusted only.
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2.0 Conclusions and Recommendations
2.1 Conclusions
The 7-month demonstration illustrated the potential effectiveness of combined biological and
chemical oxidation for the treatment of PAH-impacted soils. Overall, the following
conclusions were made:
The 80 percent CPAH destruction goal was achieved with CPAH transformation
ranging up to 84 percent.
A system HRT of approximately 37 days increased system performance.
Due to the increased transformation of PAH in reactor 1 (Rl) and reactor 2 (R2) during
optimal performance, transformation rates in reactor 3 (R3) were significantly
decreased. This result may indicate that R3 is not required for effective treatment.
It should be noted that greater than 80 percent CPAH removal was achieved during the last 2
weeks of operation, following modifications to the treatment process made during the previous
2 weeks. These results are reflective of the effectiveness of the treatment system following
achievement of steady state operation.
The modification to the treatment system included increasing the system HRT from 18.5 to 37
days. This change resulted in a HRT in Rl equal to the previous system HRT. As a result,
PAH and CPAH removal increased in Rl and R2, with a decreasing performance in R3.
Overall, operation of Rl and R2 only was adequate for effective treatment following an
increase in HRT.
2.2 Recommendations
Continued investigation under the process set points maintained during the final month of
system operation is recommended. As demonstrated by the increase in PAH and CPAH
transformation during this period, reduced solids loading, increased clay content, and extended
HRT set points proved beneficial to the treatment process.
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Modifications to the pilot-scale reactor design, decreasing the incidence of foaming should be
investigated. Process foaming, particularly when operating on the full-scale, will result in
poor system performance, reactor overflow, and the inability to effectively aerate the system.
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3.0 Treatability Study Approach
3.1 Test Objectives
The primary objective of this SITE investigation was to document accelerated PAH removal
rates using combined chemical and biological treatment techniques. The project used specific
organic (succinate and salicylate) and inorganic nutrient (ammonia and phosphate)
supplements, in combination with Fenton's reagent to achieve increased removal in a plug-
flow treatment system.
The specific objectives of the pilot-scale demonstration were:
Determine efficacy of achieving greater than 80 percent reduction in CPAH due to a
combination of biological and chemical oxidation
Estimate HRT required for operation of each reactor
Determine CPAH reduction in each reactor to compare combined biological/chemical
oxidation to biological treatment alone
Determine the need for R3
Generate performance data upon which full-scale design can be established
Provide operating data from which full-scale cost estimates can be generated.
3.2 Experimental Design and Procedures
Previous work by IT demonstrated that sodium salicylate and sodium succinate enhanced the
levels of naphthalenedegrading bacteria in a slurry reactor. Previously published research has
demonstrated that in MGP site soils naphthalene, phenanthrene, anthracene, and to a limited
extent benzo(a)pyrene [B(a)P] were mineralized (Sanseverino et al., 1993). Biodegradability
was confirmed with 14C-radiolabeled PAH. Further; the naphthalene-degrading pathway of
Pseudomonas purida NAH7 and NAH7-like organisms mineralize phenanthrene and anthracene
through the same genetic and biochemical pathway as naphthalene. Therefore, the presence of
salicylate will keep the naphthalene pathway induced, promoting degradation of these 3-ring
PAHs even when naphthalene levels diminish (Ogunseitan et al., 1991).
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The primary objective of Rl operation was to increase the biological removal of organic
carbon. Salicylate was used to induce the naphthalene degradation operon on NAH plasmids.
It was assumed that NAH plasmids were naturally occurring in microbial populations
indigenous to subject soils. Succinate, a by-product of naphthalene metabolism, served as a
general carbon source in Rl which removed easily degradable carbon and increased biological
activity against more recalcitrant PAH (i.e., 4-ring compounds and higher).
Slurry from Rl was fed to R2 where Fenton's reagent was continuously introduced, resulting
in chemical oxidation being the primary mechanism for PAH transformation in this reactor.
The pH in R2 was adjusted to 2.0 following the addition of Rl slurry. Fenton's reagent
(hydrogen peroxide in the presence of reduced iron salts) produces free radicals, which have
been shown effective in extensively oxidizing multiring aromatic hydrocarbons in both soil and
water systems (Gauger et al. 1990; Elizardo 1991). The objective of Fenton's reagent addition
was not PAH mineralization, but the hydroxylation of PAH, because hydroxylation of high-
molecular-weight PAHs generally is the rate-limiting step in biological oxidation.
R3 was used for biological oxidation of R2 slurry. R3 received no additions of salicylate and
succinate. The reactor was aerated, nutrient amended, and pH adjusted following the
introduction of R2 feed. The system process flow diagram (PFD) is presented in Figure 3-1.
3.3 Equipment and Materials
All treatability testing was completed at the BAG laboratory located in Knoxville, Tennessee.
This facility holds a special exemption from the State of Tennessee that permits execution of
treatability studies. The BAG laboratory operates in accordance with an approved Chemical
Hygiene Plan (CHP). All project activities at the BAG conformed to the standards set forth in
the CHP.
3.3.1 Soil Collection and Preparation
Soils were excavated by the on-site contractor using a rubber-tire backhoe and a Kamatso
DC200 trackhoe. Lightly impacted soils were collected from the A-cell area during site
preparation of a land treatment cell. Highly contaminated soils were collected from Catch All
Pond Sediments in the area where the SB-5 sample had been collected. Appendix B contains
all data obtained from the wood-treating facility prior to soil collection.
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The objectives of field screening were:
• Prepare adequate volume of -30 mesh soil slurry to complete the pilot-scale
investigation
• Dispose all oversized material on-site
• Prepare one 55-gallon drum of lightly impacted slurry
• Prepare four 55-gallon drums of a 50:50 blend of lightly and highly impacted material
• Collect additional volume of unscreened soil to support on-going project activities.
All objectives were met during field activities. Soils were screened in accordance with the
approved Test Plan (IT, 1994). Site soils were excavated and staged on visqueen. Soils were
transported to the wet-sieving area using a wheelbarrow. Three galvanized aluminum watering
troughs with stainless-steel mesh sieves secured to the rim with lumber were used during soil
screening. Each sieve was constructed using a -30 mesh U.S.A. Standard Testing Sieve.
During screening, the troughs were partially filled with tap water. Little Giant 2E Series
submersible pumps (aluminum housing, epoxy coating, nylon pump head and impeller, and
polypropylene screen) were placed on concrete blocks inside each trough. These pumps were
used to recirculate the wash water and, thereby, increase the slurry density of the mixture.
Evaporation of excess water could not be achieved during screening due to the limited
equipment.
Soils were characterized as sand (30 percent) and clay (70 percent). Particle size distribution
data are presented in Appendix A.
During screening, five drums of sieved material were generated - one drum of clean soil and
four drums of blended material. Blended slurry was produced through the separate screening
of lightly and highly impacted soils. The slurry produced during soil screening was then
blended in a 1: 1 ratio. In addition to soil slurry, two drums of impacted soil were collected.
All seven drums were shipped to the IT Bear Creek Facility located in Knoxville, Tennessee.
Following soil collection and screening, three drums of slurry (Drums 1, 2, and 3) were
individually mixed and separated into smaller, more manageable containers. Cross-
contamination of drum contents was avoided during mixing. A MQ Multiquip Whiteman
cement mixer with a Honda GX240 8.0 motor operated at approximately 28 revolutions per
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minute (rpm) was used to mix all slurry. The system was decontaminated using Mi-T-M
pressure washer with a Honda GX160 5.5 motor.
