EPA-600/2-78-020
March 1978
Environmental Protection Technology Series
                     PARTIAL CHARACTERIZATION  OF
                          CHLORINATED ORGANICS IN
                SUPERCHLORINATED SEPTAGES  AND
                                       MIXED  SLUDGES
                                Municipal Environmental Research Laboratory
                                     Office of Research and Development
                                    U.S. Environmental Protection Agency
                                            Cincinnati, Ohio 45268

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                 RESEARCH REPORTING SERIES

 Research reports of the Office of Research and Development, U.S. Environmental
 Protection Agency, have been grouped into nine series. These nine broad cate-
 gories were established to facilitate further development and application of en-
 vironmental technology. Elimination  of traditional grouping  was  consciously
 planned to foster technology transfer and a maximum interface in related fields.
 The nine series are:

      1.  Environmental Health Effects Research
      2.  Environmental Protection Technology
      3.  Ecological Research
      4.  Environmental Monitoring
      5.  Socioeconomic  Environmental  Studies
      6. Scientific and Technical Assessment Reports (STAR)
      7. Interagency Energy-Environment Research and Development
      8. "Special" Reports
      9. Miscellaneous Reports

 This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
 NOLOGY series. This series describes research performed to develop and dem-
 onstrate instrumentation, equipment, and methodology to  repair or prevent en-
 vironmental degradation from point and non-point sources of pollution. This work
 provides the new or improved technology required for the control and treatment
 of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                         EPA-600/2-78-020
                                         March 1978
PARTIAL CHARACTERIZATION OF CHLORINATED ORGANICS
 IN SUPERCHLORINATED SEPTAGES AND MIXED SLUDGES
                       by

                 Robert H. Wise
               Thomas A. Press!ey
                Barry M. Austern
          Wastewater Research Division
   Municipal Environmental Research Laboratory
             Cincinnati, Ohio  45268
   MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
       OFFICE OF RESEARCH AND DEVELOPMENT
      U.S. ENVIRONMENTAL PROTECTION AGENCY
             CINCINNATI, OHIO  45268

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                                  DISCLAIMER
     This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publication.
Mention of trade names or commercial products does not constitute endorsement
or recommendation for use.
                                     ii

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                                  FOREWORD


     The Environmental Protection Agency was created because of increasing
public and government concern about the dangers of pollution to the health
and welfare of the American people.  Noxious air, foul  water, and spoiled
land are tragic testimony to the deterioration of our natural environment.
The complexity of that environment and the interplay between its components
require a concentrated and integrated attack on the problem.

     Research and development is that necessary first step in problem
solution, and it involves defining the problem, measuring its impact, and
searching for solutions.  The Municipal Environmental Research Laboratory
develops new and improved technology and systems for preventing, treating,
and managing wastewater and solid and hazardous waste pollutant discharges
from municipal and community sources, for preserving and treating public
drinking water supplies, and for minimizing the adverse economic, social,
health, and aesthetic effects of pollution.  This publication is one of the
products of that research and is a most vital communications link between  the
researcher and the user community.

     This report describes the results of an analytical study performed on
sludges and septages that were chemically stabilized with the proprietary
Purifax superchlorination process. The superchlorination process is a
technological solution to the problem of sludge bio-instability.  Knowledge
of the end products of the superchlorination provides insight into potential
environmental impacts from the sludges and wastewaters discharged from the
superchlorination process.
                                       Francis T. Mayo
                                       Director
                                       Municipal Environmental
                                         Research Laboratory

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                                    ABSTRACT
      The chlorinated organic  materials  produced  by  applying  the  proprietary
 Purifax process (i.e.,  stabilization  by superchlorination) to  a  septage
 and a mixed primary/secondary sludge  were  identified  in  both the  solid and
 liquid phases  to assess the types,  amounts,  and  distribution of  chlorinated
 organics present.

      Total  organic  chlorine concentrations of the solid  phases were
 determined  by  Schoniger-flask  combustion techniques.  Total organic chlorine
 concentrations  for  concentrated hexane-ether extracts of the liquid phases
 were determined  by  microcoulometric titration.  These same concentrated
 hexane-ether extracts,  as well as the helium-purgeable "volatile" organics
 from the unextracted liquid phases, were then analyzed by gas chromatography/
 mass  spectrometry.  Analyses for total organic carbon, total  dissolved
 solids, and total suspended solids were also performed on the liquid phases
 from  one location to furnish engineering data for assessing both the feasi-
 bility and cost of applying filtration/carbon adsorption as an adjunct to
 Purifax treatment.

     The amounts of organic chlorine found in the Purifaxed solids were
 relatively large (1% by weight); however, the identities of these compounds
 remain unknown because of analytical limitations.  The specific compounds
 identified in the liquid phases do not, by themselves, eliminate super-
 chlorination as an environmentally acceptable process these compounds
 (except in lower concentrations) are the same types as those presently
 found in contaminated surface waters.  Still lacking is information about
 chlorinated gaseous organics released to the atmosphere when Purifaxed
materials are discharged from the reactor.

     This report covers a period from February 1977 to July 1977, and work
was completed as of August 1977.

