EPA 560/6-77-021
IDENTIFICATION AND ANALYSIS
OF POLYCHLORINATED BIPHENYLS
AND OTHER RELATED CHEMICALS
IN MUNICIPAL SEWAGE SLUDGE
SAMPLES
AUGUST 1977
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 2O46O
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IDENTIFICATION AND ANALYSIS OF POLYCHLORINATED BIPHENYLS AND OTHER
RELATED CHEMICALS IN MUNICIPAL SEWAGE SLUDGE SAMPLES
by
Mitchell D. Erickson and Edo D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-01-1978
Project Officer
Dr. Vincent J. DeCarlo
Office of Toxic Substances
Washington, D. C. 20460
U. S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D. C. 20460
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DISCLAIMER
This report has been reviewed by the Office of Toxic Substances, U. S.
Environmental Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the views and poli-
cies of the U. S. Environmental Protection Agency, nor does mention of
trade names or commercial products constitute endorsement or recommendation
for use.
ii
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ABSTRACT
Methods were developed for the extraction, clean-up and GC/MS analysis
of polychlorinated biphenyls (PCBs) and related chemicals in municipal
sludge samples. Each of the sludge samples received from nine major
United States cities was processed to yield a neutral fraction and two acid
fractions which were methylated with dimethylsulfate and diazomethane,
respectively. Samples were cleaned up by silica gel column chromatography.
A total of 35 chlorinated compounds were found in the full scan GC/MS
analysis, including polychlorobiphenyls, polychloronaphthalenes, polychloro-
aniline, polychlorobenzene and DDE. Some chlorinated compounds remain
unidentified.
lii
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CONTENTS
Page
Abstract ii:L
Figures vi
Tables xiv
Acknowledgements xviii
List of Abbreviations 1
1.0 Introduction 2
2.0 Summary and Conclusions ^
3.0 Recommendations ->
4.0 Objectives 6
5.0 Method Development 6
5.1 Chemicals And Instrumentation 6
5.2 Development of Sample Extraction and
Workup Procedures 6
5.2.1 Extraction of Neutral and Basic Compounds .... 6
5.2.2 Methylation of Acidic Components with
Dimethylsulfate 7
5.2.3 Methylation of Acidic Components with
Diazomethane 12
5.2.4 Column Chromatography 12
5.2.5 Summary 12
5.3 Development of Instrumental Methods 12
5.3.1 GC/MS Analysis of PCBs 12
5.3.2 Quantitation of PCBs 16
5.3.3 Selection of Samples for Analysis 18
6.0 Sampling 23
6.1 Glassware and Storage 23
6.2 Sampling Documentation 23
6.3 Sampling Details 23
iv
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CONTENTS (Cont'd)
Page
7.0 Analysis for Chlorinated Compounds in Sludge
26
Samples
7.1 Results of Analysis of New Bedford Sludge 26
7.2 Results of Analysis of Philadelphia Sludge 30
7.3 Results of Analysis of Raleigh Sludge 38
7.4 Results of Analysis of Chicago Sludge 38
7.5 Results of Analysis of Houston Sludge 38
7.6 Results of Analysis of Kansas City Sludge 38
7.7 Results of Analysis of San Francisco
Sludge 38
7.8 Results of Analysis of Seattle Sludge 38
7.9 Results of Analysis of Distilled Water Blank .... 45
8.0 References 46
APPENDIX A: Procedures Used to Extract, Derivatize and
Clean-up Sludge Samples for Analysis 47
APPENDIX B: Sampling Protocol Sheet 52
APPENDIX C: Mass Spectra of Chlorinated Compounds in Municipal
Sewage Sludge Samples 56
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FIGURES
Number Page
1 GC/MS TIC chromatogram of neutral extract of Raleigh
o
sewage sludge spiked with PCNs
2 GC/MS analysis of spiked sludge - methylated phenolics
extracted at pH = 1. a - pentachloroanisole; b -
3-chloro-4-methoxybiphenyl; c - 3,3',5,5'-tetrachloro-
4,4'-dimethoxybiphenyl ^
3 GC/MS analysis of spiked sludge - methylated phenolics
extracted at pH = 7.5 10
4 TIC chromatogram of GC/MS analysis of Raleigh sludge —
spiked and methylated with diazomethane 13
5 Flow diagram of sample extraction and work procedure . . 14
6 RMR vs. degree of chlorination for polychloro-
biphenyls 19
7 MID chromatograms illustrating PCBs in hexane eluate
of neutral extract of NBM sludge 31
C-l Mass spectrum of trichlorobenzene (M = 180) identified
in neutral extract of New Bedford sludge 57
C-2 Mass spectrum of trichloroaniline (M = 195) identified
in neutral extract of New Bedford sludge 58
C-3 Mass spectrum of dichlorobiphenyl (M = 222) identified
in neutral extract of New Bedford sludge 59
C-4 Mass spectrum of trichlorobiphenyl (M = 256) identified
in neutral extract of New Bedford sludge 60
C-5 Mass spectrum of tetrachlorobiphenyl (M = 290)
identified in neutral extract of New Bedford sludge ... 61
C-6 Mass spectrum of pentachlorobiphenyl (M = 324)
identified in neutral extract of New Bedford sludge ... 62
vi
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FIGURES (Cont'd)
Number Page
C-7 Mass spectrum of unknown dichloro-compound (M = 187)
found in diazomethane-methylated extract of
New Bedford sludge 63
C-8 Mass spectrum of dichloronaphthalene (M = 196)
tentatively identified in diazomethane-methylated
extract of New Bedford sludge 64
C-9 Mass spectrum of trichloroaniline (M = 195) identified
in diazomethane-methylated extract of New Bedford
sludge 65
C-10 Mass spectrum of chlorobiphenyl (M = 188) identified
in diazomethane-methylated extract of New Bedford
sludge 66
Oil Mass spectrum of dichlorobiphenyl (M = 222) identified
in diazomethane-methylated extract of New Bedford
sludge 67
C-12 Mass spectrum of trichlorobiphenyl (M = 256) identified
in diazomethane-methylated extract of New Bedford
sludge
C-13 Mass spectrum of trichlorobiphenyl (M = 256) and
tetrachloronaphthalene (M = 264) identified in
diazomethane-methylated extract of New Bedford
sludge 69
C-14 Mass spectrum of tetrachlorobiphenyl (M = 290)
identified in diazomethane-methylated extract of
New Bedford sludge 70
C-15 Mass spectrum of tetrachlorobenzene (M = 214)
identified in neutral extract of Philadelphia
sludge 71
C-16 Mass spectrum of tetrachloro-compound (M = 240)
found in neutral extract of Philadelphia sludge 72
C-17 Mass spectrum of monochloro-compound (M = 288)
found in neutral extract of Philadelphia sludge 73
Vii
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FIGURES (Cont'd)
Number Page
C-18 Mass spectrum of dichlorobenzophenone (M = 250)
identified in neutral extract of Philadelphia
sludge 74
C-19 Mass spectrum of DDE (M = 316) identified in
neutral extract of Philadelphia sludge 75
C-20 Mass spectrum of trichlorobenzene (M = 180)
identified in hexane eluate of neutral extract of
Philadelphia sludge 76
C-21 Mass spectrum of tetrachlorobenzene (M = 214) identifed
in neutral extract of Philadelphia sludge 77
C-22 Mass spectrum of tetrachloro-compound (M = 240)
found in hexane eluate of neutral extract of
Philadelphia sludge 78
C-23 Mass spectrum of tetrachloro-compound (M = 240)
identified in hexane eluate of neutral extract
of Philadelphia sludge 79
C-24 Mass spectrum of DDE (M = 316) identified in hexane
eluate of neutral extract of Philadelphia sludge .... 80
C-25 Mass spectrum of DDE (M = 316) identified in hexane
eluate of neutral extract of Philadelphia sludge .... 81
C-26 Mass spectrum of monochloro-compound (M = 195)
found in toluene eluate of neutral extract of
Philadelphia sludge 82
C-27 Mass spectrum of dichloroaniline (M = 161) identified
in toluene eluate of neutral extract of Philadelphia
sludge 83
C-28 Mass spectrum of monochloro-compound (M = 288)
found in toluene eluate of neutral extract of
Philadelphia sludge 84
C-29 Mass spectrum of monochloro-compound (M = 269) found
in toluene eluate of neutral extract of
Philadelphia sludge 85
viii
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FIGURES (Cont'd)
Number Page
C-30 Mass spectrum of DDE (M = 316) identified in toluene
eluate of neutral extract of Philadephia sludge 86
C-31 Mass spectrum of dichloro-compound (M = 187) found
in dimethylsulfate-methylated extract of
Philadelphia sludge 87
C-32 Mass spectrum of dichloroaniline (M = 161) identified
in dimethylsulfate-methylated extract of
Philadelphia sludge 88
C-33 Mass spectrum of dichlorobenzene (M = 146) identified
in diazomethane-methylated extract of Philadelphia
sludge 89
C-34 Mass spectrum of monochloro-compound (M = 195) found
in diazomethane-methylated extract of Philadelphia
sludge 90
C-35 Mass spectrum of trichlorobenzene (M = 180) identified
in diazomethane-methylated extract of Philadelphia
sludge 91
C-36 Mass spectrum of tetrachlorobenzene (M = 214)
identified in diazomethane-methylated extract of
Philadelphia sludge 92
C-37 Mass spectrum of tetrachloro-compound (M = 240)
found in diazomethane-methylated extract of
Philadelphia sludge 93
C-38 Mass spectrum of tetrachloro-compound (M = 240)
found in diazomethane-methylated extract of
Philadelphia sludge 94
C-39 Mass spectrum of monochloro-compound (M = 288)
found in diazomethane-methylated extract of
Philadelphia sludge 95
C-40 Mass spectrum of dichlorobenzophenone (M = 250)
identified in diazomethane-methylated extract of
Philadelphia sludge 96
ix
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FIGURES (Cont'd)
Number Page
C-41 Mass spectrum of DDE (M = 316) identified in
diazomethane-methylated extract of Philadelphia
sludge 97
C-42 Mass spectrum of dichloro-corapound (M = 356) found
in diazomethane-methylated extract of Philadelphia
sludge 98
C-43 Mass spectrum of monochloro-compound (M = 397)
found in diazomethane-methylated extract of
Philadelphia sludge 99
C-44 Mass spectrum of dichlorobenzene (M = 146) identified
in hexane eluate of diazomethane-methylated extract
of Philadelphia sludge 100
C-45 Mass spectrum of monochloro-compound (M = 195)
found in eluate of diazomethane-methylated extract
of Philadelphia sludge 101
C-46 Mass spectrum of trichlorobenzene (M = 180)
identified in eluate of diazomethane-methylated
extract of Philadelphia sludge 102
C-47 Mass spectrum of tetrachlorobenzene (M = 214)
identified in hexane eluate of diazomethane-methylated
extract of Philadelphia sludge 103
C-48 Mass spectrum of tetrachloro-compound (M = 240)
found in hexane eluate of diazomethane-methylated
extract of Philadelphia sludge 104
C-49 Mass spectrum of tetrachloro-compound (M = 240)
found in hexane eluate of diazomethane-methylated
extract of Philadelphia sludge 105
C-50 Mass spectrum of DDE (M = 316) identified in
hexane eluate of diazomethane-methylated extract
of Philadelphia sludge 106
C-51 Mass spectrum of monochloro-compound (M = 285)
found in hexane eluate of diazoraethane-methylated
extract of Philadelphia sludge ..... 107
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FIGURES (Cont'd)
Number
C-52 Mass spectrum of moaochloro-compound (M = 241)
found in toluene eluate of diazomethane-methylated
extract of Philadelphia sludge 108
C-53 Mass spectrum of monochloro-compound (M = 285)
found in toluene eluate of diazomethane-methylated
acid extract of Philadelphia sludge
C-54 Mass spectrum of monochloro-compound (M = 221)
found in neutral extract of Raleigh sludge
C-55 Mass spectrum of chloroaniline (M = 127) tentatively
identified in neutral extract of Raleigh sludge ....
C-56 Mass spectrum of dichloro-compound (M = 187)
found in neutral extract of Raleigh sludge
C-57 Mass spectrum of dichloroaniline (M = 161)
identified in neutral extract of Raleigh sludge .... 113
C-58 Mass spectrum of tetrachlorobenzene (M = 214)
identified in diazomethane-methylated extract
of Raleigh sludge 114
C-59 Mass spectrum of tetrachloro-compound (M = 240)
found in diazomethane-methylated extract of
Raleigh sludge 115
C-60 Mass spectrum of monochloro-compound (M = 302)
found in diazomethane-methylated extract of Raleigh
sludge 116
C-61 Mass spectrum of DDE (M = 316) identified in
diazomethane-methylated extract of Raleigh sludge . . . 117
C-62 Mass spectrum of DDE (M = 314) identified in
diazomethane-methylated extract of Raleigh sludge . . . 118
C-63 Mass spectrum of tetrachlorobenzene (M = 214)
identified in hexane eluate of diazomethane-methylated
extract of Raleigh sludge 119
xi
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FIGURES (Cont'd)
Number Pa&e
C-64 Mass spectrum of tetrachloro-compound (M = 240)
found in hexane eluate of diazomethane-methylated
extract of Raleigh sludge 12°
C-65 Mass spectrum of tetrachloro-compound (M = 240)
found in hexane eluate of diazoraethane-methylated
extract of Raleigh sludge ^21
C-66 Mass spectrum of DDE (M = 316) identified in
hexane eluate of diazomethane-methylated extract of
Raleigh sludge 122
C-67 Mass spectrum of dichloro-compound (M = 187) found
in neutral extract of Houston sludge 123
C-68 Mass spectrum of dichloroaniline (M = 161) identified
in neutral extract of Houston sludge 124
C-69 Mass spectrum of trichloro-compound (M = 288) found
in neutral extract of Houston sludge 125
C-70 Mass spectrum of monochloro-compound (M = 192)
found in diazomethane-methylated extract of
Houston sludge 126
C-71 Mass spectrum of monochloro-compound (M = 256)
found in diazomethane-methylated extract of
Houston sludge 127
C-72 Mass spectrum of monochloro-compound (M = 280)
found in diazomethane-methylated extract of
Houston sludge 128
C-73 Mass spectrum of dichloro-compound (M = 171)
tetatively found in neutral extract of Kansas
City sludge 129
C-74 Mass spectrum of trichlorophenyl (M = 196) identified
in neutral extract of Kansas City sludge 130
C-75 Mass spectrum of dichloroaniline (M = 161) tentatively
identified in neutral extract of Kansas City sludge . . . 131
xii
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FIGURES (Cont'd)
Number Page
C-76 Mass spectrum of trichloro-compound (M = 210) found
in neutral extract of Kansas City sludge 132
C-77 Mass spectrum of trichlorobiphenyl (M = 256)
identified in neutral extract of Kansas City sludge . . 133
C-78 Mass spectrum of dichloro-compound (M = 187) found
in diazomethane-methylated extract of Kansas City
sludge 134
C-79 Mass spectrum of dichloro-compound (M = 171) found
in diazomethane-methylated extract of Kansas City
sludge [Note: Cl cluster at m/e = 197 is from a
different compound — see previous spectrum] 135
C-80 Mass spectrum of trichlorophenol (M = 196) identified
in diazomethane-methylated extract of Kansas City
sludge 136
C-81 Mass spectrum of trichloro-compound (M = 288) found
in neutral extract of Denver sludge 137
C-82 Mass spectrum of trichlorobenzene (M = 180) identified
in diazomethane-methylated fraction of Denver sludge . . . 138
C-83 Mass spectrum of dichloro-compound (M = 187) found
in diazomethane-methylated extract of Denver sludge . . . 139
C-84 Mass spectrum of raonochloro-compound (M = 218)
tentatively found in diazomethane-methylated extract
of Denver sludge 140
C-85 Mass spectrum of dichloro-compound (M = 256) found
in neutral extract of San Francisco sludge 141
C-86 Mass spectrum of trichlorobenzene (M = 180)
identified in neutral extract of Seattle sludge 142
C-87 Mass spectrum of dichloro-compound (M = 187) found
in neutral extract of Seattle sludge 143
xiii
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TABLES
Number Page
1 PCBs Found in Neutral Extract of Spiked Raleigh
Sludge U
2 Extraction Efficiency of Methylated Phenolics at
Two pH Values n
3 Compounds Identified in Spiked Raleigh Sludge After
Methylation With Diazomethane 15
4 Parent, MID, and "Double" MID Ions for PCBs 15
5 Relative Molar Response Values for PCBs 20
6 Summary of Compounds Found in Fractions of
Philadelphia Sludge Extract 21
7 Summary of Sewage Sample Collection 24
8 Summary of Chlorinated Compounds Found in Sewage
Sludge 27
9 Halogenated Compounds Found in Neutral Extract of
New Bedford Sludge 29
10 Chlorinated Compounds Found in Diazomethane
Methylated Extracts of New Bedford Sludge 29
11 Retention Times of PCBs Found in Hexane Eluate of
Neutral Extract of New Bedford Sludge (Figure 7) .... 32
12 Quantitation of PCNs in Hexane Eluate of Neutral
Extract of New Bedford Sludge 33
13 Chlorinated Compounds Found in Neutral Extract of
Philadelphia Sludge 34
14 Chlorinated Compounds Found in Hexane Eluate of
Neutral Extract of Philadelphia Sludge 34
15 Chlorinated Compounds Found in Toluene Eluate of
Neutral Extract of Philadelphia Sludge 35
xiv
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TABLES (Cont'd)
Number Page
16 Chlorinated Compounds Found in Dimethylsulfate-
Methylated Extract of Philadelphia Sludge 35
17 Chlorinated Compounds Found in Diazomethane-
Methylated Fraction of Philadelphia Sludge 36
18 Chlorinated Compounds Found in Hexane Eluate of
Diazomethane-Methylated Extract of Philadelphia
Sludge 37
19 Chlorinated Compounds Found in Toluene Eluate of
Diazomethane-Methylated Extract of Philadelphia
Sludge 37
20 Chlorinated Compounds Found in Neutral Extract of
Raleigh Sludge 39
21 Chlorinated Compounds Found in Diazomethane-
Methylated Extract of Raleigh Sludge 39
22 Chlorinated Compounds Found in Hexane Eluate of
Diazomethane-Methylated Extract of Raleigh Sludge ... 4°
23 Chlorinated Compounds Found in Neutral Extract of
Houston Sludge 4°
24 Chlorinated Compounds Found in Diazomethane-
Methylated Extract of Houston Sludge 41
25 Chlorinated Compounds Found in Neutral Extract of
Kansas City Sludge 41
26 Chlorinated Compounds Found in Diazomethane-
Methylated Extract of Kansas City Sludge 42
27 Chlorinated Compounds Found in Neutral Extract of
Denver Sludge 42
28 Chlorinated Compounds Found in Diazomethane-
Methylated Extract of Denver Sludge 43
29 Chlorinated Compounds Found in Neutral Extract of
San Francisco Sludge 43
30 Chlorinated Compounds Found in Neutral Extract of
Seattle Sludge 44
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TABLES (Cont'd)
Number page
A-l Procedure for Extraction of Neutral Organics From
Sludge Samples 48
A-2 Column Clean-Up Procedure 49
A-3 Procedure for Dimethylsulfate Methylation 50
A-4 Procedure for Diazomethane-Methylation 51
A-5 Preparation of Samples for GC/MS Analysis 52
xvi
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ACKNOWLEDGEMENTS
The authors wish to thank Mr. Ronald Keefe for his work on extraction
and chromatography of the samples and Dr. J. T. Bursey and Mr. L. Kelner
for their assistance with and operation of the GC/MS. We also wish to
thank Drs. V. J. DeCarlo and G. E. Parris for their valuable assistance and
discussions.
