xvEPA
           United States
           Environmental Protection
           Agency
            Office Of Water
            (WH-595)
EPA 430/09-91-007
April T99T
Cooperative Testing Of
Municipal Sewage Sludges
By The Toxicity Characte
Leaching Procedure And
Compositional Analysis
                                   Printed on Recycled Paper

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COOPERATIVE TESTING OF MUNICIPAL SEWAGE SLUDGES BY THE TOXICITY

 CHARACTERISTIC LEACHING PROCEDURE AND COMPOSITIONAL ANALYSIS
               JOHN WALKER, PHYSICAL SCIENTIST
                          f
             Municipal Technology Branch, WH-547
            U.S. Environmental Protection Agency
         Office of Water Enforcement and Compliance
                  Washington, D.C.  20460

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ACKNOWLEDGEiyENTS








     The cooperation of the Office of Solid Waste, the S-Cubed




Laboratories, the AMSA coordinator, all the AMSA municipalities, all the



different laboratories doing TCLP and compositional testing, and the EPA



Central Regional Laboratory (each of whom helped with various aspects of



this study)  is very much appreciated and gratefully acknowledged.

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                       TABLE OF CONTENTS
      Section

 TITLE PAGE

 ACKNOWLEDGEMENTS

 TABLE OF CONTENTS

 ABSTRACT

 INTRODUCTION

METHODS & MATERIALS
     Sludge & POTW Characteristics
     Analytical & QA/QC Procedures
          Compounds Analyzed
          EPA Contract Lab Reporting Limits
          Standard Procedures

RESULTS & DISCUSSION
     Volatiles
          TCLP Volatiles Data
          Compositional Volatiles Data
     Semivolatiles
          TCLP Semivolatiles Data
          Compositional Semivolatiles Data
     Metals
          TCLP Metals Data
          Compositional Metals Data
          EP & TCLP Metals Data Compared
     Pesticides &  Herbicides
          TCLP Pesticides & Herbicides Data
          Compositional Pesticides &  Herbicides Data
     Pretreatment  Status of the POTWs
          Pretreatment Status of Cooperating POTWs
     Reporting Limits Impacts on Data
          Impacts on  TCLP vs.  Compositional
            Volatile Data
          Impacts on  TCLP vs.  EP Metals Data
     Quality Assurance & Quality Control
     Costs of Analysis
     Relationship Between TCLP & Compositional
       Content
         Ratio TCLP  to Compositional Metal
            Contents
         Summary of Metal Ratios, 18 POTW Sludges
         Estimate of Threshold Metal Concentrations
            for Failing the TCLP
         Ratio TCLP  to Compositional Volatile
            Content
Table No.
  12A
  12B

 12C

 13A
Page No.

   i

  ii

iii-v

 vi-x

  1-3

1

2A-2D
2A-2D
3


4A
4B

5A
5B

6A
6B
7-

8A
8B

9

10
11


3-14
2-6
6-12
7-11
7-11
13-14
12, 15-69
12, 15-25
16-19
20-23
25-32
26-28
30-32
29, 33-39
33-34
35-36
37-38
39-43
40-41
42-43
39, 44-48
45
48-51
49
51
50, 52-57
57
57-67

58-59
 61

 62

 63
                                 ill

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          Summary of Volatiles Ratios of 12 POTW
             Sludges                                 13B          64
          Estimate of Threshold Volatiles Concentra-
             tions for Failing the TCLP           .   13C          65
          Ratio TCLP to Compositional Contents for
             Semivolatiles, Pesticides & Herbicides  14A          66
          Estimate of Threshold for a Few Semivol-
             atiles, Pesticides & Herbicides Concen-
             trations for Failing the TCLP           14B          68
          Factors for Roughly Estimating TC Report-
             ing Limit Exceedance from the Total
             Content of Contaminants in Sludge       15           69

TCLP AND TC UPDATE                                             67, 70-72
          Comparison of Proposed and Final Toxicity
             Characteristics                         16          71-72

SUMMARY & CONCLUSIONS                                            73-80

REFERENCES                                                        81

APPENDICES                                                       82-136
     Appendix A  POTW Sludge Sampling Procedures                 82-85
     Appendix B  QA/QC Data                                      86-97
          QA Objectives (Organic Compounds)          B-l          87
          Compositional Matrix Spike/Matrix
             Duplicate Recovery Organic
             Analyses, No. 1                         B-2          88
          Compositional (Ibid), No. 2                B-3          89
          TCLP (Ibid) , No. 1                         B-4          90
          TCLP (Ibid) , No. 2                         B-5          91
          EP (Ibid), No. 1                           B-6          92
          EP (Ibid), No. 2                           B-7          92
          Metals Spike/Spike Duplicate Recovery
             Compositional Matrix                    B-8          93
          Metals (Ibid) TCLP Matrix                  B-9          94
          Metals (Ibid) EP Matrix                    B-10         95
          Compositional Matrix Surrogate Percent
             Recovery Summary-Organic Analysis       B-ll         96
          TCLP Surrogate  (Ibid)                      B-12         97
     Appendix C  AMSA laboratory Reporting Limits
              for Sludge                                         98-110
          TCLP Volatile Reporting Limits             C-1A        99-100
          Compositional Volatile Reporting Limits    C-1B       101-102
          TCLP Semivolatile Reporting Limits         C-2A       103-104
          Compositional Semivolatile Reporting
             Limits                                  C-2B ;      105-106
          TCLP Metal Reporting Limits                C-3A        107
          Compositional Metal Reporting Limits       C-3B        108
          TCLP Pesticide & Herbicide Reporting
             Limits                                  C-4A        109
          Compositional Pesticide & Herbicide
             Reporting Limits                        C-4B        110
                                    iv

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Appendix D  Report on Six POTW Sludge Study                111-128
     TCLP Compounds Analyzed & Not Analyzed     D-l         119
     Characteristics of Six POTW Sludges        D-2         120
     TCLP Volatiles Data                        D-3         121
     Compositional Volatiles Data               D-4         122
     TCLP Metals Data               .            D-5         123
     Compositional Metals Data                  D-6         124
     EP & TCLP Metals Data Compared             D-7         125
     Ratio TCLP to Compositional fetal
        Contents  (Pfet)                           D-8         126
     (Ibid) (Dry)                               D-9         127
     Ratio TCLP to Compositional Volatiles
        Content                                 D-10        128
Appendix E  Comments by Dolloff F. Bishop                  129-131
Appendix F  Trends in Influent & Sludge Metals             132-136
     Trends in Influent and Sludge Metal
        Contents                                F-l        133-136
                           V

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 ABSTRACT








      The Toxicity Characteristic Leaching Procedure  (TCLP) is a testing



 procedure that has been developed by the Office of Solid Waste (OSW) for



 determining whether or not solid wastes, including municipal sewage



 sludges, are hazardous based upon toxicity.  This procedure was a



 proposed replacement for the Extraction Procedure (EP), used for this



 purpose since 1980.  In the TCLP, the concentrations of analytes in the



 extracts are compared to Toxicity Characteristic (TC) regulatory levels.



 If concentrations of analytes in the TCLP extract meet or exceed these



 regulatory levels,  the wastes are classified as hazardous.








      In 1985-86,  when these studies were conducted,  it was felt that the



 proposed TCLP and TC regulatory levels might cause a number of municipal



 sewage  sludges from Publicly Owned Treatment Works (POTWs)  to  be



 classified as hazardous.   Hence,  the Office of Water (OW) ,  in



 cooperation with  OSW,  began testing municipal sewage sludges.   Both



 total and TCLP fractions of the 18  sewage sludges were analyzed for



 selected analytes.  The Association of Mstropolitan  Sewerage Agencies



 (AMSA) cooperated with EPA's  OW and OSW  in this study, analyzing split



 samples  of sludges from 12 of the POTWs  using identical analytical



 instructions  sent by the EPA laboratory.  Time  and budget did not permit



 rigid policing of the AMSA laboratories  to assure that they actually did



 use identical procedures.








     None of the  18 sludges tested by any of the laboratories had TCLP



extract concentrations that exceeded the proposed TC regulatory levels.
                                     •vi

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  In the  sludges  studied,'the volatile analytes were found to be the itost
  likely  class of contaminants that might cause them to be classified as
  hazardous,  (i.e., three of 18 sludges had. volatile TCLP analyte contents
 within  less than an order of magnitude [one of the three was within a
  factor  of three] of the proposed TC regulatory levels).  However,
 because the final promulgated TC regulatory levels are, on average, two
 to three times higher than the proposed TC regulatory levels for the
 volatile toxic organic TCLP compounds,  it would seem unlikely that the
 volatile compounds would result in any POIW sludges being classified as
 hazardous.   Because the concentrations  of the metal,  semivolatile,
 pesticide,  and herbicide constituents in  analytes in  TCLP extracts  of
 the tested sewage sludges were lower than the respective  TC regulatory
 levels by about one to two orders of magnitude,  it would  seem even  less
 likely for  these classes of contaminants  to result in sludges  being
 classified  as hazardous.

     For most contaminants except metals,  there were  non-detects in the
 TCLP extracts, and there were very few contaminants detected by both
 laboratories on  the same sludge sample.  Only for barium, p-cresol, and
 xylene did split sample analyses on the same sludge by the EPA and AMSA
 laboratories shew detected measurements.  There was substantial
variation in the split sample results for barium with the level of
barium detected by the EPA laboratory always being higher than detected
by the AMSA laboratories.  On the other hand,  the variation in the split
sample detects were less for p-cresol and xylene with no laboratory's
results being consistently higher.  The variation may have resulted
                                   vii

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because of  subsample differences, sludge matrix interferences when using



the SW-846  analytical protocol, or differences in the actual procedures



used by the laboratories.  The split sample results for barium would



have to be  viewed as questionable because of the large degree of



consistently skewed variation.








     When the concentrations of metals in TCLP and EP extracts were



compared, there were no consistent differences in the amounts of a metal



extracted.   In general, the AMSA laboratories had lower reporting limits



than did the EPA laboratory.








     The 18 sludges came from POTWs that ranged in flow from less than



10 to over  600 million gallons per day (MOD) with less than one to over



90 percent  of the flow being of industrial origin.  The total



compositional and TCLP extract contents of the proposed 52 TCLP analytes



were not particularly high in these sludges.  Some limited information



is presented in the report about the various industrial pretreatment



programs at the tested facilities.  It is not known whether these



industrial  pretreatment programs had any bearing on the relatively low



contents of analytes detected in the tested sludges.








     The volatile contaminants benzene and chloroform that came closest



to exceeding the respective TC regulatory levels were in a TCLP extract



of a sludge from a smaller POTW.  This POTW had a flow of about one



million gallons per day (MGD) and less than one percent industrial flow.
                                    viii

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 One possible reason for the higher level of volatile analytes observed



 in the tested smaller POTW is that an insufficient volume of sludge was



 generated to dilute out occasional discharges of TC contaminants that



 might have occurred.  Unfortunately our study did not include



 information for assessing how the TCLP analyte contents in the sludges



 were inapacted by the type, size,  and nature of the industries



 discharging to each POTW or by the type of wastewater and sludge



 treatment employed at each facility.








      One important limitation of  these studies is that only 18 of the



 more than 15,000 POTWs in the United States (US)  were included in the



 study.   Only one of the 18 tested POTW sludges came from a POIW that was



 close to one MGD in size.   POTWs  of less than one MGD in size constitute



 nearly 90% of all POTWs in the US.  Another limitation is that the 18



 POTWs were not selected in a manner that would allow statistically valid



 extrapolation of the results to the POTWs nationwide.   However,  the



 POTWs were selected on a basis of high to low hydraulic and industrial



 flow with the expectation  that these parameters would be somewhat



 inclusive of wastewater inputs and  resultant  sludges  that might  cause



 the  sludge to be classified  as hazardous.








      The  analytical data were  used  to obtain  a very rough estimate of



 the total content of contaminants in sludges  that would result in TC



 regulatory level  exceedance.   These rough estimates can be calculated



 from  the  following formula:   [(TC times 100)/(divided by the median



percentage)] where the median percentage  is derived from the fraction of
                                    ix

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 the total analytes extracted by the TCLP within a class of compounds.



 While these estimating percentages are different within a class of



 extracted TCLP contaminants, the median percentages of the volatiles



 extracted were generally greatest at 30%, followed by metals at 0.03%,



 and semivolatiles, pesticides and herbicides at 0.01%.  Because of the



 considerable variability in percentages of the different analytes



 extracted, additional TCLP testing would be needed where these



 estimating percentages, applied to the total compositional analyte



 contents of the TC contaminants in sludge, would predict a TCLP analyte



 content that was at all close (perhaps within an order of magnitude)  to



' the TC regulatory level.








      The cost impact upon small POEWs for testing could be substantial.



 The cost was about $1,200.00 to $1,500.00 (1988 dollars)  for the



 complete analysis of a single sample without replication.   Increased



 replication might be necessary and increase the cost for facilities if



 the TCLP extract contaminant levels were closer to the TC regulatory



 levels.
                                    x

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      COOPERATIVE TESTING OF MUNICIPAL SEWAGE SLUDGES BY THE TOXICITY

       CHARACTERISTIC LEACHING PROCEDURE AND COMPOSITIONAL ANALYSIS
                      JOHN WALKER, PHYSICAL SCIENTIST
                    Municipal Technology Branch WH-547
                   U.S. Environmental Protection Agency
                Office of Water Enforcement and Complicance
                          Washington, D.C.  20460
 INTRODUCTION
      The Toxicity Characteristic Leaching Procedure (TCLP)  is a testing

 procedure that has been developed by the Office of Solid Waste (OSW)  for

 determining whether or not solid wastes, including municipal  sewage

 sludges, are hazardous based upon toxicity.   This  procedure was a

 proposed replacement for the Extraction Procedure  (EP),  used  for this

 purpose since 1980.   Both procedures were designed to  simulate leaching

 from a landfill under a mismanagement scenario  (codisposal  of wastes

 with municipal wastes in an unlined  landfill) .