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                                  CONTENTS
Foreword	    iii
Abstract	     iv
Tables	     vi
Acknowledgments  	    vii

     1.  'Introduction 	      1
     2.   Conclusions  	      2
     3.   Recommendations  	      4
     4.   Experimental Procedures  	      5

               Sample sources, procurement,  and storage  	      5
               Preparation of samples for analysis 	      6
               Determination of percent total  organic chlorine
                 in the solids fractions 	      8
               Determination of total, hexane-ether extractable,
                 non-volatile organic chlorine in the liquid
                 phases (i.e., centrates)  	     10
               Determination of individual,  helium-purgeable,
                 organic compounds in the liquid phases  	     11
               Determination of individual,  hexane-ether
                 extractable, non-volatile organic compounds in
                 the liquid phases	     11
               Determination of additional parameters for
                 Ventura centrates to permit cost calculations
                 for filtration/carbon adsorption as an adjunct
                 to Purifax treatment  	     15
               Discussion	     19

References	     21

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                                   TABLES

Number                                                               Page
   1      Percent Total  Chlorine,  Inorganic Chloride, and
            Organic Chlorine in Air-Dried Solids  	    9
   2      Percent Total  Organic Chlorine Based on Oven-Dried
            Solids 	    9
   3      Percent Total, Hexane-Ether Extractable, Non-Volatile
            Organic Chlorine in the Liquid Phases  	   10
   4      Concentrations of  Helium-Purgeable Organic Compounds
            in  Both Raw Samples  	   12
   5      Concentrations of  Helium-Purgeable Organic Compounds
            in  Both Dechlorinated Samples	   13
   6      Concentrations of  Helium-Purgeable Organic Compounds
            in  Both Chlorinated Samples  	   14
   7      Concentrations of  Hexane-Ether Extractable, Non-Volatile
            Organic Compounds in Both Raw Samples  	   16
   8      Concentrations of  Hexane-Ether Extractable, Non-Volatile
            Organic Compounds in Both Dechlorinated Samples  ....   17
   9      Concentrations of  Hexane-Ether Extractable, Non-Volatile
            Organic Compounds in Both Chlorinated Samples  	   18
  10      Miscellaneous  Engineering Parameters for Ventura
            Centrates	   19
                                   VI

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                               ACKNOWLEDGMENTS
     We gratefully acknowledge the cooperation of Ray Thompson,  Chief,
Surveillance & Analysis Division, Region I  (EPA), and the Plainfield,
Connecticut, Wastewater Treatment Plant personnel, who cooperated to furnish
the samples of mixed primary/secondary sludges.

     We are also indebted to Robert Miele and Kieran Bergin of the Los
Angeles County Sanitation Districts and to Joseph Borgerding of the Ventura
County Regional Sanitation District for furnishing the samples of Ventura
septages used in this study.
                                    VII

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                                  SECTION 1

                                 INTRODUCTION


     The proprietary Purifax process is one  of several  systems  able  to
stabilize and disinfect sludges or septage before land  disposal.   When
required, it also is used to treat anaerobic digester supernatant.
Briefly, the Purifax process is a method developed by BIF (a  unit  of
General Signal Corporation) for superchlorinating concentrated  biological
wastes (for example, sludges and septages) to stabilize the active
solids biologically and thus enhance their dewatering characteristics.
Competing processes for the sludge treatment function include lime
stabilization, heat treatment, wet air oxidation and anaerobic  digestion.
Lime and polymer treatment with air stripping of ammonia is an  alternative
for treatment of digester supernatant.  The Purifax process,  as currently
practiced with chlorine costs of typically $12/ton of treated sludge,  is
competitive with the alternative treatment processes.

     The very high concentrations of chlorine (approximately  700 to  3,000
rog/1) typically employed during the Purifaxing of septages and  sludges
are also capable of producing chlorinated organics.  Limited  analytical
results on chlorinated organics from Purifaxed septages have  already been
reported by Mashni (1).  Before Mashni's work, the engineering  firm  of
Metcalf and Eddy (2) reported their analytical studies  of five  different
waste streams, each taken from a different geographical location.  All  of
those waste streams were being routinely subjected to Purifax treatment at
the time samples were taken.  The specific compounds of interest to  Metcalf
and Eddy were nine chlorinated herbicides (including 2,4-D and  2,4,5-T),
five chlorinated insecticides, and polychlorinated biphenyls.  Rather than
producing any of these objectionable compounds, Purifaxing actually  seemed
to lower their concentrations in most instances.  Since that  time, the
volatile organics analysis method of Bellar and Lichtenberg (3) has  been
reported, and computerized gas chromatograph/mass spectrometer  (GC/MS)
systems have become widely available.  This, in turn, has led to the
discovery that waters and wastewaters often contain a far greater variety
of undesirable chlorinated organic contaminants than those studied by
Metcalf and Eddy, especially when organically contaminated aqueous waste
streams are deliberately chlorinated for disinfection or waste  stabilization.

     The present study of Purifaxed wastes was performed to determine what
types of chlorinated organics are thus produced, how such compounds  are
likely to be discharged (that is, primarily as constituents of  the solids
phase, the liquid phase, or both) and, in each case, how much.   With the
information thus obtained, at least a tentative evaluation of the environmental
risks associated with this process is possible.

                                       1

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                                  SECTION 2

                                 CONCLUSIONS


     Purifaxed samples of one septage and one mixed primary/secondary  sludge
were each separated into solids and liquid phases, then analyzed  for their
organic contents by a variety of different techniques.

     Both solids fractions contained 0.9% to 1.0% total organic chlorine,
based on dry weight.  No attempt was made to identify individual  organic
constituents in these relatively insoluble solids.