Most importantly, we wish to thank EPA personnel who assisted with
sample collection: Ray Thompson and Greenwood Hartley III (Region I), Gary
Gardner and Gregory Koltunuk (Region III), Lee Townsend, R. W. Libby, and
J. V. Slovick (Region V), Malcolm Kallus and E. C. McHam (Region VI), Bill
Keffer and Greg Beemont (Region VII), Dr. Milton Lammering, Dan R. McDonough
and Paul Grant (Region VIII), Bob Will and Paul J. Ciesla (Region IX), and
Dick Bauer and Daniel R. Tangarone (Region X).
xvii
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LIST OF ABBREVIATIONS
ACD - Diazomethane-methylated fraction of sewage sludge.
DDE - l,l-Dichloro-2-(o-chlorophenyl)-2-(p-chlorophenyl)-
ethylene or l,l-Dichloro-2,2-bis(p-chlorophenyl)-
ethylene.
GC - Gas chromatography.
GC/MS - Gas chromatography/mass spectroraetry/computer.
HX - Hexane eluate from silica gel column chromatography.
m/e - Mass-to-charge ratio.
MID - Multiple ion detection.
MTH - Dimethylsulfate-methylated fraction of sewage sludge.
MW - Molecular weight.
NE - Neutral extract fraction of sewage sludge.
PCS - Polychlorinated biphenyl.
RMR - Relative Molar Response.
RSD - Relative Standard Deviation.
SD - Standard Deviation.
TIC - Total Ion Current.
TL - Toluene eluate from silica gel column chromatography.
xviii
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1.0 INTRODUCTION
Polychlorinated biphenyls (PCBs) are stable, highly persistent chemical
compounds used primarily as dielectrics in electrical systems and as plasti-
cizers. Because of their wide-spread use, they are found in all parts of
the environment. Due to their capability to bioaccumulate, they present a
serious human health hazard. The environmental dangers presented by
PCBs have been deemed to be so great that their manufacture will be discon-
tinued after January, 1979 in the United States (Toxic Substances Control
Act, 1976). Their use, properties, environmental effects, and levels have
been reviewed.
Analysis of sludge is indicative of the environmental pollution caused
by the release of this substance. The sludge may eventually be digested
far enough to be reinjected into the sewage plant effluent, it may be dried
and transported to landfills, or it may be used as agricultural fertilizer
and soil builder. If PCBs or other halogenated organics are present, they
may eventually enter the human food chain. PCBs with low chlorine equiva-
(2)
lents have been shown to photodegrade to dimers and dibenzofuran analogs
and to metabolize to various phenolics, anisoles, and benzoic acids.
Thus, presence of these compounds in sludge is also of interest.
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2.0 SUMMARY AND CONCLUSIONS
Methods were developed for the extraction, cleanup and GC/MS analysis
of municipal sludge samples. The samples were analyzed and the data inter-
preted.
Sludge samples from wastewater treatment plants in nine United States
cities were collected by Regional EPA personnel and Research Triangle
Institute (RTI).
Each of the nine sewage sludge samples was prepared to yield a neutral
fraction and two acid fractions which were methylated with dimethylsulfate
and diazomethane, respectively. A portion of each sample was retained as
is, but the majority was chromatographed on silica gel to yield two frac-
tions, the hexane eluate and the toluene eluate. Thus, each of the nine
samples was fractionated into 3x3=9 fractions for a total of 81 samples
for analysis. Since analysis of all 81 sample fractions would have been
unwieldy and redundant, only the most promising fractions were analyzed.
The workup procedures as executed for this task are listed in Appendix A.
The sample fractions were analyzed using a quadrupole gas chromatograph/
mass spectrometer/computer (GC/MS/COMP) using a non-polar (OV-101) column.
All methods used were validated with spiked samples.
A total of 35 chlorinated compounds were found, including polychloro-
biphenyls, polychloronaphthalenes, polychloroanilines, polychlorobenzenes
and DDE. Most chlorinated compounds remain unidentified. No brominated
compounds were observed.
A fraction of the sludge obtained in New Bedford, Massachusetts con-
tained a total PCB concentration of 10,800 (jg/jH with the trichloro- and
tetrachlorobiphenyl isomers predominating.
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The detection of phenolics in the neutral extract and of unmethylated
phenolics in the acid fractions indicates that the sample preparation pro-
cedures are not totally satisfactory. The methylation reactions may not be
quantitative because of an excess of acid equivalents in the sample extracts
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3 - 0 RECOMMENDATIONS
Six major areas of research need to be expanded and pursued to improve
the methods used here:
(1) The methylation reactions must be investigated more closely. It
appears that the conditions used were insufficient to raethylate some com-
pounds of interest.
(2) The entire sample preparation procedure, including the column
chromatography, may be improved to eliminate more interferents and enhance
the detection of trace components.
(3) Complementary analytical methods should be used to verify the
GC/MS identification. One such method would be gas chromatography/Fourier
transform infrared (GC/FTIR) spectroscopy.
(4) Quantitation of the compounds of interest should be pursued.
(5) An exhaustive study, taking into account the more volatile
components and involving more cities must be pursued.
(6) Future studies should concentrate on correlating the occurrence
of chlorinated compounds with the type of sample. This would include water
treatment procedures, sewage treatment procedures, and possible industrial
sources.
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4.0 OBJECTIVES
The major emphasis on this research was to analyze municipal sludge
samples for FCBs and related compounds by GC/MS. The specific objectives
were to (1) develop methods of extraction, derivatization, and cleanup
which yield samples containing PCBs and related compounds amenable to
analysis; (2) establish GC/MS conditions to analyze the sample fractions;
(3) analyze the sample fractions; and (4) interpret the data and identify
halogenated compounds.
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5.0 METHOD DEVELOPMENT
The methods used in this task were primarily adapted and refined from
literature methods. The most applicable methodology found was that developed
by Keith. ~9' The primary objective of this research was specifically
directed toward the extraction of neutral compounds for the detection of
PCBs. Two methylation procedures were invesigated for derivatization of
phenolics and carboxylic acids.
5.1 CHEMICALS AND INSTRUMENTATION
All solvents used were distilled in glass (Burdick and Jackson,
Muskegon, MI) and used without further purification. Where purity was
®
especially critical, solvents were redistilled in glass. Aroclor mixtures,
and pesticides were obtained from the Quality Assurance Section, Environ-
mental Toxicology Division, EPA, HERL, Research Triangle Park, NC; individual
PCB isomers and chlorobiphenyls were obtained from RFR Corp., Hope, RI; 2-
chloro-5-methoxyphenol was obtained from Aldrich Chemical Co., Milwaukee,
WI; anthracene was obtained from Matheson, Coleman, and Bell, East Rutherford,
NJ, and silica gel was obtained from Davison Chemical Division, W. R.
Grace, Maryland, MD.
Analysis of all samples for PCBS and related compounds was accomplished
using a Ftnnigan 3300 quadrupole GC/MS with a PDP/12 computer as discussed
in Section 5.3.1.
5.2 DEVELOPMENT OF SAMPLE EXTRACTION AND WORKUP PROCEDURES
5.2.1 Extraction of Neutral and Basic Compounds
The extraction of neutral and basic components in sludge was accom-
plished at pH 11 using chloroform. Details of the procedure are listed in
Appendix A.
The method was validated for PCBs by analysis of spiked samples.
Samples of water and sludge from the Raleigh, North Carolina municipal
treatment facility were spiked with VLOO |jg each of mono-, di-, tri-,
tetra-, penta-, hexa- and decachlorobiphenyl and a IN NaOH solution added
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until the pH was approximately 11. The samples were extracted four times
with chloroform (~50 ml portions) for 10-15 min each using a mechanical
reciprocal shaker at ~60 cpm. The combined extracts were dried on Na^SO^
and the solvent evaporated first in a Kuderna-Danish apparatus and then
under a nitrogen stream.
Gas chromatography/mass spectrometry (GC/MS) analysis of the sample
indicated that all PCB isomers were being extracted (Figure 1, Table 1) with
an overall recovery of 70% for monochlorobiphenyl and >90% for all other
PCBs tested.
5.2.2 Methylation of Acidic Components with Dimethylsulfate
After extraction of the neutral components, the acidic components of
the sludge fraction were methylated using dimethylsulfate and extracted
(3)
with chloroform. The details of the procedure are listed in Appendix A.
The method was evaluated using Raleigh sludge spiked with about 300-
400 |Jg each of 3,3',5,5'-tetrachloro-4,4'-biphenyldiol, 3-chloro-4-
biphenylol, pentachlorophenol (PCP), 2,3,6-trichlorophenylacetic acid
(Fenac), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and 2-chloro-5-methoxy-
phenol. The methylated derivatives of the two biphenyls and of PCP were
observed in the GC/MS analysis (Figures 2 and 3).
The effect of pH on the extraction of the methylated compounds from
the aqueous sample was investigated with the spiked solutions. The methy-
lated product was divided into two equal portions which were extracted in
parallel at pH = 11 and 7.5 to control all other variables. A comparison
of the integrated peak areas for the parent ions of the three compounds is
presented in Table 2. These results indicated extraction at pH = 11 is
more than twice as efficient as that at pH = 7.5 Based on these results,
the methylated phenolics were extracted at pH = 11.
Thus, it appeared that the dimethylsulfate methylation works well for
phenolic compounds, but not for carboxylic acids. Therefore, a methylation
reaction using diazomethane was used to methylate the carboxylic acid
fraction.
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oo
100.0-
en
§ 60. Q-
C
o 40.0-
M
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100.0-
.0-
0
10
Time (min)
TIC*5
Figure 2. CC/MS analysis of spiked sludge - methylated phenolics extracted «'it
pll = 11.
a - pentachloroanisole
I) - 3-chloro-A-methoxybiphenyl
c - 3,3'.S.S'-teLi-achloro-A.^i'-diinethoxyblphunyl
-------
IUU.O-
in
Time (min)
I
!''•
Figure 3. GC/MS analysis of spiked sludge-methylated phenolios extracted at pH = 7.5.
-------
Table 1. PCBS RECOVERED FROM NEUTRAL EXTRACT OF
SPIKED RALEIGH SLUDGE
Retention Time
Compound (min)a
C12H9C11
4.8
6.0
8.4
9.6
10.9
18.3
aChromatographic column conditions were 150° for 3 min, then 8°/min to
230° and then held at the upper limit.
Table 2. EXTRACTION EFFICIENCY OF METHYLATED PHENOLICS AT
TWO pH VALUES
Relative Response
Compound pH = 7.5 pH = 11
pentachloroanisole 0.049 0.128
3-chloro-4-methoxy- 0.194 0.386
biphenyl
S^'.S.S'-tetrachloro- 0.063 0.139
4,4'-dimethoxybiphenyl
Arbitrary response value obtained by ratio of integrated areas of
parent ions of anthracene standard and sample compound.
Extraction pH. See text for experimental details.
11
-------
5.2.3 Methylation of Acidic Components with Diazomethane
Using a separate aliquot of sludge, the acidic components of the
sludge were extracted with chloroform at pH = 2 and then methylated using
diazomethane. The details of the procedure are listed in Appendix A.
The method was evaluated in the same manner as the dimethylsulfate
methylation (Section 5.2.2). The TIC chromatogram of this sample is shown
in Figure 4 and the compounds found in Table 3. The 2-chloro-
5-methoxyphenol was only partially methylated and the 3-chloro-4-biphenylol
was not recovered. The other compounds were methylated, however.
5.2.4 Column Chromatography
Since initial GC/MS results indicated that the background was inter-
fering with detection of PCBs and related compounds, a column chromatog-
graphic step was instituted. A portion (0.25) of each sample was retained
as is, but the majority (0.75 ml) was chromatographed on silica gel to
yield two fractions, the hexane eluate and the toluene eluate. The procedure
was previously tested and validated in these laboratories. PCBs and
other halogenated organics were found to elute in the hexane fraction,
while most chlorinated pesticides (heptachlor, DDT, lindane and others) and
polar organics were eluted by toluene. The details of the procedure are
listed in Appendix A.
5.2.5 Summary
The flow diagram in Figure 5 summarizes the extraction and workup
steps for sludge samples. For each sludge sample, a total of nine frac-
tions were generated.
5.3 DEVELOPMENT OF INSTRUMENTAL METHODS
5.3.1 GC/MS Analysis of PCBs
Analysis of all samples for PCBs was accomplished using a Finnigan
3300 quadrupole GC/MS with a PDP/12 computer. The 180 cm x 2 mm i.d. glass
column, packed with 2% OV-101 on Chromosorb W was held at a temperature of
120° for three min, programmed to 230° at 12°/min and held isothermally
until all peaks had eluted. Helium flow was 30 cc/min. The ionization
voltage was nominally 70 eV and detector voltages were between 1.8 and 2.2
kV. Full scan spectra were obtained from m/e 110-500. Analysis for method
development and some initial samples were conducted under the temperature
12
-------
108.8n
CO
.0-
,,,110*10
Time (min)
Figure 4. TIC chromatograra of GC/MS analysis of Raleigh sludge — spiked and
methylated with diazomethane.
-------
NE NEHX
NE-TL
MTH MTH-HX
MTH-TL
ACO ACO-HX
ACO-TL
Figure 5. Flow diagram of sample extraction and workup
procedure.
