VOLUME II
EVALUATED METHODOLOGY FOR THE
ANALYSIS OF RESIDUAL WASTES
ac
December 1980
Contract 68-02-2685
Technical Directive 108
Final Report
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
U. S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
and
EFFLUENT GUIDELINES DIVISION
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
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EPA-
December 1980
VOLUME II
EVALUATED METHODOLOGY FOR THE
ANALYSIS OF RESIDUAL WASTES
by
Herbert C. Miller
Ruby H. James
Walter R. Dickson
Southern Research Institute
Birmingham, Alabama 35255
Contract 68-02-2685
Technical Directive 108
for
Dr. Larry D. Johnson, Project Officer
Industrial Environmental Research Laboratory
Process Measurements Branch »
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
and
Dr. Dean Neptune, Task Officer
Analytical Programs
Effluent Guidelines Division
U. S. Environmental Protection Agency
401 M Street, Southwest
Washington, D. C. 20460
and
Mr. Mike H. Carter, Task Officer
Office of Analytical Support
Effluent Guidelines Division (WH-552)
U. S. Environmental Protection Agency
401 M Street, Southwest
Washington, D. C. 20460
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DISCLAIMER
This report has been reviewed by the Analytical Programs Effluent
Guidelines Division, U. S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U. S. Environmental Protection
Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
ii
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ABSTRACT
This report presents the results of a program of evaluation of
analytical methods for "Total Content" of residual wastes. Candidate
methods were first studied and modified, and then evaluated by analyzing
a variety of industrial residuals for a broad range of organic compounds
and metals. The results, based on statistical analysis of over 10,000
data points, are quoted primarily in terms of observed accuracy and
precision. The methods depend on extraction, gel permeation chromatography
cleanup, preconcentration, and GC/MS analysis for identification and
quantitation of semivolatile organics; purge-and-trap and GC/MS for
purgeable organics; and acid digestion combined with AAS or ICP determin-
ations for metals. An edited text of the evaluated methods is presented
in the format specified by EMSL-Cincinnati for standard methods as an
appendix to this report.
Southern Research Institute and Battelle-Columbus Laboratories
exchanged methodologies developed for Total Content and Potential Mobility
and applied these procedures to the analyses of samples in an inter-
laboratory study. Results of SoRI's contribution to the interlaboratory
study are presented in the appendices to this report.
iii
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CONTENTS
Disclaimer ±±
Abstract ill
Figures vi
Tables xi
Acknowledgment xxi
1. Introduction 1
2. Conclusions 3
3. Recommendations 4
Purgeable and Semivolatile Organics 4
Metals 5
4. Selection and Modification of Methods 7
Purgeable Organics 7
Semivolatile Organics 48
Metals 54
5. Evaluation of Methods 68
Summary of Proposed Methodology 68
Description of Residual Wastes 69
Matrix of Analyses 69
Compounds Chosen for Determination 69
Analytical Instrumentation 72
Evaluation Data 72
6. Statistical Interpretation of Data 73
Introduction 73
Summary of Statistical Terms and Formulas 73
Rejection of an Observation 74
Interquartile Ranges 74
Summary Presentation of Data . 77
Appendices
I. Data Summary Tables 78
A. Summary of Average Concentrations of Compounds in
Unspiked Residual Waste Samples 80
B. Summary of Relative Standard Deviations of
Concentrations of Compounds Averaged Over All
Spike Levels (Including Unspiked Samples) 85
C. Summary of the Average Mean Recoveries of
Compounds in Spiked Residual Waste 90
II. Potential Mobility (Leachate) Interlaboratory Study Data . 95
A. Ink Pigment Leachate (Interlaboratory) 97
B. Organic Still Bottoms Leachate (Interlaboratory) .... 113
IV
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CONTENTS (Continued)
III. Total Content Interlaboratory Study Data 129
A. Ink Pigment Waste (Interlaboratory) 130
B. Organic Still Bottoms (Interlaboratory) 149
IV. Total Content Evaluation Data 167
A. Deionized, Distilled Water (Spiked Method Blank) 169
B. POTW Residual Waste 177
C. Ink Pigment Waste 195
D. Organic Still Bottoms 208
E. Paint Pigment Sludge 215
F. Coke Oven Biological Sludge 233
G- Electroplating Sludge 249
H. Electric Furnace Baghouse Dust 252
V. Text of Methods for Total Content 255
A. Proposed Method for Purgeable Organics in
Residual Waste 25^
B. Proposed Method for Base/Neutral and Acid Extractable
Semivolatile Organics in Residual Waste 275
C. Proposed Method for the Determination of Metals in
Residual Waste 302
D. Quality Assurance and Quality Control Procedures for
Determination of Purgeable Organics and
Base/Neutral and Acid Extractable Organics in
Residual Waste 312
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FIGURES
Number Page
1 Midwest Research Institute procedure for
semivolatile organics ......................................... 49
2 Battelle-Columbus Laboratories procedure for
semivolatile organics ......................................... 50
3 Summary of University of Washington procedure
for semivolatile organics ..................................... 51
4 Detailed analyses of University of Washington
procedure for semivolatile organics ........................... 52
II-l GC/MS chromatogram of purgeable organics by
purge and trap — Ink Pigment Leachate, unspiked . ............... 79
II-2 GC/MS chromatogram of purgeable organics by
purge and trap — Ink Pigment Leachate , spiked .................. 101
II-3 GC/MS chromatogram of base/neutral extractables —
Ink Pigment Leachate , unspiked ................................ 103
II-4 GC/MS chromatogram of base/neutral extractables —
Ink Pigment Leachate, spiked .................................. 105
II-5 GC/MS chromatogram of acid extractables —
Ink Pigment Leachate, unspiked ................................ 107
II-6 GC/MS chromatogram of acid extractables —
Ink Pigment Leachate , spiked .................................. 109
II-7 GC/MS chromatogram of purgeable organics by
purge and trap — Organic Still Bottoms
Leachate, unspiked ............................................
II-8 GC/MS chromatogram of purgeable organics by
purge and trap — Organic Still Bottoms
Leachate , spiked
II-9 GC/MS chromatogram of base/neutral extractables —
Organic Still Bottoms Leachate, unspiked
11-10 GC/MS chromatogram of base/neutral extractables —
Organic Still Bottoms Leachate, spiked ........................ 121
11-11 GC/MS chromatogram of acid extractables — Organic
Still Bottoms Leachate, unspiked .............................. 123
VI
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FIGURES (Continued)
Number Page
11-12 GC/MS chromatogram of acid extractables—Organic
Still Bottoms Leachate, spiked 125
III-l GC/MS chromatogram of purgeable organics by purge
and trap—Ink Pigment Waste (Interlaboratory),
unspiked 133
III-2 GC/MS chromatogram of purgeable organics by
purge and trap—Ink Pigment Waste (Interlaboratory),
spiked 136
III-3 GC/MS chromatogram of base/neutral extractables—
Ink Pigment Waste (Interlaboratory), unspiked 138
III-4 GC/MS "chromatogram of base/neutral extractables—
Ink Pigment Waste (Interlaboratory), spiked 141
III-5 GC/MS chromatogram of acid extractables—Ink
Pigment Waste (Interlaboratory), unspiked 143
III-6 GC/MS chromatogram of acid extractables—Ink
Pigment Waste (Interlaboratory), spiked 146
III-7 GC/MS chromatogram of purgeable organics by purge
and trap—Organic Still Bottoms (Interlaboratory),
unspiked 151
III-8 GC/MS chromatogram of purgeable organics by purge
and trap—Organic Still Bottoms (Interlaboratory),
spiked 154
III-9 GC/MS chromatogram of base/neutral extractables—
Organic Still Bottoms (Interlaboratory), unspiked 156
111-10 GC/MS chromatogram of base/neutral extractables—
Organic Still Bottoms (Interlaboratory), spiked 159
III-ll GC/MS chromatogram of acid extractables—Organic
Still Bottoms (Interlaboratory), unspiked 161
111-12 GC/MS chromatogram of acid extractables—Organic
Still Bottoms (Interlaboratory), spiked 164
VI1
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FIGURES (Continued)
Number Page
IV-1 GC/MS chromatogram of purgeable organics by
purge and trap—Method Blank, spiked 172
IV-2 GC/MS chromatogram of base/neutral extractables—
Method Blank, spiked 174
IV-3 GC/MS chromatogram of acid extractables—
Method Blank, spiked 176
IV-4 GC/MS chromatogram of purgeable organics by
purge and trap—POTW Residual Waste, unspiked 179
IV-5 GC/MS chromatogram of purgeable organics by
purge and trap—POTW Residual Waste, spiked 182
1V-6 GC/MS chromatogram of base/neutral extractables—
POTW Residual Waste, unspiked 184
IV-7 GC/MS chromatogram of base/neutral extractables—
POTW Residual Waste, spiked 188
IV-8 GC/MS chromatogram of acid extractables—POTW
Residual Waste, unspiked 190
IV-9 GC/MS chromatogram of acid extractables—POTW
Residual Waste, spiked 194
IV-10 GC/MS chromatogram of base/neutral extractables—
Ink Pigment Waste, unspiked 197
IV-11 GC/MS chromatogram of base/neutral extractables—
Ink Pigment Waste, spiked 200
IV-12 GC/MS chromatogram of acid extractables—
Ink Pigment Waste, unspiked 202
IV-13 GC/MS chromatogram of acid extractables—
Ink Pigment Waste, spiked 205
IV-14 GC/MS chromatogram of base/neutral extractables—
Organic Still Bottoms, unspiked 210
IV-15 GC/MS chromatogram of acid extractables—
Organic Still Bottoms, unspiked 212
viii
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FIGURES (Continued)
Number Page
IV-16 GC/MS chromatogram of purgeable organics by purge
and trap—Paint Pigment Sludge, unspiked 217
IV-17 GC/MS chromatogram of purgeable organics by purge
and trap—Paint Pigment Sludge, spiked .. . . ; 220
IV-18 GC/MS chromatogram of base/neutral extractables—
Paint Pigment Sludge, unspiked 222
IV-19 GC/MS chromatogram of base/neutral extractables—
Paint Pigment Sludge, spiked 225
IV-20 GC/MS chromatogram of acid extractables—
Paint Pigment Sludge, unspiked 227
IV-21 GC/MS chromatogram of acid extractables—
Paint Pigment Sludge, spiked 230
IV-22 GC/MS chromatogram of purgeable organics by purge
and trap—Coke Oven Biological Sludge, unspiked 236
IV-23 GC/MS chromatogram of purgeable organics by purge
and trap—Coke Oven Biological Sludge, spiked 238
IV-24 GC/MS chromatogram of base/neutral extractables—
Coke Oven Biological Sludge, unspiked 240
IV-25 GC/MS chromatogram of base/neutral extractables—
Coke Oven Biological Sludge, spiked 243
IV-26 GC/MS chromatogram of acid extractables—Coke Oven
Biological Sludge, unspiked 245
IV-27 GC/MS chromatogram of acid extractables—
Coke Oven Biological Sludge, spiked 248
V-l Purge-trap system (purge-sorb mode) 270
V-2 Purge-trap system (desorb mode) 271
V-3 Purging device 272
ix
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FIGURES (Continued)
Number Page
V-4 Sorbent trap 273
V-5 Chromatogram of purgeable organics by
purge and trap, GC/MS 274
V-6 Summary of the proposed method for extractable
base/neutral and acid organic compounds in
residual waste 298
V-7 Chromatogram of extractable base/neutral
seniivolatile organics, GC/MS 299
V-8 Chromatogram of extractable acid semivolatile
organics, GC/MS 300
V-9 Tailing factor calculation 301
V-10 Tailing factor calculation 323
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TABLES
Number Page
1 Midwest Research Institute Procedure for
Purgeable Organics 8
2 University of Washington Procedure for
Purgeable Organics 11
3 Environmental Protection Agency Procedure
for Purgeable Organics 13
4 Environmental Protection Agency Interim
Method for Purgeable Organics (September 1979) 16
5 Midwest Research Institute Procedure for
Semivolatile Organics 18
6 Battelle-Columbus Laboratories Procedure
for Semivolatile Organics 23
7 University of Washington Procedure for
Semivolatile Organics 34
8 Midwest Research Institute Procedure
for Metals 36
9 Battelle-Columbus Laboratories Procedures
for Metals 41
10 University of Washington Procedure for Metals 43
11 EMSL-Ci Interim Method for Metals 44
12 Environmental Protection Agency Procedure
for Metals 45
13 Comparison of Relative Major Events in the
Analytical Schemes for Semivolatile Organics 53
14 GC/MS Data—Percent Recovery of Semivolatile
Base/Neutral Extractable Organics in Distilled
Water 55
15 GC/MS Data—Percent Recovery of Semivolatile Acid
Extractable Organics in Distilled Water 56
xi
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TABLES (Continued)
Number Page
16 GC/MS Data — Percent Recovery of Semivolatile
Base/Neutral Extractable Organics in Coke
Oven Biological Sludge ...................................... . . 57
17 GC/MS Data — Percent Recovery of Semivolatile
Acid Extractable Organics in Coke Oven
Biological Sludge ............................................. 58
18 GC/MS Data — Percent Recovery of Semivolatile
Base/Neutral Extractable Organics in Food
Processing Sludge ............................................. 59
19 GC/MS Data — Percent Recovery of Semivolatile
Acid Extractable Organics in Food Processing
Sludge [[[ 60
20 GC/MS Data — Percent Recovery of Semivolatile
Base/Neutral Extractable Organics in
Lime Treatment Sludge ......................................... 61
21 GC/MS Data — Percent Recovery of Semivolatile
Acid Extractable Organics in Lime Treatment
Sludge [[[ 62
22 Results of Metal Determination in Coke
Oven Sludge [[[ 64
23 Results of Metal Determination of
Paint Pigment Sludge .......................................... 65
24 Spike Recovery in Paint Pigment Sludge ........................ 66
25 Description of Residual Wastes ................................ 70
26 Summary of Replicates and Spike Levels of
Purgeable and Semivolatile Organics and
Metals for the Validation Study ............................... 71
27 Summary of Interquar tiles of Relative Standard
Deviations of Concentrations of Compounds
Averaged Over all Spike Levels (Including
Unspiked Samples) ............................................. 75
28 Summary of Interquartiles of Average Percent
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TABLES (Continued)
Number Page
1-1 Average Concentrations of Purgeable Organics
in Unspiked Residual Waste Samples 81
1-2 Average Concentrations of Base/Neutral
Extractable Semivolatile Organics in
Unspiked Residual Waste Samples 82
1-3 Average Concentrations of Acid Extractable
Semivolatile Organics in Unspiked Residual
Waste Samples 83
1-4 Average Concentrations of Metals in
Unspiked Residual Waste Samples 84
1-5 Relative Standard Deviations of Concentrations
of Purgeable Organics Averaged Over all Spike
Levels (Including Unspiked Samples) 86
1-6 Relative Standard Deviations of Concentrations of
Base/Neutral Extractable Semivolatile Organics
Averaged Over all Spike Levels (Including
Unspiked Samples) 87
1-7 Relative Standard Deviations ,of Concentrations
of Acid Extractable Semivolatile Organics
Averaged Over all Spike Levels (Including
Unspiked Samples) 88
1-8 Relative Standard Deviations of Concentrations
of Metals Averaged Over all Spike Levels
(Including Unspiked Samples) 89
1-9 Averaged Percent Recoveries of Purgeable Organics
in Spiked Residual Waste Samples 91
1-10 Average Percent Recoveries of Base/Neutral
Extractable Semivolatile Organics in Spiked
Residual Waste Samples 92
1-11 Average Percent Recoveries of Acid Extractable
Semivolatile Organics in Spiked Residual Waste
Samples 93
1-12 Average Percent Recoveries of Metals in Spiked
Residual Waste Samples 94
Xlll
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TABLES (Continued)
Number
Page
II-l Purgeable Organics Data—Ink Pigment Leachate,
Spike Level 0 98
II-2 Purgeable Organics Data—Ink Pigment Leachate,
Spike Level I 100
II-3 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Leachate, Spike Level 0 102
II-4 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Leachate, Spike Level I 104
II-5 Acid Extractable Semivolatile Organics Data—
Ink Pigment Leachate, Spike Level 0 106
II-6 Acid Extractable Semivolatile Organics Data—
Ink Pigment Leachate, Spike Level I 108
II-7 Metals Data—Ink Pigment Leachate, Spike Level 0 110
II-8 Metals Data—Ink Pigment Leachate, Spike Level I Ill
II-9 Metals Data—Ink Pigment Leachate, Spike Level II 112
11-10 Purgeable Organics Data—Organic Still Bottoms
Leachate, Spike Level 0 114
H-ll Purgeable Organics Data—Organic Still Bottoms
Leachate, Spike Level I 116
11-12 Base/Neutral Extractable Semivolatile Organics
Data—Organic Still Bottoms Leachate,
Spike Level 0 118
11-13 Base/Neutral Extractable Semivolatile Organics
Data—Organic Still Bottoms Leachate,
Spike Level I 120
11-14 Acid Extractable Semivolatile Organics Data—
Organic Still Bottoms Leachate, Spike Level 0 122
11-15 Acid Extractable Semivolatile Organics Data—
Organic Still Bottoms Leachate, Spike Level I 124
XIV
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TABLES (Continued)
Number Page
11-16 Metals Data—Organic Still Bottoms Leachate,
Spike Level 0 126
11-17 Metals Data—Organic Still Bottoms Leachate,
Spike Level I 127
11-18 Metals Data—Organic Still Bottoms Leachate,
Spike Level II 128
III-l Purgeable Organics Data—Ink Pigment Waste
(Interlaboratory), Spike Level 0 132
III-2 Purgeable Organics Data—Ink Pigment Waste
(Interlaboratory), Spike Level I 134
III-3 Purgeable Organics Data—Ink Pigment Waste
(Interlaboratory), Spike Level II 135
III-4 Base/Neutral Extractable Semivolatile
Organics Data—Ink Pigment Waste
(Interlaboratory), Spike Level 0 137
III-5 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Waste (Interlaboratory),
Spike Level I 139
III-6 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Waste (Interlaboratory),
Spike Level II 140
III-7 Acid Extractable Semivolatile Organics Data—
Ink Pigment Waste (Interlaboratory),
Spike Level 0 142
III-8 Acid Extractable Semivolatile Organics Data—
Ink Pigment Waste (Interlaboratory),
Spike Level I 144
III-9 Acid Extractable Semivolatile Organics Data—
Ink Pigment Waste (Interlaboratory),
Spike Level II 145
111-10 Metals Data—Ink Pigment Waste (Interlaboratory),
Spike Level 0 147
xv
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TABLES (Continued)
Number
III-ll Metals Data—Ink Pigment Waste (Interlaboratory),
Spike Level I 148
111-12 Purgeable Organics Data—Organic Still Bottoms
(Interlaboratory), Spike Level 0 150
111-13 Purgeable Organics Data—Organic Still Bottoms
(Interlaboratory), Spike Level I 152
111-14 Purgeable Organics Data—Organic Still Bottoms
(Interlaboratory), Spike Level II 153
111-15 Base/Neutral Extractable Semivolatile Organics
Data—Organic Still Bottoms (Interlaboratory),
Spike Level 0 155
111-16 Base/Neutral Extractable Semivolatile Organics
Data—Organic Still Bottoms (Interlaboratory),
Spike Level I 157
111-17 Base/Neutral Extractable Semivolatile Organics
Data—Organic Still Bottoms (Interlaboratory),
Spike Level II 158
111-18 Acid Extractable Semivolatile Organics Data—
Organic Still Bottoms (Interlaboratory),
Spike Level 0 160
111-19 Acid Extractable Semivolatile Organics Data—
Organic Still Bottoms (Interlaboratory),
Spike Level I 162
111-20 Acid Extractable Semivolatile Organics Data—
Organic Still Bottoms (Interlaboratory),
Spike Level II 163
111-21 Metals Data—Organic Still Bottoms (Interlaboratory),
Spike Level 0 155
111-22 Metals Data—Organic Still Bottoms (Interlaboratory),
Spike Level I 166
IV-1 Percent Recovery of Organics from Spiked
Method Blank 170
xvi
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TABLES (Continued)
Number Page
IV-2 Purgeable Organics Data—POTW Residual Waste,
Spike Level 0 178
IV-3 Purgeable Organics Data—POTW Residual Waste,
Spike Level I 180
IV-4 Purgeable Organics Data—POTW Residual Waste,
Spike Level II 181
IV-5 Base/Neutral Extractable Semivolatile Organics
Data—POTW Residual Waste, Spike Level 0 183
IV-6 Base/Neutral Extractable Semivolatile Organics
Data—POTW Residual Waste, Spike Level I 185
IV-7 Base/Neutral Extractable Semivolatile Organics
Data—POTW Residual Waste, Spike Level II 186
IV-8 Base/Neutral Extractable Semivolatile Organics
Data—POTW Residual Waste, Spike Level III 187
IV-9 Acid Extractable Semivolatile Organics Data—
POTW Residual Waste, Spike Level 0 189
IV-10 Acid Extractable Semivolatile Organics Data—
POTW Residual Waste, Spike Level I 191
IV-11 Acid Extractable Semivolatile Organics Data—
POTW Residual Waste, Spike Level II 192
IV-12 Acid Extractable Semivolatile Organics Data—
POTW Residual Waste, Spike Level III 193
IV-13 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Waste, Spike Level 0 196
IV-14 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Waste, Spike Level I 198
IV-15 Base/Neutral Extractable Semivolatile Organics
Data—Ink Pigment Waste, Spike Level II 199
IV-16 Acid Extractable Semivolatile Organics Data—
Ink Pigment Waste, Spike Level 0 201
xvii
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TABLES (Continued)
Number Page
IV-17 Acid Extractable Semivolatile Organics
Data—Ink Pigment Waste, Spike Level I 203
IV-18 Acid Extractable Semivolatile Organics
Data—Ink Pigment Waste, Spike Level II 204
IV-19 Metals Data—Ink Pigment Waste, Spike Level 0 206
IV-20 Metals Data—Ink Pigment Waste, Spike Level I 207
IV-21 Base/Neutral Extractable Semivolatile Organics
Data—Organic Still Bottoms, Spike Level 0 209
IV-22 Acid Extractable Semivolatile Organics Data—
Organic Still Bottoms, Spike Level 0 211
IV-23 Metals Data—Organic Still Bottoms, Spike Level 0 213
IV-24 Metals Data—Organic Still Bottoms, Spike Level I 214
IV-25 Purgeable Organics Data—Paint Pigment Sludge,
Spike Level 0 216
IV-26 Purgeable Organics Data—Paint Pigment Sludge,
Spike Level I 218
IV-27 Purgeable Organics Data—Paint Pigment Sludge,
Spike Level II 219
IV-28 Base/Neutral Extractable Semivolatile Organics
Data—Paint Pigment Sludge, Spike Level 0 221
IV-29 Base/Neutral Extractable Semivolatile Organics
Data—Paint Pigment Sludge, Spike Level I 223
IV-30 Base/Neutral Extractable Semivolatile Organics
Data—Paint Pigment Sludge, Spike Level II 224
IV-31 Acid Extractable Semivolatile Organics Data—
Paint Pigment Sludge, Spike Level 0 226
IV-32 Acid Extractable Semivolatile Organics Data—
Paint Pigment Sludge, Spike Level I 228
IV-33 Acid Extractable Semivolatile Organics Data—
Paint Pigment Sludge, Spike Level II 229
xviii
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TABLES (Continued)
Number Page
IV-34 Metals Data—Paint Pigment Sludge, Spike Level 0 231
IV-35 Metals Data—Paint Pigment Sludge, Spike Level I 232
IV-36 Purgeable Organics Data—Coke Oven Biological
Sludge, Spike Level 0 234
IV-37 Purgeable Organics Data—Coke Oven Biological
Sludge, Spike Level I 235
IV-38 Purgeable Organics Data—Coke Oven Biological
Sludge, Spike Level II 237
IV-39 Base/Neutral Extractable Semivolatile Organics
Data—Coke Oven Biological Sludge, Spike Level 0 239
IV-40 Base/Neutral Extractable Semivolatile Organics
Data—Coke Oven Biological Sludge, Spike Level I 241
IV-41 Base/Neutral Extractable Organics Data—Coke Oven
Biological Sludge, Spike Level II 242
IV-42 Acid Extractable Semivolatile Organics Data—
Coke Oven Biological Sludge, Spike Level 0 244
IV-43 Acid Extractable Semivolatile Organics Data—
Coke Oven Biological Sludge, Spike Level I 246
IV-44 Acid Extractable Semivolatile Organics Data—
Coke Oven Biological Sludge, Spike Level II 247
IV-45 Metals Data—Electroplating Sludge,
Spike Level 0 250
IV-46 Metals Data—Electroplating Sludge,
Spike Level I 251
IV-47 Metals Data—Electric Furnace Baghouse Dust,
Spike Level 0 253
IV-48 Metals Data—Electric Furnace Baghouse Dust,
Spike Level I 254
xix
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TABLES (Continued)
Number
V-l Selected Purgeable Organics Detectable with
the Purge-and-Trap Method 265
V-2 Ions and Ion Abundance Criteria of
Decafluorotriphenylphosphine (DFTPP) 266
V-3 Ions and Ion Abundance Criteria of
p_-Bromof luorobenzene (BFB) 267
V-4 Elution Order and Detectabilities of
Selected Purgeable Organics by the
GC/MS Method 268
V-5 Characteristic Ions of Purgeable Organics 269
V-6 Base/Nuetrals and Acid Extractables
Determined by the Proposed Method 291
V-7 Elution Order and Detectabilities of Base/Neutral
Extractables by the GC/MS Method 293
V-8 Elution Order and Detectabilities of Acid
Extractables by the GC/MS Method 295
V-9 Characteristic Ions of Base/Neutral Extractables 296
V-10 Characteristic Ions of Acid Extractables 301
V-ll Ions and Ion Abundance Criteria of
Decafluorotriphenylphosphine (DFPP) 324
V-12 Ions and Ion Abundance Criteria of
p-Bromofluorobenzene (BFB) 325
xx
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ACKNOWLEDGMENTS
We are especially grateful for the individual efforts of the
professional staff of the Analytical and Physical Chemistry Division who
participated with hard work and dedication in the completion of this
task. We are indebted to Mr. Joseph M. Finkel, Research Chemist, for
general supervision and for monitoring the quality assurance/quality
control of this program; and to Mr. John Burdeshaw, Senior Biometrician,
for assistance in developing the statistical program for compilation of
the data. The organic analyses were performed by Mr. Mark A. Carter,
Miss M. Susan Duncan, Mr. W. David Fine, Mrs. Judy G. Riley and
Mrs. Cathy E. Rowe, Assistant Chemists. The inorganic analyses were
performed by Mr. David W. Mason, Associate Chemist, and Mr. John C. Harmon,
Research Chemical Technician. Miss Linda A. Burford, Associate Chemist,
assisted in the data reduction.
Editing was performed by Dr. Edward B. Dismukes, Senior Research
Advisor, and Mrs. Linda K. First, Analytical Data Coordinator.
We also acknowledge the guidance of Mr. Michael Carter and
Dr. Dean Neptune of the Effluent Guidelines Division; Mr. David Friedman
and Dr. James Poppiti of the Office of Solid Waste; and Dr. Eugene Meier
and Dr. Andrew Sauter of the Environmental Monitoring Systems Laboratory-
Las Vegas in the evaluation and selection of representative samples used
in the study.
The combined efforts of those acknowledged above and the encouragement
of Dr. W. J. Barrett, Research Director, made this work possible.
xx i
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SECTION 1
INTRODUCTION
Recent legislation, specifically the Resource Conservation and Recovery
Act of 1976 (RCRA) has required the Office of Solid Waste (OSW) within EPA's
Office of Water and Waste Management (OWWM) to identify waste materials that
may be hazardous and to provide methodology for characterizing these wastes.
As part of OSW's continuing program to develop methodology for analyzing
industrial residuals and for determining the potential mobility of toxicants
in wastes, the Effluent Guidelines Division (EGD), also within OWWM, has
provided technical and administrative support to OSW through existing contracts
for the development of analytical methodologies.
Southern Research Institute (SoRI), under Technical Directive No. 108
of EPA Contract No. 68-02-2685, was tasked with the responsibility of
developing analytical methods for total content of organic and inorganic
species in industrial residuals and Battelle-Columbus Laboratories (BCL) was
given responsibility for the potential mobility (leachate) methods. Specifi-
cally, SoRI was required to develop the methods for total content by
evaluating and modifying, as necessary, existing methods from several sources,
including Midwest Research Institute, Battelle-Columbus Laboratories, Depart-
ment of Environmental Health of the University of Washington, and EPA-
Cincinnati. Following this initial evaluation phase of the study, a more
extensive evaluation program was undertaken with the most promising methods
by analyzing a broad range of industrial residuals. The compounds that were
determined in the wastes represented a wide range of toxic pollutant classes
expected to be encountered in the hazardous wastes program. The analytical
and statistical data from the evaluation study for the proposed methodology
for total content are given in Appendices I and IV.
After evaluation of the methods, SoRI and BCL exchanged the methodologies
developed for total content and potential mobility and applied the procedures
to the analysis of nominally identical samples in an interlaboratory study
(the data resulting from SoRI's participation in this study are presented in
Appendices I, II and III).
The goals for the developed methods were that they would be:
• technically sound;
• feasible and practical to implement;
• developed within known and acceptable limits for accuracy and precision;
• within the capability of a production-type laboratory;
• similar in scope to EPA wastewater methods embodying GC/MS (e.g.,
624 and 625) and AAS or ICP;
-------
• implemented at a cost not to exceed $2000 per sample analysis
when performed routinely;
• presented in the format specified by EMSL-Cincinnati for standard
methods .
Results of the various phases of this project are presented in the
following sections of this report. The comparison of the data from the
interlaboratory study for total content and potential mobility are
presented by BCL in the final report, Task 2013, Contract No. 68-03-2552.
-------
SECTION 2
CONCLUSIONS
The primary conclusions drawn from this study were the following:
• Overall, it was concluded that the three candidate methods that
were evaluated can be applied with confidence to the survey
analysis of a relatively broad range of industrial residuals.
This conclusion was based on the statistical analysis of over
10,000 data points which were expressed primarily in terms of
observed accuracy and precision.
• The methods appear to be sound technically and practical in their
implementation. It is estimated that the analyses can be per-
formed by a production-type laboratory utilizing appropriately
supervised technicians and junior-level professionals for sample
preparation and upper-level professionals for the supervision of
GC/MS analysis and data interpretation. The cost of a complete analy-
sis by the proposed methods appears to be well within the goal of
$2000 per sample (at current typical rates) with a sample turnaround
time comparable to that experienced with similar analytical methodology
for wastewater.
• Based upon the recoveries of known amounts of compounds spiked
into seven sample matrices, the methods can be expected to yield,
in general, results whose accuracy will be in the range of
approximately -50 to 150% of the true values.
• Results of replicate analyses indicate that the methods should be
capable of yielding data with a precision in the range of 10 to
25% relative standard deviation (RSD) for organics and 3 to 7%
RSD for metals.
• Perhaps the greatest single limitation to the usefulness of data
resulting from the proposed methods lies in the practical
difficulties associated with the collection of a truly representa-
tive sample of the extremely complex matrices that are typical of
residual wastes. Indeed, isolation of a representative aliquot from
a larger sample in the laboratory has posed substantial problems in
some instances. It is probable that poor sample homogeneity and
inadequate aliquoting in the laboratory contribute substantially to
the variability observed in the analytical results.
-------
SECTION 3
RECOMMENDATIONS
The three methods described in Appendix V of this report are
applicable to the determination of various organic compounds and elements
in residual wastes. These methods depend on extraction, gel permeation
chromatographic cleanup, preconcentration, and GC/MS analysis for identifi-
cation and quantitation of semivolatile organics; purge-and-trap and GC/MS
for purgeable organics; and acid digestion combined with AAS determination
for metals. Because of the potential complexity of wastes, these methods
are broad in scope. Of course, no single method is applicable to all
wastes and some modifications (e.g., change in extraction procedures and
cleanup chromatography before final analysis) may be necessary for unusual
waste types .
PURGEABLE AND SEMIVOLATILE ORGANICS
Although 78 organic compounds were determined in the evaluation of
the proposed methods, there are many other compounds that nay need to be
determined in wastes. The nature of the waste will dictate what is to be
determined. For example, compounds such as dioxin, and mixtures such as
toxaphene and PCB's may need to be determined in a specific residual waste.
The results of this study should be helpful both in ascertaining the
appropriateness of these methods for the analysis of the specific compounds
studied as well as the much wider spectrum of compounds expected to be found
in wastes.
When a sample is submitted for analysis, a general statement should
be made with respect to solids content and organic or inorganic content.
If these data are not available, they should be determined in the laboratory
prior to further workup of the sample. This information will help determine
the sample size and the manner in which the sample will be prepared for
analysis. For example, those samples that are predominantly aqueous are
extracted with solvent after pH adjustment without the addition of dilution
water to the sample. Conversely, water is added and the pH adjustment made
prior to the initial extraction step when the sample is predominantly an
organic liquid. In all situations, attempts were made to use equal volumes
of the aqueous sample and the organic extracting solvent. The organic or
inorganic content will dictate the amount of sample taken for analysis.
Also, if concentrations of purgeable organics are relatively high, a pentane
or carbon disulfide extraction procedure may be of use as an alternative
to the purge-and-trap procedure.
-------
Because of the wide range of compounds the analyst may encounter in an
industrial residual, a limitation of compounds to be screened should be
established. One way this may be done is through an engineering assessment
of the process producing the residual waste. Also, those compounds not
having a significant environmental impact may be eliminated from the analysis
regimen, or the analytical program may be narrowed in scope by only identi-
fying and quantitating the major peaks found in the GC/MS chromatograms.
Two areas that merit additional evaluation are the liquid-liquid
extraction procedure for semivolatile organics and the capillary GC/MS
analysis for organic compounds. When a residual waste sample is free of
basic compounds, e.g., benzidine and 3,3'-dichlorobenzidine, it may be
possible that sample preparation time can be substantially reduced by per-
forming an acid/neutral extraction, thus eliminating several steps in the
sample preparation. Capillary GC/MS analyses may have sufficient resolution
to differentiate between certain isomeric compounds. For example, the
packed-column GC retention times and mass spectra of the pairs anthracene
and phenanthrene, chrysene and benzo(a)anthracene, and benzo(b)fluoranthene
and benzo(k)fluoranthene are not sufficiently different to make an unam-
biguous distinction between these compounds. In such situations, capillary
GC/MS or HPLC analyses may be preferred. Also, the utility of a single
extraction followed by capillary GC/MS should be evaluated.
METALS
The University of Washington procedure was selected as the method of
choice for digesting and solubilizing the metals in a variety of waste
types ranging from inorganic solids to samples of high organic content.
Concern over potentially hazardous conditions resulting from the oxidation
of organic material in a sealed glass vial appeared to be unfounded. Con-
sultation with researchers at the University of Washington likewise indicated
that they had encountered no problems during the digestion of many types of
samples in their laboratories.
Despite the fact that only a selected group of more toxic metals were
determined in this study, it seems reasonable to assume that the digestion
procedure should be equally effective for numerous other elements. Further-
more, the digested samples may be amenable to analysis by inductively
coupled plasma emission spectroscopy (ICP) as well as the atomic adsorption
spectroscopy (AAS) procedures used in this study.
Although the digestion procedure is considered to be applicable to
a wide range of industrial wastes, it is recognized that low recoveries of
some elements may be experienced in certain types of waste materials.
Therefore, it is imperative that each matrix be evaluated for interference
effects by determining the recovery efficiency for spikes added to the
samples prior to the digestion step.
-------
Data obtained during this study suggest that recovery problems are
more likely to occur with the following elements: antimony, arsenic,
selenium and silver. In general, spikes of these metals, added to samples
prior to digestion, resulted in poor recovery efficiencies. The same
level of spikes added to digested, filtered samples, however, gave essen-
tially complete spike recovery. On the basis of these data it seems likely
that significant losses of analyte occurred during the filtration step.
The two most plausible explanations for analyte loss are (1) the precipita-
tion of the elements as insoluble compounds and (2) the adsorption, occlusion,
or complexation of the analyte ions by the undissolved sample residue.
Unfortunately, constraints in both time and money precluded any investigative
studies to resolve this problem. Because of the relative toxicity of the
elements in question and their potential impact on the environment, it is
recommended that additional studies be conducted in order to develop adequate
analytical capability for their determination in residual wastes.
-------
SECTION 4
SELECTION AND MODIFICATION OF METHODS
Several methods for the determination of purgeable organics, semi-
volatile organics, and metals in residual wastes are available for
consideration. These methods were reviewed, modifications were proposed,
and candidate methods were then evaluated with various types of waste
materials. Summaries of the procedures with modifications are presented
in Tables 1 through 12. The rationale for selection and modification is
discussed in the following three sections that represent three major
classifications of compounds and elements to be determined in residual
wastes. Priority pollutant compounds were only used in this study because
of their availability and historical background. The methods described
below are to be applied to those organic compounds and metals found in
industrial waste.
PURGEABLE ORGANICS
Four methods for the determination of purgeable organics in residual
wastes were selected for evaluation based on recommendations of Effluent
Guidelines Division: Midwest Research Institute (MRI),1 University of
Washington (UW), Environmental Protection Agency-Cincinnati (EPA), and
Environmental Protection Agency Interim Method (EPA-IM) .**
All methods were similar to the extent that an aliquot of waste
material was purged of volatile organics with an inert gas in a specially
designed purging chamber. The volatilized organic compounds were then
collected in a sorbent trap. Following the purge cycle, the sorbent trap
was heated and backflushed to desorb the purgeable organics into the inlet
of a GC/MS system.
1. "Development of Analytical Test Procedures for the Measurement of Organic
Priority Pollutants in Sludge and Sediments," Midwest Research Institute,
Final Report EPA Contract No. 68-03-2695,. June 26, 1979.
2. "Presence of Priority Pollutants in Sewage and their Removal on Sewage
Treatment Plants," University of Washington, Annual Report Grant
R.806102, July 31, 1979.