     Hexane-ether extracts of both liquid fractions assayed approximately
100 to 200 ug/1 of total organic chlorine, or less than 1% of the total organic
contents of the unextracted liquid phases.  GC/MS analyses, both  of the
hexane-ether extracts and of the helium-purgeable, volatile organics in the
unextracted aqueous phases, yielded slightly higher concentrations of  the
same kinds of organic compounds that are typically present in U.S. water
supplies.  A notable exception, however, was the highly toxic cyanogen
chloride, present in all of the unextracted Purifaxed liquid phases in
concentrations reaching 900 yg/1.

     The centrate from Ventura contained approximately  200 mg/1  of TOC, and
less than 1  mg/1  of this TOC was  identified as specific organic molecules.
The unidentified  TOC is non-volatile and non-extractable and therefore
cannot be analyzed by GC/MS methods.   The amounts of chlorinated  organics
in that TOC are unknown.

     Standards governing maximum  permissible concentrations for the organic
compounds found in the Purifaxed  liquid  phases have not yet been  established
for drinking water supplies and wastewater discharges.   Environmental  impacts
of these molecules depend on site-specific dilution factors.  Thus,
Robert Tardiff of the Health Effects Research Laboratory in Cincinnati
has indicated that the identified  organics in the liquid centrates entering
the environment do not by themselves constitute a basis for environmental
unacceptability of the Purifax process (Personal  communication).

     Finally, the long-term environmental  impact of the chlorinated organics
in the Purifax solids placed in landfills or on soils are unknown. The
organics are likely to include chlorinated proteins and amino acids, humic
acids, carbohydrates, and fats. The toxicity of these  chlorinated materials
is unknown,  but since the chlorinated sludge resists biodegradation, the
chlorinated organics are probably  biocidal (at least to bacteria).

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     The work carried out during this project does not represent a  definitive
study of chlorinated organic material produced by the Purifax treatment of
septages and sludges.  To carry out such a definitive study is beyond the
current state-of-the-art and would require major-scale analytical  resources
(work space, trained manpower, time, and sophisticated analytical  equipment)
for analytical methods development.

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                                  SECTION 3

                               RECOMMENDATIONS


     We recommend that no further direct chemical  analyses of the solid  or
liquid phases be carried out at this time.

     In the Purifax process, a gaseous phase is also discharged from the
reactor, along with the solid and liquid phases.  An analysis of this gas
phase should be carried out.

     Other fruitful approaches to this problem would include:

     a)   Controlled studies of the extent to which chlorinated material
          in Purifaxed solids is leached from landfills over extended
          periods of time.

     b)   Suitable toxicological studies (for example,  animal feeding studies)
          to ascertain the occurrence and severity of any adverse health
          effects resulting from the chlorinated material  in Purifaxed
          liquids entering drinking water supplies.

     c)   Determinations of the extent of environmental  persistence of
          chlorinated organics produced by the Purifax  process; or,
          conversely, the rate at which such chlorinated organics are
          biodegraded in natural environments.

Naturally, approaches a and c would require considerable analytical support
and extensive analytical methods development.

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                                  SECTION 4

                           EXPERIMENTAL PROCEDURES
SAMPLE SOURCES, PROCUREMENT, AND STORAGE

     Original plans called for us to receive two samples from Region I:
a superchlorinated septage, and a superchlorinated mixture of septage plus
primary/secondary sludge.  Because of severe winter snows throughout most
of Region I from January through March of 1977, septage collections in that
Region were brought to a standstill.  When it became apparent that septage
would not be available for an indeterminate period, arrangements were made
for shipment of a Purifaxed primary/secondary sludge (plus a representative
unchlorinated control) from the Plainfield (Connecticut) Wastewater Treatment
Plant with the understanding that our septage samples probably would have to
be obtained elsewhere.

     Purifaxing was carried out on February 9, 1977, using 21.8 kg (48 Ib)
of chlorine to treat 15,369 1 (4,060 gal) of mixed sludges (1,417 mg Cl/1).
Typically, free chlorine residuals for the product leaving this reactor had
averaged 300 mg/1.  The Purifaxed sample was divided into two portions
immediately after collection.  One portion was packaged for shipment with its
free chlorine content intact; this sample was labeled "chlorinated sludge."
The other portion was allowed to stand 4 hours, then it was dechlorinated
with sodium sulfite solution and also packaged for shipment. This sample was
labeled "dechlorinated sludge."  Because both Purifaxed samples had been
biologically stabilized, they could be handled without any further need for
sample preservation.  The required control sample for this work (that is, an
untreated portion of the raw sludge fed to the Purifax unit) was highly
unstable; therefore, it had to be packed and shipped in an insulated container
filled with ice.   This control sample was labeled "raw sludge."

     All three samples were sent by Federal Express and arrived at our
laboratory less than 24 hours after shipment.  All of these samples were
immediately placed in a walk-in cold-room until they could be readied for
analysis.

     The Purifaxed septage needed for this study was obtained from the Ventura
County (California) Regional Sanitation District.  Their Purifax treatment
facility was operated solely on a septage feed for this project.  The applied
chlorine dosage was about 800 to 1,000 mg Cl/1; 4 hours after Purifaxing, the
free residual chlorine concentration had decreased to 90 mg/1.

