Presence of Priority Pollutants
in Sewage and their Removal
in Sewage Treatment Plants
First Annual
JUNE 1,1978- MAY 31,1979
Dr.F.DeWalle,University of Washington,Seattle
Dr.E.Chian,Georgia Institute of Technology, Atlanta
Grant 806102
US Environmental Protection Agency, Cincinnati
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. 832RT9905
/ f ' ' PRESENCE OF PRIORITY POLLUTANTS IN SEWAGE
AND THEIR REMOVAL IN SEWAGE TREATMENT PLANTS
by
Foppe B. DeWalle Edward S. K. Chian
David A. Kalian Ksi Keng
Cherill M. Perera Wendall H. Cross
Russell L. Dills Maurizo Giabbai
Kobin Lee Lieh P. Wei
David Eaton Kim Williamson
Department of Environmental Health Department of Civil Engineering
University of Washington Georgia Institute of Technology
Seattle, Washington 98195 Atlanta, Georgia 30372
Annual Report
June 1, 1978 - July 31, 1979
Grant R 806102
Project Officer
Sidney A. Hannah
Municipal Environmental Research Laboratory
Environmental Research Center
MUNICIPAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF AIR, LAND, AND WATER USE
U.S. EITVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
U.S. EPA Region III
Regional Center for Environmental
Information
1650 Arch Street (3PM52)
Philadelphia, PA 19103 _,
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EXECUTIVE SUMMARY OF THE PRESENT STUDY
The present study, "Presence of Priority Pollutants in
Sewage," developed methodology to monitor the removal of organics
and heavy metals in fullscale publicly-owned wastewater treatment
works (POTW). The plants sampled as of now are: Seattle (Ren-
ton) , Atlanta (Clayton), Oakland (EBMUD), Modesto, Peoria, Rock-
ford, and Kenosha. The plants were elected based on the percen-
tage of the population working in different industrial catego-
ries, and percentage of industrial waste discharged to the POTW.
The analyses to date, covering the first three plants, found
67 priority pollutants, i.e. 37 base/neutral organics, 21 vola-
tile organics, and 9 phenolics. Compounds found in the present
study that have not been detected in the parallel 40 city survey
(city A,B) are: 1,1,2,2-tetrachloroethane, bis(2-chloroethyl)-
ether, bis(2-chloroisopropyl)ether, n-nitro-di-n-propylamine,
nitrobenzene, dipheylhydrazine, n-nitrosodiphenylamine, benzo(B)-
fluorathene, and benzo(K)fluoranthene. While individual removals
show a substantial variation, some tentative conclusions can
already be made.
The volatile compounds found in highest concentration to
date were: 1,1,1-trichloroethane, tetrachloroethene, and ethyl-
benzene. Moderate removals were observed for chlorinated C\ and
C2 compounds during primary and secondary treatment for dichloro-
methane (35%), trichloromethane (16%), trichloroethene (23%),
1,1,1-trichloroethane (71%), and tetrachloroethene (56%). Higher
removals were noted for the volatile aromatics, such as benzene
(71%), methylbenzene (79%), chlorobenzene (96%), and ethylbenzene
(97%). The greater removals for the volatile benzenes seem to be
partially due to a greater absorption onto the solids, as only
these volatile compounds accumulate in the digested sludge. The
removal of the extractable chlorinated benzenes thereafter
declined with further increasing molecular weights for 1,3-di-
chlorobenzene (70%), 1,4-dichlorobenzene (85%), 1,2-dichloroben-
zene (50%), and 1,2,4-dichlorobenzene (43%). High removals were
noted for nitrobenzene (97%) and 2,6-dinitrotoluene (greater than
99%). The removal of the polynuclear aromatics increases with
increasing molecular weight, or with an increasing GC retention
time for napthalene (82%), acenaphthylene (84%), and fluorene
(95%), while it is generally greater than 99%% for higher mole-
cular weight PAH's. The increased removal is generally reflected
by increased presence of the PAH's in the digested sludge. Espe-
cially high sludge values have been noted for fluorene, pyrene,
phenanthene, and fluoranthene. High phthalate removals are
observed for the lower molecular weight homologs, such as
dimethylphthalate (99%) and diethylphthalate (93%), which is pro-
bably due to biologicl degradation as they do not accumulate in
the sludge. The higher molecular weight phthalates, such as
butylbenzylphthalate and bis(2-ethylhexyl)phthalate accumulate in
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the digested sludge, presumably due to their higher absorptive
capacity.
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NOTE: Inquiries and requests for additional information
should be directed to the follov;ing persons:
Sections 11-1,2,3,4,5
Sections 1-1,2
Sections 2-3; 3-3; 4-1,2
5-1,2,3,4; 6;
8-1,2; 9;
10-1,2,3,4,5
Sections 3-1,2
Sections 7-1,2
Sections 12-1,2,3
Foppe DeWalle
Department of Environmental Health, SC-34
University of Washington
Seattle, WA 98195
Ed Chian
Department of Civil Engineering
Daniel Laboratory
Georgia Institute of Technology
Atlanta, GA 30332
David Kalman
Department of Environmental Health, SC-34
University of Washington
Seattle, WA 98195
Hsi Meng
Department of Civil Engineering
Daniel Laboratory
Georgia Institute of Technology
Atlanta, GA 30332
Maurizio Giabbai
Department of Civil Engineering
Daniel Laboratory
Georgia Institute of Technology
Atlanta, GA 30332
David Eaton
Department of Environmental Health, SC-34
University of Washington
Seattle, WA 98195
^^^
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CONTENTS
1. Introduction 1
2. Purgeables &
2-1 Evaluation of Headspace Displacement Flask 4
2-2 Evaluation of Stripping Bubbler 1?
2-3 VOA Determination Using Glass Capillary GC 12
The Extraction Procedure 31
3-1 Separatory Funnel Separation 31
3-2 Sample Homogenation 31
3-2.1 Extraction Using Filtration 31
3-2.2 Extraction-centrifugation 33
3-3 Liquid-Liquid Extraction 3*
4. Prefractionation and Cleanup 45
4-1 Gel Permeation Chromatography. &5
4-2 Florisil Chromatography 63
5. Determination of Phenolic Compounds 74
5-1 Cleanup Protocols for Phenolic Compounds 74
5-2 Isolation of Phenols 74
5-3 Derivatization Studies of Phenols and
Fatty Acids 86
5-4 Instrumental Analysis 91
6. Priority Pollutant Integrated Analytical Scheme 101
7. Capillary GC Analysis 114
7-1 Preparation of Glass Capillary Columns for
GC Analysis x ... 114
7-2 Investigation of Stationary Phases and
GC Conditions '. . .118
iv
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8. GC/MS/DS Analysis of Priority Pollutants .........
8-1 Chromatography of Organics ...............
8-2 GC/MS Data Processing .................. 13S
A. Initialization ................... 13P,
B. Analysis of Unknowns
8-3 Complications with GC/MS Analysis
9. Proposed QA/QC Program for POTW Samples .......... 142
10. Analytical Results of POTW Samples .............. 1A7
10-1 Purgeable Organics ................... 1/17
10-2 Neutral Extractables .................. 148
10-3 Pesticides ........................ lf;,n
10-4 Fhenolics ......................... i_r,n
10-5 QA/QC Data ........................ 153
11. Selection of Sampling Sites, Sampling Procedures,
and POTW Removal Efficiencies ................
11-1 Water Use in Industry
11-2 Priority Pollutants in Industrial Wastewater
Discharged to POTW1 s .................. 17°
11-3 City Selection for POTW Sampling ........... ].7fl
11-4 Sampling Procedures of POTW's ............. I?P
11-5 Removal Efficiencies at POTW1 s ............ 18°,
12. Mutagenic Activity of POTW Samples ............. 2DP
12-1 Introduction ....................... ?0<;
12-2 Methods .......................... 206
12-3 Results and Discussion ................. 208
13. References ............................ 235
Appendix 1: Protocols ........................ 239
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Appendix 2: Analytical Data, First Three Plants 315
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TABLES
Number Page
1-1 Detection of trace organics in sewage treatment plants ... 2
2-1 Instrumental conditions during purge & trap method to
determine low molecular weight volatile organics 6
2-2 Recovery of 18 compounds from purgeable-free water using
headspace displacement flask spiked at 20 ppb as run in
triplicate 7
2-3 Effect of Matrix Organics on Recovery of Volatile Organics
Spiked at 20 ppb using the Headspace Displacement Flask. . . 9
2-4 Proposed Protocol for Measuring Purgeables in Raw Sewage with
HDF (Headspace Displacement Flask) 13
2-5 Reproducibility of Bellar & Lichtenberg System spiked with
eleven purgeable organics 100 g/1 in raw sewage & digested
sludge based on triplicate. Sewage & sludge were obtained
from Atlanta, Georgia, Clayton Plant 14
2-6 GC and GC/MS Conditions for the VOA Analysis 18
2-7 Recovery of volatile organics from different matrices using
the cryogenic trapping technique & the P/T module 22
3-1 Percent recovery of 20 ppb acids & neutrals spiked into
distilled water (500 ml) and extracted by separatory funnel
according to EPA standard protocol 32
3-2 Gravimetric Liquid-Liquid Extractor Experiments 38
3-3 Recoveries from Spiked Water Using Stirred Liquid-liquid
Continuous Extractor 41
3-4 Effect of experimental conditions of recovery of gravimetric
residue using continuous liquid-liquid extractor and com-
parison with tissumizer and separatory funnel 42
4-1 Mixture of chemicals tested during the gel permeation studies 46
4-2 Summary of gel permeation experiments. ... 48
4-3 Elution Behavior of Priority Compounds During Gel Permeation 64
4-4 Elution behavior of selected compounds during florisil
chromatography 67
vii
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Number Page
5-1 Different extraction & clean-up procedures evaluated during
the present study 76
5-2 Experimental Conditions & Results for the Derivatization
Study 90
5-3 Overall Recovery of Phenols in Spiked Distilled Water
During column Chromatography & Derivatization 92
5-4 Relative retention times of phenolic priority pollutants
on four different GC col urns 95
6-1 Recovery of Neutral Priority Pollutant Standard During
Column Chromatography 104
6-2 Recoveries of Compounds Spiked in Raw West Point Sewage . . 11?
6-3 Recoveries of Heavy PAH & Phenol fraction is Spiked Sludge
Extracts 113
7-1 Surface treatment for glass capillary columns 115
7-2 Relative Retention Time of Chlorinated Pesticides 117
7-3 Glass Capillary Columns Selected 12F>
7-4 Organochlorine Resolved from PCBs 125
9-1 Standard Compounds for QA/QC 145
10-1 Base & Neutral Extractables Renton 155
10-2 Base & Neutral Extractables Atlanta 156
10-3 Base & Neutral Extractables Oakland 157
10-4 Summary of Neutral QA/QC Data 158
10-5 Summary of Neutral QA/QC Data 159
10-6 QA/QC Summary - Base + Neutral Extractables 160
10-7 Acid Extractables (Phenols) 161
10-8 Worksheet-QA/QC - Pesticides + PCB's Renton 162
10-9 Pesticides + PCB's Renton 163
10-10 Worksheet-QA/QC Pesticides + PCB's Atlanta 164
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Number Page
10-11 Worksheet-QA/QC Pesticides + PCB's Oakland ........ 165
10-12 Worksheet QA/QC Pesticides + PCB's Summary first three
plants .......................... 166
11-1 Percentage Use of Water for Different Purposes ...... 169
11-2 Percentage of Industrial Waste Water Discharged to
Different Categories ...................
11-3 Percentage Treatment of Waste Streams Discharged to
Different Receptors .................... 172
11-4 Percentage of Plants Using Certain Wastewater Treatment
Processes ......................... 173
11-5 Percentage of Employed Population Working in Specific
Industries ........................ 176
11-5 Continued ......................... 177
11-6 Cities Selected in the Present 25 City Survey ....... 179
11-6 Continued .......................... 180
11-6 Continued ............. . ............ 181
11-7 Description of Sampling Sites ............... 187
11-8 Renton Treatment Plant Information ............ 188
11-9 Atlanta Treatment Plant Information ............ 189
11-10 Oakland Treatment Plant Information ............ 190
11-11 Priority Pollutants in Renton, Seattle POTW ........ 191
11-11 Continued Renton, Seattle ................. 192
11-11 Continued Renton Seattle ................. 193
11-11 Continued Seattle Plant (#1) ............... 194
11-12 Priority Pollutants in Clayton, Atlanta POTW ....... 195
11-12 Continued Clayton-Atlanta ................. -196
11-12 Continued Clayton-Atlanta ................. 197
ix
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Number Page
11-12 Contin. R. M. Clayton, Georgia Plant (#2) 198
11-13 Priority Pollutants in EBMUD, Oakland POTW 199
11-13 EBMUD, Oakland Cont 200
11-13 EBMUD, Oakland Cont 201
11-13 EBMUD, OAKLAND Inorganic Priority Pollutants 202
11-14 Summary of Priority Pollutants Found in 3 POTW's 203
12-1 IN VITRO Assays with SALMONELLA TYPHIMURIUM - 140 Series . . 209
12-1 Cont 210
12-1 Cont 211-
12-1 Cont 212
12-2 IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - 170 Series . . 213
12-2 Cont .... 214
12-2 Cont 215
12-2 Cont 216
12-3 IN VITRO.ASSAYS WITH SALMONELLA TYPHIMURIUM - 140 Series . . 217
12-3 Cont 218
12-3 Cont 219
12-3 Cont 220
12-4 IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - 170 Series . . 221
12-4 Cont 222
12-4 Cont 223
12-4 Cont 224
12-5 IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - 140 Series . . 227
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Number
12-5 Cont
12-5 Cont
12-6 IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - 170 Series. .
12-6 Cont
12-6 Cont
Page
228
229
. 230
231
. 232
100-1 Compounds Detected by Capillary GC Purge & Trap Analysis. . .
100-2 Instrumental Conditions for VOA Analysis 251
200-1 Volatile Low Molecular Weight Compounds Detectable with the
Purge and Trap Method 25B
200-2 Relative Retention Times of Volatile Organics on Packed GC
Column 268
300-1 Compounds Detected in Extractables Analysis 274
300-2 Calibration Mixture for GPC i 279
300-3 Instrumental Conditions for Extractables Analysis 300
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FIGURE
Number Page
2-1 Different Stripping Vessels Evaluated Suring the Study. ... 5
2-2 Percentage Recovery of Volatile Compounds Spiked at
Different Concentrations in Distilled Water 8
2-3 Recovery of Volatile Compounds Added to Diluted Sewage
Samples at a Concentration Level of 20 ppb 10
2-4 Recovery of Volatile Compounds Added to diluted Digested
Sludge Samples at a Concentration Level of 20 ppb 11
2-5 Recovery of Volatile Organics from a 50% Diluted Champaign
Sewage Spiked at Different Concentration Levels in a
Stripping Bubbler 15
2-6 Recovery of Volatile Organics from a 25% Diluted Champaign
Anaerobic Digested Sludge Spiked at Different Concentration
Levels in a Stripping Bubbler 16
2-7 Chromatrogram of 25% Diluted Atlanta Sewage Purged in the
B-L Bubbler & Separated on a 0.2% Carbowax GC Column 17
2-8 Schematic of VOA Analysis Instrumentation Using Cryogenic
Trapping and Capillary GC/MS Separation 19
2-9 Cryotrap Designs 21
2-10 Reconstructed Ion Current of a 0.40 ppb Volatile Organic
Mixture in Distilled Water. 23
2-11 Reconstructed Gas Chromatogram of the most volatile organics
of the VOA standard 25
2-11 Reconstructed Gas Chromatogram of a VOA standard 26
2-12 Reconstructed Ion Current of Renton-Seattle Raw Sewage. ... 27
3-1 Stirred Liquid-Liquid Continuous Extractor and Steam
Distillation Vapor Extractor Evaluated in the Present Study . 36
3-2 Extraction Efficiencies of the Modified Stirred Liquid-
Liquid Extractor 39
4-1 Elution Profile on BioBeads S-X2A System 49
4-2 Elution Profile on BioBeads S-X2B System 50
x^^
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Number Page
4-3 Elution Profile on S-X2C System 51
4-4 Elution Profile on BioBeads S-X2E System 52
4-5 Elution Profile on BioBeads S-X2F System 53
4-6 Elution Profile on BioBeads S-X3A System 54
4-7 Elution Profile on BioBeads S-X3B System 55
4-8 Elution Profile on BioBeads S-X8A System 56
4-9 Elution Profile on Bio Beads S-X8B System 57
4-10 Elution Profile on BioBeads S-X12A System 58
4-11 Elution Profile on BioBeads S-X12B System 59
4-12 Elution Profile on BioBeads S-X12E System 60
4-13 Elution Profile on BioBeads S-X12F System 61
4-14 Elution of Priority Pollutants Spiked in Prefractionated
Anaerobic Digested Sludge Extract During Florisil Clean-up . . 68
4-14 Continued 69
4-14 Continued 70
4-14 Continued 71
4-14 Continued 72
5-1 Chromatogram of distilled water spiked at 30 ppb phenolics
and extracted according to the EPA method 78
5-2 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted according to the EPA method 79
5-3 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted and cleaned-up according to the ion-exchange
method 80
5-4 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted and cleaned-up according to the gel permeation
method 81
x^^^
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Number Page
5-5 Chromatogram of sewage sample spiked with 30 ppb phenol ics
& extracted & cleaned-up according to the gel permeation
method followed by derivatization with BF3 in methanol .... 82
5-6 Elution Profile of Phenols and Fatty Acids on Cesium Silicate. 85
5-7 Chromatogram of Phenolic Standard on a new 3' SP-124)DA packed
column ............................ 93
5-8 Chromatogram of phenolic standard after degradation of SP-
1240 DA performance ...................... 94
5-9 Analysis of Phenol Standard on SP-1000 ............ 97
5-10 Analysis of Partially Derivatized Phenols on SP-1000 ..... 98
5-11 Analysis of Partially Derivatized Phenols on SE-54 ...... 99
6-1 Schematic Elution of Priority Pollutants During Column
Chromatography ........................ 1 ^
6-2 Modified Cleanup Scheme for Acid & Neutral Organics ......
6-3 Reconstructed Gas Chromatogram of Silicate Fraction of
West Point Primary Effluent .................. 1Q5
6-4 Hydrocarbon (discard) Florisil Fraction for Spiked Raw and Waste
Activated Sludge Sample .................... 107
6-5 Florisil Neutral Fraction of Spiked Sewage & Sludge Sample . .
6-6 Silicate Neutral Fraction for Spiked Sewage & Sludge Sample. .
6-7 Third Ether Florisil Fraction of a Spiked Sludge Sample &
Derivatized Phenol Fraction of a Spiked Sludge Sample .....
6-8 Base Extracts of Spiked Sewage and Spiked Sludge Sample. . . .
7-1 Pesticide standard solution in Hexane (200 ppb) ........
7-2 PCBs (AROCHLOR 1242) standard solution in Hexane (2 ppm) . . .
7-3 (Pesticide + PCBs)standard solution in Hexane .........
7-4 Pesticide standard solution in Hexane ............. 122
7-5 PCBs (AROCHLOR 1242) standard solution in Hexane ....... 123
artu
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Number Page
7-6 (Pesticide + PCBs) standard solution in Hexane ........ 124
7-7 Extract from pesticide + PCBs spiked distilled water ..... 127
7-8 Extract from pesticide spiked sludge ............. 128
7-9 Extract from pesticide + PCBs spiked sludge ......... 129
7-10 PCBs mixture #2 SUPELCO (AROCHLOR 1221 + 1242 + 1254) .... 130
7-11 PCBs mixture #1 SUPELCO (AROCHLOR 1016 + 1232 + 1248 + 1260). 131
7-12 Toxaphene + Chlordane mixture SUPELCO ............ 132
8-1 Analysis of Standard Mixture by GC/FID ............ 134
8-2 Analysis of Standard Mixture by GC/EIMS ........... 135
8-3 Spectra of Unresolved GC/MS peak No. 2 ............ 136
8-4 Library Search of Unresolved GC Peak #2 ........... 137
9-1 Use of Standards and Spiked Compounds ............ 143
10-1 RIC Trace of Purgables in Seattle-Renton Primary & Waste-
Activated Sludge ....................... 149
10-2 RIC Trace of Seattle (Renton) Raw Sewage ........... 151
10-3 RIC Trace of Seattle (Renton) Combined Sludge ........ 151
10-4 GC Trace of Pesticide Fraction, Renton (Seattle) Raw Sewage 1R2
10-6 Phenol ics in Renton-Seattle Raw Sewage ........... ].E4
10-7 Phenol ics in Renton-Seattle Prim. + Waste Ace. Sludge . . . 154
11-1 Frequently Distribution Plot of Size & Percentage Industrial
Inflow into POTW'S ..................... 175
11-2 Schematic of Sampling Units Employed in the Present Study . . 182
11-3 Representation of Compounds Found in Different Fractions in
EBMUD, Oakland ............. . ..........
11-4 Bioaccumulation of Compounds in Different Fractions in
EBMUD Oakland ........................ 205
xv
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Number Page
12-1 Toxicity of Different Fractions Present in Digested Sludge. .
12-2 Toxicity of Different Fractions Present in Secondary Effluent
Before Chlorination ..................... 234
100-1 Purge and Trap System Schematic ............... 243
100-2 Vessel For Purgable-Free Water ................ 245
100-4 Cryotrap Designs ....................... 247
200-1 1000 ml Erh"!enmeyer Purging Flask .............. 757
200-2 Tenax-GC Trap and Guard ................... 259
200-3 4-liter Flask for Purgable-Free Water ............ 260
300-1 Stirred Liquid-Liquid Continuous Extractor ft Steam Distillation
Vapor Extractor Evaluated in the Present Study ........ 280
300-2 Diazomethane Generator ..... ' ...............
300-3 Sample MS Data Report...?. 1-Header . .- ...........
300-3 Cont ____ P. 2-RGC Trace of Data ................ 30*
300-3 Cont ____ P. 3-RGC Trace of Data ................ 306
300-3 Cont ____ P. 4-List of Compounds searched ........... 307
300-3 Cont ---- P. 5-Quantitation Report ............... 308
300-3 Cont ---- P. 6-Quantitation Report ............... 309
300-3 Cont ---- P. 7-Reverse Search Status Report .......... 310
300-3 Cont ---- P. 8-Forward Search Quantisation Report ....... 311
300-3 Cont ---- P. 9-Forward Search Status Report .......... 31?
300-3 Cont ____ P. 10-Analysis Worksheet ............... 313
300-4 Sample Analysis Summary Sheet ................ 314
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PLATE
Number Page
I Purge & Trap Sampler, Gas Chromatograph & Cryotrap System 28
II Purge & Trap System Interfaced With Mass Spectrometer. ... 29
III Steel Cryotrap in Operation 30
IV Stirred Liquid-Liquid Extractor in Operation 43
V Extractive Steam Distillation Apparatus in Operation .... 44
VI Biobeads Gel Permeation Chromatography 65
VII Biobeads Gel Permeation Chromatography (Long Wave UV Light). 66
VIII Cesium Silicate (Left) & Florisil (Right) Chromatography . . 87
IX Phenols Trapped on Cesium Silicate Column 88
X Phenols Eluted From Cesium Silicate With Methanol 89
XI Driven-Syringe Sampler for Automated Sampling System .... 184
XII Automated Sampling System Controlling Electronics 185
XIII Sutomated Sampling System 186
xv^^
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SECTION 1
INTRODUCTION
The usage and subsequent discharge of water carries the
potential that trace pollutants enter the environment. Cur-
rently, the projected industrial water usage for 1980 is 75,000
million gallons per day (mgd); the municipal water use is
expected to reach 33,600 mgd (Steele, 1968). While past efforts
have primarily focussed on the removal of general organics, as
measured with the biochemical or chemical oxygen demand (BOD and
COD) test, current concern exists with regard to removal of orga-
nic and inorganic trace pollutants that are potentially toxic to
humans.
Several recent studies have noted the presence of trace
organics in sewage and secondary effluent (Table 1-1) indicating
that biological treatment processes do not remove all trace pol-
lutants. It was further noted that chlorination of secondary
effluent resulted in formation of potentially hazardous organics
(Glaze et. al., 1976). The above data indicate that classes of
potentially hazardous organics, such as phenols, volatile chlori-
nated hydrocarbons, pesticides, and polynuclear aromatic hydro-
carbons, are likely to be present in the discharge of sewage
treatment plants. The toxic pollutant section, 307a, of Public
Law 95-500, as redefined in the Consent Decree, specifically
limits the discharge of the above mentioned classes of "priority"
pollutants (Ward, 1977) . While previous studies have analyzed
for one or two classes of toxic pollutants, none encompassed a
comprehensive range of the defined priority pollutants. The pre-
sent study will conduct such a comprehensive study by determining
volatile chlorinated hydrocarbons, Cl/Alkyl/N/OH-benzenes, biphe-
nyls, alkanes, ethers, nitrosamines, polynuclear aromatic hydro-
carbons, pesticides, and heavy metals in sewage, primary, and
secondary effluent at 25 large sewage treatment plants located in
different regions of the United States.
Since many toxic trace organics are of a hydrophobic nature,
they adsorb readily onto bacterial solids. Substantial concen-
trations are therefore found in digested sludge. Since the dis-
posal of sludges containing hazardous substances is also regu-
lated by EPA, the current study will also determine the presence
of the priority pollutants in waste activated sludge and anaero-
bic digester sludge.
During the initial year of effort, 9 months of method
development have produced an integrated scheme for the analysis
of priority compounds, superior sensitivity and quality assurance
are indicated from developmental results. These methods have
been tested against real samples comprising three sewage treat-
ment plants: Renton (Seattle), Washington; Atlanta, Georgia; and
Oakland, California. This report describes the method develop-
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Table 1-1 Detection of trace organics in sewage treatment plants.
Author Sample
Reichert et a1(1971)
Schmidt et al (1971)
Timofeeva & Stom (1976)
Lawrence & Tosine
(1976)
Methews (1976)
Jensen & Peterson
(1971)
Chi an & DeWalle
(1977)
Glaze & Henderson
(1975)
Glaze et al (1976)
Jolley et al (1976)
Manka et al (1974)
Painter (1973)
Burlingame et al
(1976)"
Andrade et al (1975)
Mattsson et al (1975)
Ayanaba & Alexander
(1974)
Sewage
Sewage
Sewage
Sewage
Sewage
Sewage
Secondary effluent
Secondary effluent
Secondary effluent
Secondary effluent
Secondary effluent
Secondary effluent
Secondary effluent
Anaerobic dig. sludge
Anaerobic dig. sludge
Organics
Polynuclear aromatic
hydrocarbons
PCB
phenol, catechol,
quinol
PCB
Cyclohexarol & other
solvents
2,5 di(benzoxazole-2-
yl) thiophene, optic
brightener
55 Compounds, 17 priority
pollutants
30 chlorinated organics
39 chlorinated organics
60 chlorinated aromatic
compounds
Aromatic hydrocarbons
Pesticides & phthalates
28 organics: chlorinated
benzenes, phenyl ethers ,
phthalates
Mi rex & metabolites
Penta bromotoluene,
fire retardant
Anaerobic dig. sludge nitrosamines
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merit phase and initial results from the sampling phase of this
project.
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SECTION 2
PURGEABLES
The research has focussed on the evaluation of three
techniques, i.e., the headspace displacement flask as shown in
Figure 2-la (Kuo et al, 1977), the stripping bubbler (Bellar and
Lichtenberg, 1974) as shown in Figure 2-lb, and the purge and
trap sampler combined with cryogenic trapping and capillary col-
umn chromatography.
2-1 Evaluation of Headspace Displacement Flask
The headspace displacement flask (HDF) was selected for
the initial evaluations using the conditions, listed in Table
2-1. A major advantage of the method is that the purging gas
does not have to pass through the liquid, which circumvents
potential foaming of the 36 compounds listed under the purgeable
category, three of them (acrolein, acrylonitrile, and methylene
chloride) are merged with the solvent peak methanol used for dis-
solution of spiked compounds, six of them (chloroethane, dichlo-
rofluoromethane, methyl bromide, methyl chloride, trichloro-
fluoromethane, and vinyl chloride) are gases at room temperature,
while four of them (1,2-dichlorobenzene, 1,3-dichlorobenzene,
1,4-dichlorobenzene, and hexachloroethane) have too long deten-
tion times for packed columns.
The percentage recovery from purgeable-free water of 18
volatile organics spiked at 20 ppb ranged from 56% for carbon
tetrachloride to 100% for tetrachloroethylene and dichloropropane
(Table 2-2). The standard deviation ranged from 3% for tri-
chloroethylene to 23% for 1,1,1-trichloroethane. The percentage
recovery tended to decrease slightly with increasing concentra-
tion, as shown in Figure 2-2. This is likely due to some over-
loading of the Tenax GC trap.
The effect of matrix organics was tested in sewage and
digested sludge of the sewage treatment plant in Urbana, Illi-
nois. The results in Table 2-3 indicate that the recoveries in
sewage and sludge are lower than those obtained in distilled
water, due to organics present in the sample matrix that compete
for adsorption sites in the Tenax. The recoveries after 16 hour
equilibration are considerably lower for about six of the 17
spiked compounds, especially those with aromatic rings, due to
extensive adsorption onto the bacterial solids.
The matrix effect is most clearly demonstrated in Figures
2-3 and 2-4, where increasing amounts of sewage and digested
sludge decrease the recovery of the individual organics. Most
organics tend to follow a linear function on a log-normal graph.
This relationship can be used in a serial dilution method to
determine the recoveries at an infinite dilution, which protocol
-------
B
C
Figure 2-1 Different Stripping Vessels Fvaluated During the Study;
(A) Headspace Displacement Flask of 1000 nl, (B) Stripping
Bubbler of 10 ml, (C) Purginn Tube of the Purge and Trap
Module
-------
Table 2-1. Instrumental conditions during purge and trap method
determine low molecular weight volatile organics.
100 nl sample in 100 rr-1 vohimetric flask
sealed with wetted ground| glass stopper
transfer to It stripping flask (Kuo and
Chian) spike with standards and stripped
for 20 ninutes, at 60°C with 200 ml/min
He purified with molecular seive and extra
tenax trap
organics adsorb on Tenax GC 60/80 mesh
in 7", 1/4" OD stainless steel tube,
initidily baked out at 250°C with He
flushing ,
trap connected to GC, flushed with He
for 2 minutes; heating of adsorbant
column for 2 minutes at 200°C
organics flushed into GC column (1? ft.
2 irin ID with 0.2* Carbowax 1500 on
Corbopack C 60/80 mesh) for 4 minutes
at 30 ml/min
column temperature from 30°C to 200°C
at 3°/min ,
organics introduced in MS through jet
separator
MS with 70.?V electron energy; 500 ua
emission current; 6V ion energy; -100V
lens volt.i'je, 8V extractor voltage;
20-300 amn mass range, 17 msec inte-
gration/amn; MS calibrated with decal
fluorotriphenyl-phosphine
transfer 5 ml to 10 ml to
the bubbler, spike with
standards and bubble ga.>
through sample at room temp.
for 12 minutes at 40 ml/min
at 40 ml/min (Bellar and
Lichtenberg),
-------
Table 2-2 Recovery of 18 compounds from purgeable-free water using
headspace displacement flask spiked at 20 ppb as run in
triplicate
Relative Percentage Standard
Compound Retention Time Recovery Deviation
1,1-DICHLOROETHANE 0.85 . 85 14
1,2-TRANSDICHLOROETHYLENE 0.93 99 N/A
CHLOROFORM 1.00 91 17
1,2-DICHLOROETHANE 1.10 89 4
CARBON TETRACHLORIDE 1.25 ' 56 N/A
1,1,1-TRICHLOROETHANE 1.29 64 23
DICHLOROBROMOMETHANE 1.31 97 N/A
TRICHLOROETHYLENE .1.57 89 3
BENZENE 1.63 91 5
1,2-DICHLOROPROPANE 1.68 100 N/A
DIBROMOCHLOROMETHANE 1.89 100 N/A
TETRACHLOROETHYLENE 2.13 100 N/A
2-BROMO 1-CHLOROPROPANE 2.16 88 6
BROMOFORM 2.32 95 17
CHLOROBENZENE 2.35 94 10
ETHYL BENZENE 2.54 95 21
1,1,2,2-TETRACHLOROETHANE 2.71 87 12
TOLUENE 3.04 100 N/A
-------
100
a
<_>
2
80- -
60
40
20
BROMOFORM
BROMOOICHLOROMETHANE
DIBROMOCHLOROMETHANE
1,2-DICHLOROETHANE
CHLOROFORM
TRICHLOROETHYENE
TETRACHLOROETHYLENE
CARBONTETRACHLORIDE
TETRAHYDROFURAN
ACETONE
I.I.I-TRICHLOROETHANE"
10
50
100
500
CONCENTRATION (yg/1)
Figure 2-2 Percentage Recovery of Volatile Compounds Spiked at
Different Concentrations in Distilled Water.
-------
Table 2-3. Effect of Matrix Organics on Recovery of Volatile Organics
Spiked at 20 ppb using the Headspace Displacement Flask
Compound
1,1-DICHLOROETHA.IE
CHLOROFORM
1,2-DlCHLOROETHANE
CARBON TETRACHLORIDE
I.I.ITRICHLOROETHAI.'E
D1CHLOROBROMOMETHANE
TR1CHLOROETHYLENE
BENZENE
1,2-TRICHLOROETHANE
DIBROMOCHLOROMETHANE
TETRACHLOROETHYLEh'E
2-BROMO-l-CHLOROPROPANE
BROFORM
CHLOROBENZENE
ETHYLBENZENE
1,1,2,2-TETRACHLOROETHANE
TOLUENE
1,1,2-TRICHLOROETHAM
Relative
Retention
Time
0.85
1.00
1.10
1.25
1.29
1.31
1.57
1.63
1.68
1.89
2.13
2.16
2.32
2.35
2.54
2.71
3.04
Distilled
Water
85
100
89
56
64
97
89
91
100
100
100
88
95
94
95
87
100
100
Raw
Sewage
(1)
100
88
66
78
73
98
89
100
78
88
75
87
78
100
100
2%
Raw
Sludge
(2)
97
67
90
87.4
55
95
98
94
94
95
91
100
100
99
100
100
100
1.5%
Digested
Sludge
(2)
93.1
89.0
93.4
89.7
54.2
95.4
86.7
87.1
92.1
98
90.3
98.3
97
89.6
89.5
100
96.5
Equilibrated
Digested
Sludge (16 hr)
(2)
92
79
93
65*
39*
84
80
66*
90
91
88
95
89
61*
43*
93
70*
•Decreased recovery after equilibration
(1) Sewage diluted 25 ml to 100 ml
(2) Sludge diluted 10 ml to 100 ml
-------
o
o
cc.
UJ
a.
o
UJ
OL
O
UJ
o.
50
25
50
25
O CHLOROFORM
AETHYLBENZENE
D BENZENE
V 2-BROMO-l-CHLOROPROPANE
OCHLOROBENZENE
AI.I-DICHLOROETHANE
Q1.2-DICHLOROETHANE
VTETRACHLOROETHYLENE
I
25 50 75
RAW SEWAGE, ML/100 ML MIXTURE
100
Figure 2-3 Recovery of Volatile Compounds Added to Diluted Sewage
Samples at a Concentration Level of 20 ppb.
10
-------
100
75
o
CJ
LlJ
oe
UJ
CD
O
a:
50
25
o
o
o
(X
25
O 2-BROMO-l-CHLOROPROPANE
ADICHLOROBROMOMETHANE
Ol.l-DICHLOROETHANE
10
20
30
40
50
O CHLOROBENZENE
ATRICHLOROETHYLENE
D TETRACHLOROETHYLENE
DIGESTED SLUDGE, ML/100 ML MIXTURE
Figure 2-4 Recovery of Volatile Compounds Added to Diluted Diaested
Sludge Samples at a Concentration Level of 20 ppb.
11
-------
is given in Table 2-4.
2-2 Evaluation of the Stripping Bubbler
In subsequent runs, the 10 ml stripping bubbler was
evaluated. The vessel holds 10 ml and inert gas is sparged
through the fritted glass bottom. The recoveries and standard
deviation shown in Table 2-5 indicate that higher deviations are
experienced for the first and last eluting compounds, while lower
deviations are noted for compounds eluting in the middle. Simi-
lar to the HDF experiments, it was noted that the recoveries
decreased slightly with increasing levels of the spiked compound,
as shown in Figures 2-5 and 2-6. The decrease in recovery for
ethylbenzene and tetrachloroethylene tended to be greater than
for other compounds. A typical gas chromatogram of Atlanta
sewage is shown in Figure 2-7.
2-3 VGA Determination by Glass Capillary GC
The principal shortcomings of the packed Column GC/FID
and purge and trap method are: 1) poor detection of compounds
more volatile than methylene chloride, 2) multiple experiments
being required to determine matrix effects, and 3) potential
false identification of GC peaks, especially from high background
samples. An alternative method, utilizing glass capillary GC/MS
has been devised at the University of Washington. For this pur-
pose, a Hewlett-Packard 7675A Purge and Trap module has been
interfaced with the GC/MS/DS system. The interface consists of a
swagelok connectoer that has been tapped and welded to a steel
tube to serve as a splitter vent. The column end is passed
through this fitting and inserted approximately 1/4" into the
steel line emerging from the purge and trap assembly. The condi-
tions found to be optimum in operating the analysis successfully
are presented in Table 2-6. The system is shown schematically in
Figure 2-8.
In order to obtain acceptable chromatographic separation of
the sample, on-column cryogenic trapping is essential. For this
purpose, approximately 10 cm of the first coil of the column are
inserted in metal jackets of various design. The first model
consisted of a notched copper tube that has been prebent to con-
form to the column shape. Liquid nitrogen is introduced from the
exit side of the cryotrap and essentially fills the trap and
bathes the column during desorption from the Tenax trap. In
GC/MS analysis where MS acquisition is routinely begun with the
initiation of desorption and cold trapping, it is observed that
allowing sufficient time to chill the transfer lines and cold
trap itself (5 - 10 minutes) results in essentially perfect cold
trapping so long as the sample loading is reasonable (no more
than micrograms of the sample). The first peak observed to chro-
matograph after cessation of cold trapping is carbon dioxide,
followed rapidly by other gaseous and highly volatile components
12
-------
Table 2-4. Proposed Protocol for Measuring Purgeables in Raw Sewage
with HDF (Headspace Displacement Flask)
1. Establish the percent recovery of the purgeable priority pollutants
at a concentration of 50 ppb (v/v) in purgeable-free water under
the experimental conditions available at individual laboratory.
2. Measure the level of these compounds at two to three dilutions (use
10, 25, and 50% sewage addition for 100-ml sample or 25, 50, 100%
for 10-ml sample as with the Bellar and Lichtenberg's apparatus).
3. Normalize all concentration determined based on the highest dilution
employed and plot on a semilog graph paper with the abscissa in
logarithmic scale for concentration.
4. Draw a least square line through these points and extrapolate to
zero sewage addition. The value obtained represents the concentra-
tion of the given compounds to be determined in purgeable-free
water.
5. Divide the above value at zero sewage addition by the percent
recovery of the corresponding compounds determined at 50 ppb (v/v).
The actual value can be obtained by multiplying the value by the
number of the highest dilution made with the run.
6. Use the EPA internal standard, 2-bromo-l-chloropropane, in all
quantitation studies to minimize variations in FID responses and
injection sample size.
7. Concentrations are to be reported on a weight basis by multiplying
the above values by the density of each compound.
13
-------
Table 2-5. Reproducibility of Bellar and Lichtenberg System spiked
with eleven purgeable organics 100yg/l in raw sewage
and digested sludge based on triplicate. Sewage and
sludge were obtained from Atlanta, Georgia, Clayton
Plant.
Raw Sewage (1)
Digested Sludge (2)
Compound
1,1-DICHLOROETHAME
CHLOROFORM
1,2-DICHLOROETHANE
CARBONTETRACHLORIDE
D1CHLOROBROMOMETHANE
BENZENE
TETRACHLOROETHYLENE
2-BROM01-CHLOROPROPANE
CHLOROBENZENE
ETHYLBENZENE
Relative
Retention
Time
0.85
1.00
1.10
1.25
1.31
1.63
2.13
2.16
2.35
2.54
Recovery
W
73
54
76
65
67
78
65
82
68
72
Standard
Deviation
(*)
6.6
3.0
7.2
1.5
4.8
7.8
7.7
8.9
10.1
17.1
Recovery
(*)
81
75
83
78
83
83
85
83
75
63
Standard
Deviation
(«
4.8
9.5
3.7
5.3
4.8
4.4
16.3
6.5
13.4
12.8
(1) 5 ml sewage diluted to 10ml
(2) 2.5 ml sludge diluted to 10 ml
14
-------
O
o
o
ai
100
90
80
70
60
50
O
- A
-O 2-BROMO-l-CHLOROPROPANE
A TRICHLOROETHYLENE
D 1,2-DICHLOROETHANE
VA ETHYLBENZENE
ATETRACHLOROETHYLENE
50
100
150
o
UJ
C£
o:
LU
O-
100
90
80
70
60
50
O 1,1-DICHLOROETHANE
A BENZENE
D CHLOROBENZENE
V CARBON TETRACHLORIDE
50
100
150
CONCENTRATION OF THE SPIKED COMPOUND (yg/1)
Figure 2-5 Recovery of Volatile Orqanics from a 50°b Diluted
Champaiqn Sewage Spiked at Different Concentration
Levels in a Stripping Bubbler.
15
-------
o
o
100
90 f-
80
70
60
50
.O TETRACHLOROETHYLENE
A DICHLOROBROMOMETHANE
D 2-BROMO-l-CHLOROPROPANE
V7 CARBONTETRACHLORIDE
VA CHLOROFORM
o:
o
S
on
LU
O-
100
90
80
70
60
50
100
200
O TRICHLOROETHYLENE
S 1,2-DICHLOROETHANE
D 1,1-DICHLOROETHANE
7 CHLOROBENZENE
A ETHYLBENZENE
100
200
CONCENTRATION OF SPIKED COMPOUND (yg/1)
Figure 2-6
Recovery of Volatile Orqanics from a 25% Diluted
Champaign Anaerobic Digested Sludge Spiked at
Different Concentration Levels in a Stripping Bubbler.
16
-------
o>
c
to
01
o
S_
O E
i— i-
.C O
(J *+-
•r- O
-O S-
I O
"> in
n is
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c
Ol
o
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s_
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O
o
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O
u «
re n
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c
o
CD
C
O)
O)
o
S-
o
o
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S-
D
CM
g
Q.
O
CL
O
O
U
t
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o
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S-
XI
I
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C
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01
0)
c
CD
tsl
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JD
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o;
c
ro
QJ
O
S-
o
-------
Table 2-6 GC and GC/MS Conditions for the VOA Analysis
Purge time
Purge rate
Purge temperature
Purge Gas
Desorption time
Desorption temperature
Desorption flow rate
Cryo temperature
Trap condition time
GC column
GC program
MS conditions
15 minutes
20 ml/min
ambient
organic free nitrogen
purified through catalyst
10 minutes
200°C
1 ml/min
liquid nitrogen temperature (-198°C)
10 minutes
30 m SE-54
0-10 min cryotrap
10-14 min isothermal
14-18 min 4°/min
18-22 min 8°/min
34-443 mass range
0.45 sec scan time
0.5 sec scan rate
18
-------
P/T Sampler
warm I
air
Exhaust
1/16" SS Transfer
Line
Splitter
Glass Capillary
Column
GC Oven
1/8" Copper Line
Cryotrap (--10 cm)
MS
Spli
D
Res«
voit
Figure 2-8 Schematic of VOA Analysis Instrumentation Usinq Cryogenic
Trapping and Capillary GC/MS Separation.
19
-------
such as pentane, halomethanes, vinyl chloride, etc.
The cryogenic trapping thermally focusses the sample during
desorption from the Tenax trap. It is desirable to warm the cold
trap rapidly following desorption to improve chromatographic
banding. The initial notched-tube trap was deficient in that it
warmed too slowly. Two additional designs have shown much
improved chromatographic performance — a two piece design and a
steel tube, shown in Figure 2-9. Both of these permit warm air
to be blown over the cryotrap in a direction opposite to the
coolant flow. After some experimentation, the configuration
found to be most desirable is to have the coolant enter the trap
near the column exit, and the warm air enter near the GC column
entrance. Other configurations produced split peaks and peak
spreading. Subsequent conversations with the Hewlett-Packard
applications scientist working on this same approach have pro-
vided independent confirmation of these observations. As a mat-
ter of convenience, the warm air is run from a tank through a
coil of copper placed inside the transfer oven to the MS, kept at
240°. This provides 40-80°C air for warm up.
Initial chromatography of purgables was carried out with the
Tenax-Chromosorb layered trap recommended by EPA in the BAT pro-
tocols. Unfortunately, continued operation at temperatures at or
below 200°C results in significant trap background from apparent
thermolysis of the polystyrene Chromosorb. While these compo-
nents do not appear to actually obscure the priority compounds
to a large degree, the implications with regard to stable and
reproducible behavior of the trap are not encouraging. Operating
with Tenax alone provides a very clean background analysis, at
the expense of poor trapping for compounds more volatile than
methylene chloride. For the present, it appears that no fully
satisfactory trapping medium has been found.
For sludge or foamy samples, agitation of the sampling
vessel with an ultrasonic bath is recommended. This disperses
sparging gas efficiently and provides better mixing within the
sample. In extreme cases, a surface sparging technique recently
reported by Hewlett-Packard could be employed.
Recovery of spiked compounds in a variety of sample types are
reported in Table 2-7. Using this method of capillary chromato-
graphy, increased sensitivity and lower detection limits relative
to packed column analyses are observed. Figure 2-10 shows the
chromatogram of a 0.4 PPb standard purged from water and trapped
on Tenax plus Chromosorb 102. The sample size was 5 ml (10% of
the recommended upper limit for the purge and trap sampler) and
the attenuation was "8".
20
-------
crimped
CROSS SECTION
o
CO
O
a FROM CAPILLARY INJECTOR
b TO REST OF GC COLUMN, MASS SPECTROMETER
c WARM AIR INLET
d COOLANT INLET (FROM LIQUID NITROGEN RESERVOIR)
Figure 2-9 Cryotrap Designs : A) Notched Tube; B) Aluminum
Sandwich; C) Stainless Steel Tube
21
-------
Table 2-7.
ro
ro
Recovery of volatile organics from different
matrices using the cryogenic trapping technique
and the P/T module.
SEDIMENT
SEWAGE
PERCENTAGE DETECTION OF SPIKED mnp.
(^ \—
CJ LU LU LU LLJ
2: ^L CD cr CD
C5 d -«• -^ — )
LEVEL OF SPIKING (yG/ L)
NUMBER OF DETERMINATIONS
2,2-DICHLOROPROPANE
CHLOROETHANE
ACRYLONITRILE
CHLOROFORM
TRI CHLOROETHANE
BENZENE
TOLUENE
BROMOFORM
C19-3ENZENE
LAJ
OO
25
6
100
100
50
100
100
83
*83
*83
67
LLJ
OO
10
13
100
92
62
100
100
100
100
100
77
U-!
25
5
100
100
60
100
100
100
100
100
75
LLJ
CO
10
5
!100
60
100
100
80
100
100
100
80
i
00
10
2
100
50
50
100
100
100
100
100
50
:=>
c
o
Ul
o:
LU
CD
1—
"Z.
LLJ
o;
LLJ
CL.
QS**
286%
129
108
104
98
QS
QS
84
cr
i — i
I—
1— 4
UJ
O
o
D.'
et
O
•^
\—
00
420
79
14
6
12
22
o
C.'
L^J
Cf.
LJJ
CD
h-
"^
LU
CC
LU
Q-
QS
159%
153
117
103
103
QS
ns
150
DEVIATIO
o
Cf.
-------
RIC
03/13/79 18:31:8
SAMPLE: HB8913E
INTEN
186000.
i.
1410 D5-CHLOROE7HANE
1433 2-PROPANONl
1461 D1CHLOROMETHANE
1519 HEXANE
1538 06-3,3-DICHLOROPROPANE
1552 Dl-CHLOROFORM
ro 1591 03-1.1,1-TRICHLORETHANE
00 1626 D6-BENZENE
1970 D8-TOLUENE
3265 D4-1.4-DICHLOROBEN2ENE
DATA: UB8S13E »3265
CALI: C0918C 13
me
B9'IJ/79 ISiJIlK
SOWUi W83IX
OOTBi 1091X 1320
CM.II ctniec n
SDW I3M TO I7W
-Uu J
ul
IHTEN
MOW.
1.
[ I I I 'I f I I I T | I I ' I I | I I I I |
i«a \ss» \n» sea
12133 12:53 I3:» 13:<3 1«. 19 Tin
Expanded Scale
1
n r
1 1 r
1 1 r
1 1 r
-i 1 1 r
580
4:18
1608
8:20
1560
12:30
2080
15:4?
3000
3500
Expanded Scale
4000
Figure2-10 Reconstructed Ion Current of a 0.40 ppb Volatile Organic Mixture in Distilled Water.
-------
In addition to increased sensitivity, capillary analysis has
permitted the detection of more volatile compounds than are typi-
cally resolved in packed column VOA work. Figure 2-11 shows the
purge and trap GC/MS analysis of a standard containing all of the
priority purgables, except dichlorodifluoremethane, acrolein, and
acrylonitrile. In only a few instances are priority compounds
found to co-elute and these would be readily quantified in the
MS/DS analysis regardless of resolution. Initial, analyses were
performed using a 30-meter SE-54 capillary column; the initial
temperature for the analysis has varied between -10° and 30° C.
Although these temperatures are below the nominal operating range
for this column, acceptable performance has been observed.
Analysis of sewage effluent samples to determine the degree
of resolution is illustrated in Figure 2-12. For the most part,
the chromatography is qualitatively improved over the packed col-
umn results reported in the previous quarterly reports.
Remaining areas of refinement for the capillary VOA
technique include: improved Tenax trapping to retain the most
volatile priority compounds efficiently, development of alterna-
tive methods for sparging foamy samples, and improvement of tech-
niques to analyze VOAs from sludges. Plates I, II, and III show
the instrumental configuration.
24
-------
MflSb CHPOMPTOCPAM
82-'20'79 lf:05:00
SflMPLE: SUF-ELCO STO fl+B UCft'S
RANGE: G I.ib85 LABEL: N 0- 4.0
813
OflTfl:
ML I:
TOTftL'.JOfll
pflHS «5
«1509
QltoM: (\ 0, 1.0 BASE: U 20, 3
SCftNS 700 TO 1008
331664.
Peak *
Compound
rv>
en
341
eso
11:4?
PKAK «:
3 'i
C00
13:20
5 6 78 9 10 11 12 13
SOU
l
2
3
&
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
chloromethane
butene
bromo methane
chloroethane
trichlorofluoro-
methane
pentane
ethyl ether
dichloroethene
cst
methylenechloride
dichloroethene
(plus hydrocarbon)
1,1-dichloroethane
hexane
chlorofom
1,1,1-trlchloroethane
1,2-dichloroethane
cyclohexane
carbontetrachlorlde
+ benzene
cyclohexene
14
Ih 18
10
Figure
Reconstructed Gas Chromatogram of the most volatile organics
of the VOA standard
-------
NflSS CHROMftTOCRftM
02'20/?9 IF:05:68
SflMPLE: SUFELCO STD IUB UCfl'S
RANGE: G 1,2635 LABEL: N fl, 4.8
819
DfiT?-: TOFftLWWl «U
O'-LI: Pi'4i3 «5
: ft e, i.o B,U£: u 20, 3
SCANS
TO 1S60
-
45
301
-
753
1 I
II
8!
AJL
eea
13:28
9-
2
1
1
,
1138
„
10
L
84
1M2
AJL
1
I
1009
16-.-19
Peak 0 Compound
20 1,2-dichloropropane
+ 1.1,1-trichloroethane
14
i JW
1 32.3
1233
1280
jjll.
-^^.
jg 21 bronodlchloronethane
22 1,3-dlchloropropene
23 toluen*
2U 1.3-dlchloropropene
25 1.1,2-Crichloroethane
26 dlbronochloronethane
27 tetrachloroethylene
28 chlorobenzene
29 ethylbenzene
30 bronoform + styrene
31 tetrachloroethaoe
31
1598
1599 1563 (7^3
lVn0 160.T I93-3 5CW
29:83 23:20 26:^0 3e:P?"'''E
(sec blowup) PEAK 0:
2D 21 22 23 25 26 27
Figure 2-11 Reconstructed Gas Chromatogram of a VOA standard
-------
ro
ftlC
85/63/73 11:24:63
SAMPLE: PS186 (8.5 HL+25 NG RECCUERY SPIKE)
Scan #200-350 C02
1-1494 D5-CHLOROETHANE
2-1546 1,1,-DlCHLOROETHENE
3-1567 D3-ACRYLONITOLE
4-1569 D1CHLOROHETHANE
5-1597 1.2-DICHLORO(2)ETHENE
6-1618 1.1-DICHLOROETHANE
7-1671 D6-2.2-DICHLOROPROPANE
8-1694 Dl-CHLOROFORM
9-1697 TRICHLOROMETHANE
10-1742 03-1.1,1-TRICHLOROETHANE
11-1749 1,1,1-TRICHLOROETHANE
12-1771 1,2-DICHLOROETHANE
13-1786 D6-BENZENE
14-1792 BENZENE
15-2228 METHYL BENZENE
16-2456 TETRACHLOROETHENE
17-2767 ETHYL BENZENE
18-3442 04-1,4-DICHLOROBENZENE
DATA: PStdbUl «1
CM. I: C8587M »4
I fin
SCflHS 266 TO 248*
Lul
INTEH
ieeeaa.
i.
RIC
I
see
4:10
-L.
lililil
2600
.'.6:40
2583
-i i | i r i i— f i r
3099 3508
4888
33:29
Figure 2-12 Reconstructed Ion Current of Renton-Seattle Raw Sewage.
-------
ro
CO
A TENAX TRAP
B SAMPLE TUBE AND PURGE TUBE
C COOLANT COILS FOR TRAP
D VOA TRANSFER LINE TO GC COLUMN
E CRYOTRAP FOR COLUMN
F GC CAPILLARY COLUMN
G LIQUID NITROGEN TRANSFER LINE
H LIQUID NITROGEN DEMAR
PLATE I PURGE AND TRAP SAMPLER,
GAS CHROMATOGRAPH AND
CRYOTRAP SYSTEM
-------
A MASS SPECTROMETER CONTROLLING ELECTRONICS AND DATA SYSTEM
B PURGE GAS PURIFIER
C VOA UNIT
0 VOA TRAP TEMPERATURE MONITOR
E TRANSFER OVEN BETWEEN GC AND MS
F TERMINAL FOR MASS SPECTROMETER
G GC OVEN
H LIQUID NITROGEN DEWER
I GC TERMINAL
PLATE II
PURGE AND TRAP SYSTEM
INTERFACED WITH
MASS SPECTROMETER
29
-------
A INLET FROM VOA UNIT
B VOA CAPILLARY SPLITER
C FIRST COIL OF CAPILLARY COLUMN
D CAPILLARY COLUMN
E CRYOTRAP INLET FOR LIQUID NITROGEN
F CRYOTRAP INLET FOR WARM AIR
PLATE III STEEL CRYOTRAP IN OPERATION
-------
SECTION 3
THE EXTRACTION PROCEDURE
Different methods of extraction have been compared for
water, sewage, sludge, sediment, and tissue samples. For water,
sewage and sludge, the methods considered were: 1) standard EPA
separatory funnel separation; 2) homogenation of sludge or sewage
plus solvent and brine with a tissumizer followed by centrifuga-
tion; 3) a stirred liquid-liquid continuous extractor and, pre-
liminarily, steam distillation/vapor extraction.
3-1 Separatory Funnel Separation
The study initially evaluated the conventional separatory
funnel in which 100/50/50 ml portions of methylene chloride were
used to extract the organics at pH 2. The extraction efficien-
cies of 26 neutral compounds spiked at 20 ppb were 95% and 56% on
duplicate samples respectively, while it was 18% and 16% for the
15 acid extractables. Extraction of sludge samples, however,
resulted in an emulsion which could not be broken. The funnel
separation was therefore abandonned for further use.
However, the recovery of priority compounds by this method
from distilled water was determined in duplicate (Table 3-1), and
may be considered to represent an effective upper limit to reco-
veries by separatory funnel extraction for real samples.