3. "Method for Purgeable Organics," (Unpublished), Personal Communication
with MERL-EPA, Cincinnati, Ohio 45268, March 1980.
4. "Interim Methods for the Measurement of Organic Priority Pollutants in
Sludges," U. S. Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, Cincinnati, Ohio 45268, September 1979.
-------
TABLE 1. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR PURGEABLE ORGANICS
Analysis scheme
Procedure
Modifications
Problems/comments
Purge device
Trap column
00
GC column
MS calibration
compound
Tekmar Liquid Sample
Concentrator Model LSC-1.
3% OV-1 on Chromosorb-W,
100/110 mesh; Tenax-GC,
60/80 mesh; Silica gel—
Davison Grade 15, 35/60
mesh; Coconut charcoal—
Barncbey-Cheney, 26 mesh.
2.4-2.8 m x 1/8 in. OD
stainless steel or
x 2 mm ID glass column
packed with 0.2%
Carbowax 1500 on
Carbopack C, 80/100 mesh,
p-Bromofluorobenzene.
Not a direct injection.*
in. x 0.105 ID stain-
less steel tubing packed
with 4 in. of Tenax,
60/80 mesh and 2 in. of
Silica gel, Davison
Grade 15, 35/60 mesh.
1.8 m x 2 mm ID glass
column packed with 1% SP-
1000 on Carbopack B,
60/80 mesh.
p-Bromofluorobenzene,
20 ng. Direct injection.
The 3% OV-1 and the
silica gel are special
order items. Since
extract amounts of the
packing materials are not
indicated for best desorp-
tion efficiency, commer-
cial volatile trap columns
that are EPA recommended
(i.e., Supelco) should be
used. If charcoal is
desired, then commercially
bought traps can be
modified.
SP-1000 on Carbopack B
packing has a higher
degree of inertness shown
by no tailing of the
methanol solvent peak.
Solvent tailing can inter-
fere with early peaks.
If purging device is con-
nected directly to GC via
injection port, then
purging the p-bromofluoro-
benzene would prove more
efficient.
* Analyze organic-free water with 75 ng of p-bromofluorobenzene + surrogate standards and internal standards
to meet abundance criteria.
-------
TABLE 1. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR PURGEABLE OROANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
Mass spectrometer
Standards
Internal standards
Purge conditions
GC conditions
MS conditions
Sample size
Finnigan or equivalent.
Supelco mixture or neat
compounds prepared daily;
10 mL of 5 yg/L and
25 yg/L standards.
1000 yg/50 mL with 9-yL
injections; bromochloro-
methane; 2-bromo-l-
chloropropane; 1,4-
dichlorobutane. Prepare
weekly.
12 min purge at ^25 °C.
Desorb 3 min at 180 to
200 °C.
60 °C (3 min), 8 "C/min
to 160 °C (hold) . Flow—
30 mL/min.
20-275 a.m.u., 3 to 5
sec/scan.
10 mL.
Hewlett-Packard 5985A or
equivalent.
Supelco purgeables A and B
standard mixtures.
Deuterated toluene.
12-min purge at room
temperature. Desorb
4 min at 180 °C. Helium
flow 40 mL/min.
50 °C (4 min), 10 °C/min
to 225 °C (20 min). Flow-
40 mL/min.
45-345 a.m.u., 2 to 3
sec/scan.
10 mL containing a
minimum of 50 mg of
solid content.
Premix multiple standards
(i.e., Supelco). Allow for
case of spiking as well as
reducing solvent volume
being introduced into the
sample. This lessens the
chance of interference
with any early peaks (i.e.,
methylene chloride).
The three multiple component
standard would best serve as
surrogate standards to
monitor the sample through
analysis.
-------
TABLE 1. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR PURGEABLE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
Solids determination
Sample handling
Spiking
Weigh two 1-mL aliquots
before and after drying
at 110 °C.
Pipet amount of sludge
which contains 50 mg of
dry solid and dilute
to 10 mL.
Weigh vial empty and full,
spike. Put on roller mill
16 h at 4 °C with 1- or
2-1/8 in. ball bearings.
-------
TABLE 2. UNIVERSITY OF WASHINGTON PROCEDURE FOR PURGEABLE ORGANICS
Analysis scheme
Purge device
Trap column
GC column
MS calibration
compound
Mass spectrometer
Standards
Procedure
Modifications
Problems/comments
1000-mL Erlenmeyer flask
and purging headpiece
with 24/40 standard
joints.
220 mm x 6.35 mm OD
stainless steel tubing
packed with 0.4 g Tenax
GC and 0.2 g Chromosorb
102; 120 mm x 6.35 mm
OD stainless steel trap
guard packed with 0.2 g
Tenax GC.
12 ft x 2 mm ID glass
column packed with 0.2%
Carbowax 1500 on
Carbopack C, 60/80 mesh.
Not listed in method.
Not listed in method.
No protocol listed in
method.
Tekmar Liquid Sample
Concentrator Model LSC-1,
in. x 0.105 ID stain-
less steel tubing packed
with 4 in. of Tenax, 60/80
mesh and 2 in. of Silica
gel, Davison Grade 15,
35/60 mesh.
1.8 m x 2 mm ID on-column
injection column packed
with 1% SP-1000 on
Carbopack B, 60/80 mesh.
p-Bromofluorobenzene,
20 ng. Direct injection.
Hewlett-Packard 5985.
Supelco's purgeables A
and B standard mixtures.
SP-1000 on Carbopack B
packing has a high degree
of inertness shown by
no tailing of the methanol
solvent peak. Solvent
tailing can interfere with
early peaks.
Premix multiple standards
(i.e., Supelco). Allows for
ease of spiking as well as
reducing solvent volume
being introduced into the
sample and lessens the
chance of interference with
any early peaks.
-------
TABLE 2. UNIVERSITY OF WASHINGTON PROCEDURE FOR PURGEABLE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/commen ts
Internal standards 2-Bromo-l-chloropropane.
Purge conditions
GC conditions
MS conditions
Sample size
Solid determination
Sample handling
Spiking
Purge under stirring for
20 min in water bath
60 °C. Desorb 250 °C for
4 min. Nitrogen flow
200 mL/min.
40 °C, 8 °C/min to 200 °C
(hold for 16 min).
34 to 334 a.m.u. (no
scan time given).
Sample diluted up to
100 mL but NO amount was
indicated in method.
Use standard method
gravimetric.
Sludge dilution at 7 to
25% sludge, 25 to 40%
sewage.
1 mg/mL (10 yL) in 50 mL
water organic free =
2 ng/yL.
Deuterated toluene.
2-Bromo-l-chloropropane is
difficult to find except
as one of three compounds
in the internal standard
mixture from Supelco.
12-min purge at room
temperature. Desorb
4 min at 180 °C. Helium
flow 40 mL/min.
50 °C (4 min), 10 °C/min
to 225 °C (20 min). Flow-
40 mL/min.
45-345 a.m.u., 2 to 3
sec/scan.
10 mL containing a
minimum of 50 mg of
solid content.
Maximum temperature of UW
program is 200 °C for 16
min; yet the column
packing has a maximum
temperature of 175 °C.
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TABLE 3. ENVIRONMENTAL PROTECTION AGENCY PROCEDURE FOR PURGEABLE ORGANICS
Analysis scheme
Procedure
Modifications
Purge device
Trap column
Problems/comments
GC column
MS calibration
compound
Mass spectrometer
Tekmar Liquid Sample
Concentrator Model LSC-1
(or hand rigged).
3% OV-1 on Chromosorb-W,
60/80 mesh; Tenax-GC,
60/80 mesh; Silica gel—
Davison Grade 15, 35/60
mesh or equivalent;
Coconut charcoal—
Barnebey-Cheney, 26 mesh
or equivalent.
8 ft x 2 mm ID glass
column packed with 0.2%
Carbowax 1500 on
Carbopack C, 60/80 mesh.
Flow 25 mL/min.
Pentafluorobromobenzene.
Finnigan 1015 series or
equivalent.
in. x 0.105 ID stain-
less steel tubing packed
with 4 in. of Tenax, 60/80
mesh and 2 in. of Silica
gel, Davison Grade 15,
35/60 mesh.
1.8 m x 2 mm ID on-column
injection column packed
with 1% SP-1000 on
Carbopack B, 60/80 mesh.
Flow 60 mL/min.
p-Bromofluorobenzene,
20 ng. Direct injection.
Hewlett-Packard 5985.
Commercial sources of
traps can be packed in the
laboratory from special
order packing.
SP-1000 on Carbopack B
packing has a higher degree
of inertness shown by no
tailing of the methanol
solvent peak. Solvent
tailing can interfere with
early peaks.
Pentafluorobromobenzene is
a difficult compound to
locate. p-Bromofluorobenzene
is less expensive and a more
available compound for the
calibration of MS.
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TABLE 3. ENVIRONMENTAL PROTECTION AGENCY PROCEDURE FOR PURGEABLE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/commen ts
Standards
Internal standards
Purge conditions
GC conditions
MS conditions
Sample size
Complex test mixture—
100 ng/uL; "quality check"
sample 20 yg/L (made from
100 ng/uL).
Supelco's purgeable A and
B standard mixtures.
Method recovery spiking
solution.
12 min purge at room
temperature. Desorb trap
at 180 to 200 °C for 3 min.
Nitrogen or helium flow 40
mL/min.
60 °C (3 min), 8 °C/min
to 160 °C (hold until
all compounds are off).
Not given in this procedure,
10 mL.
Deuterated toluene.
12-min purge at room
temperature. Desorb
4 min at 180 °C.'Helium
flow 40 mL/min.
50 °C (4 min), 10 °C/min
to 225 °C (20 min). Flow-
40 mL/min.
45-345 a.m.u., 2 to 3
sec/scan.
10 mL containing a
minimum of 50 mg of
solid content.
Premix multiple standards
(i.e., Supelco). Allows
for ease of spiking as
well as reducing solvent
volume being introduced
into the sample. This
lessens the chance of
interference with any
early peaks.
Solid determination
Gravimetric.
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TABLE 3. ENVIRONMENTAL PROTECTION AGENCY PROCEDURE FOR PURGEABLE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
Sample handling
Spiking
Pipet amount of sludge
which contains 50 mg of
dry solids and dilute to
10 mL.
Spike at two times
concentration in samples
or ten times the lower
limit of detection.
Place sample on roller
mill at 4 °C for 16 h
to mix.
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TABLE 4. ENVIRONMENTAL PROTECTION AGENCY INTERIM METHOD FOR PURGEABLE ORGANICS (SEPTEMBER 1979)
Analysis scheme Procedure
Modifications
Problems/commen ts
Purge device
Trap column
GC column
MS calibration
compound
Mass spectrometer
Standards
Tekmar Liquid Sample
Concentrator Model LSC-1.
3% OV-1 on Chromosorb-W,
60/80 mesh; Tenax-GC,
60/80 mesh; Silica gel—
Davison Grade 15, 35/60
mesh; Coconut charcoal—
Barnebey-Cheney, 26 mesh.
8 ft x 0.1 in stainless
steel or a glass column
packed with 0.2%
Carbowax 1500 on
Carbopack C, 60/80 mesh.
p-Bromofluorobenzene,
75 ng.
Finnigan 4000 or
equivalent.
Made from neat stock
prepared daily; 5 yg/L
and 25 yg/L standard.
10k inch x 0.105 ID stain-
less steel tubing packed
with 4 inches of Tenax,
60/80 mesh and 2 inches
of Silica gel, Davison
Grade 15, 35/60 mesh.
1.8 m x 2 mm ID glass
on-column injection
column packed with 1%
SP-1000 on Carbopack B,
60/80 mesh.
p-Bromofluorobenzene,
20 ng. Direct injection.
Hewlett-Packard 5985.
Supelco purgeables A and B
standard mixtures.
Commercial sources of
traps can be packed in
the laboratory from
special order packing.
SP-1000 on Carbopack B
packing has a high degree
of inertness shown by no
tailing of the methanol
solvent peak. Solvent
tailing can cause GC
interference with early
peaks (i.e., methylene
chloride).
Standards made by the
method are time consuming
and introduce many places
for human error.
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TABLE 4. ENVIRONMENTAL PROTECTION AGENCY INTERIM METHOD FOR PURGEABLE ORGANICS (SEPTEMBER 1979) (CONTINUED)
Analysis scheme
Procedure
Modifications
P rob1ems/comment s
Internal standards
Purge conditions
GC conditions
MS conditions
Sample size
Bromochloromethane;
2-bromo-l-chloropropane;
1,4-dichlorobutane. Made
from neat standard so to
use 9-uL injections.
12 min purge at room
temperature. Desorb 3
min. Nitrogen or helium
flow 40 mL/min.
60 °C (3 min), 8 °C/min
to 160 °C (hold until
all compounds come off).
20-275 a.m.u., 3 to 5
sec/scan.
50 mg solid content
diluted up to 10 mL.
Deuterated toluene.
12-min purge at room
temperature. Desorb
4 min at 180 °C. Helium
flow 40 mL/min.
50 °C (4 min), 10 °C/min
to 225 °C (20 min). Flow-
40 mL/min.
45-345 a.m.u.
5 sec/scan.
10 mL containing a
minimum of 50 mg of
solid content.
2-Bromo-l-chloropropane
is not easily found as a
single compound.
Solid determination
Sample handling
Spiking
Gravimetric.
Pipet amount of sludge
which contains 50 mg of
dry solid and dilute to
10 mL.
Day 1 spiking—two times
concentration found or
ten times lower limit.
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TABLE 5. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR SEMIVOLATILE ORGANICS
Analysis scheme
Procedure
Modifications
Problems/comments
Sludge
Adjust to pH > 11
oo
Extract 3X
Homogenize sludge 1
min. Transfer four
80-mL aliquots to 250-mL
centrifuge tubes.
Adjust pH with 6 _N NaOH.
Homogenize briefly.
Transfer one aliquot
(10-100 ml) to a 250-mL
centrifuge tube.
Add 80 mL of CH2C12-
Homogenize for 60 sec.
Centrifuge the samples
at 3000 rpm for 30 min.
Withdraw extracts with
a 100-mL pipette and
transfer to a 500-mL
separatory funnel. Extract
sample two more times.
Adjust pH with 10 N NaOH,
Add 100 mL of CH2C12
Withdraw extract with a
100-mL glass syringe
and transfer to a
300-mL fleaker.
If the amount of suspended
solids is low, then
separation and extraction
will not be difficult.
Thus, a single but larger
aliquot of sludge may be
extracted.
With a stronger base, less
volume is required to
adjust the pH of the
sludge.
If the amount of suspended
solids is high, then the
homogenizer is difficult
to clean. Thus, the total
volume in the centrifuge
tube may approach maximum
capacity or a loss of some
of the organic priority
pollutants may occur.
If 100-mL addition not
possible, add enough to
fill to neck of centrifuge
tube. Samples are
centrifuged at 1400
relative centrifugal force.
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TABLE 5. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
Dry extract
Concentrate base/
neutral extract
Cleanup
Drain pooled CH2Cl2
extracts through column
of Na2S04 (100 mm x 20 mm)
into K-D evaporator. Wash
drying column with an
additional 100 mL of
CH2C12 and combine with
Eluent extractsv Retain
aqueous layer to be
equally distributed to
each of the four
centrifuge tubes.
Concentrate the extract
to 8 mL if viscous and
darkly colored or 5 mL
if not viscous or slightly
colored. Transfer and
dilute to 10 mL and store
at 4 °C for GPC cleanup.
A 5-mL aliquot of
concentrated extract is
put through GPC cleanup
(GPC Autoprep 1002 with
a 25-mm ID column
containing 50-60 g Bio-
Beads S-X3). Elute with
CH2C12 at 7-10 psi.
Discard first 100 mL
and collect next 150 mL
in 500-mL brown bottles.
Clean column with 100 mL
of CH2Cl2.
Drain pooled extracts
through a drying tube of
anhydrous Na2S04 (60 mm x
17 mm) into K-D
evaporator. Wash drying
column with an additional
30 mL of CH2C12 into the
K-D evaporator. Retain
aqueous phase for pH-2
extraction.
Concentrate the extract
to 10 mL and immediately
put entire amount or an
aliquot through GPC
cleanup.
Transfer total concentrate
or an aliquot quantitatively
to GPC column (450 mm x 19
mm column of Bio-Beads S-X3).
Elute with CH2C12. Discard
first fraction (^65 mL) and
collect the second fraction
(VL20 mL).
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TABLE 5. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
Concentrate cleaned
extract
Concentrate cleaned
extract to VLO mL with
K-D evaporator and then
to V3 mL with micro
Snyder column. Transfer
and dilute to 5 mL with
CH2C12-
Analysis
Aqueous phase
remaining after base/
neutral extraction
GC/MS.
Adjust pH >2 with 6 N
HC1. Homogenize briefly.
As extract elutes from
S-X3 column, pass eluent
through anhydrous Na2$04
column into a K-D
evaporator. Concentrate
extract to ^2 mL with
K-D evaporator and then
to M).5 mL with micro
Snyder column. Transfer
and dilute to 1 mL with
CH2C12.
Store sample in 1-mL
capped serum bottle at
4 °C for GC/MS analysis.
Shake by hand.
This modification reduces
the number of transfers
and minimizes sample
losses.
Care must be taken in this
step due to excessive gas
release and foaming. Two
to five mL of acid are
required to adjust pH of
the sludges examined. If
the amount of suspended
solids is high, then the
sample may have to be
divided between two
centrifuge tubes.
-------
TABLE 5. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis
'rocedure
Modifications
Problems/comments
Extract 3X
Dry extract
Add 80 mL of CH2C12-
Homogenize for 60 sec.
Centrifuge the samples at
3000 rpm for 30 sec.
Withdraw extracts with a
100-mL pipette and
transfer to a 500-mL
separatory funnel. Extract
sample two more times.
Drain pooled CH2C12
extracts through column
of Na2S04 (100 mm x
70 mm) into K-D
evaporator. Wash drying
column with an
additional 100 mL of
and combine with eluent
extracts.
Add 50-80 mL of CH2C12-
Shake by hand or
homogenize. Withdraw
extract with a 100-mL
glass syringe and transfer
to 300-mL fleaker.
Drain pooled extracts
through a drying tube of
anhydrous Na2S04 (60 mm x
17 mm) into K-D
evaporator. Wash drying
column with an
additional 30 mL of CH2C12
into the K-D evaporator.
CH2C12 is added to fill up
to neck of centrifuge tube,
For large amounts of
suspended solids and small
volumes of CH2C12, sample
is shaken by hand to
minimize foaming and
spillage. Samples are
centrifuged at 1400 R.C.F.
Concentrate acid
extract
Concentrate the extract to
8 mL if viscous and
darkly colored or 5 mL if
not viscous or slightly
colored. Transfer and dilute
to 10 mL and store at 4 °C
for GPC cleanup.
Concentrate the extract to
5 mL and immediately put
entire amount or aliquot
through GPC cleanup.
-------
TABLE 5
MIDWEST RESEARCH INSTITUTE PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Cleanup
Concentrate cleaned
extract
NJ
t-o
Analysis
A 5-mL aliquot of
concentrated extract is
put through GPC cleanup
(GPC Autoprep 1002 with
a 25-mm ID column containing
50-60 g Bio-Bead S-X3).
Elute with CH2Cl2 at 7-10
psi. Discard first 100 mL
and collect next 150 mL in
500-mL brown bottles.
Clean column with 100 mL
of CH2C12.
Concentrate cleaned
extracts to ^10 mL with
K-D evaporator and then
to V3 mL with micro
Snyder column. Transfer
and dilute to 5 mL with
CH2C12.
GC/MS.
Modifications
P roblems/comments
Transfer total concentrate
or an aliquot quantitatively
to GPC column CMSO mm x
19 mm column of Bio-Beads
S-X3). Elute with CH2C12.
Discard first fraction
(^65 mL) and collect the
second fraction (VL20 mL).
As extract elutes from
S-X3 column, pass eluent
through anhydrous Na2S04
column into a K-D
evaporator. Concentrate
extract to ^2 mL with K-D
evaporator and then to
^0.5 mL with micro Snyder
column. Transfer and
dilute to 1 mL with
Store sample in 1 mL capped
serum bottle at 4 °C for
GC/MS analysis.
This modification reduces
the number of transfers
and minimizes sample
losses.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS
Analysis scheme
Procedure
Modifications
Problems/comments
A. Neutral fraction
Sludge
Acidify
Extract 3X
Homogenize sludge.
Transfer 100 g into
200-mL centrifuge tube.
Transfer 100 mL into
250-mL centrifuge tube.
Acidify with 5 g of KHSO^ Homogenize for 30 sec.
Add 100 mL of
Homogenize for 1 min.
Centrifuge. Remove extract
with a 50-mL syringe and
transfer to 500-mL round-
bottom flask. Extract
sample two more times.
Combine extracts.
Assures uniform mixing
of the KHS04- More than
5 g KHSO^ may be
necessary.
Homogenize for 30 sec.
Centrifuge at 1400 R.C.F.
for 30 min. Remove extract
with a 100-mL glass
syringe and transfer to a
K-D evaporator.
Concentrate
extract
Wash with base
Concentrate extract to
60-80 mL on a rotating
evaporator at 35 °C.
Transfer concentrated
extract to a 1000-mL
separatory funnel. Add
200 mL of petroleum
ether. Extract 3X with
400 mL of 0.1 N; NaOH in
10% NaCl solution.
Extract 2X with 200 mL
of 10% NaCl solution.
Concentrate extract
60-80 mL in K-D
evaporator.
to
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modification
Problem/comments
A. Neutral fraction
(continued)
Dry extract
Concentrate
extract
Shake final organic layer
with 2 g of MgS04-
Decant extract into
500-mL round-bottom
flask. Concentrate to
50 mL on rotating
evaporator at 35 °C.
Transfer to 100-tnL round-
bottom flask. Concentrate
to 8-10 mL. Transfer to
15-mL Vortex evaporator
tube and dilute up to
10 mL with CH2Cl2.
Concentrate on Vortex
evaporator at 25 °C to
final concentration of
200 mg of material in
sample per mL of solvent.
Centrifuge to remove
traces of particulate
matter.
Drain pooled extracts
through a column of
anhydrous Na2S04 (60 mm x
17 mm) into a K-D
evaporator.
Concentrate to 5 mL.
Transfer to GPC cleanup
column.
Reduces the number of
transfers and minimizes
sample losses.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
A. Neutral fraction
(continued)
Cleanup
Concentrate
fraction GPC-1
A 5-mL aliquot of
concentrated extract is put
through GPC cleanup (GPC
Autoprep 1001 with a 1200
mm x 25 mm ID glass column
containing Bio-Beads S-X8).
Elute with CH2C12 at 2 mL/
min for 3 h. Discard
first fraction with retention
time represented by minimum
between di-n-tridecyl
phthalate and di-n-octyl
phthalate peaks. Collect
Fraction GPC-1 up to
retention time represented
by minimum between dimethyl
phthalate and 4-chlorophenyl
phenyl ether peaks. Collect
Fraction GPC-2 up to
retention time represented
by minimum between pyrene
and sulfur peaks.
Decant extract into 500-mL
round-bottom flask. Concen-
trate to 50 mL on rotating
evaporator at 35 °C. Transfer
to 100 mL round-bottom flask.
Concentrate to 8-10 mL.
Transfer to 15-mL Vortex
evaporator tube and
concentrate to 2 mL. Add 2 mL
of petroleum ether.
Modifications
Problems/comments
If the total volume of
the concentrated extract
is greater than 5 mL, a
second aliquot is also
put through the GPC
cleanup step. (Do not
overload GPC column.)
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comment s
A. Neutral fraction
(continued)
Fraction GPC-1
cleanup
NJ
Combine and
concentrate
GPC-1 and GPC-2
Apply concentrated
Fraction GPC-1 to a Silica
gel column (400 mm x 9 mm).
Elute with 50 mL of 50%
CH2C12 in petroleum ether
and discard. Elute with
50 mL of 25% acetone in
CH2Cl2 and collect as
phthalate fraction.
Combine the phthalate
fraction with Fraction
GPC-2. Decant extract
into 500-mL round-bottom
flask. Concentrate to 50 mL
on rotating evaporator at
35 °C. Transfer to 100-mL
round-bottom flask.
Concentrate to 10 mL.
Transfer to 15-mL Vortex
evaporator tube. Add 0.1 mL
of anthracene-dio internal
standard and 1.0 mL of
methylene chloride. Concen-
trate to 0.2 mL using
Vortex evaporator.
Analysis
GC/MS.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
B. Acid fraction
Sludge
Acidify
Extract 3X
to
VJ
Dry extract
Homogenize sludge.
Transfer 100 g into
200-mL centrifuge tube.
Acidify with 5 g KHS04.
Add 100 mL of CH2Ci2.
Homogenize for 1 min.
Centrifuge. Remove
extract with a 50-mL
syringe and transfer to
500-mL round-bottom
flask. Extract sample
two more times. Combine
extract.
Shake combined extract
with 2 g of MgS04.
Transfer 100-mL aliquot
into 250-mL centrifuge
tube.
Homogenize for 30 sec.
Remove extract with a
100-mL glass syringe and
transfer to a K-D
evaporator.
Assures uniform mixing
of KHS04.
Drain combined extracts
through a column of
anhydrous Na2S04 (60 mm
x 17 mm) into a K-D
evaporator.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
B. Acid fraction
(continued)
Concentrate acid
extract
KJ
oo
Decant extract into 500-mL
round-hottorn flask. Concen-
trate to 50 mL on rotating
evaporator at 35 °C. Trans-
fer to 100-mL round-bottom
flask. Concentrate to 8-10
mL. Transfer to 15-mL
Vortex evaporator tube and
dilute to 10 mL with
CH2C12. Concentrate on
Vortex evaporator at 25 °C
to final concentration of
200 mg of material in
sample per mL of solvent.
Centrifuge to remove
traces of particulate
matter.
Concentrate to 8 mL and
immediately transfer
entire amount on GPC
cleanup column.
Reduces the number of
transfers and minimizes
sample losses.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
B. Acid fraction
(continued)
Cleanup
Procedure
A 5-mL aliquot of concen-
trated extract is put
through GPC cleanup (GPC
Autoprep 1001 with a 1200
mm x 25 mm ID glass
column) containing Bio-
Beads S-X8. Elute with
CH2C12 at 2 mL/min for
3 h. Discard first
fraction with retention
time represented by
minimum between
4-phenylbutyric acid and
2,4-dinitrophenol peaks.
Collect phenolic fraction
up to retention time
represented by minimum
between 2,4-dichlorophenol
and sulfur peaks. If total
volume of the concentrated
extract is greater than
5 mL, a second aliquot is
also put through the
cleanup step. The phenolic
fractions are combined.
Modifications
Problems/comments
Transfer total concentrate
or an aliquot quanti-
tatively to GPC column
(M50 mm x 19 mm column
containing Bio-Beads S-X8).
Elute with CH2C12. Discard
first fraction (^70 mL)
and collect second
fraction (WO mL) .
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
B. Acid fraction
(continued)
Concentrate
cleaned extract
0 Extract with
base
Acidify
Extract 2X
Decant extract into
500-mL round-bottom
flask. Concentrate to
50 mL on rotating
evaporator at 35 °C.
Transfer to 100-mL
round-bottom flask.
Concentrate to 8-10 mL.
Transfer to 15-mL Vortex
evaporator tube and
concentrate to 2 mL.
Concentrate is trans-
ferred to 50 mL centri-
fuge tube. Add 200 mL of
hexane. Extract 2X with
20 mL of 0.1 N NaOH in
10% NaCl solution.
Combine aqueous layers in
200-mL centrifuge tube.
Acidify with 1 mL of 6 N
HC1.
Extract 2X with 20 mL
CH2Cl2« Combine organic
layers.
As extract elutes from
S-X8 column, pass eluent
through anhydrous Na2SO^
column (60 mm x 17 mm)
into K-D evaporator.
Concentrate extract to
^2 mL with K-D
evaporator.
Transfer concentrate to
250-mL centrifuge tube.
Add 20 mL of hexane.
Extract with 50 mL of
0.1 N. NaOH in 10% NaCl
solution. Centrifuge at
1400 R.C.F. for 5
min.
Remove top layer via
water aspirator.
Extract 2X with 40 mL
Reduces the number of
transfers and minimizes
sample losses.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
B. Acid fraction
(continued)
Dry extract
Concentrate
extract
Analysis
Dry over MgS04
Decant extract into
500-mL round-bottom flask.
Add 0.1 mL anthracene-d^g
internal standard and
1.0 mL ethylene dichloride.
Concentrate to 50 mL on
rotating evaporator at 35 °C.
Transfer to 100-mL round-
bottom flask. Concentrate
to 8-10 mL. Transfer to
15-mL Vortex evaporator
tube and dilute. Vortex to
10 mL with Cl^C^. Concen-
trate on Vortex evaporator
at 25 °C to a final concen-
tration of 200 mg/mL of
material in sample per mL
of solvent. Centrifuge to
remove traces of particulate
matter.
Derivation with Q^^ •
Analyze by GC/MS.
Drain combined extracts
through a column of
anhydrous N32804
(60 mm x 17 mm) into a
K-D evaporator.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
C. Base fraction.
Sludge
Dilute, pH 7
buffer
Extract 3X
N>
Extract with acid
Homogenize sludge.
Transfer 10 g into 50-mL
centrifuge tube.
Dilute with 20 mL of
0.1 M phosphate buffer,
pH 7.
Extract with 10 mL of
CHClo. Homogenize for
1 min. Centrifuge.
Remove CHC13 with a
50-mL syringe. Repeat
extraction two more times.
Combine CHC13 extracts.
Transfer CHC13 extract to
50-mL centrifuge tube.
Extract 2X with 10 mL
2 £ H2SO^. Remove
aqueous layer with a
50-mL syringe. Combine
aqueous layer in 50-mL
beaker.
Pour 10-mL aliquot into
250-mL centrifuge tube
(round bottom, screw
capped).
Dilute with 25 mL of 0.1 M
phosphate buffer, pH 7.
Extract with 25 mL CHC13.
Shake for 1 min. Centri-
fuge at 1400 RCF for
15 min. Remove CHC13 with
100-mL glass syringe and
transfer to a 250-mL
centrifuge tube.
-------
TABLE 6. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
c. Base fraction
(continued)
Neutralize
extract
Extract 2X
Add 1 mL of 0.4 M Na3P04.
Add dropwise over 2-min
period. 20% NaOH to pH 6-7.
(Do not exceed pH 8.)
Transfer to 60-mL separatory
funnel and extract 2X with
10 mL portions of
Wash combined CHClo extracts
with 5 mL of water.
u>
Concentrate
extract
Add 5 mL of methanol to
CHC13 extract. Concentrate
to 0.2 mL with Vortex
evaporator at 25 °C.
Dilute to 1 mL with 0.1 M
acetate buffer, pH 4.7.
Analysis
HPLC/EC.
-------
TABLE 7. UNIVERSITY OF WASHINGTON PROCEDURE FOR SEMIVOLATILE ORGANICS
Analysis scheme
Procedure
Modifications
P rob1ems/c ammen t s
Sludge
Acidify
Continuous extract
Basify
Continuous extract
Dry extracts
Concentrate extracts
1000 mL of mixed sample.
Adjust to pH 2 with
hydrochloric acid
solution.
Liquid-liquid continuous
extraction with CH2C12
for 12 h. Remove solvent
from side vessel of
continuous extractor.
Adjust aqueous phase to
pH 12.
Liquid-liquid continuous
extraction with Ct^C^
for 12 h. Remove solvent
from side vessel of
continuous extractor.
Dry acid and base extracts
by passage through
anhydrous
Recommend a smaller
sample size.
Sample size too large
for most solid waste.
Requires large
laboratory space and
equipment for multiple
samples to be processed
at one time.
Concentrate acid and base
extracts to 1-2 mL in K-D
evaporator.
Concentrate to 10 mL or
until active distilla-
tion ceases.
Cannot concentrate
this volume with most
waste samples
-------
TABLE 7. UNIVERSITY OF WASHINGTON PROCEDURE FOR SEMIVOLATILE ORGANICS (CONTINUED)
Analysis scheme Procedure Modifications Problems/comments
Cleanup Base extract and/or acid Aliquots of the base
extract are put through and/or acid extract are
EPC cleanup. put through GPC.
Analysis Because of the complexity
of this procedure, details
are shown in Figure 4.
to
Ui
-------
TABLE 8. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR METALS
Analysis scheme
Procedure
Modification
Problems/comments
A. Beryllium, Cadmium, Chromium, Copper,
Nickel, Silver, Thallium, and Zinc
1. Preservation
u>
2. Digestion
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
Take 25 mL sludge, add 20 mL
concentrated HN3 and 5 mL
concentrated l^SO^ and reflux.
Add 10 mL concentrated HN03
and 10 mL HClO^, heat until
fume stage of HCIO^. Transfer
to small beaker. Heat until
volume ^Q.5 mL.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
First reflux = 4 h.
Second reflux = 4 h.
3. Solids removal
4. Dilution
If precipitate is formed,
rinse and centrifuge three
times with 5 mL 5% (v/v)
HN03. Evaporate rinses to
VL5 mL.
Bring to 25 mL with 5%
(v/v) HN03.
Solutions colorless.
Dilution factor 2X.
5. Analysis
Flame and flameless AA .
-------
TABLE 8. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR METALS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
B. Antimony, Arsenic,and Selenium
1. Preservation
2. Digestion
3. Solids
removal
4. Dilution
Take 100 mL sludge, add
20 mL concentrated HN03 and
5 mL concentrated H2SO^,
and reflux 8 h. Cool, add
25 mL 30% H202 in 1-mL
aliquots. Evaporate to less
than 50 mL. Cool, add 40 mL
of HN03: HC1 (3/7, v/v) and
reflux 2 h..
None.
Bring to 50 mL final volume
with D/D H20.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
Use 50 mL sludge, add 10 mL
ULTREX HN03 and 2.5 mL
ULTREX H2S04, reflux 8 h.
Add 13 mL 30% H202.
Evaporate to ^15 mL. Add
6 mL HN03 and 14 mL
ULTREX HC1. Reflux 3 h.
1:1 sludge dilution needed
to ease sample handling
problems. pH taken to <2.
Black residue remaining
after digestion.
Solutions greenish-yellow
in color. No dilution
factor.
5. Analysis
Hydride generation.
-------
TABLE 8. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR METALS (CONTINUED)
Analysis scheme
Procedure
C. Lead
Modifications
Problems/comments
1. Preservation
do
2. Digestion
3. Solids
removal
4. Dilution
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
Take 10 mL sludge, dry
at 90 °C and then dry
ash for 8 h at 450 °C.
Add 10 mL of 50% (v/v)
HN03 and reflux 2 h.
Cool, add 5 mL of HN03,
and evaporate to 1 mL.
Centrifuge and rinse three
times with 5 mL 5% (v/v)
HN03. Combine rinses and
evaporate to less than
5 mL.
Bring to 10 mL final volume
with 5% (v/v) HN03.
Solutions golden in
color. Dilution factor
2X.
5. Analysis
Flame or flameless AA.
Flameless AA.
-------
Table 8. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR METALS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
D. Mercury
1. Preservation
2. Sample
separation
u>
3. Digestion
supernatant
4. Solid
5 mL of sludge is centri-
fuged and supernatant
decanted. Solid and super-
natant treated as separate
samples.
Add 1 mL concentrated HN03,
4 mL concentrated H2S04, and
reflux for 16 h. Then add
5 mL of 6% (w/v) KMn04
heated to 55 to 60 °C.
React 4 h.
Add 5 mL concentrated HNOo
and 20 mL concentrated H^SO^
and reflux 80 h. Then add
25 mL 6% (w/v) KMn04 and heat
to 55 to 60 °C. React 4 h.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to^SOO mL
sludge.
Take 10 mL of sludge.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
Used 5% KMn04.
Refluxed 16 h.
Used 5% KMnO/, .
All solids were dissolved
after 16 h-reflux.
-------
TABLE 8. MIDWEST RESEARCH INSTITUTE PROCEDURE FOR METALS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
D. Mercury
(Continued)
5. Solids removal None.
6. Dilution None.
Brought samples to 100 mL Dilution factor 20X
final volume with D/D H20. each fraction.
7. Analysis
Cold vapor technique,
-------
TABLE 9. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR METALS
Analysis scheme
Procedure
Modifications
P rob lems / cotnmen ts
A. Flame analyses
1. Preservation
2. Digestion
3. Solids
removal
4. Dilution
Transfer 50-100 mL sludge to
a 250-mL Griffin beaker, add
3 mL concentrated HNOo and
evaporate to near dryness,
add 3 mL concentrated HN03
and reflux with acid addi-
tions as necessary until
digestion is complete.
Evaporate to near dryness,
then add 2 mL HN03 (1:1)
per 100 mL final volume and
warm solution.
Filter.
Adjust final volume based
on expected metal concen-
trations.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
Transfer 100 mL sludge to
a 250 mL Griffin beaker.
Add 3 mL ULTREX HN03 and
evaporate to VL5 mL. Add
3 mL HN03, reflux 2 h,
add 1 mL HN03, reflux
2 h, add 2 mL H1I03, and
reflux 2 h. Evaporate
to a,15 mL, then add 0.5 mL
ULTREX HCl and warm 15 min.
Filter through No. 42
Whatman filter.
Brought to final volume of
50 mL with D/D H20.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
Procedure used for
samples with <5% solids.
Solution golden in
color. No dilution
factor.
5. Analysis
ICAP.
Flame AA.
-------
TABLE 9. BATTELLE-COLUMBUS LABORATORIES PROCEDURE FOR METALS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/comments
B. Flameless analyses
1. Preservation
2. Digestion
Transfer 100 mL sludge to a
250-tnL Griffin beaker. Add
3 mL concentrated HN03 and
5 mL 30% H202, then heat
1 h at 95 °C or until
volume is reduced to less
than 50 mL.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
Heated until volume was
^20 mL.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
Procedure used for
samples with <5%
solids.
3. Solids removal None described.
4. Dilution
Filtered through No. 42
Whatman filter.
