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.

-------
oo
               100.0-
              en


              §  60. Q-

              C
              o 40.0-
              M
              
-------
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.

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             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

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     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

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        108.8n
CO
          .0-
                                                                                       	,,,110*10
                                                   Time  (min)
        Figure 4.  TIC  chromatograra of GC/MS analysis of Raleigh sludge — spiked and
                                methylated with diazomethane.

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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

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     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

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 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

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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

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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

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           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

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          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.

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yield the most information, this fraction was selected as the methylated
fraction to be analyzed first.
                                     22

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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

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                     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

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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

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 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

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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

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                              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

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      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

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 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

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      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

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         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

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      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

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      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

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   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

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      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

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 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

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     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

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       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

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   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

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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

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   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

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     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

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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

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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

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APPENDIX A:  PROCEDURES USED TO EXTRACT, DERIVATIZE, AND
          CLEAN-UP SLUDGE SAMPLES FOR ANALYSIS
                              47

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       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

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                 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

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          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

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          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

-------
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  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.

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                         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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Figure C-4.   Mass spectrum of  trichlorobiphenyl  (M
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                                                                          256)  identified in neutral

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Figure C-5.   Mass  spectrum of  tetrachlorobiphenyl  (M = 290)  identified in
               neutral extract of  New Bedford  sludge.

-------
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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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                               diazomethane-methylated extract of New Bedford  sludge.

-------
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-------
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-------
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-------
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-------
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                                                                                   240)  found in neutral

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288)  found in neutral

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                 neutral extract of Philadelphia sludge.

-------
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               Figure C-19.  Mass spectrum of  DDE  (M = 316) identified in  neutral extract
                               of Philadelphia sludge.

-------
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-------
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                                      eluate of neutral extract  of  Philadelphia sludge.

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                                          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.

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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.

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                                  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.

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                                       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.

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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.

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                        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

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                   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.

-------
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                                    208              250               360               35£
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                                                   m/e —->•

Figure C-33.   Mass spectrum of dichlorobenzene  (M =  146)  identified  in

                  diazomethane-methylated extract of  Philadelphia sludge.

-------
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 ['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.

-------
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                     Figure C-36.   Mass spectrum  of tetrachlorobenzene  (M = 214)  identified  in
                                     diazomethane-methylated extract  of Philadelphia  sludge.

-------
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               Figure C-39.  Mass spectrum of monochloro-compound  (M = 288) found in
                              diazomethane-methylated  extract of Philadelphia sludge.

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        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.

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MASS SPECTRUM  255    12.84 MINUTES
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400
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                                                        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.

-------
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                                    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.

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                 Figure  C-46.  Mass spectrum of trlchlorobenzene (M =  180) identified  in hexane

                                eluate of diazomethane-methylated extract of Philadelphia sludge.

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                                    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.

-------
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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.

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 450                   500

1. -8. 1. 8KV. 3MCL. 04- IB-7?
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                                    eluate of diazomethane-methylated extract of
                                    Philadelphia sludge.

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"".^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.

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MOSS SPECTRUM 217    10.94 MINUTES
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                                                       •  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.

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MASS SPECTRUI1  253     12.6-1 MINUTES
        BACKGROUND  SUBTRACTED
         c-53.

-------
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                                                 200
                                                    m/e  •  %.
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                                   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-
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 to ro-
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 ti
 M 50-

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                                 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 -<.
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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

-------
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                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.

-------
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 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-
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 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-

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                                                                                  300
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 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.

-------
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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.

-------
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                            BACKGROUND SUBTPfiCTtO
                     Figure C-63.  Mass spectrum of tetrachlorobenzene (M = 214) identified
                                    in hexane  eluate of diazomethane-tnethylated extract of
                                    Raleigh  sludge.

-------
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     '  '	•-"-£-	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.

-------
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4SB
see
Figure  C-65.  Mass  spectrum of  tetrachloro-compound (M = 240)  found in

               hexane eluate of  diazoraethane-methylated extract of

               Raleigh sludge.

-------
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              Figure C-66.   Mass spectrum of DDE (M = 316) identified  in hexane eluate of
                             diazomethane-methylated extract of Raleigh sludge.

-------
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              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.

-------
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                                                                                                       i0
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 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.

-------
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506
  Figure C-70.   Mass  spectrum  of monochloro-compound  (M = 192) found  in
                   diazomethane-methylated  extract of Houston  sludge.

-------
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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.

-------
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00
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                                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.

-------
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    SPECTRUM   35      2.91 MINUTES

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                                                              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.

-------
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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.

-------
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g
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MftSS SPECTRUM   55      4.58 MIHUTES

        BHCI '.F'OMIK. OlintPfif TLI'
                                              m/e
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                                   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.

-------
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                                                                            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
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200 250 300
m/e 	 >•
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            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
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1 "I
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a ,,.
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•









                 »•*!•";•.
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                                 .,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'
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                                             21.10



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                                                                                                    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].

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  Figure C-80.   Mass spectrum of trichlorophenol  (M = 196) identified in
                   diazomethane-methylated extract of Kansas City sludge.

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                                     diazomethane-methylated  fraction of Denver sludge.

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Figure C-83.   Mass spectrum of dichloro-compound (M = 187)  found in diazomethane-

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                 Figure C-87.   Mass spectrum of dichloro-compound  (M =  187)  found in  neutral

                                   extract  of Seattle sludge.

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                                   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

-------
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EPA Form 2220-1 (R«v. 4-77) 
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