14
-------
Table 3. COMPOUNDS IDENTIFIED IN SPIKED RALEIGH SLUDGE AFTER
METHYLATION WITH DIAZOMETHANE
Compound
Retention Time
(mln)
2-chloro-5-methoxyphenol
2-chloro-l,5-dimethoxybenzene
methyl-2,3,6-trichlorophenylacetate
(methy1-Fenac)
pentachloroanisole (methyl-PCP)
methyl-2,4,5-trichlorophenoxyacetate
(methyl-245-T)
3,3', 5,5'-tetrachloro-4,4'-dimethoxybiphenyl
0.54
0.79
2.74
3.84
4.64
12.64
Table 4. PARENT, MID, AND "DOUBLE" MID IONS FOR PCBS
Compound
C12H9C1
C12H8C12
C12H7C13
C12H6C14
C12H5C15
C12H4C16
C12H3C17
C12H2C18
C12HC19
C12C110
M
188
222
256
290
324
358
392
426
460
494
M + 2
190
224
258
292
326
360
394
428
462
496
M + 4
192
226
260
294
328
362
396
430
464
498
MID Ions
188
222
256
292
326
360
394
430
464
498
"Double"
Ions
188
222
256
290
324
358
394
428
464
496
MID
190
224
258
294
328
362
398
432
468
500
15
-------
conditions: 150° for three rain, programmed to 230° at 8°/rain and held
isothermally until all peaks had eluted. These temperature conditions,
however, were found to be too severe for adequate resolution of some of the
early-eluting compounds (e.g., chlorobenzenes), so the lower initial tempera-
ture conditions were utilized.
As depicted in Figure 1, the PCBs were well-resolved and eluted within
about 18 min. The lower initial temperature employed for most sample
analysis was found to provide similar resolution of PCBs.
The detection limits were not specifically evaluated, but may be
assumed about 50-100 ng, given the high background. This detection limit
corresponded to a detection level of about 250-500 |Jg/£ of sludge.
The data output of the GC/MS was reviewed at several levels. The
instrumental operator printed out TIC chromatograms and selected spectra
(from about 10 to 100) which contained or appeared to contain halogen
clusters. The data were then reviewed by the supervisor to assure data
quality and then released for interpretation. In cases where spectra were
not identifiable or had anomalous components (e.g., ion intensities differing
from the theoretical isotope ratio), further data printout was obtained.
This included different background subtractions, no background subtraction,
printing of all spectra through a given region and ion chromatograms (plots
of individual ion intensities vs. time). These techniques generally provided
the necessary information to judge whether an observed isotope cluster was
real or merely coincidental occurrence of ions from unrelated compounds or
background. In a few instances where doubt as to the authenticity of a
compound remained, the identification was labeled "tentative".
5.3.2 Quantitation of PCBs
Polychlorinated biphenyls were quantitated by GC/MS using the multiple
ion detection (MID) mode to provide maximum sensitivity and precision. MID
has been used successfully in similar research on polychlorinated naphtha-
lenes . Multiple ion detection is an operational mode for a quadrupole
gas chromatograph/mass spectrometer where up to nine m/e values are step-
jumped at short time intervals. Since this technique allows integration of
ion intensity for a longer time period for the desired ions than in the
customary full-scan mode, the sensitivity of the instrument is increased by
16
-------
approximately two orders of magnitude. By judicious selection of tn/e
values to be monitored, interference by unwanted compounds can usually be
minimized.
Ten ions were selected for monitoring: one from the parent cluster for
each of the two chlorinated biphenyls (C^H Cl-C C11Q) . Although the
parent ions were not necessarily the most intense, the probability of
interference by PCB fragment ion or other contaminants was reduced. Ions
were chosen from the M (parent), M + 2, or M + 4 m/e values (Table 4)
according to an optimum combination of greatest intensity and least inter-
ference from other PCBs. Since only nine channels are available for MID
analysis on the Finnigan GC/MS, each sample was run twice using different
ions.
To confirm the presence of PCBs detected by MID which were not con-
firmed in the less-sensitive full scan mode, "double" MID analysis was
used. In this technique, two ions from a parent cluster were monitored and
the intensity measured compared with the theoretical isotope ratio.
The calculation of relative molar response (RMR) for the quantitation
of sample components precluded the need for a calibration curve. The RMR
ions calculated as the integrated peak area of a known amount of compound,
A° ,, with respect to the integrated peak area of a known amount of standard,
A° , (in this case anthracene), according to the equation
RMR = Aunk/m°lesunk = (Aunk} (mWuak) (gstd) (Equation 1)
Astd/molesstd (AstdKmWstd)(Vk)
From this calculated value, the concentration of an identified compound in
a sample was calculated by rearranging Equation 1 to give
g . = (Aunk) unk std (Equation 2)
(Astd)(mwstd)(RMR)
The use of RMR for quantitation in GC/MS has proven successful in
repeated application to similar research problems. ~
17
-------
Polychlorinated biphenyls were quantitated using an external standard
and a previously determined Relative Molar Response (RMR). The standard
chosen was anthracene (parent ion ra/e 178), which does not interfere with
PCB determination, nor do PCBs or their fragment ions interfere with the
determination of anthracene.
The RMRs were measured for the available PCB isomers as shown in Table
5. A plot of RMR vs. degree of chlorination yields a non-linear relation
shown in Figure 6. The points on the graph fit the equation,
2n RMR = 0.1486 - 0.3159 (degree of chlorination).
This equation, which has a correlation coefficient of 0.9941 allows extrapo-
lation to RMR values for hepta-, octa-, and nonachloronaphthalenes as
listed in Table 5. No consideration has been given to the effect of posi-
tional isomers on the RMR values.
5-3.3 Selection of Samples for Analysis
The number of fractions generated in the extraction and cleanup steps
was greater than that necessary to identify the PCBs and related compounds
in each sludge sample. Initial analyses were thus directed toward deter-
mining which fractions were most likely to contain compounds of interest.
The sample obtained from Philadelphia was selected for full analysis, since
a preliminary analysis of its ME found a wide variety of chlorinated organics.
A summary of the compounds found in the various fractions, (Table 6) illus-
trates the redundancy of analysis. Since the background was not prohibitive
and since nearly all of the compounds found in NEHX or NETL were identified
in ME, this fraction was deemed most likely to yield useful full scan GC/MS
results. Accordingly all NE fractions were analyzed. This would be the
fraction which would most likely contain PCBs.
It appeared from the analysis of the fractions of Philadelphia, Raleigh
and other sludges that neither MTH, ACD nor their chromatographed fractions
contained a significant number of identifiable compounds not already detected
in the NE fraction. It was, therefore, decided that methylated fractions
would be analyzed if and only if chlorinated compounds were seen in the NE
fraction which contained derivitizable functionalities, or which could
degrade or metabolize to acidic compounds. Since it appeared from the
analysis of the Philadelphia sludge fractions that the ACD fraction would
18
-------
1.0
0.9
0.8
0.7
0.6
0.4
0.3
0.2
0.1
0
45678
Degree of Chlorination
10
Figure 6. RMR vs. degree of chlorination for
polychlorobiphenyls.
19
-------
Table 5. RELATIVE MOLAR RESPONSE VALUES FOR PCBS
Compound
4-chlorobiphenyl
4,4' -dichlorobiphenyl
2,4', 5-trichlorobiphenyl
2 , 3 ' , 5 , 5 ' -tetrachlorobiphenyl
2,3,4,5, 6-pentachlorobiphenyl
2, 2', 4, 4', 5,5' -hexachlorobiphenyl
hep tachlor ob ipheny 1
octachlorobiphenyl
nonachlor ob iphenyl
decachlorobiphenyl
Degree of a
Chlorination RMR
1
2
3
4
5
6
7
8
9
10
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
889
588
455
375
215
157
I27d
0927d
0676d
0525
SDb
0.
0.
0.
0.
0.
0.
0.
169
094
098
096
049
035
0019
RSDC
0.
0.
0.
0.
0.
0.
0.
19
16
22
26
23
22
37
Relative Molar Response, anthracene standard = 0.268 ng/yl
Standard Deviation - nine values; three replicates at M. ng/yl, and
three at -^50 ng/yl-
°Relative Standard Deviation, SD/RMR.
Extrapolated from other RMR values using equation in text.
20
-------
Table 6. SUMMARY OF COMPOUNDS FOUND IN FRACTIONS OF PHILADELPHIA SLUDGE EXTRACT
Bases Neutrals
Retention Time + +
(min)a Compound NE NE-HX NE-TL MTH MTH-HX MTH-TL ACD ACD-HX ACD-TL
2.
3.
8.
9.
10
0.44
(0.64)
0.74
0.83
(0.74)
09 (1.09)
4 (1.14)
4.1
6-10.1 (5.8)
6-11.1 (7.2)
9.9
10.8
.3-11.1 (8.6)
12.8
12.8
15.0
d ichlorobenzene
mw = 187, C12 X
mw = 195, Cl^ X
trichlorobenzene X
tetrachlorobenzene X X
dichloroaniline X X
mw - 240, Cl, X X
mw = 240, Cl^ X
mw - 288, C^ X X
dichlorobenzophenone X
raw • 269, C^ X
mw - 241, Clj^
DDE XXX
mw « 356, C12
mw • 285, C^
mw - 397, C^
X X
X X
X X
X X
X X
X X
X
X
X X
X
X X
X
Values in parentheses are for previous GC temperature programming conditions: 150° for 5 min,
8°/min to 230°.
^Tentative identification. In cases where a compound is unidentified, the apparent molecular
weight and apparent number of chlorines are given.
-------
yield the most information, this fraction was selected as the methylated
fraction to be analyzed first.
22
-------
6.0 SAMPLING
Sludge samples were collected by EPA Regional personnel and by Research
Triangle Institute from municipal wastewater treatment plants across the
country.
6.1 GLASSWARE AND STORAGE
Wide-mouth, one liter glass bottles were thoroughly cleaned and heated
to 500°C to remove residual organics. Duplicate sample jars with a third
"blank" containing distilled water were shipped to the Regional personnel.
Samples were collected, documented, and returned. Immediately upon receipt,
Research Triangle Institute personnel logged in the samples, coded the
container and stored tham at 5°, awaiting analysis.
6.2 SAMPLING DOCUMENTATION
Each sample was accompanied by a "Sampling Protocol Sheet" reproduced
in Appendix B. This, in most cases, provided extensive documentation of
the sample history.
6.3 SAMPLING DETAILS
Table 7 lists the locations of the sludge sampling cities. While most
of the plants are in large metropolitan areas, they represent a variety of
common wastewater treatment processes and a variety of sludge sample
characteristics.
The sample collected at the New Bedford, Massachusetts wastewater
treatment plant (NBM), a primary treatment plant, was of a fluid consistency.
The sludge had been thickened and centrifuged prior to sampling. Aerovox
Corporation and Cornell Dubilier were listed by EPA Region I personnel as
potential PCB sources.
The sample collected at the Northeast Sewage Treatment Plant in
Philadelphia, Pennsylvania (PH) was collected from an anaerobic digester.
23
-------
Table 7. SUMMARY OF SEWAGE SLUDGE SAMPLE COLLECTION
Region
Municipality
Location
Site
I
III
IV
V
VI
VII
VIII
IX
X
New Bedford, MA
Philadelphia, PA
Raleigh, NC
Chicago, IL
Houston, TX
Kansas City, KS
Denver, CO
San Francisco, CA
Seattle, WA
New Bedford Wastewater
Treatment Plant
Northeast Sewage Treatment
Plant
Neuse River Wastewater
Treatment Plant
Metropolitan Sanitary
District of Great Chicago-
Stickney West-Southwest
Plant, Cicero
Sims Bayou Sludge Disposal
Plant
Kaw Point Sewage Treatment
Plant
Denver Metropolitan Sewage
Treatment Plant
SE San Francisco Water
Pollution Control Plant
Metro West Point
Between Centrifugation
and Incineration
Anaerobic Digester
No. 6
Aerobic Digester and
and Centrifuge
No. 6 Digester
Flash Dried Sludge
No. 2 Digester
Primary Digestion
After Digestion and
Elutriation
Secondary Digester
-------
The digesters were sour at the time of collection. Personnel from EPA
Region III listed Allied Chemical, Philadelphia, Pennsylvania and Rohm
and Haas Company, Bristol, Pennsylvania as suggested sources of chlorinated
hydrocarbons in the sludge.
The Neuse River Wastewater Treatment Plant serving Raleigh, North
Carolina, (RAH) a new, modern plant. At the time that sludge samples were
collected from the aeration pond, the sludge digestion system had not yet
equilibrated. Samples were also collected directly from a centrifuge.
The West-Southwest Sewage Treatment Plant of the Metropolitan Sanitary
District of Greater Chicago in Cicero, Illinois (CHI) is the world's largest
sewage treatment plant, according to sampling documentation supplied with
the sample collected by EPA Region V personnel. The sample was collected
from an anaerobic digester and is of particular interest since the dried
sludge is distributed as an organic fertilizer, "Nu-Earth".
The sludge sample collected by EPA Region VI personnel at the Sims
Bayou Sludge Disposal Plant, Houston, Texas (HOU) was a dried granular
sample. The sludge at this plant is floculated, vacuum filtered, and dried
at 1000-1200°F in a cyclone, making an average of ten passes through the
dryer.
The Kaw Point Sewage Treatment Plant serves the Kansas City, Kansas
metropolitan area (KC). A sample was collected from a digester (type
unspecified) by EPA Region VII personnel.
A sample collected at the Denver, Colorado Metro Sewage Treatment
Plant (DN) was taken from the primary digestion pipe. The sample had been
pumped from another plant approximately three km to the north.
A sample was collected at the Southeast San Francisco Water Pollution
Control Plant (SF) by EPA Region IX personnel. The sample was collected
after the elutriation tanks and before the filters. This plant serves a
heavily industrialized area and also receives sludge and scum directly from
the North Point Plant, serving a mostly residential area.
EPA Region X personnel collected a sample at the Metro West Point
Treatment Plant, Seattle, Washington (SEA). The sample was taken at the
intermediate level drained off from a completely mixed secondary digestion.
According to EPA Region X personnel, Seattle City Light and Puget Sound
Power and Light have previously been sources of PCBs in the sewage system.
25
-------
7.0 ANALYSIS FOR CHLORINATED COMPOUNDS IN SLUDGE SAMPLES
The results of the sample analysis are summarized in Table 8. A total
of 35 compounds were found in sewage sludge, although not all compounds
could be identified. In cases where a compound was identified, but no
standard was available for retention time comparison, the identification
was labeled "tentative". Where a reasonable structure or formula may be
proposed to fit the data, this was done in the text. In some cases where
the spectral quality was insufficient to definitely assign a molecular
weight and/or chlorine content to an unidentified compound, it was labeled
as "tentative". It must be noted that a large number of spectra contained
what appeared to be chlorine isotope clusters which are not reported. This
could be due to interferences, very low levels, or spurious peaks.
The following sections discuss in detail the results of the sludge
sample analyses, arranged by city. For each fraction analyzed, the TIC
chromatogram and a table of compounds found are presented. Mass spectra of
each compound found are presented in Appendix C.
7.1 RESULTS OF ANALYSIS OF NEW BEDFORD SLUDGE
The neutral and diazomethane-methylated extract of NBM sludge were
analyzed, the compounds found in these samples are listed in Tables 9 and
10, respectively. The compound with mw = 189 and two chlorines found in
the diazomethane-methylated extract may have the molecular formula CflH?NCl9,
in which case it could be a dichloro-dihydroindole or related compound, for
example:
The identification of dichloronaphthalene remains tentative because the re-
tention times of the unknown (3.7 min) and standard (6.7 min) differ markedly
and since the unknown eluted so much earlier than the corresponding biphenyl
26
-------
Table 8.. SUMMARY OF CHLORINATED COMPOUNDS FOUND IN
SEWAGE SLUDGE
Compound
dichlorobenzene
mw = 195, Cl^
mw * 221, C^
trichlorobenzene
chloroaniline (tent . )
dichloroaniline
tetrachlorobenzene
mw - 187, C12
mw - 171, C12
raw - 240, Cl,6
H j
trichloroaniline
dichloronaphthalene
trichlorophenol
mw * 302, C^
mw » 210, C13
chlorobiphenyl
dichlorobiphenyl
t r ichlor ob ipheny 1
mw « 192, Cl,
mw =• 288, Cl,
tetrachloronaphthalene
mw = 218, Cl, (tent.)
mw = 256, Cl,
•*• f
tetrachlorobiphenyl
dichlorobenzophenone
raw = 269, Cl.
mw = 256, C12
pentachlorobiphenyl
Retention Time
(min)b
0.5
0.8
0.9
1.0
1.2
2.1-4.7 (1.1)
2.2 (0.7)
2.3-2.7 (0.6)
3.0
3.0, 4.3 (1.1)
3.2, 4.4
3.7
3.7
4.5
5.1
6.2
6.3-8.2
7.5-9.6
7.6
8.6-11.1 (5.8)
8.6
9.1
9.1
9.3-10.2
9.2 (7.2)
9.9
10.1
10.2-11.1
Number of Times
Observed0
2
3
1
6
1
5
6
7
2
6
2
1
2
1
1
1
2
3
1
3
1
1
1
2
2
1
1
1
27
-------
Table 8. (Cont'd)
Compound
mw = 288, C13
mw = 280, Cl-
mw « 241, Cl
mw = 285, Cl
DDE6
mw =356, C12
mw = 397, Cl-
Retention Time
(min)a
10.5
10.7
10.8
12.6
12.7, 13.2 (8.6)
12.8
15.0
Number of Times
Observed*3
2
1
1
2
7
1
I
TJnidentified compounds are listed with the apparent molecular weight and
number of chlorines. If the identification of some compounds is tentative,
they are denoted by (tent.)