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     Sampling, packaging, and shipping protocol  for the Ventura samples was
identical to that for the samples from Plainfield,  except that the
Ventura samples were labeled "chlorinated septage," "dechlorinated septage,"
and "raw septage" (that is, the chlorinated septage was shipped with its free
residual chlorine content intact; the dechlorinated septage was treated with
Na2$03 solution 4 hours after Purifaxing; and the raw septage feed to the
Purifax unit was shipped in an ice pack).  These three samples, also received
less than 24 hours after shipment, were immediately stored in a cold-room.

     All the chlorinated samples were tested (qualitatively) for free
residual chlorine approximately 48 hours after Purifaxing.  No remaining free
residual chlorine could be detected.  Thus, in only 2 days, the 90 to 300 mg
Cl/1 that these samples had originally contained when they were shipped was
no longer present.

PREPARATION OF SAMPLES FOR ANALYSIS

     Approximately 1,500 ml of each sample slurry was batch-centrifuged at
1,800 rpm until a clear centrate resulted; this required anywhere from 20
minutes to 6 hours, depending on each sample's unique dewatering character-
istics.  The clear liquid fraction was carefully decanted into a glass-
stoppered bottle and returned to the cold-room.   The tightly packed,
damp, solid fraction was spread out on a watch glass and air-dried in a hood
for at least 3 days.

     Each air-dried solid fraction was pulverized and thoroughly macerated
with a mortar and pestle.  The somewhat fibrous  powder was stored in tightly
closed, screw-cap vials for subsequent determination of percent total organic
chlorine via the Schoniger-flask method.

     Eight hundred milliliters of each clear centrate was extracted with
three 60-ml  portions of 85% hexane-15% diethylether (Burdick and Jackson
high-purity solvents were used exclusively throughout this project).  The
three 60-ml  extracts of each centrate were combined and dried overnight with
20 g of anhydrous Na2$0/i.  A separate 180-ml portion of the mixed extraction
solvent was also treated with NaoSO/^; this solvent blank was carried through
all subsequent operations, including all analyses involving these extracts.
Each dried extract was decanted from the settled Na2SO^ through solvent-washed
glass wool;  the filtrate was collected in a Kuderna-Danish flask fitted with
a removable 10-ml graduated thimble.  A Snyder condenser was attached to each
K-D flask, and the extracts were concentrated on a hot-water bath to about
10 ml.  Each extract was further concentrated to a final volume of 0.9 to
1.0 ml by a combination of judicious heating, plus a fine stream of inert gas
directed on the surface of the extract.  Each K-D thimble was tightly
stoppered and refrigerated until its contents could be brought back to a
room-temperature volume of 1.0 ml by addition of pure hexane.  Each extract
was then transferred to a teflon-faced septum vial for subsequent GC/MS study
and for determination of total, hexane-ether extractable, non-volatile organic
chlorine via microcoulometric titration.

     Figure 1 is a line diagram illustrating the sequence of sample preparation
steps required before the analyses described as follows.

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                                     Raw Sample

                                        y (Purifax Chlorination)
                 (Centrifugation)
                                                                (Centrifugation)

                                                                    :°/;
(Same as  scheme shown  on  the right)
Helium-Purgeable
Organic Compounds
                                                                                 Total  Organic
                                                                                 Chlorine
                                    Miscellaneous
                                   •Parameters
                                    for  Engineering
                                    Calculations
Total Non-
Volatile Organic
Chlorine
Individual Non-
Volatile Organic
Compounds
     Figure  1.   Flow sheet  for  sample  processing  and  analysis  of  purifaxed  sludges  and  septage
                (A "control"  portion of  raw  sample  was  carried through  the  same  laboratory
                operations  and  analyses  as shown  on the right-hand  side of  the figure.)

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DETERMINATION OF PERCENT TOTAL ORGANIC CHLORINE IN THE SOLIDS FRACTIONS

Procedure

     Analyses for total organic chlorine in the solids fraction were carried out
using a modified Schb'niger-flask combustion procedure described by Welcher and
Ma (4).  This is a method whereby a weighed amount of each sample (in our case,
the air-dried solids) is burned in a specially designed flask, containing pure
oxygen and a suitable liquid reagent for absorbing (and neutralizing) the acidic
combustion products.  During combustion, chlorinated organic compounds yield
C02, HC1, and (if sulfur is present) S0£ and/or $03, all  of which are absorbed
as soluble salts.  After destruction of possible interferences, the contents of
the flask are transferred quantitatively to a beaker.  Chloride ion is then
titrated potentiometrically with standard AgNOo solution to permit calculation
of the total chlorine content of the sample.  If, as in our case, the sample
contains both organic and inorganic chlorine (that is, free chloride ion), a
separate portion of the unburned sample must be boiled with deionized water to
dissolve inorganic chloride; the free chloride ion is then titrated with AgNOo.
This permits calculation of percent organic chlorine by difference:

     Percent organic Cl = percent total Cl - percent free chloride ion.

     Since each sample of air-dried solids contained an unknown and variable
concentration of residual moisture, values for percent organic chlorine in
air-dried solids had to be correspondingly adjusted; otherwise, meaningful
comparisons of data might not have been possible.  Accordingly, separate
weighed portions of the air-dried solids were oven-dried to constant weight at
105 to 110 C.  The percentages of oven-dried solids were calculated and used
to adjust the Schbniger values to true organic chlorine (percent organic
chlorine based on dry solids).   By coincidence, every batch of air-dried
solids assayed 95±1%, expressed as oven-dried solids.