      The TCLP testing procedure was  proposed  as a method to extract and

 test wastes  for hazardousness.  The  test compares the concentration of

 analytes  in  the extracts to  Toxicity Characteristic  (1C) regulatory

 levels.   If  concentrations of analytes in the TCLP extract meet or

 exceed these regulatory  levels, the wastes are classified as hazardous.

 The TC regulatory levels had been proposed by the Environmental

 Protection Agency  (EPA) to identify those wastes that contain certain

 toxic constituents at  levels that can leach to groundwater and thereby

pose a threat  (hazard) to human health and the environment.   The TC

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 regulatory levels for toxic organic compounds were determined based upon

 chronic toxicity reference levels and compound specific


 dilution/attenuation factors, generated from a groundwater transport

 model.




      Both the TC regulatory levels and the TCLP were proposed in the


 Federal Register on June 13, 1986, (51 FR 21648).   This new proposed TC


 added 38 more toxic organic compounds than the 14  compounds included in

 the EP test.   While this study evaluated the 52 elements for which TCs


 had been proposed,  the rule was promulgated in final form on March 29,

 1990, (55 FR 11798)  with TC regulatory levels for  only 25 additional


 toxic organic compounds rather than the 38 originally proposed.   On June

 29,  1990,  (55 FR 26986)  the TCLP was reformated to conform to the SW-846


 method's format, including quality assurance and quality control (QA/QC)

 requirements.  OSW plans to finalize the SW-846 QA/QC requirements in

 April 1991 across all methods,  including the TCLP.




      At  the time the studies were conducted,  it was  felt that the
                                                              I
 proposed TCLP and TC regulatory levels could have a  substantial  impact


 on municipal  sewage  sludges from Publicly Owned Treatment Works  (POTWs).

 Hence, the Office of Water  (OW),  in cooperation with OSW, began  testing

municipal sewage sludges.  Six POTW sludges were tested  in November


 1985, followed by the testing of  12 additional sludges in May and June

of 1986.  The expanded testing program was undertaken because of the

very limited  number of POTWs sampled and the tentative nature of


the initial test.  The Association of Metropolitan Sewerage Agencies

 (AMSA) cooperated with EPA's OW and OSW in this expanded study, using

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 identical analytical instructions sent by the EPA laboratory.  Time and


 budget did not permit rigid policing of the AMSA laboratories to assure

 that they actually did use identical procedures.




      This report describes the results of the testing of 12 sludges that

 occurred in 1986.  It also sumnarizes the testing and discusses the

 results of the six-POTW sludge test conducted in 1985 and is updated by

 a sumnary to indicate the potential impacts on sludge management of the


 changes in the TCLP and TC rule that occurred from its proposed to final

 form.




 METHODS AND MATERIALS




                   Sludge and  POIW Characteristics




     Samples of sewage sludge were collected for the expanded study by

 each of the 12 cooperating AMSA members using the procedure given in

Appendix A.  Sludges from each of these POTWs had the properties shown

 in Table 1.  Sludge samples were split, with one split being sent to

EPA's contract laboratory  (S-CUBED*) and the second split being retained

for analysis by the AMSA cooperator for 11 of the 12 POEWs who could

arrange to either test the sludge themselves or have a contract

laboratory do it.
*Vendor and trade names are included solely for the benefit of the
 reader and do not imply endorsement by the U.S. Environmental
 Protection Agency.

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      For the most part, the attempt was to include a range of sewage



 sludges in the test program from POTWs that were expected to have higher



 levels of constituents and therefore might cause failure with respect to



 the TC.  This higher constituent level and possible failure was expected



 because of the larger size of these POEWs and their type of industrial



 input.  A second criterion for POTW selection was their willingness to



 cooperate by either testing the sludges themselves or having a



 contractor do it.  Because of this second criterion,  not all of the



 treatment facilities selected were expected to have higher levels of TC



 contaminants.




                   Analytical and QA/QC Procedures








      The collected samples were analyzed by the EPA contract laboratory



 for the targeted 42 volatile,  67 semivolatile,  10 metal  and  29 pesticide



 and herbicide compounds  shown in Tables 2A through  2D.   These compounds



 were selected for analysis by the EPA contract laboratory based upon  (1)



 a consideration  of the list of contaminants of interest  in the TCLP,  (2)



 the list of  40 CFR 261, Appendix VIII constituents  recommended for



 analysis in  "Guidance on Issuing Permits  to Facilities Required to



Analyze Groundwater for Appendix VIII Constituents" dated January 31,



 1986,  (3) "The 1986  Industrial Technology Division List of Analytes",



and (4)  the Superfund Contract Laboratory Program (CLP)  list of



analytes.  Final analyte selections from  these  lists were then based



upon  (a) the likelihood that the compound would be present in a POIW



sludge  (given the compound's general  level of commercial production and



use), its water solubility, and detectability in previous studies of



                                      6

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  TABLE 2A.   VOLATILE ORGANICS GENERAL METHOD
              MEDIA REPORTING LIMITS* (SW-846 METHOD 8240)
  Compound
Compositional
 Wet,  mg/kg
 TCLP
  mg/1
 TCLP ANALYTE5

 Acrylonitrile
 Benzene
 Carbon disulfide
 Carbon tetrachloride
 Chlorobenzene
 Chloroform
 1,2-Dichloroethane
 1,1-Dichloroethylene  (1,1-Dichloroethene)
 Isobutanol (2-Methyl-l-propanol)
 Methylerie chloride
 Methyl ethy ketone  (2-Butanone)
 Pyridine
 1,1,1,2-Tetrachloroethane
 1,1,2,2-Tetrachloroethane
 Tetrachloroethylene (Tetrachloroethene)
 Toluene
 1,1,1-Trichloroethane
 1,1,2-Trichloroethane
 Trichloroethylene (Trichloroethene)
 Vinyl  chloride

 NON-TCLP ANALYTES

 Bromidichloromethane
 2-Chloro-l,3-butadiene
 Chioroethane
 3-Chloropropene
 Dibromochloromethane
 1,2-Dibromoethane
 trans-l,4-Dichloro-2-butene
 1,1-Dichloroethane
 trans-l,2-Dichloroethene
 1,2,-dichloropropane
 trans-l,3-Dichloropropene
 cis-1,3-Dichloropropene
 Diethylether
 Ethyl acetate
 Ethylbenzene
 2-Hexanone
Methacrylonitrile
 4-Methy1-2-pentanone
Styrene
 1,2,3-Trichloropropane
Vinly acetate
Total xylenes
     0.20
     0.10
     0.10
     0.10
     0.10
     0.10
     0.10
     0.10
     0.20
     0.10
     0.20
     0.20
     0.20
     0.10
     0.10
     0.10
     0.10
     0.10
     0.10
     0.20
    0.10
    0.20
    0.20
    0.20
    0.10
    0.20
    0.20
    0.10
    0.10
    0.10
    0.10
    0.10
    0.20
    0.20
    0.10
    0.20
    0.20
    0.20
    0.10
    0.20
    0.20
    0.10
 0.010
 0.005
 0.005
 0.005
 0.005
 0.005
 0.005
 0.005
 0.010
 0.005
 0.010
 0.010
 0.010
 0.005
 0.005
 0.005
 0.005
 0.005
 0.005
 0.010
 0.005
 0.010
 0.010
 0.010
 0.005
 0.010
 0.010
 0.005
 0.005
 0.005
 0.005
 0.005
 0.010
 0.010
 0.005
 0.010
 0.010
 0.010
 0.005
0.010
0.010
0.005
*S-Cubed Laboratory

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TABLE 2B.   SEMIVOLATILE ORGANICS GENERAL METHOD
             MEDIAN REPORTING LIMITS* (SW-846 METHOD 827C)
Compound
TCLP ANALYTES
bis (2-chloroethyl) ether
0-Cresol (2-Methylphenol)
m-Cresol (3-Methylphenol)
p-Cresol (4-Methylphenol)
1,2-Dichlorobenzene
1 , 4-Dichlorobenzene
2 , 4-Dinitrotoluene
Hexachl orobenz ene
Hexachlorobutadiene
Hexachl oroethane
Nitrobenzene
Pentachlorophenol
Phenol
2 , 3 , 4 , 6-Tetrachlorophenol
2,4, 5-Trichlorophenol
2,4, 6-Trichlorophenol
NON-TCLP ANALYTES
Acenaphthene
Acenaphthylene
Aniline
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) f luoranthene
Benzo (g,h, i) perylene
Benzo (k) fluroanthene
bis (2-chloroethoxy) methane
bis (2-chloroisopropyl) ether
bis (2-ethylhexyl)phthalate
4-Bromophenyl phenylether
Butylbenzlphthalate
4-Chloroaniline
4-Cloro-3-methylphenol
2 -Chloronaphthalene
2-Chlorophenol
4-chlorophenyl phenylether
Chrysene
Dibenzacridine
Dibenz( a, h) anthracene
1 , 3-Dichlorobenzene
Compositional
Wet, mg/kg

1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
• 1.3
6.4
1.3
2.6
6.4
1.3

1.3
1.3
6.4
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
1.3
TCLP
mg/1

0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.05
0.01
0.01
0.05
0.01

0.01
0.01
0.02
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
*S-Cubed Laboratory

-------
TABLE 2B Cont.
SEMIVOLATILE ORGANICS GENERAL METHOD
 MEDIAN REPORTING LIMITS* (SW-846 METHOD 8270)
Compound
NON-TCLP ANALYTES
continued
2 , 4-Dichlorophenol
2 , 6-Dichlorophenol
Diethyl phthalate
Dimethyl phthalate
2 , 4-Dimethylphenol
Di-n-butylphthalate
4 , 6-Dinitro-2-methylphenol
2 , 4-Dinitrophenol
2 , 6-Dinitrotoluene
Di-n-octyl phthalate
Dipnenylamine
Fluoranthene
Fluorene
Hexachlorocyclopentadiene
Indeno ( 1 , 2 , 3 -cd ) pyrene
Isophorone
2 -Methy Inaphthal ene
Naphthalene
2-Nitrophenol
4 -Nitrophenol
Pentachl or oe thane
Phenanthrene
2-Picoline
Pyrene
1,2,4, 5-Tetrachlorobenzene
2,3,5, 6-Tetrachlorophenol
1,2, 3-Trichlorobenzene
1,2, 4-Trichlorobenzene
Compositional
Wet, mg/kl


1.3
6.4
1. 3
1. 3
1.3
1. 3
6.4
6.4
1 "?
U. . .J
1. 3
1.3
1-3
. o
1-5
. J
1. 3
1.3
1.3 .
1. 3
1 *}
-L . *J
1 3
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6 4
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6/
. *i
1-5
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1*3
. 3
1.3
6.4
1.3
1 T
x . .j
1.3
,TCLP
mg/1


0.01
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. Ul
0.01
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0.05
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-------
TABLE 2C.  METALS ANALYSIS GENERAL METHOD
            MEDIAN REPORTING LIMITS*
Compound
   SW-846W
   Method
Compositional
  Dry,  nig/kg
TCLP, mg/1
EP, mg/1
TCLP ANALYTES

Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Selenium
Silver
    7060
    7080
    7130
    7190
    7420
7441/7440
    7740
    7760
     4.3
    15
     5.1
    16
     4.0
     1.4
     2.7
     2.8
    0.25
    0.90
    0.10
    0.33
    0.62
    0.01
    0.10
    0.09
   0.10
   0.90
   0.10
   0.33
   0.62
   0.01
   0.10
   0.09
NON-TCLP-ANALYTES

Nickel
Thallium
    7520
    7840
    16
    20
    0.22
    0.43
   0.22
   0.43
*S-Cubed Laboratory
                              .10

-------
 TABLE 2D.  PESTICIDES AND CHLORINATED  HERBICIDES  GENERAL METHOD
             MEDIAN REPORTING  LIMITS*  (SW-846 METHOD  8080  &  8150
             RESPECTIVELY)                             :           '
 Compound
Compositional
  Wet,  mg/kg
TCLP, mg/1   EP, mg/1
TCLP ANALYTES
Chlordane
Endrin
Heptachlor
Lindane (gamma-HC)
Me thoxy chl or
Toxaphene
2,4-D
2,4,5-TP (Silvex)
NON-TCLP ANALYTES
Aldrin
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor- 1248
Aroclor-1254
Aroclor-1260
alpha-BHC
beta-BHC
delta-BHC
4, 4 -ODD
4, 4 -DDE
4 , 4-DDT
Dieldrin
Endosulfan I
Endosulf-an II
Endosulfan sulfate
Endrin aldehyde
Heptachlor epoxide
2,4,5-T

1.1
0.21
0.11
0.11
1.1
2.1
0.02
0.02

0.11
1.1
1.1
1.1
1.1
1.1
2.1
2.1
0.11
0.11
0.11
0.21
0.21
0.21
0.21
0.11
0.21
0.21
0.05
0.11
0.02

0.001
0.2
0.0001
0.0001
0.001
0.002
0.02
0.02

0.001
0.001
0.001
0.001
0.001
0.001
0.002
0.002
0.0001
0.0001
0.0001
0.2
0.2
0.2
0.2
0.0001
0.2
0.2
0.2
0.0001
0.02

0. 001
0. 0002
0.0001
0 . 0001
0 . 001
0. 002
0 . 02
0.02

0 . 0001
0 . 001
0. 001
0. 001
0 . 001
0 . 001
0. 002
0 . 002
0.0001
0.0001
0. 0001
0. 0002
0. 0002
0.0002
0.0002
0.0001
0 . 0002
0 000?
W • \J \J \J ft
0 . 0002
0.0001
0.02
*S-Cubed Laboratory
                                11

-------
 POEW wastewaters and sludges;  (b) the compound's general level of



 toxicity;  (c) the capability to effectively and quantitatively analyze



 for the compound, including availability of standards; and (d)  the cost



 of the analyses and the experience and capability of most contract



 laboratories to perform the analyses specified for the POTWs.  All of



 the originally proposed 52 TCLP contaminants were included in the target



 compound lists.