3.3.2 Reactor Description and Operation
Rl and R3 were 60-L, stainless-steel, Tekno™ (formerly Eimco) bioslurry reactors (Figure 3-
2; Salt Lake City, Utah). R2 was a 30-L glass vessel fitted with an overhead impeller
system. The system PFD is shown in Figure 3-1. Initial operational setpoints for R1,R2, and
R3 are provided in Table 3-1. All portions of the reactor system that contacted the slurry
mixture were stainless-steel, glass, or Viton tubing.
Agitation and aeration in Rl and R3 were accomplished using a combination of the Tekno™
reactor impeller, air lift, and diffuser systems. System pH was maintained through manual
additions of 10 Normal (N) sodium hydroxide to the reaction vessels as necessary.
Fresh feed was manually introduced to Rl at an average daily flow rate of 6 L/day. For the
first 4 months of operation, fresh feed was introduced to the system in 2-L batches three times
per day to equalize the load of carbon into the system. At this daily flow rate and operating
volume of 57 L, the Rl HRT was maintained at approximately 10 days.
Slurry from Rl was manually fed to R2. The working volume of this 10-L reactor was
approximately 6 L. With an influent flow rate of 6 L/day, the HRT in R2 was 1 day. In
addition to the influent slurry, Fenton's reagent was added to this reactor at a rate of 2 L/day.
Overall, 8 L/day of slurry was removed from R2 and introduced to R3.
Slurry from R2 was manually fed to R3. The working volume of this reactor was equal to Rl.
The resulting HRT at 8 L/day was 7.5 days. Volume loss due to evaporation was checked
daily and adjusted as needed. Effluent from R3 was collected and stored for disposal at a
licensed treatment storage and disposal facility (TSDF).
After 4 months of operation, the HRT was doubled to 20 days in Rl, 2 days in R2, and 15
days in R3 to reduce the loading of organic carbon on the system. The total system HRT was
increased from 18.5 to 37 days. In addition, influent feed (3 L) was introduced once per day.
For the first 4 months of operation, Fenton's reagent was prepared by mixing a 1:1 ratio of 35
percent hydrogen peroxide and 1.5 molar (M) ferrous sulfate heptahydrate solution. For the
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remainder of the study, Fenton's reagent was prepared using 8.8 milliMolar (mM) ferrous
sulfate heptahydrate. The change in the concentration of Fenton's reagent addition was
initiated to increase the efficiency of the chemical reaction. A reduced concentration
prevented the occurrence of competing side reactions.
Initially, ferrous sulfate and hydrogen peroxide were added by dripping each solution into R2
at a rate of 1.0 L each per day. This system was modified such that each solution was
introduced simultaneously below the slurry surface. This was thought to provide for better
mixing, less splashing of each reagent, and reduced foam production.
Mixing efficiency of the reactor solids was verified periodically during the course of the
investigation. Verification was accomplished through analysis of total solids (TS)
concentrations in samples extracted from sample ports located on the side of the bioslurry
reactors. If nonuniform mixing was evident, agitation speed, rake speed, airlift system, or
solids content was adjusted. Due to the combined application of a 1:1 hydrogen peroxide:iron
sulfate solution in R2, only the impeller system was used to maintain complete mixing of the
soil slurry.
3. 4 Sampling and Analysis
The reactors were charged on September 23, 1994. All reactors were operated in batch
through October 10, 1994. Initial analytical data was colkcted prior to reactor batch
operation, during batch operation, at the initiation of semi-continuous operation, and routinely
throughout the remainder of the study. Sampling dates are presented in Section 4.0.
No steps were taken to reduce biological activity in soil samples prior to testing due to a
shortage of refrigerated storage area. However, each influent batch was analyzed prior to
introduction into the reactor system to accurately determine initial concentrations.
Slurry samples were collected from sample port S2 on. Rl and R3 (Figure 3-1). Grab samples
were collected from R2. The sampling and analytical schedule for the slurry phase, as well as
volumes required for each analysis is shown in Table 3-2. In addition to the slurry phase
analyses, the headspace of Rl was sampled monthly for PAHs The influent slurry was
sampled each time a new batch was introduced into the reactors. Influent slurry was analyzed
for PAH, total organic carbon (TOC), TS/volatile solids (VS), and density.
10
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3.4.1 Physical Analyses
A summary of all analytical methods used during this investigation is presented in Table 3-3.
Physical measurements included dissolved oxygen, total and volatile solids, pH, ammonia, and
phosphate.
3.4.2 PAH Analyses
PAHs were measured in the slurry phase of each reactor, as well as the headspace of Rl.
PAH concentrations in the slurry were determined using modified EPA Method 8310. For
PAH analysis of solids, air-dried slurry samples (10 grams) were mixed with anhydrous
sodium sulfate, placed in an extraction thimble and extracted using dichloromethane (DCM) in
a Soxhlet extractor for 16 hours. (The dry weight of the solid phase was analyzed for weight
loss in a 105°C drying oven.) The DCM extract was concentrated to 1 milliliters (mL) using a
Snyder column and solvent exchanged to 100 mL acetonitrile. Following extraction the
sample was analyzed using a Dionex high performance liquid chromatograph (HPLC)
equipped with an ultraviolet (UV) detector at 254 nanometer (nm). The elution profile was
acetonitrile:water (35:65) for 1 minute followed by a gradient to 100 percent acetonitrile over
15 minutes and held for 10 minutes.
Aqueous phase PAH analysis was conducted for the first 3 months of operation. Aqueous
phase PAH were quantified by direct injection of the aqueous phase into a Perk&Elmer HPLC
equipped Vydac Cjg column (Model 201TP54; Hesperia, California) with a variable
wavelength programmable fluorescence detector (LC-240). The elution profile was
acetonitrile: water (50:50) for 2 minutes followed by a gradient to 100 percent acetonitrile over
12 minutes and held for 5 minutes.
Headspace semivolatile constituents were measured through air sampling at port Z-2 on Rl
(Figure 3-1). The air sampling train consisted of a Teflon™ probe, a 47-millimeters (mm)
Teflon™ membrane filter, and an XAD-2 sorbent sampling tube. Headspace gases were
pulled through the XAD-2 tube for 24 hours. The XAD tube was extracted with 5 mL of
acetonitrile and analyzed by HPLC.
Reactor samples were shipped to the EPA (Cincinnati, Ohio) for extraction and analysis by gas
chromatography/mass spectrography (GC/MS) for confirmation of the HPLC analysis.
11
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3.4.3 Microbial Enumerations
Total heterotrophic bacteria were quantified using BAG standard operating procedure (SOP)
009. Naphthalene degrading bacteria were quantified by DNA:DNA colony hybridization
using the NAH gene as a probe (Sayler et al., 1985; Sanseverino et al., 1993). The NAH
encodes the naphthalene dioxygenase enzyme which is the first step in naphthalene
metabolism. Enumeration of naphthalene-degrading bacteria occurred on weekly samples for
the first three months of operation at which time it was discontinued.