3-2 Sample Homogenation
For sludge samples, embodying perhaps the most difficult
separation problems, a 3 way comparison was made at the GIT labo-
ratory of different homogenation procedures.
3-2.1 Extraction using filtration
A 200 ml 10% aqueous solution of calcium chloride (w/v), and
200 ml methylene chloride was added to sludge (50 g) in a 1-liter
Erlenmeyer flask. This suspension was stirred with a stirring
bar (3n long, solvent cleaned) at fast speed for 20 minutes at
room temperature. The resulting emulsion was vacuum filtered
through a sintered glass disk into a separatory funnel. Another
extraction was performed on the retained layer with 100 ml methy-
lene chloride. The recovered total extract was 220 ml, repre-
senting a 73% solvent recovery.
To counter the thick emulsion formed during stirring, 1
liter of distilled water was added to 50 grams of sludge in a 4
liter Erlenmeyer flask. A 10% aqueous solution of calcium chlo-
ride (100ml) was added, followed by 200 ml methylene chloride.
The suspension was magnetically stirred at fast speed for 20 min-
utes at room temperature. The solution was vacuum filtered in a
31
-------
Table 3-1. Percent recovery of 20 ppb acids and neutrals spiked into
distilled water (500 ml) and extracted by separatory funnel
according to EPA standard protocol.
NAPHTHALENE
HEXACHLOROBUTAD1ENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
ANTHRACENE
PYRENE
BENZO (A) ANTHRACENE/CHRYSENE
DIBENZO (A,H) ANTHRACENE
HEXACHLOROETHANE
N-N1TROSO-DI-N-PROPYLAMINE
1,2,4-TRICHLOROBENZENE
2-CHLORONAPHTHALENE
AZPBENZENE (DIPHENYLHYDRAZINE)
N-N1TROSOD1PHENYLAHINE
PHENAHTHRENE
FLUORANTHENE
HEXAMETHYLBENZENE (l.S. )
D-10 ANTHRACENE
1.3-D1CHLOROBENZENE
1,2-DICHtOROBENZENE
BUTYLBENZYLPHTHALATE
N-NITROSODIMETHYLAM1NE
Dl-N-OCTYLPHTHALATE
HEXACHLOROBENZENE
HEXAMETHYLBENZENE (10)
2-CHLOROPHENOL
PHENOL
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL
ANISOLE
D-10-ANTHRACENE (20)
2-CHLOROMETHOXYBENZENE
4-CHLORO-3-METHYLMETHOXYBENZENE
2,4-DICHLOROMETHOXYBENZENE
2,4,6-TRlChLOROMETHOXYBENZENE
2-NITROMETHOXYBENZENE
4-N1TROMETHOXYBENZENE
4.6-DIN1TRO-2-METHYLMETHOXYBENZENE
PEN TACHLOROMETHOXYBEN ZEN E
X Recovery
45
92
59
0
250
350
370
34
0
0
54
61
83
84
38
48
116
37
100
70
96
88
70
0
290
80
100
56
0
0
26
0
95
.
<0,1
0
0
at
00
00
-01
+ 37
-08
-10
-03
+ 04
-03
-02
-01
-00
+ 01
+ 00
+ 04
+ 04
00
00
-14
-16
-03
00
+ 12
+ 02
00
-08
-
-
+ 05
-
-02
.
-05
-
.
t Recovery
62
44
35
35
11
300
190
0
54
0
36
0
56
0
46
01
31
16
100
250
66
41
28
0
22
40
100
0(OR)
0
0
92
0
60
<0.1
0
1
0
At
-09
-06
-06
-06
-
-05
-05
-33
-08
-
-04
-35
-12
-18
-07
+ 20
-09
-1
00
-01
-02
-07
-01
00
00
-04
00
-26
-
-
-10
-
-06
+05
-
+ 03
.
32
-------
separatory funnel through a sintered glass disk. The lower sol-
vent layer was collected, the upper aqueous layer and emulsion
was again extracted with 100 ml methylene chloride and vacuum
filtered. The lower layer was combined with the first extract.
The total combined methylene chloride extract was 160 ml, repre-
senting an 80% solvent recovery.
This method was found to be unsuitable for this analysis.
The time required in extracting sludge and waiting for the emul-
sion to break before filtration was frequently very long, usually
3-4 hours. The viscous emulsion also made filtration difficult.
When vacuum was applied, particulates were trapped in the frit
pores and made subsequent filtration difficult. Different salts
at different concentrations were used in an attempt to break up
the extract emulsions. A high salt (sodium chloride) concentra-
tion, 30% (w/v) was tried, and found to be comparable to 10%
(w/v) of calcium chloride, in terms of time required for the
emulsion to settle.
3-2.2 Extraction-centrifugation
A 50 ml, 10% (w/v) aqueous solution of calcium chloride and
100 ml methylene chloride were added to 100 grams of well mixed
sludge in a 500 ml Erlenmeyer flask. The suspension was homo-
genized with a Tekmar Tissumizer for 1 minute at 10,000 rpm. The
suspension was transferred to four 100 ml glass centrifuge tubes
and centrifuged at 2000 XG for 5 minutes to separate the emul-
sion. The lower solvent layer was taken up with a 30 ml syringe
and transferred to a 250 ml Kuderna-Danish flask. The sludge
cake and supernatant were combined and 50 ml fresh methylene
chloride was subsequently added. This suspension was again homo-
genized with the Tekmar Tissumizer for 1 minute at 10,000 rpm,
centrifuge separated, and the lower solvent layer combined with
the first extract. This extraction was repeated a third time
with 50 ml methylene chloride. The combined methylene chloride
extract of 160 ml, representing an 80% solvent recovery was
evaporated to 2 ml. The coffee-colored thick extract was passed
through a 5-3/4" disposable pipett packed with 3" baked anhydrous
sodium sulfate. The microcolumn was rinsed with fresh methylene
chloride and the volume was adjusted to 5 ml. The total extrac-
tion time required, including solvent evaporation time, was less
than one and a half hours.
An alternative procedure for extraction efficiency was also
tested. A 50 ml aqueous solution of 10% calcium chloride (w/v)
and 100 ml methylene chloride was added to 100 grams of sludge in
a 1 liter Erlenmeyer flask. The suspension was stirred by magne-
tic stirrer at fast speed for 10 minutes at room temperature
instead of a Tissumizer. The resulting emulsion was placed in
four centrifuge tubes and centrifuged for 5 minutes at 2000 XG.
The methylene chloride layer was taken up with a 30 ml syringe.
The sludge cake and aqueous phase was returned to the flask and
33
-------
extracted with 50 ml methylene chloride two more times. The com-
bined methylene chloride was placed in a Kuderna-Danish evapo-
rator and evaporated to 2 ml. The concentrated extract was
passed through a micro column packed with 3" baked anhydrous
sodium sulfate. The final volume was increased to 5 ml with
fresh methylene chloride. When 100 ul of the above extract was
transferred onto a weighed aluminum pan and solvent evaporated,
duplicate residues weighed 11.2 mg and 11.0 mg. When 100 ul of
the extract, which was homogenized with the Tissumizer, was simi-
larly weighed, the duplicate residues weighed 12.5 mg and 13.2
mg. The above two extraction methods therefore do not show much
difference in extracting efficiency. Mixing using Tissumizer has
the advantage of saving time, since only 1 minute was needed for
complete mixing.
The final extract volume was decided by placing 100 ul of
the extract onto a tared aluminum pan, and letting the solvent
evaporate. The residue was weighed and the solution concentra-
tion was adjusted to 100 mg/ml. This concentration is very cri-
tical for the subsequent gel permeation column chromatography
because the gel column has a fixed capacity. Overloading the
column will reduce the resolution and shorten the column life.
3-3 Liquid-Liquid Extraction
In an attempt to improve recoveries in the extraction of
organics from water, a new extractor was designed and evaluated
at the University of Washington.
The present EPA analytical protocol for the screening phase
of the BAT program calls for simple liquid-liquid extraction of
aqueous samples with 450 ml of solvent (in portions of 250, 100,
100 ml) by means of a separatory funnel. In cases where emul-
sions prevent the recovery of 85% of the extracting solvent vol-
ume, the emulsions are to be broken or continuous extraction used
at the analyst's discretion. Bulk organics in the sample matrix
cause emulsification, which varies greatly with the levels and
nature of these compounds. The actual efficiency of partitioning
between the solvent and the sample, consisting of a wide range of
compounds such as the priority pollutants, also varies consi-
derably with the matrix. For accurate and precise determinations
of these compounds in water samples, an extraction technique that
is relatively insensitive to matrix effects and is applicable to
a broad range of compounds is desirable. Conventional liquid-
liquid extraction generally satisfies these requirements but is
impractical because long extraction times (24-48 hours or longer)
are required. The rate of extraction for liquid-liquid continu-
ous extractors can be greatly improved by gentle stirring of the
phases to increase the rate of mass-transport within each phase,
while having little or no effect on the contact area or area/
volume ratio for the phases. The presumptions that the slow pro-
cess in the extraction is diffusion of solute to the aqueous/
34
-------
organic interface, and that crossing the interface is relatively
rapid, are in accordance with the observations of other investi-
gators (Dunges, 1978). Slow nonturbulent stirring without break-
ing the solvent and sample up into droplets has a minimal ten-
dency toward emulsion formation, but can substantially increase
the rate of extracton by moving solutes to the interface rapidly
relative to their diffusion rates in water.
The extractor is illustrated schematically in Figure 3-1.
Its design is modular and is constructed of stock laboratory
glassware. The main extraction chamber is a 2000 ml 3-neck round
bottom flask, modified by the addition of a stem at the bottom,
terminating in a teflon stopcock and ground glass connector. The
concentrator vessel is a standard 500 ml round bottom flask. A
standard Friedrichs condenser was modified by the addition of a
distillate inlet below the cold finger; this modification is not
essential but is convenient for the spatial arrangement of the
components. The connections between condenser, extraction ves-
sel, and concentration vessel are of corrugated teflon tubing,
which is flexible enough to permit the concentrator to be raised
or lowered relative to the extractor chamber. The stirrer shaft
is introduced through the center neck of the extractor chamber
via a liquid-seal; the stirrer itself is teflon coated. The stem
of the extractor chamber is filled with silanized glass beads to
aid in breaking any slight emulsions that may form and to retain
and separate aqueous droplets. All interior surfaces of the
apparatus are of teflon or silanized glass. For this extractor,
a special non-vortexing stirrer head (Bel-Art catalog 3H37218)
was used.
The extractor was evaluated in three ways: 1) the general
performance characteristics, such as reflux rates, degree of
stirring possible, and efficiency of solvent/water separation,
were observed; 2) recovery profiles of total extractables from
raw sewage samples were measured gravimetrically for several sets
of extractor conditions; and 3) individual recoveries of repre-
sentative priority pollutants from spiked distilled water were
measured in a preliminary experiment. The gravimetric studies
utilized untreated, unfiltered sewage that had been stored at 5
C. The total recoveries of extractable matter varied from
experiment to experiment, presumably because of varying amounts
of suspended particulates in each sample. Samples were taken at
one hour intervals by the following procedure: the reflux was
stopped, the volume in the concentrator vessel was adjusted to
200 + 5 ml, and a 10 ml aliquot was withdrawn in a class A
pipette. This sample was air dried in a tared pan, then dried in
a dessicator over P^05 to constant weight. In addition to hourly
samples, one "infinity" sample was taken at 12 or 24 hours.
35
-------
1 24/40 I LIQUID STIRRER SEAL
2 24/40.1 JOINT
3 2000 ML 3-NECK RB FLASK
4 GLASS NECK FILLED WITH SILANIZED BEADS
5 TEFLON 3-WAY STOPCOCK
6 14/20 I JOINT
7 1/4 INCH CORRUGATED TEFLON
8 HEATING MANTLE
9 500 ML 2-NECK RB FLASK
10 3/4 INCH CORRUGATED TEFLON
11 FRIEDRICHS CONDENSER
12 MODIFICATION (VAPOR INLET)
11
12
1. J 24/40 CONNECTION TO ADDITIONAL CONDENSOR
2. OUTLET COLD FINGER
3. INLET COLDFINGER
4. f 34/40 JOINT FOR COLD FINGER
5. CONDENSOR OUTLET
CONDENSOR OPENING
CONDENSOR INLET
NOTE: ONE ARM IS HIGHER
f 24/40 FLASK WITH SAMPLE
§ 24/40 FLASK WITH METHYLENE CHLORIDE
6.
7.
8.
9
10.
10
Figure 3-1 Stirred Liquid-Liquid Continuous Extractor and
Steam Distillation Vapor Extractor Evaluated in
the Present Study
36
-------
The spiked distilled water experiment utilized a standard
mixture containing approximately 10 micrograms each of 53 com-
pounds in 10 ml of methanol, diluted in 1200 ml with distilled
water and left 48 hours before extraction. Prior to extraction
the pH was adjusted to 1.9 with dilute HC1. A six hour and a 12
hour extract were taken, comprising the entire extract up to
those respective points (plus a rinse) after which the pH was
raised to 11.9 with NaOH solution, and two further 6 hour samples
were taken. The samples were concentrated to 25 mis by evapora-
tion at room temperature, then dried by standing over anhydrous
sodium sulfate for 18 hours. They were then concentrated to 1 ml
and a 10 microgram spike of anthracene solution was added as an
external standard. The samples were analyzed by GC-FID on an
SE-54 WCOT capillary column with GC/MS verification. Individual
compounds were quantified by comparison with the anthracene
external standard. The phenols were analyzed on a SP-1000 WCOT
capillary column and quantified in the same manner. All extrac-
tions were performed using methylene chloride as the extracting
solvent.
The mechanical stirrer used (Gerald Heller GT 21) provided
good control of speeds between 100 and 400 rpm. No vortexing was
observed at any of these speeds, nor v/as any significant emulsi-
fication seen during the subsequent experiements using sewage
samples. The transport of water from the extractor to the
separator was minimal, and only in microdroplet form as evidenced
by cloudiness in the extract. The reflux rate was limited by the
rate of solvent return through the glass bead bed. Too fast a
reflux rate resulted in solvent buildup in the extractor chamber
side. Refluxing at IL/hour was possible without significantly
depleting the reservoir in the concentrator vessel.
Table 3-2 presents the experimental conditions and results
of the gravimetric experiments. The results have been corrected
for the effect of removing successive aliquots from the concen-
trator while the extraction was in progress and are expressed as
a percentage of the "infinity" value. The results are presented
graphically in Figure 3-2. In general, the observed trends bear
out intuitive expectations: increasing the stirring rate
(4<3<2=1) increased extraction efficiency, while positioning the
stirrer nearer the interface (1,3,4 vs 2) also shortened the
extraction time. The degree to which intra-phase mixing can
improve extraction rate is seen most dramatically by comparing
experiment 1 with experiment 4. In the first case, with moderate
gentle stirring, 70% extraction is achieved in 2.5 hours. With
the slowest stirring possible, 70% extraction requires approxi-
mately 8 hours. With no stirring at all (as in a conventional
liquid-liquid continuous extractor), 70% extraction would pre-
sumably take longer still. Since there was no substantial inter-
phase mixing observed in any of these experiments, the improve-
ment may be attributed to intra-phase transport rate enhance-
ments. The gravimetric results suggest that with optimization of
37
-------
Experiment:
Volume, aq. (ml )
Volume, org. (ml)
Stir speed (rpm)
Placement (cm)
(distance
from
interface)
Recovered weight: mq
1 hour
2
3
4
5
6
8
12
24
1100
650
104
0.5
+_ nq (% of
1.7 (42.5)
2.5 (62.1)
3.1 (77.5)
3.4 (83.8)
—
--
--
4.0 (100)
1100
550
104
2.5
infinity value)**
1.3 (35.7)
2.1 (56.7)
2.4 (65.0)
2.8 (76.2)
--
3.2 (87.9)
--
3.6 (100)
--
1200
550
16+
0.5
1.1 (31.9)
1.8 (49.4)
2.1 (62.1)
2.2 (65.0)
2.4 (70.8)
--
--
3.4 (100)
--
1200
550
16-*
0.5
0.6 (21.1)
0.9 (32.7)
1.3 (44.8)
--
1.9 (68.0)
--
2.4 (85.2)
2.5 (89.1)
2.8 (100)
*Lowest speed attainable with mechanical stirrer.
**Inifinity values are underlined. A blank experiment under conditions of experiment
3 yielded less than 0.1 mg after 12 hours.
Table 3-2 Gravimetric Liquid-Liquid Extractor
Experiments
38
-------
100
I/O
I/O
LU
LU
t— I
ex.
50
o
c;
• EXPERIMENT 1
• EXPERIMENT 2
A EXPERIMENT 3
EXPERIMENT 4
'24
EXTRACTION TIME (HOURS)
Figure 3-2 Extraction Efficiencies of the Modified Stirred
Liquid-Liquid Extractor.
39
-------
extractor stirring, total extractables may be recovered to 80+%
within six hours.
The recoveries of 48 priority pollutants, spiked at 20 ppb,
are listed in Table 3-3. The average recovery of 46% was lower
than the gravimetric results, although 95% of v all extraction
occurred within the first six hours. The standard deviation of
21% was considerably lower than observed for the separatory fun-
nel.
Further experiments have been carried out on real matrices.
In these cases, separate recoveries for extraction are not pos-
sible since the extracts require cleanup and prefractionation
prior to quantitation. However, system recoveries determined
with water and spiked sewage samples show higher recoveries, (as
will be discussed in future sections) resulting from improved
quantification methods. A comparison of extraction performance
from real samples for this extractor involved gravimetric studies
of extracts of influent and sludge obtained by 3 methods: stirred
liquid-liquid continuous (SLLC), tissumizer and centrifuge (TC),
and sepfunnel and centrifuge (Table 3-4). In the first series,
the effect of additions of methanol or brine (CaCl2 ) to the
sludge were evaluated, with no significant difference observed.
In a second and third series, the three methods were compared
using conditions as shown. The TC conditions were those
developed at GIT, with the total volume of solvent increased in
the second experiment to match that used in the other two
methods. Based on total extractable mass, a significant increase
for the SLLC is observed.
The principal shortcomings of the SLLC are its complicated
nature and the difficulty of setting it up and operating it in a
steady state. Also, its very efficiency increases the loading of
interference in the sample. For these reasons, a steam distil-
lation vapor extractor, as shown in Figure 3-1, was investigated.
In this procedure, the aqueous sample is boiled at ambient pres-
sure and the condensate and vapor mixed with organic vapor/
condensate. The combined distillates fall into a separation
chamber and each phase is returned to its vessel. Initial
experiments recovering 35 extractable pollutants spiked in metha-
nol from distilled water at the 20 ppb level showed 89.2 * 19.9%
recovery using methylene chloride as the solvent in a 12 hour
extraction, and this unit is therefore currently the method of
choice. Plate V shows the stirrer in operation. Plate VI shows
an alternative apparatus currently under evaluation.
40
-------
Recovery:
1.4-D1CHLOROBENZENE
1.2-DICHLOROBENZENE
2-lNRESOLVED PHENOLS
HEXACHLOROETHANE
OIISOPROPYL N-NITROSAMINE
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
NITROBENZENE
TRICHLOROBENZENE
OIHETHYLPHENOL
NAPHTHALENE
TRICHLOROBENZENE
4-CHLOR0.3-METHYL PHENOL
2-CHLORONAPHTHALENE
1-CHLORONAPHTHALENE
ACENAPHTHYLENE
HEXAMETHYL BENZENE
2,4-DINITROTOLUENE
ACENAPHTHENE
2,6-DINlTRO TOLUENE
FLUORENE
DIETHYLPHTHALATE
DIPHENYLHYDRAZINE
D1PHENYLDIAZINE
(AZOBENZENE)
4-BROMODIPHENYL ETHER
a-BHC
HEXACHLOROBENZENE
DIBENZOTHIOPHENE
B-BHC
f-BHC (LINDANE)
PHENANTHRENE
ANTHRACENE
«-BHC
HEPTACHLOR
ALDRIN
(1)
(1)
(1)
(4.6)
E (4.6)
(5)
(5)
(4.6)
(4.6)
(3.6)
(3.6)
(4)
(4)
0-6 hrs
25.5
27.1
45.2
23.9
31.2
31.2
33.8
23.8
43.0
44.6
75.4
54.3
87.6
54.7
89.5
54.4
62.3
12.4
57.0
62.3
6-12 hrs 0-12 f
4.1
4.2
3.9
2.9
--
5.0
3.8
--
3.1
4.1
—
4.2
—
3.1
3.1
2.2
3.1
—
2.2
2.7
29.6
31.3
49.1
26.8
31.2
36.2
37.7
23.8
46.1
48.7
75.4
58.5
87.6
57.8
92.6
56.6
65.4
12.4
59.2
65.0
Internal Standard
87.2
19.9
24.1
—
—
87.2
19.9
24.1
0-6 hrs 6-12 hrs 0-12 hrs
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
Notes
HEPTACHLOR EXPOXIDE
FLUORANTHENE
PYRENE
P,P' DDE
DIELDRIN
ENDRIN ALDEHYDE
(fi-KETO ENDRIN)
P,P' ODD
P.P1 DDT
BENZ (A) ANTHRACENE
CHRYSENE
D1CHLOROBENZIDINE
BIS-ETHYL HEXYL PHTHALATE
MI REX
DIOCTYL PHTHALATE
BENZO (E) PERYLENE
D1BENZO (A) ANTHRACENE
BENZO (GHI) PERYLENE
PHENOL
0-CHLORO PHENOL
DICHLOROPHENOL
TRICHLOROPHENOL
1. Quantified in additional GC
(3)
(4)
(4)
(4)
(4)
(1)
(1)
(1)
(D
analysis.
2. Numbers correlate with Figures 5-4 and
61.8
50.6 1.8
43.4 1.6
20.6
57.7
33.7
16.7
22.7
12.9
71.8
23.1
46.2
38.4 2.2
36.7 1.9
48.0 2.3
51.9 1.4
5-5.
61.8
52.4
45.0
20.6
57.7
33.7
16.7
22.7
12.9
71.8
23.1
46.2
40.6
38.6
50.3
53.3
3. The analysis of this compound Is discussed in
"Instrumental" section
4. Compound not quant Hated in
5. Isomer not assigned in this
6. Not resolved by GC/FID
this experiment.
experiment.
Table 3-3 Recoveries From Spiked Water Using Stirred
Liquid-liquid Continuous Extractor.
-------
ro
Sample:
Volume,
aqueous (ml )
Volume,
MeCl0 (ml)
L
Volume,
CaCl2
Volume,
MeOH
Extraction
Method
Residue
weight from
extraction:
Acid
Base
Sewage
500
500
-0-
-0-
Stirred C.L.L.
12 hrs, pH2
12 hrs, pH12
6.1 mg
1.3 mg
Sewaoe
500
500
50 grams
-0-
Stirred C.L.L.
16 hrs, pH2
8 hrs, pH12
6.6 mg
1.45 mg
Sewaae
500
500
-0-
?00 r^l
Stirred C.L.L.
16 hrs, pH2
8 hrs, pH12
6.2 mg
1.4 mg
1° Sludge 1° Sludne
?no 200
(Fno;500) (500; 200)
(_0-;-0-) (100ml in%;
100 ml )
(200;200) (100 ml;-0-)
Stirred C.L.L. Tissumizer &
12 hrs, pH2 centrifuoe,
3 portions
3:1:1
(143.1-.113.5) (36.0;44.0)
— —
1° Sludge
200
(500; 500)
(_Q-;-0-)
(200; 200)
Separatory fun
nel & centri-
3 portions
3:1:1
'43.6;45.7)
—
Table 3-4 Effect of experimental conditions of recoverv of gravimetric residue
using continuous liquid-liquid extractor and comparison with tissumizer
and separatory funnel
-------
CO
A STIRRER MOTOR
B CONDENSER
C MERCURY SEAL
D METHYLENE CHLORIDE VAPOR TRANSFER TUBE
E STIRRER PADDLE AND SAMPLE EXTRACTION FLASK
F METHYLENE CHLORIDE LIQUID TRANSFER TUBE
G METHYLENE CHLORIDE EXTRACT
II HEATING MANTLE
PLATE IV STIRRED LIQUID-LIQUID
EXTRACTOR IN OPERATION
-------
A CONDENSER AND WATER INLET HOSE
B CONDENSATION OF WATER-MECL-, IN EXTRACTOR
C WATER LAYER
D METHYLENE CHLORIDE LAYER
E METHYLENE CHLORIDE FLASK
F HEATING MANTLE FOR METHYLENE CHLORIDE
G SAMPLE FLASk
H HEATING MANTLE FOR SAMPLE
PLATE V EXTRACTIVE STEAM DISTILLATION
APPARATUS IN OPERATION
-------
SECTION 4
PREFRACTIONATION AND CLEANUP
4-1 Gel Permeation Chromatography
Based on the reports of Stalling (1972) and others,
studies were undertaken to determine the feasibility of using gel
permeation Chromatography on BioBeads (BioP.ad Corp) for the remo-
val of lipid and other gross biological contaminants from concen-
trated sample extracts. The initial experiments, indicated that
significant reductions of interfering compounds seen in analyses
of the acidic fraction could be achieved with this method, rather
than by using the standard EPA procedure. Initially, it was
observed that, for the analysis of phenols in particular, the
most troublesome compounds present in the matrix were free fatty
acids. In order to determine whether separation of the fatty
acids from phenols is obtainable on BioBeads, and to characterize
the relative elution order and separation of interfering com-
pounds from representative acidic, neutral, and basic priority
pollutants, a series of Chromatography experiments were con-
ducted. Four types of EioBeads (SX-2, 3, 8, and 12) with nominal
exclusion limits of 2700, 2000, 1000, and 400, respectively, were
evaluated using three different solvent mixtures (cyclohexane/
methylene chloride: 75/25, 50/50, 35/65). The experiments were
conducted using a synthetic sample mixture containing representa-
tives of the chemical classes of priority pollutants, plus model
interferences such as fatty acids, cholesterol, and bile acids,
as listed in Table 4-1.
The BioBeads were pre-equilibrated in the selected
Chromatography solvent system prior to gravity packing into 2 x
50 cm silanized glass columns with silanized glass wool plugs.
The packed columns were rinsed with approximately two column vol-
umes of solvent and the surface of the gel bed was covered with a
1 cm layer of silanized 10 micron glass beads to protect the bed
from being disturbed during solvent additions. The samples were
applied by addition of a 1 ml solution pre-adjusted to the same
solvent composition as the eluting solvent, with minimal dilution
during sample application. Flow rates were then determined and
sample collection time adjusted to give approximately 10 ml frac-
tions, which were collected in silanized glass test tubes. Some
shrinkage of the gel was observed upon changing from 50/50 cyclo-
hexane/methylene chloride (solvent "A") to 75/25 (solvent "B").
Solvent "C" was increased in cyclohexane from 25% to 35% because
the former solvent mixture was dense enough to float the Bio-
Beads, creating experimental difficulties.
In the analyses of the fractions from the original 12
experiments (SX-2, 3, 8, 12 with solvents A, B, and C) difficul-
ties were encountered in the GC analysis of the acidic compounds.
Poor and inconsistent column performance from packed columns of
45
-------
PHENANTHRENE
PYRENE
CHRYSENE
BENZ(E)PYRENE
NAPTHALENE
P_-DICHLOROBENZENE
1,2,3-TRICHLOROBENZENE
HEXACHLOROBENZENE
4-CHLOR0.3-METHYLPHEMOL
2,4,6-TRICHLOROPHENOL
2,4-DIMETHYLPHENOL
NITROBENZENE
0-CHLOROPHENOL
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
P,P'-DDT
P,P'-DDE
DIELDRIM
AROCHLOR 1254
HEPTACHLOP.
LINDANE
BENZO(6HI)PERYLENE
P-NITROPHENOL
2,4-DINITROPHENOL
CAPRIC ACID
MYRISTIC ACID
CAPROIC ACID
CAPRYLIC ACID
LITHOCHOLIC ACIP
CHOLIC ACID
DEOXYCHLOLIC ACID
CHLOESTEROL
LAURIC ACID
Table 4-1 Mixture of chemicals tested during the gel
permeation"studies
46
-------
SP 1240DA, low derivatization yields, and contamination of some
samples by leaching of vial cap, prevented the detection of seve-
ral of the fatty acid and phenol components. An additional ser-
ies of experiments were subsequently carried out, focusing on the
compounds of interest (phenols, fatty acids phthalates, and
lipid) using the columns representing the extremes of performance
(SX-2 and 12). The solvent for this series ("D", "E", and "F")
was 50/50 pentane/methylene chloride with the same column dimen-
sions as for A, B, and C. Series D determined the elution beha-
vior of a lipid mixture (as modeled by corn oil) by gravimetric
analysis (for SX-2 only), while series E used a selective sample
(phthalates, phenols, and fatty acids) and series F used the same
sample as series A, B, and C, respectively. These were analysed
by GC on SE 54 and SP 1000 WCOT capillary columns. Again, frac-
tions were collected at time intervals and selected to give 10 ml
fractions. Table 4-2 summarizes the BioBead experimental condi-
tions.
The data from the GC analyses of the original BioBeads
experiments are presented in Figures 4-1 through 4-13. These
figures show the elution pattern for generalized groups of com-
pounds, with elution behaviors for selected specific compounds
indicated in the bar-graph portion. In no case was total class
fractionation (lipid from phthalates from fatty acids from phe-
nols, etc.) achieved. Also, to obtain a more complete picture of
the elution profile, the experimental results for series A, D, E,
and F should be superimposed, as the conditions were practically
the same. Inspection of the entire set of data shows a certain
insensitivity of the elution profile to solvent composition and
BioBeads exclusion limit. The differences observed are signifi-
cant, however, and can be best addressed by placing the gel per-
meation procedure in its proper context in an overall preparatory
scheme.
The gel permeation chromatography of crude extract
concentrates serves two purposes: 1) the removal of gross lipid
and other large neutral organic interferences from the sample and
2) fractionation of the sample in a way that permits convenient
subsequent treatment, such as direct instrumental analysis or
further prefractionation, derivatization, or other necessary pro-
cedures. In the context of priority pollutant analysis, highly
critical separations are the lipid contaminants and fatty acids
from the sample, particularly from the phenolic priority com-
pounds. In general, the separation of acidic from neutral chemi-
cal compounds can be readily accomplished by a variety of tech-
niques. Ion exchange is one commonly used method, and experi-
mental results and at the University of Washington suggest that
coupled chromatography on potassium or cesium silicate is suc-
cessful at differentiating organic acids from neutral compounds.
Since this type of separation is readily accomplished after the
GPC step, the more limited goal of separating neutral inter-
ferences from neutral priority compounds, and acidic inter-
47
-------
Experiment:
Solvent
(% in
methyl ene
chloride)
Sampl e
BioBeads:
SX-2
SX-3
SX-8
SX-12
50,cyclohexane 75,cyclohexane 35,cyclohexane 50,pentane 50,pentane
Standard Mix Standard Mix Standard Mix Lipid Mixture Phenols,
phthalates,
fatty acids
X X X X X
XXX
XXX
XXX X
50,pentane
Standard Mix
X
X
Table 4-2 Summary of qel permeation experiments
-------
100
o;
LU
Q.
50
50
PESTICIDES
100
ELUTION VOLUME (ML)
150
LINDANE
HEPTACHLOR
p.p'-DDT
NAPTHALENE
CHRYSENE
BENZO(A)PYRENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
Fiaure 4-1 Elution Profile on BioBeads S-X2A System
49
-------
o
-------
-------
PHTHALATE_S
PID
FATTY ACIDS //
ft
X> —C
•-O+* PHENOLS
100
ELUTION VOLUME (ML)
150
DIMETHYLPHTHALATE
DIETHYLPHTHALATE
DI-N-BUTYLPHTHALATE
BUTYLBENZYLPHTHALATE
BIS(2-ETHYLHEXYL)PHTHAL*TF
DI-N-OCTYLPHTHALATE
2-NITROPHENOL
2-CHLOROPHENOL
PHENOL
2,4-DIMETHYLPHENOL
2,4-DICHLOROPHENOL
2,4,6-TRICHLOROPHENOL
J 4-CHLORO-3-METHYLPHENOL
CAPROIC ACID
CAPRYLIC ACID
CAPRIC ACID
LAURIC ACID
MYRISTIC ACIO
Figure 4-4 Elation Profile on BioBeads S-X2E System
52
-------
o
^^
o
50
100"
ELUTION VOLUME (ML)
LINDANE
HEPTACHLOR
p,p'-DDT
NAPHTHALENE
CHRYSENE
BENZO(E)PYRENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
Figure 4-5 Elution Profile on BioBeads S-X2F System.
53
-------
100
o:
50
50
PESTICIDES/
/
FATTY ACIDS
ELUTION VOLUME (ML)
LINDANE
HEPTACHLOR
p,p'-DDT
NAPTHALENE
-• CHRYSENE
-• BENZO(E)PYRENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3,-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
CAPRYLIC ACID
LAURIC ACID
Figure 4-6 Elution Profile on BioBeads S-X3A System.
54
-------
o:
UJ
0.
50
100
ELUTION VOLUME (ML)
LINDANE
HEPTACHLOR
p.p'-DDT
NAPTHALENE
CHRYSENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
Figure 4-7 Elution Profile on BioBeads S-X.3B System.
55
-------
100
ELUTION VOLUME (ML)
150
LINDANE
HEPTACHLOR
p.p'-DDT
NAPHTHALENE
CHRYSENE
BENZO(E)PYRENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
CAPRYLIC ACID
LAURIC ACID
Fiqure 4-8 Elution Profile on BioBeads S-X8A System.
56
-------
o
«t
o:
o:
LU
O.
50
100
ELUTION VOLUME (ML)
150
LINDANE
HEPTACHLOR
p.p'-DDT
NAPHTHALENE
CHRYSENE
•—• BENZO(E)PYRENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
LAURIC ACID
Fiqure 4-9 Elution Profile on BioBeads S-X8B System.
57
-------
100
ELUTION VOLUME (ML)
150
LINDANE
HEPTACHLOR
p,p'-DDT
NAPTHALENE
CHRYSENE
BENZO(E)PYRENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
Figure 4-10 Elution Profile on BioReads S-.X12A System.
58
-------
a:
UJ
o
o;
50
100
ELUTION VOLUME (ML)
LINDANE
HEPTACHLOR
p.p'-DDT
NAPTHALENE
CHRYSENE
p-DICHLOROBENZENE
NITROBENZENE
1,2,3-TRICHLOROBENZENE
DIETHYLPHTHALATE
DI-N-OCTYLPHTHALATE
Figure 4-11 Elution Profile on BioBeads S-X12B System.
59
-------
100
50
PHTH
LATE
fX FATTY ACIDS (X
^^*"Y*\ * '''y^v
' X ;' ^PHENOLS
\ /
\ / ^
\ ; \
\
k •
I
100
150
ELUTION VOLUME (ML)
DIMETHYLPHTHALATE
DIETHYLPHTHALATE
DI-N-BUTYLPHTHALATE
BUTYLBENZYLPHTHALATE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYLPHTHALATE
4-CHLORO-3-METHYLPHENOL
2-CHLOROPHENOL
PHENOL
2,4-DIKETHYLPHENOL
2,4-DICHLOROPHENOL
2,4,6-TRICHLOROPHENOL
CAPROIC ACID
CAPRYLIC ACID
CAPRIC ACID
LAURIC ACID
Fiqure 4-12 Elution Profile on BioBeads S-X12E Systen.
60
-------
100
o
-------
ferences from acidic priority compounds, will constitute a suc-
cessful gel permeation chromatographic cleanup step. Therefore,
the BioBeads data should be used for the separation of lipid from
neutral priority pollutants and fatty acid components from phe-
nolic priority compounds.
The separation of fatty acids from phenols is demonstrated
in Figure 4-12 for BioBeads SX-12. This grade of gel showed the
best separation of acidic compounds in all experiments. The
fatty acids used in the study do not represent the entire molecu-
lar weight range that might be encountered, and shorter-chain
homologs in particular are expected to elute later, and therefore
closer, to the phenols.
The separation of lipid and other neutral interferences, as
modeled by corn oil, from the neutral priority compounds is best
achieved by SX-2 BioBeads. These interfering compounds are uni-
formly the earliest eluting and present separation difficulties
only with the earliest eluting priority neutrals, such as the
phthalate esters and possibly some of the pesticides. Among the
compounds in the experimental mixture, diocytyl phthalate elutes
the earliest in every case. Previous studies (Stalling, 1972)
characterize the separation observed between lipid (fish
extracts) and DDT for a variety of BioBeads grades and solvents.
The results obtained in the present set of experiments correlate
well with the observations of Stalling: the separation of lipid
and pesticides decreases with decreasing exclusion limit of the
BioBeads. Figures 4-4 and 4-5 present the best example of this
separation. In the SX-2 experiments, we find that there is sig-
nificant overlap between the fatty acids and the phenols, phtha-
lates, pesticides, and PAH compounds.
In general, the data presented in these figures show that
solvent mixtures with a greater proportion of cyclohexane or pen-
tane exhibit increased selectivity on a molecular size basis,
possibly with a superimposed electronic effect for aromatic mole-
cules. The effect of changing the grade of BioBeads is a complex
one. Empirically, the effect is increased separation of fatty
acids from phenols, smaller elution volumes, and increased sort-
ing within compound groups as the exclusion limit decreases.
The variation of elution behavior seen among the different
classes of compounds with changes in solvent and exclusion limit
reflects the interaction of two basic chromatographic effects in
this type of gel permeation chromatography: 1) adsorption
effects and 2) steric or molecular sieving effects. The apparent
exclusion limits assigned to grades of BioBeads will vary with
the solvent.
62
-------
A more detailed analysis of the elution behavior of most of
the neutral and acidic extractable priority pollutants has been
obtained for SX-2 and SX-8 BioBeads, as shown in Table 4-3. The
latter grade was emphasized over SX-12 because of its use by Bat-
telle and GIT in treating crude sludge extracts. These elution
profiles, and subsequent experiments, suggest that for removal of
gross biological contaminants, SX-2 is superior to SX-8. Plate
VI and VII show the columns in use.
4-2 Florisil Chromatography
The desired separation for florisil LC cleanup consists of
removal of saturated hydrocarbon material and removal of biologi-
cal contaminants, including fatty esters, glycerides and sterols.
Initial experiments yielded poor recoveries of phthalates and
isophorone, even upon elution with 100% ether. Various levels of
aqueous deactivation were therefore examined to improve chromato-
graphic behavior. Table 4-4 presents the results of several such
experiments. The Florisil columns were prepared by overnight
activation at 140° C, deactivation in a sealed bottle with the
appropriate weight percent of distilled water, followed by at
least 24 hours equilibration with periodic shaking. The separa-
tions were run on a 0.8 cm x 9" column, dry-packed with the flo-
risil and rinsed with pentane prior to sample loading. The sam-
ples were loaded in hexane and eluted with 40 mis pentane, fol-
lowed by ether/pet. ether step gradients in increments of 200
mis.
The results presented above indicate that substantial
amounts of pesticide (in particular Aldrin and Hexachlorobenzene)
appear in the first pentane fraction. This fraction contains the
saturated hydrocarbon components of the sample. Only in the case
of 0.75% and 0.50% deactivation, with some volume reductions in
the pentane eluate, could a clean separation of pesticide and
saturated hydrocarbon be achieved. For this reason, 0.75% deac-
tivated florisil was selected for further studies. Figure 4-14
illustrates the elution behavior of this activity of florisil
with a prechromatographed extract of anaerobic digested sludge
plus spike sample. The spike consists of 100 ul each of hexo-
chlorobenzene, lindane, aldrin, DDT, naphthalene, and all phtha-
lates. From this figure, it is clear that during the florisil
separation, some interfering material will co-elute along with
priority compounds, and that further subdivision of the eluent
will not permit complete separation of those contaminants. These
contaminants contain some steroidal material, as identified by
GC/MS/DS analysis. Depending upon the levels of these compounds,
the use of florisil may not be sufficient to provide an ade-
quately cleaned sample for all sludges. However, the florisil
procedure is adequate for cleanup of sewage samples. The data
shown later indicate that the majority of neutral priority com-
pounds are divided between the florisil-treated fraction and the
silicate-treated fraction. For this reason, quantitation of most
63
-------
(lullon Voliotl SI-B
H
s-
M
(0
I
00
o
3
w
s-
03
O
H
O
I
O
C
CU
0)
S)
00
o
re
n>
re
01
o
3
Olchlorobenienf II
Otchlorobenitne III
Heiichloroethln*
NUrobcnffne
Trlehlorob*ni«n* I
Trlchlortib«ni«ne II
«ptmlfn»
THcMoroMntent III
CMoron«pth«lcn« I
Cll!oroprop«n*
WC ii}
•othricnx
Ollortfuw (1)
WC (I)
Htpudilor
DlbutjrlptitlltllU
•Idrl.
Mtptichlor rpoilte
Flworintlwn*
ClilonUM (2)
CM or (tan. (])
^yr«i«
Ollordimt (<)
PP' DM
Dltldrtn
Emir In
001
000
Scnio(*)«ntnric1ti*
Cnrjrstn*
Nlrci
OloctrlphthtUU
Btnlol K )F1 uartnthm
ttnioil )F1uor*nth«nt
l«nto(E)Pyrin*
D1b«n/intnr«crnc
0-ch1orop*icno1
OUhloroptMfiol
50»1 60
PcntJthloroDhvnol
Million Volume* SI-?
Mlmt 60 '0 80
-------
PLATE VI BIOBEADS GEL PERMEATION
CHROMATOGRAPHY
01
en
-------
PLATE VII BIOBEADS GEL PERMEATION
CHROMATOGRAPHY (LONG
WAVE UV LIGHT)
-------
Table 4-4 Elution behavior of selected compounds durinn florisil chromatoqraphy
en
Percent
Deactivation
5%
3%
1.5%
0.75%
0.5%
Eluant
Pentane
15% ether
25% ether
100% ether
Pentane
15% ether
25% ether
100% ether
Pentane
15% ether
25% ether
100% ether
Pentane
15% ether
25% ether
100% ether
Pentane
15% ether
25% ether
100% ether
d> Ol S~
C C QJ QJCJO Q) 01 Qi
1- »— >^ fO IQJ t — rOi — rO-COJI — ttj to r— ro
o «o x: i — o c i c >^i — >>i — u *o o i i — . — 11. — >>• —
O O. CD E *-* X *— C O- r— "O (U •*-* r*i 4J CX O — ^* C •*-* r" X -*-* O •*-*
in TJ 31 -*-.c OJ^ZQJ QJX: • — ---.c: -r-jc o>cx m. ^cu^: 4->
-------
oo
u
(a) pentane
(b) 5% ether/pet.ether (200 ml)
Figure 4-14 Elution of Priority Pollutants Spiked in Prefractionated Anaerobic Digested Sludge
Extract During Florisil Clean-up.
-------
10
1 s
sc
(c) 10% ether/pet.ether (ZOO ml)
Si
o.
X.
O)
0)
4-1
n)
o
o
(d) 15°4 ether/pet.ether (200 ml)
Figure 4-14Continued
-------
0)
4-1
(0
£
4-1
o.
H
>.
N
C
,
1_J
3
O
f
-H
-"»
a
•>
N
V
1= S*S
? ::*s
M~^Juc/
*
pk
i^Wn—
0)
T)
-)
CO
l_i
EL
-H
>(
j
o
_|
O
*
"V
K
m
1
(e) 2Q% ether/pet.ether (200 ml)
0.
(f) 25?- ether/net.ether (200 ml)
Figure 4-14 Continued.
-------
(o) 35% ether/pet.ether (200 ml)
Figure 4-14 Continued.
-------
-•J
ro
(i) 100% ether (140 ml)
Fiaure 4-14 Continued.
-------
of these compounds will require improved cleanup for sludge sam-
ples and heavily polluted waste water samples.
73
-------
SECTION 5
DETERMINATION OF PHENOLIC COMPOUNDS
Phenolic compounds present particular difficulties among
the priority pollutants for several reasons: a) they are highly
susceptible to chemical degradation, b) they have a high affinity
for water relative to most priority compounds, c) they are sus-
ceptible to adsorbtive losses, d) they chromatograph poorly, and
e) they exhibit nonuniform efficiencies for most derivatizing
methods.
5-1 Cleanup Protocols for Phenolic Compounds
The analysis of phenols from extracts in the intergrated
scheme will therefore be discussed in three sections isolation,
derivatization, and GC analytical conditions. It should be born
in mind that these stages are not separable in a single experi-
ment, as recovery values of necessity depend on successful nego-
tiation of all three steps.
5-2 Isolation of Phenols
The eleven phenols of the so-called "acid fraction"
represent 9% of the compounds on the priority pollutant list.
The analysis of phenols in sewage is complicated by the consider-
able abundance of non-phenolic acidic compounds in the sample
matrix. These compounds are co-extracted with the phenols at low
pH and appear to be primarily fatty acids, and possibly some bile
acids and fulvic acids. The much higher relative concentrations
of these compounds, compared to the phenols, obscure the detec-
tion and quantitation of several of the latter by gas chromato-
graphic methods. Initial developmental work was directed toward
sample cleanup and isolation of the phenols from matrix interfer-
ences. Two different preparatory schemes were selected for com-
parison with the standard EPA wastewater analysis method. One
scheme utilized ion exchange on Sephadex QAE as adapted from
Renberg (1974). The other scheme utilized gel permeation chroma-
tography on BioBeads SX-3 (Stalling, 1972) coupled with flow-
through adsorbtion chromatography on potassium silicate
(Ramljack, 1977). Based on results reported in the literature,
the latter method was investigated because it offered the poten-
tial for removal of interfering acidic compounds as well as base-
neutral interferences.
Following initial development of chromatographic conditions
with standard phenols, experiments were conducted with raw sewage
as the sample matrix. A concentrated standard solution of the
eleven "priority" phenols in methanol was spiked into 800 ml ali-
quots of both sewage and blank water samples to give a final
spike concentration of 30 ppb per phenol. The samples were ana-
lyzed in parallel experiments using the three methods and quanti-
74
-------
fled with GC (without derivatization except as noted), and
detailed in Table 5-1.
The standard EPA method, i.e. adjustment of pH to 12,
removal of base-neutral organics by repeated extraction with
methylene chloride, acidification to pH 2, and removal of phenols
and other organic acids by further methylene chloride extraction.
This was accomplished for the sewage and blank samples using
silanized separatory funnels and centrifugation where necessary
to break emulsions. The acid extractable fractions were concen-
trated, dried over N32S04, and analyzed without further prefrac-
tionation.
The anion-exchange experiments were conducted using a total
organic extract obtained by direct multiple extraction of pH 2
sample with methylene chloride + 10% methanol with centrifugation
as necessary. Sephadex QAE, a strong anion exchange gel, was
used to isolate acids in the total extract by batch extraction,
after Renberg et. al. The acids were subsequently recovered
from the rinsed gel by shaking with pH 2 aqueous acid and diethyl
ether. The ether extracts were dried over Nap SO* and concen-
trated to 1 ml for GC analysis.
The gel permeation coupled chromatography experiments used
a total organic extract obtained similarly to that used in the
ion exchange experiments. The total organic extracts were dried
with anhydrous ^2864, and the solvent replaced with neat methy-
lene chloride by multiple partial evaporation. The extracts
were concentrated to 2.5 ml and diluted to 5 ml with cyclohexane.
The samples were applied to BioBeads SX-3 columns and eluted with
1:1 methylene chloride/cyclohexane, according to the method of
Stalling et. al. After elution of the first fraction (containing
much of the lipid and fatty acid components) the effluents were
allowed to pass directly through columns of potassium silicate.
The latter were prepared from silica gel and KOH-saturated iso-
propanol according to the method of Ramljack et. al. The latter
column retains acidic compounds and phenols while allowing neu-
tral components to pass through. After complete elution of the
phenol fractions from the SX-3 onto the potassium silicate, the
columns were uncoupled and the potassium silicate rinsed with
three column-volumes of methylene chloride. The adsorbed acids
were then eluted with 100% methanol. The methanol extracts were
concentrated, acidified with 1 N aqueous HC1, and extracted with
methylene chloride to recover the phenols. The final extracts
were dried over Na2SC>4 and concentrated for GC analysis.
All final extracts were reduced to 1 ml volume in methylene
chloride and 2-secbutyl phenol was added as an external standard.
GC analyses were carried out on a Hewlett/Packard 5840A gas chro-
matograph, using a SP 1240 column. The 1% SP 1240 DA column (3
feet in length and 2 mm in diameter) was held at 70 C for 1
minute and programmed at a rate of 10°C/mm till 190°C, then held
75
-------
EPA Method (I)
Ion Exchange Method (II) GPC/Adsorption Method (III)
800 ml sewage
extract at pH 12 with
100, 50, 50 ml CH2C12
i|
extract aqueous phase
at pH 2 with 100, 50,
50 ml CH,C1,
pass methyl ene chloride
through Na?SO-, column
>!
K-D to 10 ml
Microsnyder to 1 ml
GC with SP 1240 DA
800 ml sewage
extract at pH 2 with
100, 50, 50 ml CH0C10
1 2 2
K-D to 5 ml
1
extract into 2, 2, 2 ml
of pH 12 NaOH
I
equilibrate base with
3 ml of swollen gel
Sephadex QAE
rinse resin with H,0
^ 2
shake at pH 2 with HCL/
KC1 buffer and 5, 5 ml
diethyl ether
^1
pass diethyl ether through
Na2SO, column
\
Microsnyder to 2 ml , add
5 ml methyl enechloride
and reduce to 1 ml
GC with SP 1240 DA
800 ml sewage
extract at pH 2 with
100, 50, 50 ml CH2C12
pass methylenechloride
through Na2$04 column
K-D to 10 ml
Microsnyder to 2.5 ml
add 2.5 ml cyclohexane
and pass through Biobeads
SX-3 column (1.9 cm diam.,
40 cm length)
elute with 1:1 cyclohexane/
methylene chloride and
discard fraction 0-75 ml
pass fraction 75:125 ml
through 10 g KpSiO.
(1 cm diam., 15 cm length)
rinse with two bedvolumes
methylene chloride and elute
with 20 ml methanol
add cyclohexane and
K-D to 2 ml methanol
add 4 ml \H HC1 and extract
with 2, 2, 2 ml methylene-
chloride j
pass methylene chloride
through Na«SO, column
Microsnyder to 1 ml
GC with SP 1240 DA
Table 5-1 Different extraction and clean-up procedures evaluated during
tne present study.
76
-------
for 10 minutes. The gas flow rate was 30 ml/minute N with an
injector temperature of 225 C and a detector temperature of 325 °
C. The attenuation was 25 with a chart speed of 1 cm/minute.
The EPA scheme presented particular difficulty in the
primary extraction phase due to the formation of very stable
emulsions at pH 12. This problem is clearly matrix-related, and
was not observed for blank extractions. Figures 5-1 and 5-2 pre-
sent the GC results for the EPA sewage sample and blank, respec-
tively. Although high recoveries of phenols are observed
(70-140% where quantifiable), the EPA method is least selective
in excluding interfering acids and polar organics.
Figure 5-3 presents the results obtained for QAE ion
exchange isolation of phenols from sewage sample. The recover-
ies, where quantifiable, were generally low (30-90%), presumably
due to interfering organic acids overloading the resin. Again,
high levels of interfering acidic organics were noted.
The results from the coupled-chromatography isolation scheme
are shown in Figure 5-4. Recoveries were determined to be
60-110%. Subsequently, this sample was also treated with metha-
nol/boron trifluoride to derivatize any carboxylic acids present
(Figure 5-5). Some interference is again noted.
Problems common to the analysis of phenolics from sewage
samples by all three methods are variable recoveries among the
different phenols, and quantitation in the presence of high rela-
tive concentrations of interfering compounds. Among the methods
studied, the EPA method and the coupled chromatography method
gave higher recoveries, but in all cases the nitro phenols in
particular showed poor recovery. Refinement of extraction and
chromatographic procedures (especially in the quantitation phase)
is clearly needed.
The selection of methods are based on several criteria
for desirable cleanup/prefractionation procedures. First, the
procedures should reflect the known chemistry of ubiquitous con-
taminants in sewage samples. Secondarily, procedures suitable
for a unified fractionation scheme for all extractable priority
pollutants is desirable. The majority of interfering materials
observed has a carboxylic acid functionality and consists predo-
minately of fatty acids. This can be discerned from comparison
of Figures 5-4 and 5-5. The interfering contaminant peaks in
Figure 5-4 (retention times 9.28, 10.53, 11.73, and 13.10) show
the regularity of a homologous series. After derivatization to
methyl esters, a uniform shift of these compounds to shorter
retention times (3.82, 5.68, 7.21, and 8.81) was observed. This
is behavior prescriptive of homologous carboxylic acids. Since
these compounds are the dominant interferences separation methods
relying solely on acid/base properties will not remove them.
Further, although crude extracts containing carboxylic interfer-
77
-------
o
QJ
Figure 5_-| Chromatogram of distilled water spiked at 30 ppb phenolics
and extracted according to the EPA method.
78
-------
Figure 5.2 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted according to the EPA method.
79
-------
vi)
Ei
\f>
Figure 5-3 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted and cleaned-up according to the ion-exchange
method.
80
-------
10
Figure 5-4 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted and cleaned-up according to the gel permeation
method.
81
-------
Co r...
• • i •
IT, pr, ,-M...
C'J
Figure 5-5 Chromatogram of sewage sample spiked with 30 ppb phenolics
and extracted and cleaned-up according to the gel permeation
method followed by derivatization with BF3 in methanol.
82
-------
ences can sometimes be quantified by GC/MS techniques, the high
background of unwanted compounds more rapidly contaminates the
mass spectrometer and increases the difficulty of data interpre-
tation. Also, these carboxylic interferences adversely affect GC
column performance and lifetime.
The results indicate that significant reductions in
concentrations of carboxylic and lipid interferences, without
great sacrifices in phenol recoveries, are possible using gel
permeation chromatography in combination with acid-selective
adsorption. Both EPA and coupled column experiments gave good
recovery and quantitation for the less acidic phenols (i.e. those
eluted early from the GC). The recovery of nitrophenols by
either method is not yet satisfactory and requires further deve-
lopment. The removal of carboxylic interferences is substan-
tially better for the gel permeation-adsorbtion method, although
not yet optimum. The QAE ion exchange method yields poor reco-
veries and intermediate (but high) levels of interfering com-
pounds.
Coupled chromatography using base-treated silica gel after
GPC showed the best results for separating acidic compounds from
neutral ones. In the developed integrated cleanup scheme, most
of the lipid-type interferences are removed by gel permeation
chromatography from the compounds of interest prior to the silica
gel step.
Results of the initial GPC experiments indicate that some
neutral priority pollutants are removed by the silica gel and
co-elute with fatty acids when these are recovered from the
silica gel.
The initial experiments also revealed that binding of
the phenols on potassium hydroxide modified silica gel was not
complete for the most weakly acidic ones. An additional problem
encountered was precipitation of salts in the eluates from the
silicate column upon solvent exchange. Substitution of cesium
for potassium in the modified silicate has been reported to
improve retention and subsequent release of phenolics, so this
material was also evaluated.
Cesium silicate was prepared by stirring 20 grams silica gel
(MCB 100-200 mesh) for 1 hour with 50 ml of a saturated solution
of cesium hydroxide in methanol. After filtration, the cesium
silicate was soxhlet extracted for 1 hour with methanol followed
by 4 hours extraction with methylene chloride. The solid was
then dried at room temperature. Fifteen grams of the cesium
silicate was slurry-packed in methylene chloride into a 0.8 x 8cm
silanized glass column plugged with silanized glass wool. The
solvent was replaced with 50/50 cyclohexane/methylene chloride
and the sample applied in the same solvent. Samples containing
free fatty acids plus phenols and fatty acid methyl esters plus
83
-------
phenols were applied to the columns. The excess solvent was
drained and the compounds eluted with methylene chloride contain-
ing a step-gradient increase of methanol, as indicated in Figure
5-6. Ten twenty-five ml fractions were collected, concentrated
with the K/D evaporator, washed with pH 2 saline solution, and
dried over anhydrous sodium sulfate prior to GC analysis.
The results for the cesium silicate experiments are shown in
Figure 5-6. It was not possible to separate underivatized fatty
acids from phenols with an elution gradient using cesium sili-
cate. Prior derivatization of the fatty acids to methyl esters
allowed complete separation of these from phenols (as previously
mentioned in the BioBeads discussion). Some variability in the
preparation of cesium silicate from silica gel and cesium hydro-
xide is indicated by the differences in the elution of phenols in
the two column experiments.