      Analyses were run on the TCLP extracts and total digests (total



 compositional content)  of each sewage sludge (on a dry weight basis).



 The purpose of running a compositional analysis was to determine  if



 there were any direct relationship between total content of the various



 toxic constituents in the sludge and in the amount of the constituent



 extracted from the sludge by the TCLP.








     The  detailed analytical procedures used are contained in Table 3



 and in reference  (1).   The sample analyses were also subjected  to the



 QA  and QC procedures contained  in reference  (2)  and summarized  later in



 this report (See  also Appendix  B).








 RESULTS AND DISCUSSION








                             Volatiles








     Results of the analytical determinations of the total compositional



and TCLP study are contained in Tables 4A to 8B.  Only those non-TCLP




                                   12

-------
 TABLE 3.   STANDARD ANALYTICAL PROCEDURES*
                                    LEACHING
 LEACHING TECHNIQUE

 Extraction Procedure (EP Toxicity)

 Toxicity Characteristic Leaching
 Procedure (including Zero Headspace
 Extraction)
                REFERENCE METHOD

                1310  (SW-846)
                Federal  Register Vol.  51
                No.  9, Appendix 1
ANALYTE

Metals  (compositional)-
Flame and  furnace AAS
Analyses

Metals  (leachate samples)-
Flame AAS  analyses

Metals  (leachate samples)-
Furnace AAS analyses

Mercury (compositional)
Mercury  (leachate samples)-


Semivolatile Organic
 Compounds**(compositional)

Semivolatile Organic
 Compounds**(leachate Samples)

Volatile Organic Compounds-
 (compositional)

Volatile Organic Compounds-
 (leachate samples)
                               SAMPLE PREPARATION
Acid Digestion of
Sludge
Acid Digestion of
Leachate

Acid Digestion of
Leachate

Cold Vapor Analysis
Preparation

Cold Vapor Analysis
Preparation

Sonication/Solvent
Extraction

Continuous Liquid/Liquid
Extraction

Purge and Trap
Purge and Trap
    REFERENCE
METHOD (SW-846^

     3050
     3010



     3020



     7471



     7470



     3550



     3520



     5030



     5030
 *From Table by S-CUBED, A Division of Maxwell Laboratories, Inc.

**Increases Organocholrine pesticides and herbicides, PCB's and
  base-neutral/acid extractable compounds.
                                      13

-------
 TABLE 3 Cont.  STANDARD ANALYTICAL PROCEDURE
                                 METALS ANALYSES
 aw*™™,:.                                                      REFERENCE
 ANALYTE                              METHOD              METHOD /SW-R4R)

 Arsenic                         Furance AAS                   7060
 Barium                          Flame AAS                     7080
 Cadmium                         Flame AAS                     7130
 Chromium (Total)                 Flame AAS                     7190
 Lead                            Flame AAS                     7420
 Mercury (compositional)          cold Vapor AAS                7441
 Mercury (leachate)               Cold Vapor AAS                7440
 Nickel                          Flame AAS                     752o
 Selenium                        Furnace AAS                   7740
 Silver                          Flame AAS                     7760
 Thallium                        Flame AAS                     7840
                           ORGANIC COMPOUNDS ANALYSES


-.TKTV__                                                      REFERENCE
ANALYTE                              METHOD             METHOD  rsW-8451

Organochlorine Pesticides        Gas Chramatography/               8080
  and PCB's                      Electron Capture
                                 Detection

Chlorinated Phenoxy Acid         Derivatization; Gas               8150
 Herbicides                      Chromatography/Electron
                                 Capture Detection

Volatile Organic Compounds*      Gas Chromatography/Mass           8240
                                 Spectrometry

Semivolatile Organic Com-        Gas Chromatography/Mass           8270
 pounds* (Base Neutral/Acid      Spectrometry
 Extractables)

*Analysis conducted on sludge (compositional) and TCLP Leachate only.
                                    14

-------
  analytes that were found to be above the reporting limits* of any of the

  laboratories are shown in these tables.   The  results are presented as

  actual  data,  unless the constituents present were  at levels below the

  reporting limits. •  The median  reporting  limits for the TCLP and

  compositional analyses are given in  Tables 2A through 2D for the EPA

  contract  laboratory and the actual reporting limits for all the AMSA

  laboratories  or their contractors are given in Appendix C.



      In general, there were more volatile TCLP analytes reported by the

 AMSA contract and/or AMSA POTW laboratories compared to the EPA contract

 laboratory (Table 4A and 4B).  This was largely because of the

 respective higher reporting limits  for the EPA contract laboratory

 discussed elsewhere in this report.   There also were fewer volatile

 compositional analytes reported by  the EPA contract laboratory compared

 with AMSA.




     The levels of these volatile constituents were generally quite low,

but  are  the class  of compounds  that are most likely to cause sludges to

exceed -the TC.  As reported for Cities "A" and "E"  in Appendix D, Table

D-3), their sludges  came close  to exceeding the proposed TC because of

the volatile constituents chloroform and benzene in the TCLP extract.


*
 Reporting limits are defined as concentration levels below which, there
 is not good confidence in the result.  This reporting limit is for the
 concentration levels determined during the analysis of the given
       S^?r Practical *** routine laboratory conditions.   Reporting
        differ from detection limits.   Detection limits  are those

                                    •CQnpomd
                                     15

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                                                                          23

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Also, City "K"  sludge came within a factor of three of exceeding the TC

regulatory level because of the volatile constituent methyl ethyl ketone

 (MEK)  (Table 4A) .  The concentration of MEK in the TCLP extract of

sludge  from City "K"  was 1.3 to 2.2 rag/1, depending upon the analytical

laboratory (compared  with  the proposed regulatory level of 7.2 mg/1).

 (Note:  The final promulgated TCs were higher  (Table 16) and the chance

for TC  exceedance is,  therefore,  less).




     Values reported  for volatile TCLP analytes by EPA differed from the

values  reported by AMSA laboratories by as much as six-fold [e.g., for

identical  split samples of sludge from Cities "I" and "K" analyzed for

toluene (Table  4A) ].   The  differences might actually be higher, but it

is  difficult to tell  because of all the analytical results that were

below the  reporting limits.  Such variability would make it difficult to

accurately determine  that  any given analysis is accurately indicating
                                                          t
that the tested sludge has passed or failed the TC when the resultant

concentration of the  given analyte  in the TCLP extract is close to the

regulatory level.  It might be that the variability is less when the

level of" the constituent is present in higher concentration, such as for

MEK in  City "K"  sludge rather than  for toluene in Cities "I" and "K"

sludges.   However, too little data was available to make such an

assessment.




     The total compositional level of TCLP volatile analytes in sludge

are mostly in the 0.02 to  4 mg/kg range on a dry weight basis.  There

was as much as a 21-fold variation between the results obtained by the

                                    24

-------
 two separate laboratories doing the analyses on their separate splits of



 identical sludge samples (for example, for Cities "M" and "P" for



 toluene in Table 4B).








                            Semivolatiles








      The results of the semivolatile TCLP and compositional analyses



 were similar to those  of the volatile analyses with respect to



 uniformity among laboratories (Tables 5A and 5B).   However,  there were



 far fewer semivolatile TCLP or compositional analytes detected at



 reportable levels.  Furthermore, the TCLP analyte concentrations  were



 quite low compared  to  the TC regulatory  levels.








      There was  up to an eight-fold difference in the  amount of



 semivolatile  analytes  in  the TCLP extract reported by the EPA  and AMSA



 laboratories  for their respective identical  splits of the same sample



 (for  example, for City "L"  in Table  5A for phenol).   This eight-fold



variation  for semivolatile  TCLP analytes  is  less important than the



six-fold variation  for volatile TCLP analytes with respect to exceedance



of the TC  for sewage sludge, because the overall level of semivolatile



constituents  in sludges is  so far below the proposed and final TC



regulatory levels.








     The total compositional level of TCLP semivolatile analytes in



sludge are mostly in the 0.5 to 15 rag/kg range on a dry weight basis



 (Table 5B).  There were a number of non-TCLP analytes detected where the





                                    25

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  laboratory reporting limits were  lower (e.g.,  for City  "R" in Table 5A
  for one of the  two AMSA laboratories and City  "I's" AMSA laboratory in
  Table 5B).
                                Metals
      The results of the TCLP and total compositional metal analyses,
 obtained from the laboratories doing the work for AMSA and EPA, are
 presented in Tables 6A and 6B.  The reported metal TCLP analyte
 concentrations for the EPA contract laboratory were consistently higher
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      The total compositional metal concentrations were much  closer in
value between both laboratories (generally within a factor of three).
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laboratories.  The compositional TCLP metal concentrations were mostly
in the 1 to 2000 mg/kg range on a dry weight basis.

     Extraction Procedure  (EP)  and TCLP extractions and analyses were
also run on each sludge sample by the EPA contract laboratory.  The
results of the EP and TCLP metal extract analyses were then compared
(Table 7).  Often, where there was a reportable determination for the
                                    29

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  TCLP,  the EP was below reporting limits.   However, there were no



  consistent differences in amounts of metals extracted by the TCLP or the
  EP.
                        Pesticides and Herbicides








      The results of the TCLP and rotal compositional pesticide and



 herbicide analyses were similar in most ways to those of the



 semivolatile analyses  (Tables 8A and 8B).  The total compositional




 concentration of TCLP pesticide and herbicide analytes in this study are



 in the 0.1 to 10 mg/kg range on a dry weight basis.   Also, it can be



 concluded similarly for sludge pesticide,  herbicide, semivolatile, and



 metal analytes that their TCLP extract concentrations are one to two



 orders of magnitude belcw the TC regulatory levels.   It was not possible



 to determine the variation in the amount of a specific pesticide or



 herbicide constituent  detected in a  split  sample of  a given sludge



 analyzed by the two laboratories,  since  essentially  all measurements by



 the EPA contract laboratory were below the reporting limits.








                   Pretreatment Status of  the POTWs








     The POTWs selected for this study mostly served larger communities.



The industrial contributors to many of these facilities were thought to



be of a nature that might cause the resultant sludges to have higher



levels of TCLP analytes.  This was especially true in the EPA-AMSA



cooperative 12 POTW study.  The overall study, however, also included a
                                    39

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 few facilities (especially in the six POTW study)  with less than 1%



 industrial input.  These facilities were thought to produce "domestic"



 sludges with low levels of TCLP analytes.








      The results, however showed that "domestic" sludge from the



 smallest facility (City "A" with less than 1%  industrial input and 10



 MOD flow, Table D-2 in Appendix D)  came closest of all the  POTWs studied



 to exceeding the  proposed TC regulatory levels.  The concentrations of



 both benzene and  chloroform in the  TCLP extract of City "A" sludge were



 within a factor of three or less of the respective proposed TC



 regulatory levels (Table D-3 in Appendix D).   This result was in sharp



 contrast to the very low level of TCLP analytes  found in the "domestic"



 sludge from City  "B",  which also had less than 1%  industrial input, but



 a  flow of over 300 MGD.








      Postulated reasons for the striking differences  in City "A"  and "B"



 sludge TCLP analyte  concentration were (a) differences  in pretreatment



 programs,  (b)  differences in the type of industrial input,  (c)



 differences in the type of treatment,  and/or (d) the  fact that the



 smaller facility  lacked sufficient  flow to dilute occasional discharges



 of TCLP contaminants.








      Investigation revealed that pretreatment differences were



 apparently  not the reason.   Table 9 shows the pretreatment status of all



 18 POTWs.   Both Cities  "A"  and  "B" have only begun to implement



pretreatment programs, while most of the other facilities have had




                                    44

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                           45

-------
pretreatment programs for longer periods.  This left differences in
flow, treatment or type of industrial input as the most probable reason.
                     »
     It was noted that several printing facilities discharged into the
City "A" POTW.  It is not known if this would have caused an elevated
level of volatiles in the sludge.  In any event several printing
facilities also discharge into City "B's" PO1W, but on a relative basis
their discharge make up much less of City "B's" 1% industrial flow.
Cities "A" and "B" both had primary plus waste actived treatment, with
City "B" also having nitrification and ferric chloride treatment for
phosphorus removal.  City "A" stablized its sludge by lime addition,
while City "B" anaerobically digested its sludge.  It is not known if
the differences in treatment had any influence on the levels of volatile
constituents in the sludges.  One possible reason for the higher TCLP
analytes in the smaller facility's sludge (City "A")  appeared to be its
lack of ability to dilute out discharged contaminants with large volumes
of flow.

     Smaller facilities, however, do not necessarily have increased
levels of TCLP analytes in their sludge.  For example, City "J" had a
POTW that treated less than 10 MOD flow, but that had a very high
industrial component.  City "J" also has an intensive industry-specific
pretreatment program that seems to be very effective in controlling
levels of TCLP analytes in their sludge (Table 4A, 5A, 6A, and 8A) .
This is inspite of major petrochemical industries discharging into their
facility.  Therefore, treatment differences may also be important.
                                   46

-------
       Two other facilities had a volatile TCLP analyte whose
  concentration in sludge was  relatively close  to  the proposed TC.  The
  POTW serving City "E" had about a  30 MGD average flow and 60% industrial
  input (Table D-2 in Appendix D).   City "K's"  POIW had a flow of over 65
  MGD with about a 30% industrial input  (Table  1).  Chloroform, extracted
  frcm  City "E's"  sludge, came within a  factor of  seven of the proposed TC
  (Table D-3 in Appendix D), while methyl ethyl ketone, extracted frcm
  City  "K's" sludge, came within a factor of about four of the proposed TC
  (Table 4A).