3.4.4 14CMineralization Assays
C-PAH mineralization assays were performed to estimate in situ microbial degradative
capacity for specific compounds. Two mL of slurry were placed in a 40-mL vial (Pierce,
Rockford, Ii.). Labeled l-14C-naphthalene, 9-14C-phenanthrene, UL-14C-anthracene, or 7, 10-
14C-benzo(a)pyrene (Sigma, St. Louis, Mo; specific activity 8.0, 10.4, 10.4, and 60.0
mCi/mmol, respectively) were individually added to triplicate vials. Slurries were incubated at
26°C with shaking (100 rpm). Naphthalene and phenanthrene mineralization ( C02
production) was analyzed at regular intervals over a 7-day period. Anthracene mineralization
was analyzed at intervals up to 10 days. Benzo(a)pyrene mineralization was analyzed at
intervals up to 2 weeks. Biological control samples were inhibited by acidification with 0.5
mL of 2 N sulfuric acid (HzSO^) and metabolism assays were also terminated by H2S04
addition. 14C02 was trapped in 0.5 mL of 0.5 N NaOH. The NaOH was added to 1 mL of
water and 10 mL of Beckman ReadySafe m scintillation fluid and counted in a Beckman liquid
scintillation counter (Model LS380 1).
3.4.5 Toxicity Screening
The aqueous phases of the influent feed, Rl, and R3 were tested for toxicity using
Terrahymena as a test organism. Dilutions of the aqueous phase (1:200, 1: 100, 1:40) were
added to Tetrahymena cells (approximately 1,000 cells/ml) and incubated for 16 hours. Acute
toxicity was assessed by observing each tube for cell lysis and/or lack of ciliary movement as
determined with the aid of a dissecting microscope. A lethal dose (LDso) was determined for
each sample.
3.4.6 Chemicals
Chemicals, analytical grade, and sources are listed in Table 3-4.
12
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3.5 Data Management
All data was generated and stored as specified in the approved Test Plan
3.6 Deviations from the Test Plan and QAPP
Per the project contract, work progress and quality were monitored through audits of the
laboratory and project files. Audits indicated minor nonconformances and technical changes
from the Test Plan, however, nothing was identified which adversely impacted the project
quality of work. All project technical changes and nonconformances are listed in Tables 3-5
and 3-6.
13
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4.0 Results and Discussion
4.1 Data Analysis and Interpretation
The results of the 7-month demonstration are presented in the following text.
4.1.1 Reactor Operation
Daily reactor operation was described in Section 3.3.2. Operational difficulties were
encountered, during the demonstration. First, tar balls were formed following reactor charging
and aeration. These tar balls were physically removed from the system and their mass
determined. Following removal, PAH concentrations and mass within all reactors were
recalculated to assure that physical removal was not accounted for as biological/chemical
removal.
Second, foaming of the reactor contents was a routine occurrence. Rl and R3 were fitted
with mechanical foam breakers but these were inadequate to contain the foam. Antifoam 289
(Sigma, St. Louis, Missouri) was used as required to contain the foam inside the reactors.
The third problem was clogging of the airlifts. This problem usually appeared due to
disruption of the air flow to the reactors and unusually high settling due to decreased clay
content of the soil. Periodic purging and/or dismantling of the air lifts were necessary to
restore air flow.
Table 4-1 summarizes significant upsets and changes which effected reactor operations.
4.1.2 Physical A nalyses
Results of physical analyses are presented below
4.1.2.1 pH
The pH of Rl and R3 were maintained at 7.0 (Figure 4-1) through the addition of NaOH on
an as needed basis. Rl required minor periodic adjustments in pH through the addition of 1
N NaOH. The material transferred from R2 into R3 required pH adjustment with every
transfer using 10 N NaOH. The Fenton's reagent dictated the pH in R2. When 1.5 M
14
-------
ferrous sulfate was used, the pH ranged from 2.0 to 2.5. When 8.8 mM ferrous sulfate was
used, the pH reached a new steady state at 3.5 to 4.0.
4.1.2.2 Dissolved Oxygen
For the first 3 months of operation, the dissolved oxygen concentration fluctuated between 0
and 10 milligrams per liter (mg/L) (Figure 4-2). Due to foaming within the reactors, it was
not always possible to obtain a "pure" liquid sample for dissolved oxygen analysis. The last 3
months of operation showed a steady dissolved oxygen in Rl ranging from 2.0 to 7.0 mg/L.
The dissolved oxygen in R3 ranged from 4 .0 to 9.0 mg/L over the same period.
4.1.2.3 Reactor Solids
The reactors were initially charged at 40 percent solids using the highly contaminated site soil.
This loading was necessary for the airlifts to operate properly and keep the solids in suspension
due to high sand content. Due to increased foaming problems, the impacted TS content was
reduced to 20 percent and Celatom diatomaceous earth (DE) was used to increase the TS
concentration to 35 percent. This switch occurred on December 13, 1995. Use of DE was
discontinued on December 29, 1995 and locally obtained clean clay was used to reduce the
influent organic content. The solids loading for the final 3 months of operation was 30
percent contaminated soil plus 10 percent clay for a 40 percent total solids loading.
Figure 4-3 shows the TS for each reactor. For the final 3 months of operation, the TS in Rl
was steady at 30 to 35 percent. R2 showed a decrease in TS relative to Rl. This decrease was
due to dilution of the reactor contents with Fenton's reagent. R2 and R3 showed a steady
decline in TS over time. On January 4, 1995, the TS was 29 percent. On April 19, 1995, the
TS in R3 reached a low of 9 percent.
Volatile solids for each reactor are shown in Figure 4-4. Rl VS remained steady for the last 2
months of operation ranging from 8 to 9 percent. R2 displayed wide fluctuations in VS
ranging from 5 to 14 percent. R3 showed an increase in VS with values ranging from 10 to 13
percent over the last 2 months of operation. The increase in VS may represent increased
biological growth possibly due to the metabolism of recalcitrant hydrocarbons oxidized in R2.
The VS/TS ratio (Figure 4-5) remained steady for Rl ranging from 0.2 to 0.3 while R3
showed a steadily increasing VS/TS ratio during the final 2 months of operation. R3 values
15
-------
ranged from 0.8 during early March to 1.3 on April 19, 1995. R2 VS/TS values fluctuated,
but centered around 0.4 to 0.5.
Solids distribution for Rl and R3 is shown in Figures 4-6 and 4-7, respectively. A uniform
solids suspension was dependent on the airlift operating properly, maintaining an adequate
solids loading within the reactor, and maintaining the proper volume. Stratification was a
minor problem in Rl (Figure 4-6) but was a more persistent problem in R3 (Figure 4-7). The
DE promoted stratification by binding to the clay present in the contaminated soil. This did
not pose a significant problem in Rl due to the high organics present, however, it may have
been a problem in R3 as seen in the solids distribution during the months of December, 1994
and January, 1995.
4.1.2.4 Nutrients
Ammonia was added initially once per week for the first 2 months followed by 3 times per
week for the remainder of the study. Ammonia addition to R3 was discontinued after 3
months due to carry over from Rl and R2. Ammonia values ranged from 0 to 240 mg/L over
the course of the study (Figure 4-8).
The large increase in ammonia concentrations resulted from increased addition rather than
reduced utilization. During the mid project review meeting held in December it was decided
that a possible nitrogen deficiency may have resulted in system foaming. As a result, the
nitrogen addition rate to the system was increased.