Results

     The Schoniger results for both sets of air-dried samples are shown in
Table 1.

     The values  in Table 1 for percent organic chlorine in air-dried solids
were mathematically converted to the corresponding values for oven-dried
solids (Table 2).   The values shown in Table 2 are not as insignificant as
might appear at  first glance.  For example, assume that the number-average
equivalent weight of chlorinated organics in the solids phases is only 350
(a number that is probably far too small).  Then a 1% concentration of total
organic chlorine represents a 10% concentration of monochlorinated organic
compounds.   If a more realistic number-average equivalent weight of 700 is
assumed,  then 1% of total organic chlorine represents 20% as monochlorinated
organic compounds.  These are certainly very significant concentration levels.
                                       8

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      TABLE 1.   PERCENT TOTAL CHLORINE,  INORGANIC  CHLORIDE, AND ORGANIC
                CHLORINE IN AIR-DRIED  SOLIDS

Purifaxed primary/
Parameter secondary sludge solids, %
Total Cl in raw sample
Inorganic Cl in raw
sample
Organic Cl in raw sample
Total Cl in dechlorinated
sampl e
Inorganic Cl in
dechlorinated sample
Organic Cl in dechlorinated
sample
Total Cl in chlorinated
sample
Inorganic Cl in
chlorinated sample
Organic Cl in chlorinated
sample
0.09, 0.07
Not detectable
0.08
2.52, 2.59
1.67, 1.67
0.89
2.64, 2.66
1.80, 1.83
0.83
Purifaxed
septage solids, %
0.15,
0.05,
0.14
2.26,
1.31,
0.97
3.00,
2.08,
0.94
0.21
0.04

2.28
1.28

2.99
2.04


     TABLE 2.   PERCENT TOTAL ORGANIC CHLORINE BASED ON  OVEN-DRIED SOLIDS
                                Purifaxed primary/              Purifaxed
    Parameter	secondary sludge solids, %	septage  solids.

Organic Cl in raw sample       0.08                         0.15

Organic Cl in dechlorinated    0.94                         1.01
sample

Organic Cl in chlorinated      0.87                         0.98
sample	.	

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DETERMINATION OF TOTAL, HEXANE-ETHER EXTRACTABLE,  NON-VOLATILE ORGANIC
CHLORINE IN THE LIQUID PHASES (i.e., CENTRATES)

Procedure

     These analyses were carried out on the 1.0-ml concentrates obtained  by
hexane-ether extractions of sample centrates.  The methodology involves
microcombustion of a known volume of sample or extract,  followed by
microcoulometric titration of the resulting halogen acids (in our case, HC1)
with silver ion in a special cell designed for this purpose.   The equipment
and related procedure is available from the Dohrmann Division of Envirotech
Corporation as their microcoulometric titration system,  MCTS-20-D.  Just
before each day's analyses, the equipment is checked and calibrated  with  a
suitable standard solution of a pure organic halogen compound dissolved  in
iso-octane.

Results

     The values for total halogen, expressed as  Cl, for  both  sets of centrates
are shown in Table 3.
       TABLE 3.   PERCENT TOTAL,  HEXANE-ETHER EXTRACTABLE,  NON-VOLATILE
                  ORGANIC CHLORINE IN  THE LIQUID  PHASES
                                             *yg  Cl/1  of  centrate
                             Purifaxed primary/
Sample centrate	secondary sludge	Purifaxed  septage
Raw sample                              0.9                        25.4
Dechlorinated sample                   73.4                       136
Chlorinated sample	134	170

*Each value shown is the average of replicate microcoulometric  titrations,
                                      10

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DETERMINATION OF INDIVIDUAL, HELIUM-PURGEABLE,  ORGANIC  COMPOUNDS  IN THE
LIQUID PHASES

Procedure

     These determinations were carried out by combining the  purge-and-trap
technique described by Bellar and Lichtenberg (3),  with GC/MS  detection and
analysis of the volatile (trapped-out) organic  compounds in  each  of the
liquid phases.  A suitable aliquot of liquid sample was purged for 11 min
at room temperature with 20 ml/min of helium. The gaseous effluent was passed
through a Bellar trap, the first 60% of which was packed with  60/80 mesh
Tenax-GC, and the last 40% with Davison grade 15 silica gel. Direction of gas
flow was such that the purged organics contacted first  the Tenax, then the
silica gel.  The trapped organics were thermally desorbed for  a period of
3 min using a 200 C flash heater on the trap.  During this time,  the  desorbed
organics.were swept by 20 ml/min of helium into the injection  port (200 C)
of a Finnigan Model 9500 gas chromatograph equipped with a 1.52-M (5-ft) x
2-mm ID glass column packed with 60/80 mesh Tenax-GC and maintained at a
temperature slightly below 50 C.  After the trap had been flash-heated for
3 min, temperature programming of the GC column was immediately begun for a
30-min run. Column temperature was increased at a rate  of 8°/min  from 50 C
to 190 C, and it was held at the latter temperature until the  30-min  run was
over.  All during the GC run, automatic data acquisition and display  were
accomplished with a directly interfaced Finnigan, Model 3300,  mass spectro-
meter system.  The mass spectrometer was operated in the electron impact (El)
mode at 70 eV and 10"? amps/volt sensitivity. The chosen mass  range was 20
to 260 atomic mass units with 4-sec scans.

