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
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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
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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
J. • */
6 4
w * *r
6/
. *i
1-5
. 3
1*3
. 3
1.3
6.4
1.3
1 T
x . .j
1.3
,TCLP
mg/1
0.01
Om
. U J.
On n
. UJ.
On T
. Ul
0.01
On n
• U±
0.05
0.05
Ort T
. 01
On T
. UJ.
On T
. Ux
0.01
0.01
Om
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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
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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
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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
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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
than those reported by the AMSA cooperators and POTW laboratories by a
factor of up to ten. This amount of variation could be very critical if
the levels of TCLP constituents were any closer to the TC regulatory
levels.
The total compositional metal concentrations were much closer in
value between both laboratories (generally within a factor of three).
Also, the EPA laboratory compositional metal analyte concentrations were
neither consistently higher nor lower than those reported by the AMSA
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
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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
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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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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
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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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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
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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
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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.
As can be seen in Table 12B, the mean and median ratios were different
for the different metals. In general the ratio was of greater magnitude
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).
Calculations were made using these ratios to estimate total
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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55
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66
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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
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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
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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
-------
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
-------
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
-------
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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Q
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97
-------
APPENDIX C
AMSA LABORATORY REPORTING LIMITS FOR TCLP AND
COMPOSITIONAL ANALYSES OF SEWAGE SLUDGE
98
-------
u
"
CN c
0 C
rt 0 C
rt 0 C
in if
o c
0 C
0 C
* • *
0 C
CN CN! CN
in o o c
rt 0 O C
rt O 0 C
in in in in
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0 O 0 C
0 0 0 0
CN CN CN
0 O 0
CN 0 O 0
• • • •
rt O O O
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CO O O O
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0 O O O
rt rt rt
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rt O O O
in CN
in o CN o
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in in in
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in o o o
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o o o
in in in
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in o o o
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in in in in
CN 0 0 0
0000
in in in
rt 0 0 0
0000
o o o o
_.
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ene
on disulfide
on tetrachloride
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4 CN
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> 0
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> 0 O 0
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in in in in
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o o o c
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o o o o
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0 0 0 0
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Methyl-1-propano
ylene chloride
CN 43
1
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C
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c
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c
1
p>
c
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in
CN
C
o
in
CN
o
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rt
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a 2-Butanone)
dine
s
rt
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in u-
rt r-l
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c
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§
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Ȥ Trichloroethe!
L Chloride
S
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100
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°
„
<=
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=
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0
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ro
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0
0
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CM
in
in
°
,
<=
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ro
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in
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1,1, -Dichloroethene)
CO
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ro
0
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2-Methyl-l-propanol
CO
CM
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in
*
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in
CO
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0
rH
CO
ro
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(aka Trichloroethene)
no
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in
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°
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0
in
CO
o
0
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ID
CM
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6
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101
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t
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102
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c
c
If
c
c
c
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c
c
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o
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CM
o
c
rH
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0
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g o
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> C
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cs
c
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c
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0
rH
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CM
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rH
C3
*
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c
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&
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8 *
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3 OOOOOOC
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in
in in in o rn
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> OOOOOOC
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CM O O O O O C
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o o o o o o o
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o o o o o o o
0 0 0 0 0 O 0
CM CM CM CM CM CM CM
o o o o o o o
o o o o o o o
CM CM CM CM CM CM
rH 0 0 0 0 0 0
o o o o o o o
in in
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o o o o o o o
o o o o o o o
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o o o o o o o
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0 0 O 0 0 0
o o o o o o
o o o o o o
CM CO 00 CO 00 00
000000 1
0 0 0 0 0 C3 i
1
CM CM CM CM CM CM !
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CM
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rH VD rH rH rH
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rH rH rH rH rH rH
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=> 0 O O O O
rH
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0
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104
-------
i ir
I n
' ff
3
CN
O
CN
O
CN
CO
p"
T
in
•a1
CN
.
*
in
Bis ( (2-chloroethylether)
ether 6
CN
m
o
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o
o
f>
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tn
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in
1
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f
CN
IT
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0
o
CN
PO
CO
*
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in
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
CN CN CN CN CN CN CN
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
OO O O CO CN OO CN
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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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
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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
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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
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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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128
-------
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
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