Phosphate was initially added for the first month of operation at which time it was
discontinued. The phosphate concentration in the contaminated soil was significant and
ranged from 100 to 200 mg/L in each reactor during the course of the investigation (Figure 4-
9).
4.1.2.5 Microbial Enumerations
The total heterotrophic bacterial populations in Rl ranged from 1.4 x 10' colony forming units
per mL of slurry (cfu/mL) to 4.0 x 1$ cfu/mL slurry over the course of the study (Figure 4-
10). Bacterial populations in R3 were similar to Rl except during the last 2 months of the
study. Total populations reached 2.2 x 109 cfu/mL slurry on March 2, 1995 and ranged from
3.0 to 5.0 x 10s cfu/mL slurry for the remainder of the study. This increase coincided with an
increase in the HRT set points.
-------
The naphthalene-degrading bacterial populations were 3.6 x 105 cfu/mL slurry at the time the
reactors were charged. This population dropped below the method detection limit (2.0 x 105
cfu/mL) after onset of continuous reactor operation. Naphthalene-degrading bacteria were
enumerated by colony hybridization in the April 13, 1995 samples. The influent feed
material, Rl, and R3 contained 1.5 xlO4, 1.1 x 106, and 1.1 x 108NAH positive cfu/mL
slurry. The large increase in NAH positive cells in R3 was surprising since there was no
detectable naphthalene in R3.
4.1.2.6 TotalRecovemblePetroleum Hydrocarbons
Total recoverable petroleum hydrocarbons (TRPH) were measured in March 16, 1995
samples. The data is summarized in Table 4-2. R2 had no apparent effect on TRPH while R3
showed a 86 percent reduction. Even though R2 had the same TRPH concentration as Rl, this
does not imply that the TRPH is in the same form as in Rl. ERA Method 418.1 does not
discriminate differences in hydrocarbon chain length or possible side chain modifications (such
as hydroxylations). Therefore, the Fenton's reagent could have broken down longer chain
hydrocarbons into shorter chains which were more susceptible to bacterial degradation in R3.
4.1.2.7 Total Organic Carbon Analysis
Solid and aqueous phase TOC concentrations are shown in Figures 4-11 and 4-12,
respectively. The average influent solid phase total carbon (TC) concentration was 19,000
mg/kg. On March 16, 1995, influent solid phase TC was 17,500 mg/kg. After treatment,
there was a 55 percent reduction in TC. R2 showed a 48 percent reduction relative to Rl.
Although this reduction was not consistent with the TRPH removals, there may have been
shorter chained organic compounds not measured in the TRPH analyses which were
mineralized in R2.
For the 4-week period from March 16 through April 19, 1995, the average solid phase TC for
Rl, R2, and R3 was 13,700; 7,900; and 6,400 mg/kg, respectively. In comparison, for the
first 6 months of the study, the average solid phase TC for Rl, R2, and R3 was 14,500;
11,900; and 10,000 mg/kg, respectively.
The average aqueous phase TOC for the 4-week period from March 16 through April 19, 1995
in Rl, R2, and R3 was 570; 1,680; and 740 mg/L, respectively. In comparison, for the first 6
months of the study, the average aqueous phase TOC in Rl, R2, and R3, was 690; 1,680; and
-------
340 mg/L, respectively. By observation of Figure 4-12, the production of aqueous phase TOC
was erratic in R2 while Rl was consistent over the 7-month period.
4.1.2.8 PAH and Mass Balance
Physical removal of PAHs during treatment were corrected during the determination of mass
removal. All tar ball removal was corrected through the recalculation of initial PAH
concentrations and mass in all reactors following physical removal. Significant wall losses
were not recognized following the dismantling of the reactors due to operation at all the
reactor's full working volume. Dilution with the addition of Fenton's reagent was corrected
by using real-time TS concentration data from each reactor to determine PAH mass.
Additionally the difference in sampling location for Rl and R3 as compared to R2 did not
create a sampling bias in PAH results. All reactors were tested for adequate mixing and PAH
mass determinations were corrected for the TS concentration of the sample. Reduced
performance in R3 during the final stages of the testing program were due to the increased
performance of Rl and R2 and reduced influent carbon concentrations in the reactor.
It should also be noted that PAH percent removal perturbations were due to operational
conditions rather than a decrease in PAH recovery efficiencies. See Section 4.2 for a detailed
discussion.
Slurry samples from each reactor were dried and analyzed by modified EPA method 8310.
This method accounted for any recoverable PAH in the soil and aqueous phases. The air
phase was monitored once per month and no substantial volatilization of PAH was observed in
Rl.
The bioslurry reactor system demonstrated 95 and 84 percent removal of PAH and CPAH,
respectively, as of April 19, 1995. Figures 4-13 through 4-16 illustrate PAH and CPAH
reductions in Rl, R2, R3, and overall. Overall, the biologically active reactors (Rl and R3)
illustrated a decreasing effectiveness in PAH transformation as a function of compound
molecular weight. This is indicated in Figures 4-17 and 4-18 which present the concentrations
of fluorene and B(a)P throughout the system.
Prior to operational changes initiated in March (following 5 months of treatment), Rl
demonstrated 62 percent transformation of PAH, with approximately 28 percent transformation
18
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of CPAH. R2 demonstrated comparable destruction of PAH and CPAH (approximately 30
percent), as expected during chemical oxidation. R3 CPAH and PAH transformations
averaged approximately 14 and 33 percent, respectively. The total system PAH and CPAH
transformations averaged 85 and 65 percent, respectively. All PAH and CPAH removal
efficiency data are presented in Tables 4-3 and 4-4, respectively. No significant volatilization
of PAH was evident in Rl.
Following operational changes initiated in March, overall PAH and CPAH transformation
rates increased up to 95 and 84 percent. Rl demonstrated 87 percent transformation of PAH,
with 65 percent transformation of CPAH. R2 demonstrated comparable destruction of PAH
and CPAH (greater than 45 percent), as expected during chemical oxidation. R3 CPAH and
PAH transformations were decreased averaging -31.6 and -26 (0) percent, respectively. The
total system PAH and CPAH transformations increased to 91 and 75 percent, respectively.
All PAH and CPAH mass removal efficiency data are presented in Tables 4-5 and 4-6,
respectively.
During optimal operation, the influent PAH concentration was decreased from 6,210 mg/kg to
325 mg/kg. Influent CPAH concentrations were decreased from 422 mg/kg to 65 mg/kg.
CPAH and PAH concentrations throughout the system are presented in Figures 4-19 and 4-20,
respectively. All PAH data is presented in Appendix C.
Mass balance data is presented in Appendix C. All mass removals were calculated per the
specifications of the approved Test Plan Table 4-3. This table has been included in Appendix
C for reference. PAH and CPAH mass balance data has been summarized in Tables 4-5 and
4-6. Over the 7-month operational period, Rl demonstrated the highest transformation of
PAH, averaging 10.6 grams/day (g/day). Following March 2, 1995, the PAH mass removal
in Rl was increased to 7.7 g/day.
R2 and R3 demonstrated 3.2 and 3.2 g/day PAH removal, respectively, during the entire
operational period (Table 4-5). R2 and R3 PAH removal efficiencies also decreased following
March 2, 1995. R2 and R3 demonstrated 1.17 and 0.48 g/day PAH removal, respectively,
from March 2 to Apnl 19, 1995.