     Because of pronounced foaming properties of the Purifaxed samples, only
well-diluted 1.0-ml aliquots could be analyzed.  That is, each 1.0-ml aliquot
had to be diluted to 5.0 ml with boiled Milli-Q water before the  purge-and-trap
step.  On the other hand, undiluted 5.0-ml aliquots of both  the raw  sludge
and raw septage could be analyzed with no difficulty, as could 5.0-ml aliquots
of calibration standards.

Results

     The values for helium-purgeable, volatile organic  compounds  in  raw
dechlorinated, and chlorinated samples are listed in Tables  4, 5, and 6,
respectively.

DETERMINATION OF INDIVIDUAL, HEXANE-ETHER EXTRACTABLE,  NON-VOLATILE  ORGANIC
COMPOUNDS IN THE LIQUID PHASES

Procedure

     The concentrated hexane-ether extracts that had already been analyzed
for total non-volatile organic chlorine were further reduced in volume  to
0.5 ml each, then analyzed for individual organic compounds  via GC/MS.  The
conditions for each GC/MS analysis were as follows:
                                      11

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         TABLE 4.    CONCENTRATIONS OF HELIUM-PURGEABLE ORGANIC COMPOUNDS
                    IN BOTH RAW SAMPLES
 Trapped volatile
     compounds
                                       Concentration  of compound,  ug/1
  Mixed primary/
secondary sludge
     Septage
 Methyl  chloroform
 Benzene
 Dimethyldisulfide
 Ethanol
 Acetone
 Dichloromethane
 1,  1-DichloroetJiane
 Chloroform
 Dithiabutane
 Toluene
 Xylenes
 Chiorotoluenes
 Dichlorobenzenes
Methanethiol
2,3,4-Tri thi apentane
        5
       10
      150
 Not quantified
 Not quantified
        60
         2

Not quantified
Not quantified
         1
        60
         8
       150
        75
        50
        95
       100
                                     12

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        TABLE 5.   CONCENTRATIONS OF HELIUM-PURGEABLE ORGANIC COMPOUNDS
                   IN BOTH DECHLORINATED SAMPLES
Trapped volatile
    compounds
    Concentration of Compounds,  yg/1
 Mixed primary/
secondary sludge	Septage
Cyanogen chloride
Dichloromethane
Chloroform
Carbon tetrachloride
Benzene
Ethanol
Acetone
3-Methylbutanal
Toluene
Hexanal
Furfural
Chloroethane
1, 1-Dichloroethane
Methyl chloroform
Di chloroaceton i tri1e
Chiorotoluenes
Dichlorobenzenes
n-Valeronitrile
      700
      100
      100
       30
        5
Not quantified
Not quantified
Not quantified
        2
Not quantified
Not quantified
     170
      10
      65
Not quantified
Not quantified
Not quantified
      60
                                 3
                                85
                                40
                                50
                               130
                               300
                          Not quantified
                                     13

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        TABLE 6.    CONCENTRATIONS OF HELIUM-PURGEABLE ORGANIC COMPOUNDS
                   IN BOTH CHLORINATED SAMPLES
Trapped volatile
   compounds
     Concentration of compounds,  yg/1
 Mixed primary/
secondary sludge	Septage
Cyanogen chloride
Acetone
Dichloromethane
Chloroform
Toluene
Benzene
3-Methylbutanal
3-Methylpentanal
     900
       5
     100
     100
       1
       1
 Not quantified
 Not quantified
      250
Not quantified
       50
      120
       60
       10
Chloroethane
1, 1-Di chloroethane
Methyl chloroform
Carbon tetrachloride
Di chl oroacetoni tri 1 e
n-Valeronitrile
Chlorotoluenes
Dichlorobenzenes
Hexane
5
60
40
2
60
50
170
260
Not quantified
                                     14

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     a.   Column--!.53-M (5-ft) x 2-mm ID glass column,  packed
          with 3% OV-1 on 80/100 mesh Gas Chrom Q.

     b.   Flowrate--20 ml/min of helium.

     c.   Column temperature--3 min at 30 C,  followed by programming
          to 230 C at 8°/min for a total  MS run time of  45 min.

     d.   Mass range--20 to 500 atomic mass units with 4-sec  scans  (i.e.,
          integration time of 8 milliseconds/atomic mass unit).

     e.   Sensitivity--10~7 amp/volt.

     f.   Electron energy—70 eV.

     g.   Real time GC attenuation--3.

     h.   Data acquisition (the 45-min MS run)  was  started 1.0
          min after injection to eliminate most of  the solvent  peak.

     Compounds identified from EI/MS spectra  during this phase  of the project
were confirmed by running standards (when these were on-hand) or by reruns
using the CI/MS side of the Finnigan system.   The reported concentrations are
accurate to only ±50%, and they are based on  the assumption that 100% recovery
of each identified compound was realized,up to the  point of GC/MS analysis.

Results

     Tables 7, 8, and 9 show the values found for  the individual, hexane-ether
extractable, non-volatile organic compounds in raw, dechlorinated,  and
chlorinated samples, respectively.