Direct comparison of potassium and cesium silicate with a
spike of priority phenols in methylene chloride showed good
retention of phenols using cesium silicate, together with high
recoveries upon elution with methanol. Since derivatization is
required to permit GC analysis and quantitation, recoveries for
the LC procedure are not separable from derivatization recover-
ies. In the case of potassium silicate, some break-through of
phenol was observed, while poor recoveries were noted upon elu-
tion with methanol for all phenols while virtually no recovery of
dinitrophenol was observed using potassium silicate.
Based upon the foregoing observations, cesium silicate is
the material of choice for use in separation of phenolics from
the neutral compounds. Its preparation is similar to that for
initial experiments: lOOg silica gel (unactivated) is placed in a
600 ml beaker, to which 300 ml of a saturated solution of CsOH in
methanol is added. The mixture is stirred for 1 hour, allowed to
settle, and decanted. The solids are washed with fresh methanol,
filtered in a sintered glass funnel, and rinsed with 200 ml
methanol, followed by 300 ml methylene chloride. The solids are
then allowed to air dry at slightly elevated temperatures by pla-
cing them on top of an oven. The dried material is used without
activation. Initial procedures called for extensive rinsing of
the cesium-modified solids by soxhlet extraction, but this was
subsequently abandoned when the simplified preparation gave
satisfactory and reproducible results.
The observation that the methanol eluate from both potassium
and cesium modified silica gel produced a white precipitate upon
concentration and solvent exchange into methylene chloride
prompted the soxhlet extraction procedure employed initially.
The solids were clearly inorganic, and may have resulted from
poor removal of free cesium or potassium salts in the silicate
preparation. However, silica gel itself displays a limited solu-
bility in neat methanol (especially hydrous methanol). The modi-
84
-------
or.
u_
:r
et
100
50
DC.
LLJ
D.
JL
2 100
o
50
O i—i
^ <*
< O
100
50
<_5
UJ
O-
50
50
1
100
100
PHENOLS
FATTY ACIDS
150
200
PHENOLS
DERIVATIZED
FATTY ACIDS
150
200
250
250
50 100 150 200 250
ELUANT VOLUME (ML)
Figure 5-6 Elution Profile of Phenols and Fatty Acids on
Cesium Silicate.
85
-------
fied silicates are therefore expected to dissolve to a greater
extent in the methanol eluant. Additional experiments showed
that transfer of eluted phenols into a suitable solvent for deri-
vatization and GC analysis, such as methylene chloride, can be
accomplished by concentrating the methanol eluate and partition-
ing it between acidic water (pH 2) and methylene chloride. This
procedure avoids the precipitation which could potentially remove
phenols by inclusion or adsorption. When a 200 ug standard of
phenols was dissolved in 2 ml methanol and partitioned between 10
ml pH 2 water and 10 irl methylene chloride, followed by two addi-
tional extractions with methylene chloride, the recoveries from
the combined extracts were virtually quantitative. Additional
extraction with methylene chloride produced no further detectable
phenol. Plates VIII, IX, and X illustrate the separation.
5-3 Derivatization Studies of Phenols and Fatty Acids
Improvement of the chromatographic behavior of acidic
compounds by chemical derivatizaton has been extensively inves-
tigated . Among the methodologies available are: 1) methylation
with BF /methanol (to give methyl esters of fatty acids in high
yield, but no derivatization of phenols) , 2) methylation with
diazomethane (to give methyl esters of fatty acids and methyl
esters of some phenols, but with notably poor yields for phenol
and alkyl phenols), and 3) methylation with base/dimethyl sulfate
or other alkylatirig agent and a suitable catalyst to give methyl
ethers of phenols but low to no yields of fatty acids esters.
Several experiments to survey the ease and efficacy of various
derivatization procedures have been carried out.
Table 5-2 summarizes the experimental conditions and results
for the derivatization experiments. The samples were dried over
sodium sulfate, solvent exchanged into cyclohexane, and analyzed
by GC and GC/MS.
The most satisfactory results have been obtained by
methylation with diazomethane. High yields can be obtained for
all but phenol and the alkyl-substituted phenols for standard
mixtures. Some encouraging results have been obtained with
dimethyl sulfate alkylation. These observations are in agreement
with other investigators (Drozd, 1975) .
To optimize derivatization yields, several experiments with
diazomethane were conducted. The effect of solvent composition
was investigated in different combinations. All samples were
bubbled with diazomethane until a persistent yellow color
appeared, followed by a two minute wait and a subsequent volume
reduction to 1 ml. The highest derivatization yields were seen
for pentane/methylene chloride. The influence of reaction time
was also investigated for times between 2 and 15 minutes, with
the increase in yields leveling off after 7 minutes.
86
-------
00
PLATE VIII CESIUM SILICATE (LEFT)
AND FLORISIL (RIGHT)
CHROMATOGRAPHY
-------
PLATE IX PHENOLS TRAPPED ON CESIUM
SILICATE COLUW
-------
PLATE X PHENOLS ELUTED FROM CESIUM
SILICATE WITH METHANOL
CD
-------
UD
O
EXPERIMENT: I
Conditions:
solvent Et2°
base none
catalyst 10% MeOII
alk. agent CII2N2 gas
temp. ambient
min. time 2 min
Derivative
Yields From:
Phenol x
2 , 4 -dimethyl- o
2,4,6 trichloro- +
4-chloro, 3-methyl- x
2-chloro- -t
2,4-dinitro +
4-nitro +
pentachloro +
4,6-dinitro, +
3-methyl
2,4 dichloro +
2-nitro +
II
CH2C12
"proton sponge"*-'
+
Me2S04
reflux
1 hr
0
o
X
X
X
0
X
*1
*1
*1
*1
III IV
CH2C12 Et2o
on" OH~
4- +•
Me2S04 Me2S04
reflux reflux
15 hrs 2 hrs
x
+ o
+ X
+ o
*1 *1
o
+ 0
+
4-
*1 *1
*1 *1
V
Kt2°
OH
-I-
Mel
reflux
2 hrs
0
o
0
o
*1
o
o
o
o
*1
*1
VI
acetone
OH~
Bu4N+
Me2S04
reflux
2 hrs
x
0
o
0
*1
o
0
0
o
*1
*1
VII
acetone
OH~
Bu4N+
Mel
reflux
2 hrs
+
0
X
o
*1 •»
-
0
-
-
*1
*1
Key: *1 - compound not present
*2 - not detected by GC
*3 -
Table 5-2
+ high yield
x some yield
- trace yield
o not detectable yield
Experimental Conditions and Results for the Derivatization Study.
"proton sponge" - N,N,N',N'-tetramethyl,
1,8-diamino naphthalene, is a trademark.
of Aldrich Chemical Co.
-------
A recovery experiment using the optimized methods of liquid
chromatographic separation of the phenols, elution from silicate,
solvent exchange, and derivatization was conducted on a spiked
water sample. This experiment determined recoveries from sili-
cate chromatography through derivatization, and compared the
standard methanol eluate with methanol plus 1% formic acid elu-
ate. Table 5-3 presents the results obtained, and shows an over-
all recovery of 66% using methanol and 69% using methanol and
formic acid, indicating that no major improvement is realized by
the addition of formic acid.
Recent advances in glass capillary technology, discussed in
Section 5-4, have permitted the more complete evaluation of dia-
zomethane derivatization for the analysis of phenols from spiked
raw sewage and digested sludge samples. Based upon this new
information, the recoveries of phenols are clearly dependent on
time elapsed between derivatization and instrumental analysis.
The lack of stability resulting from diazomethane treatment is
discussed more fully in Section 10-4, but should be understood
before this method is used.
5-4 Instrumental Analysis
Initial experiments utilized a packed SP 1240 DA column
which has recently been recommended to replace Tenax GC. Figure
5-7 was obtained from a new column and Figure 5-8 shows perfor-
mance of a different column after substantial use. At present,
this type of column is the only one capable of eluting all eleven
priority phenols without derivatization. Comparison of these
figures illustrates that: a) resolution varies between columns
and b) recoveries of the more acidic phenols declines with column
use, particularly in 4,6-dinitrophenol and 2,4-dinitro-o-cresol.
However, this column still gives superior resolution as suggested
by Table 5-4, which compares the relative GC retention times we
observe for SP-1240 DA with literature values for several other
GC liquid phases.
During extensive use of several columns prepared from this
material, however, serious shortcomings have been observed. No
two columns prepared from the same bottle of packing material
have given the same separation even though all methods used were
identical. A more serious reproducibility problem was encoun-
tered from one injection to the next on the same column. Using
identical GC conditions, reproducible peak area ratios for some
phenols could not be obtained from sequential injections of the
same standard phenol mixture. Ortho-, chloro-, and nitro- phe-
nols suffered especially from this phenomenon. A further problem
with the SP 1240 DA column, and packed columns in general, has
been insufficient resolution of phenol isomers and other com-
pounds present in actual sample extracts. Finally, column per-
formance degraded rapidly and dramatically with modest use, espe-
cially when real extracts were analyzed. Attempted regeneration
91
-------
Phenol
Derivative
Recovery
(%) Methanol
Methanol +
Formic
Acid
phenol
phenol
o-chlorophenol
o-chlorophenol
4-chloro,
3-methylphenol
4-chloro,
3-methylphenol
2,4 dimethyl phenol
2,4-dichlorophenol
2,4,6-trichlorophenol
2-nitrophenol
4-nitrophenol
4,6-denitro
2-methy!phenol
pentachlorophenol
2,4-dinitrophenol
anisole
*underivatized
*underivatized
d-chloroanisole
4-chloro,
3-methylanisole
*underivatized
2,4-dimethylanisole
2,4-dichloroanisole
2,4,6-trichloroanisole
2-nitroanisole
4-nitroanisole
4,6-dinitro,
2-methylanisole
pentachloroanisole
2,4-dinitroanisole
79
59
69
68
66
59
64
69
66
65
55
70
66
84
40
109
23
187
59
50
128
23
53
10
67
67
*not resolved by gc
Table 5-3 Overall Recovery of Phenols in Spiked Distilled Water During
Column Chromatography and Derivatization
92
-------
o
01
.c
Q.
Figure 5-7 Chromatoqram of Phenolic Standard on a
new 3' SP-1240DA packed column.
93
-------
r-
o
c
01
..c
c.
IT'
CO
Figure 5-8 Chromatogram of phenolic standard after
degradation of SP-1240 DA performance
94
-------
Compound Tenax-GC SP-2250 OV-17 SP-1240 DA
2-chlorophenol 0.63 0.66 0.64 0.88
phenol 0.66 1.26 0.76 1.41
2,4-dichlorophenol 0.96 1.00 1.11 1.83
2-m'trophenol 1.00 1.00 1.00 1.00
p-chloro-m-cresol 1.05 1.38 1.44 2.75
2,4,6-trichlorophenol 1.14 1.34 1.51 2.34
2,4-dimethyl phenol 1.32 0.98 -* 1.75
2,4-dinitrophenol 1.34 -* -* 3.47
4,6-dinitrocresol 1.42 -* -* 3.61
4-nitrophenol 1.45 -* -* 4.63
pentachlorophenol 1.60 2.09 3.23 3.82
Table 5-4 Relative retention times of phenolic priority pollutants
on four different GC col urns.
95
-------
of the column by injection of phosphoric acid solution, as per
the manufacturer's instruction, failed to restore stable and
acceptable column performance. EPA-Cincinnati has reported simi-
lar observations to EPA contractors: good separations can be
obtained with the SP 1240 DA column under ideal conditions, but
column lifetimes are short.
Other commercially available GC columns require chemical
derivatizaton of the phenolics if more sensitive and reliable
results have to be obtained. Capillary columns give better sepa-
ration but can only be used with a derivatized or partially deri-
vatized phenol sample. A capillary column coated with SP-1000
(also known as FFAP) was therefore chosen for further analysis.
A ten meter column of this type is able to chromatograph 7 of the
11 priority phenols without derivatization and with superior
resolution compared to the packed column (Figure 5-9). Only the
very acidic phenols: p-nitrophenolf pentachlorophenol, dinitro-
cresol, and dinitrophenol, are not eluted from this column. Many
of the preparatory chromatography experimental fractions were
analyzed on the SP-1000 capillary column.
Reaction with diazomethane has been shown to quantitatively
produce methyl ethers of these four most acidic compounds.
Other priority phenols are also derivatized, but not all quanti-
tatively (and very poorly in the case of phenol and dimethyl, phe-
nol) . Analysis of a partially methylated standard on the SP-1000
capillary column is illustrated in Figure 5-10 and appears to be
a satisfactory alternative if other derivatization methods are
unsuccessful. Of course, quantitative analysis by this approach
requires locating and quantitating two separate peaks (compounds)
utilizing two different retention times and response factors each
for many of the priority phenols. There are still significant
advantages to a general and quantitative chemical derivatization
method for all of the compounds as opposed to the above alterna-
tive. In particular alkyl ethers of the phenols are readily
chromatographed on the same capillary column (SE-54) used for the
base-neutral priority compounds as shown in Figure 5-11. Also
some workers have reported that phenols derivatized to pental
fluoro benzyl ethers can be detected with very high sensitivity
by GC/ECD and negative-ion GC/CIMS.
The variable performance of SE-54 and SP 1000 glass
capillary columns is reflected in the fact that sequential ana-
lyses of the same sample reveal variable chromatography for the
underivatized phenols. This problem is more serious for real
samples than stan-dards, as derivatization yields are frequently
adversely affected by the presence of background. The poor beha-
vior of these compounds on glass capillaries is a reflection of
the nonideal deactivation of the glass itself. Recent advances
in glass deactivation techniques, discussed in Section 7, provide
one solution. However, a new material for the construction of
capillary columns, fused silica (synthetic quartz), is now avail-
96
-------
10 meters SP-1000
Splitless injection - 2ul
helium, 30 cms/sec (at 200° C)
80° for 1 minute
20 /min for 3 minutes
A0/ min to 200°
200° for 10 minutes
1. o-nitrophenol
2. o-chlorophenol
3. phenol
A. 2,A- dimethylphenol
5. 2,A - dichlorophenol
6. 2,A,6- trichlorophenol
7. A-chloro-3-methylphenol
Ct!
a:
LL
OJ .
13
CM
•
'..0
a
a
•
6J-
ll!
1 2
0?
ir?
•
rn
CO
t
Tt
•
r-
Ci
N
Figure 5-9 Analysis of Phenol Standard on SP-1000
97
-------
t.I*.
• n
ED
10 meters SP-1000
splitless injection 2 ul
helium, 30 cms/sec (at 200°C)
80° for 1 minute
20°/min for 3 minutes
4°/min to 200°c
200° for 10 minutes
*
I' i'!
0''<
1. o-nitrophenol
2. o-chlorophenol
3. phenol
4. 2,4-dimethylphenol
5. 2,4-dichlorophenol
6. 2,4,6-trichlorophenol
7. 4-chloro-3-methylphenol
*
\\..
',1
...1
i_
*
!''•„.
M (7)
,...•! 0,!
.ul
N
n
I'1')
,,,.i
u
n
1' ••-
,..„!
(6)
in
••£>
"
,....;
U'
,
Lj
Figure 5-10 Analysis of Partially Derivatized Phenols on SP-1000
98
-------
VO
30 meters SE-54
splitless injection 2 ul
helium, 20 cm/sec (at 280°C)
60° for 5 minutes
6°/min to 280°C
held for 20 minutes
1. cyclohexane
2. cyclohexanol
3. anisole
4. 2-chlorophenol
5. phenol
(7)
h
(6)
If)
(9)
"
'.T'.
r-4
(ID
ID
(13)
>M
•M
10
f-4
IT
a
Q
f'.J
6. 2-chloromethoxybenzene
7. 2,4-dimethylphenol
8. 4-chloro-3-methylmethoxybenzene
9. 2,4-dichloromethoxybenzene
10. 4-chloro-3-methylphenol
11. 2,A,6-trichloromethoxybenzene
12. 2-nitromethoxybenzene
13. 4-nitromethoxybenzene
14. 4,6-dinitromethoxybenzene
15. pentachloromethoxybenzene
16. 2,4-dinitromehtoxybenzene
(14) (15)
(16)
C-n
10
in
-t-
Fiqure 5-11 Analysis of Partially Derivatized Phenols on SE-54
-------
able with SP 2100 stationary phase from Hewlett-Packard Corpora-
tion. These columns display superior inertness and are prefer-
able to any previous glass capillary for this group of compounds.
Further improvements in this area are imminent, offering the
immediate liklihood of a satisfactory analysis of phenols in
their underivatized form.
100
-------
SECTION 6
PRIORITY POLLUTANT INTEGRATED ANALYTICAL SCHEME
The results obtained in Sections 2, 3, 4, and 5 were subse-
quently utilized to develop an integrated analytical scheme for
the recovery and determination of priority pollutants in waste-
water and sludges. The scheme uses gel permeation chromato-
graphy, florisil cleanup, and silicate column chromatography.
The gel permeation chromatography of crude extract concen-
trates serves two purposes: 1) the removal of gross lipid and
other large neutral organic interferences from the sample and
2) fractionation of the sample in a way that permits convenient
subsequent treatment. The separation of lipid and other neutral
interferences from the neutral priority compounds is best
achieved by SX-2 BioBeads. These interfering compounds are uni-
formly the earliest eluting and present separation difficulties
only with the earliest eluting priority neutrals, i.e. dioctyl
phthalate and some of the pesticides. Solvent mixtures with a
greater proportion pentane exhibited increased selectivity on a
molecular size basis, possibly with a superimposed electronic
effect for aromatic molecules. Empirically, the effect is
increased separation of fatty acids from phenols, smaller elution
volumes, and increased sorting within compound groups as the
exclusion limit decreases.
Florisil chromatography is utilized following the BioBeads
to remove interferences that co-elute along with phthalates, pes-
ticides, and PAHs in the GPC step. Desired separation for flori-
sil LC cleanup consisted of removal of saturated hydrocarbon
material, and removal of biological containants including fatty
esters, glycerides and sterols. It was found that a 0.75% deac-
tivated florisil was able to separate saturated hydrocarbons and
pesticides. A spike of priority phenols in methylene chloride
shows good retention of phenols using cesium silicate, together
with high recoveries upon elution with methanol followed by deri-
vatization.
The results of the chromatography experiments and the pro-
posed analytical scheme are shown in Figure 6-1, while the
detailed steps are listed in Figure 6-2. An average system reco-
very of 113%, using a standard mixture of the neutral fraction in
methylene chloride, is presented in Table 6-1.
Initial evaluations of the separation scheme using real sam-
ples were carried out using BioBeads, florisil, and silicate
chromatography. It was found that the silicate fraction (which
begins with the early-eluting phenols) was remarkably free of
gross amounts of interfering compounds. Figure 6-3 shows a typi-
cal reconstructed gas chromatogram from an analysis of West Point
primary sewage effluent. The florisil chromatography, in its
101
-------
SLUDGE
\ / \ S--T--^
A K/ PAH \ \
A-l
t A-2 f
LIPIDS
SAT.HYDROCARB.
BIO-ORG.
PESTICIDES
PCB
AROMATICS
PHTHALATES
BIO-ORGANICS
PHENOLS
PAH
PESTICIDES
PHTHALATES
OTHER NEUTRALS
A-l DISCARD
ACID/NEUTRAL EXTR.
A-2 FLORISIL
F-l DISCARD
F-2
F-3
A-3 SILICATE
A-3
DERIV.
ACIDS
Figure 6-1 Schematic Elution of Priority Pollutants During Column Chromatooraphy.
102
-------
AQUEOUS PHASE ADJUST pH
TO 12 REEXTRACT 12 HOURS
I
METHYLENECHLORIDE EXTRACT
DRY OVER Na2S04
K-D CONCENTRATE TO 1 ML
ADD INTERNAL STANDARD
r
GC;GC/MS ANALYSIS; BASES
0-75 ML DISCARD
LIPIDS
"A,"
15 ML PENTANE DISCARD
HYDROCARBONS
200 ML 50?; ETHER/PET. ETHER
K-D CONCENTRATE-.EXCHANGE
INTO METHYLENECHLORIDE
ADD INTERNAL STANDARD
I
GC;GC/MS;PESTICIDES +
LIGHT PAH
FLORISIL FRACTION
"F2"
1000 ML AQUEOUS SAMPLE
pH SET TO 2
12 HOURS CONTINUOUS
L-L EXTRACTION WITH STIRRING
METHYLENECHLORIDE EXTRACT
DRY OVER Na2S04
K-D CONCENTRATE TO 1 ML
ADD 1 ML PENTANE
GPC ON BIOBEADS 40 S-X 2
ELUTF. WITH 50? METHYLEME
CHLORIDE/PENTANE
TAKE 3 FRACTIONS
75-110 ML: K-D TO 2 ML
EXCHANGE INTO PENTANE
AZEOTROPICALLY
-
110-230 ML: FLOW-THROUGH
COUPLED COLUMN CHROMATOGRAPHY
ON CESIUM SILICATE
* I
LOAD ON 20 GR FLORISIL +H70 COLLECT ELUATE PLUS 30ML
ELUTE WITH PENTANE AND ETRER METHYLENE CHLORIDE; K-D
ADD INTERNAL STANDARD
50 ML 100X ETHER
K-D CONCENTRATE ;EXCHANGE
INTO METHYLENECHLORIDE
ADD INTERNAL STANDARD
GC;GC/MS;ISOPHORONE
"F3"
GC.GC/MS HEAVY PAH
"SILIATE FRACTION -A3"
ELUTE CESIUM SILICATE WITH 60ML
METHANOL; K-D
PARTITION 3X BETWEEN IN ACID
AND METHYLENECHLORIDE
DRY METHYLENECHLORIDE OVER
Na2S04 |
DERIVATIZE WITH DIAZOMETHANE:
K-D I
ADD INTERNAL STANDARD
GC;GC/MS;ACIDS
"A3S"
Figure 6-2 Modified Cleanup Scheme for Acid and Neutral Organics
103
-------
RECOVERY:
COMPOUND
HEXAMETHYLBENZENE
N-N1TROSOD1METHYLAM1NE
BIS (2-CHLOROETHYL) ETHER
(1,3-) D1CHLOROBENZENE
1.4-DICHLOROBENZENE
(1.2-) DICHLOROBENZENE
B1S(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-OI-N-PROPYL AHINE
NITROBENZENE
BIX(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTAOIENE
2-CHLORO-NAPHTHALENE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
01ETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSOOIPHENYLAM1NE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
DIO-ANTHRACENE (I.S.)
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3.3'-DICHLOROBEN7.IDENE
B1S(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO
BENZO
BENZO
INDENO(i.2,3-CD)PYRENE
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
B)FLUORANTHENE
KJFLUORANTHENE
A) PYRENE
FLOR1SIL FRACTION
65.6
81.5
61.6
58.5
*
137.9
69.1
24.3
*
66.6
28.0
*
15.6
3.1
94.3
0
16.6
0
18.7
94.4
56.8
*
46.6
51.4
0
118.4
0
89.5
0
0
87.5
0
0
*
87.5
86.1
0
0
0
*
0
0
SILICATE FRACTION
5.2
11.2
23.0
26.8
*
0
0
64.7
*
43.3
41.0
*
95.8
TOTAL
81.7
0
83.3
62.3
74.9
55.9
0
8.5
72.1
106.7
65.0
86.9
59.8
0
85.7
104.2
0
122.7
217.2
0
0
182.2
183.3
192.6
*
263.4
267.8
**
*
70.7
92.7
84.6
35.4
137.9
69.1
89.0
*
109.9
69.0
111.4
64.8
94.3
83.3
78.9
74.4
74.6
94.4
65.4
118.
158,
65,
59.8
89.8
85.7
104.2
87.5
122.7
217.2
87.
86.
182.
183.
192.
263.4
267.8
* Not present In spike
** Internal standard
Table 6-1 Recovery of Neutral Priority Pollutant Standard
During Column Chromatography.
104
-------
o
en
RIC
RIC
02^86x73 .13:42:80
SOMPLE: r»4EM»3 NEUTRWLS
RflNGE: G 1,4549 LABEL: N 8, 4.0 QUON: A O, 1.0
Ij
see
8:20
16:49
1508
25:89
f.C.J-.
T 1 K-.
Figure 6-3 Reconstructed Gas Chromatogram of Silicate Fraction of West Point Primary Effluent.
-------
present state of refinement, was used to prepare sewage and
sludge extracts for instrumental analyses. The extract fractions
generated by the cleanup scheme were screened by GC-FID and are
presented for one representative raw sewage and one waste acti-
vated sludge sample (both spiked with approximately 45 priority
compounds) in Figures 6-4 through 6-8. The priority compounds
appear in the silicate, florisil, and derivatized acid fractions
(Figures 6-5, 6-6, and 6-7). Note that for the case of the rev-
sewage extract, the cleanup scheme is highly successful in remov-
ing contaminants (Figure 6-5) while in the case of the sludge
extract, the florisil fraction is insufficiently purified of
interferences.
Based on these screening analyses, the sewage sample was
analyzed for neutral priority compounds and recoveries computed
based on comparison of the spiked and unspiked results. Table
6-2 presents the computed recoveries. For the sludge samples,
recoveries could only be determined for those compounds eluted
entirely within the silicate fraction, i.e. the 12 heavy poly-
nuclear aromatics. The florisil fractions of these sludges were
not analyzable by GC/MS without further cleanup. Recoveries are
presented in Table 6-3.
The sludge and sewage samples were spiked prior to
extraction (a 1-liter sample for the sewage, 500 mis for the
sludge). The extract obtained could only be handled by the
cleanup chromatographic columns as an aliquot; a 10% aliquot of
the primary sludge extract gave 221 mg residual weight. Using
10% aliquots of the sludge extracts meant a 10-fold dilution in
the spike concentration down to 1 ug per compound. Imperfect
recoveries from the extraction and cleanup steps further reduced
the spike level. In future experiments, either smaller sludge
samples are used, or higher levels of spike are employed.
106
-------
1''A« ^ /
— -A—-f
Figure 6-4 Hydrocarbon (discard) Florisil Fraction for Spiked Raw (a) and Haste Activated
Sludqe (b) Sample.
-------
o
00
Figure 6-5 Florisil Neutral Fraction of Spiked Sewaqe and Sludge Sample.
-------
LJ
o
UD
I
s * •
»= Ss4?s fc.
. M £J I n-«nXN S
lljM^-J^J'JlW/*
^.LjlilULLAJ—
f
Figure 6-6 Silicate Neutral Fraction for Spiked Sewage (a) and Sludge (b) Sample.
-------
u
irv
iii
*--^~ 4
Figure 6-7 Third Ether (a) Florisil Fraction of a Spiked Sludge Sample and (b) Derivatized
Phenol Fraction of a Spiked Sludge Sample
-------
Figure 6-8 Base Extracts of Spiked Sewage (a) and Spiked Sludge Sample (b).
-------
COMPOUND
% RECOVERY
AZOBEN2ENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHREME
DIO-ANTHRACENE (I.S.)
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBEMZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIX(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A) PYRENE
INDENO(1,2,3-CD)PYRENE
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
HEXAMETHYLBENZENE
N-NITROSODIMETHYLAMINE
BIS (2-CHLOROETHYL) ETHER
(1,3-) DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-) DICHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALENE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
102.32
*
125.14
58.94
122.40
**
***
137.39
107.37
101.52
130.36
*•**
85.86
***
*
152.04
85.65
***
89.79
*
84.75
85.14
**
*
109.19
50.96
2.01
50.66
*
**•*•
103.13
93.91
***
29.83
131.56
*
173.74
113.95
138.98
135.95
117.84
107.67
123.18
146.63
* not present in spike ** internal standard
*** detected but not
quantitated
Table 6-2 Recoveries of Compounds Spiked in Raw West Point Sewage.
112
-------
Table 6-3. Recoveries of Heavy PAH & Phenol fraction is Sniked Sludge Extracts.
COMPOUND
Secondary Sludge
Anaerobic Digested Sludge
(A)
2, 6-DINITROTOLUENE
2, 4-DINITROTOLUENE
PHENATHRENE
FLUORANTHENE
PYRENE
BENZO(A)ANTHRACENE
CHRYSENE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BEN ZO(E) PYRENE
DIBENZO (A,H)ANTHRACENE
BE^ZO (G,H,I)PERYLENE
21.6
152.1
127.4
141.7
137.6
140.0
127.2
187.0
***
166.7
196.2
189.5
68.4
***
0
65.6
63.4
58.4
104.1
20.3
142.1
20.6
27.9
43.3
***
not quantitated
-------
SECTION 7
CAPILLARY GC ANALYSIS
The qualitative and quantitative evaluation of priority
pollutant chlorinated pesticides and PCBs mixture (AROCHLOR 1242)
was performed at Georgia Tech by high resolution gas chromato-
graphy after a preliminary cleanup step by UPC. Glass capillary
columns coated by 5 different stationary phases were evaluated in
order to establish the best performance in terms of separation
capability toward pesticide and PCBs. The gas chromatographic
system was equipped with an Electron Capture Detector and Liquid
Automatic Sampler. It was possible to resolve organochlorine
pesticides from PCBs in sludge extract by means of glass capil-
lary columns coated by different stationary phases (SP-2401 and
CARBOWAX-20M).
7-1 Preparation of glass capillary columns for GC analysis
Generally, the preparation of a glass capillary column can
be defined in the following steps:
a) column material selection
b) surface treatment
c) deactivation
d) coating
e) evaluation
a. Soda-lime borosilicate glass tubes were used as starting
material. The tubes were washed with a detergent solu-
tion, rinsed with water and acetone, and finally dried
by means of heat-gun and flow of nitrogen. Capillaries
were drawn using a Shimadzu GDM-1 glass-drawing machine.
Operating at drawing ratio 100, it was possible to
obtain capillaries with I.D. 0.35 mm and about 90 m
long from tubes with O.D. 7 mm, I.D. 5 mm and 120 cm
long. After drawing, each capillary was sealed at both
ends if not used immediately.
b. Relatively polar stationary phases exhibit surface ten-
sion values different from that of a non-treated glass
surface. As a result of this, nonuniform spreading of
the phase, and in some circumstances the formation of
droplets on the inner wall of the capillary, can occur.
Capacity, temperature stability, and deactivation of the
surface complete the list of requirements that define
suitable surface treatments for the successful prepara-
tion of glass capillary columns. Table 7-1 gives sum-
maries of all the methods of glass treatment available
in literature, together with the type of glass being
used and the effects produced. We have been using three
of the reported methods. Soda-lime glass capillaries
114
-------
Table 7-1 SURFACE TREATMENT FOR GLASS CAPILLARY COLUMNS
GLASS TYPE
METHOD AND CONDITION
DEPOSITION OF EXTERNAL MATERIAL
CARBONIZATION: CH £1 ,Pyrolysis
COLLOIDAL SUSPENSION
CRYSTALLIZATION: IN SITU
REACTION OF Ba(OH)
CHEMICAL BONDING:
ORGANOSILICONE, GRIGNARD'S
REAGENTS
Gas phase 260°C
IMPREGNATION WITH NON-
IONIC SURFACTANT
DIRECT REACTION WITH COMPONENTS OF GLASS
GAS PHASE HC1 ETCHING
(300°-350°C)
ORGANIC DECOMPOSITION
AND DEVELOPMENT OF HC1 or
HE (300°C)
STRONG ALKALI HYDROXYDE
LIQUID PHASE ETCHING
FLUOROETHER ETCHING (400°C)
Soft + Borosi1ic
Soft ••• Borosi 1 ic
Soft + Borosi1ic
Soft + Borosi1ic
Soft + Borosilie
Soft
Soft + Borosilic
Soft
Borosi1ic
EFFECT AND REMARKS
Thin layer of carbon. Suitable
for moderately polar phases;
difficult to reproduce
Layer of: siliceous material,
graphitized carbon black.
High capacity columns.
Stable BaC03 crystals
Replacement of hydroxyl groups
by organic monolayer of polymer.
Thin, physical held layer of
polar substance. Low temperature
stability. Retention behavior
High density NaCl crystals.
Easy and fast
Silicate and NaCl crystals and
thin carbon layer. Very mild
etching
Leaching Process. Phases may
deteriorate. Low column efficiency
Silicate Hiskers. Very large
surface area; suitable for wide
ramie in phase polarity. Active
surf ace.
-------
were dynamically etched by gaseous dry HC1 at high tem-
peratures (350°-380°C). Borosilicate glass capillaries
were treated in two different ways. The first method
consisted of the deposition of very fine particulate
layers of silica on the inner wall by pushing a plug
(10% entire length of column) of diluted colloidal sus-
pension of silicic acid through the capillary at a con-
stant speed of 1-2 cm/sec, as reported by Shulte (1976) .
The second method consisted of the growth of silica
whiskers on the inner wall of the glass capillary by the
action of KF developed by decomposition of 1,2-dichloro
1,2,2-trifluoroethyl methyl ether at high temperature
(360°-400°C) , as reported by Pretorius (1975).
c. The presence on the glass surface of silanol groups and
"Lewis acid active sites" (Ca++r AP+++, Mg++, B+++)
requires that a suitable deactivation be performed prior
to the coating of the glass-capillary by the stationary
phase. Glass capillary columns coated by relatively non-
polar and medium polarity stationary phases (SE-30,
OV-101, OV-17, SE-54), if not adequately deactivated,
will exhibit partial or complete adsorption of polar
compounds on the surface. Glass capillary columns
coated by relatively polar stationary phases (CARBOWAX
20M, EMULPHOR ON-870) may not require prior deactivation
since the polar groups of the phase itself neutralize
the active sites of the glass surface. Diluted solu-
tions of CARBOWAX-20M and EMULPHOR ON-870 (0.05% w/v in
methylene chloride) have been used for the deactivation
of (soda-lime) HCl-etched and (borosilicate) silic acid-
treated glass capillaries. The method used follows
Grob's instructions for the deactivation of BaC03
treated surface (1978). Whisker columns presenting
higher "activity" were deactivated by polymerisation on
the surface of N-cyclogexyl-3-azetidinol (CHAZ), as
reported by Verzele (1977) .
d. Glass capillary columns were coated following two dif-
ferent methods. CARBOWAX-20M and EMULPHOR ON-870 phases
were coated by the dynamic Hg plug method, as reported
by Schomburg (1974). 15 - 20% of the entire length of
the column was filled with 10% (w/v) solution of the
phase in methylene chloride. A Hg plug (about 3 - 4 cm
long) immediately followed the solution; any air bubble
between the two phases must be avoided. A nitrogen car-
rier-gas line, regulated by a fine pressure regulator,
was used to push the solution at a constant speed of 0.5
cm/second. In order to avoid temperature gradients that
could result in nonuniform film thickness of the sta-
tionary phase, the column was placed in a water bath. A
dummy column was connected to the open end of the glass
capillary. Since the length of the glass capillary col-
116
-------
Table 7-2 Relative Retention Time of Chlorinated Pesticides
(Relative to Aldrin)
Compound
a-BHC
6-BHC
Y-BHC
Heptachlor
*Aldrin
Heptachlor epoxide
Endosulfan
Dieldrin
pp'-DDE
pp'-DDT
pp'-DDD
Endrin
SE-30
0.69
0.75
0.76
0.93
1.00
1.07
1.15
1.21
1.20
1.20
1.27
1.23
SE-52
0.75
0.81
0.82
0.94
1.00
1.09
1.16
1.23
1.19
-
1.28
-
OV-17
0.80
0.93
0.88
0.94
1.00
1.11
1.18
1.24
1.23
-
1.35
-
SP-2401
0.89
0.99
0.95
0.96
1.00
1.16
1.22
1.27
1.18
1.35
1.32
-
CW-20M
0.95
1.42
1.12
0.98
1.00
1.31
1.34
1.47
1.49
1.49
1.84
1.50
SE-30: L = 30 m; I.D. = 0.35 mm; d - 0.2 ym (film thickness)
Working temperature: 100°- I3eC/m) - 230°C; carrier-gas = He/H2
SE-52: L = 50 m; I.D. = 0.35 mm; df = 0.2 Urn
Working temperature: 100°-(3°C/m) - 230°C; carrier-gas: He/H2
OV-17: L = 45 m; I.D. = 0.35 mm; d = 0.2 ym
Working temperature: 100° - (3°C/m) - 240°C; carrier-gas: He/H2
SP-2401: L = 40 m; I.D. = 0.35 mm; d, - 0.2 ym
Working temperature: 70°- (3°C/m) - 210°C; carrier-gas: He/H2
CW20M: L = 40 m; I.D. = 0.35 mm;
Working temperature: 100°C - (3°C/m) - 210°C; carrier-gas: He/H2
117
-------
umns prepared did not exceed the length of 50 meters,
all the relatively non-polar and medium-polar stationary
phases were coated with the static method for reasons as
reported elsewhere. Each column was conditioned in the
GC, under a flow of He (1 - 2 ml/m) at a temperature
program rate of 0.5°C/m.
e. The set of glass capillary columns used for chlorinated
pesticides and PCEs analysis was evaluated in terms of
efficiency, (expressed as number of effective plates and
separation number, with respect to chlorinated pesti-
cides) . A more extensive evaluation of the glass capil-
lary columns will be performed in order to establish
their suitability for the priority pollutants analysis.
A standard qualitative and quantitative evaluation test,
recently introduced by Grob (1977), will be treated in
detail.
7-2 Investigation of Stationary Phases and GC Conditions
The selectivity of different stationary phases and the high
separation power of glass capillary columns have been exploited
for the resolution of chlorinated pesticides and PCBs eluting in
the same gel permeation fraction. The stationary phases were
selected in order to cover a wide range in relative polarity in
an attempt to optimize the resolution of chlorinated pesticides.
The five glass capillary columns selected for this study are
listed in Table 7-2.
The evaluation of all the samples was performed by means of
a Hewlett/Packard 5830A gas-chromatograph, keyboard controlled
and equipped with a H/P split-splitless capillary injection sys-
tem, Electron Capture Detector (model 18803-A), and Liquid Auto-
matic Sampler (model 7672-A). He/Ha (91.5%/8.5%) has been used
as carrier-gas, while Ar/Me (95%/5%f has been used as make-up gas
in order to satisfy the required flow conditions for the ECD.
The samples were analyzed under temperature program.
conditions at average carrier-gas velocity of 40 - 45 cm/second.
All the components of each sample were eluted within 1 hour of
analysis time. Standard solutions of chlorinated pesticides,
AROCHLOR 1242 and chlorinated pesticides + AROCHLOR 1242 were
evaluated on each glass capillary column in order to establish
the separation capability. Figures 7-1 to 7-6 show the chromato-
grams of each standard solution for the SP-2401 and CARBOWAX-20M
stationary phases. The results relative to the resolution of
organochlorine pesticide from PCBs and their relative retention
times are reported on Tables 7-3 and 7-4, respectively.
118
-------
RT
22.59
24.47
24.91
25.85
30.87
31.53
32.69
33.23
34.39
35.95
36.70
Compound
ct-BHC
Y-BIIC
Heptachlor
B-RHC + Aldrin
Heptachlor epoxidc
pp'-DDE
Endosulfan
op'-DDT
Dieldrin
pp'-DDD
pp'-DDT
1 y£ splitless injection (30")
SP-2401; L - 40 m; I.D. = 0.35 mm
carrier gas He/H2 (91.5% + 8.5%); P = 1.5 atm
Temperature program: 50° -(4°C/m) - 200°C
CO
GJ
CL
o
>-
CO
Fig. 7-1 Pesticide stnnd.-ird solution in llcxnno (200 pph)
-------
r\>
I?'
CM
01'
IT' IT' K'MCI
CL
cc
1 V?, splitless injection (30")
Same conditions as for Fig. 1
a CM ro rt inrjj H-- ro
i"'.J CM CM rtfJCMO..! C'W CMC'JI
CM
Fig. 7-2 pcBs (AROCHLOR 12A7.) sMn,!.-rl solution in.Mcxane C
-------
RT
22.60
2tt.lt!
24.91
34.53
35.37
36.77
Compound
a-BHC
Y-BI1C
Hpptnchlor
Dlclclrln
pp'-DDI)
pp'-DDT
1 \ii split less ln)ectlon (30")
Same conditions as for Fig. 1
•t IT- OV-rtf* f'i -•
•n -« liTTl-iin •'•< r
ra ri Tfiii ur K O'
f'-J «••! t. «Mtl|r<1 T'll- r'I
IT'
•fr
If'
0.
o
F1R. 7_!
(Pesticide + TCPs) st nml.,r,l
In
-------
IP
r.
ro
ro
OL
fi Kndrin
i2 pp'-nnn
t-1
J.
^.
1 -
,
'!'
f-
(T- '
•>
.
r * N
% ~
N rol •*
a ~
Ss- - J J^
1
N 1
a
|
OJ
IN
•
i
i
r>-
•j>
1C-'-
'•i <*
m
^
M,
u
j
t
m
•p
i
in
t
K
\j
\gf
U^~
f*-* 0.6 gH split i
CARBOWAX 20M;
cnrrler gas He
injection (1:10)
L - 40 m; I.D. - 0.35 mm
/H2 (91/5Z + 8.5't); P = 1.5 atm
TcmperatureproRr.im 50"-(4°C/m)-200"C
F!R. 7.4 Pesticide standard solution In Hpxan<-
-------
0.6 uH split Injection (1:10)
Same conditions as for Fig. 4
ro
oo
a.
o
7-5 VCtos (AROCHLOR 1242) standard solution In Hcxane
-------
RT
ro
28.99
32.27
38.11
38.89
41.09
42. 79
43.59
Compound
Aldrln
Y-BHC
Heptachlor opoxlde
Endosulfan
B-BHC
IHeldrln
F.ndrtn
0.6 ul split Injection (1:10)
Same conditions as for Fig. 4
r>
a>
a.
o
Fig. 7_fc
(Pesticide + PCBs) standard solution In Hexanc
-------
Table 7-3 Glass Capillary Columns Selected
Stationary Phase
SE-30
SE-52
OV-17
SP-2401
Carbowax-20M
Etching Deactivation Coating L(m)
dry HC1 CW-20M -f Emulphor Static 30
50
45
n .. .. 40
" - Dynamic 40
l.D. (mm)
0.35
0.35
0.35
0.35
0.35
Table 7-4 Organochlorine Resolved from PCBs
Compound
Ct-BHC
B-BHC
Y-BHC
Aldrin
Heptachlor
Heptachlor epoxide
EncJosulfan
pp'-DDE
Endrin
Dieldrin
pp'-DDD
pp'-DDT
SE-30 SE-52 OV-17 SP-2401
X XX
XXX
X X X X
X X
X X
X
X
X
X X
X X X X
X
CW-20M
X
X
X
X
X
X
X
X
125
-------
In order to identify any major interference related to the
matrix, both spiked distilled water extracts and spiked sludge
extracts were evaluated. Figures 7-7 to 7-12 show the EC traces
from analyses of pesticide spiked sludge, pesticide + AROCHLOP.
1242 spiked sludge and, pesticide spiked distilled water, respec-
tively, on CW-20M stationary phase. One conclusion, suggested
from a survey of the results, is that it is possible to evaluate
organochlorine pesticides and PCBs eluting in the same gel per-
meation fraction by means of two glass capillary columns coated
by different stationary phases and Electron Capture Detection.
The correlation of results from the use of different stationary
phases will also improve the possibility of resolution and iden-
tification of any major interference related to the matrix
itself. From the results obtained in our evaluation, it was pos-
sible to determine that some minor peaks present in the non-
spiked sludge extract were themselves organochlorine pesticides
and PCBs.
Some difficulties were encountered in the evaluation of
pp'-DDT and Endrin. As reported in the literature, these com-
pounds may undergo decomposition under the gas chromatographic
conditions. Temperature is the main factor, but active sites in
the system may catalize the degradation process. Since we
observed evidence of decomposition that was particularly severe
when using glass capillary columns coated by non-polar stationary
phases (OV-17, SE-52), the responsibility of this effect was
ascribed to the presence of residual activity in the column, due
to insufficient deactivation of the surface.
The development of the gas chromatographic system will be
directed to three areas: 1) better deactivation of columns,
2) shorter analysis time, and 3) evaluation of other sta-
tionary phases. In light of the negative results for nonpolar
glass capillary columns, more complete deactivation of the sur-
face will be sought. Shorter capillaries with smaller internal
diameters will improve the analysis time; this will also imply
less contact time between the labile compound and the system, and
therefore less chance to undergo decomposition, at the expense of
some resolution and column capacity. SE-54 and 52 are among the
preferred stationary phases.
126
-------
N —
ro
N
a
pi'
•a
T
Jl
(2 UR pesticide + in 100 ml wntpr)
I ul splltless injection (30")
CARBOWAX 20M; L = 40 m; I.D. = 0.35 mm
cnrrler-gas He/H- (91.5% -I- 8.52; P =
Temperature program 50°-(4°C/m)-200°C
PJ
a
'f
in
(T> —>
ro
ft7
L.JL
7_7 Extract from pesticide + PCBs splkpcl (llsrlllcd w.itrr
-------
ro
(2 Ug pesticide in 100 ml sludge)
1 u'. splltless injection (30")
CARBOWAX 20M; L = 40 tn; I .D. = 0.35 mm
carrier-gas He/H (91.5% + 8.5%); P = 1.5 atn
Temperature program 50°-(/i°C/m)-200"r.
oo
ro
oo
F'l?- 7-8 Extract from pesticide spiked sludge
-------
ro
03
in
El
in
(2 UR pesticide + PCBs in 100 ml slu
1 Ml splltleas injection (30")
CARBOWAX 20M; L = '.0 m; I.n. - 0.33
carrlrr-Ras He/H,, (t\ . 5Z + 8.5?); P
Temperature program 1iO0-(60C/m)-20nc
1.5 «tm
7-9 Extract from pesticide + PCBs aplkoH
-------
0.3 Hi split inlectlon (1:20)
SP-2401; 1. = 60 m; l.D. - 0.35 mm
carrler-Ras He/H (91.5% + 8.5Z); P - 1.5 atm
Temperature program 500-(4°C/m)-210°C
U)
o
FIR-7-10 PCB9 mlxt..re H2 StlPELCO (AROCHI.OR 1221 + 12/.2 + 1254)
-------
0.4 \il split Injection (1:20)
SP-2401; L - 40 ra; l.D. • 0.15 mm
carrier-gas He/H (91.5Z + 8.5%): P = 1.5 atm
Temperature program 500-(40C/m)-210°C
N
N
51
i j
OT"
JL
evi
u
CD
N
•
t
j
c^
•a
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• n
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1
i
J
ON
M
co n
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0 1
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T
jiy
0
s
J 0
1
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N £
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rn.
r
i
i-
CO
Kjp>. 7-11 ;v:",3 mixture *1 SIIPFI.CO (AKncill.nR 1OU, + I21L' + 1248 -I-
-------
r-
ra
EJ
K>
r-
iPir
i.
OJ
ro
0.5 Ui split Injection (1:20)
SP-2601; I, = 40 m; I.I)'. = 0.35 mm
carrier-gas He/H (91.5% + 8.5Z); P = 1.5 atm
Temperature program 50°-(4°C/m)-2lO°C
Fig. 7-12 Toxaphene 4- Chlordane mixtnro SITKI.CO
-------
SECTION 8
GC/MS/DS ANALYSIS OF PRIORITY POLLUTANTS
8-1 Chromatography of Organics
The base-neutral and pesticide priority compounds exhibit
varying chemical properties. These compounds can be chromato-
graphed successfully on glass capillary columns coated with dif-
ferent liquid phases. Among the different types of columns, two
have proven to be distinctly superior to most others for routine
analysis of these compounds. The phases SE-52 and especially
SE-54 (10% phenyl and 5% phenyl + 5% vinyl methyl silicones, res-
pectively) are preferred in our laboratory and in others, includ-
ing the National Analytical Facility of NOAA, the Woods Hole
Oceanographic Institute, and the Swiss Federal Institute for
Water Resources and Water Pollution Control (EAWAG). While the
resolution obtained with these tv/o phases is not significantly
different from that achieved) by the commonly used methyl sili-
cones, SE-30 and OV-101 (AP-2100), the durability, stability, and
longevity of the phenyl substituted phases is generally superior.
These characteristics have been most strikingly observed during
the analysis of polynuclear aromatic hydrocarbons.
A standard mixture of acids, bases, neutrals, and pesti-
cides, as used in the liquid/liquid extractor experiments, was
analyzed by both GC/FID and GC/EI-MS. The chromatograms from
these runs are shown in Figures 8-1 and 8-2, respectively. The
analyses were done on two different 30 meter SE-54 glass capil-
lary columns using identical GC conditions without stream split-
ting. The resolution obtained in these two runs is essentially
identical. It should be noted that several compounds are still
unresolved even though the overall resolution is much greater
than that achieved on packed columns. Examples of this are the
hexachloroethane + di-n-isopropyl-n-nitrosamine (peak 2), and the
acenaphthylene + hexamethyl benzene (peak 11). In the first
case, no separation is observed, even of selected masses on the
GC/MS run. The GC/MS data system, however, is still frequently
able to identify the components of mixed peaks correctly, as is
shown in the library search report of the mixed spectrum obtained
from peak #2 (Figures 8-3 and 8-4). The severely tailing peaks,
#1, #5, and #8, in these chromatograms, represent or contain
phenols which show significant adsorption problems on this column
type. In contrast, the phenols when derivatized to their methyl
ethers, chromatograph very readily on this column, as was indi-
cated earlier.
Two of the compounds in the test mixture have shown some
degradation problems in their GC analyses, either from thermal
pyrolytic conditions during analysis, or other reaction condi-
tions on standing in solution, or both. Diphenyl hydrazine (peak
#17) is converted to diphenyl diazine which co-chromatographs
133
-------
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LIBRARY SEARCH
12/15/78 17:21:00 + B: 36
SAMPLE: DAVE'S EXTR. TEST MIX
* 516 - « 508 TO * 512 XI. 01
DATA:
CALL
DAVESTD «
C1215A «
516
6
BASE M/E: A3
R1C: 142847.
25410 SPECTRA IN L1BRARYNB SEARCHED FDR MAXIMUM FIT
280 MATCHED AT LEAST 4 OK THE 16 LARGEST PEAKS IN THE UNKNOWN
REDUCTION: PKS/100 AMU: 40; WINDOWS: 50, 7
PRE-SEARCH: ENTRIES TO PASS: 100; SAMPLE PEAKS: 16
MAIN SEARCH: MASSES: 34 - 534; NORM INT: 25; RATIO FACTORS:
RANK IN NAME
1 214 ETHANE,HEXACHLORD-
0, 1.0
ETHENE,TETRACHLQRO-
1-PROPANAMINE,N-NITROSO-N-PROPYL-
2 1626
3 3429
4 9145 1,4-DIDXANE-2, 5-DIONE.3,3, 6, 6-TETRAMETHYL-
5 1569 PYRROLIDINE
6 1773 L-PROLINE
7 3235 2-PROPANAMINE, N-<1-METHYLETHYL>-N-NITROSO-
8 556O CYANICAC1D.1-METHYLETHYLESTER
9 315 PROPANENITRILE,2-HYDROXY-2-METHYL-
RANK
1 C2.
FORMULA
CL6
2 C2.
3 C6.
CL4
H14. 0. N2
4 08.
5 C4.
6 C5.
7 C6.
8 C4.
9 C4.
H12. 04
H9. N
H9. 02. N
H14. 0. N2
H7. 0. N
H7. 0. N
M. WT
234
164
130
172
71
115
130
85
85
B. PK
117
166
43
43
43
70
43
70
43
PURITY
701
2BO
262
188
167
159
237
166
170
FIT
937
953
941
925
862
849
847
833
831
RFIT
701
233
264
195
176
173
243
184
185
Figure 8-4 . Library Search of Unresolved GC Peak #2.
137
-------
with its unaltered parent. Up to 1-2 second separation is
observed in the reconstructed mass chromatographs from the GC/MS
analysis. Endrin (peak #33) is also partially or completely oxi-
dized to Aketoendrin or endrin aldehyde in most analyses thus
far.
As mentioned previously, one of the primary objectives of
the development effort is to be able to prepare and analyze sam-
ples for neutrals and pesticides in one single fraction, with the
bases added prior to analysis. Even though certain compounds in
these groups are not resolvable by our chromatographic system
using non-specific GC detectors, the GC/MS is still able to
easily distinguish them based on their individual mass spectra.
In addition, the following compounds have been reported to be
unstable for GC analysis: 3,3-dichlorobenzidene, diphenyl-
nitrosamine, dimethylnitrosamine, and bischloromethyLether.
8-2 GC/MS Data Processing
A. Initialization
Prior to unknown sample analyses, the Supelco standard
priority pollutant mixtures were diluted in methylene chloride
and analyzed using the identical GC/MS setup and conditions later
used for unknowns. The compound peaks in these runs were identi-
fied by computer comparison of their spectra with NBS library and
other reference spectra. The best spectra obtainable from these
data, after careful background subtraction, were then used to
create a new "quantitation" library. During this process, insig-
nificant mass peaks were deleted and additional information was
added for each library entry, such as the mass to be used for
quantitation and the concentration in the standard mixture. The
quantitation library used for the majority of unknown analyses
contains spectra of all base/neutral priority compounds.
The relative retention times and relative response factors
for each compound in the library were then computed by an ini-
tialization program, using a GC/MS analysis of the complete stan-
dard mixture run under identical conditions.
The internal standard chosen for these studies was arrived
at after some experimentation. Initially, hexamethylbenzene was
used, as well as DID anthracene. In the course of early analy-
ses, it was found that multiple internal standards, spanning a
range of retention times, would greatly facilitate data proces-
sing by allowing closely set retention time windows. Further, in
several environmental samples, D10 anthracene was used as one
component of a multiple standard mixture. It was found to atten-
uate over time relative to the other internal standards. Because
of this instability, D10 phenanthrene is substituted as the
medium retention-time standard. D8 naphthalene and D12 perylene
complete the internal standards. In addition, several surrogate
138
-------
recovery compounds and other standards are included during sample
preparation. The analysis of these spiked compounds provides a
useful index of chromatographic behavior for a particular gas
chromatogram, which is a significant aid in automated data analy-
sis.
B. Analysis of Unknowns
The initalized quantitation library was utilized by a
computer program, called SINUNK, to analyze unknown samples.
Only those compounds present in the library are searched for and,
when found, are quantitated relative to the internal standard.
The essential features of this program are described as follows:
1. The internal standard is searched for in a two
minute time window around the expected reten-
tion time. If it is located, the program con-
tinues.
2. The area of the mass chromatogram peak for the
standard's base peak is calculated and com-
pared to an expected value. If it is within
acceptable limits, the program continues.
3. The actual retention time of the authenticated
internal standard peak is then stored for use
in relative retention time calculations.
4. The first library entry is retrieved and the
expected retention time calculated. If this
value plus 30 seconds exceeds the length of
the data file, the program stops searching and
reports the quantitation results up to that
point. If the file length is not going to be
exceeded in subsequent steps, the program con-
tinues.
5. The data file is then reverse searched against
the library spectrum in a window -/+ 30
seconds around the expected retention time.
If no peak is found with a statistical FIT of
750, a "NOT FOUND" is reported for that com-
pound. A FIT of 1000 is a perfect match. If
one or more peaks are found in this window,
the program continues and the scan number cor-
responding to the peak of highest FIT is
stored.
6. If the FIT is less than 850 but over 750, the
spectrum is added to a list of questionable
identifications to be forward searched against
a library containing all of the priority com-
139
-------
pounds.
7. The expected retention time is then compared
with this best fit scan number. If the "best"
retention time is -10, -5, +5, +10, +15, or
+20 seconds in error relative to the expected
retention time, then the size of the quantita-
tion window is adjusted. This window is nor-
mally -/+ 7 seconds around the expected reten-
tion time. For example, if an error of +12
seconds is calculated, the window becomes -7
to +17 seconds.
8. The mass chromatogram for the base peak mass is
generated over a one minute window around the
expected retention time. The peak areas are
then computed for only those peaks falling
within the quantitation window calculated above
and are stored along with other information for
the final report.
9. The next library entry is retrieved! and steps 4
- 8 are repeated for the entire library.
10. The amounts of each compound found are calcu-
lated using the peak areas, relative response
factors, and the data output in a tabular for-
mat .
The expected retention time, best retention time, PURITY,
FIT, library entry number, number of peaks found by sesarch, and
number of peaks quantitated are also output for each compound.