      Pretreatment efforts were probably more intensive in City "E" than
  "K",  but neither of the efforts were probably as  intensive in City "J".
 An index of the effectiveness of pretreatment is  the  change in
 concentration of contaminants in the influent wastewater and residual
 sludge with time after the initiation of  pretreatment. Such changes in
 metal concentrations can be seen in Table F-l  of  Appendix F.  For  the
 most part these metal concentrations have decreased with time as the
 pretreatment programs have become established.  Approximately 75%  of the
 influent  metal levels  (i.e.,  35  of  46 influent metal concentrations for
 which  there was data) decreased  frcm 1980  to 1986.  Likewise, about 65%
 of the sludge metal levels  (42 of 63 sludge metal levels)  decreased
 during that period.  There was very little comparable historical data on
 the levels of toxic organic chemicals from the studied facilities.

     Taking into consideration the trend toward reduced metal
contaminant content in sludges since 1980  as pretreatment  programs  have
                                     47

-------
been instituted, one can predict more improvement in sludge quality as



more attention is placed on pretreatment and management to control toxic



organic as well as inorganic constituents.  As sludge quality increases,



there will be less likelihood of the concentration of contaminants in



the TCLP extracts of sludges exceeding the TC regulatory levels.   In



addition, from the discussion within this section, one can predict that



potential problems due to elevated levels of TCLP analytes in sludge



will likely be greatest where pretreatment is not practiced and where



flow, and hence potential for the dilution of discharged contaminants,



is small.








                   Reporting Limit Impacts on Data








     A comparison of the analytical determinations as well as the



reporting limits for City "N's" sludge are given for selected volatile



TCLP and compositional analytes in Table 10.  Note for the volatile



analyte carbon disulfide that there is a reported value for its presence



in the TCLP extract by the AMSA contract laboratory but not by the EPA



contract laboratory.  Note further that the AMSA Laboratory's TCLP



reporting limit is lower than EPA's.  For this same compound there were



no reported values for the sludge's compositional content, even though



 (as just mentioned) an actual value was reported in the TCLP extract.



While this result could be because of laboratory contamination, it is



more likely a result of the considerably higher reporting limits  for the



compositional determinations as compared to the TCLP leachate analysis.




                                    48

-------
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                                                                     49

-------
     Also, please note in Table 10 that there are reported values for



chloroform both for TCLP and compositional determinations by the AMSA



contract laboratory.  These numbers are both above the AMSA contract



laboratory reporting limits, but are below the EPA contract laboratory



reporting limits.  Similar observations can be made for the other two



analytes methyl ethyl ketone (MEK) and trichloroethylene in Table 10 and



also for the metal analytes given for City "L" in Table 11.  An



additional possible reason for MEK being detected in the TCLP extract,



but not in the total sludge compositional analysis (based upon the



compound's properties and the testing procedure) may be gained from a



discussion by D. F. Bishop in Appendix E.








     An important conclusion here is that this inability to detect a



specific constituent by the EPA contract laboratory compared with the



AMSA laboratory was common for all classes of constituents because of



the higher EPA laboratory reporting limits.  This finding indicates the



often overlooked necessity to specifically request in the sampling and



analytical plan that an adequate level of sensitivity be obtained to



meet the needs of the study, (i.e., so that reporting limits are at a



level consistent with meeting the study's objectives).








                 Quality Assurance and Quality Control








     We have included a section in this report on Quality Assurance and



Quality Control  (QA/QC).  This section reports findings by the EPA



contract laboratory almost verbatim as follows:




                                    50

-------
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                                                      51

-------
 QA Objectives



 Quality assurance objectives for precision, accuracy and

 completeness were established in the QA Project Plan (2).   These

 objectives were expressed in terms of the relative percent

 deviation (RPD)  for duplicate analyses, percent recovery of matrix

 spike compounds, and percent of samples for which all analyses were

 completed, respectively.   These objectives were as follows:



      Metals (Ag, AS,  Cd,  Cr,  Pb, Hg,  Ni,  Se, Tl)'
                Precision      Accuracy       Percent
     Matrix      (RPD)       (% Recovery)   Completeness

     Sludge        30           70  - 130         95
     Leachate      20           75  - 125         95
 -    Organic Compounds



     Table B-l in Appendix B details the accuracy and precision

     objectives for the compounds used in spiked sample analyses.



QC Sample Results



Two of the 12 POIW samples  (one out of each set of six) were

subjected to a specific QC analysis, incorporating the analysis of

a matrix-spiked sample (in duplicate)  with respect to all

analytical procedures employed for both organics and metals.

Originally, a duplicate analysis was also incorporated in this

                               52

-------
 scheme.  However, because very few,  if any,  organic analytes were



 detected within the POTW sludge samples,  the performance of a



 duplicate analysis was not judged to be worthwhile.   Rather, the



 results of the matrix spike duplicate analysis were utilized to



 address analytical precision.








 Results of the matrix spike/matrix spike  duplicate  analyses  are



 provided in Appendix B Tables  B-2 to B-7.  Because  sample volume



 requirements  for the various analyses frequently approached  the



 volume received by S-Cubed,  it was necessary to use  different



 samples for the matrix spike/matrix  spike duplicate  analyses for



 some of the various analytical methods employed.








 For the volatile and semivolatile organic analyses,  recoveries of



 spiked compounds and the reproducibility of those recoveries were



 consistently within the QA. objectives with respect to two of the



 three matrices  tested (the TCLP and EP extracts, but not the sludge



matrix).  Problems were encountered with both matrix spike



 recoveries and  precision of the compositional analysis of sludge



 samples  for volatile  organic compounds.  The initial QC analysis of



these samples indicated erratic recovering of spiked compounds,



thus initiating corrective action.  Other sample aliquots were



spiked and analyzed; however, similarly erratic results were



produced.  Analytical and instrumental conditions were checked to



ensure compliance with SW-846 protocols.  It can only be assumed,



after implementation and completion of corrective action, that



                               53

-------
 SW-846 protocols have major limitations in producing acceptable



 data for the matrices of interest to this study.   The problems



 encountered are probably the result of two major  areas of



 difficulty:








      1.   An extremely complex matrix containing  many interfering



           compounds.








      2.   Possible irreversible  and variable adsorption of analytes



           within the  highly organic POTW sludge matrix.








 Results of the matrix spike analyses for pesticides indicated



 recoveries that were  consistently within the established QA.



 objectives with respect to  all three matrices.  The reproducibility



 (precision) of these  recovery measurements was well within the



 objectives, with the  exception of the EP extraction of the sample



 from City  "P", where  the second matrix spike achieved consistently



 lower recoveries than the first  (Table B-6 in Appendix B).








With respect to the herbicide QC  sample analysis,  the recovery of



 2,4-D was consistently below the minimum established QA objectives.



For the compositional matrix, the analysis was also poorly



reproducible.  It is believed that this results from the method



employed, with specific reasons as follows:
                                 54

-------
       1.   Ether is-not the optimum solvent for extraction of
           phenoxyacid herbicides frcm complex organic matrices such
           as POTW sludges.

       2.   Complex organic matrices require substantial dilution to
           reduce matrix interferences, and may interact with spiked
           phenoxyacid herbicides.

 Results of the metals QC sample analyses (Tables B-8 to B-10 in
 Appendix B)  revealed the significant difficulties associated with
 the measurement of metal spike recoveries from a complex organic
 matrix containing variable but substantial native concentrations  of
 the various  metals.

 First, because  the measured concentration in the  unspiked sample
 must be subtracted frcm the measured  concentration in the spiked
 sample prior to recovery calculations, potential  errors associated
 with the  first  measurements add to the potential  errors associated
 with the  second.  Where native metal  concentrations are similar to,
 or greater than, the spike concentration, this leads to a large
 potential error in the measured recovery and an inapplicability of
 the QA objectives.  This occurred in many of the cases where the
measured recoveries were outside the QA objectives.

Second, the complex matrix of a POTW sludge precludes the level of
analytical accuracy expected from cleaner environmental samples.
                                 55

-------
      In particular, the objective of 70 to 130 percent for recovery



      measurements set in the QA. Project Plan (2)  are probably



      unrealistic.  A goal of 50 to 150 percent is probably more



      reasonable and has been used in Tables B-8 through B-10 to mark



      measured recoveries as outside QA. objectives.  However, a recovery



      goal of 70 to 130 percent has been applied to the leachates.








      As a routine check on recovery of various  types of organic analytes



      in the GC/MS analysis, surrogate compounds were spiked into each



      sample processed.   Surrogates were spiked  at the 50 to 200 ug/1



      (0.05 to 0.20 mg/L)  level in all leachates and at the  1 to 10 mg/L



      level in the sludges for composite analysis.   The recoveries



      measured are listed in Appendix B Tables B-ll and B-12.








      All planned analyses were successfully completed,  thereby meeting



      the completeness goal.   (End of S-Cubed discussion.)








      It is of interest to compare the variability  of results of the



QA/QC study by the EPA contract laboratory with the variability between



the EPA and AMSA analytical  results  for identical  splits of a sludge



sample.  For metals, the variability of results of the TCLP extract



analysis was  far greater  for the  split  samples analyzed by two



laboratories than for the analysis of the duplicate matrix-spiked



samples by the EPA contract  laboratory.  On the other hand, the



compositional determinations by the two laboratories were relatively



close for metals results in the split samples compared with the




                                    56

-------
  compositional analysis of the duplicate matrix-spiked sainples by the EPA
  laboratory.


       Meaningful comparisons between laboratories were not possible for  '
  most contaminants other than metals because the reporting limits of the
  taro laboratories were relatively high,  especially for the EPA contract
  laboratory.   Furthermore,  sensitivity was lost due to complex sludge
  matrix interferences and low contaminant  concentrations.

      There were varying degrees of QA/QC  efforts used by  the different
  laboratories.  Using a standard set of QA/AC procedures was not an
  absolute requirement of this cooperative  study.  Rather, the various
  laboratories could choose whether or not to follow the recormended QA/QC
 procedures already discussed.
                                 Costs
      The reported costs of analyses by the various contract laboratories
 were about $2,400 per one replicate of a sludge for TCLP and
 compositional analyses with the actual cost depending upon  the differing
 amounts  of other services being performed.  The cost for one TCLP
 analysis with limited QA/QC was about  $1,200 to $1,500 in 1988.

      Relationship Between TCLP and Compositional Content in Sludges

     The ratios of the TCLP analyte concentration  (wet weight basis)  to
the compositional analyte concentration  (dry weight basis) within each
                                   57

-------
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-------
 sludge were calculated. -These calculations were used to examine whether



 the compositional content of TCLP analytes could be used as  a rough



 estimator of the respective TCLP extract analyte contents.   The ratios



 for metals are presented in Table 12A for the AMSA-EPA 12 sludge study



 and in Table D-9 in Appendix D for the earlier  six sludge study.  The



 mean and median ratios for the 18 sludges are presented in Table 12B.



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 for metals which were more readily extractable  during the TCLP.  For



 example, the metals chromium and selenium (median ratio of 0.0007) are



 not as easily extracted by the TCLP as are the  metals barium and silver



 (median ratio of 0.003).








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 compositional metal levels in sludges at which  the metal TC  regulatory



 levels might be exceeded (Table 12C).   The large variance (by more than



 two orders  of magnitude) in the ratio for  a given metal  in different and



 even in identical splits of the same  sludge, depending upon  the specific



 laboratory  and analytical  run,  indicate their value only as very rough



 estimators  of metal levels that might cause the TCs to be exceeded.



 Hence,  TCLP testing could  be  necessary if  the determined compositional



 value for a given metal in sludge was at all close to the corresponding



 estimated range of compositional metal levels for failure of the TC.








      Similarly,  ratios of  the TCLP analyte extract concentration (wet



weight basis)  to the compositional concentration  (dry weight basis) were



                                    60

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                                                                                                                66

-------
  calculated for specific analytes in the volatile,  semivolatile,  and
  pesticide and herbicide organic compound classes (Tables 13A,  13B and
  14A).   These ratios were then used to estimate  compositional analyte
  concentrations of compounds  (in these three classes of TCLP analytes)
  which might exceed the  respective TCs (Tables 13C  and 14B).  Because  of
  the very  limited  presence of  TCLP analytes, especially from the
  semivolatile and  pesticide and herbicide classes,  there were few ratios
  and compositional concentrations  that could be calculated and estimated.

      The analytical data were used to obtain a very rough estimate of
 the total content of contaminants in sludges that would result in TC
 regulatory level exceedance (Table 15).  These rough estimates can be
 calculated from the formula (TC)/(divided by the median ratio)  where the
 median ratio is derived from the fraction of the total analytes
 extracted by the TCLP  within a class of compounds.

     While different for the various compounds within a class,  the
 fraction of the various  compounds extracted by the  TCLP was generally
 greatest for volatiles and least for semivolatiles, metals, pesticides,
 and herbicides  (Table  15).

 TCLP AND TC UPDATE

     EPA proposed the TCLP and coupled with TCs in  1986 to replace the
Extraction Procedure (EP) for classifying wastes as hazardous based upon
toxicity.  The proposed TCLP added 38 additional toxic organic
                                  67

-------
  TABLE 14B.  ROUGH ESTIMATION OF THE THRESHOLD SEMIVOLATILE, HERBICIDE
               AND PESTICIDE CONCENTRATIONS FOR FAILING THE TCLP
                             TCLP            Estimated
     Constituent              Toxicity  ++     Ccnpositional
                             Threshold,       Threshold, +++
                                rag/1            mg/kg
   SEMIVOLATTT.KR
p-Cresol
(aka§ 4-*fethyl Phenol)
Hexachloroethane
Phenol 	 	 	 	
10
4.3
14.4
500
860
14,400
   PESTICIDES & HERBICIDES

  Chlordane	0.03 	  43	
  Endrin	0.003	6	


  § = Also Known As
 ++ =  proposed Regulatory  Levels
+++ =  The  Estimated Compostional Thresholds would  mostly be
       Greater when Compared with the Final Toxicity
       Characteristic Regulatory Levels  Given in Table 16 in  the
       Update Section of the Report
                              68

-------
TABLE 15.  Factors for Roughly Estimating Toxicity Characteristic
           Regulatory Level Exceedance  from the Total Content of
                       Contaminants in  Sludge.
TCLP Analyte Class
Tables
Range of Mean Ratios
for Compounds within
a Class*
                                   Median of
                                   Mean Ratios*
    Volatiles
   (limited data)

    Metals

    Semivolatiles
  (very limited data)

    Pesticides &
     Herbicides
  (very limited data)
              0.2 to 0.4


           0.0002 to 0.003

            0.001 to 0.02


           0.0008 to 0.002
                             0.3


                             0.003

                             0.001


                             0.001
*These ratios were derived from the fraction of the total analytes
 extracted by the TCLP.  A very rough estimate of the total content of
 contaminants in sludges that would result in TC regulatory level
 exceedance can be calculated from the formula (TC) / (divided by the
 median ratio).
                                69

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compounds.  EPA received many Garments on the proposed TCLP and its 52



TC regulatory levels.  The comments received and the changes ultimately



made to both the TCLP and the TCs are described in detail in the final



rule  (March 29, 1990, in 55 FR 11798).