Bring to final volume of
50 mL with D/D H20.
Solutions golden in
color. No dilution
factor.
5. Analysis
Flameless AA.
-------
TABLE 10. UNIVERSITY OF WASHINGTON PROCEDURE FOR METALS
Analysis scheme
Procedure
Modifications
Problems/comment s
Preservation
OJ
Sample
preparation
Digestion
Solids removal
Dilution
Analysis
Add 20 mL sludge to clean
25-irL vials. Add ULTREX HN03
Co adjust acid concentration
to 2% and flame seal.
Heat 1 h in 125 °C oven.
Centrifuge or filter
cooled samples.
Supernatant or filtrate
taken without volume
adjustment.
Analyze by I CAP; Hg by cold
vapor method.
and 485 mL
15 mL ULTREX HN03
D/D H20 added to 500 mL
sludge.
Added 0.5 mL ULTREX HN03
to 2 mL sludge.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
Filter through No.
Whatman filter.
Solutions golden in
color, dilution factor
2X.
Analyze by flame and flame-
less AA; Hg by cold vapor
method.
-------
TABLE 11. EMSL-Ci INTERIM METHOD FOR METALS
Analysis scheme
Procedure
Modifications
Problems/comments
1. Preservation
2. Digestion
1 gm of sludge dried at
60 °C, pulverized, and mixed
in 125-mL conical Phillips
beaker. Add 5 tnL HN03 (1:1)
and reflux to near dryness.
Cool, add 4 mL concentrated
HN03 and reflux to near
dryness. Cool, add 1 mL
HN03 (1:1) and 3 mL 30%
H202 additions (not to
exceed 10 mL total) until
effervescence is minimal.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
25 mL of sludge in a 125-
Erlenmeyer flask. Add
2.5 mL ULTREX HN03 and
reflux 8 h, remove watch
glass and evaporate to
VL5 mL. Add 0.5 mL HN03
and 3 mL 30% H202 and
heat. Cool, add 3 mL
^2^2» kh611 heat; repeat
twice.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
25 mL of 1:1 dilution
sludge contains about
0.5 g solids .
Color removed on
addition of
For flame
preparation
For flameless
preparation
3. Solids removal
4. Dilution
Add 2 mL HC1 (1:1) and
reflux 10 min.
Add 2 mL HN03 (1:1) and
reflux 10 min.
Filter through No. 42
Whatman filter.
Bring to final volume of
50 mL with D/D H20.
Solutions essentially
colorless. Dilution
factor of 4.
5. Analyses
Flame and flameless AA.
-------
TABLE 12. ENVIRONMENTAL PROTECTION AGENCY PROCEDURE FOR METALS
Analysis scheme
Procedure
Modifications
Problems/comments
A. Preparation for total
recoverable metals
Ul
1. Preservation 5 mL HNO^/L sample,
2. Digestion-
flame AA
3. Digestion-
flameless AA
4. Solids
removal
5. Dilution
Transfer 100 mL of sludge to
a beaker or flask. Add 5 mL
distilled HCl (1:1). Heat,
without boiling, to 15-20 mL.
Transfer 100 mL of sludge to
a beaker or flask. Heat,
without boiling, until con-
centrated to 15-20 mL.
Filter.
Bring to 100 mL or less to
effect concentration.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
Add 1 mL ULTREX HN03 and
heat 2 h, add 2 mL
ULTREX HNO-, and continue
heating.
Suction filter through
No. 42 Whatman filter.
Brought to 50 mL final
volume with D/D
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
No visible change in
appearance with
additional digestion.
Extremely difficult to
suction filter these
samples through No. 42
paper.
Solution golden to
light brown. No
dilution factor.
6. Analysis
Flame or flameless AA.
-------
TABLE 12. ENVIRONMENTAL PROTECTION AGENCY PROCEDURE FOR METALS (CONTINUED)
Analysis scheme
Procedure
Modifications
Problems/commen ts
B. Manual cold vapor
technique for mercury
1. Preservation 5 mL HN03/L upon collection.
2. Sample
preparation
3. Analysis
Take 100 mL sludge in 300 mL
BOD bottle, add 5 mL I^SO^,
2.5 mL concentrated HN03 and
mix. Add 15 mL 5% KMn04 solu-
tion (samples may require
more KMnO^), 8 mL 5%
potassium persulfate solu-
tion, and heat 2 h at 95 °C.
Cool, add 6 mL 12% sodium
chlo ride—hydroxylamine
sulfate solution.
After >30 sec delay, add
5 mL 10% stannous sulfate
solution. Immediately
attach the bottle to the
aeration apparatus and
sparge.
15 mL ULTREX HN03 and 485 mL
D/D H20 added to 500 mL
sludge.
Use 2 mL of sludge.
1:1 sludge dilution
needed to ease sample
handling problems.
pH taken to <2.
-------
The MRI and EPA methods use a commercial purge-and-trap (PAT) apparatus
such as the Tekmar Liquid Sample Concentrator Model LSC-1 or its equivalent
coupled to the GC/MS instrumentation. The University of Washington evaluated
the use of a commercial purge-and-trap apparatus and compared the accuracy
and precision with that obtained by an alternate procedure. Thus, the UW
procedure offered alternatives depending on the availability of a specific
purging apparatus. The alternate procedure involves the use of a PAT con-
structed from components in the laboratory. Generally, the method requires
larger samples, longer purge times, elevated temperature of the purge
chamber, and higher flow rates. The sorbent trap detaches from the system
and is manually connected to the GC/MS instrumentation for desorption with
an external heating system. Generally, recommended operating parameters
for the alternate method were considered to be more difficult to manage in
the analysis of a large number of samples; however, the apparatus does offer
the advantage of being able to purge multiple samples in the field that
require immediate analysis at the time of collection. Sorbent traps can be
closed and later analyzed in the laboratory.
The gas chromatographic program was essentially identical in all the
methods with the exception of the UW procedure, which recommended a program
that exceeded the suggested temperature limit of the column packing.
All methods used chromatographic columns of either 1/8 in. OD stainless
steel, or 2 mm ID glass packed with 0.2% of Carbowax 1500 on Carbopack C,
60/80 mesh. The length of the columns, however, varied from 2.4 to 3.7 m.
In reviewing the relative merits of the four procedures, there appeared
to be no substantial differences among the MRI, EPA, and the very similar
EPA-IM methods. The UW method was considered to be somewhat less desirable
with respect to analysis time and simplicity of operation. Therefore, a
combination of the MRI and EPA procedures, with minor modifications, was
selected as the method of choice.
The modifications recommended by SoRI include the use of commercially
available, prepacked, sorbent traps to eliminate the reproducibility problems
encountered in packing sorbent columns. The purge chamber was modified by
replacing the septum inlet with a ground glass joint and closure to permit
the introduction of solid and viscous samples into the purge chamber. Glass,
rather than stainless steel, should be used as the analytical column material
since glass columns allow the analyst to note conditions such as material
collecting at the injection port and on the column packing. Finally, 1% of
SP 1000 on Carbopack B, 60/80 mesh should be used as the column packing.
This material afforded better separation of compounds and tolerated the
higher temperature programs which were often necessary to clean and condi-
tion contaminated columns.
Because of the diversity and complexity of waste samples, preliminary
spiking tests should be conducted with each particular type of sample to
determine the applicability of the proposed method. Further procedural
modifications may be necessary to adapt the method for use with certain
waste materials. A summary of the methods and modifications is given in
Tables 1 through 4.
47
-------
SEMIVOLATILE ORGANICS
Three methods for determination of semivolatile organics in residual
wastes were selected based on the recommendations of Effluent Guidelines
Division for evaluation: Midwest Research Institute (MRI),1 Battelle-
Columbus Laboratories (BCD ,2 and the University of Washington (UW). Each
procedure was first reviewed critically to determine its utility according
to the criteria for this study. Flow charts for the three procedures are
given in Figures 1 through 3, while condensed versions of the methods,
modifications, problems, and comments are shown in Tables 5 through 7.
Because of the complexity of the UW procedure, Figure 4 presents the flow
chart in greater detail.
A comparison of major events in the analytical schemes of each
procedure, such as number of extractions, Kuderna-Danish concentrations,
column chromatographic cleanups, and individual analyses are presented
in Table 13. The UW procedure required 26 concentration steps and 8 to
12 GC/MS analyses of final concentrates when the acid extract was not
combined with the base/neutral extract prior to the gel permeation
chromatographic cleanup step. Based on the complexity of the method, the
number of analyses required, and time involved in sample preparation, the
UW procedure was eliminated from further consideration.
The BCL method required that three aliquots of the waste be extracted
for acidic, neutral, and basic compounds, respectively. The MRI method,
however, required the extraction of only a single aliquot of sample to
obtain the same acidic, neutral, and basic components. Therefore, the MRI
procedure was selected for an extended evaluation with Coke Oven Biological
Sludge, Food Processing Waste, and Lime Slurry Treatment Sludge.
It should be noted that a revised BCL procedure, requiring the extrac-
tion of only one aliquot of waste material, was received for consideration,
but only after the MRI evaluation was completed.
The MRI procedure, with the minor modifications recommended by SoRI,
is shown in Table 5. These modifications include (1) the extraction of only
one aliquot when the suspended solids content of the sample is low, (2) the
alternative use of descending liquid column chromatography techniques
instead of the gel permeation chromatography with an Autoprep 1002, and (3)
the use of more concentrated acidic and basic solutions to adjust the sample
pH, thereby avoiding excessive aqueous dilution of the sample.
1. "Development of Analytical Test Procedure for the Measurement of Organic
Priority Pollutants in Sludge and Sediments," Midwest Research Institute
Final Report EPA Contract No. 68-03-2695, June 26, 1979.
2. "Development of Analytical Protocols for Organic Priority Pollutants
in Municipal Sludges," Battelle-Columbus Laboratories, Final Report
EPA Contract No. 68-03-2624, March 30, 1979.
3. "Presence of Priority Pollutants in Sewage and their Removal on Sewage
Treatment Plants," University of Washington, Annual Report Grant
R.806102, July 31, 1979.
48
-------
Sludge
Sludge
(320 raL)
Adjust to pHj> 11
with 6N NaOH
Extract 3X with CH2Cl2
by Homogenization/
Centrifugation
Adjust to pH£ 2
with 6M HC1
Clean Up by GPC
on Bio-Beads S-X3
Eluted with CH2C12
Extract 3X with CH2Cl2
by Homogenization/
Centrifugation
Determine Base/
Neutrals &
Pesticides by GC/MS
on SP-2250
Dry with
Clean Up by GPC on
Bio-Beads S-X3 Eluted
with CH2C12
Determine Phenols
by GC/MS
on SP-1240-DA
Figure 1. Midwest Research Institute procedure for
semivolatile organics.
49
-------
SLUDGE
100 g Wet Weight
Acidify vith KHS04
100 g Wet Weight
Acidify with KHS04
Extract with CH2C12 Extract with CH2C12
Cleanup Using
Bio-Beads S-X8
Extract with 0.2 N
NaOH
Acidify Aqueous Phase
with 6 N HC1
Extract with CH2C12
Methylate Using
CH2N2
Analyze by GC/MS
Wash With 0.1 N NaOH
Fractionate Using
Bio-Beads S-X8
Collect Two Fractions,
GPC-1 and GPC-2
Cleanup GPC-1 Using
Activated Silica Gel
Combine GPC-2 and
Cleaned up GPC-1
Analyze by GC/MS
10 g Wet Weight
Dilute with 0.1 M
Phosphate Buffer, pH7
Extract with CHC13
Preserved with
Ethanol
Extract with 2
H2S04
Neutralize Aqueous
Extract to pH 6-7
Using 1 M
Extract with CHC13
Add Methanol to CHC13
Extract and
Concentrate
Dilute with 0.1 M
Acetate Buffer,
pH 4.7
Analyze by HPLC Using
Elec trochemical
Detector
PHENOLS
NEUTRALS
BENZIDINES
Figure 2. Battelle-Columbus Laboratories procedure for
semivolatile organics.
50
-------
Extract
Sludge
1000 mL
Adjust pH 2
Continuous Extract
with CH2C12
Adjust pH 12
Continuous Extract
with CH2C12
Sludge
-Discard
Cleanup by GPC on
Bio Beads S-X2
Fraction A-l Frac
:ion A-2
Analyze
Coupled Cesium
Silicate
Cleanup on
Florisil
Fraction A-3
Fraction F-l Fraction F-2 Fraction F-3
Analyze
Analyze by GC/MS
Fraction A-3S
Add 1M HC1
Extract 3X
CH2Cl2
Dry with
Derivatization
with CH2N2
Analyze by GC/MS
a. Base extract separate from or combined with acid extract,
b. Capillary GC-FID screening.
Capillary GC/MS analysis.
GC/EC analysis.
Figure 3. Summary of University of Washington procedure for
semivolatile organics.
51
-------
I
Acid CH2C12 extract
Dry over
K-D concentrated
to 1 ml
Sludge
Adjust pH 2
Continuous extraction
with CH2C12 for 12 hrs
Aqueous phase
Adjust pH 12
Continuous extraction
with CH2C12 for 12 hrs
Base CH2C12 extract
Dry over N32S04
K-D concentrated
to 1 ml
Aqueous phase
Dilute to 50%
with pentane
Cleanup Bio Beads S-X2
elute with 50% pentane CH2C12
10% aliquot
I
Dry @ 100°/3 hrs
Weigh residue
1
Fraction A-l
K-D co
to
Ana.
icentrate
1 ml
Lysis
Fraction A-2
K-D coi
to
Add 2 1
[icentrate
1 ml
il hexane
Coupled Cesium
Silicate
K-D concentrate
to 1 ml
Cleanup on Florisil
Elute with 14 ml pentane
K-D concentrate
to 1 ml
Analysis
T
K-D concentrate
to 1 ml
Add 5 ml CH2C12
K-D concentrate
to 1 ml
Analysis
Elute with 200 ml of
50% ethyl ether in pet ether
T
K-D concentrate
to 1 ml
Elute with 100%
ethyl ether
FJ3
Add 5 ml CH2C12 K-D concentrate
K-D concentrate tO j ml
to 1 ml Add 5 ml CHoCl?
I I
Analysis K-D concentrate
to 1 ml
Analysis
Fraction A-3 S
Add 140 ml hexane
K-D concentrate to 2 ml
Transfer to 60-ml separatory
funnel and add 10 ml 1 M HC1
Extract 3X with 10 ml of CH2C12
Combine CH2C12 extracts
Dry over Na2SO^ for 3 hrs
K-D concentrate to 1 ml
Derivatization with
diazomethane
Analysis
Figure 4. Detailed analyses of University of Washington procedure for
semivolatile organics.
52
-------
TABLE 13. COMPARISON OF RELATIVE MAJOR EVENTS
IN THE ANALYTICAL SCHEMES FOR
SEMIVOLATILE ORGANICS
Midwest Research Battelle-Columbus University of
Event Institute Laboratories Washington
Extractions 6 22 8
K-D concentrations 6 20 26
Cleanup 2 36
Analysis 2 3 12
Total 16 48 52
53
-------
The MRI procedure was evaluated further with samples of waste from
Coke Oven Biological Treatment, Food Processing, and Lime Treatment opera-
tions. Samples and spiked samples were analyzed in duplicate, and recovery
data were calculated for selected semivolatile organics. The results of
these analyses are presented in Tables 14 through 21.
The results indicated that recovery varied with the type of waste.
For the most part, good recoveries were obtained for the Food Processing
Sludge and the Lime Treatment Sludge. Recoveries of selected compounds
from the Coke Oven Biological Sludge were generally low, varying from near
zero to 75%. Although low recoveries from the Biological Sludge were
probably due to matrix effect involving adsorption on suspended particulates,
they can also be attributed in part to physical losses occurring in the
extraction steps of the procedure.
Based on these preliminary surveys of existing methods, all of which
used extraction, concentration, and analysis by GC/MS, the modified MRI
method was selected for further evaluation. Furthermore, the preliminary
analyses for organics in the three wastes produced results that were suppor-
tive. Therefore, the EPA-MRI procedure for purgeable organic compounds and
the modified MRI procedure for the analysis of semivolatile organic compounds
were selected for validation with other residual wastes. Results of this
in-depth study are presented in Section 5.
METALS
Comparison of Digestion Procedures with Coke Oven Sludge
Based on recommendations fromEGD» four digestion procedures developed
by Midwest Research Institute (MRI),1 Environmental Monitoring and Support
Laboratories of Cincinnati (EMSL-Ci),2 Battelle-Columbus Laboratories (BCL) ,3
and the University of Washington (UW)1* were evaluated initially. A Coke Oven
Sludge was used to compare the relative extraction efficiencies of the
procedures for the selected metals. The EPA procedure for Total Recoverable
Metals5 was also included for comparison since this procedure was used to
1. "Effluent Guidelines Division POTW Sampling and Analysis," Midwest
Research Institute, Progress Report on EPA Contract No. 68-03-2565,
November 14, 1979.
2. "Interim Method for the Analysis of Elemental Priority Pollutants in
Sludge," Environmental Monitoring and Support Laboratories in Cincinnati,
December 1978.
3. "ICAP Digestion Procedures for Metals - Aqueous Solutions," Battelle-
Columbus Laboratories, December 3, 1979.
4. "Procedure of Analysis of Heavy Metals and Other Elements in Sewage or
Sludge," University of Washington, Laboratory of Radiation Ecology
Research Report, February 21, 1980.
5. "Methods for Chemical Analysis of Water and Waste," EPA, March 1979.
54
-------
TABLE 14. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
BASE/NEUTRAL EXTRACTABLE ORGANICS IN DISTILLED WATER
Compound
1, 3-Dichlorobenzene
1, 4-Dichlorobenzene
1, 2-Dichlorobenzene
Bis(2-chloroethyl) ether
Hexachloroe thane
Bis(2-chloroisopropyl) ether
Nitrobenzene
Hexachlorobutadiene
Naphthalene
1, 2,4-Trichlorobenzene
Bis(2-chloroethoxy) methane
N-nitrosodipropylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Dimethyl phthalate
2, 6-Dinitrotoluene
2, 4-Dinitrotoluene
Acenaphthene
Fluorene
Diethyl phthalate
N-ni tr osod ipheny lamine
1, 2-Diphenylhydrazine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene/anthracene
Di-n-butyl phthalate
Fluoranthrene
Pyrene
Benzidine
Chry sene/benzo (a) anthracene
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Benzo (b) f luoranthene/
benzo(k)f luoranthene
Benzo(a)pyrene
3,3 '-Dichlorobenzidine
Benzo (ghi) perylene
Indeno(l,2,3-cd)pyrene
Dibenzo (ah) anthracene
Retention
time, min
3.8
4.2
4.9
6.8
4.8
6-7
9.0
8.5
9.2
9.6
10-12
10.5-12.5
11.1
13.0
13-15
14.3
16-17
15.9
17.1
14.9
16.4
17.6
17.6
17.1
17.8
18.1
19.7
22.0
23.4
24.1
26.0
28.0
27.0
27.7
29.7
31.2
32.3
29.3
38.2
36.7
36.9
Ion used
for
quanti-
tation
146
146
146
93
117
45
77
225
128
180
93
130/70
237
162
82
152
163
165
165
154
166
149
169
77
282
248
178
149
202
202
184
228
149
149
149
252
252
252
276
276
278
Cone Cone
found in found in
unspiked spiked
samples, samples, Average
yg/L uS/L recovery,
No. 1 No. 2 No.l
930
913
992
1090
926
1000
1270
983
1460
1060
1080
1010
842
1000
934
935
1380
854
847
885
901
1490
1340
930
849
886
2000
980
987
984
825
2340
986
2110
1140
2550
1360
970
1660
1420
1550
No. 2
840
1020
1050
1070
905
967
1190
929
1040
1020
929
953
811
920
847
882
1440
852
855
859
893
1540
1460
838
975
1020
1950
994
971
978
<100
2230
902
1930
1080
2510
1380
1030
1510
1360
1410
%
89
97
102
104
92
99
123
96
125
104
101
98
84
96
91
91
71
85
85
87
90
76
140
88
91
92
99
97
98
98
41
114
94
101
111
127
137
100
158
139
148
55
-------
TABLE 15. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
ACID EXTRACTABLE ORGANICS IN DISTILLED WATER
Compound
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethylphenol
2, 4-Dichlorophenol
2,4, 6-Trichlorophenol
4-Chloro-3-methylphenol
2,4-Dinitrophenol
Pentachloro phenol
4-Nitrophenol
Retention
time, min
4.7
5.1
6.8
8.3
8.7
10.6
12.2
15-16
16.4
20.0
Cone
found in
Ion used unspiked
for samples,
quanti- ug/L
tation No.l No. 2
128
139
94 -
122
162
196
142
184
266
139/65
Cone
found in
spiked
samples,*
Ug/L
No . 1 No . 2
1140 1050
1210 1130
1050 868
355 380
1150 1120
1190 1220
1110 1130
1530 1830
1210 1370
1340 1250
Average
recovery,
%
88
94
77
29
91
96
90
134
103
104
* Concentration spike—1250 Mg/L.
56
-------
TABLE 16. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
BASE/NEUTRAL EXTRACTABLE ORGANICS IN
COKE OVEN BIOLOGICAL SLUDGE
Compound
1, 3-Dichlorobenzene
1, 4-Dichlorobenzene
1, 2-Dichlorobenzene
Bis(Z-chloroethyl) ether
Hexachloro ethane
Bis(2-chloroisopropyl) ether
Nitrobenzene
Hexachlorobutadiene
Naphthalene
1,2, 4-Tr ichlorobenzene
Bis(Z-chloroethoxy) methane
N-nitrosodipropylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Dimethyl phthalate
2, 6-Dinitrotoluene
2, 4-Dinitrotoluene
Acenaphthene
Fluorene
Diethyl phthalate
N-ni trosod iphenylamine
1, 2-Diphenylhydrazine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene/anthracene
Di-n-butyl phthalate
Fluoranthrene
Pyrene
Benzidine
Chrysene/benzo (a) anthracene
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Benzo(b) f luoranthene/
benzo (k) f luoranthene
Benzo (a) pyrene
3,3'-Dichlorobenzidine
Benzo (ghi) perylene
Indeno(l, 2, 3-cd) pyrene
Dibenzo (ah) anthracene
Retention
time, rain
3.8
4.2
4.9
6.8
4.8
6-7
9.0
8.5
9.2
9.6
10-12
10.5-12.5
11.1
13.0
13-15
14.3
16-17
15.9
17.1
14.9
16.4
17.6
17.6
17.1
17.8
18.1
19.7
22.0
23.4
24.1
26.0
28.0
27-0
27.7
29.7
31.2
32.3
29.3
38.2
36.7
36.9
Ion used
for
quanti-
tation
146
146
146
93
117
45
77
225
128
180
93
130/70
237
162
82
152
163
165
165
154
166
149
169
77
282
248
178
149
202
202
184
228
149
149
149
252
252
252
276
276
278
Cone
found in
unspiked
samples,
yg/L
No.l
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
ND
ND
ND
ND
<100
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
ND
<100
113
ND
524
<100
590
ND
1980
1720
ND
1170
1460
468
No. 2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
ND
ND
ND
ND
<100
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
ND
<100
134
ND
627
ND
979
ND
2290
1870
ND
NA
NA
NA
Cone
found in
spiked
samples, Average
Mg/L recovery,
No.l
331
482
641
715
323
574
717
252
495
429
469
556
<100
321
554
335
644
360
438
266
282
714
582
252
200
230
571
171
228
284
2910
695
136
589
196
1620
1430
668
1230
1340
817
No. 2
444
529
584
848
257
649
723
179
442
374
599
604
<100
262
625
308
827
504
625
260
224
684
476
170
143
164
371
113
147
170
2230
361
<100
208
<100
678
548
132
341
395
202
%
39
51
61
75
29
61
72
22
47
40
46
58
<10
29
59
27
37
43
53
26
25
35
53
21
17
20
22
14
13
10
257
<10
10
<10
13
<10
<10
40
<10
<10
<10
Note: ND = Not detected.
NA = Not analyzed.
57
-------
TABLE 17. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
ACID EXTRACTABLE ORCANICS IN COKE OVEN
BIOLOGICAL SLUDGE
Cone
found in
Compound
2-Chloro phenol
2-Nitrophenol
Phenol
2, 4-Dimethylphenol
2, 4-Dichlorophenol
2,4, 6-Trichlorophenol
4-Chloro-3-methylphenol
2, 4-Dinitrophenol
Pentachlorophenol
4-Nitrophenol
Retention
time, min
4.7
5.1
6.8
8.3
8.7
10.6
12.2
15-16
16.4
20.0
Ion used
for
quanti-
tation
128
139
94
122
162
196
142
184
266
139/65
unspiked
samples,
No.
ND
ND
640
<250
ND
ND
<250
ND
ND
ND
yg/L
1 No. 2
ND
ND
338
<250
ND
ND
<250
ND
ND
ND
Cone
found in
spiked
samples,*
yg/L
No.l
693
587
1040
464
612
566
578
1050
542
1140
No. 2
773
754
1110
518
690
741
706
784
568
1230
Average
recovery,
%
59
54
47
37
52
52
44
73
44
95
Note: ND = Not detected.
* Concentration spike—1250 yg/L.
58
-------
TABLE 18. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
BASE/NEUTRAL EXTRACTABLE ORGANICS IN FOOD
PROCESSING SLUDGE
Compound
1, 3-Dichlorobenzene
1, 4-Dichlorobenzene
1, 2-Dichlorobenzene
Bis(2-chloroethyl) ether
Hexachloro ethane
Bis(2-chloroisopropyl) ether
Nitrobenzene
Hexachlorobutadiene
Naphthalene
1,2, 4-Trichlorobenzene
Bis(2-chloroethoxy) methane
N-nitrosodipropylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Dimethyl phthalate
2, 6-Dinitrotoluene
2,4-Dinitrotoluene
Acenaphthene
Fluor ene
Diethyl phthalate
N-nitrosodiphenylamine
1, 2-Diphenylhydrazine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene/anthracene
Di-n-butyl phthalate
Fluoranthrene
Pyrene
Benzidine
Chrysene/benzo (a) anthracene
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Benzo (b) f luoranthene/
benzo (k) f luoranthene
Benzo (a) pyr ene
3,3 '-Dichlorobenzidine
Benzo (ghi)perylene
Indeno(l, 2, 3-cd)pyrene
Dibenzo (ah) anthracene
Retention
time, min
3.8
4.2
4.9
6-8
4.8
6-7
9.0
8.5
9.2
9-6
10-12
10.5-12.5
11.1
13.0
13-15
14.3
16-17
15.9
17.1
14.9
16.4
17.6
17.6
17.1
17.8
18.1
19.7
22.0
23.4
24.1
26.0
28.0
27.0
27.7
29.7
31.2
32.3
29.3
38.2
36.7
36.9
Ion used
for
quanti-
tation
146
146
146
93
117
45
77
225
128
180
93
130/70
237
162
82
152
163
165
165
154
166
149
169
77
282
248
178
149
202
202
184
228
149
149
149
252
252
252
276
276
278
Cone
found in
unspiked
samples,
yg/L
No.l
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
<100
<100
<100
ND
<100
ND
516
<100
ND
ND
<100
ND
ND
ND
No. 2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
<100
<100
<100
ND
<100
ND
2170
<100
<100
<100
<100
ND
ND
ND
Cone
found in
spiked
samples, Average
yg/L recovery,
No.l
933
1130
1210
1220
1020
1120
1130
1080
1200
1110
1140
944
678
998
995
937
1670
842
856
879
891
1680
1400
868
933
976
1840
890
854
883
<100
1860
925
6810
1100
2700
1590
1020
2430
2200
2290
No. 2
303
529
662
667
504
597
604
546
633
642
544
396
226
566
525
528
957
450
487
500
522
927
805
450
544
541
1110
520
502
508
<100
1010
439
10100
593
1170
678
548
863
818
779
%
62
83
93
91
76
86
87
81
92
88
84
67
46
78
76
73
66
65
67
69
71
65
110
66
74
76
73
68
67
69
<10
71
68
AI
81
96
112
78
165
154
151
Note: ND = Not detected.
AI = Analytical interference.
59
-------
TABLE 19. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
ACID EXTRACTABLE ORGANICS IN FOOD PROCESSING SLUDGE
Cone
found in
Retention
Compound
2-Chlorophenol
2-Nitrophenol
Phenol
2, 4-Dimethylphenol
2, 4-Dichlorophenol
2,4, 6-Tr ichlorophenol
4-Chloro-3-methylphenol
2, 4-Dinitrophenol
Pentachlorophenol
4-Nitrophenol
time
4
5
6
8
8
10
12
, min
.7
.1
.8
.3
.7
.6
.2
15-16
16
20
.4
.0
Ion used
for
quanti-
tation
128
139
94
122
162
196
142
184
266
139/65
unspiked
samples,
No.
ND
ND
<250
ND
ND
ND
ND
ND
<250
<250
yg/L
1 No. 2
ND
ND
<250
ND
ND
ND
ND
ND
<250
ND
Cone
found in
spiked
samples,*
Mg/L
No.l
875
963
801
<250
1010
1080
927
<250
1330
1130
No. 2
983
874
702
272
1020
1070
863
<250
1120
1210
Average
recovery,
%
74
73
59
<20
81
86
72
<20
96
89
Note: ND = Not detected.
* Concentration spiked—1250 yg/L.
60
-------
TABLE 20. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
BASE/NEUTRAL EXTRACTABLE ORGANICS IN
LIME TREATMENT SLUDGE
Compound
1» 3-Dichlorobenzene
1, 4-Dichlorobenzene
1, 2-Dichlorobenzene
Bis(2-chloroethyl) ether
Hexachloro ethane
Bis(2-chloroisopropyl) ether
Nitrobenzene
Hexachlorobutadiene
Naphthalene
1, 2, 4-Trlchlorobenzene
Bis(2-chloroethoxy) methane
N-nitrosodipropylamine
Hexachlorocyclopentadiene
2-chloronaphthalene
Isophorone
Acenaphthylene
Dimethyl phthalate
2, 6-Dinitrotoluene
2, 4-Dinitro toluene
Acenaphthene
Fluorene
Diethyl phthalate
N-nitrosodiphenylamine
1, 2-Diphenylhydrazine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene/anthracene
Di-n-butyl phthalate
Fluor anthr ene
Pyrene
Benzidine
Chrys ene/benzo (a) anthrac ene
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-octyl phthalate
Benzo (b) f luoranthene/
benzo (k) f luoranthene
Benzo (a) pyrene
3, 3 '-Dichlorobenzidine
Benzo (ghi) perylene
Indeno(l, 2, 3-cd) pyrene
Dibenzo (ah) anthrac ene
Retention
time, min
3.8
4.2
4.9
6.8
4.8
6-7
9.0
8.5
9.2
9.6
10-12
10.5-12.5
11.1
13.0
13-15
14.3
16-17
15.9
17.1
14.9
16.4
17.6
17.6
17.1
17.8
18.1
19.7
22.0
23.4
24.1
26.0
28.0
27.0
27.7
29.7
31.2
32.3
29.3
38.2
36.7
36.9
Cone
found in
Ion used unspiked
for samples,
quanti- yg/L
tation
146
146
146
93
117
45
77
225
128
180
93
130/70
237
162
82
152
163
165
165
154
166
149
169
77
282
248
178
149
202
202
184
228
149
149
149
252
252
252
276
276
278
No.l
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
ND
ND
ND
ND
ND
ND
ND
<100
<100
<100
<100
ND
<100
ND
3560
<100
<100
<100
ND
<100
<100
<100
No. 2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<100
ND
ND
ND
ND
ND
ND
ND
<100
<100
<100
<100
ND
ND
ND
4650
<100
ND
ND
ND
ND
ND
ND
Cone
found in
spiked
samples, Average
yg/L recovery,
No.l
736
929
1030
1020
840
953
1040
981
1110
1050
1050
1060
766
976
912
933
1300
915
917
874
927
1540
1460
851
911
1060
2090
966
923
885
<100
1510
796
1530
752
1500
798
914
846
763
779
No. 2
729
938
1040
1010
852
949
1150
963
1080
1040
1030
842
783
971
873
947
1500
899
875
872
931
1580
1480
863
953
1070
2020
920
830
798
<100
1310
565
1760
495
1340
675
750
747
697
N 664
%
73
93
103
98
85
95
109
97
110
104
104
95
79
97
89
94
70
91
88
87
93
80
147
86
93
106
103
92
50
84
<10
70
68
<10
21
70
72
83
78
71
71
Note: ND = Not detected.
61
-------
TABLE 21. GC/MS DATA—PERCENT RECOVERY OF SEMIVOLATILE
ACID EXTRACTABLE ORGANICS IN LIME TREATMENT SLUDGE
Compound
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethylphenol
2, 4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-3-methylphenol
2, 4-Dinitrophenol
Pentachlorophenol
4-Nitrophenol
Retention
time, min
4.7
5.1
6.8
8.3
8.7
10.6
12.2
15-16
16.4
20.0
Ion used
for
quanti-
tation
128
139
94
122
162
196
142
184
266
139/65
Cone
found in
unspiked
samples,
Cone
found in
spiked
samples,*
ug/L ug
No.l
ND
ND
<250
ND
ND
ND
ND
ND
ND
ND
No. 2
ND
ND
<250
ND
ND
ND
ND
ND
ND
ND
No.l
871
1080
722
<250
886
979
808
2270
1440
1650
Average
/L recovery.
No. 2
870
1120
717
<250
944
1110
898
2000
1420
1440
%
70
88
57
<20
73
84
68
171
114
124
Note: ND = Not detected.
* Concentration spiked—1250 yg/L .
62
-------
analyze Coke Oven Sludge in conjunction with another program. A summary of
the digestion procedures, as well as modifications deemed necessary at that
time, are given in Tables 8 through 12.
The results of metal analysis of Coke Oven Sludge are presented in
Table 22. These results indicated that all procedures indeed have some
limitations. The MRI method required four separate digestions, was extremely
time consuming, and appeared to yield low recoveries for several of the metals.
Both the BCL and the EMSL-Ci methods required 8 to 10 h for sample preparation
with separate digestions for flame and graphite furnace analyses. The EMSL-Ci
procedure gave better (higher) recovery values. The UW digestion, however,
required only 3 h for completion and gave essentially the same elemental
recoveries, except for selenium, as did the EMSL-Ci procedure. The reason for
the low selenium recovery, approximately 65% of the concentration obtained by
the other procedures, was not determined.
Despite the apparent selenium anomaly, the UW digestion was simple,
rapid, and involved the preparation of only one sample for all metal analyses,
including mercury. On this basis it appeared to be the method of choice for
further evaluation. Some concern was expressed regarding the applicability
of the method with samples of high solids content; therefore, at the request
of the Task Officer, an additional comparison of the UW and EMSL-Ci pro-
cedures was conducted with a Paint Pigment Sludge.
Comparison of the UW and EMSL-Ci Digestion Procedures with Paint Pigment
Sludge
The "as received" Paint Pigment Sludge consisted of a liquid phase and
a densely-packed solid phase that was extremely difficult to disperse. A 1-L
sample, as representative as could be obtained, was acidified with 300 mL of
concentrated HN03 (Ultrex) to a pH <2 and diluted to a volume of 2 L with
deionized, distilled water to facilitate ease of handling. A well-shaken
sample of the diluted sludge was transferred to a beaker and agitated with
a magnetic stirrer while approximately 20 mL aliquots were transferred to
pretared ampuls or Erlenmeyer flasks for the respective digestions. Five
spiked and unspiked replicates were prepared for each method. Spike levels
were selected to give concentrations of approximately 2X the elemental
concentration of the unspiked samples. No problems were experienced with
any explosions of the sealed ampuls during digestion at 125 °C.
The results of the analyses are given in Table 23 and the results of
the spike recoveries in Table 24. As shown in Table 24, the arsenic,
antimony and selenium spikes were not recovered from either the UW or
EMSL-Ci digestates of the Paint Pigment study. Since essentially complete
recovery could be obtained when the spikes were added to the digested,
filtered samples, it seems reasonable to assume that significant concen-
trations of arsenic, antimony and selenium were lost by adsorption of the
residue or by the formation of insoluble or slightly soluble compounds.
63
-------
Element
TABLE 22. RESULTS OF METAL DETERMINATION
IN COKE OVEN SLUDGE3
Midwest Research
Institute digestion
123
Environmental
Monitoring and
Support Laboratory
_ digestion
Battelle-Columbus
digestion
123
University
of Washington
digestion
123
Standard
Environmental
Protection
Agency
digestion
123
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
d
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
b b b
9000C 11000° 11000°
<50 <50
140 140
590 590
940 840 760
200 300 310
230 230
12000° 12000° 13000°
44 44
3600 3600
12 16 12
12000 11000 11000
<100 <100 <100
<20 <20 <20
450 500 480
1100 1000 1000
1000 860 880
340 340 250
300 <300 <300
12000 12000 12000
150 100 100
<20 <20 <20
5600 5500 5500
13 24 16
11000 9000 11000
<50 <50 <50
10 12 11 b b
10000 10000 10000 9400 13000
<50 <50 <50 <50 <50
460 460 460
930 940 940
650 550 800
260 350 350
350 350 350
12000 11000 13000
90 80 110
620
730
700
390
670
620
910
640
400
670
620 470
760 750
760 690
390 450
580 310
7600° 7600° 7800° 2400
110
110
110 120
470
720
650
550 450
230
6200
120
5000 4800 4700 5000 5300 5100 5000 5000
a.
b.
c.
d.
All results expressed in micrograms per liter of dilute sludge (1:1 by volume).
Severe interference problem with furnace. Foaming could not be controlled in hydride procedure,
Hyd ri de p ro ce du re .
Cold vapor procedure.