8-3 Complications with GC/MS Analysis
1. Certain compounds, such as bischloroethoxymethane,
produce poorly diagnostic El mass spectra and some-
times are falsely identified by reverse library
searches.
2. Some isomeric pairs of compounds, such as phenan-
threne/anthracene, may not both be detected if the
retention times are greatly different from expected
values and the wrong member of the pair in the same
search window gives a better FIT than the other.
3. Single mass quantitation is not very sensitive for
many of the compounds. This is especially serious
for those that undergo extensive fragmentation, such
as the pesticides. Also interferences at the same
mass may cause significant errors in some cases.
140
-------
By selection of window sizes and FIT/PURITY criteria, one
can bias the data analysis program in favor of false negatives or
false positives. As a matter of choice, we have chosen the lat-
ter. This produces an output which must be edited to remove
artifacts. These occur when multiple peaks are assigned the same
identity (not infrequent for isometric or homologous compounds)
and when the spectrum being searched for contains significant
components in common with the background. The latter case can
produce a positive where no peak is discernable. Compounds prone
to this latter error include the chloroethers, di-nitrotoluenes,
and dimethyl nitrosamine. For these compounds, FIT criteria must
be stricter and should not be accepted blindly. Chromatographic
behavior must be relied on to a greater extent in deciding whe-
ther to accept or reject a positive identification.
Examples of potential and actual problems in automated data
analysis will be discussed in conjunction with actual analytical
results.
141
-------
SECTION 9
PROPOSED QA/QC PROGRAM FOR POTW SAMPLES
The elements of this proposal are derived from the following
key EPA documents: a November 1978 results summary of the Cin-
cinnati POTW sources pilot study QA/QC program (conducted by
Arthur D. Little, Inc.); an Arthur D. Little Company handout pre-
pared for an EPA contractors' meeting on method development March
9, 1979; "Recommended Sediment and Sludge Sample Collection Pro-
cedures for Priority Pollutant Analysis," Addendum to Sampling
and Analysis Procedures for Screening of Industrial Effluents for
Priority Compounds (March 1979, EPA - Cincinnati ENSL documents);
and BAT Screening Protocols.
QA/QC consists of the following elements: contamination
control, containment/recovery of sample, and instrumental cali-
bration. For each element, one phase of the QA/QC program is
needed. Contamination control is addressed by carefully defining
materials and cleaning procedures for all sampling and prepara-
tion materials, and is monitored by blank determinations. Field
blanks consist of distilled, organic free water samples exposed
to the same glassware and manipulations as a real sample. Lab
blanks consist of an aqueous blank run through the extraction/
cleanup steps. Containment/recovery is also dependent on sampling
and handling technique and is monitored by recovery standards
spiked into actual or blank samples. The recovery standards may
be model compounds ("surrogates") or mixtures of the actual
priority compounds. Instrumental calibration is ensured by the
use of external standards to tune instruments uniformly and
internal standards to provide cross checks detecting losses
during injection or in procedures occurring between addition of
separate standards, as well as monitoring the integrity of each
internal standard.
Figure 9-1 shows a schematic representation of the use of
various types of standards to monitor QA/QC for different seg-
ments of the analysis. The inclusion of specific, noninterfering
compounds to provide QA/QC information requires only minimal
effort for GC/MS analysis, and is therefore a preferable alterna-
tive to parallel analyses of samples unspiked and spiked with
priority pollutants.
The actual structure of a QA/QC program has two logical
phases — initiation and maintenance. In the initiation phase,
the analysis method is verified by repeated determinations and is
shown to be statistically reliable. Laboratories just beginning
to follow EPA methods, or applying alternative procedures not yet
in routine use, will determine what, if any, experimental prob-
lems exist during the initiation phase.
142
-------
ANALYTICAL STAGES:
SAMPLING -
EXTRACTION
CLEANUP
CONCENTRATION
VIAL ING
INSTRUMENTAL
ANALYSIS, -
1 I
CONTROL METHOD:
(External to Sample)
In QA/QC Sample
IN EVERY SAMPLE
(Blank)
(Spiked
Water)
PP Spike
RECOVERY
STANDARD
CONCEN-
TRATION
RECOVERY
STD
INTERNAL
(Tuning,
Calibration
Standards)
QUANTI-
TATION
STANDARDS
Figure 9-1 Use of Standards and Spiked Compounds
143
-------
EPA has suggested a 12-fold initiation program involving six
sets of replicate determinations of surrogate spiked and priority
pollutant spiked samples, with three concentration levels of the
spikes. This program provides enough repetition for statistical
validation, but is inconvenient in that it does not permit many
real analyses to take place concurrently. A reasonable modifica-
tion would be to perform the different spike concentration repli-
cates on different (but preferably similar) samples. This would
permit three real analyses rather than one. The necessity of
determining recoveries at three concentration levels, rather than
two, is also debatable. It is the extremely low concentration
range where QA/QC is most important, and most difficult. Deter-
minations at 1 ppb and 100 ppb might be acceptable in lieu of the
prescribed 2x, lOx, and lOOx spikes.
Maintenance of QA/QC involves specific analyses to "measure"
known spike concentrations. The EPA proposal for a routine QA/QC
maintenance sample is: 1) the unspiked sample, 2) a spiked sam-
ple, 3) a replicate spiked sample, 4) a spiked distilled water
sample, and 5) a system blank. If one sample in 10 is a QA/QC
sample, then 14 analyses will be required to produce 10 sets of
real data (40%). The following modification is proposed:
each sampling event needs a field blank and, if 5 samples are
taken on one day or at one time or with one set of glassware or
reagents, a blank should accompany this set. The need for repli-
cate analyses to demonstrate reproducibility could be met with
suitable recovery compounds in the (sample and sample + spike)
pair of analyses. The choice of what type of sample to use for
QA/QC (influent, sludge, etc.) will significantly effect the
final recoveries seen, since background varies substantially
among sample types. Therefore, the importance in appropriate
model compounds to provide recovery QA/QC information on each
sample cannot be over-emphasized. At present, the choices of
available surrogates is limited. Table 9-1 presents the EPA
recommendations, as well as those in use at the University of
Washington. A satisfactory set of model compounds should repre-
sent the range of chemical and physical behavior of the priority
pollutants, and may need to contain specific models for difficult
(reactive) compounds as well. Perfluorinated compounds have sub-
stantially different physical properties from their perproteo
counterparts but, together with a limited number of deuterated
and C-13 labelled priority compounds, presently are all that is
available. Specific classes of priority compounds, such as
phthalates and halogenated ethers, have no model currently avail-
able. As better sets of model compounds not present in the envi-
ronment are developed, appropriate reductions in the number of
spiked samples could be achieved, with an increase in QA/QC.
One example of the use of multiple compounds for recovery
and quantitation is the volatile recovery standard currently in
use. This standard consists of nine stable isotope-substituted
priority compounds: chloroethane-d5; 2.2-dichloropropane-d6;
144
-------
PURPOSE:
COMPOUND
COMPOUND:
(EPA)
-o.
en
COMPOUND:
(U of W)
MS Tuning
W-
F5Br0 (VOA)
F5Br0
GC Perform. Internal Internal Recovery
Quan.Std Quan.Std Standard
VOA Extract VOA
Benzldlne BrClCH. D._- none
+ Anthracene
Aldrln
Recovery Concent. Reference
Standard Recovery Internal
Extract Standard Standard
Adds: none
F500H
0-F00H
Neutrals:
Fio-
blphenyl
o-Fluoro-
AnlUne
Priority "gCl?- DRNaphth- DgChloro- E°A D.DIchloro-
Pollutants propane alene ethane COMPOUNDS* benzene
D8to1uene D10Phenanth- *1™™~ ^J
Bromoform _ po""-)- DgBenzene
'Dl 12 " D,Aceto-
Jn1tHle
D.Dichloro-
benzene
none
Hexamethyl
benzene
Table 9-1 Standard Compounds for QA/QC
-------
chloroform-d; benzene-d6; toluene-d8; acrylonitrile d3; bromo-
form-d; and dichlorobenzene-d4. (The underlined compounds are
GC quantitation standards; the rest are included for recovery
data and to cross check the quantitation standards).
In the sampling phase for the current project R806102-01,
the proposed QA/QC program consists of: a) one field blank per
sampling occasion (per plant sampled), b) one QA/QC sample per
two plants (approximately 1 in 10 samples), c) recovery compounds
to be used in every sample, d) use of recovery compounds to pro-
vide replicate verification rather than a second spiked sample
(the second spiked sample will be taken and extracted, and the
extracts archived), e) an expanded set of standards/recovery
standards for VGA as shown in Table 9-1, f) one blank per each
VOA analysis, g) replicate VOA analyses for those samples indi-
cated by poor recovery of spiked standards, and h) expansion of
recovery standard list and eventual reduction of frequency of
spiking to 1 in 20 samples.
146
-------
SECTION 10
ANALYTICAL RESULTS OF POTW SAMPLES
10-1 Purqable Organics
Of the different analyses, the VOA analysis is less prone
to false identifications, and to losses in general. This is
because 1) the sample handling is minimal, 2) the purge and trap
process is fairly selective, so the complexity of the chromato-
gram is less than for an injected sample, and 3) the compounds
themselves are generally more stable. An exception to the last
could possibly be the alkenes (vinyl chloride, acrolein, and
acrylonitrile) if the pH of the sample is extreme.
The analysis conducted at the University of Washington was
somewhat altered from the standard Bellar/Lichtenberg procedure.
As has been reported, the inclusion of additional trapping media
along with Tenax has been unsatisfactory. Chromosorb 102 pro-
duced a substantial alkylated aromatic background when heated
even modestly (not above 150°C in the University of Washington
experience, and even up to 100°C as reported by GIT). Although
this does not pose a problem for analysis of priority purgables,
it does interfere with priority aromatics, which are detected in
both the VOA and base/neutral extract. Silica gel increases the
detained water from purging to the point where analysis by capil-
lary GC is impossible. Therefore, the data from the Seattle,
Atlanta, and Oakland plants was obtained using Tenax GC alone as
the trapping medium. The most volatile organics, under the
experimental conditions used are very inefficiently trapped, and
2 - 5% of the most volatile recovery standard, deuterated chloro-
ethane is usually recovered. This data will therefore not accu-
rately reflect the presence of dissolved gases. Beginning with
dichloropropane, the trapping efficiency of Tenax GC, combined
with the improved sensitivity of the of the capillary analysis,
gives consistantly good results. A recent improvement developed
at the University of Washington will substantially increase the
sensitivity for the most volatile compounds, giving at least 50%
recovery of vinyl chloride by slightly chilling the Tenax GC
alone by cold air. Initial tests with closed-loop stripping
shows that late eluting compounds are better recovered.
The data analysis for VOA is performed by dividing the
priority purgables into three groups, according to retention time
on SE-54. Three of the nine deuterated standards are selected to
be internal standards (used to compute expected retention times
for the analyte compounds based on relative retention of the com-
pound vs standard in calibration analyses). The three standards
normally selected are: d4-2,2-dichloropropane (early eluting),
d8-toluene, and dl-bromoform (late eluting). Because the stan-
dards are purged and trapped along with the sample, they too are
subject to matrix effects and efficiencies of purging and trap-
147
-------
ping. Thus they are recovered with varying efficiency. A single
analyte quantitated against two internal standards will vary by 5
- 10% ordinarily, and by more if one or the other standard is
recovered more or less than usual. As the table shows, varia-
bility is greatest for extremely low boiling compounds (d5-chlo-
roethane) and extremely late eluting compounds (di-bromoform and
d4-dichlorobenzene). Presumably, the former trap poorly while
the latter purge poorly (and chromatograph poorly). All quanti-
tation values are therefore connected to reflect a single quanti-
tation standard (2,2-dichloropropane). The full data, as
reported in the Appendix, reflects the reproducibility of this
analysis. The increased MS scan rate means that AT is reported
in increments of 0.5 seconds. Typical RIC traces for both raw
sewage and digested sludge are shown in Figures 2-12 and 10-1.
10-2 Neutral Extractables
The particular problems of extractable analysis are of
several types: 1) chemical loss or degradation of the particular
compounds in the environment of a particular sample, 2) losses in
handling due to chromatographic adsorption, evaporation, and
handling errors; 3) contamination; 4) chemical reactions asso-
ciated with the analysis (upon acidification, in the GC injection
port, or in the instrument); and 5) errors in data processing.
Of these, the majority must be considered nonsystematic and
therefore not addressed by standard analyses, spiked analyses,
etc. Large numbers of analyses will indicate the statistical
frequency of these problems, but do not allow one to detect them
in an individual sample. Therefore, the first line of defense in
discovering artifacts is careful scrutiny of the data. An exam-
ple of 1) is the chemical attenuation of dlO-anthracene. When
this compound is used as an internal (quantitation) standard in
some samples, the quantities of compounds found appear to rise as
the sample ages. When other reference compounds are also present
(hexamethyl benzene, for example) the dlO-anthracene is seen to
diminish relative to them over time. This can also be observed
in samples that contain phenanthrene, but almost no anthracene
itself. Since these compounds arise from the same sources and
are usually found together, the absence of anthracene is probably
a sign that it is reacting. One further example is the dinitro-
toluenes. When recovery of these compounds from spiked samples
dropped off, the MS response factors for the last several months
were examined and found to decrease steadily, unlike other com-
pounds in the calibration standard. If the compounds undergo
reaction in a sample mixture in organic solvent at -10°C over
time, then by implication the same process can occur in environ-
mental samples.
Examples of handling losses will be found in the QA/QC data
for Atlanta. Losses occurring prior to extraction will only be
indicated by unusual appearance in the chromatogram (and only in
extreme cases). Adsorption losses will discriminate against the
148
-------
n
SCAN
COMPOUND
1602
1632
1714
1803
1765
1804
2222
2755
dichloromethane
1,2-dichloroethene
trichloromethane
tetrachloromethane
1,1,1-trichloropthane
benzene
methylbenzene
tetrachloroethene
ethyl benzene
1599
12:39
2890
15:40
2560
2a:5a
Figure 10-1 RIC Trace of Purnahles in Seattle-Renton Primary
and Waste-ActivateH Sluclne
-------
high retention time peaks; evaporative losses will show attenua-
tion of early eluting peaks relative to later eluting ones. At
the time of extraction, surrogates and stable isotope marker com-
pounds are introduced into the sample; recoveries of these and
later standards (as indicated in the preceding QA/QC section)
also indicate losses in handling. For the first three plants,
these standards were not yet available.
Contamination is a continuing problem. Blank analyses and
regular analyses indicate intermittent phthalate contamination
and occasionally dichlorobenzene contamination. Blanks have been
run on all chromatography materials, solvents, glass wool, glass-
ware, etc., and chromatographic materials as well as drying agent
are soxhlet extracted prior to use. Intermittent contamination
still occurs and is recognizable primarily by 1) observable quan-
tities of phthalates and 2) the relative levels of the different
phthalates present. System blanks run with each batch of samples
also can identify some contamination problems.
Data processing errors are infrequent for most compounds and
are ultimately recoverable when they do occur, provided that the
problem is identified. In terms of the data from the first three
POTW sites, data analysis errors are primarily confined to 1)
false positives for haloethers and dimethyl nitrosamine and 2)
misidentification of isomeric pairs of PAHs. Familiarity with
retention behavior of the neutral organics helps to correct the
latter problem. Typical RIC traces of the neutral fraction of
raw sewage and digested sludge are shown in Figure 10-2 and
Figure 10-3.
10-3 Pesticides
The pesticides have been quantitated by two separate
analyses: GC/MS and GC/EC. However, the response for these com-
pounds by EI-MS is such that the electron capture analysis was
the only one to find these compounds, except in the cases of
spiked samples. The quantitation by EC was performed using abso-
lute instrument response, although future analyses will employ
decafluorobiphenyl as an internal standard. The significant dif-
ficulties with this analysis are those associated with any GC
method: qualitative identification and proper integration. The
data reported in the appendix for these compounds, therefore,
includes retention time differences between standard and sample
(within 2 seconds) and also indicates unresolved peaks or other
integration difficulties. Typical traces for pesticides in raw
sewage and digested sludge are shown in Figures 10-4 and 10-5.
10-4 Phenolics
The acidic priority compounds are the most poorly handled in
the initial set of analyses. The possible difficulties here
were: 1) poor extraction (matrix effects), 2) variable efficacy
150
-------
Figure 10-2
RIC Trace of
Seattle(Renton)
Raw Sewage
SCAN
COMPOUND
706 bis(2-chloroethyl)ether
730 1,3-dichlorobenzene
744 1,4-dichlnrobenzene
789 1,2-dichlorobenzene
829 bis(2-chloroisopropyl)ether
865 N-nitrosodi-n-propylamine
1061 bis(2-chloroethoxy)methane
1099 naphthalene
1638 acenaphthylene
1884 fluorene
1657 dimethylphthalate
1702 acenaphthene
SCAN
COMPOUND
1911 diethylphthalate
1957 N-nitrosodiphenylamlne--
2225 phenanthrene
2232 anthracene
2504 di-n-butylphthalate
2658 fluoranthene
2733 pyrene
3034 butylbenzylphthalate
3174 benzo(A)anthracene
3188 chrysene
3261 bis(2-ethylhexyl)phthalate
3540 benzo(B)fluoranthpne
\
9
4068
pr. £.?
•
Figure 10-3
RIC Trace of -
Seattle(Renton)
Combined Sludge
2000
3660
-------
:f
S&
skx
*
TIME
COMPOUND
23.14
24.87
26. SB
34.65
34.63
34.66
41. S3
alpha-DHC
llndane
chlordene
dleldrln
ilphi-chlordane
ilphi-endosu)fan
methoxychlor
Figure 10-5 GC Trace of Pesticide Fraction, P.en'ton (Seattle) Sludge
S.
;-rl
i
TIME COMPOUND
TIME COMPOUND
23.14 alpha-BHC 33.73
24.88 llndane 34.67
25.0? beta-BHC 35.14
28.25 heptichlor 35.S8
31.86 heptachlorepoxide 37.00
32.99 gairma-chlordjnt 38.CC
33.44 tlpha-endosulfan 42.19
alpha-chlordine
dieldrfn
P.P' ODE
endrln
p.p' ODD
P.P1 ODI
ml rex
Figure 10-4 GC Trace of Pesticide Fraction, Rcnton (Senttle) Row SCM/.-IRC
-------
of derivatization, 3) poor GC behavior, and possibly 4) chemical
instability. Application of advanced columns materials available
after October 1, 1979 have revealed that poor gas chromatography
and chemical instability were the principal causes. Figures 10-6
and 10-7 present analysis of Renton raw sewage analyzed by SE-54
glass and fused-silica SP 2100, respectively. The data reported
for recovery in Table 10-7 (Section 10-5) are presented as SE-54
values in parentheses with the later SP 2100 values following.
Because of the recent availability of these new GC columns,
approximately 4 months elapsed between derivatization and final
analysis by SP 2100, during which time the samples were stored at
-10 degrees centigrade. The probability that chemical instabi-
lity is responsible for the uniform but low recovery is indicated
by the fact that three subsequent QA/QC studies on raw seware
(spiked at 20 ppb) and one on activated sludge (spiked at 200
ppb) showed recoveries for the priority phenols of 91.8%, 88.5%,
91.4%, and 81.6%, respectively, with a relative standard devia-
tion of no more than 25%. The elapsed time between derivatiza-
tion and analysis for these samples did not exceed 3 weeks.
The results reported in Table 11-11, 11-12, 11-13, and pages
338-352 in Appendix 2 are based on data from earlier techniques
(SE-54). These samples hve been re-analyzed and the improved
results will be reported in a subsequent quarterly research
report.
10-5 OA/OC Data
Tables 10-1 to 10-3 list individual QA/QC studies for base/
neutral recovery studies for each of the first three POTW sites.
The recovery data for these and three other samples (two sedi-
ments and one tissue) are summarized in Tables 10-4 and 10-5.
The per compound results are presented in Table 10-6. Among
these, the Atlanta sample clearly suggests evaporative losses due
to overheating, while the tissue sample shows high molecular
weight discrimination, probably due to matrix effects in extrac-
tion and/or to adsorprive losses. The variability on a per sam-
ple and on a per compound basis is higher than desirable (an ave-
rage relative standard error of 59% per sample and 43% per com-
pound, computed without including zero recovery values). The
initiation of the recovery monitoring program discussed earlier
should help to substantially reduce this variability.
The recovery samples for pesticides are presented in Tables
10-6 to 10-10 and are summarized in Table 10-11. The values are
rather consistent with the base/neutral recovery data but a bit
better (probably due to the selectivity of EC for these com-
pounds) . The average relative standard deviation was 38%. Those
compounds left blank are analyzed but not presently quantitated;
they will be added retroactively.
153
-------
* sss
5*
7*
M?
TIME COMPOUND
26.50 Hexamethylbenzene
Figure 10-6 Phenollcs in Renton-Seattle Raw Sewaqe.
en
SCAN COMPOUND
1202 phenol
1579 2-nltrophenol(methylated)
1954 pentachlorophenol (methylated)
T 1 T
Fiqure 10-7 PhenoUcs In Renton-Seattle Raw Sewage, Reanalyzed With Fused-Sillca GC/MS
-------
_ . , ,rt , QA/QC RENTON
Table 10-1 BASE 4 HEUTRAL ETTRACTABLES
QA/QC
ANALYSIS REPORT
sample: Renton-Seattle Raw Sewage
i-ab: spiked at 10 ppb
Sample Size:
late Sampled:
Ouantitatioc Standard:
Ouantitation Method:
COMPOUND
S-NITROSODIMETHYLAMINE
31 S (2-CELOROETHYL) ETHER
U,3-)DICHLORDBENZENE
1 , 4-D1CHLOR08ENZENE
(1,2-)D1CELOROBENZENE
31S(2-CHLOROISOPROPYL)ETHER
EEXACHLORDEffiANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHYOXY)METHANE
1 ,2 ,4-TRICELOROBENZENE
NAPHTHALENE
K EXA CHLORO BUTADIENE
2 - CHLORO-N APHTHALEN E
ACENAPHTHYLENE
D1METKYLPETHALATE
2 ,6-DINITROTOLUENE
ACENAPHTHENE
2 ,4-DINITROTOLUENE
FLUORENE
D1ETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
X-NITROSODIPHENYLAMINE
i-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
fLUORANTHENE
PYRENE
BUTYLBEN ZYLPHTHALATE
BEN ZO (A) ANTHRACENE
CHRYSENE
3 , 3 ' -D1CHLOROBENZIDENE
BI S ( 2 -ETHYLHEXYL ) PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO (B) FLUORANTHENE
BENZO (K) FLUORANTHENE
BENZO (A) PYRENE
INDENOd, 2. 3-CD) PYRENE
DIBENZO(A.H) ANTHRACENE
BENZO (GHI)PERYLENE
CHLOROPHENYL, PHENYL ETHER
H EXACHLOROC YCLOPENTADI EN E
BLANK
1.53
UN SPIKED
0.069
i 0.557
3.66
4.83
0.321
^ 0.046
0.126
I 0.207
1.180
_._
0.003
0.515
0.182
L 0.063
7.44
\
0.14
0.01
3.01
0.02
0.01
2.59
SPIKED
6.91
15.38
19.12
14.83
8.96
6.33
20.44
10.49
13.36
10.90
12.97
6.57
9.58
15.60
13.71
4.04
4.80
13.18
6.98
4.36
7.69
6.45
B.99
_ — •
11.11
0.62
2.37
__ _
_ —
___
- —
SPIKED
7.09
13.35
16.77
13.21
8.88
7.46
21.62
0.24
10.35
13.65
__-
9.08
13.62
6.15
14.34
18.37
13.76
10.75
14.30
7.07
6.32
14.66
8.97
4.87
9.38
9.58
13.42
10.40
9.24
7.99
36.93
12.99
3.23
2.39
___
8.73
7.38
STD
8.16
13.74
12.18
7.71
8.36
9.96
19.04
^"— —
9.45
12.04
12.94
19.08
5.68
11.06
20.80
11.07
11.61
12.93
22.98
7.16
14.77
13.05
11.47
9.84
11.604
13.44
8.30
6.33
2.78
11.33
10.21
1.355
1.25
2.40
2.26
1.15
I REC
El
84
108
127
130
—
107
64
107
—
109
101
__
84
68
108
85
75
0
0
48
18
—
67
89
52
38
48
55
67
NQ
176
NQ
—
—
65
175
NO
0
—
—
Z RZC
E2
86
93
106
109
—
106
75
113
—
107
104
—
70
71
100
128
86
124
93
53
31
—
88
99
68
42
65
82
100
94
146
287
—
376
127
238
191
0
—
386
642
blank-not found; NQ-detected but not quantltated; NA-not analyzed for.
155
-------
Table 10-2QA/QC ATLANTA
BASE & NEUTRAL EXTRACTABLES
QA/QC
ANALYSIS REPORT
saopie: Clayton-Atlanta Raw Sewage
Lab: spiked at 10 ppb
Saeple Size:
Date Saapled:
Quar.ritatlcra Standard:
Quantisation Method:
COMPOUND
K-NITRDSOD1METHYLAMINE
B I S ( 2 - CHLOROETHYL ) ETHER
(1 , 3-)DlCHLOROBENZENE
1,4-DICHLOROBENZENE
11 , 2-) DICHLOROBEN2ENE
B15(2-CKLOROISOPROPYL)ETHER
EEXACHLOROETHASiE '
K-SITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)ME THANE
1,2,4-iRICHLOROBENZESE
NAPHTHALENE
KEXACHLOROBUTADIENE
2-CHlORO-NAPHTHALENE
ACENAPHTHYLESE
DIMF.THYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORZNE
DIETKYLPHTHALATE
AZOEENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
Dl-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYBEN ZYLPHTHALATE
BENZO(A) ANTHRACENE
CHRYSENE
3, 3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
Dl-N-OCTYL PHTHALATE
BENZO (B) FLUORANTHENE
BENZO (K) FLUORANTHENE
BENZO (A) PYRENE
INDEKO( 1 , 2j 3-CD)PYRENE
DIBENZO (A, H) ANTHRACENE
BENZO (GHI)PERYLENE
CHLOROPHENYL, PHENYL ETHER
HEXACHLOROCYCLOPEKTADIENE
BLANK
10. 1)
(.05)
(.16)
(.02)
(.05)
(..04)
(.55)
(.01)
'
(.33)
3.77
(.07)
(.11)
(.95)
UNSPIKED
—
—
3.149
13.939
63.858
—
—
0.120
.613
10.941
—
,_ —
.252
—
—
.884
—
1.720
1.36
—
—
—
__
3.24
2.92
12.91
0.06
0.13
17.88
—
—
—
—
—
—
—
—
—
—
—
SPIKED
—
4.03
3.63
10.21
44.23
.71
J.61
6.76
.12
2.64
5.21
—
7.45
9.47
4.83
—
13.48
—
11.18
12.87
7.05
—
3.73
7.21
16.41
4.73
31. 8R
7.91
10.74
44.42
5.71
5.97
—
41.71
10.28
1.53
1.13
—
0.09
2.57
2.86
EXPECTED
—
7.06
16.37
14.89
B.5U
—
. 1^.40 ..
o . 6 1
21.11
__
10.53
12.28
—
14.45
21.36
6.13
14.66
21.60
14.93
11.24
11.25
16.03
—
7.75
19.44
13.49
NQ
—
13.66
18.73
8.45
12.85
10.48
—
15.75
19.43
3.53
2.13
6.67
—
6.94
6.6J
I REC
57
(3)
(<0)
l«)
(0;
(5« ;
(31)
-- 1
(19)
(<0)
—
52
43
79 1
—
58
—
84 I
102
44
— -
4B
37
98
—
—
57
57
314
44
57
—
265
53
43
53
—
—
37
* J
blank-not found; Undetected but not quantitated; NA-r.ot analyzed for.
156
-------
Table 10-3
QA/QC
ANALYSIS REPORT
Sample:
Lab:
Sample Size:
Date Sanpled:
Quantication Standard:
Quantitat ion Method:
QA/QC OAKLAND
BASE 6 NEUTRAL BCTRACTABLES
EBMUD Oakland Second. Effluent
spiked at 10 ppb
COMPOUND
N-N ITROSODLMETHYLAMINE
BI S (2-CriLOROETHYL ) ETHER
( 1 , 3- ) DI CHLOROBENZENE
1,4-DICHLOROBENZENE
(1 , 2-)3ICHLOROBENZENE
BISC2- CHLOROISO?ROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMDJE
KITRC3ENZENE
E:S(2-CELOROETHOXY)ME THANE
1,2,4-TRICHLOROBENZENE
KAPHi.-.AL^E
ID-IXACHLOROBUTADIENE
2-CHLORO-NAPHTHA1ENZ
ACENAPHTHYiENE
DIMITKYLPHTHALATE
2,6-DINITRDTOLDENE .
ACENAPHTHENE
2, 4 -DIN ITRO TOLUENE
FLUOREN'E
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITRQSODIPHENYLAMINE
4-3ROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENAKTHRENE
ANTHRACENE
DI -N -BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYBENZYLPHTHALATE
BENZOC A) ANTHRACENE
CHRYSENE
3, 3'-DICHLOROBENZIDENE
BI S (2 -ETHYLHEXYL ) PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO (B) FLUORANTHENE
BENZO (K) FLUORANTHENE
BEN7.0(A)PYRENE
INrjENO(l,2,3-CD)PYRENE
ETBp;:0 (A, H) ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL, PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
BLANK
0.006
0.003
0.005
6.24
UNSPIKED
O.AO*
0.41
2.75
1.34
0.27
—
0.10
___
_ —
0.32
5.99
SPIKED
5.78
6.13
7.74
5.28
2.H6
5.87
15.41
_ — :
5.33
8.38
9.16
11.77
3.06
8.58
14.29
4.51
8.27
3.51
7.93
. —
4.37
8.19
5.72
3.74
4.71
6.53
8.94
0.61
4.49
4.29
___
7.09
4.17
1.11
1.13
0.11
2.28
2.26
EXPECTED
8.16
13.74
12.18
7.71
8.36
9.96
19.04
_ —
9.45
12.04
12.94
19.08
5.63
11.06
20.80
11.07
11.61
12.93
22.98
7.16
14. 77
13.05
11.47
9.84
11.604
13.44
8.30
6.33
2.78
11.13
10.21
1.355
1.25
2.40
2.26
1.15
Z R£C
71
42
41
51
34
58
81
___
53
70
71
62
54
78
69
41
71
27
35
61
55
44
33
*
56
67
07
71
154
63
41
82
90
101
197
blank-not found; NO^detected but not quantltated; NA-not analyzed for.
*probable artifact.
157
-------
'Jl
00
D8-NAPHTHALENE
D4-1,4-D1CHLOROBENZENE
HEXAMETHYLBENZENE
D10-ANTHRACENE
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-) DICHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALENE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2 ,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
OTHER:
SED 1
STDS
—
81
60
67
79
—
48
74
85
—
71
162
—
81
25
82
162
57
67
71
79.5 ± 35.6
SED 2
—
99
34
46
71
—
7
122
93
—
54
107
94
0
96
84
102
70
103
73.9 ± 36.3
TISSUE
—
84
68
77
77
—
43
108
72
—
81
84
—
68
73
77
52
79
49
82
73.4 ± 15.6
POTW:
RENTON 1
—
84
108
127
130
—
107
64
107
—
109
101
—
84
68
108
85
75
0
0
84.8 ± 38.2
RENTON 2
—
86
93
108
109
—
106
75
113
—
107
104
—
70
71
100
128
88
124
93
98.4 ± 17.4
ATLANTA
—
57
3
<0
4
—
0
54
31
—
19
0
—
52
43
79
—
58
—
84
37.23 ± 29.9
OAKLAND
—
71
42
41
51
—
34
58
81
—
53
70
—
71 .
62
54
78
69
41
71
59.2+14.6
Table 10-4 Summary of Neutral QA/QC Date
-------
Table 10-5 Summary of Neutral QA/QC Data.
en
10
D10-ANTHRACENE
D4-1,4-D1CHLOROBENZENE
OS-NAPHTHALENE
HEXAMETHYLBENZENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBQCENE (FR J3IPHENYLH YDBAZ1NE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BEN ZO(A) ANTHRACENE
CHRYSENE
3,3' -D1CHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
Dl-N-OCTYL PHTHALATE
BEN ZO(B) FLUORANTHENE
BEN ZO(K) FLUORANTHENE
BENZ0(A)PYRENE
INDENOd, 2,3-CD) PYRENE
DIBENZO(A.H) ANTHRACENE
BENZO(GHl)PERYLENE
X ± O
OTHER:
SED 1
STDS
57
67
71
81
45
—
71
72
77
—
54
73
60
110
21
—
—
contain *
contain *
160
—
197
—
73
398
99 ± 86
SED 2
79
68
107
103
95
—
116
99
105
—
—
114
114
53
167
164
—
195
173
275
291
211
—
200
155
144.2 1 65.2
TISSUE
40
35
60
66
48
—
67
66
60
—
—
73
75
<0
89
91
—
0
0
0
0
97
—
0
10
46.2 ± 34.7
POTW:
RENTON 1
54
47
54
48
18
—
67
89
52
38
48
55
67
*NQ
176
NQ
—
0
65
175
NQ
0
—
0
0
55 ± 49.7
RENTON 2
64
90
68
53
31
—
88
99
68
42
65
82
100
94
146
287
—
326
127
238
191
0
—
(386)
(642)
113 ± 85
ATLANTA
58
0
84
102
44
—
88
37
98
—
—
57
57
314
44
57
--
265
53
43
53
0
—
37
43
75 + 78
OAKLAND
50
29
52
27
35
—
61
55
44
33
contain *
56
67
07 .
71
154 :
1
63
41
82
90
0
—
101
197
63 ± 45
-------
BASE + NEUTRAL EXTRACTABLES
••
Table 10-6 QA/QC SUhWARY
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
(1,3-)D!CHLOROBEMZEME
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
3I5(2-CKLOROISOPROPYL)ETHER
HEXACHLCROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
B I S ( 2-CHLOROETHOX Y ) METHANE
"1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTAOIENE
2-CHLORO-NAPHTHALANE
ACE.'IAPKTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINlTROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZCBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHREN^
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZVLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
M-N-OCTYL PHTHALAtE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
IMDEKO(1,2,3-CO)
D1BENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
% Recovery
Not Spiked
80.4 ± 13
58.3 ± 35.8
77.7 ± 34.1
74.4 t 44.3
Not Spiked
57.5 ± 40.5
79.3 ± 25.9
83.1 ± 27.1
Not Spiked
70.6 ± 32.0
104.7 ± 31.4
Not Spiked
74.3 ± 13.5
57.0 ± 19.1
85.1 ± 18.0
80.7 ± 27.0
75.4 ± 16.1
70.2 ± 32.4
84.0 ± 12.5
68.6 ± 28.5
45.1 ± 24.3
Not Spiked
79.7 + 19.2
73±9 ± 23.4
72.0 ± 22.9
38.3 ± 5.5
55.7 ± 8.6
72.9 ± 20.9
77.1 ± 21.6
115.6 ± 117.9
102 ± 61.5
150.6 ± 88.2
Not Spiked
212.3 ± 113.0
91.8 ± 56.2
153.8 ± 87.1
156.3 ± 107.1
168.3 ± 62.2
Not Spiked
102.8 ± 69.9
160.6 ± 153.5
NA
NA
Detection Rate
7 of 7
7 of 7
6 of 7
7 of 7
6 of 7
7 Of 7
7 of 7
7 of 7
'6 Of 7
7
7 of 7
6 of 7
7 of 7
6 of 7
7 of 7
5 of 7
6 of 7
7 nf 7
7 of 7
7
7 of 7
7 of 7
7 of 7
3 Of 7
3 Of 7
7 of 7
7 of 7
5 of 7
7 of 7
5 of 7
4 of 7
5 of 7
6 of 7
4 of 7
3 Of 7
4 of 7
5 of 7
5 of 7
blank=not found; NQ=detectsd but not
A-probable artifact
quantitated; NA=not analyzed for
160
-------
QA/QC
ANALYSIS REPORT
Sample:
Lab:
Sample Size:
Date Sampled:
Quantitation Standard
Quantitation Method:
Table 10-7
ACID-EXTRACTABLES (PHENOLS)
Atlanta Oakland
% Recovery % Recovery
COMPOUND
PHENOL (M)
2-CHLOROPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DINITROPHENOL (M)
(SE-54)
(0)
(179)
(129)
(68)
(or
(41)
(0)
(102)
(16)
/ O 1 Q Q \
it M /
(45)
SP2100
14 5
76.5
1?.5
27.2
25.4
NA
22.0
8.2
NA
6.4
104 8
NO
(SE-54)
SP21CO
(n)
Ibi
13.7
32.4
(n)
2.9
26.0
(0)
(0)
(64)
(0)
(pq)
31.06
NA
20.2
9.9
MA
(4n) i? i
(67)
Ml)
°1 3
1/1 /I
blank=not found; NQ=cletected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
161
-------
Table 10-8
ANALYSIS REPORT RENTON QA/QC-1
Sample: PS92E1 Neutrals
Lab:
Sample Size:
Date Sampled
Quantisation Standard: absolute
Quantitation Method: GC/EC
HORKSHEET-QA/QC
PESTICIDES * PCB's
RENTON
PS90
COMPOUND
a-BHC
6-BHC +
Y-BHC (LINDA
6-BHC
P.P'-DDD
P,P'-DDE
P.P'-DDT
DIELDRIN
ENDRIN
ENDRINALDEHY
a-ENDOSULFAN
B-ENDOSULFAN
ENDOSULFANE
HEPTACHLOR
HEPTACHLOR E
PCB 1242"^
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016^
ALDRIN
METHOXYCHLOR
MI REX
CHLORDENE
OXYCHLORDANE
Y-CHLORDANE
a-CHLORDANE
BLANK SAMPLE 5™
0.125 4
19
10
6
3
11
4
8
DE
12
1?
SULFATE
w*- EXPECTED
L 1st
.45
.041
.985
.614
.701
.086
.607
.143
70
Ifi
NQ
POXIDE .1757 8
61
5
24
12
12
6
19
9
14
7
7
12
16
.33
.69
.44
.75
.75
.53
.00
.07
HI
477
.08
.60
% RECOV.
81.1
77.1
88.3
51.9
54.8
56.8
51.2
57.9
Ifit; A
1R? fi
50.8
L NA
2
8
4.
*
3.
2.
.566
.99
683
61
79:
5
17
.81
.58
2.303
2.49
2.61
44.2
51.1
203.3
135.1
107.1
b1ank=not found; NQ=detected but not
peak; D=detected but not Integrated;
*coelutes with heptachlor epoxid
quantitated; NA=not analyzed for; M-merged
0=area obscured; I=improper Integration.
162
-------
ANALYSIS REPORT RENTON QA/QC (2) Table PESTICIDES + PCB's
Sample: PS92E2 Neutrals 10*9
Lab:
Sample Size:
Date Sampled
Quantitation Standard: absolute
Quantitation Method: GC/EC
COMPOUN D
a-BHC
B-BHC +
Y-BHC (LIN DANE)
6-BHC
P.P'-DDD
P,P'-DD£
P,P'-DDT
DIELDRIN
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN
6-ENDOSULFAN
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORDAE
OXYCHLORDANE
Y-CHLORDANE
o-CHLORDANE
BLANK SAMPI E SPIKE
OLWf, iMMCLt SAMPLE
0.125 5.649
28.091
20.218
12.911
6.96
20.74
8.45
3.88
NA
23.01
25.5R
0.18 17.42
16.04
NA
NA
NA
NA
NA
NA
NA
4.21
NA
14.70
8.59
NA
7.20
5.31
EXPECTED
5.33
24.69
12.44
12.75
6.75
19.53
9.00
14.07
7.43
7 dR
12.08
16.60
5.81
17.58
2.30
2.49
2.61
% RECOVERY
122.4
113.8
162.5
101.3
103.1
106.2
93.9
27.6
309.7
w\ R
14?. ft
96.6
72.5
83.6
373.0
289.5
203.8
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; undetected but not integrated; 0=area obscured; I=improper integration.
163
-------
Table
ANALYSIS REPORT ATLANTA QA/QC '0-10
Sample:
Lab:
Sample Size:
Date Sampled
Quantitation Standard: Absolute
Quantitation Method: GC/EC
COMPOUND BLANK
a-BHC
HORKSHEET-QA/QC
PESTICIDES + PCB's
SAMPLE SPIKE
iAWLt SAMpLE
2.93
EXPECTED
2.67
t RECOV.
1.09.9
B-BHC +
Y-BHC (LINDANE 0.13
6-BHC
P.P'-DDO
P.P'-DDE
P,P'-DOT NQ
OIELDRIN 0.07
ENDRIN 0.19
0.14 11.16
5.139
0.17 6.80
3.15
5.39
NO 4.38
7.76
12.35
6.22
6.38
3.38
9.77
4.50
7J)4
89.2
82.6
103.9
92.8
55.2
97.3
110.3
EN DRIN ALDEHYDE
o-ENDOSULFAN 0.03
B-ENDOSULFAN 0.02
13.313
8.85
7.43
7.48
179.2
118.3
ENDOSULFANE SULFATE NA
HEPTACHLOR NQ
HEPTACHLOR EPOXIDE NQ
NQ 4.07
8.26
6.04
8.30
67.3
99.5
PCB 1242 NA
PCB 1254 NA
PCB 1221 NA
PCB 1232 NA
PCB 1248 NA
PCB 1260 NA
PCB 1016 NA
ALDRIN
1.97
2.91
67.8
METHOXYCHLOR NA
HIREX NQ
CHORDNE 0.06
4.26
3.25
8.79
2.30
48.5
141.0
OXYCHLORDANE
Y-CHLORDANE
o-CHLORDASE 0.09
0.33 3.82
0.10 3.55
2.49
2.60
153.6
135.2
peak; undetected but not integrated; 0=area obscured; I=improper Integration.
164
-------
ANALYSIS REPORT OAKLAND QA/QC
Sample:
Lab:
Sample Size:
Date Sampled
Quantitation Standard: Absolute
Quantitation Method: GC/EC
HORKSHEET-QA/QC
PESTICIDES + PCB's
COMPOUND
a-BHC
B-BHC +
Y-BHC (LINDANE)
6-BHC
P.P'-DDD
P,P'-DDE
P.P'-DDT
DIELDRIN
ENDRIN
EN DRIN ALDEHYDE
or EN DO SUL FAN
6-ENDOSULFAM
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD ME
OXYCHLORDANE
Y-CHLORDANE
a-CHLORDANE
BLANK SAMPLE ^^E
0.13 4.09
0.16 15.54
5.40
.16 .15 4.78
2.30
.40 7.75
NQ 4.04
0.83 7.28
NA
0.01 0.04 11.67
0.04 0.14 9.20
4.14
NQ .40 7.65
NA
NA
NA
NA
NA
NA
NA
NQ 1.635
4.95
0.06 2.56
0.221 2.46
2.76
EXPECTED
2.67
12.35
6.22
6.38
3.38
9.77
4.50
7.04
7.43
7.48
6.04
8.3
2.91
8.79
2.30
2.49
2.61
X RECOV.
153.3
124.6
86.8
72.6
68.1
79.3
89.8
103.4
156.5
121.2
68.6
87.3
56.2
56.3
108.5
90.1
105.7
blank*not found; NQ»detected but not
peak; D*detected but not integrated;
quantitated; NA=not analyzed for; M=merged
0=area obscured; I=improper Integration.
165
-------
Table
ANALYSIS REPORT QA/QC SUMMARY- '°-12
, FIRST THREE PLANTS
Sampi e :
Lab:
Sample Size:
Date Sampled
Quantisation Standard: Absolute
Quantitation Method: GC/EC
COMPOUND
a-BHC
P-BHC +
Y-BHC (LIN DANE
6-BHC
P.P'-DDD
P,P'-DDE
P.P'-DDT
'OIELDRIN
ENDRIN
EN DRIN ALDEHYDE
a-ENDOSULFAN
e-ENDOSULFAN
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD BNE
OXYCHLORDANE
Y-CHLORDANE
a-CHLORDANE
NA
NA
NA
NA
NA
NA
NA
NA
NA
REN TON 1
81.1
77.1
88.3
51.9
54.8
56.8
51.2
57.9
165.4
162.6
NQ
50.8
44.2
51.1
203.3
135.1
107.1
WORKSHEET QA/QC
PESTICIDES -•• PCB's
REN TON 2
122.4
113.8
162.5
101.3
103.1
106.2
93.9
27.6
309.7
341.8
142.8
96.6
72.5
83.6
373.0
289.5
203.8
ATLANTA
153.3
124.6
86.8
72.6
68.1
79.3
89.8
103.4
156.5
121.2
68.6
87.3
56.2
56.3
108.5
90.1
105.7
OAKLAND
109.9
89.2
82.6
103.9
92.8
55.2
97.3
110.3
179.2
118.3
67.3
99.5
67.8
48.5
141.0
153.6
136.2
X (o)
116.7(29.95
101.2(21.8)
105.1(38.4)
82.4(24.8)
79.7(22.2)
74.4(23.9)
83.1(21.5)
74.8(39.1)
202.7(71.9)
185.9(105.8)
69.7(58.3)
83.6(22.4)
60.18(12.7)
59.9M6.2l
206.5M17.8)
167.0(85.9)
125.6M1.21
84.6(53.3)161.4(103.8)95.8(301.1)103.1(35.2)110.5(42.6)
overall
166
-------
The major cause of poor recovery for phenols (Table 10-12)
is apparently matrix-related. When spiked water recoveries are
run, the results are consistently higher than obtained in waste-
water. The prospects for improvement in this analysis are: 1)
use of new chromatographic columns which are described as elimi-
nating the need for derivatization, 2) a prompt, direct analysis
of phenols alone, probably by HPLC. This latter method is under
investigation at GIT, the former is being pursued at the Univer-
sity of Washington.
167
-------
SECTION 11
SELECTION OF SAMPLING SITES, SAMPLING PROCEDURES,
AND POTW REMOVAL EFFICIENCIES
The present study selected the municipal sewage treatment
plants in order to obtain a representative picture of the effi-
ciency of the plants to remove priority pollutants from raw sew-
age.
The amount of priority pollutants in municipal sewage is
expected to be influenced by the amount and type of industrial
discharge into the network. An initial compilation was therefore
made of the nature of the industrial water usage.
11-1 Water Use in Industry
Large industrial users, i.e. those using more than 38 gpm
of process and cooling water, utilized a total of 15,024 billion
gallons of water per year (U.S. Census, 1972). About half of the
water (49%) was subjected to different types of treatment to make
it suitable for subsequent use. Most of the water (60%) was
taken in through company water treatment systems employing fresh
surface water from rivers or estuaries, with 19% taken from salt
or brackish water, primarily for cooling purposes. The indus-
tries withdrew 11% from public water supplies and 10% from ground
water. The most common water treatment was softening, practiced
by 59% of the plants, followed by chlorination (36%), and ion
exchange (30%). While softening and ion exchange will remove
some of the priority pollutants already present, the chlorination
step will increase the number and concentration of low molecular
weight chlorinated hydrocarbons. Chlorination is most widely
used in the food industry, Standard Industrial Code (SIC)-20, and
the paper industry (SIC-26) where 52% and 46% of the plants prac-
tice it. Most of the intake w.ater is used for direct cooling
purposes (36% of intake water) followed by process water (25%),
steam-electric (13%), and boiler feed water (4%) , as listed in
Table 11-1. Industries that use a high percentage of their
intake for process water, and therefore produce a more polluted
wastewater, are paper (SIC-26), fabricated metals (SIC-34), and
lumber (SC-24) with 58%, 48%, and 48% of the intake used for pro-
cess water.
The water is reused on the average of 2.9 times before being
discharged, thus increasing the possibility of pollutant accumu-
lation. A high degree of reuse is practiced by SIC-36 (10 fold),
SIC- 37 (8.1 fold), and SIC- 28 (6.4 fold).
Most of the industrial wastewater is discharged (Table 11-2)
to streams and rivers (64%) and smaller percentages to^bays and
estuaries (16%), lakes and ponds (9%), and municipal sewers (7%).
The electrical and fabricated metal industries discharge as much
168
-------
Table 11-1 Percentage Use of Water for Different Purposes
All
20.
21.
22.
24.
25-
16.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39-
•
industries
Food
Tobacco
Texti le
Lumber
Furn i ture
Paper
Chemical s
Petroleum
Rubber
Leather
Stone
Prim. Metal
Fabr. Metal
Machi nery
Electrical
Transportation
Instruments
Mi seel laneous
u
0 i-
»4- 0)
4-1
k. Q
3
4-f
ro -
3 <"
in
SI V
in U
-
t m^
li- <
2
1
15
—
1
—
1
2
1
--
--
1
2
3
14
12
10
11
--
L.
0
V4- O)
C
u .—
0) —
4J 0
f3 O
^S <->
^ l_
V) 0)
L.
(/> i_ a>
to
I/I 4-*
O O >-
Q-3 *-
I- (D
3 -C 4->
0. in —
0) c
»- OJ
u. en
1
4
13
—
1
—
I
1
—
--
--
2
1
9
7
13
8
9
8
u
O
u-
U TJ
U 0)
4-1 0)
(0 Lk-
3
L.
.C 0)
a) n
«- 0
U- ca
4
7
13
—
12
—
4
4
9
--
—
5
2
10
5
6
10
10
9
V- l_
Q) O
4-> * U-
IQ
3 (/> U
(U U
-C U 4-1
i/> O ns t/>
— >- 3m
J^ Q- (U
U 4-J O
«D >- — O
k. O (D V.
OQ «4- CO Q.
1 1
__
__
__
1
1
--
-_
__
_-
169
-------
as 62% and 61% to municipal sewers, while petroleum, primary
metals, and paper industries rarely discharge to POTW's.
Less than half of the wastewater (43%) is subjected to
treatment (Table 11-3) before being discharged. Among the dif-
ferent waste streams, the highest degree of treatment is given to
the process water with 74% of that stream treated, with less
treatment given to used air conditioning water and boiler water
(32% and 32% respectively). Several industries, such as petro-
leum and primary metals, treat as much as 100% and 91% of their
process water, while transportation equipment and fabricated
metals treat only one third of that waste stream. The greatest
degree of treatment is given to wastes discharged to bays and
estuaries and to transferred water (65%), while the lowest treat-
ment is given to waste discharged to oceans (24%), POTW's (30%),
and ground water (30%). Some industrial categories provide very
little pretreatment, while others, such as petroleum and primary
metals, provide a higher degree of pretreatment (56% and 55% of
that waste stream).
The most commonly used treatment processes are primary
settling, used by 50% of the plants (Table 11-4), followed by pH
control (44%) for neutralization. Some industries almost all use
certain processes, such as surface skimming and flotation by 88%
of the petroleum industries, and pH control by 83% of the elec-
trical manufacturing plants. The highest degree of biological
treatment is given to wastes from textile, petroleum, and tobacco
industries. Additional solids removal by secondary settling or
sand filtration is not widely used, while chlorination of the
wastewater is half as often practiced as chlorination of the
intake water.
11-2 Priority pollutants in industrial wastewater discharged
to POTW's
Data compiled by the U.S. EPA Effluent Guidelines Division
in Washington, D.C. showed that the compounds most often found in
industrial effluents are ,bis(2-ethylhexyl), phthalate, chloro-
form, and dichloromethane with 42%, 40%, and 34% of the analyzed
samples reporting positive identification. The phthalate is one
of the most commonly used compounds and is present in most plas-
tics, chemicals, and finished products. The chloroform and
dichloromethane are likely the result of chlorination processes
practiced with the municipal water, intake water, or wastewater.
The next most common compounds, such as benzene (29%) , toluene
(29%), and phenol (26%) are used as feedstock for numerous other
chemicals. More than half of the wastewater samples contained
copper and chromium. The largest number of priority pollutants
were found in the effluent of organic and plastic industries
(106), followed by pesticide (71), iron and steel (57)^ petroleum
refining (55), and auto manufacturing (54).
170
-------
Table 11-2
Percentage of Industrial Waste Water Discharged to Different Categories
20. Food
21. Tobacco
22. Textile
2^. Lumber
25- Furni
26. Paper
27. Chemical
29. Petrol
30. Rubber
3). Leather
32. Stone
ries
CO
le
r
t ure
cal
leum
r
er
Metal
Metal
nery
rical
portation
uments
1 laneous
o
— u
•o 3
3 U
O. I/)
7
30
53
3
5
M ^~
-o
.* c
re o
-i a.
9
5
*
13
2
6
--
—
--
20
15
1
6
1
7
1
__
re
in k.
01 L-
— 01
U ^y ^.
re c c in
in 3 a 3 c
>. *^ oi o re
re »n o u L.
CD LU O t3 t-
16 1 1 1
5-65
.. .. <, ..
6 5 <1
17 1 <1 <1
25 - <1 1
7 --
-------
Table 11-3
Percentage Treatment of Waste Streams Discharged to Different Receptors
All
20.
21.
22.
2k.
25.
26.
28.
29-
30.
3T.
32.
33.
34.
35-
36.
37.
38.
39.
1 ndustri es
Food
Tobacco
Text! le
Lumber
Furn i ture
Paper
. Chemical s
Pet rol eum
Rubber
Leather
Stone
Prim. Metal
Fabr. Metal
Machi nery
Electrical
Transportation
Instruments
Miscel laneous
0
—
re >-
4-1 —
co cc.
40
31
--
67
38
—
56
28
50
21
39
27
41
39
38
41
25
61
28
"O
-* C
re o
_J Q-
45
58
--
87
0
—
67
56
--
--
--
3
41
--
78
33
3
0
—
I/)
0)
re c
in D re
>> 4J 0)
re in u
CO UJ O
65 24
8 100
__
__
__
__
52 46
67
0
100
—
0 0
76
—
1
100
0 0
__
__
•o
c
3
o
U.
u
30
53
—
--
26
--
89
0
100
7
—
21
4
54
11
14
6
0
--
nsferral
re
u
h-
53
0
--
—
--
—
15
100
26
--
--
59
3
0
—
--
0
--
—
_J
1-
o
i-
43
33
--
43
31
0
54
40
60
19
38
18
43
27
25
32
19
47
21
172
-------
Table 11-4. Percentage of Plants Using Certain Wastewater Treatment Processes
CO
All Industries
Food
Tobacco
Textiles
Lumber
Furniture
Paper
Chemical
Petrols
Rubber
Leather
Stone
Primary Metals
Fabricated Metals
Mechanical
Electrical
Transportation
Instrument
Miscellaneous
Io
o
1—
5320
1125
2
292
99
21
445
631
235
152
31
294
520
357
225
365
216
71
39
0
0) C
"*- E
CO CO
35
38
50
12
18
24
22
40
88
28
32
24
44
30
42
18
48
24
8
£
5
£
44
18
30
21
62
21
62
43
34
36
19
51
71
58
83
70
73
69
•r-
10
3
Cn
O
18
9
50
9
5
14
23
17
18
9
13
11
28
19
23
23
41
25
31
C
o
o
U-
11
18
4
9
10
11
7
28
3
13
3
7
6
11
3
22
4
10
C7>
>>.=
IO •—
E *->
•r- 4-*
i- 01
O- CO
50
36
100
34
52
48
71
61
71
38
64
50
61
43
39
40
55
44
35
10 C
U O
O IQ
i— TJ
O i-
oo o
36
35
100
60
47
24
44
43
56
28
29
30
29
19
20
14
25
27
13
IO C
C •—
O 4-*
Ol Ol
CO CO
21
15
100
30
14
24
24
26
40
14
19
18
24
17
16
19
19
21
22
5
3
41
6
3
6
6
7
6
8
5
7
6
9
6
8
i-
o
18
15
50
25
16
24
14
20
13
13
3
10
20
25
17
21
23
25
28
o
21
32
20
12
24
20
19
14
11
23
10
15
21
14
20
21
28
8
-------
The publicly owned municipal treatment plants receive
varying amounts of industrial wastewaters as shown in the 1978
EPA Need Survey which inventoried plants above 5 mgd. For exam-
ple, the 31 mgd St. Helens plant in Pennsylvania receives more
than 95% of its flow from industrial contributors, as does the
8.5 mgd Lyman plant in South Carolina and the 10 mgd Grand Rapids
plant in Michigan. For most plants, however, the percentage
industrial contribution does not exceed 15%. The surveyed plants
ranged in size from 5 mgd to the 800 mgd WSW plant near Chicago
while the median is around 12 mgd, as shown in Figure 11-1. Some
plants have high contributions of specific industries such as the
Modesto, California plant having high contributions of food
wastes; the Greensville, South Carolina plant having high textile
contributions; the Appleton, Wisconsin plant with high paper
waste contributions; and the Wilmington, Delaware plant with
large chemical waste contributions.