CPAH mass removal is summarized in Table 4-6. The same trends in PAH removal were also
evident when analyzing the CPAH removal data. CPAH mass removal in Rl, R2, and R3
19
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during the total operational period averaged 0.93,0.44, and 0.24 g/day, respectively. Rl
performance following March 2, 1995 indicated an average CPAH removal of 0.63 R2 and R3
CPAH removal was decreased following March 2, 1995 to an average of 0.22 and 0.08 g/day,
respectively.
Since February 2, 1995, R3 showed little to no transformation of PAH. In fact, there was an
increase in PAH observed in the slurry. This observation was preceded by the change in
addition of Fenton's reagent to R2. It is also known (at least for March 16, 1995 samples) that
62 percent of the total TRPH was removed by R3. It is hypothesized that if R.2 was breaking
down the larger chain aliphatic hydrocarbons to smaller chain aliphatic hydrocarbons and these
hydrocarbons were subsequently metabolized in R3, then PAH could be released from these
aliphatic hydrocarbons. The tar phase, not the soil, is considered to be the dominant phase in
manufactured gas plant sites and creosote-contaminated sites (Lane and Loehr, 1993).
Therefore, all PAH will be found sorbed to the tar. If the tar phase breaks down, the sorbed
PAH will be released. The build-up in R3 may reflect PAH being released from the tar phase
and accumulating in the reactor. Whether PAHs were being metabolized in R3 is not clear
although 14C-mineralization data discussed in Section 4.1.2.9 suggests that at least the 2- and
3-ring PAHs were metabolized.
4.1.2.9 l4C-Mineralization Assays
First-order mineralization rates were determined by calculating the available (soluble) PAH for
degradation and calculating specific activities for each 14C-PAH in each soil. To estimate the
distribution of each PAH in the aqueous phase, the tar-water partition coefficient (Ktw) was
estimated (Lane and Loehr 1992). The tar phase, rather than the particulate phase, is the
dominant force in determining partition in these soils due to the high organic carbon content.
Lane and Loehr (1992), using MGP soils in their experimental design, determined that a
relationship existed between the octanol-water partition coefficient (KoW) and K^.
log Ktw = 1.13 log Kow + 0.33 (Equation 1)
The log Rvalues for naphthalene, phenanthrene and anthracene were 3.37, 4.46, and 4.45,
respectively (Sims and Overcash 1983). Specific activities of PAH were determined by
dividing the /iCi of specific radiolabeled PAH added to the slurry by the calculated number of
jtmoles of specific PAH present in the aqueous phase. Mineralization rates were determined
20
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by plotting the number of jimoles of 14CC>2 produced vs time. The slope of the initial linear
portion (r2 * 0.95) of each curve was used as an estimate of the mineralization rate.
4.1.2.10 Toxicity Screening
To estimate the reduction in toxicity of the aqueous phase, an assay using the protozoan
Tetrahymena was performed. Table 4-7 summarizes the results with an estimate of the lethal
dose-50 (LDso) for the aqueous phases of the influent feed, Rl, and R3. Rl and R3 had
at 1: 100 dilution of the aqueous phase in comparison to an LDso at the 1:40 dilution for the
aqueous phase of the influent feed. No definitive conclusions should be drawn from this
assay. While there was a substantial reduction in PAH and TRPH, pentachlorophenol (PCP)
and arsenic were also present in this soil. Although PCP was not measured directly, past
experience has shown that there is little to no reduction in this type of treatment system.
After passage through R2, Fenton's reagent should be in its most oxidized form (As+5).
4.2 Quality Assurance/Quality Control
GC/MS analyses confirmed the correct identification of all PAH peaks measured using the
HPLC. In addition, an approximate 20 percent variance comparing the GC/MS and HPLC
analyses was noted. All other analytical measurements were made within the specifications
defined in the approved quality assurance project plan (QAPP) unless specified in Table 3-6.
With regard to accuracy criteria for matrix spikes using modified Method 8310, the stipulated
acceptance criteria provided in Table 6-1 of the QAPP was a minimum recovery of 80 percent
for each of the 16 compounds. The corrective action for those matrix spikes which did not
meet criteria was reanalysis of the sample extract. Upon analysis and reanalysis, where
necessary, 95 percent of the matrix spike recoveries met this criteria, and nonconformances
were generated for any outlying data points.
4.3 Costs/Schedule for Performing the Treatability Study
The overall budget for project execution was $209,751, All project activities were conducted
between September 1994 and October 1995.
4.4 Key Contacts
The EPA Project Manager, Brunilida Davila, can be contacted at (513-569-7849). IT contacts
including the project manager (Kandi Brown) and principal investigator (John Sanseverino)
who can be reached at 909-799-6869 and 615-690-3211 respectively.
21
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5.0 References
Brown, K.L. and J. Sanseverino, 1993, "Factors Affecting PAH Biodegradation in
Liquid/Solids Contact Reactors, " Proceedings of the 86th Annual Meeting and Exhibition of
the Air and Waste Management Association, Denver, Colorado.
Davila, B. F. Kawahara, and J. Ireland, 1994, "Combining Biodegradation and Fenton's
Reagent to Treat Creosote Contaminated Soil," In Press.
Elizardo, K., 1991, "Fighting Pollution with Hydrogen Peroxide," Pollution Engineering, pp.
106-109.
Gauger, W.K., V.J. Srivastava, T.D. Hayes, and D.G. Lrnz, 1990, "Enhanced
Biodegradation of Polyaromatic Hydrocarbons in Manufactured Gas Plant Wastes,"
Environmental Biotechnology.
IT Corporation, 1994, SITE Emerging Technologies Program E06 - Bioslurry Treatment Test
Plan, July.
Lane W.F. and Loehr R.C., 1992, "Estimating the Equilibrium Aqueous Concentrations of
Polynuclear Aromatic Hydrocarbons in Complex Mixtures", Environmental Science and
Technology, 26:983-990.
Ogunseitan, O.A., I.L. Delgado, Y.-L. Tsai, and B.H. Olson, 1991, "Effect of 2-
Hydroxybenzoate on the Maintenance of Naphthalene-Degrading Pseudomonads in Seeded and
Unseeded Soil", Applied and Environmental Microbiology, 57:2873-2879.
Sanseverino J, B.M. Applegate, J.M.H. King, and G.S. Sayler, 1993, "Plasmid-mediated
Mineralization of Naphthalene, Phenanthrene, and Anthracene," Applied and Environmental
Microbiology, 59: 1931-1937.
Sayler, G.S., M.S. Shields, E.T. Tedford, A. Breen, S.W. Hooper, K.M. Srrotkrn, and J.W.
Davis, 1985, "Application of DNA-DNA Colony Hybridization to the Detection of Catabohc
22
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Genotypes in Environmental Samples, " Applied and Environmental Microbiology, 49: 1295-1303.
Sims, R.C. andM.R. Overcash, 1983, "Fate of Polynuclear Aromatic Hydrocarbons (PNAs)
in Soil-plant Systems," Residue Review, 88: 1-68.