-------
TABLE 23. RESULTS OF METAL DETERMINATION
OF PAINT PIGMENT SLUDGE3
A. University of Washington digestion
Element
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
No. 1
<0.10
0.93
0.04
0.01
7.7
102
26
61
1.0
<0.05
0.31
<0.02
250
No. 2
<0.10
0.85
0.02
0.02
7.3
105
23
57
1.1
<0.05
0.32
<0.02
260
No. 3
<0.10
1.00
0.02
0.01
7.2
103
22
55
1.1
<0.05
0.31
<0.02
260
No. 4
<0.10
0.92
0.02
0.02
7.7
103
27
56
1.0
<0.05
0.31
<0.02
260
No. 5
<0.10
0.88
0.02
0.02
7.6
102
24
57
1.2
<0.05
0.33
<0.02
260
Mean
<0.10
0.92
0.02
0.02
7.5
103
24
57
1.1
<0.05
0.32
<0.02
260
Relative
standard
deviation,
%
—
9.0
37.3
34.2
3.1
1.2
7.5
4.0
8.9
-
2.7
-
1.9
B. Environmental Monitoring and Support Laboratory digestion
Relative
standard
deviation,
Element
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead ,
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
No. 1
<0.10
1.3
0.02
0.01
10
103
36
59
1.4
<0.05
0.28
<0.02
290
No. 2
<0
0
0
0
10
100
33
60
1
<0
0
<0
280
a. All results expressed
b. Mercury
was also
.10
.88
.01
.01
.2
.05
.30
.02
No. 3
<0.10
1.0
0.01
0.01
10
99
32
62
1.5
<0.05
0.31
<0.02
290
in micro grams
determined
The following results were
after a
obtained
No. 4
<0
1
0
0
10
102
34
63
1
<0
0
<0
300
per
.10
.2
.01
.01
.4
.05
.31
.02
gram
standard
: 76
, 70,
No.
<0
0
0
0
10
101
34
50
1
<0
0
<0
290
5
.10
.96
.01
.01
.6
.05
.27
.02
of sludge
EPA
72,
Mean %
<0
1
0
0
10
101
34
59
1
<0
0
<0
290
.10
.1
.01
.01
.4
.05
.29
.02
diluted 1:1
digestion
71,
and
of this
73 yg/g
_
16.4
37.3
0.0
0.0
1.6
4.3
8.8
8.6
-
6.5
-
1.7
by volume
sample.
with an
average of 72 ug/g and a % RSD of 32.
65
-------
TABLE 24. SPIKE RECOVERY IN PAINT PIGMENT SLUDGE£
A. University of Washington digestion
Percent recovery
Element
Antimony
Arsenic
Beryllium
Cadmium
Chromium
Copper
Lead
Mercury
Nickel
Selenium
Silver
Thallium
Zinc
No. 1
b
c
99
101
113
89
80
96
_e
29
83
104
No. 2
b
c
90
101
114
101
85
93
_e
26
90
133
No. 3
_b
c
98
104
112
99
96
88
_e
20
74
120
No. 4
b
c
93
105
99
98
126
93
_e
21
70
113
No. 5
_b
c
97
107
96
94
98
84
_e
20
72
103
Mean
_
95
104
107
96
97
91
_e
23
78
115
Relative
standard
deviation,
%
—
4.0
2.5
8.0
5.0
18
5.2
_e
17.6
11.0
11.0
B. Environmental Monitoring and Support Laboratory digestion
Percent recovery
Element No. 1 No. 2 No. 3 No. 4
Antimony -
Arsenic -c
Beryllium 91
Cadmium 100
Chromium 118
Copper 104
Lead . 115
Q
Mercury 99
Nickel 95
Selenium -e
Silver 71
Thallium 76
Zinc 112
_b b b
c c c
106 96 92
102 107 112
113 101 113
104 99 95
124 112 99
108 98 97
86 86 96
_e _e _e
92 73 73
80 106 83
118 107 109
Relative
standard
deviation ,
No. 5 Mean %
b
c
94
104
109
92
108
84
98
_e
55
86
104
_
_
96
105
111
99
112
97
92
_e
73
86
110
—
_
6.3
4.5
5.7
5.4
8.2
8.8
6.2
_e
17.0
14.0
4.9
a. Paint Pigment Sludge diluted 1:1 by volume.
b. No recovery of
c. No recovery of
d. Mercury spikes
1.0 yg/g antimony spike.
1.0 yg/g arsenic spike.
were inadvertently omitted
from the
UW and
EMSL-Ci
samples. These recoveries were obtained from sludge samples spiked
only with mercury and then digested by the standard EPA procedures.
No recovery of 0.5 yg/g selenium spike.
66
-------
Although the silver concentration was found to be the same in both
the UW and EMSL-Ci unspiked samples, the recovery of silver from the UW
spiked series was poor. No satisfactory explanation for this discrepancy
was apparent.
In general, the elemental concentrations and spike recovery data
obtained from the analyses of the UW digested Paint Pigment samples were
essentially the same as those values obtained from the EMSL-Ci digested
samples. The relative standard deviations (RSD) were satisfactory for all
elements determined to be present at concentrations of 1 yg/g or above.
These results , along with those obtained during the earlier comparison
of procedures using the Coke Oven Sludge, indicate the UW procedure to be
analytically equivalent or better than the other procedures evaluated.
Since the UW procedure is faster (approximately 3 h compared to greater
than 8 h for the other procedures) and requires the preparation of only
one sample for all metal determinations (three to five samples for other
procedures) , the UW method was selected as the preferred method for the
determination of total metals in residual waste.
67
-------
SECTION 5
EVALUATION OF METHODS
SUMMARY OF PROPOSED METHODOLOGY
The text of the proposed methods that were subjected to in-depth
evaluation for the determination of total content of toxic species in
residual wastes is given in Appendix V. The procedures include sample
preparation and analysis of purgeable organics by purge-and-trap with
GC/MS analysis, base/neutral and acid extractables of semivolatile organics
with GC/MS analysis, and acid digestion of metals with AAS analysis. These
three methods can be summarized as follows.
Purgeable organics—An appropriate weight of sludge (determined by
a preliminary screening of extractable organic content of the sample)
is diluted to 10 mL with organic-free water. The diluted sample is
then purged at room temperature' (ca. 25 °C) with an inert gas for
12 min. Compounds boiling below 200 °C and of limited solubility
in water are transferred from the aqueous phase to the gas phase.
The gas phase is passed through a sorbent trap where the organic
compounds are concentrated. The contents of the trap are then
desorbed into the GC/MS by heating and backflushing the trap. The
total analysis time is less than 1 h.
Base/neutral and acid extractable organics—A 40-g sample is extracted
with methylene chloride using liquid-liquid extraction techniques
aided by a high-speed homogenizer. Samples are extracted at pH >11
and again at pH <_2 to isolate base/neutral and acidic compounds,
respectively. The extract is dried with sodium sulfate and concen-
trated to a volume of 5 mL or less using a Kuderna-Danish (K-D)
evaporator. The compounds in the extract are separated, identified
and quantified by GC/MS. If interferences are encountered, as is
frequently the case, the method provides a general-purpose gel perme-
ation chromatography (GPC) cleanup procedure to eliminate many
interferences.
Acid digestion of metals—The sample is transferred to a clean glass
ampul, acidified with 2 mL of concentrated HNOs, and diluted to
about 20 mL with deionized, distilled water. The ampul is sealed and
placed in an oven at 125 °C for 1 h. The digested sample is suction
filtered and brought to a final volume of 50 mL with deionized,
distilled water. The selected metals are then determined by atomic
adsorption spectroscopy using direct aspiration, furnace, gaseous
hydride, or cold vapor (mercury) procedures. The use of an ICP
spectrometer may also be appropriate.
68
-------
DESCRIPTION OF RESIDUAL WASTES
After the preliminary methods evaluations study was completed, several
wastes were selected for use in the second phase of the study. Agreement as
to which of the available samples would be used was reached in a meeting of
the two analytical contractors and EPA-EGD, EPA-OSW, and EMSL-LV personnel.
Although the residuals selected for study were limited to nine by time and
cost considerations, they were thought to be representative of the wide
range of complex matrices that are likely to be encountered in the analysis
of wastes. These samples were chosen to include those with high and low
liquid organic content, high and low organic and inorganic solids content,
and basic and acidic pH values. Several characteristics of the selected
waste samples are given in Table 25.
MATRIX OF ANALYSES
Twelve sets of analyses were completed including the repeat analyses
of the Ink Pigment Waste and Organic Still Bottoms. The first set of
analyses on these samples was done on the waste as received whereas the
second set of analyses (labeled: Interlaboratory) was performed on a sample
that was remixed, reproportioned, and resubmitted to the laboratories parti-
cipating in the interlaboratory validation study. The spiked Method Blank
consisted of reagent water spiked with a mixture of the semivolatile organic
compounds determined during the initial phase of the program. A summary of
the number of replicate analyses and their spike levels for each of the
residual wastes in the study is given in Table 26. The analyses were done
in five replicates for each residual waste except for the Coke Oven Biologi-
cal Sludge, Electroplating Sludge, and Electric Furnace Baghouse Dust,
which were analyzed in triplicate. A total of 290 individual samples were
prepared. This total included 89 for purgeable organics, 109 for for semi-
volatile organics and 92 for metals. These determinations gave rise to
8908 data points with the following breakdown according to compound type:
• Purgeables 2225
• Base/Neutrals 4578
• Acids 1199
• Metals 906
The preliminary evaluation study resulted in over 1000 additional data points
for a total in excess of 10,000.
COMPOUNDS CHOSEN FOR DETERMINATION
The three major classes of compounds that were determined in residual
waste samples included 23 purgeable organics, 56 semivolatile organics and
13 metals. The semivolatile organics can be further divided into several
subcategories, which included polynuclear aromatic hydrocarbons, chlorinated
69
-------
TABLE 25. DESCRIPTION OF RESIDUAL WASTES
Residual waste
Raw POTW
Electroplating Sludge
Paint Pigment Sludge
(Latex Paint Sludge)
Lime Slurry Treatment
Sludge
Food Processing Sludge
Coke Plant Sludge
Organic Still Bottoms
Baghouse Dust
Ink Pigment Waste
PH
6.5
9.0
7.8
7.2
5.6
9.0
3.6
6.3
11.3
Solid
content,
% Category
0.8 AS
25.2 IS
14.9 AS
2.0 AS
0.5 AS
3.1 AS
35.9 OS
99.3 IS
14 . 8 AS
. . — — • — — — •
Physical description of sample
Thin, dark green, aqueous suspension
Dark, wet cake
Thick, milky, aqueous suspension
Thin, tan, aqueous suspension
Thin, tan, aqueous suspension
Dark, aqueous suspension
Thick, black, chunky, aqueous slurry
Fine, dark brown powder
Pourable, black gel
a. AS - aqueous sludge (>80% HaO) .
IS - inorganic sludge (>20% inorganic content) .
OS - organic sludge (>20% organic content).
-------
TABLE 26. SUMMARY OF REPLICATES AND SPIKE LEVELS
OF PURGEABLE AND SEMIVOLATILE ORGANICS
AND METALS FOR THE VALIDATION STUDY3
Purgeable
organics
Spike levels
Residual Waste
POTW Residual Waste
Ink Pigment Waste
Organic Still Bottoms
Ink Pigment Waste
(Interlaboratory)
Organic Still Bottoms
(Interlaboratory
Paint Pigment Sludge
Coke Oven Biological Sludge
Ink Pigment Leachate
Organic Still Bottoms Leachate
Electroplating Sludge
Electric Furnace Baghouse Dust
Spiked Method Blank
0
5
-
-
5
5
5
3
5
5
-
-
—*
I II
5 5
-
-
5 5
5 5
5 5
3 3
5
5
-
-
— —
Semivolatile
organics
Spike levels
0
5
5
5
5
5
3
3
5
5
-
-
~
I II III
555
55-
_
35-
35-
33-
33-
5 - -
5 - -
_
_
5
Metals
Spike levels"
0
_
5
5
5
5
5
-
5
5
-
-
—
I
_
5
5
5
5
5
-
5
5
3
3
—
II
_
-
-
_
_
-
-
5
5
3
3
—
a. Numbers in the table are the number of replicates of each analysis of a sample-
spike combination.
b. Spike level varied for classes of compounds; however, in general, spike levels
were between 2X and 20X of the unspiked sample. Zero spike level is the unspiked
sample.
-------
hydrocarbons, phthalate esters, chloroalkyl ethers, nitrosamines, benzidines,
phenols, and several miscellaneous compounds. The organic compounds were
intended to represent a range of boiling points and functionalities, and were
chosen from the priority pollutants primarily because of the ready avail-
ability of reference standards. The selection of the compounds was also
based on available historical information concerning potential composition
of industrial wastewaters that were thought to be associated with residual
wastes.
ANALYTICAL INSTRUMENTATION
The analytical finish in the proposed methods depends primarily on a
GC/MS for separation, identification, and quantitation of the organic com-
pounds. The requirements for the instrumentation essentially are identical
to those set forth in the familiar methods for determination of priority
pollutants in wastewater. The methods for the metals were evaluated using
an atomic absorption spectrometer, although an ICP spectrometer may be a
suitable, and in some instances, a more desirable analytical finish.
EVALUATION DATA
The analytical and statistical data from the evaluation study for the
proposed methodology for total content are given in Appendix IV. These data
include the results of each replicate determination of the concentration of
each compound; the amount of spike added and the mean percent recovery for
each spiked sample, and the calculated mean, standard deviation, and relative
standard deviation for each set of replicate analyses. These tabulations are
grouped by compound type for each of the nine residual waste samples and for
method blanks (spiked distilled, deionized water). Also, typical GC/MS
chromatograms, labeled with identified compounds, are presented after each
of the tabulations of compound types for each waste sample.
Several observations, interpretations, and conclusions based on these
data are summarized and presented in the following section of this report.
However, due to the sheer bulk of the data obtained in this study, it is
possible that several significant trends or observations might have gone
unreported in the initial data assessment that is presented in this document.
Future studies of these data should be readily facilitated by the fact that
all of the results that were obtained are presented in this report and are
also available on computer cards.
72
-------
SECTION 6
STATISTICAL INTERPRETATION OF DATA
INTRODUCTION
Because a relatively large amount of data (in excess of 10,000 data
points) was generated from the laboratory experiments conducted during this
study, several statistical interpretations were made to test the validity
and significance of these data. It was recognized that these data were not
randomly sampled from well-defined populations and that statistical inter-
pretation of these data in a formal inferential manner may not be valid.
Therefore, formal inferential statistical analysis of the data was not done;
however, the usefulness of the usual descriptive statistical devices such as
mean, standard deviation, relative standard deviation, and mean percent
recovery was recognized, and these items were included in the empirical
treatment of these data.
SUMMARY OF STATISTICAL TERMS AND FORMULAS
The following statistical terms and formulas were employed in the
analyses of the data points:
• Mean—Arithmetic mean or average, defined as the sum of the values
of all the observations divided by the number of observations (n).
• Standard deviation—Defined as the positive square root of the
variance, which is defined as the sum of squares of the deviations
of the observations from the mean (x) divided by one less than the
total number of observations (n-1).
n
£'- r'"2
std dev =
(Xi - x)'
i=l
n-1
• RSD — Relative standard deviation, defined as the standard deviation
divided by the mean and multiplied by 100.
73
-------
• Mean percent recovery—Defined as 100 times the ratio of the
difference between the mean concentration of the spiked samples
(XLI) and mean concentration of the unspiked samples (XLQ) to
the amount added.
(5L - v \
LI LO \
amount added /
REJECTION OF AN OBSERVATION
Suspected outliers among the data points were tested for rejection in
this study by application of the Dixon Criteria for Testing1 (Q-Test, 90%
confidence). A total of only 1.1% of all of the data (1.2% of the data for
organics and 0.1% of the data for metals) was found to be suspect and these
outliers were not included in the other statistical calculations.
INTERQUARTILE RANGES
A very useful means for summarizing the significance of the statistical
results of the method evaluation study involved the use of the so-called inter-
quartile range.2 This range is defined by those results, ranked according to
magnitude, that occur in the middle one-half of the ranking order (i.e., data
ranked within 25 to 75% of the total number of data points). Thus, 50% of the
results will occur in this median range, and it was the use of this range that
formed the basis of the conclusions presented in Section 2 of this report.
These interquartile ranges of the RSD and mean percent recoveries are given in
Tables 27 and 28 for each residual waste as a function of the various compound
groups. It was concluded from these results that the proposed methods for
total content could be applied to the analysis of a typical residual waste
with a reasonable expectation that an accuracy of approximately -50 to 150%
of the true values and a precision of approximately 10 to 25% RSD for organics
and 3 to 7% for metals can be obtained.
Otherwise, the summaries of the interquartile ranges indicated that
there was not a great deal of difference among the methods for the various
classes of organics with regard to accuracy and precision. On the other hand,
RSD for determination of metals (by AAS) was substantially smaller than that
for determination of organics. Accuracy of each of the methods (based on
spike recoveries) was similar, in general, with no clear trend emerging.
Also included in the summary tables is a treatment of the data from
the interlaboratory validation studies of the potential mobility (leachate)
methods and the total content methods. The detailed presentation of the
interlaboratory study data is made in Appendices II and III. These results
are not discussed in detail here, but are provided for future comparison
with the results obtained by BCL in the analysis of nominally-identical
samples by the same methodologies.
1. Dixon, W. J., "Processing Data for Outliers," Biometrics _9(1), 74-89, 1953,
2. David, H. A., Order Statistics. John Wiley and Son, Inc., New York, NY,
19 70»
-------
TABLE 27. SUMMARY OF INTERQUARTILES OF RELATIVE STANDARD
DEVIATIONS OF CONCENTRATIONS OF COMPOUNDS
AVERAGED OVER ALL SPIKE LEVELS
(INCLUDING UNSPIKED SAMPLES)3
Ln
Total content
Residual waste
Class
Base/Neutrals
Acids
Purgeables
Metals
Range
high
low
high
low
high
low
high
low
POTW IPW OSB PPS COBS EPS
25 20 33 19 16
19 12 25 78-
34 44 17 31 20
23 27 0 6 13 -
24 - - 14 15 -
11 8 10
6 10 5 - 5
473-2
EFBHD IPW-IL
29
19
21
24
26
15
6 5
3 3
OSB-IL
31
19
29
10
20
16
10
3
Potential
mobility
IPL
25
10
18
10
22
10
3
1
OSBL
22
14
19
15
22
12
3
2
a. Relative standard deviations in this table are expressed as percent (%).
-------
TABLE 28. SUMMARY OF INTERQUARTILES OF AVERAGE
PERCENT RECOVERIES OF COMPOUNDS IN SPIKED
RESIDUAL WASTE SAMPLES3
Total content
Spiked Residual waste
Class
Base/Neutrals
Acids
Purgeables
Metals
Range
high
low
high
low
high
low
high
low
blank POTW IPW OSB PPS
109 155 132 - 53
70 72 78 - 21
76 70 102 - 48
55 53 70 - 11
70 - - 147
51 - - 77
102 94 99
- 81 74 69
COBS EPS EFBHD IPW-IL
84 - - 88
59 - - 57
119 - . - 122
109 - - 109
95 52
75 24
96 94 106
64 71 98
OSB-IL
115
63
69
21
98
87
104
82
Potential
mobility
IPL OSBL
95
67
102
78
81
54
106
100
147
72
41
25
32
17
108
99
a. Recoveries in this table are expressed as percent (%).
-------
SUMMARY PRESENTATION OF DATA
A summary of the average concentrations of all compounds determined
in the various (unspiked) residual waste samples is presented in Appendix I
following this section. Tables 1-1 through 1-4 give these data separately
for the following compound groups respectively: purgeable organics,
base/neutral fraction of semivolatiles, acid fraction of semivolatiles,
and metals. These data are the mean results of replicate analyses for the
various waste samples. The key at the beginning of this group of tables
should be referred to for identification of the abbreviations used for the
various waste samples.
A brief review of these analytical results indicates the diversity and
complexity of these sample matrices.
Tables 1-5 through 1-8 in Appendix I present the average relative
standard deviations (RSD) for each determination in each sample matrix. These
data were obtained from the RSD for each compound determination at all spike
levels (including unspiked). These results are also presented separately
for compound groups and are a measure of the analytical precision of the
methods for the various compounds.
The averages of the mean percent recoveries of spikes for each compound
in the various sample matrices are given in Tables 1-9 through 1-12. These
data are also presented for each compound group and represent a measure of
accuracy of the methods. In some isolated cases, inordinately high values
(e.g., >1000%) or values less than 0% for recovery were obtained for some
compounds. These results were almost always caused by the spike level being
much smaller than the concentration of the compound in the unspiked sample.
Appropriate spiking techniques called for spiking at 2, 10, and 20 times the
unspiked concentrations in the various samples. However, out of necessity,
the spiked and unspiked samples were occasionally analyzed simultaneously,
so this procedure was not always followed.
77
-------
Appendix I. Data Summary Tables
78
-------
Symbols
POTW
IPW
PPS
COBS
EPS
EFBHD
IPW-IL
OSB-IL
IPL
OSBL
Legend for Verification Analyses
and Quality Assurance
for Total Content Data*
Identification
Not determined.
Lower detection limit of instrumentation.
POTW Residual Waste,
Ink Pigment Waste.
Paint Pigment Sludge.
Coke Oven Biological Sludge.
Electroplating Sludge.
Electric Furnace Baghouse Dust.
Ink Pigment Waste (Interlaboratory).
Organic Still Bottoms (Interlaboratory) .
Ink Pigment Leachate.
Organic Still Bottoms Leachate.
* Concentrations are reported as microgram of compound per gram of waste
(parts per million).
79
-------
A. Summary of Average Concentrations of Compounds
in Unspiked Residual Waste Samples
80
-------
TABLE 1-1. AVERAGE CONCENTRATIONS OF PURGEABLE ORGANICS
IN UNSPIKED RESIDUAL WASTE SAMPLES
COMPOUND
M6IHYLENE CHLL.RIOE
TRICHLOROFLUOROMETHANE
1,1-OICHLOROEIHYLENE
1i1-DICHLOROETHANE
00 TRANS-1,2-OICHLOROETHYLENE
t-1 CHLOROFORM
1.2-DICHLOROETHANE
1,1,1-TRICHLORUETHANE
CARBON TETRACHLORIOE
BRCJNODICHLOROMETHANE
It 2-DICHLORUPROPANE
TRANS-1,3-0ICHLOROPROPENE
TRICHLOROETHY LE NE
OIBKOMOCHLOROHETHANE
CIS-1.3-OICHLOROPROPENE
It1.2-TR1CHLORGETHANE
BENZENE
BROMQFORM
1,1,2,2-TETRACHLOROETHENE
irli2t2-TETRACHLOROETHANE
TOLUENE
CHLQROBENZENE
ETHYLBENZENE
POTM
0.66
oloo
0.00
o°:88
0.00
0.00
0.00
0.00
0.00
0.00
0.03
0.00
0.00
0.00
0.00
0.00
0.22
0.00
0.39
0.54
1.00
IPW
OSB
PPS
0.74
oloo
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.73
0.00
0.00
0.00
3.83
0.00
7.47
3.47
14.00
2.07
250.67
COBS
0.09
oloo
0.00
0.00
EPS
EFBHO
ose_iL
54.8
0.0
95.0
2168.0
804.2
262.2
1496.0
354.6
59.
577
I PL
1201.2
168.3
3525.0
0.0
1720.0
OS8L
759
7348
170600
56300
18460
96760
23740
0
0
0
149400
0
267600
0
144400
111480
-------
TABLE 1-2. AVERAGE CONCENTRATIONS OF BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS
IN UNSPIKED RESIDUAL WASTE SAMPLES
oo
NJ
COMPOUND
1,3-DICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-DICHLORObENZENE
HEXACHLORQETHANE
BISt2-ChLOROETHYL) ETHER
BISI2-CHLGROISOPROPYL1 ETHER
HEXACHLOROBUTADIEN£
NITROBENZENE
NAPHTHALENE
1.2.4-TR1CHLOROBENZENE
BlSI2-CHLOROETHOXYJMETHANE
N-NITROSODI-N-PROPYLAM1NE
HEXACHLOftOCYCLOPENTAOIENE
2-CHLORONAPHTHALENE
ISOPHORCNE
ACENAPHTHYLENE
ENAPHTHENE
DIMETHYL PHTHALATE
2,6-DINITRGTGLUENE
FLUORENE
2,4-DINlTROTOLUENE
1,2-OlPHENYLHYDRAZINE
4-CHLOROPHENYL PHENYL ETHER
01 ETHYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-BRCMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
BUTVLBENZYL PHTHALATE
BIS(2-ETHYLHEXYL> PHTHALATE
CHRYSENE/BENZOtA)ANTHRACENE
3,3'-OICHlOROBEN/IDINE
DI-N-OCIYL PHTHALATE
BEN£U(BI/BENZO(KtFLUORANTHENES
BENZO(A)PYRENE
INOENOI1,2,3-COiPYRENE
OI8ENZ01AH)ANTHRACENE
»ENZO(GHI)PERYLENE
POTH
2.08
3.88
0.79
0.00
0.00
0.00
0.00
0.00
6.12
53.80
0.00
0.00
0.30
0.00
0.00
0.00
0.00
1.30
0.00
IPH
0.0
24.6
29.2
4.6
0.0
0.0
0.0
10.7
76.0
0.0
2.9
0.0
0.0
0.0
0.0
10.9
7.6
2.0
0.0
23.2
4.1
0.0
0.0
3.7
0.0
0.0
<1.6
60.4
0.0
21.4
14.4
0.0
0.0
100.0
28.2
0.0
0.0
25.2
25.8
10.7
0.0
13.6
OSB
PPS
0.00
0.00
0.00
COBS
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
EPS
EFBHD
OSB_IL
IPL
0.00
0.00
1.49
<0.50
0.00
0.00
0.69
<0.4
0.0
OSBL
0
a
j
o
j
0
0
0
0
0
0
0
-------
TABLE 1-3. AVERAGE CONCENTRATIONS OF ACID EXTRACTABLE SEMIVOLATILE ORGANICS
IN UNSPIKED RESIDUAL WASTE SAMPLES
oo
CCMPOUNO
2-CHLOROPHENOL
2-NITRGPHENCL
PHENOL
2i4-DIMETHYLPHENGL
214-01CHLORGPHENOL
2t4,6-TRICHlOROPHENOl.
4-CHLORO-3-METHYLPHENOL
2 ,4-OINITROPHENOL
4,6-0 i NITRO-0-CRESOL
PENTACHLOROPHENOL
4-NITROPHENOL
POTH
0.00
0.00
0.82
0.00
0.00
o.oo
0.00
0.00
0.00
0.00
0.00
IPW
3.6
< 1 «o
55.4
< 1.2
olo
0.0
0.0
-------
TABLE 1-4. AVERAGE CONCENTRATIONS OF METALS
IN UNSPIKED RESIDUAL WASTE SAMPLES
00
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
CCPPER
LEAK
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
POTH
IPW
OS8
PPS
COBS
EPS
0.3
<§:?
<0.2
77.8
10.3
311.2
ilo
<0.5
<0. 1
<0.5
29.4
<0.l
1.0
-------
B. Summary of Relative Standard Deviations of
Concentrations of Compounds Averaged Over
All Spike Levels (Including Unspiked Samples)
85
-------
TABLE 1-5. RELATIVE STANDARD DEVIATIONS OF CONCENTRATIONS OF PURGEABLE ORGANICS
AVERAGED OVER ALL SPIKE LEVELS (INCLUDING UNSPIKED SAMPLES)
oo
COMPOUND
NETHYLENE CHLORIDE
TRICHLORQFLUORCMETHANE
1,1-DICHLOROETHYLENE
Ul-DICHLOROETHANE
TRANS-1.2-OICHLOROETHYLENE
CHLOROFORM
1, 2-OICHLQROETHANE
ia,l-TRlCHLOROETHANE
CARBON TETRACHLORIDE
BROHODICHLOROMETHANE
1 ,2-DICHLGROPROPANE
TRANS-1 , 3-Dl CHLOROPROPENE
TRICHLORGETHYLENE
DIBROMOCHLORCMETHANE^
CIS-It 3-OICHLOROPROPENE
1.1,2-TRICHLOROETHANE
BENZENE
il-TETRACHLOROE THANE
TOLUENE
CHLGROBENZENE
ETHVLBENZENE
POTW
37.7
IPH
QSB
* »«
ii:
PPS
27.2
1.3
6.0
3. a
10. •*
6.7
9.0
8.6
8.5
9.2
32.8
12.0
13.8
13.2
15.0
10.8
25.5
18.5
EPS
EFBHO
24.2
OSB_1L
35.5
54.6
I PL
18.0
8.9
2.4
18.6
26.5
10.3
11.0
11.6
29.9
5.9
21.4
22.6
OSBL
6.2
16*7
11. e
13.5
15.0
10.8
17.9
34.1
9.2
5.9
30.0
29.3
-------
TABLE 1-6. RELATIVE STANDARD DEVIATIONS OF CONCENTRATIONS OF BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS
AVERAGED OVER ALL SPIKE LEVELS (INCLUDING UNSPIKED SAMPLES)
COMPOUND
1,3-DICHLORQBENZ£NE
1,4-OlCHLOROBENZENE
1 ,2-DlCHLOROBENZENE
HEXACHLOROETHANE
BIS(2-CHLOROETHYLI ETHER
B1SC2-CHLGROISCPROPYL) ETHER
HEXACHLCROBUTAOl ENE
NITROBENZENE
NAPHTHALENE
It 2.4-TRICHLOR08ENZENE
BISi2-CHI.ORQETHOXYIMETHANE
N-NITROSOD1-N-PRGPYLAM1NE
HEXACHLGROCYCLOPENTADIENE
00 2-CHLORONAPHTHALENE
•vl ISCPHORONE
AtENAPHTHVLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-OINITROTOLUENE
FLUORENE
2|4-DINITRCTOLU£NE
1,2-DIPHENYLHYORAZINE
4-CHLOROPHENYL PHENYL ETHER
01ETHVL PHTHALATE
N-NITRQSODIPHENYLANINE
HEXACHLOROBENZENE
4-BRGMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
OI-N-BUTYL PHTHALATE
FLUORANTHtNE
PYRENE
BENZIDINE
8UTYLBENZYL PHTHALATE
BIS{2-ETHYLHEXYLI PHTHALATE
CHRYSENE/BENZG4A)ANTHRACENE
3,3'-OICHLOROBENZIOINE
DI-N-OCTYL PHTHALATE
BENZOCBJ/BENZOCKi FLUORANTHENES
BENZOCAJPYRENE
1NUENCIIt2i 3-CO)PYRENE
OIBENZOIAH)ANTHRACENE
BENZO(GHIIPERYLENE
POTW
IPI*
OSB
PPS
COBS
EPS
EFBHO
21.5
22.3
18.0
23.2
54.3
36.4
14.4
23.5
19.1
17.9
30.2
30.6
20*8
20^
18.9
16.1
22.1
27.5
19.4
39.6
20.0
24.8
23.0
31.2
22.7
28.0
13.4
20.6
19.7
19.0
23.4
20.6
19.9
20.0
22.1
29.8
18.6
22.4
19.7
25.1
21.0
43.0
11.6
12.2
11.0
19.0
23.5
12.2
13.7
7.1
12.6
12.3
14.5
i2:&
24^
11.2
1 X • 5
11*8
11.9
12.3
15.2
21.7
16.2
23.3
32.9
16.3
34.9
11.4
19.6
12.4
11*?
30* 2.
49.4
9.2
18.0
48.5
14: s
15.1
21.0
19.0
15.4
27.7
19.6
36.6
9.3
*
31.1
9
25.2
•
16ls
26.1
*
—
*
28^
*
33^
9
m
m
.
9
9
46.7
70.3
.
•
^
B
•
m
9
t
26.6
42.4
19.3
4.9
14.8
11.0
30.9
21.5
15.4
isli
13.6
14.7
10.4
9.8
3^
14.1
19.6
7.1
18.4
26.2
14.1
14.8
9.4
20.6
25.8
14.0
19^
19.1
20.2
23.9
23.7
15.6
7.9
m
16.2
6.7
19.2
9.3
8.1
ii:!
14.4
25.0
13^
18.7
43.1
10.8
14.6
19.7
14.3
9.6
20 • 3
13.4
17.1
10.5
11.1
8.7
8.0
24.3
11.4
6.8
9.3
8.3
8.5
22.0
11.2
14.6
11.0
16.9
12^
14.8
6.6
16^
1PH_U
19.1
26.7
26.0
21.0
47.2
37.4
10.7
60.0
24.9
24.3
21.8
33.7
48.6
22.1
17.7
34.2
25.5
30.0
16.9
24.2
16.1
11.2
14.1
25 • 6
1S.O
35.5
30.8
25.0
27.2
23.1
24.0
24.5
17.0
12.0
21.5
65.9
33.7
29.1
24.9
84.9
B
26.3
OSB_U
19.9
29.4
23.9
26.9
20.7
20.6
26.2
61.5
25.1
21.2
8.7
24.6
71.9
17.2
34.3
41.9
29.3
18.1
21.0
44.6
33.3
43.1
17.9
31.1
50.1
18.7
17.5
40.8
14.8
52.0
28.6
50.0
18.6
26.1
37.9
12.9
20.1
17.4
20.0
3.4
49.5
32.2
IPL
t
24: 8
29* 0
15.4
11.9
13.5
20.6
34.4
13.4
11.8
12.9
6.7
14^
19.2
24.6
32.9
13.6
13.2
47.5
38.9
24.2
31.1
6*9
4.4
8.9
10.2
11. a
124:4
6.8
10:4
61.1
9.7
.
OSBL
17^
5.6
fA
.2
21.0
15.4
13^
36^0
14'. 5
8.2
If:!
12.5
23.7
31.6
14.1
43.2
16*. 0
15.8
20^
12.5
16.6
21.5
19 9
53*^
19:4
23.7
"
*
-------
TABLE 1-7 RELATIVE STANDARD DEVIATIONS OF CONCENTRATIONS OF ACID EXTRACTABLE SEMIVOLATILE ORGANICS
AVERAGED OVER ALL SPIKE LEVELS (INCLUDING UNSPIKED SAMPLES)
00
co
COMPOUND
2-CHLOROPHENGL
Z-NITftOPHENOL
2?4-01METHYLPHENOL
2,4-DICHLOROPMENOL
2,1, 6-TRICHLOROPHENOL
4H;HLORO-3-H ET HY LP HENOL
2,4-DINITROPHENOi.
4,6-DINITRO-O-CRESOI.
PENTACHIOROPHENOI.
4-NITROPHENOL
POTU
22 .6
32.8
19.5
38.0
30.7
za'.a
52.6
56.7
19.2
12.5
IPU OS6
28.2
fir? 17
Hi!
27^4
77.2
42.5
39.0
32.5
1 PPS
30.6
2 30l9
30I9
16.5
20.6
44l 4
50.0
COBS
EPS
ER8HD
28.3
10.0
B:f
16.4
OSB_IL
35.8
io!e
20.8
36.3
42.0
29l 9
IPL
8.8
17^7
20.0
12.6
11.3
10.5
14*. 5
24.0
OSBL
17.6
13! 8
30.8
14^7
18.8
14.7
23J5
-------
TABLE 1-8. RELATIVE STANDARD DEVIATIONS OF CONCENTRATIONS OF METALS
AVERAGED OVER ALL SPIKE LEVELS (INCLUDING UNSPIKED SAMPLES)
oo
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
POTM
IPW
cse
PPS
COBS
EPS
EF8HD
IPH.IL
15.3
8.7
3.0
2.5
5.1
6.2
2.1
IS. 6
5.1
7.7
22.8
11.4
2.1
43.1
11.9
14.4
12.7
6.8
5.6
7.5
13.0
5.3
20.4
24.4
19.8
6.5
*
8.7
6.2
5.8
4.7
2.4
7.3
4.0
6.8
•
6.4
10.1
3.2
9.2
5.4
5.4
6.4
1.5
2.5
2.1
4.3
5.9
11.3
•
15.9
1.0
6.5
9.8
0.0
8.6
3.2
1.5
6.1
12.8
3.1
10.2
14.3
3.1
6.1
•
•
6.2
0.0
3.0
4.7
2.6
1K6
«
24.5
5.3
3.2
OSB_IL
6.2
6.2
12.3
7.9
3.6
20.9
6.7
2.9
I PL
16.2
1.5
1.7
0.9
1*.7
2.7
OSBL
6.7
1.4
0.7
2.7
2.7
-------
C. Summary of the Average Mean Recoveries of
Compounds in Spiked Residual Waste
90
-------
TABLE 1-9. AVERAGE PERCENT RECOVERIES OF PURGEABLE ORGANICS
IN SPIKED RESIDUAL WASTE SAMPLES
COMPOUND POTM
METHVLENE CHLORIDE 43.58
TR1CHLOROFLUORCMETHANE
1,1-DlCHLOROETHYLENE 29.33
Ul-DICHLOROETHANE 47.97
TRANS-li2-DICHLOROETHYLENE 37.80
CHLOROFORM 50.91
1,2-OICHLOROETHANE 58.00
Itltl-TRICHlOROETHANE 51.40
CARBON TETRACHLORIOE 52.40
BROMOOICHLOROMETHANE 63.94
1,2-DICHLOROPRCPANE 54.20
TRANS-1,3-D1CHLORCPROPENE 52.68
TRICHLOROETHYLENE 58.28
DiBROMGCHLGROMETHANE 62.00
CIS-lt3-DICHLOROPROPENE 52.59
1,1,2-TRlCHLOROETHANE 72.60
BENZENE 56.18
BRCMOFORM 65. 10
l,lt2»2-TETRACHLOROETH£NE 97.08
lil,2f2-r£TRACHLORC£THANE 94.75
TOLUENE 90.94
CHLOROBENZENE 69.96
ETHYLBENZENE 77.28
IPW
ass
PPS
182.69
117124
116.67
146.67
114.17
252.50
82.67
73.67
130.66
198.33
135.83
oloo
8.00
.00
120.06
95.83
361.00
54.31
76.67
97.83
COBS
90.52
4U39
82.83
73.67
88.00
110.83
56.00
43.75
95.63
84.33
90.00
10?Il7
95.33
115.67
74.50
118.33
86.50
75.33
78.17
87.50
86.83
EPS
EF8HD
IPN_IL
•
*
29.25
46.00
38.20
55.03
15.10
47.67
45.75
18.89
14.25
53.35
24.04
41.37
55.98
410.00
21.22
52.05
12.93
26.55
*
58.69
•
OSB_IL
92.11
98.12
98.90
86.47
87.00
95.81
86.82
80.03
88.14
99.82
113.79
97.89
68.81
96.98
91.98
72.55
53.92
121.94
62.83
77.34
97.25
112.20
100.73
I PL
72.45
*
6.09
75.40
82.40
82.72
95.52
62.44
53.84
•
%
71.64
93! 88
81.37
*
8.57
28.71
37.30
66.08
72.30
OSBL
69.86
•
27126
32.20
81.22
lolao
•
*
103^60
32.86
16.66
17.12
11.40
-------
TABLE 1-10.