Plants receiving large amounts of industrial chemicals
usually do not meet the 20/20 or 30/30 effluent requirement.
However, there are several examples of discharging plants meeting
these requirements using advanced secondary or tertiary treatment
techniques. For example, the 25 mgd Decator, Illinois plant,
receiving 50% industrial waste, meets to 20/20 requirement by
usinmg pure oxygen activated sludge and a polishing lagoon.
11-3 City Selection for POTW Sampling
Data from the U.S. Department of Labor were used to
determine which cities had a high percentage of the working popu-
lation in the different SIC categories. The data in Table 11-5,
for example, indicate that as many as 28% work in transportation
equipment manufacturing in Kenosha, Wisconsin and 28% work in
primary metals in Gary, Indiana. In order to obtain a balanced
selection of twenty-five POTW's for the present study, one to two
cities were chosen for each industrial code category. The POTW
in the city with the highest percentage workers was then con-
tacted to determine whether the major industries were indeed dis-
charging into the municipal or county sewer system. Often, it
was noted that the major industries had their own treatment
plants, while the smaller industries in that code discharged into
the POTW. If the treatment plant did not receive the waste of
the major industries, the next city on the list in Table 11-5 was
selected and contacted.
The POTW selection also sought to obtain cities with varying
death rates as such cities with high incidence of cancers and
lung disease are expected to have a high number of priority pol-
lutants in their wastewater. The death rates have to be adjusted
for the age effect, as cities with a high proportion of older
people have a high death rate. The death ratio was therefore
developed representing the number of deaths per thousand inhabi-
tants per year divided by the percent of the population above 65
174
-------
1000
O EPA Need Survey of 586 Plants
A Present 25 Plant Study
73
O
CD
m
i—t
•z.
o
-H
t—«
J>
I—
~n
r-
O
-a
o
2
Figure
20 50 80 90
PERCENTAGE SMALLER THAN
11-1 Frequency Distribution Plot of Size and Percentaae
Industrial Inflow into POTW'S
175
-------
Table 11-5 Percentage of Employed Population
T-Jorking in Specific Industries
SIC
20 Food
22 Textiles
23 Textile
Manfact.
26 Paper
28 Chemical
29 Petroleum
30 Rubber
31 Leather
33 Primary
Metals
34 Fabricated
Metals
35 Machinery
36 Electricity
37 Transportation
Equipment
Modesto. CA 16.1%; Sioux City, IA 13.5%; Battle
Creek, MI 12.2%; Fayetteville, N.C. 11.9%; Cedar
Rapids, IA 8.0%; Green Bay, WI 7.3%; Salem, OR
6.5%
Greenville, S.C. 19%; Columbus, GA 12.3%; Char-
lotte, N.C. 11.1%; Augusta, GA 10%; Fall River,
MA 9.1%
Fall River, MA 20.2%; Eugene, OR 15.6%; Allen-
town, PA 9.3%: NE Pennsylvania Scranton, PA 9.1%
Appleton, WI 21.7%; Savannah, GA 6.6%; Greenbay WI 5.3%
Wilmington, DE 17.3%; Charleston, W.V. 12.8%;
Baton Rouge, LA 12.1%; Parkersburg W.V. 9.7%;
Waterbury, CT 8.9%; Pennsacola, FL 8.8%;
Perth Amboy , N.J. 8.5%; Terre Haute, IN 4.9%;
Chattanooga, TN 4.7%
Lake Charles, LA 6%
Akron, OH 14%; Tuscaloosa, Al 3.9%; Erie, PA
3.1%
Lawrence/Haverhill, MA/N.H. 5%; Brockton, MA 4.9%
Gary. IN 28.2%; Youngstown, OH 19.4%; New Bri-
tain, CT 18.3%; Saginaw, MI 13.1%; Canton, OH
11.8%; Pittsburgh, PA 11.4%; Muskegon, MI 10.8%
Hartford, CT 13.5%; Rockford, IL 10.5%; Water-
bury, CT 8.2%; Flint, MI 6.4%; Akron, OH 6.3%
Peoria, IL 23.2%; Cedar Rapids, IA 22.7%; Daven-
port, IA 17.2%; Racine, WI 16.2%; Muskegon. MI
13.5%; Erie, PA 13.4%; Battle Creek, MI 13%;
Rockford. IL 12.4%; Dayton, OH 11.3%; Milwaukee,
WI 9.7%; York, PA 9.4%
New Britain, CT 10.8%; Fort Wayne, IN 8.1%;
Anaheim, CA 7.2%
Kenosha, WI 28.1%; Wichita, KS 18.3%; Newport-,
R.I. 18.3%; Saginaw, MI 14.7%; New Orleans, LA
14.2%; Lansing, MI 14.2%; Detroit, MI 13.4%;
Ann Arbor, MI 12.4%; Seattle, WA 10.4%
176
-------
Sic Table 11-5 Continued
38 Instruments. Rochester, N.Y. 19.8%; Waterbury, CT 6.1%
39 Mining Wheeling, W.V. 10.8%; Johnstown, PA 9.8%;
Bakersfield, CA 7.3%; Providence RI 7.8%
177
-------
years. Cities with high death ratios are: Fayetteville, North
Carolina (1.24) with major food processors; Norfolk, Virginia
(1.0) with shipbuilding; Columbia, Georgia (1.01) with textiles;
and Fall Rivers, Massachusetts (1.01) also with textiles. Cities
with low death death ratios are Fort Lauderdale, Florida (0.50);
Palm Beach, Florida (0.53); Fort Meyer, Florida (0.51); and Bra-
denton, Florida (0.45).
The POTW selection was also based on size of the plants,
percentage industrial contribution into the network, and geogra-
phical location in order to obtain a representative range for
each. The size plants in the present study range from 3.75 mgd
in Lock Haven, Pennsylvania to 276 mgd in Washington, D.C. with a
median size of 35 mgd, which is about three times larger than the
national medium size. The percentage industrial flow ranged from
0% in Fort Meyers, Florida to 73% in Muskegon, Michigan.
The POTV7 selection was finally based on the type of
treatment processes in order to determine the efficiency of each
type. While the majority of the plants used activated sludge,
three use trickling filters, while two use aerated lagoons or
algal ponds. Two of the POTW's use land spreading to meet zero
discharge limits. Twelve of the twenty-five plants have combined
sewers and are expected to receive more PAH priority pollutants
from street runoff. The final selection of plants is listed in
Table 11-6 and reflect the above discussed characteristics.
11-4 Sampling Procedures of POTW's
The sampling gear utilized in the present study is depicted
in Figure 11-2. The unit was custom made by Mr. D. Tigwell,
instrument maker, and consists of a flow measuring component and
a sampling component. The flow is measured by an ultrasonic
probe which measures the height of the water level near an over-
flow weir. The flow meter converts the signal into a measure of
flow depending on the pipe configuration. The signal then enters
the computer, where it can be stored. The computer is programmed
to initial the sampling process sequentially, with the first raw
sewage sampler starting at tl and the second primary effluent
sampler starting at tl + Dl with D representing the detention
time in the primary sedimentation basin, etc. The samplers are
also shut-off in the same sequential fashion. The computer can
also be programmed to activate the sampler when the combined
storm flow, as a result of a rainstorm, exceeds a certain preset
flow change in a given time period. An ion selective probe (Cl,
NH4) can be connected to the computer via a potentiometer to cal-
culate total mass flow (volume times concentration) in a given
time period and to allow sampling according to mass instead of
the less accurate flow. The data in the computer can be dis-
played on the video screen. The computer signals are transmitted
by air to a receiver present at each of the four sampling sta-
tions to collect the raw sewage, primary effluent, secondary
178
-------
cm
POPULATION D.R. I.E.it
ZSIC
MOD
SEWER
TREAT.FAC.
COMMENTS
-J
10
—1
o>
cr
ft>
i
CT>
0
r+
n>
t/>
to
n>
n>
o
«-••
ro
Q.
«J.
3
r+
3"
O>
T3
-5
rt>
en
ro
3
r+
ro
en
0
_ j.
s
CO
c
-J
(D
«<
Fayettevllle.NC 226,000(152)
Chattanooga, 392,000(92)
Port Meyers, Ft 154,000(195)
Hamond (Gary), 543,000(57)
IN
Fort Wayne, IN 373,000(96)
Akron, OH 667,000(55)
Atlanta, 1,790,000(18)
GA
Winston 764,000(49)
Salem, NC
Lock Haven, PA 15,000(-)
Greenvllle.SC 525,000(70
Providence, HI 904,000(38)
Modesto, CA 223.000(]54)
Peorla, IL 354,000(100)
1.24 16.
(-)
.80 36.2
(38.3)
.51 5.3
Low (-)
.96 44.2
(36.2)
.78 35.1
(39.9)
.81 39.3
(36.9)
.85 21.6
(41.0)
.81 41.3
(42.9)
_
.85 41.4
.75 36.5
(39.3)
.74 19.4
(31.3)
.75 34.1
(40.9)
NA
8.3(22)
6.0(34)
4.7(28)
NA Low
28.2(33)
3.0(34)
8.26(37)
8.0(36)
4.56(35)
6.3(34)
14.0(30)
4.7(35)
3.07(37)
2.07(30)
9 other
ground (1)
11.2(22)
2.5(23)
19.0(22)
4.9(35)
4.1(23)
7.8(39)
3.2(22)
3.0(34)
3.0(35)
16.1(20)
2.8(34)
23.2(35)
4.5(33)
4.0(20)
11.5 25
(2)
39 65
(5)
5.0 0.0
(1)
35.7 26
(1)
36.7 14
(1)
78 13
(3)
90 6
25.8 54
(5)
3.75 381
25 23
(5)
65
(5) 38*
36 Seasonal
28 21Z
(5)
SEP Tert. 02 and Cl£
Filters
(Cross Creek) WTP
COMB Sec. , Act. Sludge
SEP Sec., Trickling,
Pure Oxygen, Act. Sludge
COMB Adv. Secondary
COMB Adv. Sec. .Filters, Chetn.
Add.
COMB Sec., Act. Sludge
COMB Adv. Prim. .Act. Sludge,
Bio. Nitrification
SEP Sec. Trickling, Act.
Sludge, Single Stage
Nitrification
SEP Sec. , Aeration
SEP Tert.incnJ.ing
Filter
COMB Sec., Act. Sludge
SEP Sec., Lagoon* ,
Land Treatment
Anaerobic Digestion
COMB Sec., Act. Sludge,
Anaerobic Digestion
Building RBC's and
Textiles, Rubber
(Kelly) Carglll.
Bo r den Chen. Plant
Feed Processing
High Death Ratio
Moccasin Bend VUTP
Lots of Chen. Plants
Only Laundry and
Restaurants; Lowest
Deatli Ratio
Steel
GR.Magnavox, Essex.
Lagoonlng of Lard
Oil for Wire Drawing
Gcodyear
R M Clayton WPCP
Archie El ledge
Plant.. R.J. Rey-
nolds (Food &
tobacco), Schlltx
has 2 pretreat.
lsgoonsd/10 of
flow)
BOD, SS. Cyanide.
and chemical
violations.
Paper Mill Input;
Textiles
E. Providence,
Jewelry, high
Nl.Zn, Cd.
Canning fro*
Aug. -Sept.
Gallo Vineries
Hlran Walker,
Cataplllar
Tractor
Polishing/Holding Ponds
-------
cm
POPULATION
D.R.
I.E.*
*SIC
Men
ZINP
SEWER
TREAT.FAC.
COMMENTS
to
cr
n>
o
o
3
3
C
00
O
Rochester. NT 970,000(37)
i - '
Springfield. MA 550,000(68)
(Chlcopee-
Rolyboke)
Lawrence, Haver- 270,000(132)
hill, MA
Oakland, CA 3,140,000(7)
(SF-Berk)
Seattle, WA 1,406,000(24)
Everett, WA
Allentown.PA 624.000(59)
Bethelehera-
Eaatnn.PA.NJ
Wilmington, JJE 518,000(72)
Washington, D.C. 3,021,000(7)
Rockford, IL 272,000(131)
Applet on, WI 284,000(124)
Kenosha, WI 123,000(228)
Muskegon, MI 178,000 -
.73 45.3
(39.5)
.76 33
(28.2)
(35)
.75 16.7
Non-Agrlc
Employ.
(44.)
.76 24.2
(40.4)
.75 45.7
(40)
.92 32.4
(39.3)
.91 6.6
(44)
.73 45.3
(41.0)
.70 36.2
(37.3)
.74 42.8
(34.3)
.86 43.8
(31.8)
19.8(38)
3.7(35)
2.97(36)
3.5(26)
3.1(35)
2.7(34)
4.96(31)
2.5(30)
2.3(35)
.42(30)
1.41(27)
10.4(37)
1.34(35)
1.53(30)
11.2(34-36)
9.4(23)
3.9(35)
3.8(36)
17.3(28)
1.4(27)
.4(30)
12.5(35)
10.5(34)
8.9(37)
12.7(26)
5.7(35)
3.6(27)
28.1(37)
5.0(34)
3.B(33)
5.29(34-36)
2.65(20)
3.57(31)
69
(2)
32
(2)
10.2
(2)
60.8
(2)
29.4
30
(4)
70
(4)
276.4
(2)
39
(1)
14
(5)
19
(1)
35
(1)
22 SEP Adv. Sec., Filters or
Addition!), Lagoons
38 COMB Sec., Act. Sludge
50 by
loading
33 COMB Sec. , Act. Sludge
16. SET Sec., Act. Sludge
Oxygen fed Act.
.06 COMB Adv. Sec., Act. Sludge
40 SEP Adv. Sec. with NH3-
N03 Tertiary
50 COMB Adv. Sec., Act. Sludge
32 manf.
18 chem.
0 SEP Act .Sludge Sec.
Chen. Addition
FeCl)
45Z SEP Sec., Act. Sludge
Aerobic Digestion
Vacuum filtration
35* SEP Sec., Act. Sludge;
Polymer, Ferric
Chloride addition,
Zimmerman Process ,
Vacuum filtration
46Z COMB Sec., Act .Sludge
Chem. Addition
(Pickling liquor)
Anne rob IcDlgest ion
73 SEP Aeration, Lagoons
Land Application
to grow corn.
Frank E Van Lare
Plant_, Kodak, Xerox
Brewery, Auto Suppoit
S25milllon In pre-
treatment since "72
Paper,Monaanto,
Textile, Drop Forges
Monsanto has set-
tling, acid neutral.
Bondlts
Tanning, Dyers
Paperboard ^re-
treats for fiber
recovery
East Bay Mud
Renton WTP
Kline Is. WWTP Pre-
treatment 2MCD Dyes;
3MGD Kraft, 1.5 MGD
Brewery , Fooda , Chem.
Plants, Batteries
Dupont does some
pretreatment
Blue Plains ban a
sludge program
Low Industry
ASMA Study
Member , cyanide
problems
Piper Mill
Canning
AMC, Eaton
Transmission
Anaconda Brass
Ocean Spray
High organic
waste, have
GC/MS system
-------
Symbols Used for Headlines of Chart:
Population (Ranking, 1977)
D.R. - Death Ratio(Death per 1000 per year)
* Population above 65 years
I.E.X « Industrial Employment (1970)
( ) » (Non-Agricultural Employment)
%SIC = 2 »* workers in SIC
( ) "SIC number
MGD " Plant Size Million Gallon/Day
(Effluent Category): 1 - 20/20 4 - 60/60
2 • 30/30 5 • 100/100
3 " 45/45
2IND = % Industrial Input (Usually by Flow)
SEWER: SEP • Separate COMB • Combination
TREAT.FAC. » Treatment Facility
Trickling Filters
Greenville, S.C. Fort Meyers, FL
Winston Salem, N.C.
Combined Storm Severs
Hammond, IN Providence, RI
Fort Wayne, IN Perth Amboy, NJ
Akron, OH Wilmington,DE
Springfield, MA Chattanooga, TN
Haverhill, MA Seattle, WA
Kenosha, WI Atlanta, GA
Lagoons and Ponds
Modesto, CA Muskegon, MI
Rochester, NY
Land Spreading (Effluent)
Modesto, CA Muskegon, MI
SIC: Numbers in Parenthesis represent:
20 - Food and kindred products
21 - Tobacco
22 - Textile mill products
23 - Apparel and other textile
26 - Paper and allied products
27 - Printing and publishing
28 - Chemical and allied products
California (2)
Delaware
District Of
Columbia
Florida
Georgia
Table 11-6 Continued.
29 - Petroleum and coal products
30 - Rubber and plastic products,NEC
31 - Leather and Its products
33 - Primary metal Industries
34 - Fabricated metal-products
35 - Machinery.except electrical
36 - Electrical equipment and supplies
37 - Transportation equipment
38 - Instruments and related products
39 - Mining
Number of States in Survey (IB)
Illinois (2)
Indiana (2)
Massachusetts
Michigan
South Carolina
New York
(2)
North Carolina
Ohio
(2) Pennsylvania (2)
Rhode Island
Tennessee
Washington
Wisconsin Q)
181
-------
CD
PO
-T--T
1. ultrasonic probe
2. flow meter
3. computer
4. key board
5. CR1
6. transmitter
n
receiver
sampler control box
glas syrinqes connected
to cam and electro motor
solenoid valve activated
by magnet
submersible pump
overflow vessel
container for metal analysis
container for general analysis
. container for extractable orqanics
16. container for volatile orqanics
Figure 11-2 Schematic of Sampling Units Employed in the Present Study.
-------
effluent, and secondary effluent after chlorination or dechlori-
nation. The fifth sample, the digested sludge is collected as a
grab sample.
The receiver gives the signal to the sampler control box,
which activates the electrometer that drives the syringes of the
four sampling lines. The liquid is sucked into the teflon lines
from the overflow vessel by the negative pressure of the syringes
At that point, the teflon solenoid volume switches, and liquid is
pressurized by the syringes into each of the four collection ves-
sels. The vessel used for the volatile organic analysis contains
a floating teflon plunger to prevent any volatilization of the
organics. All glass vessels for extractable organics are sila-
nized to prevent adsorption of organics on the wall of the ves-
sel, while the polyethylene containers for the other analysis are
nitric acid rinsed. The containers are icechilled during collec-
tion and shipped by express air freight to the laboratory. The
collection system is depicted in plates XI - XIII.
11-5 Removal Efficiencies at POTW's
The tabulation of priority pollutant concentrations in each
of the first three POTW's is presented in this section. The
information in Table 11-7 shows where each of the five 24 hour
composite samples were collected. A description of each treat-
ment plant is given in Tables 11-8, 9, and 10.
The data reported in this and subsequent sections are actual
analytical results, uncorrected for QA/QC recoveries. As the
body of QA/QC information grows, estimates of actual concentra-
tions will be made and attention given to those compounds with
recoveries sufficiently low that the measured values might be
misleading indicators of actual levels present.
The actual data on Renton-Seattle (Table 11-11); Clayton,
Atlanta (Table 11-12); and EBMUD, Oakland (Table 11-13) shows
that removals tend to increase with increasing molecular weight
or increasing GC column retention. While phthalates and PAH's
tended to increase in the sludge, no such accumulation was noted
for chlorinated Cl compounds. A tabulation of individual com-
pounds in Table 11-14 shows that a wide range of compounds were
detected. A typical presentation of the total number of com-
pounds in each of the groups for Oakland is shown in Figure 11-3
while the accumulation of the different fractions in sludge is
shown in Figure 11-4.
183
-------
A INLET AND OUTLET LINES
B DIVERTING VALVES FOR INLET AND OUTLET LINES
C SYRINGE MOUNTING BRACKET
D PISTON GUIDE
E MOTOR
F SYRINGE PLUNGER
G SYRINGE BARREL
H VALVE ACTUATING SELINOID
PLATE XI DRIVEN - SYRINGE SAMPLER
FOR AUTOMATED SAMPLING SYSTEM
184
-------
A CASETTE TAPE DECK
B MICRO-COMPUTER ELECTRONICS
C CRT TERMINAL
D KEYBOARD
PLATE XII AUTOMATED SAMPLING SYSTEM
CONTROLLING ELECTRONICS
185
-------
A ULTRASONIC FLOW METER
B PUMP
C AUTOMATIC SAMPLER
D STAINLESS STEEL BUCKET
E VOA SAMPLER
F TEFLON FLOAT IN VOA SAMPLER
G SAMPLE COLLECTION BOTTLE
PLATE XIII AUTOMATED SAMPLING SYSTEM
186
-------
Table 11-7
Description of Sampling Sites
Renton-METRO
Atlanta(Clayton) Oakland(EBMUD)
Raw Sewage
Primary Sewage
Secondary effluent
before chlorina-
tion
Secondary
effluent after
chlorination
April 9
after prechlor-
ination, before
grit removal.
June 14
Before grit &
prechlorinated
July 3
after sludge
dewatering
supernatant re-
turn influent &
after prechlor-
ination
sample at out- "Channel" open Main Channel to
flow from prim- (2 hrs) between Oxygenation tanks
ary sedimentation activated sludge
basin in tunnel and primary
from second
sediment tank
outflow
from sample at
dechlorination
station
Before Chlorin-
ation (5 hrs)
"weir box"
entire plants
weir box after
15 minutes
Deep Channel
right before
chlorination box.
Outfall several
miles from plant
Primary and
Secondary Sludge
WAS from open
chambers and
primary Sludge
combined
After
digestion
After
digestion
187
-------
Table 11-8
Renton Treatment Plant Information
System Characteristics
Population (indicate year and source)
No. of Businesses
Surface area
No. of waste discharge permits
Miles of combined sewers
Plant Characteristics
Maximum flow (m /sec; MGD)
Dry weather flow
Percentage Industrial Flow
Treatment Sequence:
(Indicate details)
Solids handling
(Include disposal)
198,000 (May 1978)
NA
66 square miles
37
none
72 mgd
36 mgd
5%
screenings ground and recycled, aerated
grit channel, grit dewatered, trucked to
landfill. Primary, activated sludge,
secondary, chlorination, SOj dechlor.
Raw sludge, screen & WAS is pumped via
forced main to the West Point Treatment
Plant to be digested, dewatered & dumped
into Puget Sound.
160 cu ft/day
Screened debris volume (cubic feet/tine)
Grit Volume (cubic feet/time)
Floating oil from Skimmers (cubic feet/time)unknown
Sludge cake (dry tons/year) 18,993 metric tons primary ; 5,072 metr.
Oxygen production (metric tons/year) none tons secondary.
Chlorine usage (metric tons/year) 137.66 metric tons/year
Primary sludge stream (volume) .509 MGD
Secondary sludge stream (volume) -99 MGD
Digested sludge stream (volume) Goes to Westpoint
Plant Operation
Activated sludge loading (Ibs.BOD/lbs. Volatile SS/day)
Digestor Loading (Ibs. Total Solids/1,000 cubic feet/day)
Activated sludge age (days)
Digestor detention time (days)
Chlorine contact time (minutes)
Residual Chlorine (mg/1)
.929
No Digesters
2.03 days
No digestors
35 minutes
0.26
Wastewater Characteristics (mg/1)
BOD Influent
Effluent
SS Influent
Effluent
Total Nitrogen Influent
Effluent
Total Phosphorus Influent
Effluent
273 mg/e
12.5 mg.e total, 8.9 mg.l carbonaceons
351 mg/1
12
33
17
10
5 mg/1
5 mg/1
3 mg/1
mg/1
4.9 mg/1
188
-------
Table 11-9
Atlanta Treatment Plant Information
System Characteristics
Population (indicate year and source) 367,000
No. of Businesses not available
Surface area 162 square miles
No. of waste discharge permits 122
Miles of sewers 390 total miles of sewers (Combined & uncombined)(8"-54" sewers)
Plant Characteristics
Maximum flow (m3/sec; MGD) 150 MGD (180 MGD design)
Dry weather flow 65 MGD
Percentage Industrial Flow not available
Treatment Sequence:
(Indicate details) coarse screening, grit removal, primary
clarification, activated sludge chlorlnatlon, discharge.
Solids handling
(include disposal) Flotation thickening to Waste Activated Sludge. WAS
and primary sludge to Anaerobic Digestion. Digested sludge dmatered
by centrlfugation, incinerated and put on landfill.
•Screened debris volume (cubic fe-et/tine) not available
Grit Volume (cubic feet/time) not available
Floating oil from Skimmers (cubic feet/tine) not available
Sludge cake (dry tons/year) 21,000
Oxygen production (metric tons/year) 365,000
Chlorine usage (metric tons/year) 990
Primary sludge stream (volume) 288,000 gallons/day
Secondary sludge stream (volume) 1.1 million gallons/day
Digested sludge stream (volume) not available
Plant Operation
Activated sludge loading (Ibs.BOD/lbs. Volatile SS/day) Dot available
Digester loading (Ibs. Total Solids/1,000 cubic feet/day) Not available
Activated sludge age (days) 2
• Digestor detention time (days) 30-40
Chlorine contact time (minutes) 20
Residual Chlorine (mg/1) 1
Wastewater Characteristics (mg/1)
BOD Influent 122
Effluent 31
SS Influent 141
Effluent 40
Total Nitrogen Influent
Effluent
Total Phosphorus Influent 6.2
Effluent 4.0
189
-------
Table 11-10
Oakland Treatment Plant Information
System Characteristics
Population (indicate year and source) 575,000
No. of Businesses 7,000 ,
Surface area 215 ta <83 *1-
No. of waste discharge permits 2«300 km d.^00 miles)
Miles of combined sewers of combined severe
Plant Characteristics
Maximum flow (m /sec; MGD) 7.4 nu/second (168 mgd)
Dry weather flow 2.7 m /second (62 mgd)
Percentage Industrial Flow 15%
Treatment Sequence:
(Indicate details) prechlorination, screening, grit chamber, aerated
grit chamber, primary sedimentation, pure oxygen activated sludge,
chlorination, dechlorination, outfall.
Solids handling
(Include disposal) anaerobic digesters, vacuum filters, sanitary landfill
Screened debris volume (cubic feet/tine) 3,500 cubic feet/month
Grit Volume (cubic feet/time) 8,500 cubic feet/month
Floating oil from Skimmers (cubic feet/time) 270 cubic feet/month
Sludge cake (dry tons/year) 605 dry ton/year
Oxygen production (metric tons/year) 226 metric tons/day (250 tons/day)
Chlorine usage (metric tons/year) 2,446 metric tons/year (2,700 tons/year)
Primary sludge stream (volume) 4.6 MGD
Secondary sludge stream (volume) 3.34 MGD
Digested sludge stream (volume) 1.26 MGD
Plant Operation
Activated sludge loading (Ibs.BOD/lbs. Volatile SS/day) .42
Digestor loading (Ibs. Total Solids/1,000 cubic feet/day) 97
Activated sludge age (days) 6.6
Digestor detention time (days) 15
Chlorine contact time (minutes) 120
Residual Chlorine (mg/1) ° (dechlorlnated)
Wastewater Characteristics (mg/1)
BOD Influent 330 mg/1
Effluent 8 mg/1
SS Influent 470 mg/1
Effluent 21 mg/1
Total Nitrogen Influent 52.7 mg/1
Effluent 37.9 mg/1
Total Phosphorus Influent 12 mg/1
Effluent 8.1 mg/1
190
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-11 Priority Pollutants in Renton, Seattle POTW
TRICHLOROFLUOROMETHANE
1,1-DICHLOROETHENF
DICHLOROMETHANE
1,2-DICHLOROETHENF
1,1-DICHLOROETHAME
TRICHLOROMETHANE
1,2-DICHLOROETHANE
TETRACHLOROMETHANE
1,1,1-TRICHLOROETHANE
BENZENE
METHYLBENZENE
TETRACHLOROETHENE
ETHYLBENZENE
n -r
Un Ll
Cln-AROM.
Sewage
1.54
292.8
4.2
1.5
9.1
8.77
0.85
6.4
0.18
298.5
18.6
9.4
Primary
Effluent
62.3
2.8
0.87
0.08
4.5
5.8
265.2
9.1
4.3
Secondary
Effluent
0.52
303.5
0.28
0.45
4.0
0.53
11.2
3.0
8.4
19.8
0.17
307.5
17.3
10.1
Secondary
Effluent
Chlorinated
3.87
327.1
0.17
1.78
7.5
1.7
32.6
8.9
11.0
24.5
1.20
334.6
66.3
86.2
Sludge
NQ
1.52
4.5
0.08
12.1
5.2
35.8
38.2
1.51
4.6
65.5
42.8
191
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-11 Cont. RENTCN-SEATTLE
BIS(2-CHLOROETHYL)ETHER
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-DICHLOROBENZENE
BIS(2-CHLORISOPROPYL)ETHER
N-JJITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1.2,4-TRICHLOROBENZENE
NAPHTHALENE
ACENAPTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
FLUORENE
DIETHYLPHTHALATE
N-NITROSODIPHENYLAMINE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORATHENE
PYRENE
BU7YLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B)aUORANTHENE
ETHER
AMINE
BENZENE
AROMATIC HYDROCARBONS
PHTHALATES
Sewage
0.06
0.71
5.02
4.79
0.16
0.49
0.31
1.27
0.04
0.72
0.09
0.15
6.57
0.24
0.37
NQ
5.58
0.16
0.16
6.69
0.06
0.09
1.33
0.07
0.43
0.73
10.5
2.43
20.9
Primary
Effluent
0.07
9.56
3.57
4.83
0.32
0.05
0.13
0.21
1.18
NQ
0.52
0.+8
0.06
7.44
0.14
0.01
3.01
0.02
2.59
0.52
9.4
1.46
13.56
Secondary
Secondary Effluent
Effluent Chlorinated
NQ
0.74 1.93
2.95 3.88
0.06
0.06 0.31
0.02
0.21
0.16
0.40
NQ
1.79 5.41
0.92 12.75
0.08
0.06 0.31
3.7 5.8
0.61
2.87 18.2
Sludge
59.8
rt.o
4.2
42.6
6.0
119.2
20.0
40.09
124.0
59.8
42.6
11.0
293.5
192
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-11 Cont. RENTON-SEATTLE
Secondary
Compound
a(-BHC
LINDANE
tf-BHC
A-BHC
HEPTACHLOR
HEPTACHLOR EPOXY
DIELDRIN
p,p'-DDE
p.p'-DDD
p.p-DDT
METHOXYCHLOR
MI REX
ENDRIN
d-ENDOSULFAN
CHLORDENE
^-CHLORDANE
ot-CHLORDWE
PESTICIDES
Compound
4-CHLORO-3-METHYLPHENOL
2-NITROPHENOL
4.6-DINITRO-2-METHYLPHENOL
PENTACHLOROPHENOL
PHENOL I CS
Sewage
0.130
0.579
0.226
37.02
0.154
0.022
0.183
0.181
0.525
0.019
0.191
0.101
0.214
0.207
40.1
Sewage
-
Primary
Effluent
0.125
0.176
0.224
0.185
0.126
0.84
Primary
Effluent
1.26
23.0
1.62
4.68
10.46
Secondary
Effluent
0.895
0.084
0.009
0.097
0.198
0.078
1.36
Secondary
Effluent
5.35
11.8 •
17.2
Effluent
Chlorinated
0.889
0.012
0.085
0.001
0.188
0.066
1.24
Secondary
Effluent
Chlorinated
14.7
14.7
Sludge
0.159
0.323
0.017
0.468
0.042
0.535
0.174
1.68
Sludge
1.44
7.7
9.14
193
-------
THIS.DATA UNCORRECTEP FOR RECOVERY _ ,,1X
Table ll-ll Cont. Seattle, Washington Plant (#1)
Inorganic Priority Pollutants (ppb)
Metal
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
1-1
(A/RSl)
A
12.3
0.2
22
170
100
12
11
105
1
17.3
ND
125
1-2
(A/PE1)
3(82)
21.3
0.2(71)
20
156
72.5
10
12(80)
80
1(89)
7.9(56)
ND
80(190)
1-3
(A/SEBC)
4.5
4.4
0.2
23
35
<1
14
2
80
1
1
ND
50
1-4
(A/SEAC)
4
4.5
0.1
14
30
<1
6
1
70
i.B
i
ND
25
1-5
(A/SI)
40(90)*
396
3.4(95)
400
2225
2080
190
85(70)
9,490
9(20)
213(270)
ND
3125(112)
Cyanide 29 23 8 0
*% recovery of spikeJ sample is given in the parenthesis.
122
194
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-12 Priority Pollutants in Clsyton, Atlanta POTW
CLAYTON-ATLANTA
Compound
DICHLORODIFLUOROMETHANE
TRICHLOROFLUOROMETHANE
1, 1-DICHLOROETHENE
DICHLOROMETHANE
1, 2-DICHLOROETHENE
1, 1-DICH LORD ETHANE
TRICHLOROMETHANE
TRICHLOROETHANE
1, 2-DICHLOROETHANE
1,1,1 -TRICHLOROETHANE
BENZENE
BROMODICHLOROMETHANE
METHYLBENZENE
TETRACHLOROETHENE
ETHYLBENZENE
ci-c1
ci-c2
Cl-AROMATICS
Sewage
to
O
4-
3
O
-O
O>
O.
+J
Q
Primary
Effluent
9.2
58.8
43.2
647.1
0.89
6.7
17.1
8.4
1791.5
7.7
0.67
70.1
566.0
732.9
2416.7
76.9
Secondary
Effluent
5.9
1.2
182.5
0.56
0.38
2.5
1.3
36.1
0.65
.68
5.3
188.8
47.0
1.4
Secondary
Effluent
Chlorinated
0.65
140.6
0.56
1.8
1.1
30.8
1.08
1.51
4.37
1.27
141.2
40.0
2.6
SI udge
0
to
T3
E
O
4-
3
O
T3
0)
0.
3
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-12 Cont.
CLAYTON-ATLANTA
BIS(2-CHLOROETHYL)ETHER
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-DICHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER
N-NIRTOSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TIRCHLOROBENZENE
NAPHTHALENE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
FLUORENE
DIETHYLPHTHALATE
DIPHENYLHYDRAZINE
N-NITROSODIPHEMYLAMINE
PHENATHRENE
WTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
BIS-(2-ETHYHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
B^ZO(A)PYRENE
ETHERS
AMINES
BENZENES
AROMATIC HYDROCARBONS
PHTHALATES
Sewage
3.15
13.94
43.86
0.12
0.61
10.94
0.25
0.88
1.72
1.36
3.24
NQ
12.91
0.06
NQ
17.88
50.0
61.7
17.2
81.5
Primary
Effluent
0.36
3.8
14.26
52.87
1.38
0.89
14.55
0.23
0.94
0.35
0.63
1.05
5.50
1.56
NQ
22.92
26.07
26.21
1.14
1.38
71.4
17.81
81.64
Secondary
Effluent
0.09
0.45
2.04
1.22
0.34
0.01
0.09
4.06
0.04
0.12
0.05
0.12
0.26
0.06
0.28
0.07
4.97
0.05
0.14
1.63
11.17
0.54
0.43
0.06
3.81
4.8
18.7
Secondary
Effluent
Chlorinated
NQ
1.32
5.74
10.12
0.13
0.11
0.34
0.37
0.12
0.04
0.25
0.20
0.28
NQ
1.82
0.06
0.18
3.68
0.13
0.31
17.5
0.97
5.87
Sludge
17.0
89.4
312.4
318.6
19.6
21.50
51.27
3.6
122.6
101.0
9,6
200.2
27.2
39.6
3115.8
28.8
23.0
3794.8
181.8
14.6
13.6
8.4
126.2
418.8
652.3
7292.6
196
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-12 Cont.
CLAYTON-ATLANTA
Compound Sewage
4-BHC
LINDANE 0.140
(T-BHC
HEPTACHLOR
HEPTACHLOR EPOXY
DIELDRIN
ENDRIN
p.p'-DDE
p,p'-DDD 0.173
p,p'-DDT
METHOXYCHLOR
rf-ENDOSULFAN
P-ENDOSULFAN
EN DOS UL FAN SULFATE
CHLORDENE
f-CHLORDANE 0.327
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-12 Contin. R. M. Clayton, Georgia Plant (#2)
Inorganic Priority Pollutants (ppb)
Metal
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
2-1
2-2
60 96
4 6.3
1.1 1.3
56 " 42
21 16
117(90) 62
9.6 6.4
565 1965
3.8 2.5
9.6 7.6
1,700 900
2-3
:l
30
5.1
:l
16
31
47
0.7
1365
3.8
7.1
cl
500
2-4
2-5
30 4,950
2.9(73)*23(240)
1 (110) 770
15(187) 23,500
31 2470
22(90) 12,860
1.6 475
865 98,975
7 <1
7.1(44) 395
300
337,000
Cyanide
28
45
19,300
* % recovery of spiked samples is given in the parenthesis.
198
-------
THIS DATA UNCORRECTED FOR RECOVERY
EBMUD-OAKLAND
Table 11-13 Priority Pollutants in EBMUB, Oakland POTVI
Secondary
Primary Secondary Effluent
Sewage Effluent Effluent Chlorinated Sludoe
DI CHLORODI FLUOROMETHANE
CHLOROETHANE
TRI CHLOROFLUOROMETHANE
1,1-DICHLOROETHENE
DICHLOROMETHANE
1,1-DICHLOROETHANE
TRICHLOROMETHANE
TRICHLOROETHENE
1,2-DICHLOROETHANE
TETRACHLOROMETHANE
1,1,1-TRICHLOROETHANE
BENZENE
1,2-DICHLOROPROPANE
BROMOOICHLOROMETHANE
METHYLBENZENE
TETRACHLOROETHENE
CHLOROBENZENE
ETHYLBENZENE
TRIBROMOMETHANE
1,1,2 , 2-TETRACHLOROETHANE
Cl-Cj
ci-c2>3
Cl-AROM.
0.89
34.5
1.8
9.0
1.7
37.5
11.2
0.46
0.59
88.4
10.5
1.5
112.4
49.3
177.3
148.3
83.8
241.4
438
1.6
15.7
6.2
11.7
3.1
13.7
12.4
15.1
34.5
3.1
2.6
20.4
82.1
65.4
4.6
1.6
19.1
21.1
2.0
26.9
1.2
0.95
10.5
0.17
0.33
1.3
25.0
62.8
6.6
3.5
7.3
1.9
34.2
65.1
6.0
36.3
0.89
0.99
25.2
0.46
0.81
42.4
138.4
2.3
1.1
0.24
2.3
0.5
12.4
126.2
22.8
160.6
7.6
NO
8.3
2.9
309.6
199
-------
THID DATA UNCORRECTED FOR RECOVERY
Table 11-13 Cont.
EB MUD-OAKLAND
Secondary
Primary Secondary Effluent
Sewage Effluent Effluent Chlorinated
Sludge
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-DICHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER
N-NITRO-DI-N-PROPYL AMINE
NITROBENZENE
BIS92-CHLOROETHOXY) METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2.6-DINITROTOLUENE
ACENAPHTHENE
FLUORENE
DIETHYLPHTHALATE
.PFHENYLHYDRAZINE
N-NITROSODIPHDIYLAMIiJE
PHENATHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
BIS(2-ETHYLEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K)FLUORANTHENE
BEN Z0( A) PYRENE
ETHERS
AMINES
BENZENES
AROMATIC HYDROCARBONS
PHTHALATES
0.12
0.22
1.52
1.78
6.73
0.29
6.85
0.38
2.61
0.28
0.57
9.77
NQ
1.28
1.21
0.05
11.07
3.10
0.80
126.34
0.66
275.0
10.60
NQ
0.38
0.08
0.12
8.01
6.42
14.74
433.1
0.70
1.29
6.88
5.90
1.97
10.70
0.27
0.31
1.35
0.58
5.18
0.70
1.43
12,87
3.48
1.52
154.7
1.42
309.5
10.79
0.77
NQ
0.70
0.70
17.4
21.6
493.4
0.40
<0.01
0.41
2.75
1.34
0.27
0.10
0.32
NQ
5.99
0.28
0.50
4.8
6.0
0.01
0.30
0.23
0.23
0.05
2.87
0.11
0.02
4.90
0.38
3.35
0.26
0.02
0.53
8.8
5.5
37.0
15.8
13.5
76.0
0.75
5.8
0.01
27.3
NQ
1.8
42.31
24.8
14.0
7429.
237.0
NQ
8.0
4.8
0.01
71.8
223 J
313.84
200
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-13 Cont.
EBHUD-OAKLAND
Secondary
Compound
LIN DANE
A-BHC
HEPTACHLOR EPOXY
DIELDRIN
P,P,'-DDD
p,p'-DDT
METHOXYCHLOR
MIREX
o-ENDOSULFAN
T-ENDOSULFAN
ENDOSULFAN SULFATE
CHLORDENE
Y-CHLORDANE
o-CHLORDANE
PESTICIDES
Sewage
0.414
4.974
0.050
0.290
0.632
0.277
0.228
1.141
0.510
0.444..
8.96
Primary
Effluent
0.572
0.645
0.123
0.201
0.550
0.515
1.636
1.152
0.692
6.09
Secondary Effluent
Effluent Chlorinated
0.155 0.139
0.867
0.405
0.151
0.039
0.141
0.060 0.071
0.221
1.17 1.08
Sludge
0.122
0.149
0.273
0.550
0.021
0.386
0.403
1.327
0.101
0.72
4.05
Compound
PHENOL
2-CHLORO PHENOL
2,4-DIMETHYLPHENOL
2,4,6-TRICHLOROPHENOL
Secondary
Primary Secondary Effluent
Sewage Effluent Effluent Chlorinated Sludge
164.9
58.2
14.3
479.3
42.6
12.1
PHENOL ICS
237.4
534
201
-------
THIS DATA UNCORRECTED FOR RECOVERY
Table 11-13 Cont. EBMUI>, Oakland California
Inorganic Priority Pollutants (ppb)
Metal
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
3-1
(PS 180)
3.8
13.8
«1
34
390
140
96
17.5
640
<1
9.3
<1
1650
3-2
(PS 190)
2.5
13.8
<1
1.4
155
130
58.4
10
460
<1
11
<1
850
3-3
(PS 200)
2.5
11.3
<1
<1
41.5
140
13
13
290
<1
2.1
<1
150
3-4
(PS 210)
<1
11.3
<1
<1
66.5
70
25
10
152.5
<1
«1
<1
200
3-5
(PS 220)
120
1,375
14
3,000
1,900
15,000
4,000
275
35,000
85
250
<1
120,00
Cyanide 126 112 65 77
202
-------
Table 11-14 Summary of Priority Pollutants Found in 3 POTW'S
DICHLORODTFLUOROMETHANE
TRICHLOROFLUOROMETHANE
DICHLOROMETHANE
TRICHLOROMETHANE
TETRACHLOROMETHANE
BROMODICHLOROMETHANE
TRIBROMOMETHANE
1.2-DICHLOROPROPANE
BENZENE
METHYLBENZENE
CHLOROBENZENE
ETHYLBENZENE
CHLOROETHANF
1,1-DICHLOROETHF.NF
1,1-DICHLORnETHANE
TRICHLOROETHFNF
1 ,2-DICHLOROETHA'T-.
1,1,1-TRICHLOROFTIIANE
TETRACHLOROETHEMF
1 .1 ,2.2-TETRACHLOfrnETHANE
BIS(2-CHLOROETHYL)ETHER
BIS (2-CHLOROISOPROPYL)ETHER
BI S (2-CHLOROETHOXY)METHANE
N-NITROSODIMETHYLAMINE
N-NITROSO-DI-N-PROPYL AMINE
DIPHENYLHYDRAZINE
N-NITROSODIPHENYLAMINE
1 ,3-DICHLOROBENZF.NE
1,^-DICHLOROBENZENE
1,2-DICHLOROBENZENE
NITROBENZENE
1,2,14-TRICHLOROBENZENE
2.6-DINITROTOLUENE
NAPHTHALENE
ACENAPHTHYLEMF.
ACENAPTHENE
FLUORENE
PHENANTHREME
ANTHRACENE
FLUORANTHEME
PURENE
BENZO(A)ANTHRACENE
CHRYSENE
BENZO(B)FLL)nRAMTHENE
BENZO(K)FLUORAMTHEME
BENZO(A)PYRENE
DIMETHYLPHTHALATE
DIETHYLPHTHALATE
DIBUTYLPHTHALATE
BUTYLBENZYLPHTHALATE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
ct-BHC
LINDANE
6-BHC
ABHC
HEPTACHLOR
HEPTACHLOR EPOXY
DIELDRIN
p.p-DDE
p,p'-DDD
p.p'-DDT
METHOXYCHLOR
MIREX
CHLORDENE
ENDOSULFAN SULFATE
ENDOSULFANo<.g»
l»-CHLORO-2-METHYL PHENOL
2-NITROPHENOL
i«,6-DINITRO-2-METHYL PHENOL
PENTACHLOROPHENOL
2,A-DIMETHYLPHENOL
2,i4-DICHLOROPHENOL
PHENOL
2-CHLOROPHENOL
2,^,6-TRICHLOROPHENOL
203
-------
1000
100
10
o.
»-*
QC
o.
u.
o
I-
£
«£
0.1
O
OL
t o
CVI
oo
UJ
5
r»>i
5 .
00 K-
CO
CO
ce.
Figure 11-3 Representation of Compunds Found in Different Fractions
204
-------
UJ
CD
3
UJ
oo
cf
o:
p 100
0
UJ
D-
UJ
X
, ,
3
UJ 10
o
_i
oo
»— (
0
o
et
Ij^ ^
1
a:
l-
5
0
0
n i
oo
1 i |
•— i
oo
UJ
s
M
5
CO
CO
*
CM
1
O
f—
CJ
1
o
-------
SECTION 12
MUTAGENIC ACTIVITY OF POTW SAMPLES
/
12-1 Introduction
Two sewage samples, i.e. digested sludge (PS140) and secon-
effluent before chlorination (PS 170) from the Clayton, Atlanta
plant, each consisting of six different fractions, were examined
for mutagenic activity by in vitro microbiological assays with
five strains of Salmonella typhimurium (TA1535, TA1537, TA1538,
TA98, and TA100). An Aroclor 1254-stimulated rat-liver homo-
genate metabolic activation system was included in the assay pro-
cedure to provide metabolic steps that the bacteria either are
incapable of conducting or do not carry out under the assay con-
ditions. The purpose of this study was to determine whether the
samples elicited a mutagenic response in microorganisms.
The assay procedure with S. typhimurium has proven to be
85 to 90% reliable in detecting carcinogens as mutagens, and it
has about the same reliability in identifying chemicals that are
not carcinogenic (McCann et. al., 1975).
12-2 Methods
The Salmonella typhimurium strains used in this study are
TA1535, TA1537, TA1538, TA98, and TA100. These Salmonella
typhimurium strains are all histidine auxotrophs by virtue of
mutations in the histidine operon. When these histidinedependent
cells are grown on a minimal media petri plate containing a trace
of histidine, only those cells that revert to histidine indepen-
dence (his+) are able to form colonies. The small amount of his-
tidine allows all the plated bacteria to undergo a few divisions;
in many cases, this growth is essential for mutagenesis to occur.
The his+ revertants, resulting from their mutation in the pre-
sence of the organic mutagen, are easily counted as colonies
against the slight background growth. The spontaneous mutation
frequency of each strain is relatively constant, but when a muta-
gen is added to the agar, the mutation frequency is increased 2 -
100 fold.
Our S. tvphimurium strains were obtained indirectly from
Dr. Bruce Ames of the University of California at Berkeley via
Dr. Kristien Mortelmans of SRI International in Menlo Park, Cali-
fornia. In addition to having mutations in the histidine operon,
all the indicator strains have a mutation (rfa-) that leads to a
defective lipopolysaccaride coat; they also have a deletion that
covers genes involved in the synthesis of biotin (bio-) and in
the repair of ultraviolet(uv)-induced DNA damage (uvrB-). The
rfa- mutation makes the strains more permeable to many-large aro-
matic molecules, thereby increasing the mutagenic effect of these
molecules. The uvrB- mutation decreases repair of some types of
206
-------
chemically or physically damaged DNA and thereby enhances the
strains' sensitivity to some mutagenic agents. Strain TA1535 is
reverted to his+ by many mutagens that cause base-pair substitu-
tions. TA100 is derived from TA1535 by the introduction of the
resistance transfer factor plasmid pKMlOl. This plasmid is
believed to cause an increase in error-prone DNA repair that
leads to many more mutations for a given dose of most mutagens.
TA100 can detect mutagens such as benzyl chloride and
2-(2-furyl)-3-(5-nitro-2-furyl)acrylamide (AF2), which are not
detected by TA1535. The presence of this plasmid also makes
strain TA100 sensitive to some frameshift mutagens such as benzo-
(a)pyrene, aflatoxin Bl, and 7,12-dimethylbenz(a)anthracene.
Strains TA1537 and TA1538 are reverted by many frameshift muta-
gens. Strain TA98 is derived from TA1538 by the addition of the
plasmid pKMlOl, which makes it more sensitive to some mutagenic
agents.
All the indicator strains are routinely checked for their
genotypic characteristics. For each experiment, an inoculum from
the stock cultures is grown overnight at 37°C in nutrient broth.
After stationary overnight growth, the cultures are shaken for 3
hours to ensure optimal growth.
The Aroclor 1254-simulated metabolic activation system was
used in the present study to activate the organics in each frac-
tion. Some carcinogenic chemicals, either of the aromatic amino
type or polycyclic hydrocarbon type, are inactive unless they are
metabolized to active forms. In animals and man, an enzyme sys-
tem in the liver or other organs (e.g., lung or kidney) is capa-
ble of metabolizing a large number of these chemicals to carcino-
gens. Some of these intermediate metabolites are very potent
mutagens in the S. typhimurium test. Ames has described the
liver metabolic activation system that we use (Ames et. al.,
1975). The metabolic activation mixture for each experiment con-
sists of, for 10 ml:
1.00 ml of S-9 fraction of the rat liver homogenate
0.20 ml of MgCl2 (0.4M) and KC1 (1.65M)
0.05 ml of glucose-6-phosphate (1M)
0.40 ml of NADP (0.1M)
5.00 ml of sodium phosphate (0.2M, pH 7.4)
3.35 ml of H20
Assays in Agar
The assays in agar are conducted in the following manner:
to a sterile 13x100 mm test tube placed in a 43°C heating block,
the following are added:
207
-------
1) 2.00 ml of 0.6% agar containing a trace of
histidine and biotin
2) 0.05 ml of indicator organism
3) 0.50 ml of metabolic activation mixture (optional)
4) 0.05 ml of a solution of the test sample
For negative controls, 0.05 ml of the solvent used for the test
sample is added. For positive controls, specific mutagens known
to revert each strain are used.
The mixture is stirred gently and then poured onto minimal
agar plates. After the top agar has set, the plates .are incu-
bated at 37°C for approximately 48 hours. The number of his+
revertant colonies is counted.
12-3 Results and Discussion
Two sewage samples (140 and 170) , each consisting of six
fractions, were examined in a set of preliminary experiments
using the two most sensitive S. typhimurium strains - TA98 and
TA100. Each test vial contained a dry residue of known weight to
which 1.0 ml of either dimethyl sulfoxide (DMSO) or water had
been added. Tables 12-1 and 12-2 present the results of an exper-
iment in which all the fractions were tested at similar dilutions
regardless of their varying residue weights. The volume of each
dilution added per plate was consistently 0.05 ml. The highest
dose was 0.05 ml of the undiluted fraction. No mutagenic acti-
vity was present in these preliminary tests, either in the pre-
sence or in the absence of metabolic activation. Although the
number of histidine-positive revertants per plate is somewhat
higher than that observed on the control plates, no dose-related
increase is evident. Toxicity, however, is clearly present at
the higher doses of the 140 series of fractions. While all frac-
tions of the 140 sample produced some signs of killing, the toxic
effect was most pronounced with the PS140A3S (phenols) and
PS140A2 4A3 (neutrals) fractions. In the 170 series of frac-
tions, toxicity was present only at the highest dose of PS170
(water from the extractor).
Tables 12-3 and 12-4 present the results of a subsequent
experiment, in which the dose range for some of the fractions was
narrowed in order to better focus on those dose levels imme-
diately preceding a toxic effect. With fractions in which no
toxicity had been observed in the previous experiment, the high-
est dose was increased by adding more volume of the undiluted
test solution to the plate. Only S. typhimurium strains TA98
and TA100 were used. No mutagenic response was observed with any
fraction. Toxicity, however, was evident with all the fractions
in the absence of metabolic activation.
208
-------
Table 12-1
IN VITRO ASSAYS WITH SALMONELLA TYPHIMUPJUM - 140 Series
ro
o
10
Compound
Negative Control
Metabolic
Activation
_ *
DMSO Control
(dimethyl sulfoxide)
Water Control
Positive Controls:
Sodium Azide
2-Nitrofluorene
2- Anthramine
Micrograms
of Compound
Added per Plate
0
0
50,000
50,000
50,000
50,000
1.0
10.0
2.5
2.5
Histidine-Positive Revertants per
TA98 TA100
15,19
28,36
20,18
32,25
22,19
30,23
960
29
356
121,138
126,124
123, 103
110, 117
130,117
142,140
542
133
1150
*•- • in the absence of metabolic activation, + B in the presence of metabolic activation
-------
Table 12-1 (cont)
IN VITRO ASSAYS WITH SALMONELLA TYP11IMURIUM - 140 Series
Compound
PS140B
(unfractlonated
base extract)
Metabolic
Activation
INS
»—»
o
PS140
(water from
extractor)
•f
+
+
+
Percent Cone.
of Solution
Added jer Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
Volume
of Solution
Added per Plate
0.5 ml.
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
/og of
Residue
Added per Plate
4.6
9.2
46.0
92.0
184.0
920.0
4.6
9.2
46.0
92.0
184.0
920.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
His Revertants per Plate
TA98
20
18
19
25
10
11 + pp.
44
25
34
38
39
41
35
18
16
24
16
9 + pp.
34
31
45
35
35
32 + pp.
TA100
136
120
121
107
107
85 + pp.
172
148
170
194
183
99
201
124
152
122
197
92
142
152
177
204
207
173
pp.
- pinpoints, which is a sign of toxicity
-------
Table 12-1 (cont.)
IN VITRO ASSAYS WITH SALMDNELIA TYPIIT.HTJRTDM - 140 Series
Compound
PS140A2 +
PS140 A3
(neutrals)
ro
PS140A3S
(phenols)
Metabolic
Activation
—
-
-
-
-
-
+
+
+
+
+
+
—
-
.
.
.
-
+
+
+
+ •
+
+
Percent Cone.
of Solution
Added per Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
Volume
of Solution
Added per Plate
0.5 ml.
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
/Ug of
Residue
Added per Plate
2.5
5.0
25.0
50.0
100.0
500.0
2.5
5.0
25.0
50.0
100.0
500.0
0.8
1.5
7.5
15.0
30.0
150.0
0.8
1.5
7.5
15.0
30.0
150.0
His Revertants per Plate
TA98
10
16
8
16
13 + pp.
6 + pp.
41
37
29
32
20
16 + pp.
19
26
20
13
1 + PP.
0
23
35
42
42
27
0
TAIOO
133
110
79 + pp.
100 + pp.
74
0
158
133
126
124
142
130
124
173
138
57
0
1
137
134
142
124
140
11
* pp. • pinpoints, which li a sign of toxlclty
-------
Table 12-1 (cont.)
IN VITRO ASSAYS WITH SALMONELIA TYP1ITHURIUM - 140 Series
Compound
Metabolic
Activation
PS140A
(unfractionated
acid/neutral
extract)
ro
t-«
rv>
PS140A1
(throw away
fraction of
acid/neutral
extract)
Percent Cone.
of Solution
Added jer Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0.
5.0
10.0
20.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
/tg of
Residue
Added per Plate
96.3
192.5
962.5
1925.0
3850.0
19250.0
96.3
192.5
962.5
1925.0
3850.0
19250.0
8.3
16.5
82.5
165.0
330.0
1650.0
8.3
16.5
82.5
165.0
330.0
1650.0
His Revertnnts per Plate
TA98
18
24
18
I'* + pp.
4 + pp.
pp.
38
37
40
36
30
35
15
23
21
29
18
22
41
43
25
35
38
19 + pp.