Retention times are listed for the chromatographic temperature conditions,
120° for 3 min, then 12°/min to 230°, then hold. Values in parentheses
are for chromatographic temperature conditions, 150° for 3 min, then 8°/min
to 230, then hold.
£
The number of samples out of 24 total in which this compound was observed.
Differences in retention times indicates possibly different isomers.
Two separate isomers observed in some samples.
Several isomers observed.
28
-------
Table 9. HALOGENATED COMPOUNDS FOUND IN NEUTRAL EXTRACT OF
NEW BEDFORD SLUDGE
Retention Time
Compound (min)a
trichlorobenzene 1.0
trichloroanillne 3.2
dichlorobiphenyl 6.3 - 8.2
trichlorobiphenyl 7.5 - 9.6
tetrachlorobiphenyl 9.3 - 10.2
pentachlorobiphenyl 10.2 - 11.1
a
See Figure 7 for TIC chromatogram.
Table 10. CHLORINATED COMPOUNDS FOUND IN DIAZOMETHANE METHYLATED
EXTRACTS OF NEW BEDFORD SLUDGE
Retention Time
Compound (min)b
mw = 187, C12 2.6
dichloronaphthalene (tent.) 3.7
trichloroaniline 4.4
chlorobiphenyl 6.2
dichlorobiphenyl 7.2 - 7.9
trichlorobiphenyl 8.4 - 9.2
tetrachloronaphthalene 8.6
tetrachlorobiphenyl 9.2 - 10.0
Unidentified compounds are listed with the apparent molecular weight and
number of chlorines.
See Figure 8 for TIC chromatogram.
29
-------
compounds. Previous experience , however, has shown that the different
positional isomers among the polychlorinated naphthalenes (as well as PCBs)
can have widely different retention times. In addition, polychlorinated
naphthalenes have been identified^ in environmental samples obtained from
this area, so their presence in sludge is not surprising.
The PCB concentrations in the neutral extract of NBM sludge was
judged sufficient to warrant quantitation. Therefore, the hexane eluate of
that fraction was submitted to GC/MS analysis in the MID mode for quantita-
tion. This fraction was used to reduce the interferences. Figure 7 shows
the MID chromatograms for the lower PCB isomers, clearly illustrating their
presence. It should be noted that fragments of higher isomers are observed
at longer retention times in the channel for a lower isoraer; for instance,
fragments of trichlorobiphenyls may be observed between 7.7-10 min in the
monochlorobiphenyl chromatogram. The compounds found in this analysis and
their retention times are listed in Table 11. The quantitative results are
shown in Table 12.
7.2 RESULTS OF ANALYSIS OF PHILADELPHIA SLUDGE
All nine fractions of the PH sludge samples were analyzed. The com-
pounds found in each fraction are listed in Tables 13-19 and summarized in
Table 6. The hexane and toluene eluates of the dimethylsulfate-methylated
fraction did not contain any detectable chlorine-containing compounds. The
two compounds with molecular weight of 240 and four chlorines appear to be
isomers of CgH,Cl, which may be tetrachlorostyrene. This identification is
plausible since chlorostyrenes (hexa-through octa-) have been observed in
(9)
Great Lakes water samples. Unfortunately, an authentic sample was not
available for correlation of retention times. The dichlorobenzophenone
identified in the neutral and diazomethane-methylated fractions was confirmed
by comparison of the retention time with an authentic sample (4,4'-dichloro-
benzophenone ). In some of the fractions (e.g., the hexane eluate of the
neutral extract), two peaks were identified as DDE isomers which are
assumedly the two common isomers, o,p'-DDE [l,l-dichloro-2-(o-chloro-
phenyl)-2-(p-chlorophenyl)ethylene] and p,p'-DDE [l,l-(dichloro-2,2-
bis(p-chlorophenyl)ethylene] which generally are separable by GC.
30
-------
•sXV'
290
294
4J
•H
0)
§
JJ
C
u
cd
256, 258
Time (min)
Figure 7. MID chroraatograms illustrating PCBs in hexane
eluate of neutral extract of NBM sludge.
(Theoretical ratios: 290/294 = 100/64, 256/258
100/98, 222/224 = 100/65, 188/190 = 100/32).
31
-------
Table 11. RETENTION TIMES OF PCBS FOUND IN HEXANE ELUATE
OF NEUTRAL EXTRACT OF NEW BEDFORD SLUDGE (FIGURE 7)
•a
Compound
1 O O
O TT f^l
v« A £J, • Vj J_ ,—
C12H6C14
C12H5C15
C12H4C16
C12H3C17
C12H2C18
C12HC19
C12C110
Anthracene
MID IONS
188,
222,
256,
290,
324,
358,
394,
428,
464,
496,
(std),
190
224
258
294
328
362
398
432
468
500
179
Retention Time
(min)b
5.3
6.7
7.8
9.0, 9.5
10.2
11.4
13.0
15.4
8.1
, 6.3, 6.7
, 7.5, 8.2
, 8.2, 8.5, 8.9
, 9.7, 9.8, 10.2
, 11.0
, 11.7, 12.0
—
—
3.
Confirmed by comparison of retention time with standard and ratios of
chlorine isotopic abundance.
GC conditions: 120° for 3 mln, then 12°/min to 230°, then hold.
32
-------
Table 12. QUANTITATION OF PCBs IN HEXANE ELUATE OF
NEUTRAL EXTRACT OF NEW BEDFORD SLUDGE
Compound
C12H9C1
C12H8C12
C12H?C13
C12H6C14
C12H5C15
C12H4C16
C12H3C17
C12H2C18
C12HC19
C12C110
Total PCBs
Amount Found
(yg/ml)
8.5a
220a
760a
470a
57
76
24
-
-
14
1600
Sludge Concention
(yg/&)
57
1500
5100
3100
380
510
160
-
-
93
10,800
Average of two determinations
33
-------
Table 13. CHLORINATED COMPOUNDS FOUND IN NEUTRAL EXTRACT OF
PHILADELPHIA SLUDGE
Retention Time
Compound3 (min>
tetrachlorobenzene 0«'
mw = 240, Cl, 18
T O
dichlorobenzophenone ' •L
DDE 8-6
Unidentified compounds are listed with the apparent molecular weight and
number of Chlorine atoms.
Note: gas chromatographic conditions are 150° for 3 min, then 8°/min to
230° and then held at the upper limit.
Table 14. CHLORINATED COMPOUNDS FOUND IN HEXANE ELUATE OF NEUTRAL
EXTRACT OF PHILADELPHIA SLUDGE
Retention Time
Compound (min)
trichlorobenzene 0.8
tetrachlorobenzene 2.6
mw = 240, Cl^ 3.0
mw = 240, C14 4.3
DDE 12.7
DDE 13.2
wiidentified compounds are listed with the apparent molecular weight and
number of '.chlorine atoms.
34
-------
Table 15. CHLORINATED COMPOUNDS FOUND IN TOLUENE ELUATE OF
NEUTRAL EXTRACT OF PHILADELPHIA SLUDGE
a Retention Time
Compound (min)
mw = 195, Clx 0.7
dichloroaniline 2.1
mw = 288, C^ 9.5 - 10.1
mw = 269, C^ 9.9
DDE 13.0
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Table 16. CHLORINATED COMPOUNDS FOUND IN DIMETHYLSULFATE-METHYLATED
EXTRACT OF PHILADELPHIA SLUDGE
Retention Time
Compound (mln)**
mw » 187, C12 0.6
dichloroaniline 1.1
unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Note: gas chromatographic conditions are" 150° for 3 min, then 8°/min to
230° and then held at the upper limit.
35
-------
Table 17. CHLORINATED COMPOUNDS FOUND IN DIAZOMETHANE-METHYLATED
FRACTION OF PHILADELPHIA SLUDGE
Retention Time
Compound (min)
dichlorobenzene 0.5
mw = 195, C^ 0.8
trichlorobenzene 1.0
tetrachlorobenzene 2.2
mw = 240, C14 3.6
mw = 240, C1A 4.6
mw = 288, C^ 8.6
dichlorobenzophenone 9.6
DDE 10.5 - 10.9
mw = 356, C12 12.8
mw - 397, C^ 15.0
unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
36
-------
Table 18. CHLORINATED COMPOUNDS FOUND IN HEXANE ELUATE OF
DIAZOMETHANE-METHYLATED EXTRACT OF PHILADELPHIA SLUDGE
Retention Time
Compound (min)
dichlorobenzene 0.5
mw = 195, Cl-L 0.9
trichlorobenzene 1.1
tetrachlorobenzene 2.4
mw = 240, C14 4.1
mw - 240, C14 5.2
DDE 11.1 - 11.2
mw - 285, C11 12.8
unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Table 19. CHLORINATED COMPOUNDS FOUND IN TOLUENE ELUATE OF
DIAZOMETHANE-METHYLATED EXTRACT OF PHILADELPHIA SLUDGE
Retention Time
a
Compound (min)
mw - 241, d 10.8
mw = 285, 03^ 12.6
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
37
-------
7.3 RESULTS OF ANALYSIS OF RALEIGH SLUDGE
The neutral, diazomethane-methylated, and hexane eluate of the diazo-
methane-methylated extracts of RAH sludge were analyzed. The chlorinated
compounds found in these samples are listed in Tables 20-22, respectively.
As mentioned previously, the tetrachloro- compounds with mw = 240 are
probably tetrachlorostyrene isomers. The dichloro- compound with a molecu-
lar weight of 187 may have a molecular formula of CgH7NCl2 (Fig. C-56).
7.4 RESULTS OF ANALYSIS OF CHICAGO SLUDGE
The hexane eluate of the neutral extract of CHI sludge was analyzed.
The neutral extract portion which was not liquid chromatographed was too
viscous for direct GC/MS analysis. No chlorinated compounds were found in
the fraction analyzed, so no further fractions were analyzed.
7.5 RESULTS OF ANALYSIS OF HOUSTON SLUDGE
The neutral and diazomethane-methylated extracts of HOU sludge were
analyzed. The chlorinated compounds found in these samples are listed in
Tables 23 and 24, respectively. The dichloro- compound, mw = 187, may have
a molecular formula of CgH-NC^ (Fig. C-67). The fragmentation pattern
(Fig. C-71) of the compound with molecular weight 256 and one chlorine
found in the diazomethane-methylated fraction repeatedly loses 32 mass
units, indicating losses of 0~ or S.
7.6 RESULTS OF ANALYSIS OF KANSAS CITY SLUDGE
The neutral and diazomethane-methylated fractions of KG sludge were
analyzed. The chlorinated compounds in the samples are listed in Tables 25
and 26, respectively. The dichloro- compounds, mw = 187 may have a molecular
formula of CQH-NC10 (Fig. C-78).
o / /
7.7 RESULTS OF ANALYSIS OF SAN FRANCISCO SLUDGE
The neutral extract of SF sludge was analyzed. Since only one chlori-
nated compound was found (Table 29), the other fractions were not analyzed.
7.8 RESULTS OF ANALYSIS OF SEATTLE SLUDGE
The neutral extract of SEA sludge was analyzed. Since only two chlori-
nated compounds were found (Table 30), the other fractions were not analyzed.
The compound containing two chlorines, mw = 187, may have the molecular
formula C«H,NC1/,.
38
-------
Table 20. CHLORINATED COMPOUNDS FOUND IN NEUTRAL EXTRACT OF
RALEIGH SLUDGE
Retention Time
Compound (min)
raw • 221, C^ 0.9
chloroaniline (tent.) 1.2
raw - 187, C12 1.9
dichloroaniline 3.5
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Table 21. CHLORINATED COMPOUNDS FOUND IN DIAZOMETHANE-METHYLATED
EXTRACT OF RALEIGH SLUDGE
Retention Time
Compound (min)b
tetrachlorobenzene 0.7
mw - 240, Cl^ 1.2
mw - 302, C^ 4.5
DDE 8.8
DDE 9.7
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Note: gas chromatographic conditions are 150° for 3 min, then 8°/min
to 230, then held at the upper limit.
39
-------
Table 22. CHLORINATED COMPOUNDS FOUND IN HEXANE ELUATE OF
DIAZOMETHANE-METHYLATED EXTRACT OF RALEIGH SLUDGE
Retention Time
Compound (min)
tetrachlorobenzene 2.4
nw = 240, Cl^ 4.2
mw = 240, C14 5.1
11.0
HJnidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Table 23. CHLORINATED COMPOUNDS FOUND IN NEUTRAL EXTRACT OF
HOUSTON SLUDGE
Retention Time
Compound (min)
raw = 187, C12 2.7
dichlo roanilin e 4.7
mw = 288, Cl. 10.5
wiidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
40
-------
Table 24. CHLORINATED COMPOUNDS FOUND IN DIAZOMETHANE-METHYLATED
EXTRACT OF HOUSTON SLUDGE
a Retention Time
Compound (min)
mw = 192, C^ 7.6
mw = 256, C^ 9.2
mw = 280, Cl-L 10.7
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Table 25. CHLORINATED COMPOUNDS FOUND IN NEUTRAL EXTRACT OF
KANSAS CITY SLUDGE
Retention Time
Compound (min)b
mw = 271, C12 (tent.) 3.0
trichlorophenol 3.7
dichloroaniline (tent.) 4.6
mw = 210, C13 5.1
trichlorobiphenyl 9.8
unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
41
-------
Table 26. CHLORINATED COMPOUNDS IN DLAZOMETHANE-METHYLATED EXTRACT OF
KANSAS CITY SLUDGE
Retention Time
Compound (min)
mw = 187, C12 2.4
mw = 171, C12 2.7
trichlorophenol 3.4
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
Table 27. CHLORINATED COMPOUND FOUND IN NEUTRAL EXTRACT OF
DENVER SLUDGE
Retention Time
Q
Compound (min)
mw = 288, C13 11.1
unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
42
-------
Table 28. CHLORINATED COMPOUNDS FOUND IN DIAZOMETHANE-METHYLATED
EXTRACT OF DENVER SLUDGE
a Retention Time
Compound (min)
trichlorobenzene 1.2
mw = 187, C12 2.3
mw = 218, C (tent.) 9.1
Unidentified compounds are listed with the apparent molecular weight and
number of chlorine atoms.
Table 29. CHLORINATED COMPOUND FOUND IN NEUTRAL EXTRACT OF
SAN FRANCISCO SLUDGE
Retention Time
g^
Compound (min)
mw = 256, C12 10.1
Unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
43
-------
Table 30. CHLORINATED COMPOUNDS FOUND IN NEUTRAL EXTRACT OF
SEATTLE SLUDGE
Retention Time
r>
Compound (min)
trichlorobenzene 2.0
mw = 187, C12 2.5
unidentified compounds are listed with the apparent molecular weight
and number of chlorine atoms.
44
-------
7.9 RESULTS OF ANALYSIS OF DISTILLED WATER BLANK
Distilled water blanks (1 £) were sent along with the sample jars to
each sampling city and returned with the samples. The blank from pH was
extracted and analyzed. No chlorinated compounds were found. There was no
reason to believe that any other samples had been contaminated, so their
blanks were not analyzed.
45
-------
8.0 REFERENCES
1. National Conference on Polychlorinated Biphenyls, November 19-21,
1975, Chicago, IL. EPA 560/6-75-004 (PB 253 248).
2. 0. Hutzinger, S. Safe, and V. Zitko, "The Chemistry of PCB's", CRC
Press, Cleveland, 269 pp, 1974.