AVERAGE PERCENT RECOVERIES OF BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS
IN SPIKED RESIDUAL WASTE SAMPLES
COMPOUND
1,3-DICHLOROBENZENE
1,4-D1CHLORGB£NZENE
1,2-OICHLOROBENZENE
HEXACHLOROETHANE
B1S(2-CHLOROETHYL» ETHER
8ISI2-CHLOROISOPROPVL) ETHER
HEXACHLGROBUTADIENE
NITROBENZENE
NAPHTHALENE
it2.4-TRICHLOROBENZENE
BISI2-CHLOROETHOXVIMETHANE
N-NITRGSODI-N-PROPYLAMINE
HEXACHLORCCYCLOPENTAOIENE
2-CHLORONAPHTHALENE
so ISOPHURONE
M ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-DJNITROTOLUENE
FLUORENE
2i4-OINITROTOLUENE
1,2-OIPHENYLHYDRAZINE
4-CHLOROPHENYL PHENYL ETHER
OIETHYL PHTHALATE
N-N1TROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
OI-N-8UTYL PHTHALATE
fLUQRANTHENE
PYRENE
BENZID1NE
8UTYLBENZYL PHTHALATE
6IS(2-ETHVLHEXYL» PHTHALATE
CHRYSENE/BENZOCAIANTHRACENE
3,3'-OICHLORUBENZIOINE
DI-N-CJCTYL PHTHALATE
BENZOCBI/BENZCXIOFLUORANTHENES
BENZ01AIPYRENE
INOENO(li2t3-C01PYRENE
OIBENZOCAH)ANTHRACENE
BENZOCGHIJPERYLENE
POTW
IPh
OSB
PPS
COBS
126.52
72.40
74.61
124.13
98.27
62.72
94.40
23.98
74.33
142.89
52.75
155.40
8.22
93.47
31.69
83.70
80.08
77.76
41.30
77.44
32.79
57.80
86.57
81.28
283.32
82.71
94.54
72.37
63.41
107.56
115.58
33.43
196.85
199.94
467.57
171.73
54.38
206.82
155.84
247.89
228.45
221.74
69.99
72.75
09. 76
82.13
118.00
82.73
107.92
86.79
82.31
133.18
70.33
401.86
29.70
123.12
63.90
99.21
95.43
89.64
756.24
96.84
78. 54
66.45
122.64
169.86
655.00
98.57
107.30
84.52
79.66
74.67
81.37
33.80
157.66
131.34
120.00
48.30
29.57
159.92
233.00
163.83
193.97
180.65
EPS EFBHO IPh_U OS6.1L
IPL
OSBL
20.47
15.98
17.49
55.30
138.33
20.82
42.82
92.41
19! 70
43.41
207.79
17.32
58.16
34.50
50.56
46.08
45.55
17.41
52.94
19.04
37.38
48.79
33.22
36.67
43.82
57.06
38.22
32.17
52.76
54.31
17.42
32.60
40!64
42.88
47.96
65.28
62.26
51.50
62.51
84.88
69.00
84.17
73.78
74.74
74.83
75.46
24.17
84.19
113.02
22.92
89.93
74.81
75.99
75.91
57.30
55.47
76.66
59.33
71.45
76.00
95.33
41.00
78.86
88.98
66.28
96.02
92.75
101.86
31.69
67.18
16.97
70.71
71.99
14.78
118.47
127.05
48.94 106.29
87.ea
5i. 45
237*03
1 78* 79
80.07
60.87
81.82
28.49
53.58
127.73
71.59
49.28
18.30
57.48
117.87
79.82
235.74
42.08
363.02
81.67
70.62
80.41
73.74
64.09
135.56
88.48
87.48
10.84
57.30
63.55
53.15
56.63
93.27
59.78
65.77
53.57
66.71
58.30
76.32
121.25
48.46
27.16
34.04
98.77
77.22
367.05
261.21
54.84
109.13
191.52
151.19
158.68
64.58
66.00
58.83
40.11
97.02
51.34
89.58
56.02
120.20
63.06
131.74
85.40
2929.14
115.17
73.24
83.93
101.00
100.18
39.03
68.34
81.80
95.33
17.92
JgjfJ
66*88
20.20
9
159.60
77.28
95.32
80*40
153*.50
91.20
89*04
105.00
119*.80
Io:2o?
78.36
79*60
45*68
116.20
75*90
65.96
309.20
10.00
49*48
55*60
*
66*45
80.25
107 I 56
72.56
147.00
206*80
10*00
70.80
102*24
90.00
88*25
73.80
101.60
69.56
187180
165.96
131*40
123.36
95*20
111.72
100.00
15.60
159*92
35.32
160.48
193.25
123.73
150.06
-------
TABLE 1-11.
AVERAGE PERCENT RECOVERIES OF ACID EXTRACTABLE SEMIVOLATILE ORGANICS
IN SPIKED RESIDUAL WASTE SAMPLES
Co
COMPOUND
2-CHLCROPHENOL
2-NITROPHENOL
PHENOL
2,4-DIMETHYLPHENOL
2,4-DlCHLOROPHENOL
2,4t6-TRICHLORQPHENCt
4-CHLORO-3-MErHYLPH£NOL
2.4-OIN1TROPHENOL
4,6-DINITRO-O-CRESOl.
P^NTACHLOROPHENOL
^-NITROPHENOL
|?'Z9
3*«??
68.61
25.67
S9*}|
104.42
52.61
i?S'U
663.25
IP*
92.51
100.18
69.83
22.56
46.16
123.11
102.50
92.30
31.48
131.99
103.85
OSB
PPS
COBS
111.78
133.08
118.75
20.99
125.77
119.52
108.75
116.50
101.45
50.18
118.14
EPS
EFBHD
IPH_IL
IPt
4.00
ttrtt
78.00
117.00
97^60
102^50
105.20
41.46
o!oo
46.20
-------
TABLE 1-12.
AVERAGE PERCENT RECOVERIES OF METALS
IN SPIKED RESIDUAL WASTE SAMPLES
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
POTW
IPH
OSB
PPS
COBS
80.98
103.93
101.64
95.7*
109.78
94.53
91.54
68.85
100.00
97.7f»
2. 30
75.41
102.61
1.68
91.68
83.72
92.92
99.00
86.84
98.60
74.40
92.50
&f nrt
4t>.60
42.80
93.50
5.56
4.44
»j.33
103.33
106.67
98.78
98.89
•
69.11
0.00
23.33
72.22
117.22
EPS
53.78
oj!60
96.22
110.09
9'*l33
81.68
87.35
53.58
0.00
86.87
110.54
EFBHO
IPH_IL
OSB_IL
IPL
OSBL
74.40
26.67
86.40
65.33
114.67
94.40
88. 67
112.53
98.53
60.00
.
70.67
•
•
10l'.43
98.57
108.84
96.55
105.69
•
99.00
•
3.86
98.06
126.90
•
83 53
103^53
132.35
69.41
120.00
82^59
«
22.12
94.82
95.29
•
*
10 6 '.49
34. 12
102 !86
106^08
.
114^46
.
*
103^86
48.21
99.36
107.94
99^01
*
114^22
-------
Appendix II. Potential Mobility (Leachate) Interlaboratory Study Data
95
-------
Legend for Verification Analyses
and Quality Assurance
for Potential Mobility (Leachate) Data*
Symbols Identification
Not determined.
< Lower detection limit of method.
( ) Found to be a statistical outlier and not included
in the calculations.
Z Standard deviation was not calculated because all
points in the data set were less than lower
detection limit of method and/or zero.
N Percent recovery was calculated to be less than
zero.
* Concentrations are reported as microgram of compound per liter of leaching
medium (parts per billion).
96
-------
A. Ink Pigment Leachate (Intel-laboratory)
97
-------
TABLE II-l.
PURGEABLE ORGANICS DATA—
INK PIGMENT LEACHATE, SPIKE LEVEL 0
00
COMPOUND
METHYLENE CHLORIDE
1 ,1-OICHLCROETHYLENE
1,1-OICHLOROETHANE
TRAN$-lt2-DICHLCROE¥HYLENE
CHLOROFORM
1, 2-OICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLORIOE
BROHOO1CHLOROME THANE
1,2-01CHLOROPROPANE
TRANS-lVa-OICHLOROPROPENE
TRICHLOROETHYLENE
OIBRONOCHLORONETHANE
CIS-1,3-OICHLOROPROPENE
1,1,2-TRICHLOROETHANE
BENZENE
l?l?2f2-T£TRACHLOROETH£NE
it 1,2,2-1ETRACHLOROE THANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED
N0_l
N0_2
930
400
(1550)
(959)
3220
0
1140
N0_3
19
N0_5
MEAN
26
0
0
8
745
46
Hz
3570
0
2090
328.86
9.63
7.05
2.45
6.07
106.19
73.87
95? 26
63.13
216.10
631.98
RSO
8.1
9.4
18.7
•
•
•
uJo
«
•
17ll
RECOVERY
6.
36*. 7
-------
Figure II-l. GC/MS chromatogram of purgeable organics by purge and trap—
Ink Pigment Leachate, unspiked
-------
TABLE I1-2.
PURGEABLE ORGANICS DATA—
INK PIGMENT LEACHATE, SPIKE LEVEL I
COMPOUND
o
o
1,1,2-TRICHLOROETHAN
BENZENE
l2-T
THANE
ADDED
2500
500
500
2500
500
2500
500
2500
0
NO. I
2780
114
394
1990
381
2450
334
1380
0
0
2490
0
46?
2380
0
379
366
4330
1760
3790
N0_2
(5660)
N0_3
2900
88.3
408
N0_4
1940
383
2330
256
840
8
0
2570
0
0
382
2390
0
226
248
(6490)
-------
Figure II-2.
GC/MS chromatogram of purgeable organics by purge and trap-
Ink Pigment Leachate, spiked
-------
TABLE II-3. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
INK PIGMENT LEACHATE, SPIKE LEVEL 0
o
t-o
COMPOUND
1,3-0 1C HLOROBENZENE
If 4- JICHLORU BENZENE
1,2-0 1C HLOROBENZENE
HEXACHLORQETHANE
B1S< 2-CHLOROEIHYLI ETHER
BIS(2-CHLOROISOPKDPVLJ ETHER
HEXACHLGROBUTADIENE
NITROBENZENE
NAPHTHALENE
1, 2, 4-TRlCHLCRQ BENZENE
B1S12-CHLOROETHCXYJ METHANE
N-NITROSOOI-N-PROPYLAMINE
HEX ACHL&ROCYCLO PENT ADI ENE
2-CHLC/RONAPHTHALENE
ISOPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-DINITROTOi.UENE
FLUORENE
2,4-DINITROTOLUENE
1 ,2-UIPHENYLHYORAZINE
4-CHLOROPHENYL PHENYL ETHER
DIETHYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
^-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ ANTHRACENE
UI-N-BUTYL PHTHALATE
fLUORANTHENE
PYRENE
BENZIOINE
BUTYLBENZYL PHTHALATE
PHTHALATE
BENZOUIPYRENE
INDENO<1,2,3-CDJPYRENE
OIBENZO « AH I ANTHRACENE
BENZOtGHI JPERYLENE
ADDED
0
0
0
0
0
0
0
0
0
0
0
0
0
0
J
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
N0_l
N0_2
N0_3
NQ_5
MEAN
RSD
RECOVERY
0
34
12U
19
0
0
0
171
306
0
207
8
0
0
26
17
0
<1o
Q
433
0
0
0
-10
0
0
0
0
'I
17
0
0
0
0
0
0
95
287
41
0
0
0
222
371
0
194
0
0
0
0
45
25
48
0
(16)
11
0
715
0
Q
< 10
12
0
0
0
74?
0
0
78
0
0
0
0
0
0
105
246
31
0
0
0
281
568
0
241
0
0
8
48
16
59
0
(29)
113
81
0
1150
8
0
11
(21)
0
0
0
42
0°
11
0
0
0
0
78
261
49
0
0
0
259
762
0
245
0
0
0°
47
13
29
0
11
59
30
0
453
8
0
<10
0
0
0
0
1090
8
156
0
0
o
8
0
84
335
65
0
0
0
245
804
0
258
0
0
o-
0
55
14
19
0
11
39
18
0
363
0
0
0
< IQ
0
0
0
0
0
0
< 10
0
0
0
8
5
79.2
251.4
41
0
0
0
235.6
562.2
0
229
8
0
0
44.6
<15.6
34.4
0
<10.6667
56.6
41.8
0
622.8
0
<10.2
<10.5
0
0
0
0
<379.4
0
0
<54.4
0
0
0
8
z
27.31
76.82
17.49
Z
Z
Z
42.00
223.95
Z
27.16
Z
Z
10.01
5.68
18.43
Z
0.58
41.64
27.25
Z
323.57
Z
0.45
1.00
Z
Z
z
504.92
63.51
Z
z
1
*
34.5
30.6
42.7
*
^
•
17.8
39.8
11*9
*
•
*
22.5
36.4
53.6
•
5.4
73.6
65.2
•
52.0
•
•
4.4
9.5
*
•
•
133*.l
1 16 • 7
•
*
•
•
-------
i i i i—i—i—r—T—i—\—I—T—i
Figure II-3. GC/MS chromatogram of base/neutral extractables—
Ink Pigment Leachate, unspiked
-------
TABLE II-4. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA —
INK PIGMENT LEACHATE, SPIKE LEVEL I
o
•P-
COMPOUND
1,3-OlCHLOROBENZENE
ADDED
N0_l
N0_2
N0_3
N0_4
M0_5
MEAN
RSO
1,2-DICHLORGBENZ
HEXACHLOROETHANE
BISI2-CHLOROETHYU ETHER
BISU-CHLOROISOPROPYL) ETHER
HEXACHLORGBUTAOIENE
NITROBENZENE
NAPHTHALENE
1,2,4-TRICHLOROBENZENE
BISiZ-CHLOROETHOXVt METHANE
N-NITROSODI-N-PROPYLAMINE
HEXACHLCROCYCLOPENTADI ENE
2-CHLORGNAPHTHALENE
1SOPHORONE
ACENAPHTHYtENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2.6-OINITROTOLUENE
FLUORENE
2,4-DlNlTROTOLUENE
1,2-DIPHENYLHYDRAZINE
4-CHLOROPHENYL PHENYL ETHER
OIETHYL PHTHALATE
N-NITROSODI PHENYL AM INE
HEXACHLGR08ENZENE
4-BfiUMJPHENYL PHENYL ETHER
PHENANTHRENE/ ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUOR AN THEN E
PYRENE
BENZ10INE
8UTYLBENZYL PHTHALATE
BIS<2-ETHVLHEXYL> PHTHALATE
EN
BENZOC AIPYRENE
JND£NG(l,2.3-CDtPYRENE
01 BENiOC AH) ANTHRACENE
BENZOJGHIIPERYLENE
J
500
ICO
0
100
500
500
100
0
100
0
100
100
0
500
100
0
100
100
500
500
0
100
500
0
500
500
0
100
500
100
100
0
0
500
500
500
100
0
0
0
0
442
303
31
167
413
447
70
661
85
165
178
9S
425
172
10
162
95
425
420
<10
83
600
0
241
610
<10
90
m
<10
246
88
*t7
0
8
0
0
331
248
25
140
358
476
52
538
88
159
138
93
0
377
152
12
151
77
404
355
*76
564
0
229
585
87
435
283
* 0
251
76
459
58
0
0
0
0
0
461
306
31
155
402
399
55
430
63
182
(58)
94
0
433
169
13
159
86
410
440
86
599
0
237
624
•ao
95
502
320
0
(277l>
98
(765 )
5^
0
0
0
0
0
364
232
23
138
322
486
77
333
77
153
137
8o-
440
113
124
91
286
416
10
50
479
0
213
525
< 10
76
395
267
0
22°7
94
440
58
0
0
0
0
0
470
269
23
198
437
575
91
387
89
233
161
97
a
551
142
175
67
530
611
13
103
631
0
222
561
< 10
84
396
361
0
99
490
61
9
§
0
0
413.6
271.6
26.6
159.6
386.4
476.6
69
479.8
80.4
172.4
153.5
9l'g
445.2
149.6
154.2
83.2
411
448.4
<10.6
79.6
574.6
0
228.4
581
<10
86.4
429.8
309.2
0
<23.75
247.4
91
5$ • fr
0
0
0
0
z
62.28
32.79
4.10
24.50
46.00
64.55
16.08
138.91
10.81
20.24
19.74
6.10
64.09
23.88
1.41
18.97
11.28
86.65
96.29
1.34
19.30
58.47
Z
11.30
39.50
Z
7.09
43.79
36.40
Z
Z
27.50
16.89
9.43
24.64
5.41
Z
\
^
15.1
12.1
15.4
15.4
11.9
13.5
23.3
29.0
11 7
12.9
6.7
1 4*. 4
16.0
12l3
13.6
21.1
21.5
12.7
24.2
10.2
4» 9
6.8
8 1 2
.2
11.8
iisla
6.8
10.4
5.4
9.7
"
*
RECOVERY
67
20
160
77
95
N
80
153
91
89
105
120
83
80
73
90
N
46
116
76
86
339
10
18
80
56
-------
Figure II-4 .
GC/MS chroma togram of base/neutral extractables —
Ink Pigment Leachate, spiked
-------
TABLE II-5.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT LEACHATE, SPIKE LEVEL 0
COMPOUND
2-CHLOROPHENOL
2-NITROPHENOL
PHENOL
2, 4-DIMETHYLPHENOL
2t4-DICHLCROPHENOt
2t4,6-TRICHLOROPHENOL
4-CMLORO-3-ME THYtP HENOL
2,4-OINITROPHENOL
4,6-DINITRO-0-CRESOL
PENTACHLOROPHENOl
4-NITROPHeNQL
ADDED
N0_l
N0_2
N0_3
0
8
0
0
0
0
0
0
0
0
(218
0
3060
88
0
0
0
0
439
3338
12S
0
0
0
0
0
0
495
0
3100
95
0
0
0
0
0
0
0
416
0
3210
104
0
0
0
0
8
0
NQ_5
2840
92
0
0
0
0
0
MEAN
442.75
3108
101.2
36.21
182.95
14.96
RSO
8.2
L4l8
RECOVERY
-------
TI
15
Figure II-5.
GC/MS chromatogram of acid extractables•
Ink Pigment Leachate, unspiked
-------
TABLE II-6.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA —
INK PIGMENT LEACHATE, SPIKE LEVEL I
o
oo
COMPOUND
2-CHLGROPHENOL
2-NIIROPHENOL
PHENOL
2,4-DIMETHlTLPHENOL
2,4-DICHLOROPHENOL
2i4,6-TRICHLOROPHENOL
4-CHLORG-3-METHYLPHENQL
2,4-DINITROPHENGL
4,6-DINITRO-OCRESOL
PE NTACHLQROPHENOL
*-NITROPHENOL
ADDED
500
o
1000
100
100
500
500
o
100
100
N0_l
(795)
0
4210
244
56
693
7*3
543
0
N0_2
475
0
3350
167
75
544
726
545
0
87
105
N0_3
510
0
3090
174
92
521
751
458
0
118
141
N0_4
460
0
3270
149
94
"I
0
112
115
N0_5
406
a
3300
166
73
537
578
451
0
93
91
MEAN
462.75
0
3t*8S
58§
685.2
488
0
102.5
105.2
S
43.25
Z
439.29
36.94
15.57
73.77
77.62
51.40
Z
14.84
25.26
RSD
9.3
•
zollf
20.0
iols
9
14.5
24.0
RECOVERY
4
•
n
78
117
98
^
ioi
-------
Figure II-6. GC/MS chromatogram of acid extractables—
Ink Pigment Leachate, spiked
-------
TABLE II-7. METALS DATA—
INK PIGMENT LEACHATE, SPIKE LEVEL 0
ELEMENT ADDED N0_l N0_2 N0_3 N0_4 N0_5 MEAN S RSO RECOVER*
CADMIUM 0 12 8 8 4 4 7.2 3.35 46.5
CHROMIUM 0 336 336 350 336 343 340.2 6.26 1.8
COPPER 0 <50 <50 <50 <50 <50 <50 Z .
LEAD 0 7610 7460 7510 7510 7610 7540 67.08 0.9
NICKEL 0 64 64 64 64 64 64 0.00 0.0
ZINC 0 1560 1480 1560 1650 1560 1562 60.17 3.9
-------
TABLE II-8. METALS DATA—
INK PIGMENT LEACHATE, SPIKE LEVEL I
ELEMENT
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
ZINC
AOOED
200
500
500
XOOOO
500
2000
N0_l
213
502
544
18400
598
3790
N0_2
221
481
556
18100
576
3700
N0_3
213
509
533
18300
576
3790
N0_4
213
502
544
18000
4050
N0_5
217
509
544
18400
576
3880
MEAN
215.4
500.6
544.2
18240
584.8
3842
S
3.58
11.50
8.14
181.66
12.05
132.55
RSO
1.7
1 5
1.0
2.1
3.5
RECOVERY
104
114
-------
TABLE II-9.
METALS DATA —
INK PIGMENT LEACHATE, SPIKE LEVEL II
ELEMENT ADDED
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
ZINC
1000
5000
LOOO
50000
1000
15000
N0_l
1100
2150
N0_2
1090
2130
1050
56500
11 TO
18700
N0_3
1090
2160
1090
56500
1120
18900
N0_5
5750
187*
MEAN
1096
2148
1064
56900
1S800
§.48
.95
19.49
547.72
33.62
141.42
RSO
8:1
i:8o
2.9
O.S
RECOVERY
-------
B. Organic Still Bottoms Leachate (Interlaboratory)
113
-------
TABLE II-10.
PURGEABLE ORGANICS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL 0
COMPOUND
METHYLENE CHLORIDE
St 1-D1CHLORCJE IH YLENE
t1-OICHLOROETHANE
RANS-lt2-OICHtOftO£TMVLENE
CHLOROFORM
1,2-OlCHLOROETHANE
1,1 ,1-IRICHLOROETHANE
CARBON TETRACHLORIOE
BROMOOKHLOROME THANE
1,2-DICHlCROPROPANE
TRANS-li3-OICHLOROPRCPENE
TRICHLOROETMYLENE
OIBROMOCHLOROMETHANE
CIS-1,3-0 JCHLORCPRGPeNE
1,1,2-TRICHLOROETHANE
BENZENE
BROMOfORM
1,1,2,2-TETRACHLOROETHENE
U1.2I2-TETRACHLGROETHANE
TOLUENE
CHLOROBENZENE
ETHYL8ENZENE
AD0ED
0
0
0
0
0
a
o
a
o
o
0
0
0
0
0
0
0
0
N0_l
(1080)
8120
153000
55500
17200
8T600
19300
0
0
0
0
148000
0
0
234000
0
0
183000
142000
646
0
0
738
5340
157000
51900
15300
85200
24800
0
140000
262000
132000
102000
486
N0_4
706
6960
178000
55800
19600
105000
26600
0
0
152000
0
282030
N0_5
815
0653
201000
63500
23400
101000
26600
1321
102i
325
0
0
MEAN
758.75
7348
170600
56300
18460
96760
23743
0
0
149400
0
267600
144403
111480
493
0
47.17
1282.33
19475.63
4311.03
3163.54
9634.73
3266.19
Z
Z
12361.23
22733^24
24684.00
18930.19
131.20
Z
RSO
6,2
17.5
17.1
8.3
es
I7.l
17.0
26.6
RECOVERY
-------
-------
TABLE 11-11.
PURGEABLE ORGANICS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL I
COMPOUND
METHYLENE CHLORIDE
I,1-OICHLCROETHVLENE
1,1-DICHLGROETHANE
TRANS-1,2-OICHLOROETHYLENE
CHLOROFORM
1,2-DICHLOROETHANE
It1,1-TRlCHLGROETHANE
CARBON TETRACHLORIDE
BRGM&DICHLOROMETHANE
1,2-DICHLUROPROPANE
IRANS-1,3-OICHLOROPROPENE
TR1CHLOROETHYLENE
OIBROMOCHLOROMETHANE
CIS-U3-OICHLOROPROPENE
1,1,2-TRICHLOROETHANE
BENZENE
BROMOFORN
l.li2»2-TETRACHLOROETH£NE
l,l,2f2-TETRACHLUROETHANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED
250000
50000
250000
50000
250000
50000
250000
0
250000
0
0
50300
250000
0
50000
50000
250000
250000
250000
N0_l
178000
8960
127000
135000
36200
323000
17300
32400
0
0
0
151000
0
0
317000
109000
0
20300
23300
52500
56700
42200
N0_2
162000
104000
96200
253000
11400
21200
0
0
0
132000
0
0
309000
59800
0
15800
19000
33700
35800
24600
NQ_3
166000
6250
113000
106000
30800
283000
15600
16600
0
132000
0
323000
66200
0
13200
18200
36100
38300
25200
N0_4
1840JO
9730
121000
128000
32300
297000
14400
21100
0
0
0
151000
312000
66700
17300
21400
32800
34400
20600
N0_5
187000
8030
48800
29900
MEAN
175400
8200
121600
124440
34560
299800
15920
25762.2
0
0
0
146600
0
319400
82140
0
16620
20390
42640
42800
28500
10990.91
1301.81
14758.05
24092.90
4432.04
34945.67
3519.52
8783.37
14842.51
10691?12
24670.18
2568.46
2049.39
11787.20
9604.95
8339.06
RSD
6.3
15.9
12.1
19.4
12.8
11.7
22.1
34.1
3.3
30.0
.
8:5
RECOVERY
70
N
27
32
81
N
10
104
33
•
N
N
17
17
11
-------
Figure II-8.
GC/MS chromatogram of purgeable organics by purge and trap —
Organic Still Bottoms Leachate, spiked
-------
TABLE 11-12.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL 0
CUNPOUNU
1,3-DICHLOROBENZENE
1.4-OICHLOR08ENZENE
1,2-OtCHLOROBENZENE
HEXACHLOKOETHANE
blSC2-CHLORGETHYL) ETHER
BIS(2-CHLOROISOPRCPYL) ETHER
HEXACHLOROBUTA01 ENE
NITROBENZENE
NAPHTHALENE
1, 2.4-TRICHLOROBENZENE
BIS12-CHLOR PHTHALATE
Aooeo
N0_l
N0_2
N0_3
N0_4
NO_5
MEAN
RSO
RECOVERY
DIPYREN
OIBENZGl AH) ANTHRACENE
0
0
0
0
0
8
0
0
0
0
0
0
0
0
0
0
13
0
0
0
46
0
546
0
0
0
0
0
0
0
8
0
8
0
8
0
0
0
3
0
Q
0
0
0
0
0
0
0
0
0
(30)
0
0
0
26
0
Q
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
8
Q
Q
Q
0
-------
VD
I I ! I 1 I 1 I
Figure II-9. GC/MS chromatogram of base/neutral extractables
Organic Still Bottoms Leachate, unspiked
-------
TABLE 11-13.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL I
COMPOUND
It 3-OICHLORiJBENZENE
1,4-OICHLORCBENZENE
i ,2-OICHLOROBENZENE
HEXACHtOROETHANE
BIS(2-CHLCROETHYLJ ETHER
8IS<2-CHHJRGISOPRGPVL) ETHER
HEXACW.OR08UTADIENE
NITROBENZENE
NAPHTHALENE
lt2t4-TRlCHLOROBeNZENE
BIS 12-CHLOROET HCXVI METHANE
N-NITROSODI-N-PROPYLAMINE
HEXACHLOROCYC10PENTAOIENE
2-CHLORCNAPHTHALENE
ISOPHORDNE
ACENAPHTHYLENE
ACENAPHTHENE
OIHETHYL PHTHALATE
2,6-OINITROTOLUENE
FLUORENE
2t4-DINIIROTOLUENE
1,2-DIPHENYLHYORAZ1NE
4-CHLOROPHENYL PHENYL ETHER
01 ETHYL PHTHAtATE
M-NITROSUOIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
OI-N-BUTYL PHTHALATE
FLUCRANTHENE
PYRENE
BENZIdlNE
BUTYLBENZYL PHIHALATE
B1S<2-ETHYLHEXYL> PHTHALATE
CHRYSENE/BENZOfA)ANTHRACENE
3,3»-QICHLORGBENZIOINE
OI-N-OCTYL PHTHALATE
BENZOt BJ/BENZOIKIFLUORANTHENES
BENZCIAJPVREN6
INOENOI1,2,3-CDJPYRENE
01BENZOtAH)ANTHRACENE
BENZCHGHIIPERYLENE
ADDED
0
500
100
J
100
500
500
100
0
100
0
100
100
0
500
100
0
1JJ
100
500
500
0
100
500
0
500
500
100
500
100
100
0
0
500
500
500
100
0
0
0
N0_l
N0_2
N0_3
N0_4
N0_5
HE AN
RECOVERY
0
(708)
80
0
200
516
445
143
0
212
0
^3
0
534
100
0
97
49
503
409
206
920
Q
593
600
0
97
523
100
18
0
1010
35
1050
248
0
0
0
0
0
286
74
0
215
521
344
170
0
202
0
<39
0
450
91
Q
It
454
254
77
149
882
0
530
535
0
95
466
82
18
0
(211)
638
166
635
153
0
0
0
0
0
364
83
0
192
475
297
117
0
204
0
*67
0
461
85,
0
91
84
471
436
2 05
1340
0
742
713
0
80
567
86
17
0
10
710
215
714
158
0
0
0
0
0
282
84
0
1 73
579
287
136
0
169
0
<10
65
0
480
84
0
97
77
496
269
85
1320
0
636
514
0
122
583
110
15
0
14
742
193
811
214
0
0
0
0
0
397
(123)
0
276
596
441
169
0
247
3
110
0
631
(140>
0
119
108
616
371
95
208
1410
J
784
722
0
132
654
122
<1Q
0
898
274
(1170 )
0
0
0
0
0
332.25
80.25
0
537 ^ 9
362.8
147
0
206.8
0
70.8
0
511.2
90
0
99
73.8
508
347.8
81
187.8
1174.4
o
657
616. 8
558.6
100
<15.6
0
799.6
176.6
802.4
193.25
o
0
0
0
Z
57.34
4.50
I
39.26
49.25
76.32
22.64
I
27.85
Z
25.50
I
74.35
7.35
Z
11.58
24.59
63.48
82.27
9.27
26.57
252.16
I
104.90
97.29
21.25
70.02
16.61
3.36
z
2.00
151.17
88.59
155.90
45.79
I
I
17 3
5,6
18*6
9.2
21.0
15.4
13*5
36*.0
14*5
8.2
ii:5
If:!
1 A I
21*5
16*0
15.8
12*,5
16.6
21.5
ttii
50.2
19.4
23.7
*
.
66
80
211
108
73
147
207
10
71
102
90
74
102
70
188
166
131
123
95
112
100
16
160
35
193
*
*
•
-------
Pigure 11-10.
GC/MS chromatogram of base/neutral extractables
Organic Still Bottoms Leachate, spiked
-------
TABLE 11-14.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL 0
NJ
COMPOUND 400EO
2-CHLOROPHENOi 0
2-NITROPHENOL 0
PHENOL 0
2t4-DlMETHVLPHENOL 0
2,4-DICHLCRGPHENOC 0
2i«.6-TRICHLOROPHENCL 0
4-CHLORO-3-HETHYLPHENOC 0
2.4-DINITROPHENOI. 0
4,6-QINITRO-O-CRESOL 0
PENTACHLOROPHENOL 0
4-NITRUPHENOL 0
N0_l
N0_2
N0_3
N0_5
MEAN
0
0
231
0
0
o
0
0
0
0
0
236
0
0
0
0
0
0
0
0
0
0
217
0
0
0
0
0
0
0
0
0
0
174
0
0
0
0
0
0
0
0
0
0
117
8
§
0
0
0
0
0
0
195
0
8
A
Q
o
I
49.96
Z
Z
»
z
I
RSO
25
RECOVERY
-------
TI
Figure 11-11. GC/MS chromatogram of acid extractables—
Organic Still Bottoms Leachate, unspiked
-------
TABLE 11-15.
ACID EXTRACTABLE SEMI VOLATILE ORGANICS DATA —
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL I
COMPOUND ADDED
2-CHLORCPHENOt 500
2-NITROPHENCL , nA
PHENOL 1000
2t4-DIMETHYLPHENOL 100
2,4-OICHUDRCPHENOL 100
214,6-TRICHLQROPHENOL 500
4-CHLORO-3-METHYLPHENOC 0
2,4-DJNITROPHENOL 500
4,6-DINITRO-a-CRESOL 0
PENTACHLOROPHENOL 100
4-NITROPHENOL 100
N0_l
17o8
<25
108
77
0
47
N0_2
187
0
<25
io!
202
0
0
37
N0_3
14
N0_4
N0_5
231
MEAN
34
S
31.88
29.87
10.11
14.69
15.73
30.53
10.85
RSO
17.6
2ll
30.6
! 7
.8
.7
& T» I
18.8
14. T
23.5
-------
NJ
TI
T 1 T
T 1 1 T
T 1 T
Figure 11-12. GC/MS chromatogram of acid extractables—
Organic Still Bottoms Leachate, spiked
-------
TABLE 11-16.
METALS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL 0
ELEMENT AOOEO
CADMIUM 0
CHROMIUM 0
COPPER 0
LEAD 0
NICKEL 0
ZINC 0
N0_l
12
23600
268
1480
6090
N0_2
16
23200
268
1460
5650
N0_3
12
23600
293
1440
5560
N0_4
12
(29)
23600
268
1460
5560
N0_5
12
24300
243
1400
6090
MEAN
12.8
23640
268
1448
5790
S
1.79
0.00
296.65
17.68
30.33
276.32
RSD
14.0
0.0
1.3
6.6
2.1
4.8
RECOVERY
-------
TABLE 11-17.
METALS DATA-
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL I
to
ELEMENT
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
ZINC
AODEO
200
200
25000
1000
2000
4000
N0_l
227
113
47900
1380
3160
10900
N0_2
Hi
47400
1360
3210
10300
N0_3
223
125
47900
1380
3250
10200
N0_4
219
125
48700
1360
3230
10300
N0_5
219
125
47900
1360
3250
10600
MEAN
223.8
1368
3220
10460
S
5.22
3.83
466.90
10.95
37.42
2S8.10
RSD
2.3
3.1
1.0
o.a
1.2
2.8
RECOVERY
105
ill
11
-------
TABLE 11-18.
METALS DATA —
ORGANIC STILL BOTTOMS LEACHATE, SPIKE LEVEL II
oo
ELEMENT ADDED
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
ZINC
N0_l
1010
479
49000
5570
18400
45200
N0_2
1HS
49000
5570
18000
44700
N0_4
1070
49000
5570
17700
44600
N0_5
1080
479
49000
5500
17500
45200
HE AM
37.75
3:2}
294.1
RSO
3.6
1:1
0.7
RECOVERY
102
18
109
112
-------
Appendix III. Total Content Interlaboratory Study Data
129
-------
Legend for Verification Analyses
and Quality Assurance
for Total Content Interlaboratory Study Data*
jaymbols Identification
Not determined.
< Lower detection limit of method.
( ) Found to be a statistical outlier and not included
in the calculations.
Z Standard deviation was not calculated because all
points in the data set were less than lower
detection limit of method and/or zero.
N Percent recovery was calculated to be less than
zero.
* Concentrations are reported as microgram of compound per gram of residual
waste (parts per million).
130
-------
A. Ink Pigment Waste (Interlaboratory)
131
-------
TABLE III-l.
PURGEABLE ORGANICS DATA—
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL 0
UJ
K>
COMPOUND
l-
RCEIHANE
D
TRICHLOROETHYLENE
1,1,2-TRICHLOaOETHANE
BENZENE
Wi^-TETRACHLCROETHENI
tJlIzII-TETRACHLOROETHANE
CHLORO&ENZENE
ETHYLBENZENE
ADDED
N0_l
NO, 2
N0_3
N0_4
N0_5
MEAN
RSO
RECOVERY
0
o
0
o
0
0
0
0
0
°0
o
o
0
0
0
0
0
8
8.2
1.1
/%
Q
0.39
0
°0
0
9.4
Q
3-i
5.8
"£
Vi
7.4
0.8
0
0
0
o
*0
0
8.1
o
0
4.5
^t
80
5.8
0.45
0
0
8
0.34
0
0
8
5.5
0
2.8
0
3.7
2.9
2?7
56
4.6
0.66
0
0
8
0.35
0
0
0
0
0
Z.I
0
4
2.r
48
1.8
46
3.8
0.45
0
0
0
0
0.25
8
4.3
0
0
l'l
2.4
1.8
36
1.4
33
5.96
0.692
0
0
0
0
0.346
0
!
6.46
0
2.8?
5:8
52.4
573i
1.85
0.27
Z
Z
i
0.06
Z
2.18
Z
0.83
o!&8
18.86
39 : 3
*
•
*
•
*
•
33?8
«
*
29! 2
30^9
22.1
29.5
33.0
-------
CO
OJ
Figure III-l.
GC/MS chromatogram of purgeable organics by purge and trap—
Ink Pigment Waste (Interlaboratory), unspiked
-------
TABLE III-2.