TA100
182
107
7?
126
39 + pp.
20 + pp.
147
135
155
189
164
129
131
157
150
122
158
105 + pp.
165
129
166
165
165
150
* pp. - pinpoints, which IB a sign of toxicity
-------
Table 12-2
IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - 170 Series
oo
Negative Control
Metabolic
Activation
EMSO Control
(dimethyl sulfoxlde)
Water Control
Positive Controls:
Sodium Azide
2-Nltrofluorene
2-Anthramlne
- *
+
Mlcrograms
of Compound
LAdded per Plate
0
0
50,000
50,000
50,000
50,000
1.0
10.0
2.5
2.5
lllstldtne-Pofiittve Revertnnts j)cr._Pl_at.e_
TA98 TA100
15,19
28,36
20,18
32,25
22,19
30,23
960
29
356
121,138
126,124
123, 103
110, 117
130,117
142,140
542
133
1150
* - • In the absence of metabolic activation, + - In the presence of metabolic activation
-------
Table 12-'. (cont.)
IN VITRO ASSAYS WITH SAIMOKEL1A TYrilTMlllOUH - 170 Scrleg
Compound
Metabolic
Activation
PS170B
(unfractlor.ated
Base)
ro
PS170
(water from
extractor)
Percent Cone.
of Solution
Added per Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
Volume
of Solution
Added por Plate
0.5 ml.
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
/ttfi of
Residue
Added per Plate
3.8
7.5
37.5
75.0
150.0
750.0
3.8
7.5
37.5
75.0
150.0
750.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
His
TA98
23
30
21
16
19
15
26
25
33
31
33
33
22
30
18
16
20
1
47
46
36
38
37
0
Revertants per Plate
TA100
183
143
17.3
159
152
187
157
102
163
194
179
143
137
123
137
126
135
0
201
203
186
163
161 *
161 + pp.
pp.
• pinpoints, which la a sign of toxlclty
-------
Table 12-? (cent.)
IN VITRO ASSAYS WITH SAI.MDNEUA TYP11IMURIUM - 170 Scriea
Cfflnp otino
PS170A2 +
PS170A3
(neutrals)
Metabolic
Activation
ro
i-«
Ui
PS170A3S
(phenols)
•f
•f
•f
Percent Cone.
of Solution
Added per Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
/Og of
Residue
Added per Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
1.0
2.0
10.0
20.0
40.0
200.0
1.0
2.0
10.0
20.0
40.0
200.0
His Revertants per Plate
TA98
20
19
24
31
17
22
29
58
53
50
37
40
22
29
20
25
22
32
35
41
44
43
38
42
TA100
129
123
154
150
152
96
169
158
149
163
168
142
184
145
162
160
161
155
127
156
149
. 168
208
198
-------
Table 12-2 (cont)
IN VITRO ASSAYS WITH SAIMDHELTA TYVllT.MUimiM - 170 Series
Contpounj
PS170A
(unfractlonated
acid/neutral
extract)
ro
Metabolic
Activation
„
ted -
1
—
-
+
+
+
+
+
+
Percent Cone.
of Solution
Added per Plate
0.5
1.0
5.0
10.0
20.0
100.0
0.5
1.0
5.0
10.0
20.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
A« of
Residue
Added per Plate
12.5
25.0
125.0
250.0
500.0
2500.0
12.5
25.0
125.0
250.0
500.0
2500.0
+
His Revertants per Plate
TA98
27
17
23
18
19
29
39
43
32
47
45
45
TAIOO
124
126
154
136
134
165
197
131
155
130
163
140
PS170A1 - 0.5 0.05 0.0 21 173
(throw away - 1.0 0.05 0.0 24 149
from acid/ - 5.0 0.05 0.0 30 175
neutral) - 10.0 0.05 0.0 29 178
20.0 • 0.05 0.0 22 149
100.0 0.05 0.0 28 150
+ 0.5 0.05 0.0 59 136
+ 1.0 0.05 0.0 54 147
+ 5.0 0.05 ' 0.0 40 130
+ 10.0 0.05 0,0 43 137
+ 20.0 0.05 0.0 28 120
+ 100.0 0.05 0.0 21 142
-------
Table 12-3
IN VITRO ASSAYS WITH SA1XONEU.A TYP1ITM1IHT.UH - 140 Scries
ro
Compoxtnd
Negative control
Metabolic
Activation
_ *
IMSO control
(dimethyl sulfoxlde) +
Water control
Positive controls:
Sodium azlde
2-Nltrofluorene
2-Anthramlne
Mlcrograms
of Compound
Added per Plate
0
0
50.000
50,000
50,000
50,000
1.0
10.0
2.5
2.5
Htsttdlne-Posltlve Revertants per Plate
TA98 TA100
23,13
44,40
26,29
39,45
22,18
47,50
1113
31
481
163,169
144,144
177,152
163,178
176,178
178,178
488
178
497
* - • In the absence of metabolic activation, + • In the presence of metabolic activation
-------
Table 12-3 (cont.)
IN VITRO ASSAYS WITH SALMONEUA TYl'llT.MUIUUM - 140 Series
Percent Cone. Volume /ig of +
Metabolic of Solution of Solution Residue His Revcrtants per Plate
Compound Activation Added per Plate Added jer Plate Added per Plate TA98 TA100
PS140B - 2.0 0.5 ml. 18.4 28 88
(unfractlonated - 5.0 0.5 46.0 35 116
base extract) - 10.0 0.5 92.0 32 121
20.0 0.5 184.0 31 101
50.0 0.5 460.0 23 ^ 103
100.0 0.5 920.0 22 + pp. 67 + pp.
+ 2.0 0.5 18.4 40 172
+ 5.0 0.5 46.0 34 172
+ 10.0 0.5 92.0 49 159
2 + 20.0 0.5 184.0 48 144
00 + 50.0 0.5 460.0 54 148
+ 100.0 0.5 920.0 48 147
2.0 0.5 0.0 29 124
(water from - 5.0 0.5 0.0 28 157
extractor) - 10.0 0.5 0.0 31 131
20.0 0.5 0.0 31 142
50.0 0.5 0.0 33 162
100.0 0.5 0.0 17 + pp. 93 + pp.
+ 2.0 0.5 0.0 55 178
+ 5.0 0.5 '• 0.0 45 157
+. 10.0 0.5 0.0 49 149
+ 20.0 0.5 0.0 35 168
+ 50.0 0.5 0.0 32 171
+ 100.0 0.5 0.0 43 139 + pp.
* pp. * pinpoints, which Is a sign of toxiclty
-------
Table 12-3 (cont.)
IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - WQ Series
Compound
FS140A2 -i-
PS140A3
(neutrals)
ro
PS140A3S
(phenols)
Metabolic
Activation
•
-
.
-
.
-
+
+
+
+
+
+
.
.
.
.
-
+
+
+ •
+
+
+
Percent Cone.
of Solution
Added per Plate
0,1
0.2
0.4
1.0
4.0
20.0
0.1
0.2
0.4
1.0
4.0
20.0
0.2
1.0
2.0
4.0
10.0
20.0
0.2
1.0
2.0
4.0
10.0
20.0
Volume
of Solution
Added per Plate
0.5 ml.
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
/oe of
Residue
Added per Plate
0.7
1.0
2.0
5.0
20.0
100.0
0.7
1.0
2.0
5.0
20.0
100.0
0.3
1.5
3.0
6.0
15.0
30.0
0.3
1.5
3.0
6.0
15.0
30.0
His Revertants per Plate
TA98
21
24
30
32
19
21
46
40
42
56
55
44
28
27
27
28
21
pp.
48
51
48
38
37
45
TA100
144
136
150
109
105
185
187
141
182
138
156
107
168
152
178
121
89
pp.
170
116
162
171
143
148
*pp. • pinpoints, which is a sign of toxlcity
-------
Table 12-3 (cont.)
IN VITRO ASSAYS WITH SALMONELLA TYPI1TMURTUM -
Series
Compound
Metabolic
Activation
PS140A
(unfractlonated
acid/neutral
extract)
ro
ro
o
PS140A1
(throw-away
fraction of
acid/neutral)
+
+
+
Percent Cone.
of Solution
Added per Plate
0.2
1.0
2.0
10.0
50.0
100.0
0.2
1.0
2.0
10.0
50.0
100.0
5.0
10.0
20.0
50.0
100.0
100.0
5.0
10.0
20.0
50.0
100.0
100.0
Volume
of Solution
Added per Plate
0.5 ml.
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1.0
0.5
0.5
0.5
0.5
0.5
1.0
A*& of
Residue
Added per Plate
38.0
192.5
385.0
1925.0
9625.0
19250.0
38.0
192.5
385.0
1925.0
9625.0
19250.0
82.5
165.0
330.0
825.0
1650.0
3300.0
82.5
165.0
330.0
825.0
1650.0
3300.0
His Revertants per Plate
TA98
22
25
30
31
17
6
50
47
57
57
28
20
27
22
19
20
19
20
33
50
41
41
42
37
TA100
134
110
95
100
19
31
199
158
155
119
100
75
123
109
87
98
78
72 + pp.
161
171
115
114
118
117
*pp. • pinpoints, which is a sign of toxicity
-------
ro
rsj
Table 12-4
IN VITKO ASSAYS WITH SATWONl-U A TYPllTr.lIl'.TllM - 170 Scries
Metabolic
Compound Activation '
•it
Negative control
+
DMSO control
(dimethyl sulfoxide) +
Water control
+
Positive controls:
Sodium nzide
2-Nitrofluorene
2-Anthramine
+
Micrograms
of Compound
Added per Plate
0
0
50,000
50,000
50,000
50,000
1.0
10.0
. 2.5
2.5
Histidine-Positive
TA98
• i i
23,13
44,40
26,29
39,45
22,18
47,50
1113
31
481
Rcvortants per P\0to_
TA100
163,169
144,144
177,152
163,178
176,178
178,178
488
178
497
* - • In the absence of metabolic activation, + « in the presence of metabolic activation
-------
Table 12-4 (cont.)
IN VITRO ASSAYS WITH SALMONELLA TYPllIMURtUM - 170 Series
Compound
PS170B
(unfractlonated
base extract)
Metabolic
Activation
r\>
ro
Percent Cone.
of Solution
Added per Plate
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100.0
100.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.10
0.15
/tfi of
Residue
Added per Plate
150.0
375.0
750.0
1500.0
2250.0
150.0
375.0
750.0
1500.0
2250.0
His Rcvertants per Plate
TA98
32
23
37
20 + pp.
3
42
44
45
TA100
163
145
124
o**
157
172
147
PS170
(water from
extractor)
2.0
5.0
10.0
20.0
50.0
100.0
2.0
5.0
10.0
20.0
50.0
100.0
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
24
22
25
23
15 + pp.
1
58
57
43
41
35 + pp.
16 + pp.
156
124
86
115
89
12
145
162
137
138
148
95
pp.
pp.
*pp. • pinpoints, which Is a sign of toxlclty
** - Indicates that no plate count Is available at the specific dose listed. This Is due to the limited
volume of sample.
-------
Table 12-4 (cent.)
IN VITRO ASSAYS WITH SALMONELLA TYPllIMURIUM - 170 Series
Compound
PS170A2 +
PS170A3
(neutrals)
Metabolic
Activation
ro
ro
oo
PS170A3S
(phenols)
Percent Cone.
of Solution
Added per Plate
10.0
20.0
50.0
100.0
100.0
100.0
10.0
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100.0
100.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.05
0.10
0.20
0.05
0.05
0.05
0.05
0.10
0.20
0.05
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.10
0.15
Ag of
ResIdue
Added per Plate
10.0
20.0
50.0
100.0
200.0
400.0
10.0
20.0
50.0
100.0
200.0
400.0
40.0
100.0
200.0
400.0
600.0
40.0
100.0
200.0
400.0
600.0
His Ucvertants per Plate
TA98
3
7
14
«
19 + pp.
- **
29
42
49
24
37
31
20
20
27
-
41
45
39
TA100
190
152
163
137
152
7
166
131
127
156
123 + pp.
136
140
155
51
6
156
176
151
*pp. • pinpoints, which la a sign of toxlclty
** - Indicates that no plate count Is available at the specific dose listed.
volume of sample.
This Is due to the limited
-------
Compound
PS170B
(unfractionated
base extract)
PS170
(water from
extractor)
ro
r\j
Table 12-4 (cont.)
IN VITRO ASSAYS WITH SALHOliF.T.IA TYPIimiUTlJM - 170 Scries
M£ of
Residue
Added p?r Fl.lto
150.0
375.0
750.0
1500.0
2250.0
150.0
375.0
750.0
1500.0
2250.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
Metabolic
Activation
-
-
.
-
+
+
+
+
+
.
.
.
.
•V
+
+
+
+
+•
+
Percent Cone.
of Solution
Ad^od nar Plr.te
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100.0
100.0
100.0
2.0
5.0
10.0
20.0
50.0
100.0
2.0
5.0
10.0
20.0
50.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
Kls Rcvertants per Vlr.
F.A98
32
23
37
20 + pp.
3
42
44
45
24
22
25
23
15 + pp.
1
50
57
43
41
35 + pp.
16 + pp.
TA100
163
145
124
°**
-
157
172
147
156
124
86
115
89
12 + pp.
145
162
137
138
148
95 + pp.
*pp.
pinpoints, which Is n sign of toxtclty
** - Indicates that no plate count Is available at the specific dose listed. This Is due to the limited
volume of sample.
-------
Table 12--4 (cont.)
IN VITRO ASSAYS WITH SA1K|NELIA TYPllIMUUIUM - 170 Series
Compound
Metabolic
Activation
PS170A
(un fractionated
acid/neutral
extract)
r\j
i\s
en
PS170A1
(throw-away from
acid/neutral
extract)
+ ,
+
•f
Percent Cone.
of Solution
Added per Plate
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100.0
100.0
100.0
20.0
50.0
100,0
100.0
100.0
Volume
of Solution
Added per Plate
0.05 ml.
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.10
0.15
0.05
0.05
0.05
0.10
0.15
/Ufi of
ResIdue
Added per Plate
500.0
1250.0
2500.0
5000.0
7500.0
500.0
1250.0
2500.0
5000.0
7500.0
0.0
0.0
0.0
0.0
0.0
0.0
:0.0
0.0
0.0
0.0
His Rovertants per Plate
TA98
20
29
36 ^
17 + PP.
pp.
48
40
41
.**
29
26
23
7 + pp.
"
36
33
44
TA100
138
169
164
110
82 + pp.
208
183
144
-
147
162
124
90
4
161
145
128
* PP» " pinpoints, which la a sign of toxicity .
** - indicates that no plate count is available at the specific dose listed. This is due to the limited
volume of sample.
-------
The results of an experiment using all five strains of
typhiinuriuni — TA 1535, TA1537, TA1538, TA98, and TA100 ~ are
shown in Tables 12-5 and 12-6. Only three of the six fractions
of each sample were tested. However, these three fractions con-
tain all the potential mutagenic pollutants in the sewage sample.
They are the fractions PS140A and PS170A (the unfractionated
acid/neutral extract), PS140B and PS170B (the base extract), and
PS140 and PS170 (the water from the extractor). The dose ranges
were varied in order to best utilize the limited volumes of sam-
ple, while at the same time reaching for the highest doses. In
some cases, only four doses were used. No mutagenic activity was
evident with any of the strains, in the presence or in the
absence of metabolic activation.
None of the experiments conducted indicate that the frac-
tions of the sludge sample 140, or the fractions of the secon-
dary effluent sample 170, are mutagenic in the standard Ames
Salmonella/microsome procedure, either with or without meta-
bolic activation.
Because of the toxicity at higher doses, it was difficult
to determine if these fractions possessed mutagenic activity at
very high doses. However, the fact that bacterial toxicity was
evident is of interest in itself. An evaluation of the cytotoxic
actions of these samples is shown in Figures 12-1 and 12-2 and
correlate the amount of residue weight (dose) with the decrease
in spontaneous revertants. The data show that the bacterial
toxicity of the fractions did qualitatively demonstrate a log
dose-response relationship for both TA98 and TA100 strains of JiL.
typhimurium. A critical dose of about 10 ug of residue per
plate for the phenol fraction in digested sludge was suggested
from this plot (Figure 12-1). Other fractions which produced
bacterial toxicity, observed a lesser decrease in the number of
spontaneous revertants over the control. The least toxic was the
A-l throw away fraction containing the lipids. A different pic-
ture emerged for the secondary effluent (Figure 12-2) where the
non-extractable organics containing fulvic and humic substances
were the most toxic followed, as in the sludge, by the neutrals
and phenols. The unfractionated extract was the least toxic,
possibly indicating that the extracted compound exerts less
effect in a complex mixture than do the individual fractions.
While the current study is primarily concerned with the purgeable
and extractable organics, the non-extractable organics may in
fact be more toxic and should receive further study.
226
-------
Table 12-5
IN VITRO ASSAYS WITH SALMONELLA TYPHTHUKT.UH -
Metabolic
Compound Activation
*
Negative control
+
DMSO control
(dimethyl sulf oxide) +
Water control
+
Positive controls:
Sodium azide
9-Aminoacridine
2-Nitrofluorene
2- Anthramine
+
Microgramg
of Residue
Added per Plate
0
0
50,000
50,000
50,000
50,000
1.0
100.0
10.0
2.5
2.5
— i A
.'•f W iJ i; L X C D
Histidine Rovertants per Plate
TA1535
22,17
14,19
16
20
31
18
312
21
759
TA1537
4,4
6,6
6
11
4
9
1022
18
939
TA1538
11,9
24,26
12
13
14
16
472
15
876
TA9U
24,21
30,26
25
31
23
28
967
30
&G8
TA100
115,121
116,113
121
106
129
110
595
156
903 •
* - * in the absence of metabolic activation, + » in the presence of metabolic activation
-------
Table 12-5 (cont.)
IN VITRO ASSAYS WITH SALMONELLA TYPHIMURIUM - 140 Series
Compound
PS140A
(unfractionated
acid/neutral
extract)
Metabolic
Activation
ro
ro
00
PS140B
(unfractionated
base extract)
Mlcrogratns
of Residue
Added per Plate
19.3
38.5
192.5
385.0
1925.0
9625.0
Htatidtne Rcvcrtants per Plate
19.3
38.5
192.5
385.0
1925.0
9625.0
16.4
41.0
82.0
164.0
410.0
820.0
16.4
41.0
82.0
164.0
410.0
820.0
TA1535
11
20
25
30
22
31
10
18
14
12
7
5
10
12
14
12
12
14
16
12
16
15
5
7
TA1537
5
4
5
6
6
6
6
8
6
7
8
8
6
4
5
4
9
10
9
7
7
8
6
12
TA1538
13
12
18
9
17
14
12
18
21
18
19
17
6
9
6
10
8
18
23
22
23
22
34
19
TA98
31
18
25
19
21
15
25
21
26
24
30
18
38
25
21
30
24
21
29
30
25
23
18
21
TA100
110
138
116
85 +
89
39
109
123
105
122
133
40
136
126
137
98
151
96
141
99
101
95
96
106
pp.
* pp. • pinpoints-, which IB a ilgn of toxlclty
-------
Table 12-5,(cont.)
IN VITRO ASSAYS WITH SALMONELLA TYPIITMIIRIIIM - UO Scries
Micrograms
Metabolic of Residue Histidtne Revertants per Plate
Compound Activation Added per Plate TA1535 TA1537 TA1538 TA98 TA100
PS140 - ' 0.0 (2.0%)* 9 6 12 34 120
(Water from extractor) - 0.0 (5.0%) 11 5 7 28 105
0.0 (10.0%) 18 10 19 21 80
0.0 (20.0%) 12 5 14 31 130
0.0 (50.0%) 10 3 15 25 69
+ . 0.0 8 9 17 28 94
+ 0.0 10 7 21 25 81
+ 0.0 98 15 22 96
+ 0.0 10 8 21 ^ 19 64
+ 0.0 5 5 17 + pp.23 85
* The percent concentration of solution added per plate is listed in the parentheses. In each case,
0.05 ml. was the volume added.
** pp. • pinpoints, which is a sign of toxicity
-------
Table 12-6
IN VTTRQ ASSAYS WITH SALMONffJA TYPHTTjimiUM - 170 Series
Metabolic
Compound Activation
Negative control -*
a.
DMSO control
(dimethyl sulfoxfde) +
Water control
+
ro
o Positive controls:
Sodium azide
9-Aminoacridine
2-Nitrof luorene
2-Anthramine
+
Micrograus
of Residue
Added PC-..- Plate
, o
0
50,000
50,000
50,000
50,000
1.0
100.0
10.0
2.5
2.5
Hist.ldinc Rovertants per Plnte
TA1535
22,17
14,19
16
20
31
18
312
21
759
TA1537
4,4
6^6
6
11
4
9
1022
18
939
TA1538
11,9
24,26
12
13
14
16
472
15
876
TA90
24,21
30,26
25
31
23
28
9G7
30
868
TA100
115,121
116,113
121
106
129
110
595
156
903 •
* - 3 in the absence of metabolic activation, + a in the presence of metabolic activation
-------
Table 12-6 (cont.)
IN VITRO ASSAYS WITH SALMONELLA TYPHTMURIUM -170 Series
(A)
Compound
PS170A
(unfractionated
acid/neutral
extract)
Metabolic
Activation
PS17OB
(unfractionated
base extract)
Micrograms
of Residue
Added per Plate
250.0
625.0
1250.0
2500.0
250.0
625.0
1250.0
2500.0
75.0
188.0
375.0
750.0
75.0
188.0
375,0
750.0
Histidine Reyertants per. Plate
TA1535
19
27
39
30 +
' 13
8
11
15
38
24
31
36
11
18
22
17
TA1537
5
10
* 8
PP. 0
9
12
12
5
4
10
8
pp.
7
7
10
4
TA1538
18
9
5
5 +
34
21
25
20
7
9
9
8 +
26
20
3i
13
TA98
30
28
21
pp. o
35
24
30
21
24
28
20
pp. 7 +
23
31
35
20
TA100
115
112
105
109
114
107
105
103
93
103
89
pp. 0
88
94
98
115
pp.
pinpoints, which la a sign of toxlcity
-------
ro
u»
ro
Table 12-6 (cont.)
IN VITRO ASSAYS WITH SALMONELLA TVPHIMURIUM - 170 Series
Compound
PS170
(Water from extractor)
Metabolic
Activation
Micrograms
of Residue
Added per Plate
V?
0.0 (2.07.)
0.0 (5.0%)
0.0 (10.07,)
0.0 (20.0%)
0.0 (50.0%)
0.0 (2.0%)
0.0 (5.0%)
0.0 (10.0%)
0.0 (20.0%)
0.0 (50.0%)
Histidine Rcvertants per Plnte
TA1535
18
29
24
33
34
40
22
14
18
26
TA1537
11
7
8
4
10
5
10
6
13
6
TA1538 TA90
10
15
10
12
5
26
16
33
21
14
28
23
20
** 31
+ pp.18
35
34
28
30
21
TA100
109
104
109
95
113
112
119
92
99
119
* The percent concentration of solution added per plate is listed in the parentheses. In each case,
0.05 ml, was the volume added.
** PP- • pinpoints, which is a sign of toxicity
-------
ro
CO
CO
§ 100
CD
80
<:
00
0 60
5
00
? 40
o
oc.
LU
Q.
20
TA-100 WITHOUT
METABOLIC ACTIVATOR
DIGESTED SLUDGE
PHENOLS
10 TOO 1000
AMOUNT OF MATERIAL ADDED PER PLATE (>JG)
10,000
Figure.12-1 Toxicity of Different Fractions Present in Digested Sludne.
-------
ro
u>
TA-100 WITHOUT
METABOLIC ACTIVATOR
SECONDARY EFFLUENT
BEFORE CHLORINATION
1 10 TOO " 1000 10,000
AMOUNT OF MATERIAL ADDED PER PLATE (JJG)
Fiqure 12-2 Toxicity of Different Fractions Present in Secondary Effluent Before Chlorination.
-------
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-------
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22. Little, A. D. "Development of Protocols for Analysis of Priority
Pollutant Pesticides and PCBs in Raw Municipal Waste Water." A. D.
Little, Inc., EPA Contract Task 5, July (1978).
23. McCann, J., Spingarn, N. E., Kobori, J. and Ames, B. N. "Detection
of Carcinogens as Mutagens: Bacterial Tester Strains With R Factor
Plasmids." Proc. Nat. Acad. Sci. USA 7£, 979-983 (1975).
24. McCann, J. Choi, E., Yamasake, E. and Ames, B. N. "Detection of
Carcinogens as Mutagens in the Salmonella/Microsme test: Assay of
300 Chemicals." Proc. Nat. Acad. Sci. USA 72, 5135-5139 (1975).
236
-------
25. Manka, J. et. al. "Characterization of Organics in Secondary
Effluents." Envrion. Science Technology 8_, 1017 (1974).
26. Matthews, P. J. "Growth Characteristics of a Sewer Sline."
Environ. Pollut. 1_0, 79 (1976).
27. Mattsson, P. E. et. al. "Gas Chromatographic Determination of
Polychlorinated Biphenyls and Some Chlorinated Pesticides in
Serage Sludge Using a Glass Capillary Column." 0. Chromatography
124. 265 (1976).
28. National Pollutant Discharge Elimination System, Appendix A,
EPA (1972).
29. Oiler, W. L. and Cranmer, M. F. "Analysis of Chlorinated
Insecticides and Congeners." 0. Chromatog. Sci., 1J3, 296 (1975).
30. Painter, H. A. "Organic Compounds in Solution in Sewage Effluents."
Chem. Ind. £.818-822 (1973).
31. Poirier, L. A. and Simmon, V. F. "Mutagenic-carcinogenic Relation-
Ships and the Role of Mutagenic Screening Tests for Carcinogenicity."
Clin. Toxicol. £(5), 761-771 (1976).
32. Reichert, J. et. al. "Carcinogenic Substances Occuring in Water
and Soil - XXVII: Further Studies on the Elimination From Waste-
water of Carcinogenic Polycyclic Aromatic Hydrocarbons." Arch.
Hyg. Bakt. _155_, 18-40 (1971).
33. Sandra, P. and Verzele, M. "Surface Treatment, Deactivation and
Coating in (GC) (Glass Capillary Gas Chromatography)." Chrom-
atographia 10, 419 (1977).
34. Scheike, 0. D., Comins, N. R. and Pretorius, V. "Wisker-Walled
Open Tubular Glass Columns for Gas Chromatography." J. Chrom-
atography 112, 97 (1975).
35. Schieke, J. D. Comins, N. R. and Pretorius. V. "Whiskers: A
New Support for Glass Open Tubular Columns in Gas Chromatography."
Chromatographia §, 354 (1975).
36. Schmidt, T. T. et. al., Bull. Envrron. Contam. Toxicol £,
532 (1971).
37. Schomburg, G. Husmann, H. and Weeke, F. "Preparation, Performance
and Special Applications of Glass Capillary Columns." J.
Chromatography 9£, 63 (1974).
38. Shulte, E. "Coating Glass Capillary Columns After Deposition
of Colloidal Silicic Acid." Chromatographia £, 315 (1976).
237
-------
39. Southwest Research Institute, "Centrifuge Method for Analysis of
Chlorinated Pesticides and PCBs in Sludge." Southwest Research
Institute on EPA Contract, Nov., 1978.
40. Stalling, D. L. m et al. "Cleanup of Pesticides and Polychlorinate
Bichenyl Residues in Fish Extracts by Gel Permeation Chromatography."
J. Assoc. Offic. Anal. Chemists, 55, 32 (1972).
41. Steele, H. A. "The Nations Water Resources." Dept. Interior,
Washington D. C. (1968).
42. Timofieva, S. S. and Stam, D. I. "Separation by Thin Layer
Chromatography of Polyhydric Phenols and Their Oxidation Products
in Waste Water." J. Anal. Chem. 31_, 198 (1976).
43. Ward, P. S. "Toxic Pollutants Control: Progress at Last." J.
Water Pollution Control Fed. 49, 6 (1977).
44. Zweig, G., "Analytical Methods for Pesticides, Plant Growth,
Regulators and Food Additives." Vol. V, Academic Press, NY (1967).
238
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Appendix I
Protocols for Integrated
Analysis of Priority Pollutants
239
-------
Method 100 - Purgeable Organics by Purge and Trap/Capillary GC/MS
110 Scope and Application
111 This method allows the determination of low molecular
weight organics contained in a water, sewage, or sludge
sample. It has also been utilized for sediment sam-
ples. Table 100-1 lists the compounds appropriate for
this method. Among these, those indicated by an aster-
isk are poorly retained in the trapping stage and
therefore quantitate with a lower sensitivity than com-
monly seen for the majority of these compounds.
120 Summary
121 This method is a modification of the standard Bellar-
Lichtenberg technique developed by EPA. It has been
devised using a Hewlett-Packard 7675A Purge and Trap
Sampler, but is applicable to any system capable of the
purge and trap technique. In this method, the aqueous
sample is spiked with a recovery/quantitation standard,
diluted if necessary with purgeable-free water, and
purged with a stream of organic-free helium. The gas
stream is then passed through an inert adsorbent trap
at room temperature where the entrained organics are
240
-------
Volatile*
2 * Acrolein
3 * Acrylonitrile
4 Benzene
18 Bis(2-chloroethyl)-
ether
17 Bischloromethylether
48 Bromodichloromethane
47 Bromoform
6 Carbontetrachloride
7 Chlorobenzene
51 _. Chlorodibromoroethane
16 * Chloroethane
19 2-chloroethylvinylether
23 Chlorofonn
25 1,2-Dichlorobenzene
26 ' 1,3-Dichlorobenzene
27 1,4-Dichlorobenzene
13 1,1-Oicnlo'oetnane
10 1,2-Dichloroethane
29 1.i-Dichlc^oetnyiens
32 1,2-Oichlo'-opropane
33 1,2-Oichloropropylene
50 * Dichlorodiflouramethane
33 Ethylbenzene
12 Hexachioroethane
46 Methylbromiae
45 * Methylchloride
44 Methylenechloride
15 1,1,2,2-Tetrachloroethane
8S Tetrachloroethylene
86 Toluene
30 1,2-Transiiichloroethylene
11 1,1.1-Trichloroethane
14 1,1,2-Tricnloroethane
87 Trichloroethylene
49 Trichloroflouromethane
88 * Vinylchloride
Table 100-1 Compounds Detected by Capillary GC
Purge and Trap Analysis
241
-------
retained. Upon completion of the purging, the trap is
heated and back-flushed with organic-free helium to
desorb the trapped organics. This sample stream is
^ passed directly into a capillary GC column where it is
cryotrapped at liquid nitrogen temperatures. When all
of the sample has been desorbed and cryotrapped, the
coolant is turned off and the cryotrap warmed with a
flush of hot air. The GC or GC/MS analysis then
ensues.
122 This method is recommended for use only by an analyst
experienced in purge and trap analysis, or under the
close supervision of such a person.
130 Apparatus and Reagents
131 For sample preparation, see section 140.
132 Purging system, Figure 100-1
a. Hewlett-Packard 7675A Purge and Trap Sampler,
or equivalent
b. Replacement glass-filled teflon gaskets
c. Steel 1/4" tube traps packed with Tenax-GC
(0.4 g) and pre-conditioned at 250 degrees
centigrade.
242
-------
FIGURE 100-1 Purge and Trap System Schematic
PRE-PURGE CYCLE
Coolant
PURGE CYCLE
Cooltnt
*-To Column
DESORB CYCLE
Coolant
L»-ToColurT
VENT CYCLE
Coolsnl
243
-------
133 Glassware — all purgeable-free and stored in an oven
at 150 degrees centigrade prior to use. No chemicals
or solvent vapors should be permitted in the oven. No
open containers of solvent should be allowed in the
room where this analysis is performed.
a. Sample thiefs — cut off 10 ml pipettes with
at least 1 ml graduations showing.
b. Sample tube — threaded top centrifuge tubes
(15, 70 ml)
c. Syringe — 10 microliters with teflon-tipped
plunger
134 Organic-free water and holding vessel, Figure 100-2
a. Magnetic stirrer
b. Teflon stir bar
135 Soap bubble flowmeter, 25 ml
136 Purging gas — ultrapure helium
a. Catalytic scrubber for gas — Aadco #173 or
equivalent
244
-------
TO AIRLOCK
STOPCOCK
PURGE GAS INLET
FRITTED GLASS
BUBBLER
TEFLON STIR BAR
FIGURE 100-2 Vessel For Purgable-Free Water
245
-------
137 Cryotrap system, Figure 100-3
a. Thin wall stainless steel trap, Figure 100-4
b. Swage or millitorr high vacuum connectors
c. Liquid nitrogen reservoir with pressure deli-
very
138 GC/MS System
a. Capillary-capable GC with split/split less
injector
b. SE-54 (JS.W Scientific) 30 M capillary column,
or equivalent
c. MS/DS System or FID Detector
139 Recovery/Quantitation Internal Standard
a. Solution in water prepared daily from a metha-
nol stock
140 Sample Preparation and. Pjes.e.rya.tj.P.n
141 Sample must be collected in a screw-cap vial with zero
headspace, sealed with a teflon cap liner or face. The
sample bottle should be muffled in an oven or kiln at
450 degrees for at least 1 hour and then sealed prior
246
-------
crimped _^
CROSS SECTION
o
O
a FROM CAPILLARY INJECTOR
b TO REST OF GC COLUMN, MASS SPECTROMETER
c WARM AIR INLET
d COOLANT INLET (FROM LIQUID NITROGEN RESERVOIR)
Figure 100-4 Cryotrap Designs : A) Notched Tube; B) Aluminum
Sandwich; C) Stainless Steel Tube
247
-------
to use. Caps and teflon liners should be boiled! in
organic free water immediately prior to sealing the
muffled vials.
142 Samples should be refrigerated immediately after col-
lection, stored at 5 degrees centigrade and analyzed
prior to the formation of bubbles or within a week,
whichever is sooner.
143 Sludge and sediment samples should have a dry weight
determination, according to Standard Methods.
150 Sample Furqirio;
151 Prior to an analysis, the Tenax trap must be condi-
tioned and the analytical system shown to be contami-
nation-free. Standard analyses of reference compounds,
including the actual priority volatiles, are needed to
supply quantitetion and chromstographic behavior indi-
ces.
152 The Tenax trap should be replaced periodically.
153 The sample tube with 3 ml of organic-free water is
shown to be background-free by blank analysis.
248
-------
154 A recovery spike for that day's analyses is prepared as
follows:
a. 50 ml of tested organic-free water is placed
in an organic-free 50 ml volumetric.
b. A 10 microliter syringe is rinsed several
times with boiling water.
c. After a few minutes cooling, 10 microliters
from a 1 mg/ml methanol stock solution is
injected into the water. The volumetric is
now immediately capped and the spike dis-
persed with sonication or gentle swirling.
This spike is now 2 ng/ul.
155 Using an organic-free sample thief, 1 or 2 ml of mixed
sample (with solids resuspended prior to opening) is
transferred to the 3 ml organic-free water. The sample
is then immediately spiked with 5 ul of the recovery
standard using a boiling-water rinsed syringe.
156 The sample is sealed to the purge and trap system. The
purge is begun and carried out at a gas flow rate of 20
ml/minute for 15 minutes.
157 Five minutes prior to the end of the purge period, the
coolant for the cryotrap is activated to bring the
249
-------
cryotrap to a stable cold condition prior to initiation
of the desorbtion.
158 The desorbtion occurs at a flow rate of 1 ml/minute for
10 minutes, with a trap temperature of 200 degrees cen-
tigrade. During this time the splitter should be
closed. Typically, the Mass Spectrometer analysis is
initiated at the beginning of the desorb cycle in order
to detect any failure of the cryotrap.
159 Breakthrough of components of masses higher than 45
during the desorb phase invalidates the analysis.
160 GC/MS/DS Analysis
161 Upon the successful completion of cryotrapping, the
coolant flow is stopped and warm air is blown over the
column in the reverse direction for 60 seconds. These
events should be synchronized with the cessation of
desorb flow from the Tenax trap and with the opening of
the splitter.
162 The GC analysis is then carried out according to the
parameters presented in Table 100-2.
163 The data reduction of raw MS results should utilize the
250
-------
INSTRUMENT PARAMETERS:
MASS PARAMETERS:
INTERFACE NUMBER 0
SUB-INTERFACE 0
2ND ACQU INTERFACE -1
SUB-INTERFACE -1
NUMBER OF ACQU BUFFERS 16
INSTRUMENT TYPE Q
FULL SCALE MASS 1024
ZERO SCALE MASS 1
INTENSITY/ION 2
ACQUISITION DIRECTION UP
SAMPLES/PEAK - CENTROID 10
SAMPLES/PEAK - FRAGMENT 10
PEAK WIDTH (MMU) 1OOO.
OFFSET AT LOW MASS (MMU) O
OFFSET AT HIGH MASS (MMU) 0
VOLTAGE SETTLING TIME(MS) 4
MINIMUM PEAK WIDTH
MIN FRAG WID AS 7. PEAK WID
BASELINE TO SUBTRACT
MINIMUM AREA AFTER MERGE
MERGE TOL AS 7. PEAK WIDTH
AREA TOL (DELTA SORT AREA)
ALIGN TOL AS 7. PEAK WIDTH
MAX tt OF PEAKS TO READ
MASS DEF AT 10O AMU (MMU)
NOISE REJ FOR ENHA (O-4 S.D
TAIL REJ FOR ENHA (-1=NONE)
BKGND MULTIPLIER IN ADD
ADD OR AVERAGE IN ADD
3
BO
0
1
80
20
80
2000
30
) 2
0
1. 003
AVER
LOW MASS. 34
HIGH MASS: 334
CENT S/P: 10
FRAG S/P: 10
ACTUAL:
ACTUAL:
10
10
MIN PEAK WIDTH:
A/D THRESHOLD:
UP: 0. 45 L*
DOWN: 0. OO L
SAMP INT (MS): 0. 150
SAMP INT (MS): O. ISO
TOP:
BOTTOM:
0. 00
0. O5
PEAK WIDTH: 1000.
INTEN/ION: 2
MIN FRAG WIDTH 7.:
BASELINE: 0
80 MIN AREA: 2O
MODE:
CENTROID POSITIVE ION
GC Parameters
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Table 100-2 Instrumental Conditions for
VOA Analysis
0. 3tJ
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251
-------
internal reference compounds for quantitation and/or
recovery standards. The sensitivity of the method will
depend on the detection limit for the individual GC/MS
system, but ppb analyses should be achievable by using
an appropriate sample size. With initial calibration
of the instrument in an appropriate concentration range
(to give a signal/noise of no less than 50), both quan-
titation and recovery information can be obtained from
the reference standards.
164 Recalibration with standards should be performed fre-
quently, at least every 15 analyses.
170 Control of Contamination
171 Organic-free water is prepared by boiling distilled
water under a purge of organic-free gas. The purging
system for organic-free water should be equipped with
an air lock, or otherwise isolated from the atmosphere.
No solvents should be permitted in open containers any-
where in the room where these analyses are performed.
172 Between samples, the purge tube that actually con-
tacts the sample should be heat-gunned or replaced.
Care should be taken to avoid introduction of the sam-
ple into the lines, or on exposed surfaces of the
252
-------
instrument or purging system.
173 To document the integrity of the analysis, blank deter-
minations must be made between every pair of real ana-
lyses. These water blanks also can be used as dilution
water for the following analysis.
174 The gaskets, or other sealing devices used to connect
the sample tube, should be inspected for wear or conta-
mination. The effluent flow from the Tenax trap can be
monitored during purging to assure a closed system with
no pressure losses.
175 The stock solutions used to make the recovery standard
should be stored at sub-zero temperatures and protected
from losses and contamination.
176 The EPA EMSL recommendations for method verification
and quality analysis assurance for volatiles are appli-
cable to this method.
253
-------
Method 200 — Purge and Trap Method for Volatile (Alternative)
210 Scope and Application
211 This method covers the determination of various low-
molecular weight hydrocarbons, including most of the
halogenated Cl and C2 compounds. The complete list of
compounds included in this procedure is provided in
Table 200-1.
212 This method is applicable to the measurement of these
compounds in municipal sewages and sludges. It can be
used to meet the monitoring requirement of the National
Pollutant Discharge Elimination System (NPDES). As
such, it presupposes a high expectation of finding,
quantitatively, specific compounds of interest. If the
user is attempting to screen samples for all of the
compounds in Table 200-1, he should refer to Section 282
for general guidance.
220 Summary
221 The method offers several procedural alternatives,
dependent on the availability of specific purging appa-
ratus and the nature and extent of interferences. The
254
-------
TABLE 200-1 Volatile Low Molecular Weight Compounds
Detectable with the Purge and Trap Method
Compound
Cl/Br/Methanes
methylchloride
methylenechloride
chloroform
carbontetrachloride
methyl bromide
.bromoforn
chlorodibromomethane
bromodichloro methane
dichlorodifluoramethane
trichlorofluoromethane
Cl Ethanes
chloroethane
1,1 - dichloroethane
1,2 - dichloroethane
1,1,1 - trichloroethane
1,1,2 - trichloroethane
1,1,2,2 - tetrachloroethane
hexachloroethane
Alkenes^
acrolein
acrylonitrile
Compound
Cl Ethylenes, Propane
vinylchloride
1,1 - dichloroethylene
s
1,2 - transdichloroethylene
trichloroethylene
tetrachloroethylene
1,2 dichloropropane
1,2 dichloropropylene
Ethers
bi schloromethylether
2-chloroethylvinyl ether
bis (2-chloroethyl) ether
bis (2-chloroisopropyl) ether
Cl-Benzenes
benzene
chlorobenzene
1,3-dichlorobenzene
1,2-dichlorobenzene
1,4-dichlorobenzene
toluene
ethylbenzene
255
-------
procedure describes the use of purging with a purified
inert gas, and trapping with a solid adsorbent or a
combination of two solid adsorbents to efficiently
recover the materials with a minimum of contamination.
Chromatographic conditions are suggested for the accu-
rate measurement of the compounds.
222 This method is recommended for use only by an analyst
experienced in the analysis of trace organics at ppb
level, or under the close supervision of such qualified
persons.
230 Apparatus and Reagents
231 For sample preparation, Section 250
231.1 Purging system, Figure 200-1
a. Erlenmeyer purging flasks — 1000 ml
with 24/40 ground joint
b. Purging head piece with 24/40 ground
joint
c. Glass covered magnetic stirring bar
(approximately 50 mm long x 6 mm OD).
d. Water bath — electric frying pan
e. Magnetic stirring table with heater
256
-------
FIGURE 200-1 1000 ml Erhlenmeyer Purging Flask
257
-------
f. Thermometer — glass, 0-100@C
232.2 Trap, Figure 200-2
a. Stainless steel traps (approximately
220 mm long x 6.35 mm OD) containing
0.4 g of Tenax GC, followed by 0.2 g
of Chromosorb 102, and marked by an
arrow on the swagelok for the direc-
tion of gas flow
b. Stainless steel trap guards (approxi-
mately 120 mm long x 6.35 mm OD) con-
taining approximately 0.2 g of Tenax
GC
c. Stainless steel plugs (6.35 mm)
231.3 Volumetric flasks — 100 ml with glass stopper
231.4 Purgeable-free water glassware, Figure 200-3
a. Erlenmeyer flasks — 4000 ml with 40/50
joint
b. Purging head pieces with 40/50 joint
c. Teflon-coated magnetic stirring bar
(762 mm long x 12.7 mm)
258
-------
FIGURE 200-2 Tenax-GC Trap and Guard
Guard
Trap
6.35 mm OD
259
-------
FIGURE 200-3 4-liter Flask for Purgable-Free Water
Teflon Stopco
260
-------
231.5 Torch — propane
231.6 Soap bubble flowmeter — 100 ml
231.7 Springs for fastening the purging vessels
231.8 Purging gas — N2, water compressed
231.9 Catalytic gas purifier
a. Tubular heater -- 1000°C
b. Quartz tubing (approximately 460 mm
long x 19 mm OD)
c. Catalyst for TOC analysis — Beckman
d. Molecular sieve (approximately 460 mm
long x 13 mm OD)
231.10 Rotameter —.0 to 500 ml/minute of air
231.11 Muffled furnace or pottery kiln — 450° C
231.12 Trap conditioning oven (drying) — 275°C
231.13 Glass tubing (approximately 610 mm long x 25 mm
OD) with one end sealed and packed with 10 mm
thick wool at the end
261
-------
231.14 Screw cap septum vials with Teflon-lined septum:
7 ml, 25 ml, 40 ml
231.15 Aluminum tares
231.16 Distilled water
232 For quantitation, Section 260
232.1 Gas chromatograph — equipped with a 4-way valve
gas injection system. The recommended detectors
and columns are discussed in Section 260.
232.2 Heating tape (approximately 500 mm long)
232.3 Portable tubular heater (approximately 250 mm x
25 mm ID) ~ 250°C
232.4 Variac
232.5 Recorder — potentiometer strip chart (10 inch)
compatible with the recorder. Preferable with
the microdata processor for integrating detector
readings.
262
-------
232.6 Reference materials — assay quantity of com-
pound(s) of interest, and purgeable-free water,
Section 250.
240 Sampling and Preservation
241 Sample must be collected in screw cap vials with zero
head space and sealed with an inert liner (teflon)
incorporated into the septum. The number of samples
required is discussed in Procedures 272 and 281. The
vials should be muffled at 450°C overnight and the sep-
tum pre-washed with methanol, boiled in distilled
water, and dried at 103°C to minimize contaminations
and loss of volatiles. Conventional sampling practices
should be followed to collect representative samples.
242 Preservation requirements can be found in EPA BAT
screening protocols. As a general guideline, refrig-
erate or ice the sample within 7 days, and complete the
analysis within 30 days of collection. Procedures for
storing the sample in the trap are provided in Section
250.
243 Dry solids of the sludge sample should be determined
according to Standard Methods.
263
-------
250 Sample Purging
251 Condition the traps with the guard attached at 250°C
overnight and adjust N2 gas flow at 20 ml/minute for
each trap.
252 Set the temperature of the catalytic gas purifier at
900°C one day before purging the sample and check for
flow of N2 through the purifier.
253 Install on a daily basis a freshly conditioned trap on
the purified purging gas line so that residual impuri-
ties in the purge gas can be further removed.
254 Place the muffled 1000 ml Erlenmeyer flask in the water
bath at 60°C. Attach the purging head to the flask and
secure with springs. Connect a well-conditioned trap
along with the guard and the N2 purging gas line to the
head piece, and adjust the N2 flow to 200 ml/minute by
measuring the flow with the soap bubble flowmeter con-
nected to the end of the guard. Transfer 100 ml purge-
able-free water (Procedure 259) into the flask and
purge under stirring for 20 minutes.
255 Analyze the trap by GC for system and purgeable-free
water blank, Section 260.
264
-------
256 Quantitatively transfer the entire amount of sample
from the sample vial into a muffled 100-ml volumetric
flask and fill with the purgeable-free water to mark.
Transfer the diluted sample to the 1000 ml purging
flask with a well-conditioned trap along with the guard
connected to the purging head and purge under stirring
for 20 minutes.
257 Analyze the trap on GC immediately after purging, Sec-
tion 260.
258 If the purged sample cannot be analyzed immediately,
the trap should be capped and placed in a muffled glass
tubing with one end sealed and padded with glass wool.
The glass tubing is pull sealed with the aid of a pro-
pane torch long with a stream of N2 gas blowing into
the tube. This is necessary to prevent contamination
of the trap from the air trapped in the glass tubing.
259 Preparation of purgeable-free water
259.1 Boil vigorously 2-3 liters of good quality dis-
tilled water in a 4-liter flask for 15 minutes.
259.2 Allow to cool gradually under positive pressure
as supplied by a stream of N2 gas purging con-
265
-------
tinuously through the water under stirring.
259.3 Fill the muffled 100 ml volumetric flask full to
overflow with the purged warm distilled water.
Place the muffled stopper tightly on the flask
with no dead volume, and let it cool down fur-
ther to room temperature. In this way, diffu-
sion of volatiles from ambient air into the
water can be minimized.
259.4 Use the purgeable-free water from the 100 ml
volumetric flask. Prepare purgeable-free water
on a daily basis.
260 Ouantitation
261 Quantitative measurements with this method are made by
gas chromatography. While the choice of detector and
column packing is left to the discretion of the ana-
lyst, recommendations are made below based on general
applicability of all of the parameters included in this
test procedure. A flame ionization detector is recom-
mended for routine analysis. The detector of the gas
chromagraphic system must be operated within its linear
response range and the noise level should be less than
2% of fullscale deflection. Standards prepared from
266
-------
the assayed reference materials must be injected fre-
quently as a check on the stability of operating condi-
tions. It is suggested that the concentration of stock
standards be prepared on a volumetrical basis. A volu-
metric concentration of 50 ul/ml for the stock stan-
dards is suggested. Serial dilution can be prepared in
methanol until a concentration is reached that is
suitable for calibration of the instrument. The weight
concentration can be computed by multiplying the den-
sity of the specific reference materials.
262 The 38 volatile organics listed in Table 211A can be
determined by this procedure. A 12 ft x 2 mm ID Pyrex
glass column packed with 0.2% Carbowax 1500 on Carbo-
pack C, 60/80 mesh, is suggested. The sample is
injected by desorbing from the trap at 250°C for 4
minutes with the aid of a tubular heater (250°C) and a
4-way valve wrapped around with a heating tape (80°C).
After flushing the sample into the column for 4 min-
utes, the temperature of the column is programmed to
increase from 40°C to 200°C at a rate of 8°C/minute and
hold at 200°C for 16 minutes. Table 200-2 lists the
relative retention times of these volatile organics
under the conditions given above. The procedures have
good general utility for overcoming interferences in
the analysis of volatile organics in sewage and sludge.
267
-------
TABLE 200-2
Relative Retention Times of Volatile
Organics on Packed GC Column
(0.2% Carbowax 1500 on Carbopack C)
Compound
1,1-dichloroethane
1,2-transdichloroeth.vlene
Chloroform
1,2-dichloroethane
Carbon tetrachloride
1,1,1-trichloroe thane
Di chlorobromomethane
Trichloroethylene
Benzene
1,2-dichloropropane
Dibromochloromethane
1,1,2-trichloroethane
Tetrachloroethylene
2-bromo-l-chloropropane
2-chloroethyl vinyl ether
Bromoform
Chlorobenzene
Ethylbenzene
1,1,2,2-tetrachloroethane
Toluene
bis(2-chloroethyl) ether
Relative Detention Tine
Chloroform Z-Bromo-l-chloropropanc:
0.85
0.93
1.00
1.10
1.2L,
1.29
1.31
1.57
1.63
1.G8
1.69
1.89
2.13
2.16
2.16
2.32
2.35
2.54
2.71
3.04
3.31
0.37
0.43
0.46
0.53
0.58
0.60
0.61
0.71
0.75
0.77
0.87
C.G7
0.9a
1.
1,
1,
1,
1.
1.
1.
00
01
07
Oci
17
25
40
1.53
268
-------
270 Removal of Interferences
271 The dilution procedures in this section have proven
utility in wastewater and sludge analysis. When this
procedure is followed, recoveries of standards prepared
from the assayed reference materials at a concentration
of approximately 50 ppb (v/v) in purgeable-free water
must be established. If use of this procedure fails to
show the need for the dilution technique to eliminate
interferences with a specific purge and trap glassware,
wastewater, or sludge, the analyst may elect to delete
this procedure with proper justification.
272 Determine the level of compounds of interest, Section
260.
\
272.1 Measure the level of these compounds in waste-
water or sludge at two dilutions — 7 and 25%
for sludge or 25 and 40% for sewage. Section
260.
272.2 Normalize all concentrations determined on the
basis of the higher dilution employed (7% for
sludge or 25% for sewage), and plot on semilog
graph paper with the ordinate in logarithmic
scale for concentration.
269
-------
272.3 Draw a straight line with a negative slope
through these points and extrapolate to zero
sewage or sludge addition. The value obtained
at the intercept on the ordinate represents the
concentration of a given compound to be deter-
mined in purgeable-free water.
272.4 Divide the above value obtained at zero sewage
or sludge addition by the recovery of these com-
pounds of interest determined at approximately
50 ppb (v/v) in purgeable-free distilled water.
This gives the amount of these compounds in 100
ml of clean water. The actual concentration of
these compounds in the original sewage and
sludge can be obtained by dividing by 25% and
7%, respectively. Section 290.
272.5 Use the EPA internal standard, 2-bromo-l-chloro-
propane, in all quantitation studies to minimize
variations in FID responses.
280 Quality Assurance (EMSL Protocol)
281 Standard quality assurance practices should be used
with this method. Field replicates should be collected
to validate the precision of the sampling technique.
270
-------
Laboratory replicates should be analyzed to validate
the precision of the analysis. Fortified samples
should be analyzed to validate the accuracy of the ana-
lysis. The use of an internal standard for computing
the relative FID response (Procedure 272.5) would
improve the accuracy of the analysis by minimizing the
effect of instability of the instrument. Where doubt
exists over the identification of a peak on the chroma-
togram, confirmatory techniques, such as mass spectro-
scopy, should be used.
282 If the sample contains a large number of compounds, so
that the peaks on the gas chromatogram are too close to
each other, the verification of identifications by the
relative retention times becomes extremely unreliable
by GC retention times. A GC-mass spectrometer becomes
the detector of choice.
290 Calculation and Reporting
291 Determine the concentration in the sample according to
the following formula:
291.1 Sewage
Micrograms/liter
271
-------
A = Concentration of compounds of interest
in ppb (v/v), obtained by extrapo-
lating to zero addition of sewage
B = Recovery from purgeable-free water
C = Percentage of the highest dilution made,
25% for sewage
D = Density of the compound of interest
291.2 Sludge
Micrograms/grair, = (BJDJF|EJG)
E = Concentration of compounds of interest
in ppb (v/v)
F = Percentage of the lowest dilution made,
7% for sludge
G = Percentage of dry solids in the sludge
272
-------
Method 300 — Determination of Extractable Organics
by Integrated Analysis
310 Scope and Application
311 This method allows the determination of the acid, neu-
tral, and base fractions of the EPA Priority Pollutants
(Table 300-1) and for non-priority compounds of similar
structure and behavior. The detection of compounds in
the ppb range or below is frequently possible with this
method, depending on the specific compound and on the
sample type.
312 This method has been developed primarily for POTV7
industry samples, and is demonstrably effective for
sewage, effluent, and water samples. It has also been
applied to sediment, sludge, and tissue samples with
some success. It is anticipated that other types of
samples could be handled by this method, with or with-
out modifications.
320 Summary
321 This method consists of three stages: extraction,
cleanup/prefractionation, and analysis. Some varia-
273
-------
Neutral/Base Extractable
Acid Extractable
ro
-4
1
77
78
5
72
73
74
79
75
43
42
66
41
67
40
20
76
82
29
70
1
35
36
68
69
37
39
60
9
52
53
12
83
54
55
56
61
62
63
84
81
8
Acenaphthene
Acenaphthvlene
Anthracene
Benzidine
Benzo(a)anthracene
Benzo(a)pyr»ne
Benzojb)fluoranthene
Benzo(gh1)perlyene
Benzo(k)f1uoranthene
Bis(2-chloroethoxy)methane
Bis(2-chloroUopropyl )ether
BisU-ethyinesv!ipnthalate
q-Bromopnenylphenyl ether
Butylbenzylphthatlate
4 -Chlorophenylphenylether
2-Chloronaphthalene
Chrysene
Diben7o(a,q)anthracene
3,3-Oichlorobenzidine
UietnylphthaUte
OimethyIphthai ate
Dinitrotoluene
2.6-Din1trotolueno
Di-n-butyipht.nalate
Di-n-octylphthalate
1,2-Diphenylhydrazine
Flutranthene
Fluorene
Hexachlorobenzene
Hexachlorob'jtadlene
Hexachlorocyclopentadiene
Hexachloro<" thane
Indenoll ,2.3-cd)pyrene
Hophorone
Naphthalene
tlitrobenzlne
H-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Ni trosodipropylamine
Pyrene
Phenanthrene
1,2.4-Trichlorobenzene
24
31
34
60
59
5/
58
22
64
65
21
102
103
104
105
91
93
94
92
90
98
95
96
97
99
100
101
106
107
108
109
110
111
112
2-Chlorophenol
2,4-Dichlorophenol
'(,4-Oimethyl phenol
4,6-Oinitro-o-cresol
2,4-Oinitrophenol
2-Nitrophenol
4-HItrophenol
2.2-Parachlorometacresol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol
Pesticitlfs/PCB*
a-BHC-Alpha
b-BHC-Beta
*-BHC-(1indane)Ganma
/-BHC-Delta
chlord.me
4,4i-nnn
4.4'-nnE
4,41-UOF
Oieldrin
Endrin
a-endosulfan-Alpha
b-endosulfan-Beta
endosulfan-sulfate
pndrinaldehyde
heptachlor
heptachlorepoxy
PCS 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
Table 300-1 Compounds Detected in Extractables Analysis
-------
tions in the details of the method will exist, depend-
ing on what type of sample is handled.
a. Extraction consists of a stirred liquid-liquid con-
tinuous extraction for 12 hours at pH 2, followed
by 12 hours at pH 12 for most samples. Sediment,
tissue, and sludges too heavy in particulates to be
handled by this method are extracted by alternative
methods. The extracts are dried and concentrated,
and residue weights determined on an aliquot.
b. Cleanup/prefractionation consists of size-exclusion
chromatography followed by secondary chromatography
steps to deal with specific interference problems
using a variety of techniques: adsorption, ion-
exchange, and reverse-phase chromatography. The
acidic components in the acid/neutral extract are
separated at this point for derivatization and spe-
cial analysis.
c. Analysis consists of screening of each fraction by
capillary GC-FID, subsequent recombination of the
neutral components, capillary GC/MS analysis of the
neutral and derivatized acid fractions, and GC/EC
analysis of the neutral fraction to pick up low
levels of PCB's and pesticides. The GC/MS data is
275
-------
analyzed by an automated data searching routine
capable of applying both spectrum matching ~and GC
retention time criteria for qualitative identifica-
tion, and capable of either single-ion or multi-
ple-ion quantitation.