DETERMINATION OF ADDITIONAL PARAMETERS FOR VENTURA  CENTRATES TO PERMIT COST
CALCULATIONS FOR FILTRATION/CARBON ADSORPTION AS AN ADJUNCT TO  PURIFAX
TREATMENT

Procedure

     Each of the three Ventura centrates was analyzed for total dissolved  solids,
total suspended solids, and total organic carbon by procedures  described in
Standard Methods for  the Examination of Water and  Wastewater (5).  A separate
portion of each centrate was then filtered through a 0.45-ym Millipore membrane,
and these filtrates were also analyzed for total organic carbon.

Results
     The analytical values for these additional engineering parameters are
listed in Table 10.
                                       15

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TABLE 7.   CONCENTRATIONS OF HEXANE-ETHER EXTRACTABLE,  NON-VOLATILE
           ORGANIC COMPOUNDS IN  BOTH RAW SAMPLES

Extracted compound
Di ethyl phthalate
Isobutyl phthalate
Di-n-butyl phthalate
Isopropyl phthalate
Di-(Z-ethylhexyl) phthalate
Farnesol
Chlorotoluene
3-hexanone
Fenchyl alcohol
Camphor
Myrcenol
Isoborneol
Terpinene-4-ol
Alpha-terpineol
Indole
3-Methylindole
1 ,1-Dibutoxye thane
Ethyl -p, p'-dichlorobenzilate
Concentration of
Mixed primary/
secondary sludge
2
80
40
2
10
2
-
-
-
-
-
-
-
-
-
-
-
-
Compound, yg/1
Septage
-
-
-
-
-
-
20
50
20
20
150
20
20
800
20
30
30
10
                                  16

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   TABLE 8.   CONCENTRATIONS OF HEXANE-ETHER EXTRACTABLE,  NON-VOLATILE
              ORGANIC COMPOUNDS IN BOTH DECHLORINATED SAMPLES
                                        Concentration of  compound, yig/1
                                    Mixed primary/
Extracted compound	secondary sludge	Septage
Pentachloroacetone                       100                        50
Chloroform                                10
2,4,6-Trichlorophenol                      2
Diethyl phthalate                          2                         5
Di-(2-ethylhexyl) phthalate              100
Dodecan-6,7-dione                          2
3,7,7-Trimethyl-bicyclo-(3.1.1)-
  2-heptanol                               5
3-Hexanone                          Not,quantified
Acetone                             Not quantified
Chlorotoluene                              -                        10
Isovaleric acid                            -                        20
Dichlorobenzene                            -                        20
Butyric acid                               -                        30
(2-chloroethyl)-benzene                    -                        30
Fenchyl alcohol                            -                        50
3-Pentanol                                 -                        40
Isoborneol                                 -                        50
2-Ethylbutanoic acid                       -                         5
Stearic acid                               -                       150
1,1-Dibutoxyethane                         -                        30
Toluene                                    -                Not quantified
Farnesol                                   5
                                     17

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   TABLE 9.   CONCENTRATIONS OF HEXANE-ETHER EXTRACTABLE, NON-VOLATILE
              ORGANIC COMPOUNDS IN BOTH CHLORINATED SAMPLES
                                        Concentration of compound, yg/1
                                    Mixed primary/
Extracted compound	secondary sludge	Septage
3-Methyl-3-pentanol                        2
3-Hexanone                                30
Pentachloroacetone                       100                       40
Chloroform                                30
2,4,6-Trichlorophenol                      2
Diethyl phthai ate                          2
Isobutyl phthalate                        80
Di-(n-butyl) phthalate                   100
Di-(2-ethylhexyl) phthalate                2                       10
Farnesol                                   5
2-Methyl-3-pentanol              Tentative identification
Chlorotoluene                              -                       10
Dichlorobenzene                            _                       10
(2-chloroethyl)-benzene                    -                       20
Fenchyl alcohol                            -                       30
Camphor                                    -                       30
3-Pentanol                                 -                       30
Iso-borneol                                -                       30
n-Butyl-n-butyrate                         -                       20
Stearic acid                               -                      150
1,1-Dibutoxyethane                         -                       10
Elemol                                     -                       10
Nerolidol isomer                           -                       20
Di ethyl ether	-	     50
                                     18

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               TABLE 10.   MISCELLANEOUS ENGINEERING PARAMETERS
                           FOR VENTURA CENTRATES

Concentration of parameter, mg/1
Centrate
parameter
Total dissolved solids
Total suspended solids
Total organic carbon
Raw
1,984
31.0
375
Dechlorinated
2,855
21.0
200
Chlorinated
3,158
21.0
190
Rerun of total organic carbon
  after filtration through
  0.45-yim millipore membranes	325	175	175	


DISCUSSION

     Relatively high percentages (1% by weight) of organic chlorine were
found in the Purifaxed solids phases.  These chlorinated organics represent
a significant potential environmental hazard.  If these solids phases are
disposed of as landfill material, and if subsequent long-term landfill
leaching occurs, at least some of these chlorinated organics are sure to
re-enter the environment with unknown health-effects risks.  Unfortunately,
the present state-of-the-art of analytical chemistry does not permit identi-
fication of more than a small fraction of the individual chlorinated organic
constituents in Purifaxed solids phases. Such solids are extremely insoluble
in most organic solvents and therefore resist ordinary extraction methods.
Even extractive steam distillation of Purifaxed solids probably would permit
isolation and analysis of only small percentages of the chlorinated organics
actually present.