     Of particular importance to this sewage sludge study, there TCs for



only 25 additional toxic organic compounds in the final rule.  The



promulgated and proposed TCs are compared in Table 16.  The final



promulgated TC regulatory levels remained unchanged from the proposal



for the eight metals and some of the other contaminants.  Most of the



other contaminants had a less stringent TC, except for several



semivolatile toxic organic compounds where the TCs were slightly



decreased.  Since all of the TCs for volatile toxic organic contaminants



have been made less stringent in the promulgated final rule, sewage



sludges are even less likely to exceed the TC and be considered



hazardous.
                                     70

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TABLE 16.  COMPARISON OF PROPOSED AND FINAL TOXICITY CHARACTERISTICS
Toxicity Toxicity
Constituent Characteristic Characteristic
Proposed, Promulgated Final,
mg/1 • mg/1
VOLATILES
Acrylonitrile
Benzene
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1,2, -Dichloroethane

5.0
0.07
14.4
0.07
1.4
0.07
0.40

not promulgated
0.5
not promulgated
0.5
100
6.0
0.5
1,1,-Dichloroethylene (aka§
1,1, -Dichloroethene)
Isobutanol (aka§
2-Methyl-l-propanol)
Methylene chloride
Methyl ethyl ketone
(aka§ 2-Butanone)
Pyridine
1,1,1,2, Tetra-
chloroethane
1,1,2,2, Tetra-
chloretnane
Tetrachloroethylene (aka
Tetrachloroethene )
Toluene
1,1, 1-Trichloro-
ethane
1,1, 2-Trichloro-
etnane
Trichloroethylene
(aka Trichloroethene)
Vinyl Chloride
0.1

36
8.6

7.2
5.0

10.0

1.3

0.1
14.4

30

1.2

0.07
0.05
0.7

not promulgated
not promulgated

200
5.0+

not promulgated

not promulgated

0.7
not promulgated

not promulgated

not promulgated

0.5
0.2
 + = Reporting limit is greater than the calculated regulatory
     level, hence reporting limit is used.
 § = Also Known As (aka)
                              71

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TABLE 16 cont.  COMPARISON OF PROPOSED AND FINAL TOXICITY CHARACTERISTICS
Constituent
Toxicity
Characteristic
Proposed,
ng/1
Toxicity
Characteristic
Promulgated Final,
ng/1
 SEMIVOLATILES

Bis (2-chloroethyl) ether   0.05
o-Cresol
   (aka§ 2-Methyl Phenol)  10
m-Cresol
   (aka 3-Methyl_ Phenol)  10
p-Cresol
   (aka§ 4-Methyl Phenol)  10
Cresol
1,2 Dichlorobenzene        4.3
1,4 Dichlorobenzene       10.8
2,4 Dinitrotoluene         0.13
Hexachlorobenzene          0.13
Hexachlorobutadiene        0.72
Hexachloroethane           4.3
Nitrobenzene               0.13
Pentachlorophenol           3.6
Phenol                     14.4
2,3,4,6-Tetrachlorophenol   1.5
2,4,5-Trichlorophenol       5.8
2,4,6-Trichlorophenol       0.30

 METALS

Arsenic                    5.0
Barium                   100
Cadmium                    1.0
Chromium                   5.0
Lead                       5.0
Mercury                    0.2
Selenium                   1.0
Silver                     5.0

 PESTICIDES AND HERBICIDES
                  not promulgated

                      200*

                      200*

                      200*
                      200*
                  not promulgated
                        7.5
                        0.13+
                        0.13+
                        0.5
                        3.0
                        2.0
                      100
                  not promulgated
                  not promulgated
                      400
                        2.0
                        5.
                       100
                        1,
                        5,
                         5.0
                         0.2
                         1.0
                         5.0
Chlordane
Endrin
Heptachlor
Lindane (ganita-BHC)
Methoxychlor
Toxaphene
2,4-D
2,4,5,TP (Silvex)
0.03
0.003
0.001
0.06
1.4
0.07
1.4
0.14
0.03
0.02
0.008
0.4
10.0
0.5
10.0
1.0
     * = If o-,  m-,  & p-cresol cannot be differentiated, the total
         cresol regulatory level of 200 is used
     + = Reporting limit is greater than calculated regulatory
         level,  hence reporting limit is used.
     § = Also Known As (aka)
                               72

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  SUMMARY AND CONCLUSIONS

       The Toxicity Characteristic Leaching Procedure (TCLP)  is a testing
  procedure that has been developed by the Office of Solid Waste (OSW)  for'
  determining whether or not solid wastes, including municipal sewage
  sludges,  are hazardous based upon toxicity.   This  procedure was a
  proposed  replacement for the Extraction Procedure  (EP),  used for this
  purpose since 1980.   In the TCLP,  the concentrations of  analytes in the
  extracts  are compared to Toxicity Characteristic  (TC) regulatory levels.
  If concentrations of analytes in the TCLP extract meet or exceed these
  regulatory levels, the wastes are  classified as hazardous.

      In 1985-86 when the studies were conducted, it was felt that the
 proposed TCLP and TC regulatory levels might cause a number of municipal
 sewage sludges from Publicly Owned Treatment Works  (POIWs)  to be
 classified as hazardous.  Hence, the Office of Water (OW), in
 cooperation with OSW, began testing municipal sewage sludges.  Both
 total and TCLP,fractions of the  18 sewage sludges were  analyzed for
 selected analytes.   The Association of Metropolitan Sewerage Agencies
 (AMSA)  cooperated with EPA's OW  and OSW in this study, analyzing split
 samples of sludges  from 12 of the  POIWs  using identical analytical
 instructions  sent by  the EPA laboratory.  Tiine  and budget did not permit
 rigid policing of the AMSA laboratories  to assure that they actually did
 use identical procedures.

     These 18 analyzed sludges, included in two separate tests, were
obtained from POIWs that ranged in flow from less than 10 to over 600
                                     73

-------
million gallons per day  (MGD) with less than one to over 90 percent of



the flow being of industrial origin.








     Any change of TC regulatory levels from proposal to final



promulgation have been accounted for in the following important



conclusions:








1)   No POTW sewage sludge will likely exceed the TC regulatory levels



     and be considered hazardous.








     -    None of the 18 sludges tested by any of the laboratories had



          TCLP extract concentrations that exceeded the proposed TC



          regulatory levels.








          In these studied sludges  the volatile analytes were  found to



          be the most likely  class  of contaminants that might  cause a



          sewage sludge to be classified as hazardous,  (i.e.,  three of



          18 sludges had volatile TCLP analyte contents within less than



          an order of magnitude [one  of the three was within a factor  of



          three] of the proposed TC regulatory levels).








              Sludge from one POTW (City  "K",  Table  4A), came close to



              exceeding the proposed TC regulatory level because of the



              volatile constituent methyl ethyl ketone.  This result



              was  similar to  the results  of our earlier six sewage



              sludge TCLP study.   In the  six POIW study two of the six



              sludges also approached exceedance of the respective TC




                                    74

-------
                regulatory levels because of their content of the
                volatile components benzene and chloroform (Table D-3 in
                Appendix D).

           However,  because the final promulgated TCs are on  average,  two
           to three  times higher than the proposed TCs for the volatile
           toxic organic TCLP compounds,  it would seem unlikely that the
           volatile  compounds will  result in any POIW sludges being
           classified as hazardous.

           Because the concentrations  of  the metal, semivolatile,
           pesticide, and herbicide constituents in analytes in TCLP
           extracts of the tested sewage  sludges were lower than the
           respective 1C  regulatory levels by about one to two orders of
          magnitude, it would seem even  less likely for these classes of
          contaminants to result in sludges being classified as
          hazardous.

2)   To summarize the results in a different way, TCLP analyte
     concentrations  in 15 of  the 18 analyzed PCTW sludges were one to
     two orders of magnitude  below the TC regulatory  levels.   These 15
     POIWs were larger in size and most contained an  industrial flow
     component of 30%  or more.  Two smaller POWs (less than  10 MOD in
     size)  and one moderately-sized POTW  had sludges with TCLP volatile
     analyte contents that were from 3 to 7 times  below the proposed TC
     regulatory levels.   It may be  that sludges  from smaller  facilities
     are more likely to  be considered  hazardous than from larger
     facilities.
                                     75

-------
 The TCLP contaminants benzene and chloroform that came closest



 to exceeding the proposed TC regulatory levels were in a TCLP



 extract of a sludge from a smaller POTWs'  sludge.  This POTW



 had a flow that was a little over one million gallons per day



 (M3D)  and less than one  percent  industrial flow.








 One possible reason for  the higher level of volatile analytes



 observed in the tested smaller POOW is  that an insufficient



 volume of sludge was generated to dilute out  occasional



 discharges of TC contaminants  that have occurred.



 Unfortunately,  this study did  not include  information for



 assessing how the TCLP analyte contents  in the sludges were



 impacted by the type,  size,  and nature of  the industries



 discharging to  each POTW or  by the  type of wastewater and



 sludge  treatment employed at each facility.








 The total compositional and TCLP extract contents of the



proposed  52 TCLP analytes were not particularly high in the



tested  sludges.  Some limited information is presented in the



report about the various industrial pretreatment programs at



the tested facilities.  It is not known whether these



industrial pretreatment programs had any bearing on the



relatively low contents of analytes detected in the tested



sludges.
                             76

-------
          These findings for the tested sludges are contrary to the
          common assumption that sewage sludges from larger more
          industrial immunities are likely to contain higher levels of
          volatile, semivolatile, metal, and herbicide and pesticides.

3)    For most contaminants except metals,  there were non-detects in the
     TCLP extracts, and there were very few contaminants detected by
     both laboratories on the same sludge  sample.   Only for barium,
     p-cresol,  and xylene did split sample analyses on the same  sludge
     by the  EPA and AMSA laboratories show detected measurements.  There
     was substantial variation in the split sample  results for barium
     with the level of barium detected by  the EPA laboratory always
     being higher  than detected by the AMSA laboratories.  On the other
     hand, the variation in the split sample detects were  less for
     p-cresol and xylene with no laboratory's results being consistently
     higher.  The split sample  results for barium would have to be
    viewed as questionable because of the large degree of consistently
    skewed variation.

         The EPA contract laboratory concluded in their QA/QC analysis
         that such analytical variability  may have resulted because of
         compounds within the complex sludge matrices that interfered
         when using the SW-846 protocols.   Further, they concluded that
         there  was possible irreversible and variable adsorption of
         analytes  within the  highly organic POIW sludge matrix.  A
                                   77

-------
          third factor might be differences in subsample contaminant



          content.  In general, the AMSA laboratories had lower



          reporting limits than did the EPA laboratory.








     -    This considerable degree of analytical variability could



          increase the amount of duplication and cost to obtain adequate



          confidence in the results, especially where the analyte



          concentrations in the TCLP extracts are close to the TC



          regulatory levels.








          The cost impact upon small POTWs could be substantial.  The



          cost was about $1,200.00 to $1,500.00 (1988 dollars) for the



          complete analysis of a single sample without duplication.








4)   The analytical data were used to obtain a very rough estimate of



     the total content of contaminants in sludges that would result in



     TC regulatory level exceedance.








          These rough estimates can be calculated from the following



          formula:








               (TC times 100)/(divided by the median percentage)








          where the median percentage is derived from the fraction of



          the total analytes extracted by the TCLP within a class of



          compounds (Table 15).




                                     78

-------
           While these estimating percentages are different within a
           class of extracted TCLP contaminants,  the median percentages
           of the volatiles extracted were .generally greatest at 30%,
           followed by metals at 0.03%,  and  semivolatiles,  pesticides and
           herbicides at 0.01%.

           Because of the considerable variability in percentages  of the
           different analytes extracted  (see Tables  12B, 13B,  14A),
           additional TCLP testing would be  needed where these estimating
           percentages,  applied to the total.compositional analyte
           contents of the TC contaminants in sludge, would predict a
           TCLP analyte  content that was at all close (perhaps within an
           order of magnitude) to the TC regulatory level.

5)   When the concentrations of metals in TCLP and EP extracts were
     compared, there were no consistent differences in the amounts of a
     metal extracted.

6)   One important limitation of these studies is that  only 18 of the
     more than 15,000 POIWs in the United States  (US) were included in
     the study.   Only one of the 18 tested POTW sludges came from a POIW
     that was close to one M3D in size.   POIWs of less  than one MGD in
     size constitute nearly 90%  of all POTWs in the  US.  Another
     limitation  is that the 18 POIWs were not  selected  in a manner that
     would allow statistically valid extrapolation of the results  to the
     POIWs nationwide.  However,  the POTWs were selected on a basis of
                                   79

-------
     high to lew hydraulic and industrial flow with the expectation that



     these parameters would be somewhat inclusive of wastewater inputs



     and resultant sludges that might cause the sludge to be classified



     as hazardous.