PURGEABLE ORGANICS DATA —
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL I
CO
COMPOUND ADDED
METHYLENE CHLORIDE 1.9
Itl-OlCHLOROETHVLENE 1.9
1,1-DICHLOROETHANE 2
TRANS-1.2-DICHLOROETHYLENE 2
CHLOROFORM 1.9
1,2-OICHLOROEIHANE 2
l.ltl-TRICHLOROETHANE 2
CARBON TETRACHLORIDE 2
BRQMODICHLOROMETHANE 1.9
1,2-DICHLOROPROPANE 2
TRANS-lt3-DICHLOROPROPENE 2
TRICHLOROETHYLENE 1.9
01BROHOCHLGROHETHANE 2
CIS-lr3-DICHLOROPROPENE 1.6
1,1,2-TRICHLOROETHANE 2
BENZENE 1.9
BRCHOFORM 2
1,1.2,2-TETRACHLOROETHENE 2
l,l,2t2-TETRACHLOROETHANE 1.9
TOLUENE 2
CHLOROBENZENE 1.9
ETHYLBENZENE 1.9
N0_l
1.2
0.92
0.97
0
0.94
0
0
0.9S
5.3
0.89
0.9
7.6
2.9
0.93
4.6
3.4
41
3.3
47
N0_2
(12)
1.4
0.72
0.66
0.64
0
0.87
0.41
0
0
N0_4
N0_5
.8
02)
MEAN
4.15
1.234
0.956
0.892
1.0S8
RSD
RECOVERY
0.85
0.33
0.19
0.26
0.31
0.24
0.32
0.25
0.42
0.04
0.27
0.25
0.35
0.95
7.09
0.69
7.89
-------
TABLE III-3.
PURGEABLE ORGANICS DATA—
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL II
COMPOUND
METHVLENE CHLORIDE
It1-QICHLCROETHYLENE
1,1-DICHLOROETHANE
TRANS-lt2-OICHLOROEIHYLENE
CHLOROFORM
1,2-OICHLOROETHANE
IfItl-rRICHLOROETBANE
CARBON TETRACHLGRIDE
BROMOD1CHLQROMETHANE
1,2-DICHLOROPROPANE
TRANS-1.3-OICHLOROPROPENE
TRICHLOROETHYLENE
DIBROMOCHLOROMETHANE
CIS-l,3-01CHLOROPROPENE
1,1,2-TRICHLOROETHANE
BENZENE
BROMOFORM
1t1i2t2-TEIRACHLOROETHENE
1.1.2t2-TETRACHLOROETHANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
AOOEO
N0_l
N0_2
N0_3
N0_4
N0_5
MEAN
RSO
9.9
9.9
10
10
10
10
10
10
9.9
10
10
9.9
10
10
10
10
10
10
10
10
7.7
4.3
5.5
3.6
6.1
3.1
6.5
5.5
4.8
(5)
(5*i)
7.4
6.2
7.8
6.2
60
U
5.2
3.2
4.6
2.9
5.2
2.9
5.1
2l9
4.8
8.2
3.9
3.5
0
4.9
1.1
4.4
3.6
36
6.9
39
6.5
3.6
4.2
3.1
4.9
3.1
5.2
4.5
3.5
2.7
4.3
10
3.8
3.5
5.°7
4.9
6.6
6
43
75§
4.8
3.5
4.8
3.4
4.9
5.4
4.5
3.5
2.6
4.6
6.7
3.9
3.5
5ll
3.4
2.7
3.7
2.9
5.3
1:1
3.2
3.2
4.9
6.3
3.8
4.1
4.1
2.5
5.34
3.66
4.82
3.18
5.28
3.02
5.54
4.74
3.74
2.85
4.82
8.84
3.85
3-5S
5.32
4.28
4.94
4.16
37.6
6.9
40.6
1.23
0.40
0.48
0.31
0.49
0.08
0.56
0.43
3.62
0.26
9.44
2.74
0.06
0.10
1.30
U83
14.91
2.82
22.77
21.1
11.0
10.0
9.8
9.3
l|*:!
*J:S
8:i
U:t
39.7
40.8
56.1
RECOVERY
N
30
31
\l
38
28
48
38
44
25
43
9
II
N
46
N
-------
u>
o>
p
OJ
O
H
-------
TABLE III-4. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL 0
U)
CGMPOUND
lt3-OICHLOROB£NZENE
1,4-OICHLOROflENZENE
1,2-OICHLOROBENZENE
HEXACHLtROETHANE
BIS(2-CHLOROETHYL» ETHER
BIS(2-CHLOROISOPROPYL1 ETHER
HEXACHLOROBUTADItNE
NITROBENZENE
NAPHTHALENE
1,2.4-TRICHLORCbENZENE
BlS(2-CHLOROETHOXY)HETHANE
N-N1TROSOOI-N-PROPYLAMINE
HEXACHLOROCYCLOPENTADIENE
2-CHLORONAPHTHALENE
1SCPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-OINI TROTOLUENE
FLUORENE
2 , 4-0 INI TROTOLUENE
1,2-OIPHENYLHYDRAZINE
4-CHLOROPHENYL PHENYL ETHER
OIETHYL PHTHALATE
N-NITROSODIPHENYLAMINE
HEXACHLOROBENZENE
4-BKONGPHENYL PHENYL ETHER
PHENANTHRENE/ANTHfcACENE
OI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZI01NE
BJTYLBENZYL PHTHALATE
BISI2-ETHYLHEXYLJ PHTHALATE
CHRYSENE/8ENZOUJAN.THRACENE
t
OI-N-OCTYL PHTHALATE
BENZOm/BENZOJKIFLUORANTHENES
BENZCHA1PYRENE -
tNOENOC 1,2,3-CDIPYRENE
DIBENZGIAHIANTHRACENE
BENZCHGHIIPERYLENE
AOOEO
0
0
0
3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
j>
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
N0_l
0
20
24
0
0
0
0
0
47
0
12
0
S
0
4.7
5.8
1.5
0
11
8
0
1.5
0
0
0
25
0
7.1
4.8
0
0
11
6.5
0
0
5.3
6.4
Q
0
N0_2
0
27
33
0
0
°0
0
67
0
8.6
0
°0
0
11
7.7
1.8
0
18
0°
0
4.2
0
0
0
42
0
9.3
5.7
0
0
^2
7
0
0
3.2
5.2
Q
(2.2)
N0_3
0
52
65
0
0
0
0
0
165
0
22
0
0
0
0
36
18
3.8
0
33
8
0
4.9
0
0
0
82o
18
12
0
0
(13)
0
0
111)
8.7
0
0
N0_4
0
26
29
0
0
0°
0
82
0
16
Q
2
Q
13
12
2.3
0
20
8
0
2.5
0
0
0
68
11
6.2
0
0
12
6.6
0
0
3.4
5.3
Q
0
N0_5
Q
45
50
0
0
0
0
0
114
0
15
g
0
23
13
2.9
0
28
8
0
4.2
0
0
0
13
8.4
0
0
14
7.9
0
0
3.7
6.5
4.7
0
0
MEAN
0
34
40.2
0
0
0
95
14.72
0
0
17.54
11.3
2.46
0
22
0
3.46
0°
0
57.8
11.68
Q
0
12.25
7
0
0
4.78
5.85
<3.68
0
0
S
Z
13.73
16.96
Z
Z
1
46.15
Z
4.99
Z
Z
Z
12.24
4.78
0.92
Z
8.63
Z
7
1.41
\
24.54
4.15
2.88
Z
1.26
0.64
Z
Z
3."l3
Z
I
RSO
t
40.4
42.2
*
^
4-fl* 6
9
33.9
*
^
69.8
42.3
37.3
S9*.2
40.7
42.5
35^5
38.9
^
10.3
9.1
44.7
11.9
84.9
*
RECOVERY
-------
to
00
TI
IS
_£5_
Figure III-3.
GC/MS chromatogram of base/neutral extractables—
Ink Pigment Waste (Interlaboratory), unspiked
-------
TABLE III-5. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL I
COMPOUND
1.3-DICHLOR08ENZENE
1.4-DICHLGROBENZENE
i,2-OICHLQROBENZENE
HEXACHLORGETHANE
81SC2-CHLCRGETHYLI ETHER
BIS(2-CHLGrtOlSOPROPYL» ETHER
HEXACHLOR08UTADIENE
NITROBENZENE
NAPHTHALENE
1,2,4-TRtCHLORGBENZENE
BIS(2-CHLOROETHOXYJMETHANE
N-N1TROSODI-N-PROPYLAMINE
HEXACHLOROCYCLOPENTAOIENE
2-CHLORONAPHTHAL ENE
ISOPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2.6-i)INITROTOLUENE
FLUORENE
2t4-DIN1TROTOLUENE
I.2-DIPHENVLHYDRAZINE
4-CHLOROPHENYL PH6NVL ETHER
OlETHYL PHTHALATE
N-N1TROSOOIPHENYLAH1NE
HEXACHLOROBENZENE
4-BRGHOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZID1NE
BUTYLBENZYL PHTHALATE
BISC2-ETHYLHEXYLI PHTHALAIE
CHRYSENE/BENZO(A IANTHRACENE
3,3'-DlCHLOROBENZIDINE
DI-N-OCTYL PHTHALATE
BENZOi Bl/BENZCHKJFLyORANTHENES
BENZOIAIPYRENE
1NDENCH 1,2,3-COJPYRENE
DIBENZOIAH)ANTHRACENE
BENZOiGHlIPERYLENE
ADDED
N0_l
N0_2
NO 4
N0_5
MEAN
RSD
1.71
10.96
17.04
2
2
2
2.05
10.03
32.1
2.2
8.07
2.02
1.92
2.02
22.17
17.11
7.04
2.01
12.05
12.19
2.01
2.02
2
1.61
2.07
41.34
2.01
22.49
23.21
2.01
2.02
32.23
12.1
2.01
2.03
26.32
12.38
0
0
12.03
1.1
16
18
3.1
J.64
0.67
0.94
i.5
37
l.l
4.6
1.4
<0.5
0.79
0.59
15
10
4.3
6.7
12
6.4
<0.5
i
2.5
2.5
1.6
1.9
47
22
20
1.9
2.3
41
12
<0.5
<0.5
it
0
0
14
0.92
21
24
3.2
3.1
1.1
0.96
4.6
44
1.4
4.9
1.2
<0.5
0.96
0.56
18
13
2.6
5.9
15
7.9
0.53
1.3
1.9
2.7
2.6
2.5
52
0,57
26
20
2.6
2.6
47
16
<0.5
<0.5
27
14
8
15
0.97
16
2.1
1.5
0.6
0.95
0.48
31
0.8
3.7
1.9
<0.5
0.6
0.39
12
8.5
2.1
4.9
10
5.3
<0.5
1.2
0.72
2.1
34
1.2
12
1.8
7.5
<0.5
<0.5
15
6.3
8.6
0.996667
17.3333
19.3333
2.8
1.74667
0.79
0.95
2.19333
37.3333
4.4
1.5
<0.5
0.783333
0.513333
15
10.5
3
5.83333
12.3333
6.7
<0.51
1.16667
2.23333
2.9
1.64
2.16667
44.3333
1.02333
17.3333
2.1
2.16667
40.3333
11.8333
<0.5
<0.5
22.6667
10.4333
0
0
12.5333
0.09
3.21
4.16
0.61
1.25
0.27
0.01
2.15
6.51
0.30
0.62
0.36
Z
0.1S
0.11
3.00
2.29
1.15
0.90
2.52
1.08
0.02
0.15
0.31
0.53
0.94
0.31
9.29
4*62
0.44
0.51
7.02
4.25
Z
I
6.66
3.88
3***
9.3
18.5
21.5
21.7
71.5
34.3
1.1
97.8
17.4
27.3
14.2
24.0
23*0
!o:o°
21.8
38.4
15.5
20.4
16.1
3.4
13.1
13.7
18.2
57.4
21*0
38.7
26.5
26.6
20.8
23.7
17.4
35.9
m
29.4
37.2
27.5
RECOVERY
SB
N
N
1*0
87
39
46
22
N
50
N
75
25
N
N
8
290
N
55
25
58
N
145
102
105
5?
37
43
25
68
37
104
-------
TABLE III-6.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL II
COMPOUND
1,3-OlCHLOROBENZENE
1,4-DICHLOROBENZENE
1 ,2-OICHLORGBENZENE
HEXAtHLOROETHANE
BIS(2-CHLGRQETHYL) ETHER
BIS(2-CHLOROISOPROPYL» ETHER
HEXACHLOROBUTAOIENE
NITROBENZENE
NAPHTHALENE
1,2.4-TRICHLOROBENZENE
BIS42-CHLQROETHOXYJ ME THANE
N-NITROSODI-N-PROPYLAMINE
HEXACHLOROCYCLOPENTAOIENE
2-CHLORONAPHTHAL ENE
I- ISOPHORONE
*• ACENAPHTHYLENE
O ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-DINITROTOLUENE
FLUORENE
2t4-OINITROTOLUENE
1,2-DIPHENYLHYDRAZlNE
4-CHLOROPHENYL PHENYL ETHER
DIETHYL PHTHALATE
N-NITROSODIPHENYLAMINE
HEXACHLORO BENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUOR ANTHENE
PYRENE
BENZI01NE
BUIYLBENZYL PHTHALATE
BIS42-ETHYLHEXYL) PHTHALATE
BENZO( A) PYRENE
i«iB?Mtfja
BENZOtGHUPERYLENE
ADDED
85.22
10.02
1J
10.02
10.23
50.13
160.51
11
40.34
10.02
10.12
9.6
10.08
110.83
85.56
35.22
10.05
60.24
60.96
10.02
10.04
10.11
10.11
8.07
10.33
206.68
10.05
112.44
116.04
10.34
10.09
161.16
60.48
10.04
10.13
131.59
61.88
0
0
60.16
N0_l
6.2
44
189
18
5.7
8.1
8
13
169
17
39
2.7
1.5
5.6
21
92
182
24
34
59
41
14
6.6
7.2
5i!
6.5
72
6.4
97
78
0.5
8.8
64
47
4
J
52
N0_2
N0_3
N0_4
N0_5
MEAN
RSD
9.1
58
263
29
10
12
2 2
202
24
56
3.9
1.8
8.6
25
126
249
33
42
81
56
17
9.9
10
15
7.4
11
112
76
1.1
(4.0)
68
68
14
11
76
96
0
0
111
9.3
62
227
23
7.5
11
20
I72i
45
2.2
1.4
5.4
20
96
202
29
48
68
50
9.7
11
12
5.9
8.5
ioi
84
0.91
7.5
69
Ii
8.6
69
75
0
0
95
11
67
260
19
6.9
6.2
12
19
168
41
1.8
1
7.7
23
103
202
27
40
68
52
14
9.6
13
(6.3)
5.9
1.8
82
6.7
118
89
1.1
8.6
57
74
10
6.5
78
94
0
0
89
14
8J
272
20
6.3
3.9
14
14
*s
37
1.2
0.29
8.3
17
113
233
34
55
80
64
9.8
9.1
8.5
12
6
"ft
7.9
108
79
3.8
7.1
(23)
52
4.3
16
66
75
0
84
9.92
62.2
z«:i
7.28
8.24
1 T* 6
181
22.6
43.6
2.36
1.198
7.12
21.2
106
213
29.4
43.8
71.2
52.6
13.56
8.98
9.94
12.75
6.06
108
81.2
0.882
8
64.5
62.4
8.26
11.02
68.8
77.4
0
0
86.2
2.86
13.12
34.27
4.44
1.66
3.35
2.45
3.91
15.51
4.83
7.54
1.02
0.58
1.52
3.03
13.73
26.40
4.16
8.01
9.26
8.41
2.58
1.36
2.24
1.50
0.83
?:8
5.26
0.25
0.83
5.45
12.10
5.44
3.71
9.15
19.73
Z
Z
21.65
28.8
21.1
14.2
20.4
22.8
40.6
20.4
22.2
8.6
21.4
17.3
43.3
48.6
21.3
14.3
13.0
12.4
I3lo
16.0
19 .0
15.2
22.5
11.8
13.7
17*3
&Is
28.3
10.4
8.4
19.4
65.9
33.7
13.3
25.5
25.1
RECOVERY
l«
III
73
iH
II
205
72
24
74
236
76
436
82
86
135
89
64
'ft
I?
64
86
64
9
79
32
92
82
109
49
116
143
-------
M
a
5
c
OJ
•a
(0
.c
4J
•n
ft
a
M
O
O
I
a
H HI
•a c
c >,
i (C ^
•c xra
4J 0) I
a «•»
15_
Figure III-4.
GC/MS chromatogram of base/neutral extractables—
Ink Pigment Waste (Interlaboratory), spiked
-------
TABLE III-7.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL 0
COMPOUND
2-CHLUROPHENOL
2-NITROPHENOL
PHENOL
2,4-DIMETHYLPHENOt
2i4-OlCHLOROPHENOL
2,4,6-TRICHLCROPHENOl
4-CHLORO-3-METHVLPHENOL
2.4-DINITROPHENOL
4I6-DINI TRO-0-CRESOL
PENTACHLORQPHENOl
4-NITROPHENOL
ADDED
0
0
0
0
0
0
0
8
0
0
N0_l
2.5
77°
8
0
o
§
1.2
0
N0_2
73
0
0
0
g
u
0
N0_3
6
0
59
0
0
i
V
'•I
N0_4
1 • 8
0
0
g
u
0
2.8
0
M0_5
3.5
6?
0
0
2.7
0
MEAN
3.62
0
68.4
0
0
0
0
2.48
0
S
1.64
6*91
|
OJT9
RSO RECO
45.2
;
31*7
-------
TI
10
-IS.
Figure III-5,
GC/MS chromatogram of acid extractables—
Ink Pigment Waste (Interlaboratory), unspiked
-------
TABLE II1-8.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL I
COMPOUND ADDED N0_l
2-CHtOROPHENOt 6.08 6.2
2-NITROPHENOL 2.01 1.7
PHENOL 26.25 83
2t4-OIMETHVLPHENOL 6.27 2.8
2,4-OlCHLOROPHENOL 2.02 1.5
2,4.6-TRiCHtOROPHENOl. 2.01 2.3
4-CHLORO-3-METHYLPHENOL 2 1.6
2,4-OINITROPHENOL 2 1.5
4,6-DINITRO-O-CRESOL 2.01 0.95
PENTACHLOROPHENOL .17.2 33
4-NITROPHENOL 14.07 13
N0_2
N0_3
ND_5
MEAN
8.53333
2.56667
39.6667
3.76667
§.86667
.43333
2.03333
1.56667
2.65
42.3333
13.3333
RSD
RECOVERY
-------
TABLE III-9.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA —
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL II
COMPOUND
2-CHLORQPHENOL
2-NITROPHENCL
PHENOL
2,4-OIMETHYLPHENOL
2,4-01CHLOROPHENOL
2i4t6-TRICHLORGPHENOL
4-CHLORO-3-METHY».PHENOt
2.4-DINITROPHENOL
4t6-OINlTRO-0-CRESOL
P ENT ACHLORQPHENOL
4-NITROPHENOL
ADDED
N0_l
N0_2
N0_3
N0_4
NO_5
MEAN
30.38
10.05
131.25
31.34
10.11
10.06
10.02
10
10.04
86 .02
70.37
48
14
191
17
d§>
18
15
13
84
67
40
'11
11
10
9
8*5
73
64
51
ill
21
i!
15
13
50
106
41
10
172
13
1?
11
49
82
51
13
11
12
62
?4
46.2
11.8
189
16
13.2
14
11.3
65.2
78.6
5.36
1.64
23.70
!:!l
3.16
13 59
16*.82
RSO
21.4
RECOVERY
140
117
92
11
-------
Figure III-6.
GC/MS chromatogram of acid extractables—
Ink Pigment Waste (Interlaboratory), spiked
-------
TABLE I11-10.
METALS DATA —
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL 0
ELEMENT
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
SILVER
THALLIUM
ZINC
ADDED
0
NOL.2
N0_3
N0_4
N0_5
MEAN
<0.2
<0.2
9.4
242
1.5
<0.2
26
<0.2
<0.2
56
9.2
237
2
<0.2
26
<0.2
<0.2
56
9.9
241
1.7
<0.2
-------
TABLE III-ll.
METALS DATA —
INK PIGMENT WASTE (INTERLABORATORY), SPIKE LEVEL I
ELEMENT
ADDED
oo
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
SILVER
THALLIUM
ZINC
14
14
43
29
429
1!
29
N0_l
16
14
lil
731
78
68
N0_2
14
14
102
33
675
16
0.8
61
N0_3
N0_4
14
0.5
70
61
MEAN
14.4
14
3 • »6
0?74
71.6
63
S
8.89
.00
3.35
2.19
26.74
0.89
0.18
3.78
2.92
RSO
6.2
0.0
3.3
5.8
1:1
24.5
5.3
4.6
RECOVI
101
99
109
97
106
99
4
98
127
-------
B. Organic Still Bottoms (Interlaboratory)
149
-------
TABLE 111-12.
PURGEABLE ORGANICS DATA—
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL 0
COMPOUND
METHVLENE CHLORIDE
TRICHLGROFLUOROMETHANE
ItI-OICHLOROETHYLENE
1,1-OICHLGROETHANE
TRANS-1.2-OICHLOROETHYLENE
CHLOROFORM
1,2-DICHLOROETHANE
1,1,1-TRlCHLOROETHANE
CARBON TETRACHLORIOE
BRONODICHLGROMETHANE
lt2-DICHLORUPROPANE
TRANS-1.3-OICHLOROPROPENE
TR1CHLOROETHYL£NE
DIBROMOCHLOROMETHANt
CIS-I,3-giCHLOROPROPENE
1,1,2-TRICHLOROETHAN
BENiENE
M^ETRACHLOROETHENf
l,lt2,2-TETRACMLCROETHANE
TOLUENE
CHLOROBENiENE
ETHVLBENZENE
ADDED
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
N0_2
15
0
132
2680
974
321
i no
0
0
6590
0
0
7700
0
0
20100
18900
30
15
0
786C
845C
N0_3
33
0
99
2050
766
MEAN
RECOVERY
95
231
1160
53
0
0
S22JJ
0
6190
0
16500
14500
25
13
0
224
1373
226
35
0
0
0
3730
g
6340
0
0
(7710)
6890
20
3
5460
7240
42.66
31.50
567.82
217.07
59.72
259.87
117.84
22.69
1549.25
945.06
2125.05
11884.6
26.8
13*. 2
61.5
21.9
5.8
-------
-i
0 °
g .H
o £•
rH 0
^JiH
0-0
-r-t 1
01
C
4J
O
o
0
-H
Q
OJ
C
2°
^rH
0^3
rH o
f «
CJ ,,
-
10
T—r
0)
«
Q) O
C H
o
H .
Figure III-7,
GC/MS chromatogram of purgeable organics by purge and trap
Organic Still Bottoms (Interlaboratory), unspiked
-------
TABLE 111-13.
PURGEABLE ORGANICS DATA-
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL I
Ui
IV3
COMPOUND
METHYLENE CHLORIOE
TRICHLORGFLUORGMETHANE
1,1-OICHLCROETHYLENE
Itl-DlCHLOROETHANE
TRANS-i.2-OICHLOROETHYLENE
CHLOROFORM
lt2-DICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TEIRACHLORIOE
BROMOOICHLOROMETHANE
lt2-01CHLOROf>ROPANE
TRANS-li3-OICHLOROPROPENE
IRICHLOROETHYLENE
DIBROHOCHLOROHETHANE
CIS-lt3-OICHLORO(>ROPENE
ltl.2-TRICHLOROETHANE
BENZENE
BROMOFORM
l»l,2t2-TETRACHI_OROETHENE
1,1,2,2-IETRACHLOROETHANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED
1990
0
1990
2000
2010
2000
2010
2010
2010
1960
2010
2000
2000
2010
1620
2010
1990
2020
2010
2000
2010
2000
1990
N0_l
2*00
2660
5250
3200
27*0
4070
2430
2400
2290
2980
2670
(12500)
2870
1560
10000
2650
3730
21200
20000
2660
2760
2860
NQ_2
N0_3
2150
0
2180
4200
2660
2290
3940
2040
1930
"170
N0_4
N0_5
1860
0
1871
3230
2140
2030
3050
1770
1910
2730
2000
7490
2180
12BO
8280
1890
2230
19700
18700
2020
2270
2180
MEAN
2052
17860
17080
2294
2530
2430
235.52
362.15
763.43
427.88
393.66
620.78
237.66
311.82
146.70
308.92
285.0
385.7
349.4
192.92
936.71
319.58
601.14
RSO
11.5
18.7
tfcl
16.6
7.0
11.3
12.9
lI'.O
13.4
10.8
i!:?
11.2
11.2
11.6
RECOVERY
100
96
91
136
96
83
91
m
116
89
108
153
N
N
113
126
122
-------
TABLE I11-14.
PURGEABLE ORGANICS DATA-
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL II
Ln
LO
COMPOUND
HETHVLENE CHLORIDE
TRICHLOROFCUORGHE THANE
Jil-OlCHLOKOETHYLENE
, 1-OICHLOROETHANE
RANS-lt2-DICHLOROETHYiENE
CHLOROFORM
1,2-OICHLOROE THANE
1.1,1-TRICHLOROETHANE
CARBON TETRACHLORIDE
BRGMGDICHLOROME THANE
I • 2-OICHL OROPROP ANE
TRANS-l ,3-DlCHLORCPROPENE
TRICHLOROEIHYLENE
DIBROMOCHLORONETHANE
CIS-1.3-DICHLORGPROPENE
2-TRICHLOROETHANE
r.T,'2",2-TETRACHLOROETHENE
1,1,2,2-TETRACHLOROETHANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED
795
800
T96
6680
805
800
38500
6160
803
792
805
802
40700
804
650
26600
797
810
59200
112000
802
796
798
N0_l
582
635
715
6570
1440
839
28700
4280
591
507
570
504
23800
487
633
25700
0
561
52300
94400
657
762
693
N0_2
N0_3
N0_5
799
50800
97300
85,
608
832
1010
919
8160
1670
1010
35300
5560
811
821
603
728
41700
774
600
28100
696
66800
117JOO
516
482
426
118000
864
978
843
MEAN
721.4
785
864.2
7308
1476
944.8
31340
5092
746.2
746
737
685.6
33280
625
617.2
26540
lllzl
105940
684. 8
798.8
633.2
RSO
RECOVERY
105.58
1021.82
270.43
150.26
3683.48
692.94
175.27
227.58
189.83
130.10
7677.69
128.50
59.18
2532.39
127.84
6984.77
11002.64
124.17
193.97
152.10
-------
"-%
01
ex
JO
> PUQJ
*0 fj
joxs
r-JrH 4J
OX! 0)
§00
a-H M
OT3 O
I rH
e
O
_ «O
QrH-H
I M
,
8
g
ix i — r-
-i1"1 jiii
10
— i 1 1 r-
15
—i "" ~r~ i i i
20
1 ' 25 *
Figure III-8.
GC/MS chromatogram of purgeable organics by purge and trap-
Organic Still Bottoms (Interlaboratory), spiked
-------
TABLE 111-15.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL 0
COMPOUND
1,3-OICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-OICHLORGBENZENE
HEXACHLGRGETHANE
BIS{2-CHLOROETHYLI ETHER
B1S(2-CHLOROISGPRGPYL) ETHER
HEXACHLOROBUTADIENE
NITROBENZENE
NAPHTHALENE
1.2.4-TRICHLGRCBENZENE
Bi Si2-CHLORQETHOXYI ME THANE
N-NITROSODI-N-PRQPYLAMINE
HEXACHLGRGCVCLGPENTADIENE
2-CHLORONAPHTHALENE
ISOPHORDNE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-01NITROTOLUENE
FLUORENE
2.4-D1NITROTOLUENE
1,2-DIPHENVLHYORAZINE
4-CHLGRQPHENYL PHENYL ETHER
OIETHVL PHTHALATE
N-N1TRGSODIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
01-N-BUTYL PHTHALATE
FLUOKANTHENE
PVRENE
8ENZIOINE
BUTYLBENZYL PHTHALATE
B1SJ2-ETHYLHEXYL» PHTHALATE
CHRYSENE/BENZUIA(ANTHRACENE
3,3«-OICHLOROBENZIOINE
OI-N-OCTYL PHTHALATE
BENZOI B)/BENZO(KIFLUORANTH£NES
BENZO
-------
1 1 1 1 1 1—1 1 1—
Figure III-9.
GC/MS chromatogram of base/neutral extractables —
Organic Still Bottoms (Interlaboratory), unspiked
-------
TABLE 111-16.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL I
COMPOUND
i,3-OJCHLOR06eNZEN£
1,4-DICHLGROBENZENE
U2-D1CHLUROBENZENE
HEXACHLOROETHANE
aiSl2-CHLUROETHYLI ETHER
BISiZ-CHLORGISOPROPYL) ETHER
HEXACHLGROBUTADIENE
NITROBENZENE
NAPHTHALENE
It2,4-TRICHLOROBENZENE
BIS(2-CHLOROETHCXY)METHANE
N-NITROSODI-N-PROPYLAMINE
HEXACHLOROCYCLOPENTAOIENE
2-CHLORONAPHTHALENE
ISOPHGRONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2t6-DINITRGTOLUENE
FLUORENE
2,4-OINITROTOLU£N£
1.2-0 IPHENYLHYDRAZINE
4-CHLORGPHENYL PHENYL ETHER
DIETHYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-aROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
OI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIDINE
BUTYLBENZYL PHTHALATE
BIS(2-ETHYLHEXYL) PHTHALATE
CHRYSENE/BENZO(A)ANTHRACENE
3.3'-DlCHLOROBENZIDINE
DI-N-OCTYL PHTHALATE
BENZO(B)/BENZO(KJFLUORANTHENES
BENZO(A)PYRENE
INOENOJ1,2.3-COIPYftENe
QIBENZOIAH)ANTHRACENE
BENZOIGHIJPERYLENE
AOOEO
8.5
37
8.8
1.1
2130
3.7
4.8
39
3.5
4.4
4.6
1.1
1.2
<0.5
<0.5
1.2
13
2.3
<0.5
141
3.4
1.8
1.6
1.4
<0.5
2.1
5.6
1.6
O.5
2.3
3.1
1.7
<0. 5
<0.5
2.5
N0_2
9.8
62
16
248
6.5
1.6
3200
10
6.8
70
1:?
11
1.6
1.6
0.99
394
2.2
<0.5
2.7
<0.5
3.7
ia
3.4
<0.5
5.1
2.1
2.2
<0.5
2.2
7.7
2.2
<0.5
3.2
4.6
1.6
<0.5
<0.5
3.5
N0_3
151
6.7
1.8
8.7
3.6
5.3
1.4
1.6
•
<0.5
2.1
<0.5
1.5
4.5
<0.5
297
2.5
5.4
2.9
3.5
2.4
<0.5
2.6
2.4
<0.5
3.9
4.1
N0_4
N0_5
MEAN
RSO
RECOVERY
19.
196
-------
TABLE 111-17.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA —
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL II
COMPOUND
1 ,3-OICHLCROB£NZENE
1,4-DICHLOROBENZENE
1,2-OICHLOROBENZENE
HEXACHLGfUJETHANE
BlS<2-CHLOfcOETHYL» ETHER
BIS»2-CHLOR01SOPROPYLI ETHER
HEXACHLGR08UTA01ENE
NITROBENZENE
NAPHTHALENE
I ,2 ,4-TRICHLORO BENZENE
BIS (2-CHLGROETHGXYJ ME THANE
N-N1TROSODI-N-PROPVLAMINE
HEXACHLGROCYCLCPENTAOIENE
2-CHLORONAPHTHALENE
ISOPHORONE
h- ACENAPHTHYLENE
Ui ACENAPHTHENE
00 DIMETHYL PHTHALATE
2,6-DINITRGTOLUENE
FLUORENE
2t4-OINlTRCiTOLUENE
1 ,2-OIPHENYLHYDRAZlNE
4-CHLORQPHENYL PHENYL ETHER
OIETHYL PHTHALATE
N-NITROSGOIPH£NYLAHINE
HEXACHLORUBENZENE
4-BRCMOPHENYL PHENYL ETHER
PHENANTHRENE/ ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BUTYL8ENZYL PHTHALATE
B1SC2-ETHYLHEXYL) PHTHALATE
CHRYSENE/BENZOl A) ANTHRACENE
3t3'-DICHLOROBENZIDINE
BENZOIGHJIPERYLENE
ADDED
29.23
214.12
63.7
1016.64
10
10.02
1803.61
10.03
27.07
140.25
10.09
10.02
10.12
9.6
10.08
10.08
2523.06
10.07
10.05
10.04
10.16
10.02
79.12
10.11
10
8.07
10.33
20.18
10.05
10.04
10.09
10.34
10.09
33.08
10.08
10.04
10.13
22. 11
10.4
10. 12
N0_l
N0_2
N0_3
N0_4
N0_5
MEAN
RSO
RECOVERY
41
2C5
50
993
11
6.1
2420
1.9
18
154
22
3.1
3.7
5.8
11
5.9
1590
9.7
8.7
8.6
8.5
17
65
8.2
20
146
7.3
8.2
10
12
11
5.3
11
63
13
*8
12
10
< I
a. 7
73
254
52
1202
17
9.9
2560
175
26
7.1
9.2
6.9
6.4
2120
13
10
12
14
16
84
14
11
(217)
1 13
9
12
14
16
9.6
13
51
15
(4.7)
7.3
14
13
^ J
14
61
202
48
879
11
7.8
l£S
&
18
5.4
5.8
4.7
2.5
8.5
1500
a. 9
6.3
8.2
6.4
10
63
6.9
22
125
9.8
8.7
8
8.6
9.4
5.2
8.5
35
12
1.3
4.8
9.2
13
^ J_
9.4
58
164
39
977
12
7.7
1920
19
18
3.4
7.7
5.7
8.1
4.2
1260
8.8
8
8.6
7.8
12
71
8
3.9
131
12
8.4
9.7
8.8
8.9
2.3
8.5
30
11
1.1
5.7
11
11
^ J
9.4
21
49
34
315
11
8.3
671
17
21
3.9
4.2
6.4
3.6
5.9
868
9.7
6.1
10
7.7
12
(17)
11
16
150
12
7.8
10
10
7.5
4.3
6.1
19
10
1
7.6
11
9.9
^ J
11
50.8
174.8
44.6
873.2
12.4
7.96
1S82.2
15.14
21.8
150
21
4.58
6.12
5.9
6.32
6.72
1467.6
10.02
7.82
9.48
8.38
13.4
70.75
9.62
14.58
138
10.82
8.42
9.94
10.68
10.56
5.34
9.82
39.6
12.2
6.68
11.44
11.38
< !_
10. 5
20.20
77.24
7.73
333.49
2.61
1.36
744.79
11.89
6.53
18.85
3.32
1.66
2.33
0.83
3.43
2.03
459.42
1.72
1.65
1.57
2.96
2.97
9.46
2.88
7.30
11.92
2.29
0.46
1.42
2.30
3.29
2.67
2.12
17.43
1.92
0.14
1.37
1.75
1.54
Z
2.13
39.8
44.2
17.3
38.2
21.0
17.1
39.6
78.5
30.0
12.6
15.8
36.3
38.0
14.0
54.3
30.2
31.3
17.2
21.0
16.5
22* \
13.4
29.9
50.1
8.6
21.2
5.5
14.3
21.5
31.1
50.0
21.6
44.0
15.8
12.9
20.5
15.3
13.5
20.3
159
65
51
68
88
79
86
151
68
93
208
46
38
61
63
67
40
100
78
91
87
134
79
95
146
45
105
40
92
132
105
53
85
110
116
11
N
52
139
*
104
-------
H
i Is
Hit
>r\ a M
£ >i(X ~
5&5g
3«8&W
S cg-^ o «
SS5«S5
^s^s^-g.
.,XI V ^-G "•
O^^ UC
<1) M--.M 10 O
*-• *A «^ v kj
X!
O.
n
C
ill
,
S
S
s
Figure 111-10.
GC/MS chromatogram of base/neutral extractables—
Organic Still Bottoms (Interlaboratory), spiked
-------
TABLE I11-18.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA —
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL 0
COMPOUND ADDED
2-CHLOROPHENOL 0
2-NiTRGPHENQl 0
PHENOL 0
2,4-DIMETHYiPHENOL 0
2,4-DICHLOROPHENGL 0
2f4,6-TRlCHLOROPHENOL 0
4-CHLORO-3-HETHYLPHENOC 0
2t4-DINITROPHENOL 0
4,6-DINITRG-O-CRESOL 0
PENTACHLOROPHENOL 0
4-NITROPHENOL 0
N0_l
0.93
0
6.6
0
N0_2
0.53
'0
4.6
N0_5
0.54
0
6.2
0
HEAN
0.22
0.97
Z
Z
I
I
RSD
33 2
16
RECOVERY
-------
TI
10
I1 I
20
Figure III-ll,
GC/MS chroraatogram of acid extractables—
Organic Still Bottoms (Interlaboratory), unspiked
-------
TABLE 111-19.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL I
COMPOUND
2-CHLOROPHENOL
2-NITROPHENOL
PHENOL
2,4-DIMETHYLPHENOL
2,4-DICHLOROPHENOL
2,4,6-TRICHCOROPHENOL
4-CHLORO-3-HETHVLPHENOt
2,4-OINITROPHENOL
4,6-01NITRO-0-CRESOL
PENTACHLORCPHENOL
4-NITKOPHENOt
ADDED
N0_l
N0_2
N0_3
N0_4
N0_5
2.01
2.01
8.56
2.01
2.02
2.01
2
2.01
2
2.4
0.55
12
<0.5
2.3
2.4
0.87
0.59
0.58
1.4
0.56
1.7
0.55
12
<0.5
1.2
1.1
0.95
<0.5
<0.5
1.3
0.56
§ftf
^5
*
<0.5
1.6
2.5
1
<0.5
<0.5
1.6
0.91
MEAN
2.16667
<. 533333
-------
TABLE II1-20.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL II
o\
COMPOUND
2-CHLGROPHENOL
2-N1TRGPHENCI
PHENOL
2,4-DIMETHYLPHENOL
2,4-DlCHLOROPHENOL
2,4,6-TRlCHLORQPHENOl
4-CHLORO-3-METHYLPHENOL
---
PENTACHLOROPHENOL
4-NITROPHENCL
ADDED
10.03
10104
10106
10.02
10
10.04
10.02
10.02
N0_l
7.2
<1
35
2.2
8.8
7.8
6.5
<1
4
<1
N0_2
7.4
41
1.8
8
8.7
7.5
< \
< J
5.8
N0_3
7.7
48
1.5
6.2
6.9
9
< ^
< J
5.5
N0_4
12
51
(8.8)
7.1
11
9.9
<^
< \
6.3
N0_5
(1.3)
1.4
2.2
2.1
< \
< ^
3
-------
TI
I
5
I
10
15
Figure 111-12,
GC/MS chromatogram of acid extractables—
Organic Still Bottoms (Interlaboratory), spiked
-------
TABLE 111-21.