     Evaluation of all the data on the Purifaxed liquid phases shows that
less than 1% of the total organic carbon in these phases were accounted for
by recovered chlorinated organic compounds.  For example, the centrates from
Ventura contained approximately 200 mg/1 total organic carbon, and less than
1 mg/1 was identified as specific organic compounds.  This strongly indicates
that recoveries of chlorinated organics before analysis were very low.  This
result is readily understandable for the following reasons:

     a.   The microcoulometric titration values obtained for total,
          hexane-ether extractable, non-volatile organic chlorine
          in the liquid phases were in turn dependent on the relative
          fractions of dissolved chlorinated organics extracted
          (for subsequent analysis) by the solvent mixture employed for
          this purpose.  Had most of the chlorinated organics in the
                                      19

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          aqueous phases been highly polar  in  nature  (that  is,  highly
          water-soluble), then no simple extraction procedure could
          have recovered more than a small  fraction of  the  compounds
          actually present.

     b.   When the hexane-ether extracts had to  be concentrated from
          180 ml  down to 0.5-1.0 ml  for microcoulometric  and GC/MS
          analyses, significant (but unknown)  percentages of the
          extracted chlorinated organics were  lost because  of volatility.
          Some of these volatiles obviously would have  been accounted
          for during the independent determinations of  helium-purgeable
          constituents.  On  the other hand, much of the lost volatile
          material  would not have been thus accounted for,  but  instead
          would have completely escaped detection.

     Better recovery methods could no doubt be devised, but this would
require a major analytical  undertaking.
                                  20

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                                  REFERENCES

1.   Mashni, C. I.  Effect of Purifax Chiorination Treatment on Septic
     Tank Waste.  Memorandum to Record, U.S. Environmental  Protection
     Agency, Cincinnati, Ohio, August 28,  1974.  4 pp.

2.   Sawyer, C. N.  Effects of Chiorination during Purifax  System of Sludge
     Treatment.  Metcalf and Eddy,  Inc., Engineers, Boston, Massachusetts,
     April 2, 1971.   31 pp.

3.   Bellar, T. A.,  and J.  J.  Lichtenberg.   Determining Volatile Organics
     at Microgram-per-Litre Levels  by Gas  Chromatography.   J.  Amer.  Water
     Works Assoc., 6602):  739-744, 1974.

4.   Weicher, F. J.  (ed.),  and T.  S.  Ma.  Microdetermination of Chlorine,
     Bromine, or Iodine by the Closed Flask Method. In: Standard Methods
     of Chemical Analysis.  6th Ed.,Vol. Two, Part A, pp.  389-392.   D. Van
     Nostrand Co., Princeton,  New Jersey,  1963.

5.   Standard Methods for the  Examination  of Water and Wastewater.   14th
     Ed.  American Public Health Association-American Water Works Association-
     Water Pollution Control Federation, Washington, D.C.,  1975.
                                     21

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                                  TECHNICAL REPORT DATA
                           (Please read Instructions on the reverse before completing)
 REPORT NO.
 EPA-600/2-78-020
                                                           3. RECIPIENT'S ACCESSION>NO.
 TITLE AND SUBTITLE
 Partial  Characterization of Chlorinated Organics in
 Superchlorinated Septages and Mixed  Sludges
               . REPORT DATE
               March 1978 (Issuing  Date)
              6. PERFORMING ORGANIZATION CODE
 . AUTHOR(S)
                                                           8. PERFORMING ORGANIZATION REPORT NO.
 Robert  H.  Wise, Thomas A. Pressley,  and
 Barry M. Austern
 . PERFORMING ORGANIZATION NAME AND ADDRESS
 Municipal Environmental Research Laboratory—Cin.,OH
 Office of Research and Development
 U.S. Environmental Protection Agency
 Cincinnati,  Ohio  45268
                                                           10. PROGRAM ELEMENT NO.
                1BC611
               11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
               13. TYPE OF REPORT AND PERIOD COVERED

               Tnhnusp Rppnrt  ?/in/77-fi/?a/77
 Same as above
               14. SPONSORINGiAGENcV CODE



                EPA/600/14
15. SUPPLEMENTARY NOTES

  Project Officer-  Robert H.  Wise 513/684-7627
16. ABSTRACT

 The chlorinated organic materials  produced by applying  the  proprietary Purifax  process
 to a  septage and a mixed primary/secondary sludge were  studied to assess the  types,
 amounts,  and distribution of chlorinated organics present.   Total organic chlorine
 in the  solids phases was determined  by Schohiger-flask  combustion.  Concentrated
 hexane-ether extracts of the liquid  phases were also analyzed for total organic
 chlorine  by microcoulometric titration; these same extracts were then analyzed  by
 GC/MS for individual organic compounds.  Helium-purgeable organics in the liquid
 phases  were also determined by GC/MS.   Liquid phases from one Purifax installation
 were  analyzed for TOC, TDS, and TSS  to furnish engineering  cost data for applying
 filtration/carbon adsorption as a  Purifax-treatment adjunct.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
 b.lDENTIFIERS/OPEN ENDED TERMS
                                                                         c. cos AT I Field/Group
 *Sludge  disposal
  Sludge
  Septic  tanks
 *Chlorination
 *Chemical  analysis
 *Chemical  Composition
    *Purifax Process
    *Superchlorination
     Septages
     Sludge treatment
     Septage treatment
    *Sludge analysis
    *Septaae analysis
13B
18. DISTRIBUTION STATEMENT

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                                                                         22. PRICE
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