3. L. H. Keith, Environ. Sci. Technol., 10, 555 (1976).
4. L. H. Keith, "Analysis of Organic Compounds in Two Kraft Mill Waste-
waters", EPA-600/4-75-005 (1975).
5. L. H. Keith, "Identification and Analysis of Organic Pollutants in
Water", L. H. Keith, Ed. Ann Arbor Science, Ann Arbor, MI, 1976,
Chapter 36.
6. M. D. Erickson, R. A. Zweidinger, L. C. Michael and E. D. Pellizzari,
"Environmental Monitoring Near Industrial Sites: Polychlorinated
Naphthalenes", EPA Contract No. 68-01-1978, Task I Final Report, 1977
submitted.
7. E. D. Pellizzari, "Analysis of Organic Air Pollutants By Gas Chro-
matography and Mass Spectrescopy", Publication No. EPA-600/2-77-100,
Contract No. 68-02-2262, 112 pp., June, 1977.
8. M. D. Erickson and E. D. Pellizzari, "Analysis of a Series of Samples
for Polybrominated Biphenyls (PBBs)", EPA Contract No. 68-01-1978,
Task 5 Final Report, 1977, submitted.
9. D. W. Kuehl, W. L. Kopperman, G. D. Veith, and G. E. Glass, Bull.
Environ. Contamin. Toxicol., 16, 127 (1976).
46
-------
APPENDIX A: PROCEDURES USED TO EXTRACT, DERIVATIZE, AND
CLEAN-UP SLUDGE SAMPLES FOR ANALYSIS
47
-------
Table A-l. PROCEDURE FOR EXTRACTION OF NEUTRAL ORGANICS
FROM SLUDGE SAMPLES
1. Adjust pH to 11 with NaOH.
*
2. In separatory funnel, shake sample (V300 ml) 10 minutes with 80 ml
chloroform.
3. Drain off chloroform.
4. Repeat Steps 1 and 2 successively with 70, 50, 25, 25 and 100 ml of
chloroform (total extract volume ca. 350 ml).
5. Add Na SO, to CHC1 fraction to remove HO.
6. Vacuum filter CHC1 fraction through Whatman No. 50 filter paper to
remove gross particulate matter.
Reduce volume of CHC1 fraction
by nitrogen blowdown to 2.0 ml.
Reduce volume of CHC1 fraction in Kuderna-Danish apparatus, followed
*
For dilute sludge samples. Very viscous, solid or dried samples were
extracted after addition of sufficient water of a smaller aliquot to
make the same consistency as the dilute sample.
Reference: Adapted from L. H. Keith, "Analysis of Organic Compounds in
Two Kraft Mill Wastewaters", EPA-600/4-75-005 (1975).
48
-------
Table A-2. COLUMN CLEAN-UP PROCEDURE
1. Silica gel (Davison Chemical Division, W. A. Grace, Baltimore, MD),
grade 923 (100-200 mesh) washed with toluene, followed by hexane,
dried at 130° for 16 hour and stored in sealed amber bottle.
2. Using 1.0 x 30 cm glass column, pack with a plug of glass wool, add
silica gel in a hexane slurry to 10 cm height, and top with 1.0 cm
Na2S04.
3. Wash column with 50 ml hexane to settle the bed and clean any
residual contaminants.
4. Save a 0.25 ml aliquot of the 2.0 ml sample, and transfer the other
1.75 ml to the column with washing.
5. Elute the PCBs with 50 ml hexane.
6. Other compounds, including pesticides are eluted with 50 ml of
toluene.
7. Concentrate hexane eluate in Kuderna-Danish apparatus, followed by
nitrogen blowdown to <1.9 ml.
8. Concentrate toluene eluate in a flat-bottomed boiling flask with an
attached Snhyder column, followed by nitrogen blowdown to <1.9 ml.
Reference; Adapted from D. Snyder and R. Reinert, Bull. Environ.
Contamin. Toxicol., 6, 385 (1971).
49
-------
Table A-3. PROCEDURE FOR DIMETHYLSULFATE METHYLATION
1. Extract the original sample to remove the neutral organics (see
Table A-l). The remaining aqueous slurry is methylated in this
procedure.
2. A 100 ml, three-necked (standard taper 24/40 round bottom flask),
equipped with a fourth neck for a thermometer, is fitted with two
pressure-equalizing addition funnels, a glass stirring rod, and a
magnetic stirrer.
3. Nitrogen is introduced into the top of the first addition funnel
and exits from the top of the second one. Place 40 ml of Eastman
reagent grade dimethylsulfate into the first addition funnel and a
50% solution of sodium hydroxide into the second.
4. Pour the sample (see Step 1) into the flask and flush the system
with nitrogen.
5. After raising the temperature to 85°C, begin dropwise addition of
both the dimethylsulfate and the sodium hydroxide solution. Main-
tain temperature between 80 and 90°C, and the pH between 10.5 and
11. Since dimethylsulfate is not readily soluble in water vigorous
stirring must be used. The addition time is about one hour.
6. After all the dimethylsulfate is added, maintain the reaction
vessel at 85-90°C for an additional 15-20 minutes and then cool to
room temperature.
7. Add 5 ml concentrated ammonium hydroxide to destroy excess dimethyl-
sulfate, and re-extract according to procedure for neutral organics
(Table A-l).
8. Column clean-up (see Table A-2).
Note: Dimethylsulfate is a suspected carcinogen. Appropriate pre-
cautions and safety procedures should be maintained.
Reference; Adapted from L. H. Keith, "Analysis of Organic Compounds in
Two Kraft Mill Wastewaters", EPA-660/4-75-005 (1975).
50
-------
Table A-4. PROCEDURE FOR DIAZOMETHANE-METHYLATION
1. Bring an original 300 ml aliquot of the sample to pH 2 with vLO%
H2SV
2. Extract with chloroform according to procedure for neutral organics,
deleting Step 1.
3. Slowdown sample in chloroform just to dryness and suspend in M3.5 ml
anhydrous ethyl ether.
4. Add 1 ml diazomethane in ether [prepared according to Fales, H. M. ,
et al., Anal. Chem., 45, 2302 (1973)] and stopper the sample for
one hour.
5. Allow the esterified sample to stand unstoppered for 1.5 hour to
allow excess diazomethane to escape from the ether solution into
the fume hood.
6. Bring volume to 2.0 ml.
7. Column clean-up (see Table A-2).
Note; The N-methyl-N*-nitro-N-nitrosognanidine used to generate the
diazomethane is a carcinogen. All work with this compound must be done
in a carcinogenic substances laboratory and appropriate precautions
taken.
Reference; Adapted from L. H. Keith, "Analysis of Organic Compounds in
Two Kraft Mill Wastewaters", EPA-660/4-75-005 (1975).
51
-------
Table A-5. PREPARATION OF SAMPLES FOR GC/MS ANALYSIS
External standard (53.6 |Jg anthracene) is added to each fraction
(<1.9 ml volume) and the volume adjusted to 2.0 ml. The concen-
tration of anthracene is thus 26.8 ng/|Jl.
Samples were stored at 5°C in teflon-lined screw cap vials until
analysis by GC/MS as described elsewhere.
52
-------
APPENDIX B: SAMPLING PROTOCOL SHEET
53
-------
Page 1 of 2
SAMPLING PROTOCOL SHEET
Sewage Sludge Samples (31U-1277-4)
Date and Time Collected:
Site (Full Name of Plant):
Address:
Collection Location (Digestion #, Lagoon #, etc):
Name of Person Collecting Sample:
Please describe the sewage plant in general and/or provide a diagram if
available. Also please outline the area served by this plant.
Please list the treatment steps which preceed collection of the sample:
54
-------
Page 2 of 2
Please list any known or suspected sources of chlorinated hydro-
carbons which may contribute to this sample and any suspected compounds.
Please add any comments which would further aid in characterization
of this sample.
55
-------
APPENDIX C: MASS SPECTRA OF CHLORINATED COMPOUNDS FOUND IN MUNICIPAL
SEWAGE SLUDGE SAMPLES
56
-------
BflCK-88
Ln
100-
90-
P"» 80-
"m 70-
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Percent
to ul i.
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SPECTRUM 21 l.B-1 I1UIUTES
BHCK&POUHH SUBTPHCTED
4&0 4'jQ SC
IIIBUIE.2XOVIOI. I28*3hl2» I1.-Q. 1.8KV.3MCL.04-19-??
Figure C-l. Mass spectrum of trichlorobenzene (M = 180) Identified in
neutral extract of New Bedford sludge.
-------
00
|ini
r-n'i
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Intensi
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Percent
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100-
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. Mll| lll|l^l| ll^lllll^.llllll^K,),. ||mt),U,|4»44)«l|l
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250 300
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Intensi'
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I
Percent
ro M £.
o o o
i i i
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WSS SPEC1PUM 138 6.69 MINUTES
BACKGROUND SUBTRACTED
400 450 SB
IHD1ME.2XOVIOI. l2B*3Hl2*. H.-8. I .Ot V,31CL.04-19-77
Figure C-3. Mass spectrum of dichlorobiphenyl (M = 222) identified in neutral
extract of New Bedford sludge.
-------
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On
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§
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PM
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MOSS SPECTRUM 1M B. 19 II I MUTES
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400 450 5C
1HBUIE.2XOVIOI. l26*3MI2"/n.-8. 1.81 V.3tCL.84-19-77
Figure C-4. Mass spectrum of trichlorobiphenyl (M
extract of New Bedford sludge.
256) identified in neutral
-------
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9.c? MINUTES
SUBTPflCTED
SO 450 500
IIIOIHE.2XOV10l.l20*3t112*'Ii;-8. 1.61 V. 3tCL.04-19-77
Figure C-5. Mass spectrum of tetrachlorobiphenyl (M = 290) identified in
neutral extract of New Bedford sludge.
-------
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BiiUbKOUIID SUBTRilCTED
408 450
IIIBIHE.2XOVI01. 128*3(112*/M.-8. 1 .ei:V.3l1CL.lM-|9-7r
*T"T""r
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Figure C-6. Mass spectrum of pentachlorobiphenyl (M = 324) identified in neutral
extract of New Bedford sludge.
-------
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WSS SPECTRUM 31 ?.5fl MINUTCS
BHCKGROUtll) SUBTRACTED
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p — ,~,.p
500
Figure C-9. Mass spectrum of trichloroaniline (M = 195) identified in
diazomethane-methylated extract of New Bedford sludge.
-------
BOCK-81
ON
ino-i
>•» 90-
"w e°-
8 ro-
4J
M 60-
a »-
cu
O .\(\~
Q)
^'0-
10-
00-
1
100-
£ 9°-
•H
CO 80-
|ro-
H 60-
g
50-
J-l '
(U
m-
30-
20
18-
ea-w
ISO
T
250
300
m/e
,..-.,—• 1 ......... .....,.—, ......... I-...,....,
3SB . ,
fK>cc CPPCTPUM 74 6.16 MINUTES
8 458 500
lNBIflcb.2;;OVle)l.l20*3Ml2*/ri,-e.l.?kV.OPR20.?7
Figure C-10. Mass spectrum of chlorobiphenyl (M = 188) identified in
diazomethane-methylated extract of New Bedford sludge.
-------
ON
IHB-
90-
2 60-
a
M so-
Percent
fJ ul i.
O O G
I I 1
10-
00-
1
llll till ,1 i,U
00 15i
>i >|>- I'-'l >l ill l| i ill) „
3 200 250 300
m/e >
IOO-,
90
^ eo-
•H
W 7O-
g
4J 60
4-1
0)
0
M 31-
0)
^ 20
10-
nn-
WSS SPECTRUM 87 7.24 MIHUTES
BftCKGROUIID SUBTRACTED
460 450
IHBIflCD.2f:OV101. l20f3ni?*/M.-8. 1.7KV.fiPR2B.77
Figure C-ll. Mass spectrum of dichlorobiphenyl (M = 222) identified in
dlazomethane-methylated extract of New Bedford sludge.
-------
Pnri - wr,
00
tt GO
•H
8 -
•
350 400 450 50
MASS SPECTRUM 101 8.41 MINUTES INBU1CD.2SOV101, l20*3M12*/tl.-B. 1.7KV.HPR28.77
CACKGPUUHP
Figure C-12. Mass spectrum of trichlorobiphenyl (M = 256) identified in
diazomethane-methylated extract of New Bedford sludge.
-------
nnrr inr,
0\
vo
ion-
^ 9ll
4J
•rl 60-
(0
g ™
4J
a 60
H
50-
g 40-
^J 3fl-
0)
ft, 20-
10-
00-
1
n
ion
>> 911
4J
•H 80-
CO
fi 70-
0)
•y eo
H
g *>-
M ™
0)
Pl pn
10-
flH-
•
III
III
Hill 1 1
III 1
|
. Jjl,
Ul
,
0
|
kll i
.itiliL,!)!),
260
We — >
i i
250
J
'ill,!, . ,,,,
"'''"'I I1' |>-'Ml"M |....,....|...
3(10
*
Figure C-13. Mass spectrum of trlchlorobiphenyl (M = 256) and tetrachloro-
naphthalene (M = 264) identified in diazomethane-methylated
extract of New Bedford sludge.
-------
run-, -
Zt 30
Intensi
>.n r. -/
•3 O =•
Percent
rj vi i.
0 = 0
i • i
10-
nn-
iL
250
ii,^,w. ^, L. , I.LI 4
3*0
MflSS SPECTRUM 110
9. IS M1IIUTES
450 500
.-8.1.7KV.ftPR28.?r
S
B
IMDinrD.3vOVIOI.
Figure C-14. Mass spectrum of tetrachlorobiphenyl (M = 290) identified in
diazomethane-methylated extract of New Bedford sludge.
-------
Illll-
•H
to re-
el
£» 60-
H 50-
4->
S4Q~
S 30
Q)
P* 20-
10-
eo-
Jl
1
100-
90-
£ 80-
•H
W 7B-
s
4J 60-
0
W 50
4J
fl 40-
0)
O
V4 30-
0)
o<
•^^ *'0~
10-
nn-
1
mmi>»TCitm i»
U.ll
ii 1 1. .11 ...l.ll. ,1 . I ii i ii_. .. . J.i.. i . .
ISO 200 258 300
m/e — »•
»ii»»nin»»in»irT»»ii»T»r'»^*i*«»'l'"'l«"*l' **•!•" n-"*|'"»l'»»
-------
N>
• Mil-
£* 30-
•H
s ™-
0)
4J in-
5 ,o-
4J
g -10
0
fc 3°-
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JO
10-
00-
IClfl-
90-
>» 80-
4J
.-^|
*M -.«
oo -0-
c
<" bO-
4J
c
M 50-
§ »
2 »-
(1)
A< 20-
10-
nn-
JlJI
Ilili.,,
tj
|| l|llll ||J , , l||||,.,l ,,llll|l,,,, ,,!„
;-'(Vi zso ?An
m/e ^»
MUSS SPECTRUI1 23 1. 14 MINUTES
BACKGROUND SUBTRAC1ED
45B 500
11 IPHIME.2J.'OV101.15B*3n8*^1.-8.1.8KV.3I*:L,03-11-77
Figure C-16. Mass spectrum of tetrachloro-compound (M
extract of Philadelphia sludge.
240) found in neutral
-------
100
30
>> 80
4J
CD re-
| 60n
W 50
e 4$
a)
g 30
0)
P4 20-
ia
OD-
too
90
^ BO
•H 70
(0
3 60
iS "50-
^^
d 4°"
O 30-
|2| 20
10-
00
150
3no
m/e
1 ' r- • i • i • i • i •
350 400
SPECTRUM 116 5.79 MINUTES
BACKGROUND SUBTRACTED
I""' ""'"" (—-•—•!• — . —-|—- , ! | .. — -,....,
450 500
111PHIHE.2XOVIO I. ISO*3m*/M. -8, 1.8KV.3MCU03-11-77
Figure C-17
Mass spectrum of monochloro-compound (M
extract of Philadelphia sludge.