U.S. Environmental Protection Agency, 1990, "Slurry Biodegradation, " EPA/540/290/016
23
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Table 1-1
Physical/Chemical Properties of CPAH Constituents
IT Project No. 408250
Carcinogenic Polynuclear
Aromatic Hydrocarbons
benz(a)anthracene
benzo(a)pyrene
benzo(b)fluoranthene
benzo(k)fluoranthene
chrysene
dibenz(a,h)anthracene
benzo(g,h,i)perylene
indeno(l ,2,3-c,d)pyrene
Kow
Cog)
5.61
6.04
6.57
6.84
5.61
5.97
7.23
7.66
Aqueous
Solubility
(MR/0
14
3.8
1.2
0.55
2
.50
0.26
62
V.P at
20°C
(torr)
S.OxlO'9
S.OxlO'7
S.OxlO'7
S.OxlO'7
6.3xlO'7
l.OxlO40
l.OxlO40
l.OxlO40
Sims, R. C. and M, R. Overcash "Fate of Polynuclear
Aromatic Compounds (PNAs) in Soil - Plant Systems," Residue Reviews, 1983.
jig/1 - micrograms per liter
V.P. - vapor pressure
24
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Table 1-2
General Influent Feed Characteristics
for Bioslurry Treatment
IT Project No. 408250
Parameter
Target
Oiganics
Solids
Water
Solids Particle Size
Temperature
PH
0.025 -25 percent by weight
10-40 percent by weight
60 - 90 percent by weight
Less than 1/4 inch
15-35°C
4.5 - 8.8
EPA, 1990, "Slurry Biodegradation,' EPA/540/290/016
25
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Table 3-1
Initial Operational Set points
IT Project No. 408250
Parameter
Feed Flow
Hydraulic Retention Time
Temperature
Dissolved Oxygen
oH
Agitation
Working Volume
Ammoniacal Nitrogen
0-phosphate
Sodium Salicvlate
Sodium Succinate
Fenton's Reagent
Addition
Rl
6L/day
10 days
25°C ± 5°C
3 mg/L
7.0 ±05
500 rom
57 L
50 mg/L
10 mg/L
100 me/L
10 mg/L
R2
6L/day
1 day
24°C + 5°C
...
<5.0
250 rpm
6L
---
___
«.«.«.
--_
2L/day
R3
8L/day
7.5 days
25°C ± 5°C
3 mg/L
7,04:0.5
500 rpm
57 L
=»*»
10 mc/L
—«.
-..'
26
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Table 3-2
Sampling and Analytical Schedule for Rl, R2, and R3 Slurry Phase
IT Project No. 408250
Volume
(mL)
Frequency
Volume
(mL)
Frequency
Analysis
PAH
100
1/wk
TOC N&P
100
1/wk
100
1/wk
DO
First 1
1
2/wk
PH
TS/VS
Density
Microbial
Enumerations
Particle
Size
"our Months of Operation
-
daily
20
2/wk
-
daily
10
1/wk
500
1 /month
(Rl only)
Last Two Months of Operation
too
Biweekly
100
biweekly
100
1/wk
1
2/wk
-
daily
20
2/wk
-
daily
10
biweekly
500
1 /month
rat nnlvt
27
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Table 3-3
Summary of Analytical Methods
IT Project No. 408250
Parameter
PAH
PAH
TOC
TC
TS
VS
NH3
o-PO4
Total
Heterotrophs
Naphthalene
Degraders
PH
DO
Particle Size
PAH
Sample Type
soil/water
soil
waler
soil
slurry
slurry
flurry
slurry
slurry
flurry
flurry
flurry
flurry
headspace
Method Number
modified EPA Standard
Method 8310
EPA Method 8270
BAC008
BAC031
Standard Methods
2540G or 2540B
Standard Methods
2540G or 2540B
BAC022
BAC015
BAC009
NA
BAC014
BAC021
ASTM Method D422
modified NIOSH 5506
Method Title
Polynuclear Aromatic Hydrocarbons
Polynuclear Aromatic Hydrocarbons
Carbon Analysis Using the Dohrmann Total
Carbon Analyzer
Total Carbon Analysis
Total, Fixed, and Volatile Solids in Solid and
Semisolid Samples or Total Solidr Dried at
103-105°C, respectively
Total, Fixed, and Volatile Solidr in Solid and
Semisolid Samples or Total Solids Dried at
103-105°C, respectively
Electronic Ammonia Analysis
Phosphate Analysis
Microbial Enumeration Analysis
Application of DNA-DNA Colony
Hybridization to Ihe Detection of Catabolic
Genotypes in Environmental Samples
pH Analysis
Oxygen Analysis
Particle Size Analysis
Polynuclear Aromatic Hydrocarbons
Method Type
HPLC
GC/MS
TOC Analyzer
Persulfate
Oxidation
Drying oven
Drying oven
Ion Probe
Colorimetric
Spread Plate
Colony
Hybridization
Membrane probe
Galvanic cell
Sieve and
Hydrometer
HPLC
Reference
SW-846
SW-846
BAC Proprietary
BAC Proprietary
Standard Method
Standard Method
BAC Proprietary
BAC Proprietary
BAC Proprietary
Saylcr, et al.,
1985
BAC Proprietary
BAC Proprietary
ASTM
Standard
Methods
28
-------
Table 3-4
Summary of Chemicals
IT Project No. 408250
Chemical
Sodium salicylic
Sodium succinic
Grade
Reagent
Source
J.T. Baker, Philhpsburg, N.J.
Reagent Mallinckrodt. Paris, KE.
Ammonium chloride Reagent
Potassium phosphate dibasic 1 Reagent
Hydrogen peroxide (35%)
Sodium Hvdroxide
Ferrous sulfate • 7H20
Sodium sulfate anhydrous
Methylene chloride
PAH standards
| Acetonitrile
Reagent
Reaeent
Reagent
Reagent
Nanograde
Nanograde
Mallinckrodt, Paris, KE.
J.T. Baker, Phillipsburg, NJ.
PB&S Chem. Co., Hendersonville, KE.
J.T. Baker. Philliosbure. NJ.
Sigma Chemical Co., St. Louis, MO.
Mallinckrodt, Paris, Kentucky
Burdick & Jackson, Muskegon, WI.
Supelco, Inc., Belief onte. PA.
Burdick & Jackson, Muskegon, WI.
29
-------
Table 3-5
List of Technical Changes
IT Project No. 408250
CHANGE
NUMBER
TECHNICAL CHANGE
EPA
APPROVED3
1
4
5
6
7
8
9
10
11
12
13
14
15
16
17
BAG completion of initial EIMCO soil
evaluation.
Use of 1.3 M ferrous sulfate and 30 percent
peroxide solution to prepare Fenton's
reagent.
Only reagent grade chemicals used are
nutrients.
Reactor 2 equipment change.
No influent air filtration.
All reactors sampled from middle port.
Calibration of thermocouple by manufacturer.
Change in components of air sampling tram.
Placement of anhydrous sodium sulfate
during sample extraction.
Vessel volume change during initial batch
study.
Correction of QAPP concerning surrogate
additions.
Addition of GC/MS confirmation for PAH
and PCP.
Fenton's reagent addition at 2.0 L/day.
PAH extract exchange and dilution.
Preparation of surrogates through 1-gram vial
additions and analysis.
QA/QC analyses for PAH at 10 percent of ail
samples collected.
Surrogate switched to 1-Fluoronapthaiene.
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
10/7/54
10/7/94
10/7/94
10/7/94
10/7/94
10/7/94
Verbal on 10/7/94
30
-------
LIST OF TECHNICAL CHANGES (CONTINUED)
IT Project No. 408250
CHANGE
NUMBER
18
19
20
21
TECHNICAL CHANGE
Increase reactor and influent feed TS
concentration to 40 percent.