METALS DATA —
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL 0
ELEMENT
BERYLLIUM
CAOMIUM
CHROMIUM
COPPER
LEAD
NICKEL
SILVER
THALLIUM
ZINC
ADDED
0
0
0
0
0
0
0
N0_l
N0_2
N0_3
N0_4
N0_5
MEAN
ft SO
<0.2
<0.2
50
885
22
107
<0.2
<1
213
<0.2
<0.2
38
821
22
84
<0.2
223
<0.2
<0.2
30
919
21
79
<0.2
<1
229
<0.2
<0.2
36
902
21
98
<0.2
226
<0.2
<0.2
41
893
22
88
<0.2
-------
TABLE II1-22.
METALS DATA —
ORGANIC STILL BOTTOMS (INTERLABORATORY), SPIKE LEVEL I
ELEMENT
ADDED
N0_l
N0_2
N0_3
N0_4
N0_5
MEAN
RSO
RECOVERY
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
SILVER
THALLIUM
iINC
tf
34
8S,
340
is
85
15
kl
154°3
381
3.9
82
289
13
17
78
1730
39
389
4.4
76
309
il
82
1280
44
333
3.4
87
309
15
19
82
1360
43
364
87
311
14
17
88
1500
3)1
57*
299
14.4
17.8
84
1474
42
372
3.96
81.6
303.4
0.89
1.10
4.90
171.41
2.00
24.47
0.83
5.50
9.32
6.2
6.2
5.8
11.6
4.8
6.6
20.9
6.7
3.1
84
104
132
69
120
83
22
95
95
-------
Appendix IV. Total Content Evaluation Data
167
-------
Legend for Verification Analyses
and Quality Assurance
for Total Content Validation Study Data*
Symbols Identification
Not determined.
< Lower detection limit of method.
( ) Found to be a statistical outlier and not included
in the calculations.
Z Standard deviation was not calculated because all
points in the data set were less than lower
detection limit of method and/or zero.
N Percent recovery was calculated to be less than
zero.
* Concentrations are reported as microgram of compound per gram of residual
waste (parts per million).
168
-------
A. Deionized, Distilled Water (Spiked Method Blank)
169
-------
TABLE IV-1. PERCENT RECOVERY OF ORGANICS FROM SPIKED METHOD BLANK
CuMPuUNO
1,3-UlCHLuRUBENZENt
1 ,4-OICHLGkOBENZCNF-
1,2-OlCHLGRGUCKZENt
HEXACHLLKUETHANE
8IS(2-CHLGRGE1HYL I tTHER
6IS<2-CHtbRGISGPRU?YL) ETHER
HEXACHLGR
NG_1
N0_2
N0_3
N0_5
NEAN
RSO
NAPHTHALENE
1,2»4-TP ICH
BIS(2-CHLGtNCJLTHCXY) -ILlHANfc
N-NI TRGil'DI-N-PRGPYLAMlNE
HtXACHLUKGCYCLUPEMTAOl ENfc
2-CHLGkGMAPHTHALENE
ISGPHGRCNE
ACENAPHTHYLENE
ACENAPHTHENE
JIMETHYL PltTHALATE
2,6-OlNl TFvQTOLUENE
FLUOkENE
2,4-DINITRLTiJLUENE
l.^-lHPHE.MYLHYURAZl.Mf
4-CHLGRGPHENYL PHENYL ETHLR
OIETHYL PHTHALATE
N-N I T kGS UDI PH E N YL AM I AiL
HfcXACHLGKuBCNZENE
4-BRG-MGPHENYL PHFNYL ETHER
PHENANTHRENE/ANTHRAtc.^E
OI-N-BUTYL PHTHALATE
FLUDRANTHENE
PYRENE
BENZIDINE
BUTYLBENZYL PHTHALATt
BIS12-ETHYLHEXYL) PHTHALATE
CHRY SEN E/bENZC( A) ANTHRACENE
3,3'-OICHLCkCBtiNZI DINE
DI-N-OCTYL PHTHALATE
BENZQ(BJ/3ENZ.G(K)f-LUGRANTHENtS
BENZOlAJPYRENt
I Ni)E NCI lt2t3-CDJ PYRENE
ul Bff NZG ( AH) ANTHRACJiNt
BENZG(GMI)PERYLENE
2-CHLGRGPHENGL
2-NITRuPHENUL
PHENCL
2,4-01.'1ETHYLPHENGL
2,4-OICHLURUr>HENljL
2f4,6-TKlCHLL;KuPHENwL
4-CHLuRU-:>-.viETHYLPHElMUL
2,4-UliMlTkUPHENOL
4,6-i)INITRL-G-CRLSLL
HENTACHLCKUPHLiNGL
4-ixI TkuPHuNUL
2-FLUuRGPMEMljL
TRIFLJLnG-M-LPESUL
PENTAFL'JuKUPHfcNDL
2-FLJGKGNAPHTHALti'Jb
r-i
Z-FLOORUaiPHUNYL
33
62
Bo
78
86
70
131
15
82
64
7J
5
102
47
100
99
112
308
107
94
4b
118
158
125
112
129
92
106
93
85
88
153
122
32
131
216
112
129
98
53
43
36
6
32
20
14
lo
12
13
42
31
19
24
68
72
76
83
93
111
86
77
47
119
102
17
56
78
105
109
50
97
92
93
58
96
66
40
96
91
55
100
90
89
92
91
95
68
44
33
87
55
2
157
165
9
132
70
93
63
51
164
58
12
6
bO
113
67
59
4i)
79
•92
92
62
32
180
154
72
97
120
39
93
174
116
42
29
67
295
88
230
82
370
97
85
180
89
105
67
74
70
32
66
74
21
88
58
598
71
5
37
61
,
78
104
122
121
40
145
115
101
6
61
31
115
85
49
93
87
95
83
6
35
128
124
23
58
115
120
84
171
86
53
17
80
163
75
212 „
58
82
105
83
113
106
89
58
96
94
35
71
96
94
5
69
119
81
10J
5
42
97
,
«
1UJ
87
85
107
50
85
83
92
22
252
66
86
162
60
174
87
73
62
15
45
85
65
19
112
110
102
102
73
58
82
12
134
140
114
115
78
108
108
81
118
90
236
12
52
87
100
124
104
125
12
81
106
88
46
12
69
82
*
*
42
80
61
44
19
164
294
126
31
,
209
18
143
96
67
100
98
84
39.8
63.4
118.0
101.4
55.4
76.8
119.0
64.8
92.6
108.6
76.0
65.0
33.6
98.4
139.0
94.8
149.6
84.6
185.2
102.6
81.8
99.4
99.8
135.8
63.4
86.8
94.0
69.6
91.8
93.8
94.6
23.0
74.0
93.8
195.2
60.8
5.8
87.2
124.2
112.0
129.0
90.0
78.8
81.8
74.2
23.8
95.4
135.2
78.2
17.4
82.8
75.8
74.8
97.6
56.6
79.6
84.2
86.0
79.4
32.3
24.3
39.1
36.7
31.8
27.1
7.8
44.3
9.5
66.8
25.3
17.0
40.9
26.1
101.6
14.5
66.0
19.9
143.2
5.7
10. I
57.9
12.2
62.6
40.5
23.8
21.6
33.2
24.2
7.0
19.0
25.8
18.5
225* 7
26.1
3.7
54.0
64.4
.
33.1
19.0
28.8
38.0
20.5
57.6
103.3
43.4
9.6
115.5
77.5
43.3
54.2
27.6
59.0
11.8
12.5
11.3
81.05
38.39
33.11
36. 19
57.46
35.27
6.54
68.40
10.29
61.48
33.34
26.15
121.62
26.49
73.10
15.28
44.13
23.49
77.32
5.54
12.39
58.24
12.24
46.10
63.82
27.44
22.98
47.72
26.33
20. O/
112.33
24.97
51.31
115.65
42.91
63.82
61.98
51.88
9
36.75
24.14
35.26
51.15
86.13
60.36
76.20
55.46
55.06
139.57
102.27
57.90
55.51
48.72
74.08
13.99
14. 55
14.18
-------
Key to Figure IV-1.
GC/MS chromatogram of purgeable organics by purge and trap-
Method Blank, spiked
Symbol Purgeables
A Methylene chloride
B Trichlorofluoromethane
C 1,1-Dichloroethylene
D trans-1,2-Dichloroethylene
E 1,1-Dichloroethane
F Chloroform
G 1,2-Dichloroethane
H 1,1,1-Trichloroethane
I 1,1,2-Trichloroethane
J Carbon tetrachloride
K 1,2-Dichloropropane
L trans-1,3-Dichloropropene
M cis-1,3-Dichloropropene
N Bromodichloromethane
0 Dibromochloromethane
P Chlorobenzene
Q Trichloroethylene
R Benzene
S Bromoform
T 1,1,2,2-Tetrachloroethene
U 1,1,2,2-Tetrachloroethane
V Ethylbenzene
W Toluene
171
-------
ISJ
A
I R M
O Q
TI
JLS.
K L
T U
V
25
Figure IV-1. GC/MS chromatogram of purgeable organics by purge and trap—
Method Blank, spiked
-------
Key to Figure IV-2.
GC/MS chromatogram of base/neutral extractables —
Method Blank, spiked
Symbol
A
B
C
D
E
F
G
H
I
J
K
L
M
N
0
P
Q
R
S
T
U
v
w
X
Y
Z
AA/BB
CC
DD
EE
FF
GG
HH
II/JJ
KK
LL
MM/NN
00
PP
QQ
RR
Base/neutrals
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Hexachloroethane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
Nitrobenzene
Naphthalene
1,2,4-Trichlorobenzene
Bis(2-chloroethoxy) methane
N-nitrosodipropylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Acenaphthene
Dimethyl phthalate
2,6-Dinitrotoluene
Fluorene
2,4-Dinitrotoluene
1,2-Diphenylhydrazine
Diethyl phthalate
N-Nitrosodiphenylamine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene/anthracene
Di-n-butyl phthalate
Fluoranthrene
Pyrene
Benzidine
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Chrysene/benzo(a)anthracene
3,3-Dichlorobenzidine
Di-n-octyl phthalate
Benzo(b)fluoranthene/benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd) pyrene
Dibenzo(ah)anthracene
Benzo(ghi)perylene
173
-------
i i i i i i t i i i * i t 4 i i j i i
LS
i t i i i i i
25 - 22
i i i i i i i i i i i
25 _ 42
Figure IV-2. GC/MS chromatogram of base/neutral extractables-
Method Blank, spiked
-------
Key to Figure IV-3.
GC/MS chromatogram of acid extractables
Method Blank, spiked
Symbol Acids
A 2-Chlorophenol
B 2-Nitrophenol
C Phenol
D 2,4-Dimethylphenol
E 2,4-Dichlorophenol
F 2,4,6-Trichlorophenol
G A-Chloro-3-methylphenol
H 2,4-Dinitrophenol
I Pentachlorophenol
J 4-Nitrophenol
175
-------
E
A B
TI
D
*/J
H
1SL
1 ( j p=»f—j_j j p=Y—T
T—I—I
£5.
Figure IV-3. GC/MS chromatogram of acid extractables—
Method Blank, spiked
-------
B. POTW Residual Waste
177
-------
TABLE IV-2.
PURGEABLE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL 0
00
COMPOUND
METHYLENE CHLORIDE
itl-OICHLORGETHYLENE
1.1-0ICNLOROETHANE
TRANS-1,2-DICHLOROETHYLENE
CHLOROFORM
1,2-DICHLOROETHANE
1*1,1-TRICHLOROETHANE
CARBON TETRACHLORIDE
BROMODItHLOROMETHANE
If2-DICHLUROPROPANE
TRANS-li3-OICHLOROPROPENE
TRICHLOROETHYLENE
01BROHOC HLOROME THANE
CtS-1,3-OlCHLOROPROPENE
1 • 112-TRICHLOROETHANE
BENZENE
BROMGFGRM
111,2 ,2-T ETRACHLOROETHENE
1,1,2,2-TETRACHLGROETHANE
TOLUENE
CHLOROBEN£EN£
ETHYLBENZENE
AOOEO
N0_l
0.5,
0
0
0
0
(t
0
0.0*3
0
0
0.27
0
1.2
0.64
1.1
N0_2
0.3
0
0
8
8
0
0
0
0
0.039
0
0
0
0.24
0
0.65
1.2
0.78
0
0
0
a
o
o
0.02!
0.21
0
0.71
3.45
0.94
N0_5
0.34
0
J
0
0
3
0
0
0.032
0
0
0
0
0
0.2
0.79
0.47
0.88
MEAN
0.41
I
i
i
Z
z
0.01
i
z
0.03
0.20
0.10
0.14
RSO
61 4
RECOVERY
24
13
18
-------
TI
T 1 1 1 r
10
T 1 \ T
T 1 T
T 1 1 T
Figure IV-4. GC/MS chromatogram of purgeable organics by purge and trap—
POTW Residual Waste, unspiked
-------
TABLE IV-3.
PURGEABLE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL I
oo
o
COMPOUND
METHYLENE CHLORIDE
lil-DICHLOROETHYLCNe
1,1-UICHLOROETHANE
TRANS-1,2-DICHLOROETHYLENE
CHLOROFORM
1,2-DICHLOROETHANe
1.1.1-TRICHLOROETHANE
CARBON TETRACHLORIOE
8ROMOOICHLOROMETHANE
1,2-OICHLOROPROPANE
TRANS-1,3-DICHLOROPROPENE
TRICHLOROETHYLENE
DIBROMOCHLOROME THANE
CIS-1i3-OICHLOROPRDPENE
1,1,2-TRlCHLQRCETHANE
BENZENE
BROMGFORM
Ltlt2t2-TETRACHLOROETHENE
l,l,2t2-TETRACHLORO£THANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED N0_l
0.99
1 0
1
*l)
1 (0.64)
1
1 (0
;
0
i
.1 (0.
:
L 0
»
0.99 0.
1 0.
1 0.
0.9<
> 0
A
1 0.
0.81 i).
:
0
(0
0
0
w
B
.
i
2
1
.5
66)
.1
65)
71
79
44
24
66
ii
74
78)
49
.1
94
.2
.2
.8
NO_2
0.
0
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0
0.
0.
1
0.
1
1
72
.2
37
32
42
42
42
52
56
48
12
53
52
• o
53
49
.1
98
.9
.3
N0_3
0.65
0.18
0.32
0.28
0.4
0.7
0.42
0.48
0.61
0.46
0.16
0.55
8:?!
0.64
0.44
0.53
1.2
1
1.9
1.4
Z.I
N0_4
0.31
0.17
0.32
0.24
0.38
0.46
0.39
0.35
0.47
0.41
0.038
0.53
0.51
0. 1
0.58
0.43
0.47
1.1
0.94
1 » 7
1.3
1.8
N0_5
1.1
0.18
0.3
0.29
0.36
0.52
0.41
0.44
0.57
0.4
0.17
0.53
0.61
0.37
0.62
0.42
0.56
1.2
1.1
1.9
1.4
2
MEAN
0.996
0.1825
0.3275
0.326
0.39
0.64
0.41
0.5
0.6
0.438
0.1556
0.56
0.566
0.242
0.636
8.455
.508
1.14
0.992
1.92
1.32
1.94
S
0.43
0.01
0.03
0.10
0.03
0.28
0.01
0.13
8.12
.03
0.06
§.06
.05
0.16
0.06
0.05
0.04
0.05
0.07
0.18
0.08
0.13
RSD
43.1
6.9
9.1
31.1
6.6
43.5
3.4
26.6
19.6
7.6
36.9
10. I
a s
O . 3
67.2
9.8
11.1
7.2
4. 8
6.6
9.3
6.3
6.9
RECOVERY
34
18
33
33
39
64
41
50
61
44
16
30
64
45
51
92
99
94
-------
TABLE IV-4. PURGEABLE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL II
CO
COMPOUND
M£THYLENE CHLORIDE
li1-DICHLOROETHYLENE
1,1-01CHLOROETHANE
TRANS-1.2-DICHLOROETHYLENE
CHLOROFORM
1,2-OICHLOROETHANE
1,1,1-TRlCHLOROETHANE
CARBON TETRACHLORIDE
BROMOOICHtOROMETHANE
1.2-OICHLOROPROPANE
TRANS-lt3-DICHLOROPROPEIME
TRICHLOROETHYLENE
OIBROHOCHLOROMETHANE
ClS-lt3-DICHtOROPROPENE
1,1,2-TRICHLOROETHANfc
BENZENE
8ROMOFORM
I, 1,2,2-TETRACHLOROETHENE
1,i,2i2-TETRACHLOROETHANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED
9.9
9.9
10
10
9.9
10
10
10
9.9
10
10
9.9
10
a.i
10
9.9
10
10
9.9
10
9.5
10
8
N0_l
5.6
5.3
5.2
6.2
5.9
7.3
6.4
3
6
9
8.7
7.3
5.8
8.6
6.1
8.9
19
15
8.6
6.1
7.3
N0_2
5.5
2.6
6.2
4
5.9
5.7
4.2
6.2
7.4
8.7
6.5
6.B
6.1
8.8
6.6
0
12
11
9.1
6.9
6.3
NC_3
(3.1)
3.8
5.3
3.6
5.1
5.5
5.1
4.9
6
7.4
5.1
5.8
5.5
7.3
5.7
8.1
6.1
8
4.9
6.7
N0_4
6.1
3.6
6.3
4.2
6.2
3.8
5.3
4.7
6.5
5.4
8.8
5.9
5.6
7.1
5.9
7
6.2
5.5
9.5
5.3
7.1
N0_5
MEAN
5.95
6.14
4.3
6.22
5.2
6.18
5.48
6.66
6.46
8.98
6.3
6.74
6.1
8.16
6.62
7.94
10.48
8.94
8.8
6.38
7.1
S
0.51
1.04
1.01
0.67
0.94
1.23
1.2S
1.18
1.28
0.94
1.29
1.49
0.90
0.82
0.89
1.26
0.93
5.25
4.01
0.65
1.51
0.68
RSO
8.5
26.0
16.4
15.6
15.1
23.7
20.6
21.5
19.2
14.5
14.4
3.7
3.4
3o:S
19.1
11.7
50.1
44.8
7.4
23.6
9.6
RECOVERY
53
40
u
63
52
62
55
67
65
II
82
67
79
103
90
79
62
61
-------
oo
N>
Figure IV-5. GC/MS chromatogram of purgeable organics by purge =>nd trap—
POTW Residual Waste, spiked
-------
TABLE IV-5. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA —
POTW RESIDUAL WASTE, SPIKE LEVEL 0
oo
u>
COMPOUND ADDED
lt3-DlCHLORCBENZENE 0
1,4-OICHLOROBENZENE 0
lt2-01CHLOROBENZENE 0
HEXACHLOROETHANE 0
BIS12-CHLORGETHYLJ ETHER 0
BIS(2-CHLOROISOPROPYLJ ETHER 0
HEXACHLOROBUTADIENE 0
NITROBENZENE 0
NAPHTHALENE 0
1,2,4-TRICHLOROBENZENE 0
BIS(2-CHLOROETHOXVIMETHANE 0
N-NITRGSODI-N-PROPYLAM1NE t)
HEXACHLOROCYCLOPENTADIENE 0
2-CHLORONAPHTHALENE 0
ISOPHORONE 0
ACENAPHTHYLENE 0
ACENAPHTHENE 0
DIMETHYL PHTHALATE 0
2,6-DINITROTOLUENE 0
FLUORENE 0
2.4-OINITROTOLUENE 0
1,2-DIPHENYLHYDRAZINE 0
4-CHLGRCPHENYL PHENYL ETHER 0
01 ETHYL PHTHALATE 0
N-NITROS001PHENYLAMINE 0
HEXACHLOROBENZENE 0
4-BROMOPHENYL PHENYL ETHER 0
PHENANTHRENE/ANTHRACENE 0
DI-N-BUTYL PHTHALATE 0
FLUORANTHENE 0
PYRENE 0
3ENZIOINE 0
BUTYLBENZYL PHTHALATE 0
BIS«2-ETHYLHEXYL> PHTHALATE 0
CHRYSENE/BENZOCAIANTHRACENE 0
3,3>-DICHLOROBENZlDlNE 0
Dl-N-OCTYL PHTHALATE 0
BENZO(8)/BENZO(K>FLUORANTHENES 0
BENZOIA1PYRENE j
lNDENUIlt2,3-CD»PYRfcNE 0
DIBENZOIAHIANTHRACENE 0
BENZOJGHIIPERYLENE 0
N0_l
N0_2
N0_3
1.8
3.6
0.75
0
o
o
5.7
1.4
a
o
6.4
2.1
3.3
2.7
0
8.6
46
2.1
0
1.4
0.82
0
0.57
N0_4 N0_5
2 2.5
3.8 4.4
0
0
7.1
59o
0
0
0
0
0
0
8
0
6.8
1-.8
2.7
0
8.6
49
2J
0
89
MEAN
2.08
3.88
0.738
0
0
6.12
53.8
0
0
9
0
0
0
1.3
0
0
0
0
3.44
2.76
0
9.48
41.8
2.06
0
2.5
3.42
1.56
0.9025
0
<0. 708
0.41
0.58
RSO
19.6
16.3
15.6
RECOVERY
9.4
16.5
13.7
16.6
11.9
13.5
U.t
& V •
14:
-------
oo
TI ,
JLS_
~T—T
30
I—T
T—I
35
"I TT 1 1 r
Figure IV-6.
GC/MS chromatogram of base/neutral extractables—
POTW Residual Waste, unspiked
-------
TABLE IV-6. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL I
oo
COMPOUND
1 i3-DICHLOROBENZENE
1i4-01CHLOROBENZENE
1.2-DICHLOR08ENZENE
HEXACHLOROETHANE
BIS12-CHLGROETHYL) ETHER
BISC2-CHLO«OISOPfcOPYL) ETHER
HEXACHLOR06UTADIENE
NITROBENZENE
NAPHTHALENE
It2,4-TRICHLOROBENZENE
B I S< 2-CHLORGE THOXYIME THANE
--osooi-
LOROCY
RONAPh
N-N1TROS001-N-PROPYLAMINE
HEXACHLOROCYCLOPENTA01ENE
2-CHLORONAPHTHALENE
ISOPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2i6-DINITROTOLUENE
fLUORENE
2t4-DINITRQTOLUENE
li2-DIPHENYLHYDRAZINE
4-CHLOROPHENYL PHENVL ETHER
DIETHYL PHTHALATE
N-NITROS001PHENYLAMINE
HEXACHLOROBENZENE
4-BROMGPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
BUTYL BENZYL PHTHALATE
BISC2-ETHVLHEXYL) PHTHALATE
CHRYSENE/BENZOiA)ANTHRACENE
3i3'-OICHLOROBENZIDINE
OI-N-OCTYL PHTHALATE
B£NZOm/BENZC
-------
TABLE IV-7. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL II
COMPOUND
1,3-01CHLORG6ENZENE
It 4-OlCHLORUBENZENE
1,2-OtCHLORQBENZENE
HEXACHLOROETHANE
BIS12-CHLOROETHYLJ ETHER
BISC2-CHLOROISOPROPYL) ETHER
HEXACHLOROBUTAOIENE
NITROBENZENE
NAPHTHALENE
ADDED
iiii£
N-NITR
,-TRlCHLOROBENZENE
CHLOROETHOXYIMETHANE
AMINE
TROSOOI-N-PROPYL
HEXACHLOROCYCLOPENTADIENE
H- 2-CHLORONAPHTHALENE
CO ISOPHORQNE
<^ ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-DlNITROTOLUENE
I^SfKlTROTOLUENE
l.2~P!?HENyLHYDRAZIN£
4. • c Lf !• rTICi* » l-ni trr*«t » i«^.
4-CHLOROPHENYL PHENYL ETHER
DIETHYL PHTHALATE
N-NI TROSOOI PHENYLAM INE
HEXACHLORO&ENZENE
4-BROMOPHENVL PHENYL ETHER
PHENANTHRENE/ ANTHRACENE
DI-N-dUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
8UTYLBENZYL PHTHALATE
BISI2-ETHYLHEXYLJ PHTHALATt
CHRYSENE/BENZO(AJ ANTHRACENE
S.a'-DlCHLOROBENZIOINE
. PYRENE
N0_l
5.8
4.6
7.2
9.8
7. 8
7.1
9.2
<1
10
145
3.6
4?
7.1
2.2
6.6
6.7
6
1.8
7.5
^
4.9
8.2
12
13
2.4
41
207
ai
16
7.2
37
9.2
20
20
16
N0_2
N0_3
N0_4
7.3
7:!
9.2
<1
7.2
11
-------
TABLE IV-8. BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL III
00
COMPOUND
113-0ICHLOROBENZENE
1 ,4-DlCHLGROBENZENE
1,2-OICHLOROBENZENE
HEXACHLOROETHANE
BIS(2-CHLQKOETHYL) ETHER
BISt2-CHLOROISOPROPYL) ETHER
HEXACHLOROBUTAOIENE
NITROBENZENE
NAPHTHALENE
1,2,4-TRlCHLOROBENZENE
B IS(2-CHLOROETHOXY)METHANE
N-NITROSOOt-N-PRGPYLAMIN£
HEXACHLORUCVCLOPENTAOIENE
2-CHLORONAPHT HAL EN E
ISOPHQRONE
ACENAPHTHVLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-OINITROTOtUENE
FLUORENE
2i4-DINITROTOLUENE
1,2-OIPHENYLHYDRAZINE
4-CHLOROPHENVL PHENYL ETHER
DIETHYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMGPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
BUTYLBENZYL PHTHALATE
BIS{2-£THVLHEXYL) PHTHALATE
CHRYSENE/8ENZO< A) ANTHRACENE
31S'-DICHLOROBENZIOINE
DI-N-OCTYL PHTHALATE
BENZO(B)/BENZQ(KJFLUORANTHENES
BENZO(AjPYRENE
lNOENOUr2f3-CO)PYRENE
01BENZCHAH)ANTHRACENE
BENZU(t»HUPERYLENE
ADDED
17.1
21.9
20.1
20
20
20.1
20.5
20.1
20
159.5
20.2
20
20.2
19.2
20.2
20.2
20.1
20.1
20.1
20.1
20.3
20
20.1
20.2
20
16
20.7
40.4
20.1
20.1
20.2
20
40.3
161
33.6
20
20.3
2*0:2-
20.2
20.2
20.1
NO_1
ia
20
20
21
31
24
238
i?
-------
00
oo
o u o
c n c
41 U 41
N t-1 N CJ
c c c c
0) a) 0) «J
AM
O O O *"
l-l V< H 4)
O O O O
rH rtr-l
o
O O'O
I—I—I—I—I—i—I—1
Figure IV-7.
GC/MS chromatogram of base/neutral extractables—
POTW Residual Waste, spiked
-------
TABLE IV-9.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
POTW RESIDUAL WASTE, SPIKE LEVEL 0
oo
COMPOUND
2-CHLGROPHENOL
2-NlTROPHENOt
PHENOL
2,*-OIMETHrLPHENOL
2t*-DICHLOROPHENOL
2t4i6-TRICHLOROf>HENOL
4-CHLORO-3-M£THrLPHENOL
2.4-D1NITROPHENOL
*,6-DINITRO-0-CRESOL
PENTACHLORQPHENOL
4-NITROPHENOL
ADDED
N0_l
N0_2
0
0
0
0
0
0
0
0
0
0
0
0
0
0.66
0
0
0
0
0
0
0°
0
0
0.92
0
0
0
0
0
0
0
0
N0_3
0
0
0.83
0
0
0
0
0
0
N0_5
MEAN
0.822
I
0.11
Z
Z
I
I
RSO RECOVERY
13
-------
TI
I i I I I I I I
is
» i
as.
Figure IV-8. GC/MS chromatogram of acid extractables —
POTW Residual Waste, unspiked
-------
TABLE IV-10.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL I
COMPOUND
2-CHLOROPHENOL
2-NITROPHENOL
PHENOL
2,4-OIMETHYLPHENOL
2,4-OlCHLORGPHENGl.
2.4t6-TRICHLOROPHENQl
4-CHLORO-3-METHYLPHENOL
lltt-DINITRG-O-CRESOL
PENTACHLOROPHENOL
4-NITROPHENOL
ADDED
N0_l
N0_2
N0_3
N0_4
N0_5
MEAN
RSD
5
c
c
I
5
5
e
5
3.3
0.61
4.8
1.2
2.5
2l5
<0.5
4.2
5.9
23
3.6
5
1.9
3
6.1
1.9
<0.5
8.2
44
2.8
1.2
3.1
1.3
2.5
3.8
1.7
1.1
1.9
6
31
5.9
1.1
6.6
1.6
5.3
3.2
1.6
3.7
8
46
5.4
(3.1)
5.6
2.7
4.6
4.8
3.2
1.5
4.8
11
55
4.2
3.9775
5.02
1.74
3.58
4.76
2.5
<1.04
4.32
7.82
39.8
1.37
0.26
1.28
0.60
1.29
0.90
0.70
0.53
1.85
2.08
12.72
32.5
26.4
25.5
34.6
36.1
18.8
28.1
50.7
42.8
26.6
32.0
RECOVERY
0
84
7*0
95
50
21
86
156
796
-------
TABLE IV-11.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL II
COMPOUND ADDED
2-CHLOROPHENOL 10
2-NITROPHENOL 10.1
PHENOL *"**
2,4-OIMETHVLPHENGL 10
2,4-OKHLDRCPHENOL 10.1
2.4.6-TRICH4.0ROPHENOL 10
4-CHLORO-3-METHYLPHENOL 10
2,4-DINITROPHENOL 10
4i6-DINITRO-0-CRESOL 10
PENTACHLOROPHENOL 10
4-NITROPHENOL 10
N0_l
6.2
1.8
6.3
3.9
6.3
8.2
3.8
4.3
N0_2
7.7
3.4
T.4
2.6
7.6
7.9
4.4
6.7
4.1
u
N0_3
5.6
3.4
6.3
3.8
5.6
5.8
13
4.5
74
N0_4
5.8
1.9
4.5
2.2
5.1
10
3.5
5.7
1.4
10
79
N0_5
MEAN
6.22
5.76
7.28
3.94
<5.48
4.02
10.66
76.5
S
0.86
0.82
1.14
0.96
1.28
2.15
0.78
4.96
1.61
1.04
2.89
RSO
13.8
29.8
19.2
28.3
22.3
29.6
19.8
90.4
40.0
9.7
3.8
RECOVERY
-------
TABLE IV-12.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
POTW RESIDUAL WASTE, SPIKE LEVEL III
COMPOUND ADDED N0_l N0_2
2-CHLOROPHENCL 20.1 14 15
2-NITROPHENCL 20.1 12 15
PHENOL 20 18 16
2f4-DlM£THYLPHENOL 20.1 2.2 2.8
2t4-DICHLOROPHENOL 20.2 13 16
2|4,6-TR1CHLGROPHENOL 20.1 22 52
4-CHLORO-3-MEIHYLPHENOL 20 24 11
2,4-DlNlTRGPHENOL 20 (114) (29)
4,6-OINlTRO-O-CRESQL 20.1 11 13
PENTACHLOROPHENOL 20 (75) 40
4-NITROPHENOL 20 85 (gs)
N0_3
14
16
17
0.99
8.4
33
16
14
4.9
30
87
12
9.1
13
1.5
7.5
23
15
12
1.1
30
87
N0_5
8.2
^» 3
^ 1
8.8
U
10
1.4
f^
4
HE AN
12.64
11.28
15
1.652
10.74
29.2
19
12
6.28
31
85.75
S
2.71
4.75
,'.92
0.85
3.62
15.96
7.31
2.00
6.63
1.50
RSO
21.4
42.1
19.4
51.2
33.7
54.7
38.5
16.7
87.2
21.4
1.7
RECOVERY
63
56
71
8
ill
95
60
ill
429
-------
Figure IV-9. GC/MS chromatogram of acid extractables—
POTW Residual Waste, spiked
-------
C. Ink Pigment Waste
195
-------
TABLE IV-13,
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
INK PIGMENT WASTE, SPIKE LEVEL 0
COMPOUND
1,3-DICHLOROBENZENE
1.4-D1CHLUROBENZENE
1,2-DICHLDROBENZENE
HEXACHLOROETHANE
BIS« 2-CHLOROETHYLJ ETHER
BIS(Z-CHLOROISOPROPYL) ETHER
HEXACHLQR08UTAOI ENE
NITROBENZENE
NAPHTHALENE
l,2f4-TRlCHLOROBENZENE
flISi2-CHLOROETHOXY) METHANE
N-NITRGSODI-N-PROPYLAmNE
HEXACHLOROCYCLOPENT ADI ENE
2-CHLOR ONAP H T HALE NE
ISOPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-OINITROTCLUENE
F LUCRE NE
ADDED
N0_l
N0_3
2t4-DINlTRCTOLUENE
1.2-DIPHENYLHY
A-CHLOROPHEMrt . ..
01 ETHYL PHTHALATE
:VI.IV W
ORAZINE
PHENYL ETHER
u A c • rt r •_ ni* f i ***.** I t
N-NITROSOOlPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
Dl-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIDINE
BUTYLBENZYL PHTHALATE
BISt2-ETHYLHEXYL) PHTHALATE
BENZOIAIPYRENE nvnfu,
INOENOC I i2,3-CO) PYRENE
OIBENZOI AH) ANTHRACENE
BENZO(GHI)PERYLENE
MEAN
24.6
29.2
0
0
10.7
78
2.88
0
10.86
7.62
1.96
0
20.2
0
3.66
0
0
<1.6
60.4
100
28.2
0
25.S
25.8
10.72
13.2
RSD
L0.2
L2.7
5.1
12.9
9.7
nla
9.0
9.1
8.5
lOll
5.3
27*7
*
63ll
14.4
9ll
10.5
4.4
13.6
12.0
14.9
4.8
RECOVERY
-------
TI
T T
' ' ' '
' ' ' '
1—i—i—r
Figure IV-10. GC/MS chromatogram of base/neutral extractables —
Ink Pigment Waste, unspiked
-------
TABLE IV-14.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT WASTE, SPIKE LEVEL I
oo
COMPOUND
1,3-DlCHLCIROBENZENE
1,4-0ICHLOR08ENZENE
U2-DICHCOROBENZENE
HEXACHLGRQETHANE
BIS12-CHLOROETHYLJ ETHER
BIS12-CHLORCJISUPROPYL1 ETHER
HEXACHLORGBUTADIENE
NITROBENZENE
NAPHTHALENE
1,2,4-TRICHLOROBENZENE
BIS(2-CHLOROETHOXV JMETHANE
N-N1T ROSOOI-N-PROPYLAMINE
HEXACHLGROCYCLOPENTADIENE
2-CHLORONAPHTHALENE
ISCPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
OIHETHYL PHIHALATE
2,6-DlNlTROTOLUENE
FLUORENE
2,4-DINITROTOLUENE
1,2-DIPHENYLHVDRAZINE
4-CHLOROPHENYL PHENYL ETHER
01ETHYL PHTHALATE
N-NITRCISODIPHENYLAHINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIDINE
BUTYLBENZYL PHTHALATE
B1S(2-ETHYLHEXYL) PHTHALATE
CHRYSENE/BENZOI A)ANTHRACENE
3,3'-DICHLOROBENZ10INE
OI-N-OCTYL PHTHALATE
BENZO(B)/BENZC1K)FLUORANTHENES
BENZOIAIPYRENE
INOENO«l,2i3-COJPYRENE
01 BENZQtAHIANTHRACENE
8ENZCHGHI JPtRYLENE
AOOEO
1.71
46.05
77.2
2
2
2. M
42.1
152.5
2.2
12.12
2.02
1.92
2.01
22.16
17.11
7.06
52. 2
12.18
!:8J
1.61
2.07
190.5
2.01
22.51
23.22
2.02
32.21
123.25
2.03
124
60.45
50.1
61.4
62
N0_l
64
95
6.9
2.3
1.7
17
170
3.2
11
11
<1
2.5
33
24
10
26
72
14
1.7
2.3
6.9
24
1.3
3.8
216
1.8
32
34
<1
4.9
120
185
231
119
88
120
133
N0_2
56
96
6.7
1.6
2*1
3.2
13
14
<1
2.5
11
24
69
7.1
2.2
3.2
213
1.6
5.7
157
158
189
155
79
94
108
N0_3
N0_4 N0_5
MEAN
RSO
94.4
LIT.8
135.4
U95
21.15
26.10
18.60
RECOVERY
59
75
89
94
104
130
72
660
50
131
76
100
100
131
1210
98
129
259
I960
93
99
85
70
65
84
50
235
124
125
50
49
ztl
96
-------
TABLE IV-15.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT WASTE, SPIKE LEVEL II
VO
COMPOUND
1 .3-OICHLOROBENZENE
1.4-OICHLOROBENZENE
1,2-DICHLOROBENZENE
HEXACHLOROETHANE
BIS(2-CHLORGETHYLJ ETHER
BISC2-CHLOROISOPROPYLI ETHER
HEXACHLOROBUTADIENE
NITROBENZENE
NAPHTHALENE
It 2.4-TRICHLGRGBENZENE
BIS(2-CHLOROETHQXYJMETHANE
N-NITROSOOI-N-PROPYLAMINE
HEXACHLORQCYCLCPENTAOIENE
2-CHLORONAPHTHALENE
ISOPHORONE
ACENAPHTHYLENE
AC EN A P HI HE NE
DIMETHYL PHTHALATE
2t6-DINIT«OTOLUENE
FLUORENE
2,4-DINITROTOLUENE
1,2-D1PHENYLHYDRAZINE
4-CHLOROPH6NYL PHENVL ETHER
OIETHYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-8UTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
BUTYJ.BENZYL PHTHALATE
B1M2-ETHYLHEXYLI PHTHALATE
CHRYSENE/BENZOIA)ANTHRACENE
3.3'-DICHLOROBENZlDINE
Ol-N-OCTYL PHTHALATE
BENZOlBI/BENZCKKIFLUORANTHENES
BENZO(AJPYRENE
INDENO(1,2,3-C01PYRENE
DlBtNZOIAHJANTHRACENE
BENZUJGHIJPERYLENE
ADDED
8.54
54.8
85.2
10.02
10
10.02
10.23
10.03
.5
40.34
10.02
10.11
9.6
10.08
110.8
85.55
35.21
10.05
60.25
60. <95
10.02
10.04
10. 11
10
8.06
10.34
206.7
13.06
112.45
116.05
10
10. 09
161.15
10.13
124
60.95
50.1
61.4
62
N0_l
Vo
10,
13
226
16
5.9
122
86
18
27
74
i!