288) found in neutral
-------
•u
•H
(0
a
*j
c
M
•U
S
U
0)
to
4-1
0)
C
0)
4J
Pi
H
4J
§
U
H
0)
P*
en
re»
60
50-
40-
30-
20-
in-
00-
100-
0(1-
60-
ro-
60-
50
40-
30-
20-
10-
00-
_^u
UrrTTT^lrT«|»4*T|K»'|^»Tt|tTTr|t>ILUTT|MHj>T4»T"<«yTTttT^"»T"»"l**nl"»t|ni»Mlll|lttlt>T*»^»T»« ill 1 [llttHi*^ . IHI n. -| 1 1 • 1 • • n 1 [ li • 11 1 l»*r~ ^.|>T»^. .1.11. .» | • . •. p.,^... .*,*•*,, ~
I'M ?Ao 2SO 701)
m/e — ^
350 40a
MflSS SPECTRUM 144 7.19 MINUTES
BflCKGPOUMI' SUBTPHCTED
1...^ .... T,mTm^, I "•" | T" |"^™ I f"
. 450 500
I I1PIMHE.2XOV10I. 150*3M8*/-M.-8. 1.8KV.3fCL.03-11-77
Figure C-18. Mass spectrum of dichlorobenzophenone (M - 250) identified in
neutral extract of Philadelphia sludge.
-------
Ul
.nn-
98-
£ 80-
•H
CO 70-
§ 60-
M so-
Percent
r.j OJ i.
o o o
i i i
10-
00-
• j
150
100-
90-
intensity
en "j at
o o eo
1-1 50-
*;
g 48-
g 30-
tt t+Jm,** " *t •— > tr-
200 2^0 300
m/e >•
3Se 400
WSS SPEC1RUH 172 B.59 MIHUTES
BftCKGROUUD SUDTRflCTED
lllPHIHE.2xOVlOl.l50i<3t18*/M.-8.l.OICV.3ICL.03-ll-77
Figure C-19. Mass spectrum of DDE (M = 316) identified in neutral extract
of Philadelphia sludge.
-------
ON
100
•111
30-
g
4J
4J
S
u
t-4 30-
*tT*"ir*T**i "**»*" *!**("
50B
r-|»»»»f»»"«|»""»f •••••••••|»"'»|'»"f T»»»|«'
-------
rr.p
(^
4J
•H
§
4-1
,9
0
0)
0
(U
PS
4-t
•H
CO
g
4J
0
H
4J
0
0)
a
M
(U
PM
IllO
90-
00-
PO
60-
50-
-10 •
30
id-
10-
00-
1
1
00
1,
4
i ....
100-
90-
eo-
70-
60-
50-
.10-
30-
PCi-
10
J IL 1 1, i, il
*
i
1
i.-l •-_ I -i >l i.i ..».._. ._. I.I.I i 1.
ISO 2QQ 250 300
m/e — >
T^*m«>Tr^**t.»n>T>iTi>.t t,|tit»pT"t>'*'i"*'i<"-n**''M»"*rM'r>"'i"^n'r*"i""i'*"i""i""i"*'n^'*i —
35(D «l60 450 560
MflSS SPECTRUM 26 2.16 MINUTES 11 IPHIHEHX.2XOV1B1. l20*5IH2*x||.-8.1 .BKV.SICL.flPRB
BACKGROUND SUBTRftCTEP
Figure C-21. Mass spectrum of tetrachlorobenzene (M = 214) identified in
neutral extract of Philadelphia sludge.
-------
rr.p M
00
CO
§ (.0-
4J
« 50-
•u .in
§,0-
10
00-
10U
li'O
f-n
g ,C
S
O 30-
M
(1) .
P4 -
|n-
00-U-
rJlltr
I'.n
I-WSS SPECTRUM 3G 3.00 IIIHUTES
BnCKGROUMD SUBTPnCTEU
i.,llll|l.l.nii.r..l
m/e
ll
1*+*JI
•>c.
2SO
„! ,™,T^.-p-,^....,...-,„.. |.„,-.-]-
y.i.ir.1
l- l•- i l p-i—-| --, - , | -[—•,--,-.-,..-., , , -.
400 4^0 500
IIIPHIMEHX.2KOV10I. 120+T.II12+/TI.-8. I .BKV.SIICL.flPPe
Figure C-22. Mass spectrum of tetrachloro-compound (M - 240) found in hexane
eluate of neutral extract of Philadelphia sludge.
-------
I'ln-
•rl
*o ro-
cs
0)
U fjfi-
M
4J
§ -I0-
o _
M 30-
Q)
* ;-o
in
00-
u
SB
ill i li i!
i i * i
lit
1 1
1 ll^LjIUlUKlrfTTpKllllll 1 1 III I . H » I.I, 1 1 1 |L, , . 1.11, , , , , t
200 2^.0 700
m/e — >
mo-
00-
1 '"-
4J 60-
4J
g -«o-
o
^ 38-
^ ?0-
19-
OB-
i 1 , jj liliit t i i li L 1 inn. HTT if ini 1 1 1 r| fn 1 1 j n jri'i H ri i i iin pr-r* — ^— — -
i»..i""| -I \ -r~.i-.--i \" ,—•,•'""•"} •'••(••••'••••I i" ""71 • ' i • i '--i • i • i
-.in .toe Jst) sA0
MAC«; rocpTOUH so'" ^TTMIHincC 1 1 IDUIHFUV ^wn\M»^ . |r.nH.c|,ps,/n,_q . |
-------
00
o
Kin
'in
4J
•H
CD
g
4-1
a
4J .1.)
8 -,
O -I'
tH
$ -•'
P^i
10
III!
1
1UU
i nn-
0) MD
S J°-
s
O 30-
M
2 »'
10-
BB-
— -I—-.-—I-—
330
MfiSS SPECTRUM 152
12.66 MINUTES
-lilf4»rr|»r»»T»t**|! 1 *|rr»4 Ut«|m*|tt«If^Kvp*^. r^H**^*! jt.«»T^
200
m/e —>
'|'">'"n|''>lt
. - .. ..-T-— !—, — , — •••••r-'""i"""-| ......... i ......... i""' — |— •>""i»"i»"|
400 450 500
1 1 IPMlNEHX^xOvlol. 12Q*5M12*/M. -B. I .BKV.3MCL. flPRB
Figure C-24. Mass spectrum of DDE (M = 316) identified in hexane eluate of
neutral extract of Philadelphia sludge.
-------
00
inn
•m-
p.n
a "'
o> --.n
4J
M ^
0)
O ?n-
14
j2I i»
on
1
liul
\"~
,1
,... |
»*4
1
j
III
lb
i
ill
,1
lUil
i
.
1
I
i
I1""! 2iii3
j
.LUJjIillJiuul
?io 7i a
m/e — ^
100-
90-
on
>^ ro-
W 60-
0
C
H .in
S ^
O :.|,
(ii
A< m-
an_
,Li,i
aau
tu»fa
rrrrrr'
trtTnii
mn»«l
TTuriHTr^rr*
•T-'""l I I
350
MftOS SPECTRUM 159 H.?4 (1IHUTES
BfiCKGPOUHI' S
00 *l5fl 503
IIirHIHEHX.2r;OVl01.l26*'5t1l2*/t1.-8.l.8KV.3l1CU.flPRa
Figure C-25. Mass spectrum of DDE (M « 316) identified in hexane eluate of
neutral extract of Philadelphia sludge.
-------
00
N5
JJ
•H
CO
g
4J
M
4J
c
y
3ljO
.100 -4'jlJ
flfiSB SPECTRUM 16 0.?4 IHIIUTES
500
II II'MltltTL.^.'OVlOl, l20t3IU2i-/n-2
Figure C-26. Mass spectrum of monochloro-compound (M = 195) found in
toluene eluate of neutral extract of Philadelphia sludge.
-------
00
Lo
90-
roH
0)
u 7n
Q)
PU I'll
00-
T**"l"
100
kpl
100-
90-
£> 80-
60-
3
o ,,
01
40
0-
0-
10-
00
WSS SPECTPWI
150
200
m/e
• fMMll*|MHI»~'M'n*-"^*TT*|**>rV>TT|rfT*TT*™1
300
259
?.R5> MINUTES
TEI>
""T"^T~T""r"n^1— i T""-'i |....,..«,.........r..,.,..| -
00 450 500
IIIPHlHETL.2S-OV181.l2B*3Ht2*/t1-250*.-8.2|fV.4-4-77
Figure C-27. Mass spectrum of dichloroaniline (M = 161) identifed in
toluene eluate of neutral extract of Philadelphia sludge.
-------
00
W
C
«u
Percent
rn
.
i-.n
r
mo
811
§
4J Ml
4J
P -in
0)
U
M >i'
0)
* .'u
ID
00-
T"T' '""I"
2iO
m/e
T
TT
"T~
son
?no
,™- • ••( "j...- |- ......| ..| ...j. | i ..|.
3SO -ino '150
MOSS SPECTRUM \K 9.5^1 IIHIUTES I I inillltrL.r,;OVIf11, l20r3IU2*'-l1-2?0-».-8.2I.V. J-4-"
BflCKGROUMI' SUBTFTiLTfl'
Figure C-28. Mass spectrum of monochloro-compound (M = 288) found in toluene
eluate of neutral extract of Philadelphia sludge.
-------
00
Ul
to
s
4J
S
U
M
0)
fe
inn
•'h
s
-------
CO
m '"
0) ,.n
M ID
s
u
0)
•in
;o
iu-
oo
.Ir^J^pr..!^.^,.,...!...!
IOU
l...l....,...r..>..T....l....T..^.IJI
• up *•>•!••tl|imf*r*|ll i»f»»»r|ll»»^I.Hl*i t»yTTT»i-rJ»|l"-»
m/e —*
2'o
m
S
3
g
o
Q)
PU
IUO-
90-
80-
ro-
10-
00-Ln-
"1 ,...n—p-T—T-T.-! ! |....,.~p..~T~^~r~T~T...,....| | —,—,™p-
350 «tl)l) -4^0 bOH
MASS SPECTRUM 262 13.0^ MINUTES 11 IPHltlETL.2;.'OVlOl. 120*3f1l2*/t1-250*.-B.2KV.4-4-7r
BACKGROUND SUBTRACTED
Figure C-30. Mass spectrum of DDE (M = 316) identified in toluene
eluate of neutral extract of Philadelphia sludge.
3MII
-------
00
fe
-H
00
g
4J
M
•U
g
O
0)
4J
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CO
g
4J
M
g
U
M
-------
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oo
100
90
fx, BO
4J
To ™
g 60
H 50
a 40
8 30
& 20
10
00
tea
90
eo
70
60
50-
05
g
ti
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s
a
a>
30-
20-
10-
oe
lMtT»*
200
t.^.t.,
250
.^r^..tK.^^.T
300
m/e
400
MASS SPECTRUI1 22
1.09 MINUTES
••i ••—-••—i —-1 --i i i
450 500
11 IPH1MTH. 2XOV1BI, 150*3I1B*/I1.-8.1.8KV.3ITL. 3-11-77
Figure C-32. Mass spectrum of dlchloroaniline (M = 161) identified in
dimethylsulfate-methylated extract of Philadelphia sludge.
-------
MO BfiCKGP SllBTR
00
VD
100-
90-
80-
70-
a to
{j 50-
•9 40-
30-
2B-
10-
eei-
i
MOSS SPECTPUM 8
I I III I
l'HlM|»MllHl^llllllll»|llllllMl|UIUMIl|illl[lMl|llll|ltll|.i.iil.tl|ilit.liii^
208 250 360 35£
0.49 MINUTES PHlf)CD,2;:UVIOI. l?0 I3III2I-- fl.-8. 1 .BKV. 31 tl..05-16-7?
m/e —->•
Figure C-33. Mass spectrum of dichlorobenzene (M = 146) identified in
diazomethane-methylated extract of Philadelphia sludge.
-------
13
IHU
MO
£ao-
•H
3*.
0)
SO
g 40
O
fc 30
Oil
„
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I Mil
(0 70
§ 60
H 50
d 40"
0)
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0)
A< 20-
10-
2QO
300
m/e
350
MflSS SPECTRUM 15
BHCKC.ROUIIII si
O.e-1 IIIIIUTCS
,..^^.T™T,^rm,—i i"••'•••• i—••-T •—r •—i—•—i
M
-------
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>>
•H
0)
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M
g
o
14
0)
^
4J
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(0
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4J
£
4J
g
o
n
0)
100
90-
eo
ni-
60-
56-
48-
30-
20-
18-
00-
1
168-
90-
80-
70-
60-
50-
48-
38-
20-
10-
nn-
Liu, 1
] 1 • J*-1^!
00
J4i
ll..r^..r
150 r
1
200 250 3(\0
m/e — >
(
3iO
S SPECTRUM 19 1.0-1 illllims
PrtCKGPOUIIli SUOTPftfTtlt
flR 4'jQ 500
['HIACD.2XOVIOI. l20k3MI2* -II.-8. I .OIV. 3ICL.05- IC-iV
Figure C-35. Mass spectrum of trichlorobenzene (M = 180) identified in
diazomethane-methylated extract of Philadelphia sludge.
-------
no
;.iir;iK"
vo
4J
•H
CO
*J
a
M
*J
S
O
H
0)
100-
90-
t:o-
70
60
50
.10-
2U
JO-
10
oe-
i
MflSS SPECTRUfl
Ju
MltlUTFS
—I—••—I •
20'e 250
PHIOCD.2xOViai.)20+3l1l2*/n.-B.
......
300
m/e
i"»
350
Figure C-36. Mass spectrum of tetrachlorobenzene (M = 214) identified in
diazomethane-methylated extract of Philadelphia sludge.
-------
BocK-67
VO
u>
I OH
98-
5^88-
4J
ffl ?°-
8 eo
4J
H 50-
i"-
O 38-
S-
10-
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100
108-,
9B
j^eo-
+j
"m ™~
§60-
M 50-
d *>H
0)
030-,
-------
i tin
98-
80-
4J 60-
R
M 50-
£
S 4U
2 30-
-l 30
"tfr"
250
m/e
Ao
SPECTRUM 93 J.T-1 MINUTES
BflC KGROUI ID SUD TPUL TK D
.......... , T-I I—- ,—.,.-,—.,—| ( |—-• -r-"i- "j
400
-------
BnCK-180
VO
Ul
108-
98-
3 OQ-
(0
§ ?a~
C 68-
O
» 80-
4J
- 1
01
S 68-
4J
•2 50-
g
O 30-
M
(2J 20-
IB-
•-|— i |
••,
4.
, 1
1
le"'
nvrrrm
•|""l
•
ll,
Tw(|*lrl)l
1
,
1 ,
i
m/e
rTt«TT»*I^»tl|«mi»»Kl>»tf|>l»»|»»»»|TTgT|HI»|»HHI
1
1
-^
..III. ill 1
, ' 1 ..1,
• »"T**"I«"I*'"|" '|""l""f **"!•" 'l""|""|""|**"1
250
MflSS SPECIRUM l?l 8.6^1 MINUTES
SUBTRHCTED
f...,.
500
Figure C-39. Mass spectrum of monochloro-compound (M = 288) found in
diazomethane-methylated extract of Philadelphia sludge.
-------
VO
o\
100-i
90
tlO-
W 78-
T1
CO
G (.0-
-------
BflCK-205
188-
90-
>> BB-
4J
"OB 'B-
8 68-
M 50-
Percent
fj UI A
o o 5
i i i
10-
00
1
F"
oo
III,.
|
l
.1,.,
ISO
~,
L^
T^
L
2(
a
, (
'
1 1 .
ill
1" '
i |
..I.I 1 . . 1 II. 1 II .1
258 300
m/e — ^
100-
90
^ 80-
Intensi
Ol (T> -M
0 O O
1 I I
(•} 40-
01
8-
to 20-
18-
aa-
im«m>»lTTHim'
'ir»*fi»rrr
HHi|imMM'imnt»mr»»*«l'«"T "' "• • " -
ll.
WSS SPECTRUM 288 10.-43 MINUTES
BACKGROUND SUBTRACTED
400 450 500
PHinCD.2XOVIOl.l20*3m2*/M.-8.1.8KV.3HCL.05-16-??
Figure C-41. Mass spectrum of DDE (M = 316) identified in diazomethane-methylated
extract of Philadelphia sludge.
-------
OnCK-251
vo
oo
ifle-
90-
!>» 68-
4-1
W fe-
ll 60
fl •*
g J°-
JJ 30-
P* 20-
10
t)0-
ioe-
30
to ?o-
60-
50
joiL
"lE
260
r-Ti"*T'
250
•"•••|""'""|-
300
m/e
a 40-
3
M 30-
0)
^ 20-
10-
00-
350
MASS SPECTRUM 255 12.84 MINUTES
BACKGROUND SUBTRACTED
400
.p.>r|T»ryp..»T^...».»TT™rni"Mr"'["™l"»'l'"'l''"|'r'-M "*»] i»m»»iii -
158 560
PHlflCD,2XOVlBI, 128*3«I2*XM.-B. I .BKV.StCL. 05- 16-77
Figure C-42. Mass spectrum of dichloro-compound (M = 356) found in
diazomethane-methylated extract of Philadelphia sludge.