7)   The applicability of the test from the viewpoint of reflecting a



     potentially toxic and hazardous condition for sewage sludges,



     whether used or disposed in air, on land or into water and at  what



     rate,  was not evaluated in this report.  We also did not compare



     TCLP results of sludge and other waste materials.
                                    80

-------
                               REFERENCES
(1)   Proposed analytical techniques - POTW sludge testing, S-Cubed
     Laboratories, La Jolla,  CA for USEPA, phone 619-453-0060.

(2)   Quality assurance project plan for POTW sludge testing,  S-Cubed
     Laboratories, La Jolla,  Ca for Dynamac Corporation for USEPA,  phone
     619-453-0060, May 1986.
                                  81

-------
           APPENDIX A
POTW Sludge Sampling Procedures
              82

-------
  APPENDIX A:  POIW Sludge Sampling Procedures

       The sampling of sludge at your wastewater treatment facility should
  be performed at the location previously specified.

       It is important that four basic objectives be kept in mind
  regardless of where the sludge samples are actually collected:
       (1)   Samples should be representative of the  bulk material from
            which they are collected;
       (2)   ^6 sample should be  identical in each of the six glass mason
            jars  (about one quart in volume)  and six 40 ml glass vials
            (VOA vials) having teflon septums at the  top;
       (3)   Sludge character or quality should not be altered as a result
           of sampling; and
       (4)  Proper QA procedures such as sample icing for refrigeration,
           fully filling all containers, and labelling of containers.
           Also,  all  procedures employed relative to sample collection
           are properly documented.

      Factors such as accessibility and physical characteristics  of the
 sludge (i.e.,  solids content, viscosity, etc.)  should be considered when
 selecting a sampling device  and/or procedure.   To the extent possible,
 the sampling device  should be clean and constructed of an inert or
 unreactive  substance  such as glass, stainless steel  of teflon.  The
 sampling method will vary depending upon the type of sample requested.
Dried sludge in either a  "cake" form or within a drying bed should be
easily accessible and can be sampled using either a trowel, scoop,
shovel, or auger.
                                    83

-------
     Availability and ease of use will probably be the determining



 factor.  A shovel or an'auger are better suited for sampling from a



 deeper bed of material  (integrated sample).  A sample of a thin layer of



 sludge cake such as that produced by a centrifuge, belt filter press,



 vacuum filter, etc. would be more easily collected by means of a trowel



 or scoop.  Sampling the bottom sludge from either a lagoon or settling



 tank can be accomplished using a small, light weight mechanical grab or



 dredge sampler.  Examples of this type of sampler are an Eckman grab or



 box dredge, ponar grab or Peterson grab.  Mechanical grab samplers



 generally  have closeable jaws, some of which are messenger activated.



 If the sludge layer is extremely thick, (i.e., several feet or more)  a



 teflon or  glass lined coring device can be used.  These latter samplers



 have the added advantage of creating a lesser degree of disturbance but



may require more drops.  Again, it should be emphasized that whichever



 sampler is used, proper cleaning procedures should be followed.



Moreover,  it should be dropped at a location within the lagoon or tank



where sludge deposits are most likely to accumulate.








     When multiple drops with a sampling device are required or multiple



 scoops are taken of drier material, it is essential to manually mix



these individual samples prior to filling the sample containers.  The



 final composite of these multiple samples should be thoroughly but



carefully mixed and then distributed among the six glass jars and six



vials.  (NOTE:  If the conditions of sampling require time compositing



or handling which would allow significant loss of volatiles, the taking



of separate grab samples in each 40 ml VOA vial is appropriate.



Although some sample representativeness may be compromised, the loss of



                                    84

-------
   volatile organics through volatilization  is extremely rapid and
   preservation of this  fraction through zero headspace storage is simply a
   more important  consideration.)

       For purposes of this sampling program, it will be necessary to fill
  three glass mason jars  (about 1 quart volume)  and three 40 ml glass
  vials having teflon septums in the top for each of the two ice chests.
  One ice chest (with three quart jars and three VOA vials)  should be sent
  to the EPA lab and one ice chest (with the other three quart jars  and
  three VOA vials) is for your lab.   Each  glass  jar and vial should  be
  filled  as completely full as possible in order to avoid the loss of
  volatile compounds.  Preservatives must  not be added to any of the
  samples.   Samples should be  refrigerated and shipped as soon as
  possible.   (See  the enclosed May 17th memo for timing.)  WE MUST
  EMPHASIZE AGAIN  THAT THE smDRB IN EACH OF THE SIX QUART JARS AM. STy
 VOA VIALS BE AS NEARLY IDENTICAL AS POSSIBLE.
      Lastly, it is ditportant that all samples are properly labelled with
 your identification number and packaged prior to shipment.  The  samples
 should be packaged on water ice (not "Freeze  Paks") and every attempt
 should be made  to ensure that the sample bottles will not be broken
 during transit.   The mason jars should be wrapped in the provided
 packing material  to prevent their coming into contact with one another.
 The three  40 ml VOA containers  can be wrapped and sealed in the
 collapsed plastic container being sent to you.  The ice chest should
also be taped, labelled with the label proved and shipped by
overnight shipment.
                                 85

-------
             APPENDIX B
QUALITY ASSURANCE/QUALITY CONTROL DATA
                  86

-------
 TABLE  B-l.   QA OBJECTIVE (ORGANIC COMPOUNDS)*
Accuracy
Matrix Spike Compound
VOLATILE COMPOUNDS
Benzene
Chlorobenzene
1, 1-Dichloroethene
Toluene
Trichloroethene
BASE-NEUTRAL EXTRACTABLE
COMPOUNDS
Acenaphthene
1,3, 4-Trichlorobenzene
2 , 4-Dinitrotoluene
Di-n-butyl Phthalate**
Pyrene
1,2, 4-Trichlorobenzene
ACID EXTRACTABT.E COMPOUND
4-Chloro-3-Methylphenol
2-Chlorophenol
4-Nitrophenol
Pentachl orophenol
Phenol
PESTICIDES
Aldrin
4,4' -DDT
Dieldrin
Endrin
Heptachlor
Lindane
HERBICIDES
2,4-D
*S-Cubed Laboratn™
% Recovery
Leachate

76-127
75-130
61-145
76-125
71-120


46-118
39-98
24-96
11-117
26-127
39-98
C
23-97
27-123
10-80
9-103
12-89

40-120
38-127
52-126
56-121
40-131
56-123

40-130
Sludge

66-142
60-133
59-172
59-139
62-137


31-137
38-107
28-89
29-135
25-142
38-107

26-103
25-102
11-114
17-109
26-90

34-132
23-134
31-134
42-139
35-130
46-127

25-130
Precision
RPD rv
Leachate

11
13
14
13
14


31
28
38
40
31
28

42
40
50
50
42

20
27
18
21
20
15

25
Sludge

21
21
22
21
24


19
23
47
47
36
23

33
50
50
47
35

31
50
38
45
31
50
"""
45
ompleteness
%

95
95
95
95
95


95
95
95
95
95
95

95
95
95
95
95

95
95
95
95
95
95

95
**Deleted from matrix spike list prior to implementation of analysis
                                     87

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TABLE B-2.  COMPOSITIONAL MATRIX  SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
             ORGANIC ANALYSES, NO.  1*
Spike Added % %
Compound City
VOLATILES (METHOD 8240)
Benzene K
Chlorobenzene
1 , 1-Dichloroethene
Toluene
Trichloroethene
SEMI VOLATILES f METHOD 8270) B/N
Acenaphthene N
1 , 4-Dichlorobenzene
2 , 4 -Dinitrotoluene
Pyrene
1,2, 4-Trichlorobenzene
SEMIVOLATILES fMETHOD 8270) ACID
4-Chloro-3-methylphenol N
2-Chlorophenol
4 -Nitrophenol
Pentachlorophenol
Phenol
PESTICIDES fMETHOD 8080)
Aldrin N
4 -4 '-DDT
Dieldrin
Endrin
Heptachlor
Lindane
HERBICIDES fMETHOD 8150)
2,4-D M
* S-Cubed Laboratory
** Interference
+ Outside QA objectives
%Rec1 Percent Recovery for Matrix
%Rec2 Percent Recovery for Matrix
RPD Relative Percent Difference
No . mg/kg

0.0004
0.0003
0.0003
0.0004
0.0003

5.0
5.0
5.0
5.0
5.0

10.0
10.0
10.0
10.0
10.0

0.36
0.90
0.90
0.90
0.36
0.36

0.7



Spike.
Spike Duplicate.
= (%Rec2 - %Rec,)
Rec,

109
114
167**
531**
99.7

102
60
94
94
78

72
63
123
21
63

64
77
84
85
93
99

0+





- (%Rec,
Rec2

107
120
183**
,+ 505**
109

90
58
80
84
70

65
56
103
16+
55

52
66
95
74
85
87

6+





RPD

1
5
,+ 9
,+ 5
9

13
3
16
11
11

10
12
15
27
12

21
15
12
14
9
13

200+





+ %Rec2)/2
                                    88

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TABLE B-3.
                                  pE/MATRIX SPIKE DUPLICATE
Compound City No.
VOLATILES (METHOD 8240)
Benzene L
Chlorobenzene
1 , 1-Dichloroethene
Toluene
Trichloroethene
SEMIVOLATILES (METHOD 8270) R/N
Acenaphthene G
1,4-Dichlorobenzene
2 , 4-Dinitrotoluene
Pyrene
1 , 2 , 4-Trichlorobenzene
SEMIVOLATILES (METHOD 8270) ACID
4-Chloro-3-methylphenol G
2-Chlorophenol
4 -Nitrophenol
Pentachlorophenol
Phenol

PESTICIDES (METHOD 808O)
Aldrin G
4-4 '-DDT
Dieldrin
Endrin
Heptachlor
Lindane

HERBICIDES (METHOD 8150)
2,4-D H
* S -Cubed Laboratory
** Interference
+ Outside QA objectives
Spike Added
mg/kg

0.0004
0.0003
0.0003
0.0004
0.0003

5.0
5.0
5n
• v
5rj
• U
5.0
-
10.0
10.0
10.0
10.0
10. 0


0. 40
1. 0
1f\
, 0
1.0
0.40
0. 40

0.94



%Rec, Percent Recovery for Matrix Spike.
%Rec2 Percent Recovery for Matrix Spike Duplicate.
RPD Relative Percent Difference = (%Rec2 - %Rec ) -
Rec,

92.8
127
0**
119
126

70
62
a c
DO
r- r-
55
66

61
34
23
54
56


56
112
62
93
69
70

4+



(%Rec, •
Rec2

95.4
132
,+ 205**,+
131
121

68
58
66
53
64

58
33
18
43
56


57
119
69
103
80
78

0+



+ %Rec2)/2.
RPD

2
3
200**,+
8
4

3
7
0
3
3

5
3
24
23
0


2
6
11
10
15
11

200+




                                   89

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TABLE B-4.  COMPOSITIONAL MATRIX  SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
             ORGANIC ANALYSES, NO.  2*
Spike Added % %
Compound City
VOLATILES fMETHOD 8240)
Benzene K
Chlorobenzene
1 , 1-Dichloroethene
Toluene
Trichloroethene
SEMIVOLATILES (METHOD 8270) B/N
Acenaphthene J
1 , 4-Dichlorobenzene
2 , 4-Dinitrotoluene
Pyrene
1,2, 4-Trichlorobenzene
SEMIVOLATILES (METHOD 8270) ACID
4-Chloro-3-methylphenol J
2-Chlorophenol
4 -Nitrophenol
Pentachlorophenol
Phenol
PESTICIDES (METHOD 8080)
Aldrin J
4 -4 '-DDT
Dieldrin
Endrin
Heptachlor
Lindane
HERBICIDES (METHOD 8150)
2,4-D J
* S-Cubed Laboratory
+ Outside QA objectives
%Rec1 Percent Recovery for Matrix
%Rec2 Percent Recovery for Matrix
RPD Relative Percent Difference
No. mg/kg

0.04
0.04
0.04
0.04
0.04

0.20
0.20
0.20
0.20
0.20

0.40
0.40
0.40
0.40
0.40

0.0004
0.001
0.001
0.001
0.0004
0.0004

0.84


Spike .
Spike Duplicate.
= (%Rec2 - %Rec1)
Rec1

102
102
100
105
102

115
80
85
95
90

53
68
45
0
45

72
61
113
101
95
92

31+




- (%Rec, -
Rec2

104
102
102
105
102

105
75
70
90
80

43
65
30
0
60

75
71
116
107
93
94

30+




*• %Rec2)/2
RPD

2
0
2
0
0

9
6
19
5
12

21
4
40
0
29

4
6
3
6
2
2

3




•
                                     90

-------
TABLE B-5.
            TCLP MATRIX SPIKE/MATRIX SPIKE  DUPLICATE RECOVERY
             ORGANIC ANALYSES, NO. 2*
Spike Added % %
Compound City
VOLATILES fMETHOD 8240)
Benzene P
Chlorobenzene
1, 1-Dichloroethene
Toluene
Trichloroethene
SEMIVOLATILES fMETHOD 8270) B/N
Acenaphthene P
1 , 4-Dichlorobenzene
2 , 4-Dinitrotoluene
Pyrene
1,2, 4-Trichlorobenzene
SEMIVOLATILES fMETHOD 8270) ACID
4-Chloro-3-methylphenol p
2-Chlorophenol
4 -Nitrophenol
Pentachlorophenol
Phenol
PESTICIDES CMETHon «nsn)
Aldrin p
4 -4 '-DDT
Dieldrin
Endrin
Heptachlor
Lindane
HERBICIDES fMETHOD 8150)
2,4-D p
* S-Cubed Laboratory
+ Outside QA objectives
%Rec, Percent Recovery for Matrix
%Rec2 Percent Recovery for Matrix
RPD Relative Percent Difference
No . mg/kg