Change in salicylate and succinate
concentration additions.
Discontinued use of the clarifier.
Increased daily TS and density measurements
EPA
APPROVEDa
Verbal on
Verbal on
Verbal on
Verbal on
10/7/94
10/7/94
10/7/94
10/7/94
22
23
24
25
26
27
28
29
30
and reduced DO measurements during period
of varying reactor solids distribution.
Rerun samples when matrix is out of ±_ 20
percent
Recalculate MDLs
Changes in the analytical schedule for
TS/VS, DO, aqueous PAH, nitrogen, gene
probe, and pH
Increased impeller speed to control DO
Adjust volume of Rl
Decrease influent organic loading by one-half
through the mixing of clean clay
Reduction in Rl and R3 HRT from 10 to 20
days
Reduce feed introduction to each reactor from
twice/day to once/day
Discontinued addition of salicylate and
succinate
Verbal on 10/7/94
Verbal on 10/7/94
12/20/94
12/20/94
12/20/94
12/20/94
12/24/95
12/24/95
4/6/95
a Date indicates date of EPA correspondence documenting technical variance approval.
31
-------
Table 3-6
List of TechnicalNonconformances
IT Project No. 408250
NONCONFORMANCE
NO.
NONCONFORMANCE
DATE
REPORTED
1
2
3
4
5
6
7
Influent feed added as 2, 3L transfers
instead of 3, 2L transfers.
Bottle study recoveries
Influent T0 MS and MSD
SRM acceptance criteria
PAH not identified during aqueous
analyses
Method calibration for chrysene 10/14/94
Missing check standards
10/19/94
11/8/94
11/8/94
12/12/94
12/12/94
12/12/94
12/12/94
32
-------
Table 4-1
Summary of Reactor Upsets and Operational Modifications
IT Project No. 408250
„ - * Date ~%i
29 November, 1994
5 December, 1994
13 December, 1994
29 December, 1994
HJanuary,1995
24 January, 1995
27 February, 1995
22 March, 1995
TT . IK r VI* :' • -WWXvM-K-fftJK-W-S
UpsetsMcohcations
Rl airlifts clogged
Rl dismantled to remove clogs from airlifts; tar balls
responsible for clog
In order to reduce organic loading in Rl, solids were
reduced to 20% and 15% diatomaceous earth was
added
Discontinued use of diatomaceous earth as a solid
supplement; caused air lifts to clog
Supplemented solids with a local, clean clay
Switched to 8.8 mM FeS04.7H20
Increased HRT to 20 days for Rl , 2 days for R2, and
20 days for R3
Discontinued salicylate and succinate addition to Rl
33
-------
Table 4-2
Summary of Total Recoverable Petroleum Hydrocarbons (TRPH), PAH, and CPAH for
March 16 Samples
IT Project No. 408250
Sample-"" '\ ,
Influent Feed
Reactor 1
Reactor 2
Reactor 3
;?>5:,,TKPH
27,000
14,000 (48%)1
14,000 (48%)
3,700(86 %)
PAH
5860
710 (88%)
430 (93%)
560 (90%)
^ICPABu
430
130 (70%)
70 (84%)
110 (74%)
Number in parenthesis represents the percent reduction relative to the influent feed TRPH
concentration.
34
-------
Table 4-3
PAH Removal Efficiencies (Percent)
IT Project No. 408250
Date
10/10
10/19
10/26
11/2
i 11/9
11/16
11/22
Reactor 1
85
65
29
55.5
59.2
61.7
55.3
Reactor 2
' -180
, 58.2
45.2
37.7
26.7
41
42.9
12/2 30.4 62
12/8 56.9
12/15 68.6
12/30 , 71.6
1/5
1/26
2/2
2/16
3/2
3/9
3/16
3/30
4/13
4/19
Total Operational
Period Average
Average Prior to
3/2
Average Following
3/2
63.6
69.3
71.6
79.8
85.9
87.9
86
85.8
88.6
88.3
69. 17 ±17.9
6 1.5 ±15.45
87.08 ± 1.32
44.1
~72
51.1
64
44.8
38
22.3
33
39.1
37
65.9
37
55.4
32.7 ±50.3
28 ± 58.95
44.6 ± 13.04
1
Reactor 3 I Overall
36.1 72.6
67
59.3
42
44.8
59.6
69.5
28.9
5.7
31.7
6.5
44.8
12.1
1.2
-19
-82
-31
10.3
-66
12.9
-1.1
15.87 ± 40.57
32.68 ±26.56
-26.2 ± 40.53
95.2
84.2
83.9
83.5
90.9
92.2
81
77.2
83.3
87
92.8
85.1
82.6
81.3
82.8
90.4
92
91.9
93.8
94.7
86.59 ±6. 17
84.85 ± 6.05
90.93± 4.26
± Indicates standard deviation.
35
-------
Table 4-4
CPAH Removal Efficiencies (Percent)
IT Project No. 408250
Date
10/10
10/19
10/26
11/2
11/9
11/16
11/22
12/2
12/8
12/15
12/30
1/5
1/26
2/2
2/16
3/2
1 3/9
3/16
3/30
4/13
1 4/19
Total Operational
Period Average
Average Prior to
. 3/2
Average Following
I1 3/2
Reactor 1
60
20.2
-16
2.5
-1.1
9.3
30.4
10.4
30.9
32.7
43.5
38
30.7
37.6
44.4
66.4
71
59.9
60.9
69
64.8
36.83 ±25. 18
27.99 ±22.11
65.33 ± 4.39
Reactor 2
-58.2
56.9
48.5
40.5
23.9
50
33.4
51
48.3
15
43.3
59
35.3
40
23.3
34
46.3
44
69
44
55.9
38.26 ±25.52
34.01 ±27.51
48.87 ±12.08
Reactor 3
40.9
49
33.9
26
44
44.5
51.2
26.3
-7.1
1 36.1
!
12.9
-26
14.4
-8.4
-5
-105
-63
2.5
-93
-1.2
-3.1
3.3 ±44. 19
14.23 ± 39.51
-31.56 ±43.75
Overall
62.2
84.3
60.5
56.9
56.9
74.7
77.4
67.7
61.8
63.4
72.1
67.7
61.6
59.4
55.2
54.2
74.7
7S \
76.6
82.6
84
68.19 ± 9.92
65.45 ±8.42
75.02 ±10.79
-1- Indicates standard deviation.
36
-------
Table 4-5
PAH Mass Removals (Grams/Day)
IT Project No. 408250
Date
10/10
10/19
10/26
11/2
11/9
11/16
11/22
12/2
12/8
12/15
12/30
1/5
1/26
2/2
2/16
3/2
3/9
3/16
3/30
4/13
4/19
Total Operational
Period Average
Average Prior to
Average Following
3/2
1 - \
Reactor 1 | Reactor 2 , Reactor 3
j
35.5 0
0 1.78
0 i 3.68
15.6 4.00
19.7 I 4.90
7.13 2.78
2.65 5.35
7.86 4.14
9.57 11.23
12.67 4.30
13.82 4.96
17.50
11.49
0
0
0
5.95
4.24
0
1.43
6.75
10.55
|
12.48 1.26 5.61
12.52
13.02
14.01
7.62
7.70
7.85
7.54
7.90
7.71
10.61 ±7.5
11.51 ±8.45
7.74 ±0.14
3.15
4.06
3.32
2^7
1.26*
0
1.75
1.47
1.38
3.21 ±2.43
3.93 ± 2.49
1.17 ±0.68
0
0
0.90
1.10
0
0.29
0.58
0.47
1.06
3.23 ± 4.83
4.29 ±5.39
0.48 ±0.39
± Indicates standard deviation.