-------
OnCK-302
I
VO
VD
100-
90-
>» BO-
4-1
*W 70-
® 60-
H so-
Percent
M W &
O O .
trtrrrl
400
450
MflOS SPECTRUM 290 15.OH MINUTES
BACKGROUND
-------
COCK - 10
o
o
IUU-
fr '^' "
CO ?ll-
1 co-.
H 50-
a •"'
01
o
M 3U
-------
nno: '••
100-
•lll
•H
m ra
2 co-
H 50-
rt .in -
o>
o -
fc
to :•
I fi-
i no
!0u
o> rn-
4J t-d
4J
8* llI
O
M i1'
0)
P* -,„
i ii-
no-
.i.i|!L|J.IU,^.
U UT^»|
MO-V-, SPECTklltl
n^.™^™^™, ,,...,,...,
350
19 8.U9 I1IIUJTF.S
i.ll|MM|llH|llll|
.'.ftO
m/e
^1T
„.....,
70U
............ .....(........^, j........-!....^.^,^..,^^ ^..^|....,....)nnTnn1
400 'ISO 500
HPHIfiCDH;:. l2B*«1l2t>/M. -3. I .BKV. 3HLL.Q-1-18-77
Figure C-45. Mass spectrum of monochloro-compound (M = 195) found in hexane
eluate of diazomethane-methylated extract of Philadelphia sludge.
-------
nnrr -'
o
ro
to ro
Percent
T- C-- —
lltl
1
nO
100-
90-
^ t;0-
•H
w ?-n-
s
4J bO-
c
M 50-
u
n
0)
in-
oo-U-r-T—r
^4o
?3
'.MCii.nr.ri.il
son
m/e
p-rm..*rf,.lt*ii-rTn..|ll< -f. .. ,™-.ip ••> t i .. ,tf • .«« ».r"" I •'
400
450
SOE
Figure C-46. Mass spectrum of trlchlorobenzene (M = 180) identified in hexane
eluate of diazomethane-methylated extract of Philadelphia sludge.
-------
IUU-
•
-------
M
o
lllll-
•III-
^ :ji I
4J
•H ,M
(0
§ MI
4J
« 5.1-
•U -IU-
0 '•'
M
(2 -"
111
Cin-
1
1 .
nn
'"'"I' "'
ISn
1 1
2UO 250 300
s
4J
5
g
0
h
0)
p,
SO
8CI-
6U-
50-
40
|(i-
aa-1^
m/e
r^--l........ ..
350
SPRCTPUM 8T
f:iiLl i.Piniiili ^.
.J.n9 MIIIIITES
l i.r Trii
..^.^™, j™, , ......... , "—I— T--I ....... ,.........,.- ..... r
O <)50
I IPHIOCDHX. l?0*3MI2*''M.-e. 1 .8KV.3fr.L. 04-10-77
500
Figure C-48. Mass spectrum of tetrachloro-compound (M = 240) found in
hexane eluate of diazomethane-methylated extract of
Philadelphia sludge.
-------
o
Ln
100-
9(1-
ts Ort-
.O
Intensi
if • 80-
•rl
S ?°~
4j 60-
Percent ]
t '•••' = '--
10-
0U-
MfiSS
,,....,.,..,...., ..,..,. | | [,,.,,..,.[....|..,.|....|...,| t j , ...I........... ,....,...., ( -. ,
350 '100 450 500
SPECTRUM 185 5. 19 MINUTES 1 IPHlfOHX. l20*3l1l2*/n.-8. 1.8KV.3hCL.B4-IB-?7
Figure C-49. Mass spectrum of tetrachloro-compound (M = 240) found in
hexane eluate of dlazomethane-methylated extract of
Philadelphia sludge.
-------
liiO-
CT>
(Q
8
4J
H
g
0)
100
§
0)
+J
ti
4-1
g '
o
M i-n-
0)
^ I'l-
00-
«|M>^«
L..|llll|J!.!L,|i
150
Juu
m/e
Mft'35 SPECTPUM 2?2 11.0-4 HINUTES
Bin'1'fif'iiiiiiii r.uf:Tr'iii. rrn
40U
IlPHlflCDHX. I
450 500
1. -8. 1. 8KV. 3MCL. 04- IB-7?
Figure C-50. Mass spectrum of DDE (M = 316) identified in hexane
eluate of diazomethane-methylated extract of
Philadelphia sludge.
-------
lon-
nn-
80-
4J
•H ro
CO
§ 60-
4J
A "-
4J • li 1 -
d
Q> T|1
o •"
M
0) Mi-
fi*
in-
oci-
i
1
00
100-
90-
^ 80
4J
§ eu -
4J
4J -111
S \
O •-'!-
« n
(li 'n
10-
llll|ll«l|llll|fll*|f>l.|IJl Uli|ll>l|llll 1 |I|||||I|I||ML 111 II Illlljl ll|llll|llll IIIIILII Itiuj .iij »i f
1...
150 200 250 300
m/e — ^
«
00 .^^^^^^ ^
MOSS ^PFrTPIIM ?S?
tnL( lif'nMIUi rjllt:
j...i,. p^p^^^^^.,^.,....!....,...-! ! | -i ,....,....,....,. .,....,....,
40$ 4io see
"".^S niHMTES IIPHIftPDHX. l20*3rU?*.t1.-B.I.BKV.3ICL.04- 10-77
ll'in 11.1-
Figure C~51. Mass spectrum of monochloro-compound (M = 285) found in
hexane eluate of diazomethane-methylated extract of
Philadelphia sludge.
-------
o
00
100
91)
4J 60
gro
0)
ti so
a
so-
g
u
$
*
,?0
10
00-
I
So
Lrwlu
l.l|.lllr.^.|.lllrlUl|mnTrT)jll,l1lll^.lrt|ll,|.«,)f,l.l|^.r
I'io 200
90-
CO
§ re
§ ,
o
QJ 30-
PU
2P-
HV
00-V
l.llt" — l..l...ll.l....,.l..l ..l.(
200
m/e . »
2L
i — . i' i i -"i [ -i- i -i | "i- |
350
MOSS SPECTRUM 217 10.94 MINUTES
BACKGROUND SUBTRACTED
• i i | i— |-->- |" ....... j- • i i | |-.--,.. -^ • ,....,— ,
400 450 500
I IIPHlflCDTL. !20*3M12*/M.-8. I .8KV.3ICL. 04-10-77
Figure C-52. Mass spectrum of monochloro-compound (M = 241) found in toluene
eluate of diazomethane-methylated extract of Philadelphia sludge.
-------
nr.R-3-u
fp^
4J
•H
CO
4J
&
y
§
o
M
0)
P*
Ps
4J
•H
CO
g
4-1
a
M
4J
g
0
I_J
n
0)
P4
IIILl-
«U1-
eo-
70-
60-
50-
JO-
50-
20-
10-
00-
1
1.
ill
1 1
xjulLui^Li
-i i , . j ....... ,
00
L*j^iri.ll.
15
109-
90-
80-
70-
60-
'jd-
.\a
•?o-
;TJ-
10-
00-'-i""| | | | |
1
lllrU,U
0
•—I—--—
1 1 1
1
200 250 300
m/e — >
|— •!—••••• -f-| | .—,"",...., ...-J....,....,....,..-,.... ,....,...., .-^|....,..~, •
MASS SPECTRUI1 253 12.6-1 MINUTES
BACKGROUND SUBTRACTED
c-53.
-------
CilO -I?
H"
M
O
0)
g •=••"
4J
ti 5u
j_i JO -
o '
a) _ii
IM-
nn
itio
1ULI-
,0
CO
711
*j
« c.f
8 n
cj iO-
10-
OQ-lr^^
|""«-j-«r-
350
> Ktp-Tjn*- |>'« |nw*ri I r^t»pTtT-fmrt>«>i|tt»ii ritT|mT-|»-*t»|-rTTrpT»nin.»i i^jr»»»|l»l<|T
200
m/e • %.
"' r*T*"TIT"TT*"T*""*l • *"l fT'-T*'•!-"•• (» i ••! >••»(»»»•-I"..,...-."
250 3nu
MftSS SPECTRUM 19 11.94 MIIIUTES
OACKGROUIID SUBTRHCTED
"*TT"""'^ l""1""1 '""""I ' ' ' i""'-j-
<|QB 450 SOB
tVpf)2IIE.2XOVl8l.l20*3Hl2i'/11.-8. I .B.3HCL.04-19-7?
Figure C-54. Mass spectrum of monochloro-compound (M = 221) found
In neutral extract of Raleigh sludge.
-------
inn-
on
to ro-
25 e.n~
ti
M 50-
§ 4°-
8 30-
0)
10-
100
100-
90-
^ 80-
r°-
4J 60-
fl
§
o
^ rn-
10-
200
.
250
^.....
3iV)
m/e
^^
•^^T
T
T"^"T
T
T
450
T
T
T
T
450 500
IVRn?IIE.2XOVIOI.l20*3MI2*^1.-B. I.B.3MCL.B4-I9-77
SPECTRUM 24 l.!9MINUtES
BflCKGROUtID SUOTPnCTtl'
Figure C-55. Mass spectrum of chloroanillne (M = 127) tentatively identified
in neutral extract of Raleigh sludge.
-------
Phi I -<.
WJ
8,«
4J
c
H^ c<
-
§
O v
in
00-
Itn
1 00
9(1-'
£ co-
in 70-
j 00-
H 50-
01
"M—l
350
Sf'tCTfUH 30
SUOTfiu f[
.. .1.^.*! j ll.|.r*i|l.|rT4l.l|l.>lT. 1 I 4»l|*Utp(r«rm.|K«l|^t.j»l.r.T^>|rn1r.1,|,.,t|*«Trp,rrTn
IMJ 200 ~Ao
m/e —y
300
Figure C-56. Mass spectrum of dichloro-compound (M
neutral extract of Raleigh sludge.
500
M-\9-77
187) found in
-------
tmCK-r.5
4J
•H 711
CO
0) 60
s ""
O iD
Oil
....( • •vlplrvYi-rl
I 111)
(0
§
4J
(3
01
ino-
'10
80-
rn-
20-
10
00 +T-
SPECTPIIM 71
*™*"lH"
m/e
2-.0
3.54 MIHHTFS
fPiir II I'
r"n— •— [•— •— | • i----| ••— (••• .- -i .— (•- ..... , -•- . ,
460 450
l'-Tri?MF,?vnviOI , I20*3t1l.'' > M. -8, I .B. 3ICL.
r-. .......
500
Figure C-57. Mass spectrum of dichloroaniline (M = 161) identified in
neutral extract of Raleigh sludge.
-------
100
98
80
Os 70
4-1
» 60
G
o) T.Q
00-
100-
90
80
•H
CD 60-
£ 50-
H 40-1
4J
O 30-
0)
10-
00
T-^-T"'-" I'"
300
m/e
'I I p—r-T—,.™
350
MflSS SPECTRUM 15 B.74
BACKGROUMO SUBTRACTED
[""'•"T" I I I I I--!""! -i |
450 500
IVR02flCD.2XOViei.l50*3n8*/n.-8.1.BKV.3I-CL.3-11-??
Figure C-58. Mass spectrum of tetrachlorobenzene (M = 214) identified in
diazomethane-methylated extract of Raleigh sludge.
-------
100-
90
4J
v4
ra so-
rt
2 50-
d
H 4Q.
4J
O 30-
3
M 28-
B-
nn.
u.
..1
ll
I
i
.
ll
)
1 t
1 Mill |il . jllilli, ...illili,,, , ||,
200 250 ' ' ' ' 300
m/e — >
tlftSS SPECTRUM 24 1.19 tWIUTES
DflCKGPOUHD SUBTRACTED
<45B 500
lVP«2nCD>2XOV10l.l58*3M8*/H.-B,l.eKV.3ttL.3-11-77
Figure C-59. Mass spectrum of tetrachloro-compound (M = 240) found in
diazomethane-methylated extract of Raleigh sludge.
-------
inn-
90
on-
±t 70
CO 60
§ 50
a
H 40
C 30
0)
10-
00-
100-
90
BO
70
60-
0)
g
•P 50-
4J
g 30
H 20
^ 10
iiO
150
Ot],
POO
wtUlJul|,U.|lll.
300
m/e
MflSS SPECTRUM 91 4.54 MIHUTES
MCKGROUHD SUBTPnl Tfc!)
450 500
IVP.ft2flCD.2xOVI0l. 150*3(18*/ri. -8. 1.6KV.3ICL. 3-11-77
Figure C-60. Mass spectrum of monochloro-compound (M = 302) found in
diazomethane-methylated extract of Raleigh sludge.
-------
100-
90-
88-
Intensit]
'ji tn ~»
(9 (B (9
Percent
fj U £.
at o o
i i i
18-
08-
I'"
1
100-
98-
5^88-
4J
s?"
S 60-
4J
M 50-
*J 40-
0 30-
" 28-
18-
88-
1
ll ,,|.
U.
„.. ...... ,....,. ..
358
•
1 ilullliluiuLl.tljul
158
,....|....,....| ,....,....,
. , 4t
Will ii i illil.il
I,, 1
T»|«lf >l>l*r|f Vfrpl.^fT...
200
i »-r— •-
8
"I'"'
ll .i.ll.ll.i.il. il.i.illi ,1
,1
ll ...II.. i.- _ .Ll .i. .III.. .. .1 ll. M..
250 2QQ
m/e <»
""1 '" 1 (....,-—,.-..,-—! -...,.-..,- -i.--. ,
450 500
MOSS SPECTRUM 17? B.84 MINUTES
BACKGROUND SUBTRACTED
. I50»3l^*>'t1.-e, I.BKV.3MCL.3-11-7?
Figure C-61. Mass spectrum of DDE (M = 316) identified in
diazomethane-methylated extract of Raleigh
sludge.
-------
00
4J
•H
CO
a
-------
nr,R-5?
VO
100-
90-
g 70
S 6°-
4j 50-
8 40
t-l
0) 70 -
&4
10-
00-
1
1
Jo
tao-i
>s 'JO-
I l
t Intensit
s r. -v to
> 9 o o
g 48-
0)
(X, 30-
20-
10
ee-
,|
It
r
^.i..,....,....,....,,....- ....
3Sa
SPECTRUM 49
1 i
llul
150
!,„
J,V
j,
'I' | IJT - - r |ll | 1 ,| , ,„ ,1 ,, ,„. I U J^-L,™^. |..| .... W
200 2^0 3m5
m/e >
.. (.. .,....t. •• i ' i • i • i • i • i • i • i ' i • i < i ' i • i
400 . 450 SOB
2.44 H1IIUTES IVRflZOCDHX. l20*3m2Ml.-B. l.eKV.SMcL.B^-iel-??
BACKGROUND SUBTPfiCTtO
Figure C-63. Mass spectrum of tetrachlorobenzene (M = 214) identified
in hexane eluate of diazomethane-tnethylated extract of
Raleigh sludge.
-------
11)11
911
(0 7(1-
jj bil-
d •<"
(U
0)
(*4 JO
10
OU"
mo-.
E >,90"
-80-
0)
d ro-
Q)
4J
Q) -40-
U
M 7n
0) ^0-
1 1 1 1 1 1 1
j.LL^ll.^i.llljuii.iil
00
MI
III II lit i . MI Mill i iLi i . Lin. i
200 250 ?ijn
m/e >
20-
10-
00-1'
i i I i-'i-'i r-'-i i i i
SB 45fl si
IVRfl2fiCDMX. l2B*3Hl2*/H.-B. 1.8KV.3ICL.B4-IB-77
' ' •-"-£- f----i ,
MflSS SPECTPUI1 84 4.19 HlNUltS
BACKGROUND SUB1RACTED
Figure C-64. Mass spectrum of tetrachloro-compound (M = 240) found in hexane
eluate of diazomethane-methylated extract of Raleigh sludge.
-------
Br.R-106
100-|
90
Ps
CO
g ™-
w 50-
§ 40-
(0 30-
20
10-
00-
1
, ,! , ||
1 •' " ' "*'!'" n ^" ^**n
00
100-]
Ps 90
^j
o eo-
* 70-
H so-
Percent
* g § o"
10-
nn-
150
"*7 "*
i
II III | . I- ,„ (it ,.
200 250 300
m/e — >
T
MfiSS SPECTRUM 103 5.14
BACKGROUND SUBTRACTED
4SB
see
Figure C-65. Mass spectrum of tetrachloro-compound (M = 240) found in
hexane eluate of diazoraethane-methylated extract of
Raleigh sludge.