0.05
0.05
0.05
0.05
0.05

0.20
0.20
0.20
0.20
0.20

0.40
0.40
0.40
0.40
0.40

0.0002
0.0005
0.0005
0.0005
0.0002
0.0002

0.16


Spike.
Spike Duplicate.
= (%Rec2 - %Rec1)
Rec,

94
82
88
84
104

85
60
70
90
64

58
60
28
43
38

77
106
84
90
80
80

30+



- (%Rec, •
Rec2

96
84

RR
o o
86

95
80

60

68
68
22
73
45

80
98
85
88
78
80

28+



+ %Rec2)/2.
RPD





19

11
1 "}
J- J
8

1 fi
-L o
12
52
18

4
8
1
2
3
0

7




                                  91

-------
 TABLE B-6.   EP MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
              ORGANIC ANALYSES, NO. 1*

Compound City No.
PESTICIDES f METHOD 8080^
Aldrin G
4-4 '-DDT
Dieldrin
Endrin
Heptachlor
Lindane
HERBICIDES (METHOD 8150^
Spike Added
mg/kg
0.0003
0.0008
0.0008
0.0008
0.0003
0.0003


^
Rec,
55
74
68
102
56
98


^
Rec2
44
57
55
94
43
106



RPD
22
26
21
8
26
8


2,4-D
                                            0.76
                                                        26+
                                                                26+
TABLE B-7.  EP MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
             ORGANIC  ANALYSES,  NO. 2*
Compound
City No.
Spike Added %
mg/kg Rec,
Rec2 RPD
Pesticides  rMethod 8080^

Aldrin
4-4'-DDT
Dieldrin
Endrin
Heptachlor
Lindane

HERBICIDES  (METHOD 8150)

2,4-D
0.003
0.0007
0.0007
0.0007
0.0003
0.0003
                                            0.16
 49
102
 86
110
 75
 91
                                                          7.5+
35
52
56
73
51
85
                                                                 21
33
65
42
40
38
 7
                                                                         90
*
+
%Rec,
%Rec,
RPD
S-Cubed Laboratory
Outside QA objectives
Percent Recovery for Matrix
Percent Recovery for Matrix
Relative Percent Difference


Spike .
Spike Duplicate.
= (%Rec2 - %Rec,) + (%Rec, + %Rec2)/2.
                                 92

-------
 TABLE B-8.
             METALS SPIKE/SPIKE DUPLICATE RECOVERY
              COMPOSITIONAL MATRIX*
                                    SET No. 1
Compound
Arsenic
Barium
Cadmium
Chromium
Lead
Nickel
Selenium
Silver
Thallium
Cone . Unspiked
Sample
Method mg/kg
7060
7080
7130
7190
7420
7520
7740
7760
7840
4.5
548
24
340
99
60
ND
ND
ND
Cone . Spike
Added
mg/kg % Rec,
27
540
5.4
27
27
27
5.4
263
27
97
145
141
134
127
131
143
86
137
"
% Rec2
91
37+
131
120
47+
131
106
77
137
RPD
6.4
119+
7.4
11
92 +
0
30
11
0
                                    Set  No.  2
Compound
        Cone. Unspiked
            Sample
Method     (mg/kg)
Cone. Spike
   Added
 (mg/kg)    % Rec.
                                                            Rec,
                                                        RPD
Arsenic 7060 53
Barium 7080 751
Cadmium 7130 15
Chromium 7190 109
Lead 7420 257
Mercury 7440 ND
Nickel 7520 59
Selenium 7740 ND
Silver 7760 8.9
Thallium 7840 ND
* S-Cubed Laboratory
ND Not detected
+ Outside QA objectives
RPD Relative Percent Difference =
%Rec, First Sample Recovery
%Rec2 Duplicate Sample Recovery
27
540
5.4
27
27
2.0
27
5.4
27
27



(%Rec, -
32+
91
100
157+
136
72
129
59
55
70



%Rec2) + (%Rec,
0+
91
109
90
128
78
105
84
9+
54



+ %Rec
200+
0
8.6
27
6.1
8.0
20
35+
144+
26



2)/2 X 100
                                    93

-------
TABLE B-9.  METALS  SPIKE/SPIKE DUPLICATE RECOVERY
             TCLP MATRIX*
                                    Set No. 1
Compound
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Method
7060
7080
7130
7190
7420
7440
7520
7740
7760
7840
Cone . Unspiked
Sample
mg/L
ND
1.6
ND
ND
ND
ND
ND
0.23
ND
ND
Cone . Spike
Added
mg/L
5.4
108
1.08
5.4
5.4
0.216
5.4
1.08
5.4
5.4
% Rec.,
111
64+
97
122
99.4+
111
94
30+
81
95
% Rec2
88
65+
100
117
99.4
117
99
45+
73
107
RPD
23 +
1.6
3.0
4.2
0
5.3
5.2
40+
10.4
12
                                    Set No. 2
Cone. Unspiked
Sample
Compound Method mg/L
Arsenic 7060 ND
Barium 7080 0.98
Cadmium 7130 ND
Chromium 7190 ND
Lead 7420 ND
Mercury 7440 ND
Nickel 7520 ND
Selenium 7740 ND
Silver 7760 ND
Thallium 7840 ND
* S-Cubed Laboratory
ND Not detected
+ Outside QA objectives
RPD Relative Percent Difference =
%Rec1 First Sample Recovery
%Rec2 Duplicate Sample Recovery
Cone. Spike
, Added
mg/L %
5.4
108
1.08
5.4
5.4
0.216
5.4
1.08
5.4
5.4



(%Rec., - %Rec2)



Rec, %
110
5.2+
107
93
4+
97
97
75
6.2+
106



+ (% Rec




Rec2 RPD
189+
5.
106
101
59+
91
100
82
2.
107



1 + '


53 +
2+ 0
0.94
8.2
175+
6.4
3.0
8.9
4+ 88+
0.94



's Rec2)/2 x 100


                                    94

-------
TABLE B-10.  METALS SPIKE/SPIKE DUPLICATE RECOVERY
              EP LEACHATE MATRIX*
                                   Set No. 1
Compound   Method
Cone. Unspiked
    Sample
     mg/L
Cone. Spike
 Added
  mg/L     % Rec1
Rec,
RPD
Arsenic 7060
Barium 7080
Cadmium 7130
Chromium 7190
Lead 7420
Mercury 7440
Nickel 7520
Selenium 7740
Silver 7760
Thallium 7840
0.20
2.6
0.11
ND
ND
ND
0.30
ND
ND
ND
5.4
108
1.08
5.4
5.4
0.216
5.4
1.08
5.4
5.4
102
95
102
123
109
-
98
86
92
108
115
76
95
118
111
80.5
94
66+
93
105
12
18
7.1
4.1
1.8
-
4.2
26+
1.1
2.8
Set No. 2
Cone

Compound Method
Arsenic 7060
Barium 7080
Cadmium 7130
Chromium 7190
Lead 7420
Mercury 7440
Nickel 7520
Selenium 7740
Silver 7760
Thallfum 7840
. Unspiked
Sample
mg/L
0.43
ND
ND
ND
ND
ND
ND
ND
ND
ND
Cone . Spike
Added
mg/L ;
5.4
108
1.08
5.4
5.4
0.216
5.4
1.08
5.4
5.4


1 Rec,
99
95
101
102
11+
66+
102
71
97
110


% Rec2
95
76
103
105
9+
65+
105
92
99
109


RPD
4.1
22+
2.0
2.9
20
1.5
2.9
26+
2.0
0.9
* S -Cubed Laboratory
ND Not detected





+ Outside QA objectives
RPD Relative Percent
Difference
%Rec, First Sample Recovery
%Rec2 Duplicate Sample
Recovery
= (%Rec, - %Rec2/


) + (%


Rec, + %


Rec2)/2 X 100


                                  95

-------


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-------
                APPENDIX C







AMSA LABORATORY REPORTING LIMITS FOR TCLP AND




   COMPOSITIONAL ANALYSES OF SEWAGE SLUDGE
                      98

-------
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ro
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1
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ro
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0
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in
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ro
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no
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*


in
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6
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Pyrene
                                                                               104

-------
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' ff

  3

CN
O
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CO
p"
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in
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ether 6

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m-i-resoj.
(aka 3-Methyl Phenol) 6

CN CN CN CN CN CN CN
in ro ro ro i-H t-* 00
O O O O O O o
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O O O O O O O
CN CN CN CN CN CN CN

ro ro ro PO ro ro ro
PO no PO ro PO ro ro
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in in in in in in in
CO CN IO

*******
in in in in in in in
p-^resoj.
(aka§ 4-Msthyl Phenol) 6
1,2 Dichlorobenzene 6
1,4 Dichlorobenzene 6
2,4 Dinitrotoluene 6
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Hexachloroethane 6

CN CN CN CN CN CN
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* = No Data Available
                                                                       105

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-------
APPENDIX C. TABLE C-4A. TCLP PESTICIDE AND HERBICIDE REPORTING LIMITS FOR POIW SLUDGE ANALYSES
t
»—
5
c
:ide & Herbicide Reporting Limits of AMSA Contract Laboratories* for Analysis of Pa
Constituent EPA Contract TCLP Pestic
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1 11- \
+ = AMSA Contract Laboratory Unless Indicated by " (POTW) " Meaning AMSA POTW Laboratory
-H- = Letter Denotes Minicipal POTW, (Number) Denotes the Specific AMSA Contract Laboratory
* = No Data Available
109

-------
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               APPENDIX D






    REPORT CN SIX POTW SLUDGE TCLP STUDY




(from a memo  by John Walker,  dated 7-11-86)
                   111

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APPENDIX D:   Report on Six POTW Sludge TCLP Study




PURPOSE




     This report describes the  results of Compositional and Toxicity


Characteristic Leaching Procedure  (TCLP) testing of sewage sludges from


six publically owned treatment works  (POTWs).




INTRODUCTION




     The six  POTW sludges were  sampled in November 1985 and subsequently

                        *
analyzed by a laboratory  under contract to the EPA Office of Solid


Waste and Emergency Response.  Results are incomplete because limited


equipment was available at the time of testing and some test procedures


have subsequently been revised.  More specifically, (1) the zero


headspace extractors were unavailable for use on this project until


nearly two months beyond the desired maximum two week holding period for


sludge samples to be extracted  for volatiles, (2) final adjustments were


still being made during this period to chemicals being used for the TCLP


extraction of samples which are different pH's and (3)  necessary


equipment and procedures were not available for determining the presence


of all 52 compounds in the solutions extracted from the sludges.


Because of these difficulties, 15 of the 52 TCLP compounds listed in


Table D-l, were not analyzed.
*
 ERCO Laboratories in Cambridge, Mass.  Mention of tradenames and names
 of vendors is for the benefit of the reader and does not imply
 endorsement by the US Environmental Protection Agency.



                                   112

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  POTW AND SLUDGE CHARACTERISTICS








       Characteristics of the six POTWs involved and their sampled sludges



  are presented in Table D-2.  Average daily flows  for the six POIWs



  ranged from less than 10 to over 500 million gallons per day (MGD) with



  the industrial contributions varying from less than one  percent  to about



  60  percent.  Most of the sludges were anaerobically digested and most



 were dewatered.   One sludge was  aerobically digested and not dewatered.



 The sludge pH's  ranged  from about 6.4 to 8.0.








 RESULTS AND DISCUSSION








      The TCLP extract concentrations for those volatile analytes



 detected (including both the volatiles listed for TCLP analysis or other



 volatiles found) are given in Table D-3.   The data indicated that sludge



 for City "A" was the worst based upon its volatile contents being



 closest to the Toxicity Characteristic Regulatory  Levels  (TCRLs).



 Sludge "A"  came from a POIW with less than 10 MGD  flow of which



 industrial  sources contribute less than 1 percent.   This  sludge



 approached  "failure"  of the TCLP  test due to  the chloroform and benzene



 concentrations  in the TCLP extract.   In fact, this sludge would have



 been considered "hazardous" based upon an earlier proposed TCRL for



 chloroform that was lower.  The presence of several printing and



 photographic business, discharging wastewater to City "A's" POIW may be



part of the explanation of this phenomenon.  Sludge "E" also approached



 "failure".  However, it came from a coirounity with about 60 percent of



its almost 30 MGD flow from industrial sources.   This sludge would also
                                  113

-------
 have failed, based upon earlier threshold concentration proposals, again



 because of its TCLP extract chloroform content.








      Still another sludge  from City  "B" with greater than 300 M3D flow,



 of which  less than one  percent was of industrial origin, actually had



 one  value for a volatile compound in the TCLP extract that exceeded the



 TCRL.   The compound was tetrachloroethylene with one measurement



 indicating a content of 11.0 mg/ml as compared with the TCRL for this



 compound  of 0.1 mg/ml.  However, this same volatile compound was not



 detected  in three  other TCLP extracts of this same sludge and the high



 value may likely have been the result of laboratory contamination.



 Also, the total compositional  content of tetrachloroethylene was only



 0.16 mg/ml (a mean of two  determinations) (Table D-4).








     The  TCLP extract concentrations for heavy metals are given in



 Table D-5.  None of the sludge TCLP extract metal concentrations were



 very close to the  TCRLs.   The  TCLP concentrations nearest the TCRLs were



 for  lead  and cadmium in POTW Sludge  "C".  Those TCLP concentrations are



 about one-tenth the TCRL.  The compositional dry weight concentrations



 of metals (Table D-6) were used along with the TCLP extract



 concentrations (Table D-5) to  calculate the ratios in Table D-9.








     Extraction Procedure  (EP) metal analyte concentrations were usually



 lower for the six  POTW  sludges than were the TCLP metal analyte



 concentrations except for  Sludge from City "C" (Table D-7).  While TCLP



metal levels were  higher than  EP metal levels, as might be expected




                                  114

-------
  because of a somewhat more vigorous TCLP extractant,  the differences
  were not great.   Since metal concentrations in the EP extracts  have
  rarely caused sludges to fail and since the EP and TCLP extract levels
  are not very different,  few POTW sludges are expected to fail because of
  their metal contents.