37
-------
Table 4-6
CPAH Mass Removal (Grams/Day)
IT Project No. 408250
Date
10/10
10/19
10/26
11/2
11/9
11/16
Reactor 1
0.44
0
0
0.65
1.61
0.18
11/22 0
12/2 1 0
12/8 2.33
12/15
12/30
J
1/5
1/26
]
2/2
2/16
3/2
3/9
3/16
3/30
0.24
4.02
0.50
0.32
1.90
0.95
3.33
1.06
0
0.44
^
4/13 . 1.31
4/19
Total Operational
Period Average
Average Prior to
3/2
Average Following
3/2
0.33
0.93 ± 1.13
0.88 ±1.14
0.63± 0.54
Reactor 2
0
0.31
0.52
0.47
0.76
0.59
0.73
0.43
1.00
0.24
0.76
0.19
0.34
0.69
0.49
0.55
0.23
0
0.34
0.29
0.25
0.44 ± 0.26
0.50 ± 0.26
0.22 ±0.13
Reactor 3
0.29
0.56
0
0
0
0.97
0.44
0.28
0.13
0
1.82
0
0
0.12
0.06
0.01
0
0.08
0.07
0.10
0.16
0.24 ± 0.43
0.29 ± 0.49
0.08 ± 0.06
•S. Indicates standard deviation.
38
-------
Table 4-7
16-Hour Toxicity Determination Using Tetrahymena
IT Project No. 408250
?$amp le
Influent Feed
Reactor 1
Reactor 3
Sample Dilution
1:10
1:20
1:40
1:100
1:40
1:100
1:200
1:40
1:100
1:200
Percent Mortality
100
90
50
NOEC1
100
50
NOEC
100
50
NOEC
-No observable effect concentration
39
-------
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IKTEHHAT10HAL
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40
-------
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41
-------
9
8
7
6
FIGURE 41
REACTOR pH DATA
4 -
3
2
1
i
0
i .•
10
20 30
Days of Operation
40
50
• Reactor 1
• Reactor 2
^ Reactor 3
42
-------
FIGURE 4-2
DISSOLVED OXYGEN DATA
50
40 -
I "30
a
"C
O)
ba
>s
T3
Ol
£ 10 -
0 -
0
10 5 20 25
Days of Operation
30 35
40
Reactor 1
Reactor 2
Reactor 3
43
-------
FIGURE 4-3
REACTOR TOTAL SOLIDS
60 -
50
CO
140
C/D
I
-------
FIGURE 4-4
REACTOR VOLATILE SOLIDS
30
20
~o
CO
1
0)
Q.
10
0
4 Oct 1 Nov
1
4 Jan 19 Jan 2 Feb
—•— 2
3
-------
FIGURE 4-5
RATIO OF VOLATILE SOLIDS
TO TOTAL SOLIDS
0.1
0.01
40ct
1 Nov
2 Dec
Reactor 1
4 Jan 2 Feb
Sampling Dates
—•— Reactor 2
46
19 Apr
Reactor 3
-------
70 -T-
4-6
IN 1
80
50
^**
-------
70
60
50
c
m
I40
"••^
at
to 30
ts
20
10
FIGURE 4-7
SOLIDS DISTRIBUTION IN REACTOR 3
10Oct
2Nov
Sample Port 1
8 Dec 4 Jan 2 Feb
Sampling Date
•• Sample Port 2
2 Mar 18 Apr
Sample Port 3
48
-------
0
FIGURE 4-8
REACTOR AMMONIA CONCENTRATION
Reactor 1
i i i i
30 Dec 19 Jan
Sampling Date
Reactor 2
i i i
8Feb
i i i
2 Mar
i i r
30 Mar 19 Apr
Reactor 3
49
-------
500
400
30°
.§3
li 200
c
o
FIGURE 4-9
REACTOR PHOSPHATE CONCENTRATION
CO
E?
o
c
100
0
6Oct
2Nov 22Nov
Reactor 1
15-Dec 19 Jan 8 Feb 2 Marie Mar
Sampling Date
19 Apr
Reactor 2
50
• Reactor 3
-------
FIGURE 4-10
REACTOR TOTAL HETEROTROPHIC BACTERIAL POPULATIONS
3Oct
Reactor 1
5 Jan 2 Feb
Sampling Dates
—•— Reactor 2
51
2 Mar
30 Mar 19 Apr
Reactor 3
-------
FIGURE 4-11
SOLID PHASE TOTAL CARBON
25000
20000
15000
10000
5000
0
13
O
o
o
2
CM
Reactor 1
a
OJ
O
CM
c
m
~3
to
xa
ID
y_
CM
Sampling Date
(0
CM
Reactor 2
52
Reactor 3
CO
o
CO
Q,
<
o>
Influent feed
-------
FIGURE 4-12
TOTAL
^ H
'£
CL
a.
c
s
"t.
18
u
1500
o
tf)
CO
f
to
o
03
3
O"
^^ 500
0
t3
O
o
o
Z
CM
O
0>
Q-
©
U.
CO
10
Q.
<
O>
Sampling
Reactor
2
53
-------
Figure 4-13
% REDUCTION - REACTOR 1
SAMPLE DATE
- PAH
CPAH
CPAH GOAL
54
-------
Figure 4-14
% REDUCTION - REACTOR 2
CM
_ — _f_ — ,
-CJ
tt
u.
to
m
— — i — —
*«»
so
2
*
CD
u.
m
5
I
»*-— —t— —
*«,
2
o
a
*
-— i
Q.
cn
en
SAMPLE DATE
PAH
CPAH
CPAH GOAL
55
-------
Figure 4-15
% - 3
PAH
56
-------
Figure 4-16
% REDUCTION - OVERALL
z
o
p
o
Q
UJ
CC
100 -I
90
80
70 !
60 l~
50
40
30
20
o -
o
O
6
o
O
o
(O
CN
O
2
CN
o
z
o
2
(O
o
Z
CN
CM
PAH
T ' — 1 '
tl O
0) at
3 0
N CO
_j__
O
«
Q
i
T^
O
O
6
SAMPLE
— — t— — i — -
c c
ra ro
-, -j
to
GOAL
— — f-
10
2
ci
TO
2
6
ex
<
CO
a.
57
-------
Figure 4-17
FLOURENE CONCENTRATIONS
u.
DATE
DR3
• R2
• RI
S3 INFLUENT
58
-------
FIgyre 4-18
DATI
DR3
BR2
• «,:
E
-------
Figure 4-19
PAH CONCENTRATIONS
a
jj
"ra
JE
2
DATE
DR3
Bn2
• R1
SI INFLUENT
60
-------
Figure 4-20
CPAH CONCENTRATIONS
DATE
S; « m
-$lisStn
en ^i tO ^- OJ J»l
* * ri r- o ^? P
^ 12 52 o>
«^5
R1
R3
DR3
• R2
• RI
d INFLUENT
61
------- |