330 General Preparation
331 Glassware
a. All glassware, including sampling vessels, beakers
and flasks, chromatography columns, glass beads,
etc., are cleaned by immersion in a pH sulfuric
acid solution of tetramethylammonium peroxydisul-
fate ("no chromix") followed by a distilled water
rinse. The glassware is then pyrolyzed in a pot-
tery kiln at 450 degrees centigrade for 1 hour.
Upon cooling, the glassware is silanized by treat-
ment with a 5% solution of dichlorodimethyl-silane
in pet ether for 5 minutes, followed by successive
rinses with methanol and methylene chloride.
b. Teflon stopcocks and other teflon parts are acid
washed and water-rinsed, followed by a methylene
chloride solvent rinse.
276
-------
c. An exception to the above is vessels used to col-
lect and contain samples for VGA analysis. In this
case, the glassware is muffled and sealed without
silanization.
332 Preparation of chromatographic materials
a. All common materials in contact with the sample:
teflon boiling stones, sodium sulfate, silica gel,
florisil, glass wool, etc. are soxhlet-extracted
for 6-8 hours with methylene chloride.
b. The florisil and silica gel are screened to remove
fines and lumps.
c. Florisil: After extraction and drying, the flori-
sil is activated in an oven at 140 degrees centi-
grade. In a narrow mouth cleaned jar, a weighed
amount of the activated florisil is deactivated by
adding 0.75 wt % distilled water, and rolling the
sealed bottle on a jar mill overnight. The deacti-
vated florisil must be carefully protected from any
further contact with moisture.
d. Cesium silicate: Silica gel (after extraction,
drying and screening) is slurried in methanol satu-
277
-------
rated with cesium hydroxide (100 grains silica gel
in 300 mis methanol solution). After stirring
vigorously for 1 hour, the suspension is allowed to
settle and is decanted. 100 ml fresh methanol is
added as a rinse and the solids are separated by
filtration through fritted glass. The filtered
solids are washed with 200 ml methanol followed by
300 ml methylene chloride. The solids are air
dried at 40-50 degrees centigrade and stored in a
dessiccator. (Note: This material is used with-
out activation).
e. SX-2 BioBeads: After extraction, the beads are
air-dried and 40 grams are swollen in 50% methylene
chloride/hexane for several hours prior to use.
Upon packing into a column, several column-volumes
of solvent are run through the material prior to
use. After this column is thoroughly rinsed, it
must be calibrated prior to use. Table 300-2 pre-
sents the mixture used for column calibration in
order of elution from SX-2 BioBeads. The cuts
taken for the fractions are indicated. The cali-
bration run is made similarly to a real sample run,
but with 60 ml followed by eighteen 5 ml fractions
taken and analyzed upon conclusion by GC-FID.
278
-------
TABLE 300-2 Calibration Mixture for GPC
COMPOUND FRACTION
2,4,6-trichlorophenol A3
2-chlorophenol* A3
Di-n-octylphthalate* A2
Di-ethylhexylphthalate A2
Heptachlor Epoxide A2
Aldrin A2
Heptachlor A2
Hexanoic Acid Al
* indicates compounds marking the start of the fraction
279
-------
1 24/40 I LIQUID ST1RRER SEAL
2 24/40.1 JOINT
3 2000 ML 3-NECK RB FLASK
« GLASS NECK FILLED WITH SILANIZED BEADS
5 TEFLON 3-WAY STOPCOCK
6 14/20 I JOINT
7 1/4 INCH CORRUGATED TEFLON
8 HEATING MANTLE
9 500 ML 2-NECK RB FLASK
10 3/4 INCH CORRUGATED TEFLON
11 FRIEDRICHS CONDENSER
12 MODIFICATION (VAPOR INLET)
12
1. } 24/40 CONNECTION TO ADDITIONAL CONKXSOR
2. OUTLET COLD FINGER
3. INLET COLDF1NGER
4. ] 34/40 JOINT FOR COLD FINGER
5. CONDENSOR OUTLET
6. CONDENSOR OPENING
7. CONDENSOR INLET
8. NOTE: ONE ARM IS HIGHER
9. § 24/40 FLASK WITH SAMPLE
10. § 24/40 FLASK WITH METHYLENE CHLORIDE
s—\
10
Figure 300-1
Stirred Liquid-Liquid Continuous Extractor and
Steam Distillation Vapor Extractor Evaluated in
the Present Study
280
-------
f. Preparation of glass chromatographic columns: After
columns are silanized and dry, the stopcock is
reassembled. Tamp a small pug of silanized glass
wool into the throat of the column using a glass
stirring rod. Add 5 ml silanizing solution and run
through to cover glass wool. After 5 minutes,
drain into methanol and rinse column with 60 ml
methanol. Disassemble stopcock and rinse barrel
and glass with methanol from a squeeze bottle.
Reassemble stopcock and rinse column thoroughly
with methylene chloride, or pentane in the case of
a florisil column.
340 Extraction
341 Apparatus and materials
a. Stirred liquid-liquid continuous extractor
(Figure 300-1)
b. pH meter
c. Silanized glass beads
d. Variac
e. 500 ml heating mantle
f. Stirring motor
g. Toploading balance
h. Graduated cylinder
281
-------
i. Distilled-in-glass methylene chloride and
methanol
j. Reagent HCL and NaOH solutions
342 Sample handling and preparation sampling techniques
appropriate to trace organics analysis must be used:
sampling apparatus and bottles must be constructed of
glass or teflon, glass surfaces must be clean (muffled
at 450 degrees if possible), and containers to hold
samples for extraction should be silanized or be of
teflon. Refrigeration and prompt analysis is important
for sample integrity, particularly for phenolic com-
pounds.
343 Extraction of water and sewage samples
a. This procedure is the recommended alternative for
all samples excepting those with physical proper-
ties such that this technique is impossible.
b. The components of the extractor apparatus are
cleaned and muffled; the glass parts are silanized.
c. The neck of the extractor is filled with clean
silanized glass beads. 1000 ml of a mixed (solids
resuspended) sample is measured out and the pH
282
-------
adjusted to 2.0 with hydrochloric acid solution.
d. The extractor is filled with approximately 200 ml
distilled-in-glass methylene chloride to cover the
glass beads. The sample is poured in to float
above the methylene chloride. The side vessel is
charged with about 300 ml methylene chloride.
e. The stopcock connecting the extractor vessel and
the side vessel is opened and the relative heights
of the two components adjusted to position the
aqueous-organic interface about 2 cm above the top
of the neck.
f. The stirrer is positioned in place and sealed in
with the mercury seal. It is turned on and set to
a moderate rate, sufficient for rapid mixing, but
gentle enough to prevent emulsification. (For most
samples this is between 50 and 200 rpm).
g. The side vessel is heated to reflux with a mantle
heater. The rate of reflux is adjusted to equal
the maximum flow rate through the glass bead bed.
This requires periodic checking to readjust rela-
tive height of the side-arm vessel and the variac
setting. The extractor should be in a stable con-
283
-------
dition for at least an hour before being left
unattended.
h. At the end of 12 hours reflux, the solvent in the
side-arm vessel is removed and the pH of the aque-
ous phase is raised to 12. A fresh 300 ml of sol-
vent is placed in a new side-arm vessel and step g
is repeated.
i. The extraction is stopped after 12 hours and the
base extract removed. Both the acid and the base
extracts are dried over or by passage through anhy-
drous sodium sulfate (soxhlet-extracted prior to
reactivation), and are K/D concentrated to between
1 and 2 mis.
j. A 10% aliquot of the extract is transferred to a
tared weighing . boat, dried at 100 degrees centi-
grade for 3 hours and weighed on an analytical
balance to £.0.5 mg. The residue is then heated for
an additional period and reweighed. The final
weight, after no further change is seen, is used to
compute the extracted residue in the remainder of
the extract.
284
-------
350 Size-exclusion Chroinatography
351 Apparatus and materials
a. 40 gram SX-2 BioBeads column, pre-equilibrated
and calibrated according to protocols (Sec-
tion 330)
b. Distilled-in-glass pentane, methylene chloride
c. Vortex mixer
d. Precleaned and silanized pasteur pipettes
e. Graduate cylinder, 3, 100 ml, precleaned and
silanized
f. K/D concentration apparatus
352 Preparation
a. The sample (acid or base extract preconcentrated to
1 ml in methylene chloride, residue weight deter-
mined) is diluted 50% with pentane to a find volume
of not more than 3 ml. The sample is mixed by vor-
texing. If acid and base extracts are to be com-
bined, further concentration may be required. For
either separate or combined extracts, the total
residue weight should not exceed 200 mg.
285
-------
b. The column should be rinsed with at least 100 ml
50% pentane/methylene chloride. Care must be taken
to assure the proper equilibration of the column.
If the column has been stored for several hours or
more under a reservoir of solvent, the solvent
should be pipetted off and replaced, rather than
eluted through. This is necessary as evaporation
will change the solvent composition, even if the
column is stoppered.
353 The Elution
a. The solvent head is allowed to diminish to less
than 2 ml by eluting from the column.
b. The sample is applied with a pasteur pipette and
the flow restarted. Starting at this point, the
eluent is collected in a graduated cylinder. The
container that held the sample is rinsed with 3
successive 2 ml portions of 50% pentane/methylene
chloride which are each gently added to the column
with the pipette as the solvent level approaches
the gel bed.
c. The rinses are allowed to drain into the column
until the top of the gel is nearly exposed. The
286
-------
solvent reservoir over the column is charged with
250 ml of 50% pentane-methylene chloride.
d. Elution continues with 3 fractions being taken
("Al, A2, A3") according to the volumes determined
in the calibration of the particular column used,
of approximately 80, 40, and 130 mis for a 40 g
column.
e. After the second fraction has eluted, the last
fraction is eluted through a coupled column of
cesium modified silica gel, as described in Section
350.
f. After last fraction is eluted, 100 ml 50% pentane/
methylene chloride is added as a rinse.
g. After rinsing, the column is inspected by UV light
for uneluted polycyclic aromatics. It is also
inspected visually for cracks, bubbles, and residue
at the top of the column.
h. The fractions are K/D concentrated to 1 ml. If a
concentration standard (such as D4-dichlorobenzene)
is to be used, it is added prior to K/D concentra-
tion .
287
-------
360 Coupled Cesium-Silica Gel Chromatography
361 Apparatus and materials
a. Cesium-modifled silica gel
b. Glass Chromatography column, 8 x 20 mm ID,
prepared as indicated in Section 230.
c. Distilled-in-glass solvents: pentane,
methylene chloride, and methanol
d. Prepared glass containers — 50, 100 ml
Erlenmeyer flasks
e. Graduated cylinder, 100 ml
362 Preparation
a. The column is prepared by slurrying 5.0 grams of
the cesium silicate in 10 ml 50% pentane-methylene
chloride and pouring the suspension into a prepared
column. The beaker used to slurry the silica
is rinsed with more of the same solvent to
quantitatively transfer the silica gel.
b. The silica is allowed to settle and is rinsed from
the sides of the column. The excess solvent is
allowed to drain until the top is basely covered.
288
-------
363 Coupled column chromatography
a. The prepared column IE inserted under the BioEeads
SX-2 column immediately after the collection of the
second fraction from the BioBeads. A small head of
eluent is allowed to accumulate over the silicate,
then the elution rates are matched between the
columns by use of the stopcocks on the columns.
The flow-through eluent from the silicate is
collected as fraction A3.
b. After the entire fraction from the BioBeads has
eluted onto the silica column, a 30 ml rinse of the
pentane-methylene chloride solvent is run through
the silica gel and combined with A3.
c. The retained components are eluted into a separate
contained following this rinse by application of 60
ml methanol.
d. If dinitrophenol is present in the sample, or has
been spiked into the sample, it will indicate the
proper functioning of the silicate column. This
compound forms a bright yellow band at the top of
the column, which eluted as a yellow solution in
methanol. Only upon acidification does this
289
-------
material (presumably cesium dinitrophenoxide) turn
colorless.
e. The A3 eluent is concentrated as described in
Section 240. The A3S (methanol eluent) fraction is
treated with 140 ml hexane and K/D evaporated to 2
ml. After cooling, this concentrate is
quantitatively transferred to a 60 ml separatory
funnel. 10 mis each of methylene chloride and 1 M
HC1 are added and the separatory funnel is shaken
vigorously. The mixture is allowed to settle, and
the methylene chloride is carefully drained into
a 50 ml Erlenmeyer flask. The aqueous phase is
extracted twice more with 10 ml portions of
methylene chloride, and the combined extracts dried
over prepared sodium sulfate for at least one hour,
with intermittent agitation.
f. The sample is concentrated to 1 ml prior to
derivatization.
370 Florisil Chromatography
371 Apparatus and materials
a. Florisil, 0.75% H20 deactivated (Section 230)
290
-------
b. Glass column, 8 x 20 mm ID, prepared
according to Section 230.
c. Glass pipette, cleaned and silanized
d. Distilled-in-glass solvents: pentane, pet
ether, ethyl ether, and methylene chloride
e. Graduate cylinder, 100 ml
f. K/D apparatus
372 Preparation
a. The A2 fraction from the BioBeads column is K/D
concentrated to 1 ml. 2 ml hexane is added and the
fraction further concentrated to a final volume of
1 ml.
b. The column is prepared by slurry-packing 10 g pre-
pared florisil in pentane into the column using a
long-stemmed funnel. The column should be prepared
as described in Section 230. The florisil is
washed into the column with a hexane wash bottle
and 50 ml hexane eluted through as a rinse.
c. If bubbles or cracks develop, resuspend the flori-
sil by shaking the stoppered column with a solvent
head of hexane and allow to resettle. After prepa-
ration, the solvent head is allowed to drain to
291
-------
barely cover the florisil.
373 Florisil chromatography
a. The prepared fraction is applied to the top of the
column with a pasteur pipette and allowed to drain
as a 1 ml pentane rinse is used to effect quantita-
tive transfer of the sample to the column.
b. The collection of the eluent begins with the sample
application and may be collected directly in a K/D
concentrator tube.
c. 14 ml pentane is applied to the column and eluted.
The eluent from this rinse and the sample loading
is collected as fraction "Fl".
d. When the solvent head approaches the florisil bed,
the collection vessels are changed and 200 ml 50%
ethyl ether/pet ether is added. This solvent
should be stored in a sealed container, or else
prepared freshly. The eluent from this solvent is
collected as fraction "F2n.
e. Upon elution of this solvent, 50 ml 100% ethyl
ether is added and its eluent collected as fraction
292
-------
'F311.
f. All three fractions are K/D concentrated to 1 ml,
treated with 5 ml methylene chloride, further con-
centrated to 1 ml, and vialed for GC analysis.
380 Derivatization of Fraction A3S with Diazomethane
381 Apparatus and materials
a. Diazomethane generator, see Figure 300-2
b. N-methyl,N-nitro,N-nitrosoguanidine (MNNG)
c. Wipes
d. Small spatula
e. Solvents: diethyl ether, methanol, glacial
acetic acid, pentane, and methylene chloride
f. SN NaOH solution
g. Aluminum foil
h. K/D concentration apparatus
i. Gloves
j. Face shield
k. Fume hood
382 Preparation (in a fume hood)
a. Setting up the diazomethane generator:
293
-------
SHRINKABLE
TEFLON SLEEVES
t
SAMPLE
TUBE
FROM NITROGEN TANK
CLEARSEAL JOINTS
THICK-WALL GLASS
(NO SHARP EDGES)
FIGURE 300-2 DIAZOMETHANE GENERATOR
294
-------
1) Check the nitrogen tank for pressure.
2) Spread aluminum foil under the apparatus.
3) Place a small amount of MNNG in tube 1.
A spatula tip will do. Weighing of this
material or other unnecessary manipula-
tions are to be avoided. More can be
added, if necessary, during derivatiza-
tion.
4) Any MNNG on outside of apparatus or other
exterior surfaces should be immediately
wiped up with a tissue which is disposed
of in a plastic bag.
5) 30 ml diethylether is added to each tube,
rinsing the MNNG down the sides and into
the bottom of the first tube.
6) Ready samples, connect nitrogen purge
line, and reseal both tubes.
7) 1 ml 5N NaOH is added to tube 1 with a
pipette. This tube is immediately
resealed and the nitrogen flow begun by
cautiously opening the needle valve.
8) Diazomethane and its precursors are
extremely hazardous materials. Gloves
and face shield should be worn and a
good fume hood used to contain vapors.
295
-------
b. Sample preparation: The 1 ml concentrates are
treated with 1 ml pentane and 0.2 ml methanol. The
actual derivatization is very fast, so the samples
can be arranged in a rack to permit rapid switching
from one to another.
383 Derivatization
a. The bubbler tip is inserted into the first sample
tube, and the gas stream containing the diazome-
thane is bubbled through the sample until formation
of a yellow color that persists upon removal from
the bubbler. If the sample is already yellow prior
to bubbling, bubble for 90 seconds.
b. Set aside and let stand at room temperature for 7
minutes.
c. 9 ml pentane and 2 ml methylene chloride is added
and the sample K/D concentrated to 1 ml. It can
then be vialed for GC analysis.
d. When all of the samples have been derivatized, the
gas is shut off and the generator is carefully dis-
assembled. The excess diazomethane and/or MNNG is
deactivated by addition of a few mis of glacial
296
-------
acetic acid (added dropwise). The parts of the
apparatus are rinsed with methanol and then with
methylene chloride. All waste is carefully sealed
in plastic bags for disposal.
390 Instrumental Analysis
391 Apparatus and materials
a. Internal standard solutions
b. Gas chromatograph (H/P 5840 or equivalent)
equipped with FID and GC
c. GC/MS (Finnigan 4023 or equivalent)
d. Syringes (gas tight, 10 ul)
392 Preparation
a. The readied fractions: Al, A3, A3S (derivatized),
Fl, F2, and F3 are vialed in 1 ml methylene chlo-
ride solvent. Appropriate 10 ug hexamethylbenzene
is added to each as a preliminary standard.
393 Instrumental analysis
a. GC/FID Screening: Each of the fractions except Al
is screened on a 15 meter SE-54 glass capillary
297
-------
using a temperature program between 30 and 280
degrees centigrade. Fractions Fl, F2, and F3 are
screened using split injections with a split ratio
of 20:1. Fractions A3 and A3S may be screened
using a splitless injection.
b. If the results from the GC screening indicate ade-
quate cleanup, fractions F2, F3, and A3 may be com-
bined prior to GC/MS quantitation.
c. GC/EC analysis: The response and linearity of the
priority pesticides and arochlors between 1 and
1000 picograms must be predetermined in standard
runs and checked with standards periodically. An
appropriate internal standard, such as decafluoro-
biphenyl, must be added to the sample. A 10% ali-
quot of the combined sample is spiked with a quan-
titation standard, translated into hexane azeotro-
pically, and analyzed by GC/EC using a 15 meter
SE-54 column with splitless injection. The analy-
sis is temperature-programmed between 30 and 280
degrees centigrade. Priority compounds peaks are
identified by retention time, reported to 0.01 min-
utes, and are tabulated along with integration val-
ues and expected retention times. Analysis of
standards must show retention behavior to within 2
298
-------
seconds of expected values.
e. GC/HS analysis: The instrument must be pretuned
with FC-43 and decafluorotriphenylphosphine refer-
ence spectra specifications met.' The sample is
spiked with a multiple internal standard including
the DFTPP MS standard. Injections are splitless
with a 30 meter SE-54 column. Data is acquired at
1 second intervals for 5000 seconds to a final tem-
perature of 280 degrees centigrade. The mass range
and other acquisition praameters are as presented
in Table 300-3.
400 Data Analysis
401 Apparatus and materials
a. This procedure is developed for an INCOS Data Sys-
tem operating on quadruple low resolution mass
spectral data (Finnigan 4023 or equivalent).
b. Authentic standards of all EPA priority compounds,
standards for quantitation and recoveryr and
instrument tuning are required.
402 Preparation
299
-------
INSTRUMENT PARAMETERS:
MASS PARAMETERS:
INTERFACE NUMBER O
SUB-INTERFACE O
2ND ACQU INTERFACE -1
SUB-INTERFACE -1
NUMBER OF ACQU BUFFERS 16
INSTRUMENT TYPE Q
FULL SCALE MASS 1024
ZtRO SCALE MASS 1
INTENSITY/ION 2
ACQUISITION DIRECTION UP
SAMPLES/PEAK - CENTROID 10
SAMPLES/PEAK - FRAGMENT 10
HbAK WIDTH
-------
a. Data acquired in a GC/MS analysis, as described in
Section 270 and available on magnetic disc, is
needed.
b. Initialization: Standard response factors, reten-
tion times, and mass spectra for the priority com-
pounds must be obtained from calibration analysis
of standards. The actual retention times and spec-
tra for each compound must be obtained by hand
manipulation of the data and stored in a library or
libraries on the system. Once this is done, the
response and retention of each compound can be
updated using the programs SININ and UPDATE. These
are modified versions of a proprietary program of
the Finnigan Corporation. The calibration analysis
treated with SININ to generate a quantitation list
which is then hand-edited. When it is complete and
correct, UPDATE is used to add this information to
the quantitation libraries. The formats for using
the programs are WQ DATAFILE,CALFILE,SININ
(return), and UPDATE (return), respectively, where
DATAFILE is the name of the calibration analysis
data file. In order for UPDATE to run properly,
the MSDS variable table must show the appropriate
files (i.e., DATAFILE in variable 1 and DATAFILE.QL
in variable 8).
301
-------
c. Data analysis: The program SINUNK is used to
reduce the data. It is begun by typing WQ DATA-
FILE,CALFILE, SINUNK, (return). Prior to this, the
library list of the libraries to be searched for in
the data must be entered in variable 6 of the MSDS
table, and the total library to be used for forward
searching of questionable identifications must be
entered in the program Other critical parameters to
be set or changed as the data requires are the win-
dow for the internal standards search, the window
for the unknown search, and the fit/purity test
threshold. The proper set of these parameters will
determine the frequency of false positive/negative
identifications, and must be arrived at by expe-
rience on a per-compound basis. Initially, it is
wise to use larger windows and lower fit criteria,
to bias the analysis toward false positives. These
can be edited out by hand. This program has been
modified to allow for additional analysis for com-
pounds with a fit below an arbitrarily high value
(850 in this version) but above a minimum fit (750
here). These marginal compounds are forward
searched against a total library. If the fit from
the forward search is not above 800, the identifi-
cation can be safely rejected (based on analysis of
standards and spiked samples).
302
-------
d. Quantisation is carried out on a single-ion basis
for most compounds, although a several component
abbreviated spectrum could be used for quantitation
in cases of low response if desired.
e. The data analysis report is reduced to a summary
(an example is included) which includes retention
behavior, statistical quality of the identifica-
tion, quantitation and integration information, and
the analysis of several spiked compounds to provide
QA/QC information on each sample.
f. Figure 300-3 shows a sample data analysis Figure
300-4 shows a sample data summary sheet.
303
-------
PARAMETERS DATA: PS600V2. TI (PS6OOV2 MI)
10/03/79 11:46:00 + 33:20 CALI: C0917A SCANS 1 TO 4000
SAMPLE: PS600V2 10UL PS606 » IOUL RECOV STD FORT WANYE
CQNDS. : C0926A. CT
FORMULA. WB1003A INSTRUMENT: FINN WEIGHT: 0.000
SUBMITTED BY: COLOTRAP ANALYST: RD ACCT. NO. :
ACC. VOL. : 8OOO THRESHOLD 3 INTEN/ION: 3
A/D S. I. : 0. 023 CENT S. I. : O. ISO FRAC S. I. : 0. ISO
PEAK WIDTH. 1000. CENT SAMP/PK: 10 FRAC SAMP/PK: :
MIN. WIDTH: 3 HIN. FRAG WIDTH (X): BO MIN AREA: Zu
4000 SCANS (739 SECTORS) OF LINEAR UP CENTR01D DATA
LOW MASS: 34 SCAN TIMES (SECS. ) UP: O. 43 TOP: 0.00
HI OH MASS: 334 DOWN: 0.00 BOTTOM: 0. OS
THERE 18 A SCAN LIST WITH 0 ENTRIES
THERE IS A OUANTITATION LIST WITH 61 ENTRIES
Figure 300-3 Sample MS Data Report
Page 1 - Header (Acquisition Parameters)
304
-------
CO
o
en
at
10
rv>
73
O
O
-5
a>
o
n>
o>
IQ
C
-$
O>
LO
o
o
I
CO
o
o
RIC
18-83/79 11:46:80
SflMPLE: PS600U2 18UL PS686
(WTO: PS600U2 •!
CflLI: C891TA §5
18UL RECOU STO FORT UflNYE
SCANS 208 TO 2488
1HTEM
188888.
1.
RIC
4:19
I
1888
8:20
StM
Tint
-------
CO
o
(jQ
c
ft)
U)
o
o
CO
TO C~>
en o
O 3
O O)
n> o.
QJ
rfr
QJ
RIC
18/03x73 11:46:68
SflMPLE: PS680U2 18UL PS686
DATA: PS688U2 •!
CAU: C0917A §5
10UL RECOU STD FORT HflMYE
SCAHS 24B8 TO 4088
INTEN
109688.
1.
RIC
29:10
4908
33.20
SC«
Tini
-------
OUANTITATION REPORT FILE: PB600V2
DATA: PS600V2. TI
10/03/79 11: 46: OO
SAMPLE: PS600V2 10UL PS606 + 1OUL RECOV STD FORT HANYE
CONDS. : C0926A. CT
FORMULA: UB1003A INSTRUMENT. FINN HEIGHT. 0. OOO
SUBMITTED BY: COLDTRAP ANALYST: RD ACCT. NO. .
AMOUNT-AREA • REF. AMNT/ (REF. AREA* RESP.FACT)
NO NAME
1 D6-2, 2-DICHLOROPROPANE
2 D9-CHLOROETHANE
3 D3-ACRYLONITRILE
4 Dl-CHLOROFORM
9 D3-1. 1. 1-TRICHLOROETHANE
6 DA-BENZENE
7 DO-TOLUENE
8 Dl-BROnOFORM
9 D4-1.4-DICHLORODENZENE
10 METHANE. DICHLORODIFLUORO-
11 ETHENE, CHLORO-
12 METHANE, CHLORO-
13 METHANE, BROMQ-
14 ETHANE, CHLORO-
15 METHANE, TRICHLOROFLUORO-
16 ETHENE, 1. 1-DICHLQRO-
17 S-PROPENAL
18 2-PROPENENITRILE
19 PROPANE. 2. 2-DICHLORO-
20 METHANE, DICHLORO-
21 ETHENE, 1.2-DICHLORO-. (2)-
22 ETHANE, 1. 1-DICHLORO-
23 METHANE,TRICHLORO-
24 ETHENE, TRICHLORO-
29 ETHANE. 1. 2-DICHLORO-
26 METHANE. TETRACHLORO-
37 ETHANE. 1.1, 1-TRICHLORO-
28 BENZENE
29 D8-TOLUENE
3O Dl-BROMOFORM
31 D4-1,4-DICHLOROBENZENE
32 ETHENE, TRICHLORO-
33 ETHANE. 1. 2-DICHLORO-
34 METHANE, TETRACHLORO-
39 03-1. 1. 1-TRICHLOROETHANE
36 ETHANE, 1, 1, 1-TRICHLORO-
37 D6-BENZENE
38 BENZENE
39 PROPANE, 1.2-DICHLORO-
4O METHANE, BROMODICHLORO-
41 1-PROPENE. 1. 3-DICHLORO-. -
44 ETHANE. 1, 1. 2-TRICHLORO-
49 METHANE. DIBROMOCHLORO-
46 ETHENE. TETRACHLORO-
47 Dl-BROMOFORM
Figure 300-3 Continued
Page 4 - List of Compounds Searched
307
-------
NO
48
49
90
31
92
93
94
99
NO
1
2
3
4
9
6
7
B
9
10
11
12
13
14
19
16
17
18
19
20
21
22
23
24
29
26
27
28
39
3O
31
32
33
34
33
36
37
38
39
4O
41
42
43
44
49
46
NAME
METHANE. DIBROMOCHLORD-
ETHENE. TETRACHLORO-
BENZENE. CHLORO-
BENZENE. ETHYL-
METHANE. TRIBROMO-
ETHANE. 1,1.2, 2-TETRACHLORO-
D4-1. 4-DICHLOROBENZENE
BENZENE. 1.4-DICHLORO-
M/E
83
69
96
84
100
84
98
NOT
190
NOT
NOT
NOT
NOT
NOT
NOT
NOT
NOT
NOT
NOT
49
NOT
NOT
83
130
NOT
NOT
NOT
78
98
174
130
130
NOT
NOT
100
NOT
84
78
NOT
NOT
NOT
91
NOT
NOT
NOT
NOT
SCAN
1919
1412
1449
1331
196B
160O
1931
FOUND
3239
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
1491
FOUND
FOUND
1919
1697
FOUND
FOUND
FOUND
1604
1931
2629
3229
1697
FOUND
FOUND
1368
FOUND
16OO
1604
FOUND
FOUND
FOUND
1934
FOUND
FOUND
FOUND
FOUND
TIME
12
11
12
12
13
13
16
26
12
12
14
13
16
21
26
14
13
13:
13
16
39
46
04
49
04
2O
03
94
09
39
08
22
09
34
34
OS
04
20
22
17
REF
1
1
1
1
1
1
1
1
1
1
1
1
29
29
29
29
29
29
29
29
1
0
0
1
1
1
1
2
0
1
1
1
1
1
1
0
0.
0.
0.
1.
RRT
OOO
930
954
008
032
033
271
126
939
OOO
117
036
000
361
672
879
813
829
831
012
METH
A
A
A
A
A
A
A
A
A
A
A
A
A
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
BB
AREA
12893
8904
3989.
39161.
19724.
72733.
63302
43700.
6728
12893.
1470.
2336.
63367
14377.
44797.
1470.
19734.
72733.
3336.
117O4OO.
AMOUNT
11. 120 NG
IB. 632 NG
33. 031 NC
14. 9B8 NC
13. 3O3 NG
13. 116 NC
SO. 799 NG
8. 031 NG
1.889 NG
0. 968 NG
1. 167 NG
0. 376 NG
8. 670 NG
8. 036 NG
10. 070 NG
0. 618 NG
7. 149 NO
7. 998 NC
0. 303 NC
133.491 NC
XTOT
2. 39
4. 27
12 62
3. 43
3. 09
3. 46
11. 64
1. 84
0. 43
0. 22
0. 27
0. 13
1. 99
1.84
2. 31
0. 14
1.64
1. 83
0. 07
30. 39
Figure 300-3 Continued
Page 5 - Quantitation Report
308
-------
NO H/E SCAN TIME REF RRT HETH AREA AMOUNT XTOT
47 174 2629 21:94 47 1. OOO ABB 14377. 289OONC 6.62
48 NOT FOUND
49 NOT FOUND
90 NOT FOUND
SI 91 24B5 20:42 47 0 949 A BB 8677 3.388 NC 0 78
92 NOT FOUND
93 NOT FOUND
94 190 3229 26:94 47 1.228 A BB 44397. 39.891 NC 8.22
55 NOT FOUND
Figure 300-3 Continued
Page 6 - Quantitation Report
309
-------
UNKNOWN SAMPLE QUANT I TAT ION
EXPECTED BEST
SCAN SCAN FIT
REVERSE SEARCH STATUS REPORT
PURITY LIBRARY ENTRY
1519
1401
1440
1S33
1572
160*5
1939
2649
3235
1377
13BB
138B
139B
1401
1415
1433
1747
1443
1519
1445
1467
1482
1535
1706
1590
1609
1577
1609
1931
2633
3218
1696
15E31
1599
1563
1568
1595
1599
1696
1725
1B47
1949
1969
1996
2108
2162
2630
?105
:.160
•- 'o
24B3
2638
2825
3214
3214
1519
1412
1449
1531
1568
1600
1931
2630
3229
0
0
0
0
0
0
0
0
0
0
1451
0
0
1519
1697
0
1568
0
1604
1931
2630
3229
1697
0
1568
1568
0
1600
1604
0
0
O
1954
0
0
0
0
2630
0
0
0
2535
0
0
3229
0
943
959
946
991
B94
9B9
9BB
951
958
0
0
0
0
0
0
0
0
0
0
971
0
0
B27
906
0
942
0
641
988
951
958
906
0
942
894
0
9B9
841
0
0
0
989
0
0
0
0
951
0
0
0
962
0
O
95B
O
803
697
381
885
616
920
BB4
322
673
0
0
0
0
O
0
0
0
0
0
549
0
0
219
265
0
119
0
169
684
322
673
265
0
119
B16
0
920
169
0
0
O
900
O
0
0
0
322
0
0
O
679
0
O
673
0
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
VI
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V2
V3
V3
V3
V3
V3
V3
V3
V3
V3
1
2
3
4
5
6
7
B
9
1O
11
12
13
14
15
16
17
18
19
20
21
22
23
34
25
26
27
86
1
2
3
4
9
6
7
8
9
10
11
12
13
14
15
16
17
16
1
2
3
4
5
6
7
e
9
• PEAKS
POUND
0
o
0
o
o
0
0
0
0
0
2
0
0
1
1
0
1
0
t
1
t
1
1
0
1
1
0
1
1
0
0
o
1
o
0
o
0
1
0
0
0
2
0
0
1
0
• PEAKS
QUANT
0
1
0
o
0
0
0
0
o
o
0
0
1
0
0
1
1
0
0
0
t
1
1
1
1
0
0
1
0
I
1
0
o
o
1
o
0
0
0
1
0
0
0
1
0
0
1
0
DATA PROCESSINC OF PS60OV2 COMPLETED ON 10/03/79 21:07:29
Figure 300-3 Continued
Page 7 - Reverse Search Status Report
310
-------
QUANT I TAT ION REPORT
FILE: TEMPS
DATA PS6COV2 TI
10/03/79 11:46:00
SAMPLE: PS600V2 10UL PS606 * JOUL RECOV STD FORT UANYE
CONDS : C0926A CT
FORMULA: WB1003A INSTRUMENT: FINN
SUBMITTED BY: COLDTRAP ANALYST: RD
AMOUNT-AREA • REF. AMNT/(REF. AREA* RESP. FACT)
NO NAME
1 METHANE, D1CHLORO-
3 Dl-CHLOROFORM
3 D6-2. 2-DICHLOROPROPANE
4 UNKNOWN
S UNKNOWN
6 METHANE, DICHLORO-
7 D6-2, 2-DICHLOROPROPANE
B Dl-CHLOROFORM
9 UNKNOWN
UEIOHT:
ACCT NO
0 000
NO
1
2
3
4
S
6
7
8
M/E
TOT
TOT
TOT
NOT
NOT
TOT
TOT
TOT
SCAN
1451
1531
1519
FOUND
FOUND
1451
1519
1531
TIME
12
12:
12:
12:
12:
12:
05
45
39
05
39
45
REF
8
8
8
8
e
8
0.
1
0.
0.
0.
1.
RRT
948
000
992
94B
992
000
METH
A
A
A
A
A
A
VB
BB
BB
VB
BB
BB
AREA
19511.
63660.
57765
19511
57765
B366O.
AMOUNT
6. 629
37. OOO NC
25. 548 NC
8. 629
25. 348 NC
37. OOO NC
XTOT
6. 06
25. 99
17. 95
6. 06
17. 95
25. 99
9 NOT FOUND
NO
1
2
3
4
5
6
7
8
9
RET(L)
RATIO r
IRT(L)
. 000
. OOO
. 000
. 000
. 000
000
RATIO
0 95
1. 00
0. 99
0.
0
1.
95
99
OO
AMNT
8. 63
37 00
25. 55
8
25
37
63
55
00
AHNT(L)
100. 00
37. 00
27.80
1OO
27
37
00
80
00
R. FAC R.FAC(L) RATIO
0086 l.OOO 0.09
1. OOO 1. 000 1. OO
O. 919 l.OOO 0.92
0. 086 l.OOO O. O9
0.919 l.OOO 0.92
l.OOO l.OOO l.OO
Figure 300-3 Continued
Page 8 - Forward Search Quantitation Report
311
-------
SAMPLE PS600V2 AUTDCC RUN ON 10/03/79 21:07:36
SCAN FIT PURITY LIBRARY ENTRY
1451 791 956 VT 19
1331 993 985 VT «
1519 948 923 VT 3
16O4 7B1 730 VT 26
1604 781 750 VT 26
1451 991 956 VT 19
1519 948 923 VT 3
1531 993 985 VT 4
1604 781 750 VT 26
ANALYSIS OF TEMPS COMPLETED ON IO/O3/79 21:14:43
Figure 300-3 Continued
Page 9 - Forward Search Status Report
312
-------
ANALYSIS REPORT
Sample: .'--:- ^
Lab:
Sample Size: .'C '- :: T-
Date Sampled:
Cluantitation Standard:
Ousntitation Method:
PU3GABLE ORGAN!CS
COMPOUND AMT FIT AT
D5-CHLOROETHANE il3l5 ,?tr °'=) /(
D3-ACRYLONITRILE Vtti^ fc : C <*wi "J
D6-2. 2-DICKLOROPROPANE «tt ||.I~ «|H2 C
Dl-CHLOROFORM 'J'SiCl iMll 111 -2
D3-1-.1. 1-TRICSLQRDETHANE \VTi^ ii.-: r--' -f
Do-BENZEUE TnSJ j«,|^_ "i* -k
1
METHANE. DiCHLOR3DIFLUDRO-
E:THENE. CHLORO-
t-.ETHANE. CHLORQ-
METHANE. BRQMO-
ETHANE. CHLORO-
r.ETrlANt. TRiCKLORDFUUORO-
EiTHEME. 1. 1-DICHL.aRQ-
2-PROPENAL
2-PRDPENEMITRII.E
PROPANE, 2. 2-DICHLDRO-
l'l=- iHrtiSE.. L/i(.HLOrlU- .90 o-j (^
ETHENS, 1. 2-DICHI.ORQ-, (Z>-
ETHANE, 1. 1-DICHLORQ-
1'iETKANE, TR1CHLORQ- c si g,-,
LTHENE. TRICHLORO- , |7 q-j. ,c^
li I Hr^'xt, 1 , ^-Li ILt-.LUriU-
r'iETHANE, TETRACHLORO-
ETHANE. 1.1, 1-TRICHLORO-
LENZENE 0.54 *u , .3
PROPANE, i. 2-DICHLOSO-
htlri^Nc.. UrtUIILiiJiCHLUHU-
1-PROPEN-i. 1. 3rDICHLOHO-. (Z>-
L'ENZENE. METHYL- IM'll c'*1 '^
1-PRDPENE, i, 3-DICHLDRO-. «E>-
ETHANE, 1, 1. 2-TRICHLORO-
1'ic.lhANti IVluHQI'iUCHLOKU-
ETHENE. TETHACHLORO-
PEMZEN?. CKLO":0-
CEKZENE. ETHYL- j. -. i,.^' 1
I'.ETHANE. TRIEROMQ-
1. 1 Hrtl'Je., i , i , «:. =i— I c. i tv^Chi_tjr\U-
EENZENE. 1, 4-UICHLCWO-
AMT FIT AT
l.r: "<•-, ^
e.;c =1-1 i
?.U7 J'". :
4. CM 3: ; «i/H1: ^1
;.;T ttt; i I/?-.T^ •••
•
. HI ajj /
; • I »., / «
bunk=not found; NQ=detected but not quantitated; NA=not analyzed for
Figure 300-3 Continued
Page 10 - Analysis Worksheet
313
-------
OUANTtTATJON RFPORV
ru.r.. rr.f.oovr?
AMOUNT -AUfA » PEF. AMN1 / -
22 ETHANE.1.1-DJCHLOnO-
23 METHANE. TFMCHLOntJ-
.74 ETHENE. TR I CHLOnO-
23 ETHANE. 1. 2-D1 CHl.DftO-
26 METHANE. TETRACHI.DRO-
27 ETHANE. 1, 1. 1-TR1CHLORO- '
29 BENZENE
29 DO-TOLUENE
30 Dl-BROMOFORtt
31 D4-l,4-OICHLOROnENZENE
32 ETHENE. TR I CHLOr>0-
33 ETHANE. I, 2-01 Clfl.ORO-
34 METHANE. TETRACin.nno-
33 D3-1, I, 1-TRICin.CirtOETHANE
36 ETHANE. I, 1. t-TRICHLORO-
37 06-8ENZENE
39 BENZENE
39 PROPANE. I. 2-DtCHLORO-
4O METHANE. BROMODICHLORO-
41 I-PROPENE. I. 3-niCHLORD-. -
42 BENZENE.METHYL-
43 I-PROPENE. 1. 3-niCHLORO-, -
44 ETHANE. 1. 1. 5-TRICHLORO-
43 METHANE. DIBROMOCHUORO-
46 ETHENE. TETRACHLOnO-
47 DI-DROMOFORM
49 METHANE,DIBROMCCHLORO-
49 ETHENE. TETRACHt.DRO-
30 BENZENE. CHUORO-
31 BENZENE.ETHYL-
32 METHANE. TRtBROITI-
53 ETHANE. 1. 1. 2. 2-TETRACHLORO-
54 D4-1, 4-DICHLOl'nnrNZENt:
r>3 DENZTNC. i. 4-nion.oRn-
NO
1
2
3
4
3
6
7
8
9
10
II
12
13
14
13
16
17
to
19
20
21
22
33
24
23
26
27
28
29
30
31
32
33
34
33
36
37
30
39
40
41
42
43
44
43
46
47
48
49
30
31
32
33
54
S'j
M/E
H3
69
36
04
1OO
04
98
NOT
1T>0
NOT
NOT
NOT
NOT
NOT
NOT
NOT
NOT
NOT
NOT
49
NOT
NOT
93
130
NOT
NOT
NOT
79
98
174
ISO
130
NOT
NOT
100
NOT
84
78
NOT
NOT
NOT
91
NOT
NOT
NOT
NOT
174
NOT
NOT
NOT
91
NOT
NOT
150
NOT
SCAN
1319
1412
1449
1331
1568
1600
1731
FOUND
3229
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
FOUND
1431
FOUND
FOUND
1319
1697
FOUND
FOUND
FOUND
1604
1931
2627
3227
1677
FOUND
FOUND
1360
FOUND
16OO
1604
FOUND
FOUND
FOUND
1934
FOUND
FOUND
FOUND
FOUND
2627
FOUND
FOUND
FOUND
2183
FOUND
FOUND
3229
FOUND
TIME
1?: 3V
1 1 . 46
12:04
12: 43
13: 04
13:20
16: O3
26: 54
12: 03
12: 39
14: O8
13:22
16: O3
21: 34
26: 34
14: O8
13:04
13: 20
13: 22
16. 17
21: 34
20:42
26: 54
RF.I-"
1
1
1
1
1
29
29
29
29
29
29
29
27
47
47
47
1
0
0
1
1
1
1
p
0.
1.
1.
1.
1.
1.
1.
0.
0.
0.
o.
1.
1.
0.
1.
Htlt
OOD
93O
9r>4
000
033
053
,-?71
1P6
753
OOO
1 17
036
OOO
361
672
O79
812
829
031
012
OOO
743
229
MMH
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
A
on
no
nn
DB
DO
DB
(ID
DO
BO
BB
DD
BB
BB
BO
BB
DB
DB
DB
DB
BB
BB
BB
BB
AIM. A
lanvn
OW4
3r,ij7.
3"lt61.
157^1.
7?/rrj
bjws.
4Ti7OO.
672O.
12093.
I47O.
2336.
63367.
14377.
44797.
147O.
13724.
72733.
C536.
11704OO.
14377.
8677.
44377.
AMOIJMT
1 1
in
3D
14
13
13
•50
0
1.
0
I
O
8
8.
10.
O.
7.
7.
O.
133.
28.
3.
33.
120 NG
632 NO
O!)l NC
7OO NC
OO3 NC
1 16 NC
797 NC
031 NO
893 NC
769 NC
167 NC
376 NC
67O NC
036 NO
07O NC
618 NC
143 NO
770 NO
303 NC
471 NO
7OO NO
398 NO
091 NC
F.XPtC.TlrD
".CAN
1319
I4O1
1440
1333
ir>72
16O5
1939
36 4 7
3235
13/7
I3UO
inno
1370
1401
1413
1433
1747
1443
1319
1443
1467
1482
1333
17O6
1390
16O9
1377
I6O9
1931
2633
3216
1696
1391
1399
1363
1368
1393
1399
1696
1723
1847
1949
1969
1996
2108
2162
2630
2103
2160
2306
24B3
2630
2D?5
3214
n::i4
DP.GT
SCAN
1319
1412
1449
1331
I56E)
I6OO
1731
2630
3? :> 9
o
0
o
o
0
0
o
o
o
o
1431
o
0
1319
1697
0
1368
0
1604
!931
2630
3229
1697
O
1368
1368
0
1600
1604
O
0
0
1934
O
0
O
O
263O
O
0
0
2333
0
O
3227
O
Fit
943
939
946
971
D74
9O9
7UU
931
von
O
O
O
0
o
o
0
o
o
o
971
0
O
827
906
O
942
O
841
998
931
958
906
O
942
094
0
909
041
O
O
O
999
0
O
O
0
931
0
O
O
962
0
O
930
0
PUIt I TY
OO3
697
301
003
016
720
OU4
322
673
O
O
O
0
0
0
0
0
0
0
349
0
O
319
263
O
119
O
169
884
322
673
263
0
119
016
0
920
169
O
O
O
90O
O
O
O
O
322
0
O
0
699
0
O
673
0
Figure 300-4 Sample Analysis Summary Sheet
-------
Anpendix II
Analytical Data
From First Three
POTW Sites
The following tables report actual analytical results
together with ancillary information concerning the analysis. No
correction for recovery or other QA/QC result is applied to these
results.
315
-------
ANALYSIS REPORT
Sarr.ple: -Renton, Raw Sewage
PS106V1
Lab: U of W
Sample Size: i ml
Date Sarnaled:
PURGABLE ORGANICS
-
ETHAUE. 1, 1-DICHLORO-
METHANE, TRICKLORO-
ETHENE. TRICHLORO-
tlMMNc.i If a— UiLKLUKU-
HETHANE. TETRACHLORG-
ETHANE. 1.1. 1-TRICHLORO-
BENZENE
PROPANE. 1. 2-DICHLORO-
Indicated
GC/MS
PPB
29.14
23.65
27.80
50.99
36.02
28.21
21.70
72.30
51.20
7.74
654.2
0.34
3.56
15.02
3.48
65.18
17.70
by (*)
FIT
965
656
992
996
904
997
SD3
986
923
944
891
931
940
852
946
937
936
AT
.^
-6
0
0
1
-1
0
0
in
0
-5
-5
-3
1
-2
1
0
rit IHAixh. bHUriUiJlCriv.Qi-
EENZENE. METHYL-
1-PROPEKE, 1.2-DICHLOP.O-. - 1 c, i KftLML-OhU-
EENZEKE. 1. 4-D'iCHLORO-
blank=not found; NQ=detected but not
A=probable artifact
21.96
49.08
1.20
quantitated
992
950
996
-1
9
PPB FIT AT
1
-5
; KA=not analyzed for
316
-------
ANALYSIS REPORT
Sample: Renton, Primary Effluent
PS95V1
Lab: U of W
Sample Size: 1 ml
Date Samoled:
PURGABLE ORGAN ICS
r.janfit£--.c:n Standard:
s-janti t£V. en Method:
COMPOUND
D5-CHLS3DETHANS
D3-ACRYLONITRILE
*P6-2, 2-DICKLORDPROPANE
31-CHi.OROFORM
D3-I..1. 1-TRICHLOROETHANE
Do-aENZENE
*DS-TLILUENE
*Dl-aROHOFORH
D4-1. 4-DICHLORDBENZENE
fiETHAIxE, D1CHLORODIFLUORO-
ETHENE, CHLORD-
riETHANE. CKLORO-
METHANE. BROnO-
ETHANE. CHLORO-
riETHAN€, TK1CHLORDFLUQRQ-
ETHENE. 1. 1-DICKLORO-
2-PRDPENAU
2-PROPENENI7RILE
PROPANE, 2, 2-DICHUORQ-
I'ltlMANt. DICKLOKU-
ETHENE. 1. 2-DICHLORO-, (Z)-
ETHANE, 1. l-DICHLORO-
METHANE, TRICKLQRO-
ETHENE, TRICHLORO-
tlt-IANt., i. eJ-LULI-lUUKiJ-
ttETHANE. TETRACHLQRG-
ETHANE, 1,1. 1-TRICHLORO-
BENZENE
PROPANE. 1.2-DICHLORO-
hkl MAINE, BRUriUDltriLOr-
EEU2ENE. METHYL-
1-PROPENE, 1,3-DICHLORO-. (E)-
ETHANE, 1. 1. 2-TRICHLORO-
ht.if4A.iNc., L!bRi3MOCrti_0.^0-
ETHENE, TETRACKLORO-
PENI=N-,CH10RO-
BENZENE. EiHYL-
METHANE. TRIBROMO-
tlHAist, A. I, 'd, t>- It-IKACHLUhU-
BEWZEKE. 1, 4-D1CHLORO-
Indicated
GC/MS
PPB
67.52
27.80
37.96
34.61
18.46
21.70
72.30
16.08
i.rw
606.94
0.56
0.90
7.96
1.06
22.48
5.96
16.78
39.50
0.34
by (*)
FIT
998
987
995
987
990
997
982
977
p.?n
<928
848
822
848
850
987
972
988
980
994
AT
-19
0
2
5
7
0
0
24
-T*
-6
-5
-3
2
5
5
6
-2
11
-9
PPB FIT tj
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
317
-------
ANALYSIS REPORT PURGABLE ORGANICS
Sample: Renton, Secondary Fffluent
PS85V2
Lab: U of W
Sample Size: 1 ml
Date Sampled:
?uantit2ticn Standard:
Quantisation Method:
COMPOUND
D 5-CHl_2R DETHANE
D3-ACR YLQN I TR ILE
*D=-2, 2-DICHLORQPRDPANE
Dl— CKLJDROFORN
r3-I..l, 1-TRICHLOROETHANE
Du ZZHZEME
*re— TDLUENE
*3l-9f*Or10F'ORt1
54-1. 4-DICHLOROBENZENE
PitlHANii, D1CHLORODIFLUQRO-
ETHENE, CHLDRO-
MiiHANE, CHLORO-
M=THANH,BROnn-
ETHANE. CHLOHQ-
ME7HAN£, TK1CHLOROFLUORO-
ETHENE. 1. 1-DICHLORO-
2-PRDPENAL '
2-PROPENENITRILE
PROPANE, 2, 2-DICHLORD-
1'it.lMANt, DICKLOrtG-
ETHENE. 1. 2-DICHLORO-. (Z>-
ETHANE, 1. 1-DICKLORO-
METHANE, TRICKLORO-
ETHENE, TRICHLORO-
tlHANt. 1, a-DiChLUKU-
METHANE. TETRACHLORC-
ETHANE. 1.1. 1-TRICHLORO-
BEN2ENE
PROPANE, 1,2-DICHLORO-
Indicated
GC/MS
PPB
5.74
35.30
27.80
56.15
31.74
19.34
21.70
72.30
130.52
5.56
1.74
0.16
8.92
by (*)
FIT AT
923 11
988 -1
994 0
999 1
QP.P. .0
984 -13
998 0
983 0
982 1
83Q -•>
931 -7
965 -4
979 -5
RtlMANt, bKL)nUUlCl-iLOi'-
BEN2ENE, METHYL-
1-PROPENE, 1.3-DICHLORO-, (E)-
ETHAtvE, 1. 1, 3-TRICHLORD-
htlHAwE. DlfcRdrlDCHLCteLJ-
ETHENE, TETRACHLORO-
PEts'iEWS, CKLDRO-
BENZENE, ETHYL-
METHANE, TRIBROMO-
tlMANt, i, 1, 2, y- It-iKACHLDKU-
EEW2ENE, 1, 4-DICHLORO-
11.68
979 1
PPB FIT AT
blank=not found; NQ-nletected but not quantitated; NA=not analyzed for
A= probable artifact
318
-------
ANALYSIS REPORT PURGABLE ORGANICS
Sample: Renton, Secondary effluent, dechlorinated
PS76V1
Lab: U of W
Sample Size: 1 ml
Date Sampled:
^-ant-.£2"::n otancera:
^u£n i i w2 „ i cn piei-fiou:
COMPOUND
D5-CHLDS DUTHANE
D3-ACSYLONITRI1_E
*D6-2J 2-DICHLQROPROPANE
Dl -CHLOROFORM
I>3-I,.l, l-TRICHLOROETHANE
3a-S£NZENE
*i;S-TDLUENE
*31 aROMOFQRH
D4-1. 4-DICHLOROBENZENt
Ms. THANE, D1CHLORODIFLUQRD-
ETKENE.CHLORD-
hETHANE. CHLORO-
METHANE, BROIin-
ETHANE, CHLOSO-
r.ETMANt. TKICHUOKOFLUORD-
ETHENE, 1, 1-DICHUORO-
2-PRDPENAL
2-PROPENENITRILE
PROPANE. 2, 2-DICHLORO-
I'ltlHANt. DICKLOrtG-
ETHENE. 1.2-DICHLORO-, (Z>-
ETHANE. 1, 1-DICHLORO-
METHANE. TRICHLORO-
ETHENE. TR ICHLORO-
tlMftNt. i. et-UiLHl-UKU-
I1ETHANE. TETRACHLQRO-
ETHANE. 1.1. 1-TRICHUORO-
BENZENE
PROPANE, 1. 2-DICHLORO-
nt IHAiNt. t(KL!riUUiCriLU;--
BENZENE. METHYL-
1-PROPEKE, 1.3-DICHLORO-. (E>-
ETHANE. 1. 1.2-TR1CHLORO-
ntiHANc., UlBROnaCrtuQKO-
ETHENE. TETRACHLORO-
PEKZEN2, CKLORO-
BENZEKE. ETHYL-
METHANE, TRIBROHO-
ti'HAUt, 1. x.ii. ^-'l£TKACHLDKu-
BENZEKE. i. 4-DICHLORO-
Indicated
GC/MS
PPB
98.16
27.80
35.75
24.61
21.70
72.30
51.61
3.08
585.68
8.38
3.00
18.10
17.36
1.70
12.70
0.36
by (*)
FIT
99C
992
QftK
94'1,
99C;
933
925
759
<921
844
934
995
990
817 •
939
801
AT
-2
0
T;
17
0
0
3
-2
-7
5
15
15
17
-3
-4
4
PPB FIT ^T
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
319
-------
ANALYSIS REPORT PURGABLE ORGANICS
Sample: Renton, Prim.+ Haste Act.Sludge
PS115V1
Lab: U of W
Sample Size: 1 ml
Date Sampled:
r'-antitaticn Standard:
Q-antTtsv. en Method:
COMPOUND
D5-CHLDSOETHANS
D3-ACRYUDNITRILE
*r'6-2> 2-DICHLOROPROPANE
31— CKLnROFORN
-3— I.-l. 1-TRICHLDROETHANE
£=— -ssNZENE
*Dl-3ROnOFORM
D4-1, 4-DICHLOROBENZENE
METHANE, D1CHLORDD1FLUORQ-
ETHENE, CHLORO-
t'.iiHANE. CKLORQ-
METHANE. BRQI-in-
ETHANE, CHLORO-
METHANt. TKICHLORQFLUORO-
ETHENE, 1, 1-DICKLORO-
2-PROPENAL
2-PROPENENI7RILE
PROPANE, 2, 2-DICHLORO-
I'lt. IHANt. DICHLC1KU-
ETHENE. 1.2-DICHLORO-. CD-
ETHANE, 1. 1-DICHLORD-
METHANE, TRICKLORO-
ETHENE. TRICHLORO-
t-lHKNt, i , ii-LiitKLUKU-
tlETHANE. TETRACHLORC-
ETHANE. 1.1, 1-TRICHLORO-
BENZENE
PROPANE, 1, 2-DICHLORO-
1-PROPENE. 1.3-DICHLORO-, <2)-
EENZENE, METHYL-
1-PROPENE. 1.3-DICHLORO-. (E)-
ETHANE, 1, 1,2-TRICHLORO-
ETHENE, TETRACHLORO-
PEN2£N-.,CHLORO-
BENZEKE, ETHYL-
METHANE, TRIBROHQ-
E'l HAUL, i . I . ii, «>- I c. i hi ACHLUKu- "
EEWZEKE. 1. 4-DICHLQRO-
Indicated
GC/MS
PPB
2.97
27.80
33.09
34.13
17.34
21.70
72.30
A 193.10
3.24
24.10
9.08
0.08
24.10
10.30
71.54
76.34
3.02
4.36
by (*)
FIT
954
929
985
880
985
998
955
985
806
-975
760
762
975
855
992
942
986
815
AT
5
0
-4
IP
-13
0
0
18
7
-8
-5
-12
-8
-14
•-1
6
-4
8
PPB FIT tj
. blank=not found; NQ^fletected but not quantitated; NA=not analyzed for
A=probable artifact
320
-------
ANALYSIS REPORT PURGABLE ORGANICS
Sample: Atlanta, Primary Effluent
PS126V1
Lab: U of W
Sample Size: 1 ml
Date Sampled:
Quantitation Standard:
Quentitation Method:
COMPOUND
D5-CHLORQETHANE
D3-ACR YLON I TR I LE
*D6-2, 2-DICHLOROPROPANE
Dl -CHLOROFORM
D3-I..1. 1-TRICHLOROETHANE
Do-EENZENE
*DS-70LUENE
*Dl-BROf10FORM
D4-1, 4-DICHLOROJJENZENE
METHANE, D1CHLORODIFLUORO-
ETHENE. CHLORO-
HETHANE. CHLOKO-
NETHANE. BROMD-
ETHANE, CHLORQ-
METHANt, TK1CHLORDFLUORO-
ETHENE. 1, 1-DICHLORO-
2-PRDPENAL
2-PROPENENITFJILE
PROPANE, 2, 2-DICHLORO-
I'lb. IHANt, D1CKLOHO-
ETHENE. 1.2-DICHLORO-, (Z>-
ETHANE. 1. 1-DICHLORO-
fiETHANE. TRICHLORO-
ETHEN.E, TRICHLORO-
tlMANt, 1, ii-UlCKUJNU-
METHANE, TETRACHLQRO-
ETHANE, 1.1. 1-TRICHLORO-
BENZENE
PROPANE. 1, 2-DICHLORO-
flfc. IHANt. BROriUDJCHLU!-
BEI^ZENE, METHYL-
i-PROPEUE, 1. 3-DICHLORO-. (E)-
ETHANE, 1, 1, 2-TR1CHLORO-
Mfc. lHANt, DIBROIIOCHLDKO-
ETHENE. TETRACHLORO-
PEN-2ENE, CKLDRO-
BENZEME. ETHYL-
METHANE, TRIEROhO-
t'lHAl^t.. it. i.y. ii-lLlMACHLOKU-
EENZEKE. 1, 4-DICHLORO-
Indicated by (*)
GC/MS
PPB FIT AT
317.99
4.53
11.22
15.45
9.25
8.76
29.18
3.71
23.72
17.42
261.96
0.36
7.71
6.91
3.37
723.05
3.11
n.?7
28.30
224.42
PPB FIT AT
blank=not found; NQ-detected but not quantitated; NA=not analyzed for
A=probable artifact
321
-------
ANALYSIS REPORT
Sample:
PURGABLE ORGANICS
Atlanta, Secondary Effluent before Chlorination
Lab:
Sample Size:
Date Sampled:
:;uantit2fi.in Standard:
wjanz'iZai'ion Method:
COMPOUND
D5-CHLDHCETHANS
D3-ACSYLON I TR I LE
D6-2. 2-DICKLOROPROPANE
D1-CKU3ROFDRN
D3-a,JL. 1-TRICHLOROETHANE
DO-BENZENE
DS-7DLUENE
Dl-aROMOFORt1
D4- 1, -
BEWZENE. METHYL-
1-PROPENE. 1.3-DICHLORO-. (E>-
ETHANE, 1. 1. 2-TRTCHLORO-
ETHENE. TETRACKLORO-
BENZENE. ETHYL-
METHAWE. TRIBROHO-
t-lHAlvifc. 1, 1 . ii, e>- 1 t.i KACHLOKU-
BENZENE. 1, 4-DI.CHLORO-
PPB
19.63
11.12
13.539
13.51
15.00
B.b7
-------
ANALYSIS REPORT
Sample: PS167
Lab:
Sample Size:
Date Sampled:
:-jar,t:t2-:2:i Standard:
Quantitavisn Method:
PURGABLE ORGANICS
Atlanta, Secondary Effluent after Chlorination
COMPOUND
D5-CHLDSQETHANE
D3-ACRYLONITRILE
Ds-Z. 2-DICHLOROPROPANE
31— CHU3ROFDRM
23-1. _1» 1-TRICHLORDETHANE
£o-=£NZENE
25-TDLUENE
Dl-sROMOFORM
£4-1, 4-DICHLOROBENZENE
?-;=.7HANE, DXCHLORQDIFLUQRD-
ETHENE, CHLORO-
fi=.iHANE. CHLORO-
METHANE, BRDrin-
ETHANE. CHLORO-
METHANt. TK1CHLOROFLUORQ-
ETHENE, 1. 1-DICHLORO-
2-PROPENAL
2-PROPENENITRILE
PROPANE, 2- 2-DICHLORO-
1-it.lHANt. DICKLDKU-
ETHENE, 1. 2-DICHLORQ-. (Z)-
ETHANE. 1, 1-DICHLQRQ-
METHANE, TRICKLORO-
ETHENE, TR ICHLQRO-
tlHMNt., i, ii-UiLKLUKU-
I1ETHANE. TETRACHLORO-
ETHANE, 1. i. 1-TRICHL.ORO-
BENZENE
PROPANE, 1. 2-DICHLDRO-
nt iHANh. BKCriUL»iCriLUi-
EENZENE, METHYL-
1-PROPENE, i,3-DICHLOSO-, (E)-
ETHANE, 1, 1, 2-TRICHLORO-
htl MAwt, D !EROHoCHi_0^0-
ETKENE, TETRACHLORO-
PEN:2ENZ, CHLDRO-
BENZENE. ETHYL-
METHANE, TRIBROMO-
L I HANt. i , 1 , k, «>- 1 b. I KALHLOHU-
BEKZEKE. 1. 4-DICHLORO-.