-------
10
inn
C'O
il
s r°-
2 f.rt-
M 50-
4J
C -m-
0)
o vn
0)
f^i 20
10
00-
1
^.
00
,,,.,
l.V_
i
1
[111
1
.,.i..|....,.ii.|ii..,..i. .Ill
iio
•J
(vt>
0
L^,^,
11
i
L|| ^J.L... ||||i|,... , 1
250 3nn
m/e — >
100-
99-
il 80-
m
g 70-
4J
0 60-
4j 50-
§ 4B-
M
0) 30-
28-
1B-
ee-
mss
'•""t r— ,-.-. . --
SPECTRUH 221
i
T"'i'— | | | I ••••! |— • |—
400
1 1 .04 HIHUTES IVROZOCbHX. 12(14-31
'1 ' 1 ' 1 ' 1' 1 ' 1 i 1
Jso see
1i2*xM.-8. 1 .6KV.3McL.B4-lB-7f
BACKGROUND SUBTRACTED
Figure C-66. Mass spectrum of DDE (M = 316) identified in hexane eluate of
diazomethane-methylated extract of Raleigh sludge.
-------
BOCK-4Q
Is)
U>
4J
CO
«
M
'ercent
KM
£
to
g
0
"
g
o
M
0)
\ 4
14
100-
90-
ee-
70-
60-
58-
-10
30
20-
10
00-
1
,!,<
io
108-
98-
80-
70-
60-
50
48-
30-
20-
10
MR-
ilJUI|ji
•
ISO
«MH^
J _
200 250 300
m/e >•
i 1 |.iii.inr|i.i.iini| |......r..l..in..'.| 1 I...H.......HI...MI.III....
350
MRSS SPECTRUH 33 2.74 MINUTES
BACKGROUHD SUBTRACTED
400
111 =
VIHIHE.2XOVieltl. l28*3Ml2*''rt.-8. t .?>:V.3rCL.OPR27
508
Figure C-67. Mass spectrum of dichloro-compound (M = 187) found in
neutral extract of Houston sludge.
-------
BflCK-61
to
4J
•H
(0
8
4-*
A
4-1
0
0)
o
^
(!)
PL.
^
•H
(0
s
w
s
o
M
-------
DHCK-123
ro
Ui
(0
g
01
n
*J
9
o
&
to
60
20-
10-
00
100
100-
80
70
.10
>ll-
in-
88-
1,
150
T™*
44^r
3ir^
MASS SPEHTPUH 125 16.41 MltltlTES
SDOTftil TEH
200
m/e
,-p-JiiL
250
i0
T p-i-T""""! i -I i I i i -i
408 450 500
VIMIHE,2XQVieiN. l2B'f3Mi2*xl1.-a. l.7tfV.3ICL.flPR27
Figure C-69. Mass spectrum of trichloro- compound (M = 288) found in
neutral extract of Houston sludge.
-------
rnri'-ivi
Mil
•hi
•H
CO rn
8 6,
i 1 b '
4«J •*
c
M "Ml
4J
C i'1
Q)
1-4 "
I'l
(111
1
(I I'l
1,
T
llll,,!
,,l.
io
1, , ,|h J,,
I'i'io "^ ' **" ;-io ^ ' -iiio
m/e — >
4J O'l
•rl
CO -n
d ' °
li.i
.100 500
VllllftCD.2.-;OVlBl. 120H'3I1I2*/M.-8. l.B.3rd.05-02-77
506
Figure C-70. Mass spectrum of monochloro-compound (M = 192) found in
diazomethane-methylated extract of Houston sludge.
-------
DUCK-irs
N)
130-
90-
0>
g
4J
0 60-
13 5°"
3 .10-
o
8 3>
20-
10-
03-
1
100-
90-
^^
Intensity
->a CD
o a c
I ! t
4j 50-
I 40-
0) 30-
20-
10-
ea-
•»»
Jo
ll
lilj,l
i
ii
Lllillilk.HJllililii
i i i i -i i
150
1
200 250 31111
m/e ^.
MASS SPECTRUM 164 9. 19 MINUTES
OOCKGRUDMD SUBTPnClCD
00 450 5
vmmcD.2;:ovi6i. i2o»3rii2<-M.-B. i .e, anct .05-03-7?
Pieure C-71. Mass spectrum of monochloro-compound (M = 256) found in
diazomethane-methylated extract of Houston sludge.
-------
Illfl
00
00
g
8
o
M
•H
0)
0)
o
0)
10-
i
.,11
.7,11
'..PIXIF'UN LM-I
[•MI I f,f niiiiii •;
|l).i.'« IIIIIMIIS
'IIMLiU ill'
m/e
rt»*l...TJ.~-Tm«|«~Tn»..|rWrM..~«..p~T.J*.rTT»»»J'.HT*".|'«»T'r~'|" '-.— '(
400 '-lill
1.1;'Hr.;ni;>,-n.-e. i .n. siri .11'.- ic-i'r
Figure C-72. Mass spectrum of monochloro-compound (M = 280) found in
diazomethane-methylated extract of Houston sludge.
-------
100-
vo
4j 50-
8*H
Q> 30
PD
20-
00-
ida
100-
90-
I
80-
£
4J
§,-
0) 30
P-i
20
10-
00-^
T
liL.i.iii.ii....i.i.»|....iLl.i..i.|ilii.i ....ipi ..,
150 200
m/e —>
rvrt-r*-r~rt rrrr
250
>Tp*"I""j •*•»•! ".-|"i
•"""I"11'""! V
SPECTRUM 35 2.91 MINUTES
BflCKCPOIJIIIi SUBTPftCTEIi
VIIKr|ME.2>!OVIOI.
-"T*1^1"
450
see
Figure C-73. Mass spectrum of dichloro-compound (M = 171) tentatively found
in neutral extract of Kansas City sludge.
-------
CfK. . .13
H«
10
O
4-1
•H
CO
a
3
,3
i— i
4J
g
O
l-l
0)
^^
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CD
4J
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M
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fM
,n
^A
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50
40-
30-
:-o-
10
1
100-
90-
60-
70-
60
50-
40-
t
30-
20
10
08-
, ,LI.H-I.J'
ia
lLhJ, ,,Ui,.(,vi L
150 2l!lO 25tl 3^0
m/e y
3lo
MASS SPECTRUM 45 3.74 MINUTES
BACKGROUND SUBTRACTED
80 450
VI 1KCIHE.2HOVIBI. I20*3M12*/M.-B. I .7.3MCL.flPR27
Figure C-74. Mass spectrum of trichlorophenol (M = 196) identified in
neutral extract of Kansas City sludge.
-------
Inn
CO
g
4J
g.',,
§.-
s.
IM
no-
inn
100-
S 70-
« 60-
8""
o -in
lu
MftSS SPECTRUM 55 4.58 MIHUTES
BHCI '.F'OMIK. OlintPfif TLI'
m/e
"i j TT
4BQ
VI IKCHIE.2XOV10I. I20*3M12*'(1.-B. 1.7.
r*rT'"p"'p*"T'r'
3(10
560
Figure C-75. Mass spectrum of dichloroaniline (M = 161) tentatively
identified in neutral extract of Kansas City sludge.
-------
u>
to
3 ;"
8 '"
sn
•u
g •"'
u
M •:)
4)
IHO
•1,1
a •"
01
Q) .10
u
in
80-W
.ljl
I ll.lJlll
I l.i i
T I 'I I T-I--I | p-
3S0 <100
?i5o ;4u
m/e *•
--*3r
3i\0
SQO
1,-B. 1.7.
Figure C-76. Mass spectrum of trichloro-compound (M = 210) found in neutral
extract of Kansas City sludge.
-------
nncK-126
10
ino-
911-
fc eo
•H
*""* 50-
Percent
V 'i' If
00
1
llJ
r;0
i Imn
All
1
le
1 1.
L^
u
|. .lii. , III 4 i w i i i > 1 lilllh • 1 1 1 1
200 250 300
m/e >•
til
i r"
a
g
u
:•»•
m
^™^ . ,--.— ! . , •
3^0
.j SPECTPUH 118 9.33
BHCl:i,POUM|. SUBTPrtCTED
,..,.,....,....,...., , , ,....,....,.... ,
4e 450
VI NT HIE. 2J.W101. t20*3HI2t/rt. -8.1.7.3tn .
Figure C-77. Mass spectrum of trichlorobiphenyl (M » 256) identified in
neutral extract of Kansas City sludge.
-------
CO
•II)
1 "I
^J tl'
a ,,.
y
8 "'
g ••
•
»•*!•";•.
HI HI i
ic. ?.~i Miti'nrr.
.,ir n in u:n
•/( n r?-i> n.rvnvioi.
i .b.-s. ..i.e.: -r
Figure C-78. Mass spectrum of dichloro-compound (M - 187) found in
diazomethane-methylated extract of Kansas City sludge.
-------
I I'll'
(jj
Cn
i •-
4J CO
4-1
g
10
00
1UO
4-1
•H
CD
S
S
loo-,
90
3H
7U
Id
80
Jj,.i
t,,.ul,
Ttmtirrfl.ri|Trrrtil-.t^lrn1Y»r»ytrr*f.»»4U^lt|nl»p,(,^
21.10
m/e >.
l| i f I f »TTrr« ( »T^ 11K i
.,.m|..^,..| .,..,.. , (......
350
.PECTRUn 51 2.M MINUTES
r.iifnnu U'l'
ino 45a sou
VII»T?nrn.2xnwiai. i2B»'ini?*'n. i.e.-a. ,«4.(v-;v
Figure C-79. Mass spectrum of dichloro-compound (M » 171) found in diazomethane-
methylated extract of Kansas City sludge. [Note: Cl cluster at
m/e « 197 is from a different compound — see previous spectrum].
-------
4J
••J
•n
CO
d
S
^
4J
§
U
M
0)
*
1 1.1 ' i
Bij
I'M
bO
SO-
•in
3i.l
JO-
10-
(lit
UU
•.^...iHLlLKJIllhilll.!...,...!,....,....,-...
I^U
l| „....,....,...,, !„..„„! „,.„., , „
-•'.'0 -M iiio i'lo
m/e
100-
90-
4J 00
*P1
d 7tl
rt Ii0
50
§ ioH
u
SI ™
20-
10-
400 *I58 5LlB
MflSS SPECTRUM 6? 3.44 M1HUTES VI JK2HCD.2XOV101.120*3M12*/I1. 1.8.-8. .4.82-??
DACKGROUIID SIIOTPOCTFP
Figure C-80. Mass spectrum of trichlorophenol (M = 196) identified in
diazomethane-methylated extract of Kansas City sludge.
-------
UJ
1DU-
*j em-
I r"-
w
0 '"
4J
0) -lii-
o
0) ''""
2'0
IU
OU
|
rr«-|-m
,11
ll
Jl
1.
.1
(III _ ,,J Jl],,,,,
en
g
3
4J
U
-------
WITHOUT nnric sun it-
00
CO
3
4-1
A
•
g
0)
§
M
01
in.)
01)
no
ro
-10
?.o-
10-
00-
100-
eo-
6U-
50-
30-
20-
10-
00-
ll,
ISO
2$Q
m/e
.
-.i
.n
SPECTRUM 15
400
1,24 MINUTES
^ f "T"•' '-i""•—I ' l T i
'ISO 500
VIll'IMOrD.rwOVIOI.120*3Ml2*/M,-B. l.B.3rCL.IBY2.rr
Figure C-82. Mass spectrum of trichlorobenzene (M = 180) identified in
diazomethane-methylated fraction of Denver sludge.
-------
I niniiT pnri. rnn
mo
<>t)
4J UO-
- •
•n
GO
S ""
*i 60-
P
5U
4J
g -I"
O
H .,,
0)
jn
U3
on-
ill .I || - ||
li Illlill III hllr Jillll |||H. i flu!, ll,,.^,^..^.,!*,
150 21'UI
100-
h-1 90-
(jj
vo r?
m ~o
g
fl 60
H
50-
4J
O
£ «"
20-
10-
na
400 4
rm--': SPECTPUM ?n 2.^3 IHHIITLS VIIM
250 7.00
m/e —•>
« ITT<
580
£
'III
Figure C-83. Mass spectrum of dichloro-compound (M = 187) found in diazomethane-
methylated extract of Denver sludge.
-------
CO
g ;•"
4J
d ^o-
M
S .0-
o
Q) 11
,-n
10
So
T''' -I"
100-
•H eo
(0
g ?n
§
M
Q)
50
10-
00-
iilMi|»»i*rr*»»|
iiln
350
"•7
|.n.Ji
.7,1(1
m/e
T-—t
....I......
458
-T-"-|-
SOP
MOSS SPECTRUM 103 9.OH rilMUTES
TiUDtFiM'. tCli
IU <43D J
VllIi||llU.n.2::OVIol.|2D*3HI2*/tl,-B.I.B.3rCL.mY2.7r
Figure C-84. Mass spectrum of monochloro-compound (M = 218) tentatively found
in diazomethane-methylated extract of Denver sludge.
-------
nun:-i
liiu-
90-
m
g '-o.
g
o
30-
Z'U
10-
150
00-1^^...^....,..,,...^...^
350
MASS SPECTRUM 121 IB.OS MIIIUTCS
'.unwir ire
200
m/e
:»jKHt»il|liM*M|!Ul!JI IWiilt)ii-|il»!|(il,f,Mi<.'^.T^«,,..
250 3iio
ll'jlltilllll^MlI'M^lT^^, i .,,
-r —i r
T
I—'""I I |~"i»»| .(•»•
480 450
IXSF HIE. 2;;OVIOI. |20*3MI2*
-------
i ,irr -ii
co
a
Percent
f'H
-10
Ml
2 i.i
10-
110
II',
100
90
0) TO-
S .
4J bU
H 50-
§ *'•
£ 30
-------
nncK-* BO-
'S 70-
g 60_
H 50-
g •""
0 30-
0)
(^ 20-
10-
00
1
1
So
1
4.
il,
ill
•
J|
1
,l
Hj
ii
D
1,1 hi, 1,
200 2SO
100-
90
^* 80-
•H
(0 7
4J 60-
4J
g "°-
M 30-
0)
P* .;,,.
III-
00
m/e
i i '] i""'""i r""-i 'I i i i i 'I i i i r-.--i-i~~,
350 400 450 500
TOSS SPECTRUM 29 2.41 IIIHUTES XSTE1NE.2XOVIBU 12fl*3MI2*/M.-B. l.?KV.3»CL.B4-28-7r
BACKGROUND SUBTRACTED
Figure C-87. Mass spectrum of dichloro-compound (M = 187) found in neutral
extract of Seattle sludge.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/6-77-021
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Identification and Analysis of Polychlorinated
Biphenyls and Other Related Chemicals in Municipal
Sewage Sludge Samples ^^
5. REPORT DATE
Preoared August. 1977
0. PERFORMING ORGANIZATION COOE
7. AUTHOR(S)
Mitchell D.
Erickson and Edo D. Pellizzari
8. PERFORMING ORGANIZATION REPORT NO.
Task IV Final Report
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina
10. PROGRAM ELEMENT NO.
27709
11. CONTRACT/GRANT NO.
EPA-68-01-1978
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
401 M Street, South West
Washington, D. C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final December 6. 1976 - June 5
14. SPONSORING AGENCY CODE 1977
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Methods were developed for the extraction, clean-up and GC/MS analysis of
polychlorinated biphenyls (PCBs) and related chemicals in municipal sludge samples
Each of the sludge samples received from nine major United States cities was
processed to yield a neutral fraction and two acid fractions which were methylated
with dimethylsulfate and diazomethane, respectively. Samples were cleaned up by
silica gel column chromatography. A total of 35 chlorinated compounds were found
in the full scan GC/MS analysis, including polychlorobiphenyls, polychloro-
naphthalenes, polychloroaniline, polychlorobenzene and DDE. Some chlorinated
compounds remain unidentified.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATi Field/Group
Polychlorinated Biphenyls
PCBs
Municipal Sewage Sludge
Sewage Sludge
GC/MS
Chlorinated aromatics
18. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (ThisReport)
unclassified
21. NO. OF PAGES
165
20. SECURITY CLASS (This page)
unclassified
22. PRICE
EPA Form 2220-1 (R«v. 4-77) PREVIOUS EDITION is OBSOLETE
-------
INSTRUCTIONS
1. REPORT NUMBER
Insert the EPA report number as it appears on the cover of the publication.
2. LEAVE BLANK
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17. KEY WORDS AND DOCUMENT ANALYSIS
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EPA Form 2220-1 (R«v. 4-77)
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