       Some persons have proposed using wet weight compositional analysis
  as  an index for predicting the TCLP extract concentration.  The
  usefulness  of this "index" should depend upon demonstrating that such a
  relationship exists.

      The TCLP extract to wet weight sludge compositional metal content
 ratios are given in Table D-8.  An examination of this data revealed
 that this ratio is not constant for a given metal.   In fact,  it  varies
 over 1000-fold for a given metal analyte with the variance apparently
 being strongly affected by the sludge moisture content.  On the  other
 hand, the ratio of the TCLP extract to dry weight sludge compositional
 metal content ratios  (given in Table D-9)  varied less  (only about
 10-fold).  Examination of the ratios in  Table D-9 for  individual metals
 shows that the ratios  are about 100-fold different  from one another
 because of the difference in  the TCLP extractabilities  (solubilities)  of
 the  various  metals tested (lead being the most insoluble and barium and
 especially nickel being the most soluble).  Using different ratios each
 derived from an individual metal or the median ratio derived from all of
 the  individual metal ratios could be used as a multiplier times the dry
weight sludge compositional concentration to obtain a rough estimate of
                                   115

-------
the TCLP extract concentration of that metal.  While using individual



ratios would be more precise, using the median of all ratios could be



useful to obtain a very rough estimate.








     A similar examination of the ratio of TCLP extract to dry weight



compositional concentration for volatiles was attempted (Table D-10).



Since volatiles were detected for many fewer compounds, reliable



evaluations are not possible for either the constancy of the ratio or



its usefulness in predicting the TCLP extract concentrations of



volatiles.








     The only semivolatiles analytes detected were 1,4- and



1,2-dichlorobenzene  (0.31 and 0.35 mg/ml, respectively).  Furthermore,



no herbicide and pesticide TCLP analytes were detected.  Hence, ratios



could not be calculated for these three classes of TCLP analytes.








CONCLUSIONS








     We reached the following tentative conclusions based upon the



incomplete results shown in Tables D-2 through D-10.








     1.   No PCTW sewage sludge failed the test.








     2.   Two of the six POTW sludges approached failure of the TCLP



          test for volatile components and would have failed if an



          earlier set of TCRLs had not been recalculated and changed.





                                  116

-------
      One of the POIW sludges that approached failure was from a
      smaller community  (less than 10 MGD) with 99% of its
      wastewater input being of domestic origin.

 3.   Volatile components in POIW sewage sludges are most likely to
      cause failure of the TCLP test.   Failure caused by
      semivolatile and herbicide and pesticide contents  is most
      unlikely.


 4.    Since  the EP  and TCLP analyte concentrations are not too
      different and since  few sludges have had metal analyte
      concentrations exceeding the EP toxicity thresholds in the
     past,  few sludges are expected to fail the TCLP test and
     hence, be considered hazardous because of metal content.

5.   The ratios of TCLP extract metal  concentration to .
     compositional dry weight metal concentration varied only
     within a factor of about 10 for a given metal  in all six
     sludges.  These  rations  could be  used to very roughly predict
     the TCLP metal extract concentration  in sludges.

     Use of  wet weight sludge compositional metal concentrations to
     determine the  ratio for predicting the TCLP extract metal
     concentrations was unsuitable because the different sludge
    moisture levels caused as much as  a 1000-fold variation in the
    ratio of TCLP extract concentration to wet weight sludge
    concentration.
                                 117

-------
           The use of the TCLP extract concentration to dry weight sludge



           concentration ratio may be suitable for estimating



           concentrations of volatiles compounds, but the data were



           insufficient  to support such an hypothesis.








      6.    Only two semivolatile analytes were detected and these were in



           only one of the six sludges examined.  No pesticides or



           herbicides were detected in the six sludges.








FUTURE








     The above conclusions are clearly tentative, recognizing the



uncertainties  discussed.  To obtain better results and hopefully sounder



findings, twelve additional POTW sludges underwent compositional and



TCLP testing.  Better quality assurance and quality control procedures



were used.  Samples were collected and split to allow separate testing



by each of the 12 POTWs or their contractors and the EPA contract



laboratory.  Results of both sets of analyses have been assembled and



compared.  The results of this study constitute the main body of this



report to which Appendix D is attached.
                                   118

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-------
         APPENDIX E






COMMENTS BY DOLOFP F. BISHOP
             129

-------

        UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                 OFFICE OF RESEARCH AND DEVELOPMENT
                 WATER ENGINEERING RESEARCH LABORATORY
                           CINCINNATI, OHIO -15268


DATE:     June 17, 1987            __

SUBJECT:  Comments on "Cooperative Testing of  Municipal Sewage
          Sludges by the TCLP and by  Compositional  Analysis"
FROM:     Doll of f F. Bishop, Chief
          Technology Assessment Branch, WRD

TO:       John M. Walker, Physical Scientist, WH-595
          Residuals Management Branch


     My overall impression of the above report is that a larger data
basis is essential to appropriately evaluate the probable impact of
toxics on sludge disposal.  The TCLP results of the study are, however,:
consistent with expected partitioning chemistry of the toxics.  That is,
those organics with a strong tendency to partition to the solids in
wastewater (high octanol/water partition coefficient [Kow])will not be
efficiently extracted by an acetic acid aqueous extraction (TCLP).
Those organics with more affinity for the aqueous phase (lower Kow),
such as many of the volatile organics, will be found at higher concen-
trations in the TCLP extract even though they may be at lower concen-
trations in the sludge.

Conversely, organics with a hign Kow will partition more completely onto
the  sludge than those with lower Kow and, therefore, for equal influent
wastewater concentrations, would appear at higher concentrations in the
sludge during compositional analyses.  Unfortunately, the analytical
measurements by the EPA and AMSA Laboratories in the study are even more
variable for the compositional analyses than for the TCLP analyses.  Thus
I  am not sure that the existing data substantiates this high  Kow effect
of the partitioning chemistry.  It is my opinion, however, that the
composition analysis will be the more important measurement,  especially
if the new sludge  regulations establish regulatory compositional concen-
trations for both  organics and metals.  Thus, the compositional analytical
effort needs to be substantially improved.

     The lack of comparison data between the EPA and AMSA Laboratories on
the  same sludge samples is most often  related to different detection limits.
In the study, the  EPA  Laboratory  used higner detection limits.  It  appears as
if the EPA Laboratory  limits have been rather arbitrarily established.   I
would expect that  all  laboratories should  have used the same  procedures  and
thus have similar  detection limits.  The use of different detection limits
by the various  laboratories, however, may  indicate the use of different
analytical options  in  the analytical methods.  Your report does not address
the  issue and  it  needs clarification.

                                 130

-------
-      If the analytical methods were the same, then approximately similar
detection  limits should be agreed to by all laboratories.  If, the signifi-
cantly lower detection limits, as apparently used by the AMSA Laboratories
can actually be observed, I would suggest that the EPA Laboratory also apolv
tnose limits to its existing data tapes.  The use of the lower limits would
produce a  larger data base for evaluation  In any event, roughly similar
detection  limits should be applied to all data if identical methods and
similar equipment were used.

      It may be possible to strengthen the qualitative conclusion of the studv
that municipal sludges are not likely to fail the TCLP test.  Specifically
a  statistician with analytical chemistry competency could evaluate the aonro-
pnateness of applying a statistical test for significance (students "t" test
or other comparison tests) to paired results from the EPA and AMSA Laboratories
compared to the TCLP regulatory levels.  The comparison using the observed
analytical variability would indicate the probability of the sludges in the
existing data base for exceeding the TCLP regulatory levels.  Paired results
(precision) within laboratories could also be used in the statistical evalu-
ation.  The availability of more paired results, such as would occur if lower
analytical 1 units were applied to the existing EPA Laboratory measurements
might strengthen the analysis.  The statistician, however, needs to assess'
the effect on the validity of the statistical comparison of having a large
number of  samples in the study near the methods detection limits.
 fMn
-------
                    APPENDIX F






TRENDS IN AMSA POIW INFLUENT AND SLUDGE METAL CONTENTS




           AS INFLUENCED BY PRETREATMENT
                       132

-------
APPENDIX TABLE F-l.  TRENDS IN INFLUENT AND SLUDGE METAL CONTENTS

Appi
City
A
C
D
G
H
L
N(a)
P(b)
R
City
A
C
D
G
H
L
N(a)
P
R
City
A***

D
G
H .
L
N(a)
P
R

(a) =
(b) =
§ =
* _
** =
*** =
+ =
++ =
+++ =
Influent, mg/1
•ox. Year 1975 1980 1983


0.104 0.076
1.02 0.42 0.29
1.15+ - 0.23
2.44 2.22
0.135 0.096
- - -
0.022* 0.035 0.030
0.139 0.073

1.48 0.89
- - -
1.16+ - 0.63
0.193 0.187
0.162 0.120
- - -
1.117* 0.233 0.030
0.102 0.083

0.090 0.075
0.31 0.21 0.22
0.67+ - 0.14
0.137 0.119
0.105 0.057
- - -
0.503* 0.115 0.165
0.207 0.153

different labs for 1981/83 and
hexavalent chromium in influent
another POTW input
1977 data
1982 data
limited data
1973-74 data
1978 data
1981 data
1

1986
CHROMIUM

0.062
0.18
0.20
1.17
0.046
-
0.005
0.067
COPPER
0.91
-
0.22
0.094
0.113
-
0.005
0.095
NICKEL
0.076
0.10
0.14
0.038
0.037
-
0.052
0.182

1986
not in sludge
33
Sludge,
1975 1980


241
2184 1567
420+
6262
- —
574++-
392* 596
207
560
2375 '
1819 957
4700++
466
— _
3178+++
585* 571
157
20
58
481 449
500
93
— _
521+++
193* ' 32
204


mg/kg
1983


151
937
900
4170
385
- .471
303
139
440
2270
763
1700
393
613
2323
371
214
48
50
362
250
125§
89
357
165
322


— •••—
1986


128
512
950
5740
180
506
207
124
359
2498
535
800
381
568
3506
397
195
90
59
169
260
86
60
543
111
248



-------
APPENDIX TABLE F-l COnt.  TRENDS IN INFLUENT AND SLUDGE METAL CONTENTS
                      Influent, mg/1



 Approx. Year  1975    1980    1983    1986
       Sludge,  nxj/kg
1975    1980    1983
1986
City
A
C
D
G
H
L
N(a)
P
R
City
A
C
D

0.051 0.026
0.035 0.026
0.24x 0.13
0.052
0.018
-
0.027* 0.012
0.002

12.6
1.55 0.85

0.026
0.034
0.03**
0.023
0.015
-
0.013
0.002

5.0
1.00
CADMIUM
_
0.043
0.014
0.02
0.012
0.005
-
0.011
0.001
ZINC
«•
3.2
0.75
"» R
81
93 75
900
113
- -
234-H-
54* 21
7.2
1240
8700
4821 3233
9
52
76
500
45
46
12
29
4.7
982
8425
3370
5
102
44
40
39
25
15
32
3.2
510
6500
1368
G ____ ____
H
L
N(a)
P
R
City
A
C
D
0.555
0.789
- -
1.188* 0.980
0.338

0.58
0.36 0.17
0.540
0.441
-
0.685
0.313

0.40
0.15
0.289
0.239
-
0.400
0.242
LEAD
0.42
0.14
1103
-
3327+++
3529* 3172
479
220
1395
1437 663
1300§
2479
2376
2119
572
106
1099
430
1185
1134
3802
1990
437
58
1137
398
G -___ ____
H
L
N(a)
P
R
0.152
0.153
- -
0.500* 0.210
0.064
0.127
0.048
-
0.105
0.044
0.101
0.038
-
0.086
0.024
394
- -
401+++
843* 736
.. 195
409§
307
347
608
404
325
215
365
449
73

(a) =
§ =
** r=
*** =
+ =
•H- =
H-H- =
X =
different labs for 1981/83 and 1986
another POTW input
1977 data
1982 data
limited data
1973-74 data
1978 data
1981 data
1976 data
134

-------
APPENDIX TABLE F-l Cant.  TRENDS IN INFLUENT AND SLUDGE METAL CONTENTS
Influent, n»g/l
Apprax. Year 1975 1980 1983 1986 1975
City ARSENIC
C - 0.01 0.03 0.008
D 0.016 0.006 0.008 0.012 20
City SELENIUM
C - 0.010 0.018
D -
City MERCURY
A ____•_
C - 0.0007 0.003 0.006
D 0.0013 0.0009 0.0013 0..0011 4.9
N(a) -
City SILVER
C - 0.028 0.024 0.022
D - 42
N(a) -
City CHROMIUM"*"6
N(a)
Sludge,
1980
3.4
10
0.4
8.4
2.6
2.4
4.5
rag/kg
1983
5.5
17
2.3
8.6
1.1
1.9
6.2
0.16+++ 1.63
11.6
36
24.7
46
24-f-w- 30
18
1.4

1986'
2.9
15

12.3
. 1.4
1.6
4.6
1.1
2.1
41
64
129

(a) = different labs for 1981/83 and 1986
-H-f = 1981 data
                                     135

-------
 APPENDIX TABLE F-l Cont.   TRENDS IN INFLUENT AND SLUDGE CONSTITUENTS
                                                           Sludge, nig/kg
  Approx. Year  1975     1980     1983    1986'       1975    1980    1983    1986
                                         CYNAIDE
                        0.27    0.27    0.47          -      296     144
                0.28    0.11    O4    0702	1	r2
 City                                     DDT


  D              -
                                                    10.2     2.0     0.
 City


  D
                                                    18.8      1.8      0.
 City                                    TICH

 D              -
                                                   31.3     3.8     1.1
City
                                     OIL & GREASE
                 90       75       70      65
                                        PHENOLS

               3.7     2.3     2.4     2.4
 (a) = different labs for 1981/83 and 1986
+++*= 1981 data
                                     136

-------