PPB
19.26
11.12
13.73
13.50
14.83
50.27
28.90
8.98
0.65
140.59
0.564
1.77
1.13
30.82
1.08
1.51
4.37
1.269
FIT
951
945
972
878
997
981
944
853
762
976
<865
964
800
982
901
971
955
943
AT
14
0
-1
-3
-5
-10
1
-5
*-Q
+ 7
-2
-8
-4
-4
-4
• + 1
-2
-1
PPB FIT JJ
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
323
-------
ANALYSIS REPORT
Sample: Oakland, Raw Sewage
PS205V1
Lab: U of W
Sample Size: 1 ml
Date Sampled:
PURGABLE ORGANICS
Quantitation Standard:
Quantitation Method:
COMPOUND
Indicated
GC/MS
PPB
by (*)
FIT
AT
D5-CHLORQETHANE
D3-ACRYLONITRILE
*D6-2, 2-DICHLOROPROPANE
Dl-CHLDROFORM
D3-1..1, 1-TRICHLOROETHANE
Dfa-EENZENE
*D8-TOLUENt
*D1-BROMQFORM
D4-1. 4-DICHLOROBENZEf4E
METHANE, DICHLORODIFLUORO-
ETHENE, CHLORO-
METHANE, CHLORO-
METHANE, BROMO-
ETHAWE. CHLORO-
METHANE. TK 1CHLOROFLUORO-
ETHENE, 1, 1-DICHLORO-
2-PRDPENAL
2-PROPENENITRILE
PRUPANE, 2, 2-DICHLQRO-
I'lETHANt, D1CKLOKU-
ETHENE, 1, 2-DICHLORO-, (Z)-
ETHANE, 1, 1-DICHLORO-
METHANE, TRICHLCWO-
ETHENE, TRICHLORO-
tlHAIMt, i, y-DlCI-lLOKO-
METHANE, TETRACHLORO-
ETHANE, 1,1, 1-TRICHLORO-
BEN7ENE
PROPANE, 1, 2-D1CHLORO-
Ht IMANb, BKOriUDlCHLOND-
1-PROPENE. 1,3-DICHLORO-. (Z)-
BEWZENE, METHYL-
1-PROPEUE, 1.3-DICHLORO-, (E)-
ETHANE. 1,1, 2-TRTCHLORO-
HL1HANE., DIEROHOCHLORO-
ETHENE, TETRACHLORO-
PEN2EM7, CHLDRO-
BENZEK'E, ETHYL-
METHANE, TRIBROMO-
tlHANh, 1, 1, bi, 2-1 ETRACHLOHU-
EENZENE, 1, A-DICHLORO-
38.49
11.12
24.09
13.68
11.69
8.67
28.90
19.45
NQ
4.63
1.57
19.13
21.10
2.02
26.86
1.20
0.95
10.54
0.17
0.33
1.29
987
991
984
987
990
994
980
993
987
951
830
982
909
982
600
990
966
781
847
708
-7
0
1
3
4
-1
0
-4
-6
-4
2
1
5
4
4
-2
-2
5
3
-1
PPB FIT AT
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=Probable artifact
324
-------
ANALYSIS REPORT
Sample: Oakland,
PS215V1
Lab: U of W
Sample Size: 1 n
Date Sampled:
Quantitation Standard:
Quantitation Method:
PURGABLE ORGANICS
Priwiry Effluent
Indicated by (*)
GC/MS
COMPOUND
PPB
FIT
AT
D5-CHLORQETHANE
D3-ACRYLQNITRILE
*D6-2. 2-DICHLOROPROPANE
Dl -CHLOROFORM
r-3-1,.:, 1-TRICHLOROETHANE
Db-EENlENE
*BS-70LUENE
*Dl-aR3nOFORM
D4-1. 4-DICHLORQBENZENE
fiETHANE, U1CHLORODIFHJORQ-
ETHENE, CHLORO-
t'.ETHANE, CHLORO-
ME7HANE. BROMO-
ETHAWE. CHLORQ-
ttETHAN£. TKlCHLOROFLUaRO-
ETHENE, 1, 1-DICHLORO-
2-PROPENAL
2-PROPENENITRILE
PRDPANE, 2, 2-DICKLDRO-
1'iE.lHANt.. D1CKLOKU-
ETHENE, 1, 2-DICHLORO-. (Z>-
ETHANE. 1. 1-DICHUORO-
METHANE. TRICHLORO-
ETHENE, TRICHUORO-
tlHANt. i. ii-UlUHLUNU-
METHANE. TETRACHLORO-
ETHANE. 1,1, 1-TRICHLORO-
BEN2ENE
PROPANE, 1. 2-DICHLDRO-
ntlHANt, BKUriUUiCril_UHU-
1-PROPENE. 1.3-DICHLORO-, (7.)-
BENZENE. METHYL-
i-PROPENE, 1.3-DICHLORO-, (E>-
ETHANE, 1, 1,2-TRICHLORD-
htlnAut. niBROHOCrtLO^O-
ETKEUE, TETRACHLORO-
PENiEN^, CKLORO-
BENZENE, ETHYL-
METHANE. TR I BROHO-
hiriAUL. 1. i.y.a-itlKA'CHLOFtCJ-
EEWZENE, 1, 4-DICHLORO-
34.48
11.12
16.64
12.88
8.67
8.67
28.90
15.22
3.45
7 34
1.94
34.19
65.11
5.71
34.58
0.89
0.99
25.22
n si
971
969
873
975
989
994
975
993
619
<1R?
891
870
978
934
971
847
967
966
-------
ANALYSIS REPORT PURGABLE ORGANICS
Sample: Oakland, Secondary Effluent
PS185V1
Lab: U of W
Sample Size: 1 m^
Date Sampled:
Quantitaticn. Standard:
Quantitation Method:
Indicated by (*)
GC/MS
COMPOUND
D5-CHLOROETHANE
D3-ACR YLON I TR ILE
*D6-2. 2-DICHLQRQPROPANE
Dl -CHLOROFORM
D3-J..1, 1-TRICHLOROETHANE
Do-EENZENE
*DB-TDLUENE
*D1-BRDMOFORH
D4-1. 4-DICHLORQBENZENE
METHANE, D1CHLORODIFLUORO-
ETH=NE, CHLORO-
t'.ETHANE, CHLORO-
ME7HANE, BRDMO-
ETHANE, CHLORO-
METHANt, TK1CHLQROFLUORQ-
ETHENE, 1, 1-DICHLORO-
2-PROPENAL
2-PROPENENITRILE
PROPANE, 2. 2-DICHLORO-
I'ltlHANt. D1CKL.OKO-
ETHENE. 1. 2-DICHLORO-, (Z)-
ETHANE. 1. 1-DICHLORO-
nETHANE, TRICHLORO-
ETHENE. TRICHLORO-
tlHrtNc., i . ci-Ul LI-JLOKU-
METHANE, TETRACHLORO-
ETHANE. 1. 1. 1-TRICHLORO-
BENZENE
PROPANE, 1, 2-D1CHLORD-
nt IHANh. BKUriLJDiCKl-UKU-
1-PROPENE, 1,3-DICHLORO-, (7)-
EENZENE, METHYL-
1-PROPENE. 1.3-DICHLORO-. -
ETHANE. 1.1. 2-TRTCHLORO-
rit i HANh.. JjIBROIIQCHLOKO-
ETHENE. TETRACHLORO-
PEts'ZEN?. CKL.ORO-
EENZEK'E, ETHYL-
METHANE, TR I BROMO-
tlHAUL, 1, i. y, y-!E.1KA(JHLOKu-
SENZENE. 1. 4-DICHLORO-
blank=not found; NQ=detected but not
A=probable artifact
PPB
8.78
10.48
11.12
13.78
18.36
6.80
8.67
28.90
15.25
0.89
34.47
1.83
9.03
1.74
37.28
11.22
0.46
0.59
88. 37
10.46
1.47
112.41
49.25
117.25
148. ?7
quantitated;
FIT
984
964
940
853
975
991
992
945
747
713
906
850
973
939
939
991
758
958
069
991
928
989
995
992
989
'AT
-2
-3
0
1
-10
6
0
0
-14
-2
-1
-1
-2
-4
1
13
6
fi
5
6
-2
3
-4
-3
0
PPB FIT AT
NA=not analyzed for
326
-------
ANALYSIS REPORT PURGABLE ORGANICS
Sample: Oakland, Secondary Effluent, dechlorinated
PS195V2
Lab: U of W
Sample Size: i ml
Date Sampled:
Quantitation Standard:
Quantitation Method:
COMPOUND
D5-CHLORQETHANE
D3-ACRYLONITRILE
*D6-2. 2-DICHLOROPROPANE
Dl-CKLDROFORM
D3-1..1, 1-TRICHLDRDETHANE
Do-EENZENE
*DB-TCLUENE
*Dl-BROriOPORM
D4-1, *~DICHLOROB£NZENE
METHANE, DICHLORQDIFLUORO-
ETHENE, CHLORO-
KETHANE. CHLORO-
f'.ETHANE, BROMO-
ETHANE, CHLORO-
METHANt, TKICHLOROFLUQRO-
ETHENE, 1, 1-DICHLORO-
2-PROPENAL
2-PROPENENITRILE
PROPANE, 2, 2-DICHLQRQ-
1'it.lHANt. D1CHLDKU-
ETHENE, 1, 2-DICHLORO-. (Z)-
ETHANE, 1, 1-DICHLORO-
METHANE, TRICHLORO-
ETHENE, TRICHLORO-
tlHAIxt, l,ii-UitKl_aKU-
METHANE, TETRACHLORO-
ETHANE. 1,1. 1-TRICHLDRO-
BENZENE
PROPANE, 1, 2-DICHLORO-
ht iHANt, BHUr.UDiCi-iLDUb-
1-PROPENE, 1. 3-DICHLORO-, -
BENZENE, METHYL-
i-PROPENE, 1.3-DICHLQRO-, (E>-
ETHANE, 1, 1.2-TR1CHLORO-
hEldAWt, DIERDhOCHLOhiO-
ETHENE, TETRACHLORO-
EENiENE. CKLDRO-
BENZEK'E. ETHYL-
METHANE, TRIBRQIIQ-
t'l HANt, 1 , 1 , k, «!- 1 L 1 K A'CHLDKU-
' BENZENE, 1, 4-DICHLQRO-
Indicated
GC/MS
PPB
3.31
9.29
11.12
15.71
12.46
7.59
8.67
28.90
47.11
NQ
1 .bt
6.0
6.16
11.65
3.05
13.73
]2.41
15.09
34.54
3.12
2.56
by (*)
FIT
965
945
987
981
963
995
992
946
843
yyb
813
980
958
948
981
974
861
991
643
647
AT
i
-3
-1
0
3
6
0
0
-2
-t
0
12
4
t
-1
-2
-3
0
0
-5
PPB FIT AT
-
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
327
-------
ANALYSIS REPORT
Sample: Oakland.
PS220
L£b: U of W
Sample Size: \
Date Sampled:
PURGABLE ORGANICS
Digested Sludge
C-entitation Standard:
Quantitation Method:
COMPOUND
Indicated
GC/MS
PPB
by (*)
FIT
AT
D5-CHLORQETHANE
D3- AC R YLON I TR I LE
*D6-2. 2-DICHLOROPROPANE
Dl-CHLDROFORM
D3-1,.!, 1-TRICHl.OROETHANE
Ds-££NZ£NE
*DB-TDLUENE
*Di-aROMQFORM
D4-1. 4-DICHLOROBENZENE
t"iETHAN^, D1CHLORODIFLUORQ-
ETHENE. CHLORO-
t'iETHANE, CHLORO-
METHANE. BRDMO-
ETHANE, CHLORQ-
METHANE, TK1CHLQROFLUORQ-
ETMENE, 1, 1-DICHLORO-
2-PRDPENAL
2-PROPEUENITRILE
PROPANE. 2. 2-DICHLDRD-
1'it.THANt:, D1CHLDKQ-
ETHENE, 1.2-DICHLORO-, (Z)-
ETHANE. 1. 1-DICHLORO-
KETHANE. TRICHLQRO-
ETKENE. TRICHLORO-
tlHANc.. 1. cJ-UItKL-UKU-
METHANE. TETRACHLQRO-
ETHANE. 1.1, 1-TRICHLORO-
BENZENt
PROPANE, 1. 2-DICHLDRO-
43.49
11.12
17.29
14.19
9.23
8.67
28.90
1 .Ob
0.24
NO
2.34
1.17
12.43
974
980
993
973
987
994
970
706
980
871
620
982
0
0
-1
0
2
0
1
6
2
-1
6
1
Ht IHANt. KHUnUUJLHLDKU-
1-PRDPENE. 1.3-DICHLORO-, (Z)-
BENZENE, METKYL-
1-PROPENE. 1. 3-DICHLORO-, (E>-
ETHANE, 1,1, 2-TR1CHLORO-
htlnAiNlL, DIEROfiOChLOKO-
ETHENE. TETRACHLORO-
PENiEMt:, CHLDRO-
BENZENE, ETHYL-
METHANE, TRIBROI10-
1. 1 HAIJt, 1 , 1 , 'd.,
-------
ANALYSIS REPORT
Sample: Renton, Primary Effluent
PS90N1
Sample Size: 1 liter
Date Sampled
Quantitation Standard:
Q-2-titation Method:
BASE + NEUTRAL EXTRACTABLES
DgNaphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
BiS(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1 ,2,4-TRICHLOROBENZENE A
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE A
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE A
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE •
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT
AT
0.07 890
0.56 991
3.57 <995
4.83 997
0.32 <803
-6
-5
-6
-5
-3
0.05 <845
0.13 816
0.21 738
1.18 990
0
3
4
0
0.52 998
0.18 628
0.06 827
14
17
23
7.44 996
-4
0.14 963
0.01 <959
3.01 998
0.02 <650
2
1
15
14
2.59 985
27
NA
NA
PPB FIT AT
"
blank=not found; NQ=detected but not
A=probable artifact
quantitated; NA=not analyzed for
329
-------
ANALYSIS REPORT BASE + NEUTRAL EXTRACTABLES
Sample: Renton, Secondary Effluent before chlorination
, i. PS8°
Lab: y of w
Sample Size:
1 liter
Date Sampled
Quantitation Standard:
Cuantitation Method:
Dg^aphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL) ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
B!S(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
D1METHYLPHTHALATE
2,6-DINlTROTOLUENC
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
D1ETHYLPHTHALATE
AZOBENZENE (FROM 01PHENYLHYDRAZINE)
N-NITROSODIPHENYLAM1NE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO( A) ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B)FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
D1BENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
0.02 791 7
0.74 945 5
2.95 994 6
0.06 839 0
0.06 <812 -2
0.02 848 6
0.21 986 1
0.16 _983 0
0.40 942 2
NO
1.79 992 0
0.92 839 -4
NA
NA
PPB FIT AT
frprobable artifact
330
-------
ANALYSIS REPORT BASE + NEUTRAL EXTRACTABLES
Sample: Renton, Secondary Effluent after dechlorinatlon
Lab: UofW PS7°
Sample Size: 1 liter
Date Sampled
Quantitation Standard:
Qusntitation Method:
Dgflaphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
(1,3-}DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
BIS (2-CHLOROISOPROPYL) ETHER
HEXACHLOROETHANE
N-;iITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-N1TROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
NO
1.93 834 -R
3. SB 994 -fi
0.31 <841 -6
5.41 971 -2
12.75 976 6
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
331
-------
ANALYSIS REPORT
Sample: Atlanta, Raw Sewage
. . PS150N2
Lab: il of W
Sample Size: 1 liter
Date Sampled
Quantitation Standard:
Quantitation Method:
BASE + NEUTRAL EXTRACTABLES
DgNaphthalene
GC/HS
COMPOUND
N-NITROSODIMETHYLAMINE
B1S(2-CHLOROETHYL) ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
B1S(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AM1NE A
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1 ,2 ,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE A
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
3.15 <975 2
13.94 975 2
43.86 <982 2
NQ 783 >10
0.12 <844 2
0.61 788 0
10.94 988 0
0.25 846 0
0.88 942 -2
1.72 979 -2
1.36 950 14
NQ <862 9
"? ?4 <3fi? Ifi
NQ
-------
ANALYSIS REPORT
Sample- Atlanta, Primary Effluent
PS120
Lab: u of W
Sample Size: j liter
Date Sampled
Quantitation Standard:
Q-jantitation Method:
BASE + NEUTRAL EXTRACTABLES
Dg^aphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
B1S(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
BIS (2-CHLOROISOPROPYL) ETHER
HEXACHLOROETHANE
N-N1TROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE A
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE A
DIMETHYLPHTHALATE
2,6-DlNITROTOLUENE A
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
D1ETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
Dl-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT
AT
0.36
-------
ANALYSIS REPORT BASE
Sample: Atlanta, Secondary Effluent
Lab: U of W PS171
Sample Size: 1 liter
Date Sampled
Quantitation Standard:
C'jantitation Method:
+ NEUTRAL EXTRACTABLES
DgN aphtha! ene
GC/MS
COMPOUND
N-N1TROSOD1METHYLAM1NE
BIS(2-CHLOROETHYL) ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
B!S(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-niTROSO-DI-N-PROPYL AMINE
NITROBENZENE
B1S(2-CKLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE) A
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBEMZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
bl-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT
AT
0.09 950
0.45 935
2.04 993
1.22 988
0.34 B72
3
3
1
3
-2
0.01 <801 <1
0.09 883
4.06 993
1
1
0.04 <864
0.12 858
3
0
0.05 802
1
0.12 893
0.26 952
0.06 <887
0
-1
-14
0.28 993
0,07 986
4.97 995
0.05 899
0.14 976
1.63 975
1
3
-1
4
4
-2
11.17 969
0.54 823
-3
-3
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not
A=probable artifact
quantitated; NA=not analyzed for
334
-------
ANALYSIS REPORT BASE + NEUTRAL EXTRACTABLES
Sample' Atlanta discharge, Secondary Effluent
•' PS160N ' after chlorination
Lab: u of W
Sample Size: \ liter
Date Sampled
Quantitation Standard: Dgflaphthalene
Quantitation Method: GC/MS
COMPOUND
N-MITROSODIMETHYLAM1NE
B!S(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBEN2ENE
B!S(2-CHLOROISOPROPYL)ETHER
HEXACHLCROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)ME:THANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE A
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL .PHENYL 'ETHER
HEXACHLOROCYCLOPENTAD1ENE
PPB FIT AT
1.32 996 9
5.74 <996 7
10.12 997 8
0.13 <862 2
0.11 840 -1
0.34 963 1
0.37 95? 1
0.12 869 -16
0.04 835 -16
0.25 941 2
0.20 807 1
0.28 984 1
NO
1.82 991 -9
0.06 782 -3
0.18 956 -5
3.68 992 -17
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
335
-------
ANALYSIS REPORT
Sample- Atlanta, Digested Sludge
PS141
Lab: M nf u
Sample Size: 50 ml
Date Sampled
Quantitation Standard:
Method:
BASE + NEUTRAL EXTRACTABLES
Dgflaphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
B1S(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DKHLOROBENZENE
(1,2-)DICHLOROBENZENE
3IS(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
8!S(2-CHLOROETHOXY)METHANE
1,2,4-TRlCHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIKETHYLPHTHALATE
2,6-DINlTROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE A
1NDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT
AT
17.0 961
89.4 <962
312.4 996
4
2
2
318.4 992
1
19.6 805
7
21.50 947
0
51.2 929
0
3.6 <784
12'2.6 <930
6
0
101. 993
9.6 <991
2002. 978
27.2 986
39.6 976
3115.8 993
28.8 893
23.0 931
1
2
-2
3
2
0
6
5
3794.8 987
181.8 819
1
0
14.6<811 <11
13.6<832
8.4 759
10
-3
NA
NA
PPB FIT AT
"
blank=not found; NQ=detected but not
A=probable artifact
quantitated; NA=not analyzed for
336
-------
ANALYSIS REPORT
Sample: Oakland, Raw Sewage
PS181
Lab: u of W
Sample Size: j liter
Date Sampled
Quantitation Standard:
"•-.jantitation Method:
BASE + NEUTRAL EXTRACTABLES
Djfl aphtha! ene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DlCHLOROBENZENE
n,2-)DICHLOROBENZENE
BiS(2-CHL3ROISOPROPYI.) ETHER
HEXACHLOROETHANE
M-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE A
BIS(2-CHLOROETHOXY)ME THANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIHETHYLPHTHALATE
2,6-DINITROTOLUENE A
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM D1PHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE A
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO( A) ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BI S( 2-ETHYLHEXYL )PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENOd, 2, 3-CD) PYRENE
DIBENZO(A,H)ANTHRACENE
BENZO(GH1)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
0.12 881 -4
0.22 861 3
1.52 <869 1
1.78 983 3
6.73 <834 6
0.29 <824 -6
6.85 995 0
0.38 913 -3
2.61 792 5
0.28 892 -2
0.57 933 -2
9.77 989 -1
1.28 <844 -2
1.21 987 1
0.05 983 4
11.07 993 1
3.10 995 2
.0.80 978 2
126.34 996 -1
0.68 <941 1
0.66 948 0
275.03 995 -1
10.60 916 -4
0.38 854 -3 '
0.08 839 5
NA
NA
PPB FIT AT
"
b!ank=not found; NQ=detected but not
A=probable artifact
quantltated; NA=not analyzed for
337
-------
ANALYSIS REPORT
Sample- Oakland, Primary Effluent
PS190
Lab: u of W
Sample Size: 1 liter
Date Sampled
Quantitation Standard:
Q-artitation Method:
BASE + NEUTRAL EXTRACTABLES
D^aphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL) ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
BIS(2-CHLCROISOPROPYL)ETHER
HEXACHLOROETHANE
N-N1TROSO-DI-N-PROPYL AMINE
NITROBENZENE A
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLCRO-NAPHTHALANE
ACENAPHTHYLENE A
DIMETHYLPHTHALATE
2.6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
0.70 <859 6
1.29 <977 4
6.88 <984 2
5.90 980 -3
NO <845
1.97 <955 -10
NQ <785
10.70 993 1
0.27 <804 11
0.31 757 -1
1.35 <788 7
0.58 802 1
5.18 825 ,2
0.70 <867 -1
1.43 961 0
NO
12.87 978 0
3.48 992 2
1.52 965 3
154.72 997 -2
1.53 <923 1
1.42 926 -1
309.50 990 -2
10.79 835 -6
NO
0.77 774 -1 '
NQ <760
NA
NA
PPB FIT AT
"
blank=not found; NQ=detected but not
/^probable artifact
quantitated; NA=not analyzed for
338
-------
ANALYSIS REPORT
Samnip-Renton, Raw Sewage
' PS100
Lab: u of W
Sample Size: i liter
Date Sampled
Quantitation Standard:
Qua,",titaticn Method:
BASE + NEUTRAL EXTRACTABLES
DgNaphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL) ETHER A
(1,3-}D1CHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
B1S(2-CHLOROISOPROPYL)ETH£R
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE A
NITROBENZENE
BIS(2-CHLOROETHOXY)ME THANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINlTROTOLUENE A
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-N1TROSODIPHENYLAMINE A
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZlDENE
BIS(2-ETHYLHEXYL)PHTHALATE
Dl-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
0.06 <944 -6
0.71 979 4
5.02 <997 3
4.79 993 4
0.16 <829 2
0.49 <854 -4
0.21 839 5
1.27 977 1
0.04 <757 1
0.72 979 -2
0.20 <780 7
0.09 830 -1
0.15 9?4 -1
6.57 996 -1
0.24 <827 -7
0.37 <996 1
NO
5.58 992 1
0.16 975 3
0.16 986 2
6.69 991 -4
0.06 <930 1
0.09 930 1
1.33 914 -6
0.07 811 1
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not
A=probable artifact
quantitated; NA=not analyzed for
339
-------
ANALYSIS REPORT BASE + NEUTRAL EXTRACTABLES
Sample- Renton, Primary & Waste Activated Sludae
PS110
Lab: U of W
Sample Size: 50 m]
Date Sampled
Quantitation Standard:
Ofantitation Method:
DgNaphthalene
GC/KS
COMPOUND
N-NITROSODIMETHYLAMINE
B1S(2-CHLOROETHYL) ETHER
(1,3-)DICHLOROBENZENE
1,4-DlCHLOROBENZENE
(1,2-)D1CHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE A
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINlTROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE A
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K) FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
59.8 <832 -2
11.0 851 2
4.2 934 -1
42.6 791 9
6.0 895 -2
119.2 990 -1
20.0 845 1
4009 988 2
124.0 798 1
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
340
-------
ANALYSIS REPORT
Sample-* Oakland, Secondary Effluent
PS200N
Lab: u of W
Sample Size: \ liter-
Date Sampled
Quantitation Standard:
Quantitation Method:
BASE + NEUTRAL EXTRACTABLES
Dj^l aphtha! ene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL) ETHER
(1,3-}DICHLOROBEN2ENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER A
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DlNITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE)
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO(A)ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
1NDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GH1)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
0.40 <832 2
<.01
0.41 <996 8
2.75 <995 7
1.34 <996 7
0.27 916 -2
0.10 <871 0
0.32 958 1
NO
5.99 994 -9
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
341
-------
ANALYSIS REPORT BASE + NEUTRAL EXTRACTABLES
Sample: Oakland, Secondary Effluent after Dechlorination
Lab: n
Sample bi
1 liter
jize:
Date Sampled
Quantitation Standard:
Q-jantitation Method:
Dgflaphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL) ETHER
(1,3-)DICHLOROBENZENE
1,4-DICHLOROBENZENE
(1,2-)DICHLOROBENZENE
BIS(2-CHLOROISOPROPYL)ETHER A
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1 ,2 ,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DINITROTOLUENE
FLUORENE
D1ETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE) A
N-N1TROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO( A) ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE
BENZO(B) FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACENE
BENZO(GHI)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB FIT AT
0.01 <883 -3
0.30 962 -1
0.23 943 3
0.23 <888 13
0.05 902 -1
0.11 906 -1
0.02 <833 -16
4.90 992 -1
0.38 971 -1
3.35 967 -3
NA
NA
PPB FIT AT
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
342
-------
ANALYSIS REPORT
Sample- ""l
PS220
Lab: u of W
Sample Size:
Date Sampled
Quantisation Standard:
Quantisation Method:
IN. j ,
Digested Sludge
liter
BASE + NEUTRAL EXTRACTABLES
Dgf^aphthalene
GC/MS
COMPOUND
N-NITROSODIMETHYLAMINE
BIS(2-CHLOROETHYL)ETHER
(1,3-)DICHLOROBENZENE
1,4-DlCHLOROBENZENE
(1,2-)DICHLOROBENZENE
B IS (2-CHLOROISOPROPYL) ETHER
HEXACHLOROETHANE
N-NITROSO-DI-N-PROPYL AMINE
NITROBENZENE
BIS(2-CHLOROETHOXY)METHANE
1,2,4-TRICHLOROBENZENE
NAPHTHALENE
HEXACHLOROBUTADIENE
2-CHLORO-NAPHTHALANE
ACENAPHTHYLENE
DIMETHYLPHTHALATE A
2,6-DINITROTOLUENE
ACENAPHTHENE
2,4-DlNITROTOLUENE
FLUORENE
DIETHYLPHTHALATE
AZOBENZENE (FROM DIPHENYLHYDRAZINE) A
N-NITROSODIPHENYLAMINE
4-BROMODIPHENYL ETHER
HEXACHLOROBENZENE
PHENANTHRENE
ANTHRACENE
DI-N-BUTYLPHTHALATE
FLUORANTHENE
PYRENE
BUTYLBENZYLPHTHALATE
BENZO( A) ANTHRACENE
CHRYSENE
3,3'-DICHLOROBENZIDENE
BIS(2-ETHYLHEXYL)PHTHALATE
DI-N-OCTYL PHTHALATE A
BENZO(B)FLUORANTHENE
BENZO(K)FLUORANTHENE
BENZO(A)PYRENE
INDENO(1,2,3-CD)
DIBENZO(A,H)ANTHRACEME
BENZO(GH1)PERYLENE
CHLOROPHENYL.PHENYL ETHER
HEXACHLOROCYCLOPENTADIENE
PPB
FIT
AT
5.5
37.0
15.8
942
944
981
5
2
5
13.5
76.0
982
990
2
1
0.75
754
6
2.8
981
3
5.8
983
3
0.01
823
-3
27.3
996
1
NO
1.8
42.3
Z4.8
862
992
995
-1
2
3
18.8
14.0
991
990
6
5
P.429
!37
984
870
5
-3
NO
8.0
4.8
905
909
8
-4
NA
NA
PPB FIT AT
"
blank=not found; NQ=detected but not quantitated; NA=not analyzed for
A=probable artifact
343
-------
ANALYSIS REPORT ACIQ-EXTRACTABLES (PHENOLS)
Sample: Oakland, Digested Sludge
; PS220
Lab: u of W
Sample Size: 4QML
Date Sampled: 7/3/79
Quantitation Standard: HMB
Quantitation Method: GC FID
COMPOUND AMT FIT AT
PHENOL (M)
2-CKLOROPHENOL
PHENOL
2-CHLOROPHEMOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-HETHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOI. (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DIMITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
344
-------
ANALYSIS REPORT ACID-EXTRACTABLES (PHENOLS)
Sample: Oakland, Secondary Effluent, dechlorinated
PS210
Lab: U of W
Sample Size: 1000ml
Gate Sampled: 7/3/79
Quantisation Standard: HMB
Quantisation Method: GC FID
COMPOUND AMI FIT AT
PHENOL (M)
2-CHLOP.GPHENOL
PHENOL
2-CHLORCPHENOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-fiITROPHENOL (M)
4-NITROPHEMOL (M)
4,6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHEMOL (M)
2,4-DINITROPHENOL (M)
AMI FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
345
-------
ANALYSIS REPORT
ACID-EXTRACTABLES (PHENOLS)
Sample: Oakland, Secondary Effluent
PS200
Lab: U of W
Sample Size: 1000ml
Date Sampled: 7/3/79
Quantitation Standard: HMB
Quantitatlon Method: GC FID
COMPOUND AMI FIT AT
PHENOL (M)
2-CHLOROPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIMETHYLPHEMOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHEMOL (M)
4-NITROPHENOL (M)
4.5-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethans
346
-------
ANALYSIS REPORT
Sample: Oakland, Primary Effluent
'• PS190
Lab: u of W
Sample Size: IQOOml
Date Sampled: 7/3/79
Quantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND AMI FIT AT
PHENOL (M)
2-CHLOROPHENOL
PHENOL
2-CHLOROPHENOL (M) 479.26
2,4-DIMETHYLPHENOL 42.57
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M) 12.12
2-NITROPHENOl (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
347
-------
ANALYSIS REPORT
Sample: Oakland, Raw Sewage
PS 181
Lab: U of W
Sample Size: 1000ml
Date Sampled: 7/3/79
Quantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND
PHENOL (M)
2-CHLCRC-HENOL
pi-i-~MQ|_
2-CHLORGPHENOL (M)
2,4-DIMEiHYLPHENOL
4-CHLORG-3-METHYLPHENOL (M)
2,4-DICHLOROPHEMOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICKLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHEMOL (M)
2,4-DINITROPHENOL (M)
AMI FIT AT
163.89
201.67
58.17
14.33
ANTT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
348
-------
ANALYSIS REPORT
Sample: Renton, Prim.+Ac.Sludge
PS110
Lab: U of W
Sample Size: 767ml
Date Sampled: 4/12/79
Quantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND AMI FIT AT
PHENOL (M)
2-CHLORGPKENOL
PHENOL
2-CHLGROPHENOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M) 1.44
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M) 7.70
PENTACHLOROPHENOL (M)
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
349
-------
ANALYSIS REPORT ACID-EXTRACTABLES (PHENOLS)
Sample: Renton , Secondary Effluent, dechlorinated
PS70
Lab: U of W
Sample Size: 1000ml
Date Sampled: 4/12/79
Qu'antitation Standard: MM3
Quantitation Method: GC FID
COMPOUND - AMI FIT AT
PHENOL (K)
2-CHLOP.OPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHEMOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4.5-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M) 14 71
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
350
-------
ANALYSIS REPORT
Sample: PS90S
Renton, Primary Effluent
Lab: U of W
Sample Size: 1000ml
Date Sampled: 4/12/79
Quantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND
PHENOL (M)
2-CHLOROPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DIMITROPHENOL (M)
AMI FIT AT
1.26
23.02
1.62.
4.68
AMT FI'
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
351
-------
ANALYSIS REPORT
Sample: Renton, Raw Sewage
PS100
Lab: u of W
Sample Size: lOOOml
Date Sampled: 4/12/79
Quantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND AMI FIT AT
PHENOL fM)
2-CHLOROPHENOL
PHENOL
2-CHLGROPHENOL (M)
2,4-Q!ME7riYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CKLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-MITROPHENOL (M)
4,6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DIMITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
352
-------
ANALYSIS REPORT
Sample: PS80S
Renton, Secondary Effluent
Lab: U of W
Sample Size: 1000ml
Date Sampled: 4/12/79
Qua.ntitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND AMI FIT AT
PHENOL (M)
2-CKLORGP-iENOL
PHENOL
2-CHLORCPHENOL (M)
2,4-DIMEHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M) 5.35
PENTACHLOROPHilNOL (M) 16.80
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
353
-------
ANALYSIS REPORT
Sample: Atlanta, Sludge
PS141
Lab: U of W
Sample Size: 20ml
Date Sampled: 6/14/79
Q'uantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND - AMI FIT AT
PHENOL (M)
2-CHLOROPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIHETHYLPHENOL 11.42
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M) 9.41
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-MITROPHENOL (M)
4-MITROPHENOL (H)
4.6-DINITRO-2-METHYLPHENOL (M) Q 14
PENTACHLOROPHENOL (M)
2,4-DINITROPHENOL (M)
AMT FIT
blctnk=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
354
-------
ANALYSIS REPORT ACID-EXTRACTABLES (PHENOLS)
Sample: Atlanta, Secondary Effluent, chlorinated
PS160
Lab: U pf W
Sample Size: lOQOml
Data Sampled: 6/14/79
Quantitation Standard: HMB
Qua'ntitation Method: GC FID
COMPOUND AMI FIT AT
PHENOL (M)
2-CHLQ?,0?HENOL
PHENOL
2-CHLORGPHENOL (M)
2,4-Q!ME7HYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4,6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M) 13.47
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
355
-------
ANALYSIS REPORT
Sample: Atlanta, Secondary Effluent
Lab: U of W
Sample Size: 1000ml
Date Sampled: 6/14/79
Quantitation Standard: HNB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND - AMI FIT AT
PHENOL (M)
2-CHLOROPHENOL
PHENOL
2-CHLOROPHENOL (H)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4,6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M)
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
356
-------
ANALYSIS REPORT
Sample: Atlanta, Primary Effluent
PS120
Lab: U of W
Sample Size: 1000ml
Date Sampled: 6/14/79
ACID-EXTRACTABLES (PHENOLS)
Quantitation Standard:
Quantitation Method: GC FID
COMPOUND AMI FIT AT
PHENOL (M)
2-CKLQRCPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIMETriYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHEMOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRlCHLOROPHENOL (M)
2-MITROPHENOL (M)
4-iiITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M) 13.31
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=derivatized with diazomethane
357
-------
ANALYSIS REPORT
Sample: Atlanta, Raw Sewage
PS150
Lab: U of W
Sample Size: 1000ml
Date Sampled: 6/14/79
Quantitation Standard: HMB
Quantitation Method: GC FID
ACID-EXTRACTABLES (PHENOLS)
COMPOUND AMI FIT AT
PHENOL (M)
2-CHLOP.OPHENOL
PHENOL
2-CHLOROPHENOL (M)
2,4-DIMETHYLPHENOL
4-CHLORO-3-METHYLPHENOL (M)
2,4-DICHLOROPHENOL (M)
4-CHLORO-3-METHYLPHENOL
2,4,6-TRICHLOROPHENOL (M)
2-NITROPHENOL (M)
4-NITROPHENOL (M)
4.6-DINITRO-2-METHYLPHENOL (M)
PENTACHLOROPHENOL (M) 29.56
2,4-DINITROPHENOL (M)
AMT FIT
blank=not found; NQ=detected,not quantitated; NA=not analyzed for
(M)=dsrivatized with diazomethane
358
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS 100 Renton Raw Sewage
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND
a-BHC
6-BHC
Y-BHC (LIN DANE
6-BHC
P.P'-DDD
P.P'-DDE
P.P'-DDT
• BIELDRIN
ENDRIN
EN DRIN ALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAN
ENDOSULFPNE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD WE
OXYCHLOR
Y-CHLORDWE
a-CHLORDPNE
PPB AT
0.130 MI
0.579 MI
0.226 MI
0
0.181
0.183 I
0.525 MI
0.022
0.191
f
0.101 0.00
0
37.019 OMI
0.154
0.019
0
0.214 0.6
0.207 2.4
peak; D=detected but not integrated; 0=area obscured; I=improper integration.
359
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS90 neutral Renton primary effluent
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND PPB AT
a-BHC 0.125 +0.6
B-BHC
Y-BHC (LINDANE
6-BHC
P.P'-DDD
P,P'-DDE
P.P'-DDT
DIELDRIN N_Q +0.6
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN D
B-ENDOSULFAM
ENDOSULFANE SULFATE °_
HEPTACHLOR
HEPTACHLOR EPOXIDE 0.1757 +0.6
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN NQ +0.6
METHOXYCIILOR
Ml REX
CHORD HE 0.224 MIO -1.2
OXYCHLOR
Y-CHLORDANE 0.185 1.2
a-CHLORDANE 0.126 3.0
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; l=improper integration.
360
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: p$80 neutral Renton secondary effluent
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND
a-BHC
B-BHC
Y-BHC (LINDANE
6-BHC
P,P'-ODD
P,P'-DDE
P.P'-DDT
'JDIELDRIN
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAN
ENDOSULFME SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
M1REX
CHORD BE
OXYCHLOR
Y-CHLORDWE
a-CHLORDANE
PPB AT
0 +1.2
0.895 IM +1.2
0
0.009 1.8
0.084 +0.6
+0.6
0.097 2.4
0.198 3.0
0.078 1.2
peak; D=detected but not integrated; 0=area obscured; I=improper Integration.
361
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS70 neutral Renton secondary effluent dechlorinated
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND PPB AT
o-BHC
B-BHC •
Y-BHC (LINDANE
6-BHC 0.889 -2.4
P,P'-DDD
P.P'-DDE
P.P'-DDF
•JDIELDRIN 0.001 +1.8
ENDR1N 0.188 +1.8
ENDRINALDEHYDE
a-ENDOSULFAN
6-ENDOSULFAM
ENDOSULFANE SULFATE
HEPTACHLOR 0.012 +1.2
HEPTACHLOR EPOXIDE 0. 0849 +2.4
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248 '
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MI REX +1-2
CHORDAE
OXYCHLOR
•y-CHLORDANE 0.066 2.4
o-CHLOROANE
blank=not found; N0/=detected but not quantitated; NA=not analyzed for; tt=merged
peak; D=detected but not Integrated; 0=area obscured; I=improper integration.
362
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS151 neutral Atlanta Raw Sewage
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND
o-BHC
6-BHC
Y-BHC (LINDANE
6-BHC
P,P'-DDD
P,P'-DDE
P,P'-DDT
DIELDRIN
ENDRIN
EN DRIN ALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAN
ENDOStfLFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD BE
OXYCHLOR
Y-CHLORDANE
a-CHLORDANE
PPB
2.934 M
11.157 M
5.139
6.799
3.147 M
5.392
4.379
7.764
13.313 M
8.845
4.066
8.2575
1.973
4.260
3.246
3.815 MI
3.548
AT
+06
+ 0.6
+ 0.6
+ 0.6
+ 0.6
+0.6
+ 1.2
1.2
0.6
-2.4
+ 0.6
+ 1.2
+ 0.6
+ .1
1.8
0.6
1.2
peak; D=detected but not integrated; 0=area obscured; I=intproper integration.
363
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS110 neutral Renton Sludge
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUN D PPB AT
o-BHC 0.159 +Q.6
B-BHC
Y-BHC (LINDANE 0.323 I +0.6
6-BHC
P.P'-DDD
P.P'-DDE
P.P'-DDT
DIELDRIN 0.017 I -0.6
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN 0.042 0.00
B-ENDOSULFAN
ENDOSULFANE SULFATE 0
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR 0.468
MIREX
CHORDBSE 0.535 HI -1.2
OXYCHLOR
Y-CHLORDANE D
a-CHLORDANE 0.174 -1.8
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=improper integration.
364
-------
ANALYSIS REPORT PESTICIDES + PCB's
-Sample: PS150 neutral Atlanta Raw Sewage
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND PPB AT
a-BHC
B-BHC
T-BHC (LINDANE 0.140 M +1.2
6-BHC
P,P'-DDD 0.173 +0.6
P.P'-DDE
P.P'-DDT
DIELDRIN
ENDRIN
EN DRIN ALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAfl
EN DOS UL FANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232 :
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD WE
OXYCHLOR
Y-CHLORDANE 0.327 0^6
a-CHLORDANE 0.100 MI 1.2
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=improper Integration.
365
-------
ANALYSIS REPORT
Sample: PS120 Neutral
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
PESTICIDES + PCB's
Atlanta primary effluent
COMPOUND
o-BHC
e-BHC
•y-BHC (LIN DANE
6-BHC
P.P'-DDD
P.P'-DDE
P.P'-DDf
OIELDRIN
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN
6-ENDOSULFAN
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD BE
OXYCHLOR
Y-CHLORDANE
o-CHLORDANE
PPB
0.123
0.171
0.180
0.569
o.o'ie
0.038
0.050
0.012
0.484
0.078
0.349
0.324
AT
MI -0.6
+ 1.2
0
-0.6
0
0.00
. -3.0
-0.6
0
I 1.8
0.00
0.6
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=improper Integration.
366
-------
ANALYSIS REPORT
Sample: psi?l neutral
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
PESTICIDES + PCB's
Atlanta Secondary effluent
COMPOUN D
a-BHC
B-BHC
>-BHC (LIN DANE
6-BHC
P.P'-DDD
P.P'-DDE
P,P'-DDT
OIELDRIN
ENDRIN
ENDRINALDEHYDE
o-ENDOSULFAN
B-ENDOSULFAM
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MI REX
CHORD WE
OXYCHLOR
T-CHLORDANE
a- CH LORD WE
PPB AT
0.126 MT -0.6
0.147 0
0.143 +1.8
0.048 M -0.6
0.401 -1.8
0.048 M -0.6
0.009 0.00
0.12R -5.4
+ 0.6
/ 0.197 MI 0.61
'0.249 0.00
0.325 0.6
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=1mproper integration.
367
-------
ANALYSIS REPORT
Sample: PS160 neutral
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
PESTICIDES + PCB's
Atlanta secondary effluent chlorinated
COMPOUND
a-BHC
B-BHC
•Y-BHC (LIN DANE
6-BHC
P.P'-DDD
P.P'-DDE
P,P'-DDT
'JDIELDRIN
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN •
B-ENDOSULFAM
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MI REX
CHORD HE
OXYCHLOR
f-CHLORDANE
o-CHLORDANE
PPB
0.437
0.165
0.169
0.187
0.456
0.036
0.391
0.045
4.837
0.3608
0.501
0.106
0.823
0.609
AT
+ 1.8
-1.8
-1.8
0
-1.8
-2.4
0.6
+ 1.8
I 0.6
MI -0.6
M 3.0
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=improper integration.
368
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS141 neutral Atlanta Sludge
Lab:
Sample Size:
Date Sampled
Quantisation Standard:
Quantitation Method:
COMPOUND PPB AT
a-BHC
3-BHC
Y-BHC (LINDANE 0.130 +0.2
6-BHC
P.P'-DDD 0.203 + 1.2
P.P'-DDE '
P.P'-DDT
DIELDRIN 0.060
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN 0.219 1.2
B-ENDOSULFAN 0.049 -1.1
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE 0.2632 +0.6
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR _.:
MIREX
CHORDAE
OXYCHLOR
•Y-CHLORDANE 0.710 1.2
o-CHLORDANE 0.470 1.2
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; undetected but not integrated; 0=area obscured; I=improper integration.
369
-------
ANALYSIS REPORT PESTICIDES * PCB's
Sample: PS181 neutral Oakland Raw Sewage
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND
a-BHC
B-BHC
Y-BHC (LIN DANE
6-BHC
P.P'-DDD
P,P'-DDE
P.P'-DDT
'JDIELDR1N
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAN
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORDAE
OXYCHLOR
Y-CHLORDANE
a-CHLORDANE
PPB AT
0.414 0 -i-0.fi
0.290 +0.6
0.050 +0.6
0.277 1.8
0.228 -3.6
0
4.974 -1.2
0.632
1.141 MO ' -1.2
0.510 1.2
0.444 1.8
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; undetected but not integrated; 0=area obscured; I=improper Integration.
370
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS190 neutral Oakland Primary effluent
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND PPB AT
a-BHC
B-BHC
Y-BHC (LIN DANE 0.572 0 -0.6
6-BHC
P,P'-DDD 0.201
P,P'-DDE
P,P'-DDT
OIELDRIN 0.123 -13.2
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN 0.515 0.6
B-ENDOSULFAN
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE 0-6*51
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR 0.550
MIREX
CHORDWE 1.636 MO -1.6
OXYCHLOR
Y-CHLORDANE 1.152 I 0.00
a-CHLORDANE 0.692 1.2
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; l=improper integration.
371
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS200 neutral Oakland secondary Effluent
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUN D
o-BHC
B-BHC
Y-BHC (LIN DANE
6-BHC
P.P'-DDD
P.P'-DDt
P,P'-DDT
DIELDRIN
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAfl
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
METHOXYCHLOR
MIREX
CHORD NE
OXYCHLOR
>-CHLORDANE
o-CHLORDANE
PPB AT
0.155 +1.2
0.151 +1.2
0.039 1.2
0.141 2.4
0.4049 +1.8
0
0.060 I 3.0
0.221 0.6
blank=not round; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=improper Integration.
37?
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: PS210 neutral Oakland secondary effluent dechlorinated
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND PPB AT
a-BHC
B-BHC •
Y-BHC (LINDANE 0.139 +0.6
6-BHC 0.867 + 0.6
P.P'-DDD
P.P'-DDE
P,P'-DDT
DIELDRIN '
ENDRIN
ENDRINALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAN
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232 •
PCB 1248
PCB 1260
PCB 1016
ALDRIN +Q.6
METHOXYCHLOR
MIREX
CHORD WE 0.071 I 1.2
OXYCHLOR
f-CHLORDANE D -2.4
a-CHLORDANE
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not integrated; 0=area obscured; I=improper integration.
573
-------
ANALYSIS REPORT
Sample: PS220 neutral
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quanti tation Method:
PESTICIDES + PCB's
Oakland Sludge
COMPOUND
PPB
AT
a-BHC
B-BHC
Y-BHC (LINDANE
6-BHC
P,P'-DDD
P.P'-DDE
P.P'-DDT
CIELDRIN
ENDRIN
EN DRIN ALDEHYDE
a-ENDOSULFAN
B-ENDOSULFAM
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDR1N
METHOXYCHLOR
MIREX
CHORDAE
OXYCHLOR
Y-CHLORDANE
o-CHLORDANE
0.122
0.273
0.550
0.149
0.386
1.327
0.101
0.72
+1.2
-0.6
-3.6
0.6
0.403 MI -4.2
2.4
4.06
blank=not found; NQ=detected but not quantitated; NA=not analyzed for; M=merged
peak; D=detected but not Integrated; 0=area obscured; I=improper Integration.
374
-------
ANALYSIS REPORT PESTICIDES + PCB's
Sample: 2-119 neutral Oakland Blank
Lab:
Sample Size:
Date Sampled
Quantitation Standard:
Quantitation Method:
COMPOUND
a-BHC
e-BHC
V-BHC (LIN DANE
6-BHC
P.P'-DDD
P.P'-DDE
P,P'-DDT
DIELDRIN
ENDRIN
EN DRIN ALDEHYDE
a-ENDOSULFAN
e-ENDOSULFAM
ENDOSULFANE SULFATE
HEPTACHLOR
HEPTACHLOR EPOXIDE
PCB 1242
PCB 1254
PCB 1221
PCB 1232
PCB 1248
PCB 1260
PCB 1016
ALDRIN
HETHOXYCHLOR
MIREX
CHORD BNE
OXYCHLOR
Y-CHLORDANE
a-CHLORDANE
PPB TA
0.127 I +0.6
0.159 +1.8
0.404 0
M -1.2
0.83 0
0.012 -0.6
0.043 -3.0
0
-1.2
peak; D=detected but not integrated; 0=area obscured; I=improper integration.
375
------- |