Til
12
225
9.9
126
116
2.5
6
301
209
4.5
85
107
131
NQ_2
N0_3
5.3
T4
120
14
17
23
223
15
33
13
<1
13
6
23
32
90
63
5.9
27
11
18
261
7.4
133
112
2.1
6.9
in
265
140
111
142
139
N0_4
N0_5
12
iS!
12
14
5.8
11
26
231
13
34
J
124
fl
83
6.4
u
44
8
13
232
10
107
110
1.2
16
369
90
7.2
248
230
96
139
115
H f
MEAN
6.96
63.4
106
11.84
13.2
6.56
223.6
12.8
30.6
14.4
11.04
5.26
120
85
19
30.4
77.8
56.2
5.3
1.64
1.78
8.38
13.6
233.8
9.02
116.4
104.6
1.76
8.14
324.2
169.6
4.66
221.4
184.6
91.2
120.4
115.8
RSO
RECOVERY
81
4.70
19.62
14.34
19.03
-------
ISJ
O
O
TI
<«c --
«s«-<- ...
a lijji I
t"r«*
IS
ga
gg
•^a
35
I
^a
I
45
Figure IV-11. GC/MS chromatogram of base/neutral extractables —
Ink Pigment Waste, spiked
-------
TABLE IV-16.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
INK PIGMENT WASTE, SPIKE LEVEL 0
COMPOUND ADDED
2-CHLOROPHENOL 0
2-N1TRGPHENOL 0
PHENOL 0
2f4-DIMETHYLPHENOL 0
2t4-DICHLORCPH£NOL 0
2i4i6-TRICHLORGPHENOL 0
4-CHLORO-3-METHVLPHENOL 0
2,4-DINlTRCPHENfU. 0
4,6-DlNlTRO-O-CRESOL 0
PENTACHLOROPHENOL 0
4-NITROPHENOL 0
N0_l
4.9
54
1
< j_
0
Q
Q
1.4
5.2
N0_2
2.3
49
1
0
0
0
0
0
3
6.7
N0_3
1.9
57
< 1
< I
0
0
0
0
1.5
4.5
N0_4
3.2
62
1.2
0
0
0
0
2.9
6.2
N0_5
5.6
55
1.6
a
0
a
a
<]_
3.6
7.9
MEAN
3.58
55*4
< j_ ^ K)
<0.4
8
0
<0.4
2.48
6.1
S
1.61
4.72
0.26
z
£
2
0.96
1.32
RSO
45.1
B'S
22.5
•
^
^
39.4
21.7
RECOVERY
-------
ISJ
O
T J } 1 1 1 1 1
Figure IV-12. GC/ES chromatogram of acid extractables —
Ink Pigment Waste, unspiked
-------
TABLE IV-17.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT WASTE, SPIKE LEVEL I
o
U)
COMPOUND
2-CHLOROPHENOt
2-NUROPHENOL
PHENOL
2f4-OIMETHVLPHENGL
2,4-DICHLORGPHENOL
214,6-TRICHLOROPHENOL
t^CHLGRO-3-METHYLPHENOL
2,4-OINITRCPMENOL
4,6-DINlTRO-C-CRESGL
PENTACHLOROPHENOL
4-NITROPHENOL
AOOEO
N0_l
N0_2
N0_3
26.45
2
123.25
6.26
2.02
2.01
2
2.01
17.2
62.35
35
3.6
153
2.3
1.1
1.6
1.3
3.6
1.6
31
77
27
3.1
2 • 5
0.7
1.3
0.9
0.8
9.1
55
32
3.7
133
3
1.3
l.l
29
88
26
2
106
2.1
0. 7
0.6
0.8
1.7
°225
62
0_4
26
2
106
2.1
0. 7
0.6
0.8
1.7
0.5
22
62
N0_5
45
3.9
203
/ 2 4 )
2.5
<0.5
104
MEAN
33
3.26
140.2
2.475
1.025
1.28
1.3
<1.56
1.02
23.62
77.2
S
7.65
0.76
40.31
0.39
0.25
0.79
0.44
1.22
0.59
8. 78
19.74
RSO
23.2
23.4
28.8
15.6
24.4
61.4
34.0
78.2
57.8
37.2
25.6
RECOVERY
111
113
69
21
31
64
65
78
31
-------
TABLE IV-18.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
INK PIGMENT WASTE, SPIKE LEVEL II
NJ
O
COMPOUND
2-CHLORCPHENOl
2-NITROPHENOL
PHENOL
2t4-DlMETHVLPHENOL
2,4-DICHLORQPHENOL
2,4t6-TIUCHLOROPHENOI.
4-CHLORO-3-METHYLPHENOL
2,4-DINlTROPHENOL
416-OINITRO-O-CRESOL
PENTACHLORQPHENOL
4-NITROPHENOt
AOOEO
N0_l
N0_2
N0_3
N0_4
NO_S
MEAN
RSO
30.38
10.05
131.25
31.34
10. 1
10.08
10
10
10.04
86
70.35
24
129
10
a
14
ia
24
2. a
95
75
23
7.7
140
7.2
5.8
26
13
6.7
4.9
140
63
23
8.8
150
7.6
5.3
17
14
3
18
27
11
156
9.7
7.7
14
15
7.6
3.9
138
87
33
13
167
9.1
6.2
21
IB
12
is!'
,M
148.4
8.72
6.6
18. 4
14
10* 66
123l|
4.24
2.18
14.60
1.26
1.19
2* 92
8*12
50102
36.25
16.3
22.3
9.8
14.4
18.0
27.9
20.8
76.1
27.2
40.4
50.3
RECOVERY
7*
II
24
61
183
'
-------
Figure IV-13. GC/MS chromatogram of acid extractables—
Ink Pigment Waste, spiked
-------
TABLE IV-19.
METALS DATA—
INK PIGMENT WASTE, SPIKE LEVEL 0
K5
o
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
ADDED
0
0
0
0
0
0
0
0
0
0
N0_l
N0_2
0.2
11
316
<0.l
-------
TABLE IV-20.
METALS DATA—
INK PIGMENT WASTE, SPIKE LEVEL I
ELEMENT
ho
o
ADDED
N0_l
NC_2
N0_3
N0_4
N0_5
MEAN
RSO
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
6.1
6.1
6.1
6. 1
36. B
24.5
367.5
6.1
6.1
6.1
6. 1
6.1
24.5
5.3
6.2
6.3
6.2
122
37.3
656
?:*
7.1
0.3
6.1
52.7
5.8
7.4
6.3
6.1
122
33
652
4.2
6.9
6.1
0.2
4.9
54.9
5.2
7.6
6
5.8
116
32.4
635
4.2
7.2
6.1
4» T
56
5.1
7.5
6.5
6
122
32.6
665
3.4
7.3
6.1
0.2
4.7
54
4.8
7.6
6.4
109
32.2
630
4.1
7.1
6.9
0.2
5. I
55.1
5.24
7.26
6.3
6.04
118.2
33.5
647.6
6^46
0.24
5.1
54.54
0.36
0.60
0. 19
0.15
5.76
2.14
14.67
0.80
0.15
5.50
0.05
0.59
1.25
8*2
2* £
3.0
2. 5
4.9
6.4
2.3
18.6
7l7
?? -, ft
*. C • 9
11.4
2.3
RECOVERY
81
104
92
69
100
98
,jf
-------
D. Organic Still Bottoms
208
-------
TABLE IV-21.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS, SPIKE LEVEL 0
COMPOUND
1,3-OICHLOROBENZENE
1,4-DICHLOROBENZENE
1,2-DlCHLORGBENZENE
HEXACHLORUETHANE
BISJ2-CHLORDETHYLJ ETHER
BIS{2-CHLQROISOPRQPYL) ETHER
HEXACHLOROBUTADIENE
NITROBENZENE
NAPHTHALENE
l,2t4-TRlCHLOR08ENZENE
BISC2-CHLOROETHOXV)METHANE
N-NITROSOOI-N-PROPYLAMINE
HEXACHLGROCYCLOPENTADIENE
2-CHLORONAPHTHALENE
ISCPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2t6-OINiTROTOLUENE
FLUORENE
2t4~DINITROTOLUENE
1,2-01PHENYLHYDRAZI NE
4-CMLOROPHENYL PHENYL ETHER
DIETHYL PHTHAJ.ATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHKENE/ANTHRACENE
DI-N-BUTYL PHTHALAIE
FLUQRANTHENE
PYRENE
BENZIOINE
BUTYLBENZYL PHTHALATE
BIS12-ETHYLHEXYLJ PHTHALATE
CHRYSENE/BENZOUI ANTHRACENE
3,3'-OICHLOROBENZIOINE
DI-N-OCTYL PHTHALATE
BENZO(B)/BENZO(KIFLUQRANTHENES
BENZO(AIPYRENE
INDENO«l.2t3-C01PYRENE
01BENZOCAH)ANTHRACENE
BENZOCGHUPERYLENE
ADDED
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
N0_l
2.7
N0_3
19
135
59
665
0
0
3190
0
3?
0
0
0
38
492
0
0
0
0
3.9
0
78
0
0
0
0
0
0
0
1.3
3.5
0
0
0
0
0
0
0
N0_4
(2«)
(123)
(1226)
(7240)
0
(7§)
0
0
(52)
(955)
0
0
0
0
4.5
83
0
0
0
0
0
1.9
4.6
0
0
0
0
0
0
0
N0_5
MEAN
24.7!
1.07
RSO
31.1
16.5
26.1
28.4
RECOVERY
46.7
70.3
-------
n 1
c
a
fi c:
o £
•H 0
•O rtj
•fl .
3 1
/) 1
0 j
° 1
"2 I
u n
* 1
9) II
a
i
I
II
1 N H N 0)
e; c cc
'1 * +•
i 5 « -as
•o ft S 2 "3
o rj v* «
° ti g1 S S 8
•go ^o 5 S
"^ O ^ O e* ••
1 1, Jl II
" V S 19
» 1 i ' m -I £
r-tl.fJ ^ *^ O
A- AJw / U\ A .,.. , r L
^!™yi rnT i ^ i — i — i — i ^r i — i — i — i gi0 • i — i — i — i gis i — i — i — r—r-1 — i — i — i ^ i — i — i — rnr— i — i — i — P-T.
Figure IV-14.
GC/MS chromatogram of base/neutral extractahles
Organic Still Bottoms, unspiked
-------
TABLE IV-22.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
ORGANIC STILL BOTTOMS, SPIKE LEVEL 0
COMPOUND
Z-CHLOROPHENOL
2-NITROPHENCL
PHENOL
2.4-DIMETHYLPHENOL
2,4-DICHLOROPHENOL
2,4,6-TRICHLOROPHENOl.
4-CHLORO-3-METHYLPHENOI.
2,4-DINlIRUPHENOL
4U-DINI TRO-0-CRESOL
PENTACHLOROPHENOL
4-NITROPHENOL
ADDED
0
0
0
0
0
0
0
0
0
N0_l
N0_2
N0_3
N0_4
4
0
0
•8
0
0
0
0
0
8
0
0
5.5
0
0
0
0
8
0
0
0
0
4.9
0
0
0
§
0
0
0
0
0
3.5
0
J
0
0
0
0
3
0
N0_5
MEAN
0
0
0
0
0
s
0
a
0
0
0
4.46
0
Q
Q
§
0
0
0
z
I
0.77
Z
I
I
|
£
z
z
RSO
17
RECOVERY
-------
ho
M
I-O
Figure IV-15. GC/MS chromatogram of acid extractables—
Organic Still Bottoms, unspiked
-------
TABLE IV-23.
METALS DATA —
ORGANIC STILL BOTTOMS, SPIKE LEVEL 0
U)
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
AOOED
0
8
DOOOOOOOC
0
N0_l
Ol9
-------
TABLE IV-24.
METALS DATA-
ORGANIC STILL BOTTOMS, SPIKE LEVEL I
ELEMENT
AOOEO
N0_l
N0_2
N0_3
N0_4
N0_5
MEAN
RSO
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
5
5
20
500
10
200
5
5
50
0.2
4.7
3.6
4.12
51
1071
18
3.7
263
2.4
4.3
98
0.2
6.2
4.8
5.6
61
1194
22
4.9
318
3.6
5.7
2.6
116
0.1
3.8
4.4
53
902
19
4.4
266
2.3
4.3
2.1
95
0.12
4?2
4.8
58
1037
21
4.9
286
3.2
5.1
2.3
90
0.3
6.52
5.03
5.31
61
1104
22
til
3.5
5.8
3.2
111
0.184
5.584
4.286
4.846
56.8
1061.6
20.4
4.48
289
3
5.04
2.44
102
8:?7
8.62
.61
4.60
106.65
1.82
0.49
25.42
0.61
0.73
0.48
11.02
43.1
13.8
14.4
12.7
8.1
10.0
8.9
11.0
8.8
20.4
14.4
19.8
10.8
RECOVERY
2
92
84
93
99
87
96
43
93
-------
E. Paint Pigment Sludge
215
-------
TABLE IV-25.
PURGEABLE ORGANIC S DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL 0
COMPOUND
METHYLENE CHLORIDE
i, l-OICHLOROETHYLENE
1.1-01CHLOROETHANE
TRANS-1,2-DICHLOROETHYLENE
CHLOROFORM
1,2-OICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLORIOE
BROMOOICHLORCMETHANE
1.2-01CHLOROPROPANE
TRANS-lt3-DICHLOROPRQPENE
TRICHLOROETHYLENE
01BRO HOC HLOROME THANE
CIS-1.3-OICHLOROPROPENE
1,1.2-TRICHLORCETHANE
BENZENE
BROMQFORN
11It 2.2-TETRACHLOROETHENE
liIt 212-T ETRACHLOROETHANE
TOLUENE
CHLOROBENZENE
ETHYLBENZENE
ADDED
0
0
0
0
0
0
0
0
N0_l
0.65
0
0
0
0
0
0
0
"I
0
0
4.
N0_3
N0_5
8.
15
2.4
261
MEAN
0.743333
1.73333
3.83333
0
7.4666?
3.46667
2.06667
250.667
RSO RECOVERY
19.5
32.8
*
*
18*5
18.9
20.1
18.5
-------
(U
X)
•H
42
O
(U
C
QJ
4-1
(U
S
TI ?a«
i
0)
QJ
O <1)
M C
O 0)
r-H N
ft a
U
» 01
rH H
• I
CM
(U
c
r-H
O
H
QJ
01
N
C
OJ
O
1-1
O
N
C
0)
Aft.
AS-
2SL
£S-
Figure IV-16.
GC/MS chromatogram of purgeable organics by purge and trap—
Paint Pigment Sludge, unspiked
-------
TABLE IV-26.
PURGEABLE ORGANICS DATA —
PAINT PIGMENT SLUDGE, SPIKE LEVEL I
to
i-1
oo
COMPOUND
NETH/LENE CHLORIDE
l,l-DICMLOROETHYLENE
Itl-OICHLOROETHANE
TRANS-l,2-DlCHLORQ£THYLENE
1.2-DICHLOROETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLORIDE
BROMOOICHLOROMETHANE
1,2-0ICHLOROPROPANE
TRANS-113-D 1CHLCROPROPENE
TRICHLOROETHYLENE
OI8ROHOCHLOROMETHANE
CIS-1.3-OICHLOROPROPENE
1,1, 2-TRI CHJ.OROETHANE
BENZENE
BROMOFORM
1,1 ,2.2-TETRACHLOROETHENE
11112f 2-TETRACHLGROETHANE
TOLUENE
CHLDROBENZENE
ETHYL8ENZENE
ADDED
N0_l
2.5
2.4
2.3
2.2
*.4
1.5
1.3
2.6
3.5
2.2
0
0
0
0
108
1.4
10
10
0
2.9
0
N0_2
7.4
2.2
2.3
2.9
2.2
1.4
2.5
3.3
2.4
0
0
0
4.3
0
N0_3
4.4
!:!
1:1
4.T
1.7
N0_4
NO. 5
122
lii
8.9
0
4.2
0
HE AN
4.76667
2.26667
2.86667
2.23333
4.96667
116.
2.47
Ol 06
0. 15
-- 74
0.12
0.15
0.10
0.36
0.36
Z
7.57
0.26
0.58
0.57
0.78
RSO
51.8
8.3
2.5
5.3
2.6
14.8
3.8
10.0
14.4
6.5
17.6
5.4
6.1
2CK6
RECOVERY
-------
TABLE IV-27.
PURGEABLE ORGANICS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL II
ro
COMPOUND
METHYLENE CHLGRiDE
111-DICHLOROETHYLENE
1,1-DICHLOROETHANE
TRANS-1,2-DICHLOROETHYLENE
CHLOROFORM
lt2-DICHLORGETHANE
1,1,1-TRICHLOROETHANE
CARBON TETRACHLOR1DE
BROMOOICHLORCNETHANE
1,2-DJCHLOROPROPANE
TRANS-1.3-D1CHLOROPROPENE
TRICHLOROETMYLENE
OIBROMOCHLORCMETHANE
C1S-1.3-D1CHLOROPROPENE
1.1,2-TRlCHLOROETHANE
BENZENE
BRONOFORM
1,1,2 ,2-TETRACHLOROETHENE
1,1 ,2 ,2-TETRACHLOROETHANE
TOLUENE
CHLORC6ENZENE
ETHYLBENZENE
AODEO
N0_l
N0_2 N0_3
N0_4
N0_5
9.9
9.9
10
10
10
10
10
10
9.9
10
10
280
10
3.1
10
494
10
70°
10
10
8000
19
12
12
16
12
26
9.3
a.i
12
23
15
0°
0
57?
5i
49
22
7.9
0
16
11
12
15
11
27
8.5
7.6
15
22
15
0
598
11
66
62
21
17
0
16
11
12
12
24
8.3
7
12
20
14
0
1
706
13
74
39
22
0
ME AM
17
11.3333
12
15
11.6667
25.6667
8.7
7.56667
21.6667
14.6667
0
0
627
11.6667
63.6667
50
21.6667
12.9667
0
S
1.73
0.58
0.00
1.00
0.58
1.53
0.53
0.55
1.73
1.53
0.58
Z
|
69.22
1.15
11.68
11.53
0.58
Z
RSD
10.2
5.1
O.Q
6.7
4.9
6.0
6.1
7.3
3^9
•
9 9
1!:?
2.7
35.8
RECOVERY
164
114
120
1 50
|57?
87
76
131
217
147
8
126
117
562
tt
109
N
-------
to
O
Figure IV-17,
GC/MS chromatogram of purgeable organics by purge and trap-
Paint Pigment Sludge, spiked
-------
TABLE IV-28.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL 0
COMPOUND AOOEO
1,3-DICHLORQBENZENE 0
1,4-DICHLORUBENZENE 0
1,2-DICHLOROBENZENE 0
HEXACHLGRCETHANE 0
8ISC2-CHLOROETHYLI ETHER 0
B1SI2-CHLOROISOPROPYL) ETHEk 0
HEXACHLOROBUTAOIENE 0
NITROBENZENE 0
NAPHTHALENE 0
lf2.4-TRICHLOROBENZENE 0
8IS12-CHLOROETHOXYIMETHANE 0
N-NITROSGDI-N-PRQPYLAMINE 0
HEXACHLOROCYCCCPENTADIENE 0
2-CHLORGNAPHTHALENE 0
ISQPHORONE 0
ACENAPHTHYLENE 0
ACENAPHTHENE 0
DIMETHYL PHTHALATE 0
2f6-DINITROTOLUeNE 0
FLUGKfcNE 0
2,4-DINlTROTOLUENE 0
1 ,2-DIPHENVLHVORAZlNE 0
4-CHLORGPHENYL PHENYL ETHER 0
OIETHYL PHTHALATE 0
N-NITROSOOIPHENVtAMINE 0
HEXACHLOROBENZENE 0
4-BROMOPHENYL PHENYL ETHER 0
PHENANTHRENE/ANTHRACENE 0
JI-N-BUTYL PHTHALATE 0
FLUORANTHENE 0
PYRENE 0
SENZIOINE 0
BUTYL8ENZYL PHTHALATE 0
BIS(2-6THYLHEXYL) PHTHALATE 0
CHRYSENE/BENZOiAJANTHRACENE 0
3,3'-OICHLCiROBENZIDINE 0
OI-N-OCTYL PHTHALATE 0
BENZO(BJ/BENZG
-------
i i i i i—r—i—i—r~*i
Figure IV-18. GC/MS chromatogram of base/neutral extractables-
Paint Pigment Sludge, unspiked
-------
TABLE IV-29.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL I
COMPOUND ADDED N0_l
1,3-DlCHLOROBENZENe 1.71 < 0. 5
U4-OICHLOROBENZENE 3.19 <0.5
lt2-DICHLORCBENZENE 2 <0.5
HEXACHLOROETHANE 2 2
BIS<2-CHLGROETHYL* ETHER 2 3.3
BIS12-CHLOROISQPROPYLJ fcTHER 2 <0.5
HEXACHLOROBUTAOIENE 2.05 0.58
NITROBENZENE 2.01 3.3
NAPHTHALENE 2 4^4
lt2i4-TRICHLOROBENZENE 2.2 0.9
BIS(2-CHLORCETHCXrjMETHANE 2.02 1
N-NITROSODI-N-PROPYLAMINE 2 8.5
HEXACHLORUCYCLOPENTADIENE 2.02 <0.5
2-CHLORGNAPHTHALENE 1.92 1.1
1SOPHORQNE 2.02 0.98
ACENAPHTHYLENE 2.02 0.77
AC6NAPHTHENE 2.01 0.76
DIMETHYL PHTHALATE 2.01 0.61
2t 6-DIMTROTOLUENE 2.01 <0.5
FLUORENE 2.01 0.7*
2i4-DINITROTOLUENE 2.03 0.62
If 2-OIPHENYLHYORAZINE 2 0.5
4-CHLGROPHENYL PHENYL ETHER 2.01 0.63
OIETHYL PHTHALATE 2.02 1.1
N-N1TROSODIPHENYLAMINE 2 <0.5
HEXACHLOROBENZENE 1.61 <0.5
4-BROMOPHENYL PHENYL ETHER 2.07 1
PHENANTHRENE/ANTHRACENE 4.04 1.7
DI-N-BUTVL PHTHALATE 2.01 1.6
FLOORANTHENE 2.01 0.76
PYRENE 2.02 1.1
BENZIOINE 2.01 <0.5
BUTYLBENZYL PHTHALATE 2.02 0.7
BISJ2-ETHYLHEXVL) PHTHALATE 2.01 2
CHKYSENE/BENZO
-------
TABLE IV-30.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL II
N>
S3
•C-
COMPOUNO
1i3-01CHLOROBENZENE
1,4-OICHLOROBENZENE
1,2-01CHLOROBENZENE
HE XACHLOROETHANE
B1S(2-CHLOROETHYL) ETHER
BIS(2-CHLOROISOPROPYLI ETHER
HEXACHLCROBUTAOIENE
NITROBENZENE
NAPHTHALENE
li2.4-TRICHLOROBENZENE
BIS(2-CHLOROET HOXYJMETHANE
N-NITROSOOl-N-PROPYLAMINE
HEXACHLOROCYCLOPENTAOIENE
2-CHLORONAPHTHALENE
ISOPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2,6-DINIIROTOLUENE
FLUORENE
2i4-DINITRC)TOLUENE
1.2-PIPHENYLHYDRA7INE
^« f, — LF-i T I I UIV »•-«*" «*r* **«- *'»«-
4-CHLOROPHENYL PHENYL ElHER
01 ETHYL PHTHALATE
N-NITROSOOIPHENYLAN1NE
HEXACHLOROBENZENE
4-9ROHOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
OI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
8UTYLBENZYL PHTHALATE
BISC2-ETHYLHEXYLI PHTHALATE
CHRYSENE/BENZOUI ANTHRACENE
3,3'-OICHLOROBENZlOINE
OI-N-OCTYL PHTHALATE
8ENZOiB»/BENZO(KJFLUORANTHENES
BENZOiAIPYRENE
INDfcNOll,2,3-CDjPYRENE
01BENZOCAHJANTHRACENE
BENZCHGH1 JPERYLENE
ADDED
8.54
10.96
10.02
10.02
10
10.02
10.23
10.03
10.01
10.09
10.02
10.12
9.6
10.08
10.08
10.06
10.07
10.05
10.04
10.16
10.02
10.04
10.11
10
8.07
10.33
20.18
10.05
10.04
10.09
10.04
10.09
10.06
10.08
10.04
10.13
2?6il
o
0
10.12
N0_l
N0_2
ND_3
2.7
17
1.9
6.2
3.4
4.5
-------
N>
Ul
Figure IV-19.
GC/MS chroraatogram of base/neutral extractables—
Paint Pigment Sludge, spiked
-------
TABLE IV-31.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL 0
N)
COMPOUND
2-CHtORt)PH£NOl
2-N1TROPHCNOL
PHENOL
2,4-OIMETHVLPHENOL
2.4-OICHLOROPHENOL
2,4,6-TRlCHLGRQPHENOL
-------
ho
NO
--J
TI
r
10
1
15
1 - r
Figure IV-20. GC/MS chromatogram of acid extractables—
Paint Pigment Sludge, unspiked
-------
TABLE IV-32.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL I
ro
N3
00
COMPOUND
2-CHLOROPHENOL
2-NITRGPHENOL
PHENOL
2t4-01HETHVLPHENQL
2i4-D1CHLOftOPHENOL
2t4i6-TRICHLOROPHENOL
^CHLORg-3-METHrLPHENOL
ADDED
N0_l
N0_2
N0_3
N0_5
4-CHLORO-3-METHrL
2,4-DINITROPHENOL
4,6-OlNITRO-Q-CRE
PENTACHLOROPHENOL
4-NITROPHENOL
SOL
4.01
4.02
4
4.02
4.04
4loi
A
4.02
4.01
4.01
1.3
<0. 5
1.7
<0.5
1.5
<0.5
<0.5
<0.5
3.1
1.5
1
<0.5
<0.5
<0.5
1.8
<0.5
<0.5
<0.5
3.3
1
0.76
<0.5
0.79
<0.5
0.6
1.6
-------
TABLE IV-33.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA—
PAINT PIGMENT SLUDGE, SPIKE LEVEL II
COMPOUND
2-CHLOROPHENOL
2-NITROPHENOL
PHENOL
2,4-OIMETHVLPHENOL
2t4-DICHLOROPHENOL
2f*.6-TRICHLOROPHENOL
4-CHLORO-3-METHYLPHENOL
2i4-OINITROPHENOL
4,6-OINITRO-O-CRESOL
PENTACHLOROPHENGL
4-N1TROPHENOL
ADDED
10.03
10.05
10
10.04
10.1
10.06
10.02
10
10.04
10
10.02
N0_l
8
< J
5.6
< J[_
7.7
8
2.2
<1
5
-------
NJ
LO
O
Figure IV-21
GC/MS chromatogram of acid extractables-
Paint Pigment Sludge, spiked
-------
TABLE IV-34.
METALS DATA-
PAINT PIGMENT SLUDGE, SPIKE LEVEL 0
NJ
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
ADDED
0
0
0
0
8
0
0
0
0
0
0
0
N0_l
<0 I
1.7
^0*1
-------
TABLE IV-35.
METALS DATA —
PAINT PIGMENT SLUDGE, SPIKE LEVEL I
OJ
ELEMENT
AOOEO
N0_l
H0_2
N0_3
N0_5
MEAN
RSO
RECOVERY
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
1.8
1.8
1.8
1.8
18
180
18
9
0.9
1.8
1.8
360
<0.2
1.7
1.8
1.9
34
348
63
8.6
ils
838
<0.2
2
1.9
1.8
378-
67
8.4
<0.1
1.6
936
<0.2
1.5
1.8
2
37*
62
7.9
<0.1
0.9
1.3
921
<0.2
1.8
1.8
2
32
362
58
8.4
lii
<0.2
1.7
1.6
2.1
30
352
59
7.6
'Sri
k?
<0 2
1. 74
1.78
1.96
32.8
363.2
61.8
8.18
1.02
1.4
886.4
I
0.18
0.11
0.11
1.79
13.61
3.56
0.41
8:il
10.4
6.2
5.8
I:?
5.8
5.1
loJi
4.7
6
4
93
103
99
69
0
,8
-------
F. Coke Oven Biological Sludge
233
-------
TABLE IV-36.
PURGEABLE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL 0
COMPOUND
HETHYLENE CHLORIDE
Itl-OICHLOROETHYLENE
1,1-OICHLOROETHANE
TRANS-1,2-OICHLCROETHVLENE
CHLOROFORM
N> 1,2-DICHLGROETHANE
W 1,1,1-TRlCHLOROETHANE
*• CARBON TETRACHLORIOE
BROMOO1CHLOROMETHANE
1,2-DICHLORCPROPANE
TRANS-1.3-0ICHLOROPROPENE
TRICHLOROETHYLENE
DIBROMOCHLCROMETHANE
C I S-lt3-OICH1.0ROPROPENE
1,1,2-TRICHLOROEIHANE
BENZENE
BROMOFORM
1.1,2,2-TETKACHLOROETHENE
1 ,1 ,2 ,2-T ETRACHLOROETHANE
TOLUENE
CHLOR06ENZENE
ETHVLBENZENE
ADDED
N0_l
0.12
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
N0_2
0.055
N0_3
0.087
8
0
0
N0_>
N0_5
MEAN
.0873333
0
S RSO RECOVERY
0.03 37 2
-------
TABLE IV-37,
PURGEABLE ORGANICS DATA —
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL I
N5
w
Ln
COMPOUND ADDED
METHYLENE CHLORIDE 2
Itl-DICHLUROETHYLENE 2
1,1-DICHLOROETHANE 2
TRANS-1,2-DICHLOROETHYLENE 2
CHLOROFORM f
1,2-OlCHLOROETHANE 2
1,1,1-TRICHLOROETHANE 2
CARBON TETRACHLORIOE 2
BROMOOICHLOROMETHANE 2
1,2-DICHLGROPRGPANE 2
TRANS-1,3-DICHLOROPROPENE 2
TRICHLGROETHYLENE 2
UIBROMOCHLOROMETHANE 2
CIS-1.3-OICHLOROPROPENE 1.6
l.li2-TRICHLOROETHANE 2
BENZENE 2
BROMOFORM 2
l,lf2t2-TETRACHLOROETHENE 2
l,lf2t2-TETRACHLQROETHANE 2
TOLUENE 2
CHLOROBENZENE 2
ETHVLBENZENE 2
N0_l
0.87
1.7
1.5
1.9
f:23
0.94
1.9
2.2
I.I
2.2
1.6
2.6
1.8
2.6
2.3
1.3
1.7
1.9
1.8
N0_2
0.75
1.7
1.5
i.a
0.85
1.9
1.6
1.8
k!
1.6
1.7
N0_3
1.5
0.62
1.4
1.3
1.6
0.68
1.5
1.6
1.2
1.3
1.9
1.3
2.3
2.1
1.7
1.1
1.3
1.5
N0_4
N0_5
HE AN
1.83333
0.746667
1.43333
1.7*667
2.26667
0.823333
1.76667
1.8
1.66667
1.5
1.36667
2.43333
1.4
2.46667
1.43333
1.6
1.66667
RSO
15.7
>.7
I:!
8.6
6.7
9.1
16.0
13.1
19.2
25.0
11.5
8.2
15.2
6.3
28.6
21.3
18.8
9.2
RECOVERY
-------
NJ
Figure IV-22,
GC/MS chromatogram of purgeable organics by purge and trap'
Coke Oven Biological Sludge, unspiked
-------
TABLE IV-38.
PURGE ABLE ORGANIC S DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL II
COMPOUND AOOEO N0_l N0_2 N0_3
METHYL ENE CHLORIDE 9.9 9.2 11 7.9
Itl-DICHLOROETHYLENE 9.9 4.4 4.9 4.2
lil-OICHLOROETHANE 10 8.4 9.9 7.4
TRANS-1.2-D1CHLOROETHYLENE 10 7.7 8.4 6.6
CHLOROFORM 10 8.5 9.9 7.9
1,2-DICHLOROETHANE 10 11 12 9.5
1,1,1-TR1CHLOROETHANE 10 5.2 6.6 5.3
CARSON TETRACHLORIOE 10 4.5 5 4.4
BRQM001CHLOROMETHANE 9.9 10 11 9.6
1,2-LHCHLOROPROPANE 10 6.8 9 7.8
TRANS-1.3-OICHLOROPROPENE 10 9.3 11 8.7
TRICHLORGETHYLENE 9.9 7.9 9.4 7.3
D1BROHOCHLOROMETHANE 10 9.9 13 9.9
CIS-lt3-OICHLOROPROPENE 8.1 7.8 10 7.8
1,1,2-TRICHLOROETHANE 10 11 12 9.9
BENZENE 10 7.6 9 7.1
BROHOFORM 10 11 13 10
l,lt2,2-TETRACHLOROETHENE 10 7.7 6.5 7.7
l,lt2i2-TETRACHLOROETHANE 10 8.9 10 8.3
TOLUENE 10 8.6 9.4 7.4
CHLOROBEN2ENE 10 9.3 11 8.2
ETHYLBENZENE 10 9 9.8 8.3
N0_4
M0_5
MEAN
9.36667
4.5
8.56667
7.56667
B.76667
10.8333
4.63333
10.2
7.86667
9.66667
a. 2
10.9333
8.53333
10.9667
7.9
11.3333
7.3
9.06667
8.46667
9.5
9.03333
RSO
16
14
?:?
.6
13.7
6.9
7.1
14.0
12.3
13.2
16.4
9.5
9.5
11.9
RECOVERY
-------
U>
oo
Figure IV-23.
GC/MS chromatogram of purgeable organics by purge and trap-
Coke Oven Biological Sludge, spiked
-------
TABLE IV-39.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL 0
COMPOUND ADDED
1.3-OlCHLORGBENZENE 0
1,4-DlCHLORtBENZENE 0
1,2-QICHtOROBENZENE 0
HEXACHLUROETHANE 0
BIS(2-CHLGRGETHYLJ ETHER 0
BIS«2-CHLOROISCPRCPYL) ETHER 0
HEXACHLOROBUTAOIENE 3
NITROBENZENE o
NAPHTHALENE 0
If2f4-TRICHLOR08ENZENE 0
BIS(2-CHLOROETHCXy)METHANE 0
N-NITROSCDI-N-PRGPYLAMINE 0
HEXACHLOROCYCLOPENTAOIENE 0
2-CHLORONAPHTHALENE 0
1SOPHORCNE 0
ACENAPHTHYLENE 0
ACENAPHTHENE 0
DIMETHYL PHTHALATE 0
2,6-DINITROTOLUENE 0
FLUORENE 0
2.4-OINITROTOLUfcNE 0
1,2-OIPHENYLHYDRAZlNE 0
4-CHLOROPHENYL PHENVL ETHER 0
DIETHYL PHTHALATE 0
N-NITROSOD1PHENYLAMINE 0
HEXACHLOROBEN2ENE 0
4-BROMOPHENYL PHENYL ETHER 0
PHENANTHRENE/ANTHRACENE J
UI-N-8UTYL PHTHALATE 0
FLUORANTHENE 0
PYRENE 0
BENZIDIME 0
BUTYLBENZYL PHTHALATE 0
BIS(2-ETHYLHEXYLI PHTHALATE 0
CHRYSENE/BENZO
-------
t-o
.£>
O
TI
JJ2L
_LS_
_aa_
35
Figure IV-24 .
GC/MS chromatogram of base/neutral extractables
Coke Oven Biological Sludge, unspiked
-------
TABLE IV-40.
BASE/NEUTRAL EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL I
COMPOUND
1. 3-01CHLOROBE NZENE
1.4-OICHLORUBENZENE
1,2-OICHLORCBENZENE
HEXACHLOROETHANE
BISI2-CHLOROETHYLJ ETHER
BIS(2-CHLOROISOPROPYL» ETHER
HEXACHLOROBUTADIENE
NITROBENZENE
NAPHTHALENE
1,2,4-TfUCHLOROBENZENE
BIS«2-CHLGROETHOXYIMETHANE
N-NITROSODI-N-PROPYLAM1NE
HEXACHLGROCYCLOPENTADIENE
K> 2-CHLORCNAPHTHALENE
-P- ISOPHGRGNE
I— ACENAPHTHYLENE
ACENAPHTHENE
01 METHYL PHTHALATE
2t6-DINlTRUTOLUENE
FLUORENE
2i4-OINITROTOLUENE
1.2-OIPHENVLHVDRAZINE
4-CHLOROPHENYL PHENVL ETHER
OIETHYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
4-BROMOPHENYL PHENYL ETHER
PHENANTHRENE/ANIHRACENE
OI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZIOINE
BUTYCBENZYi. PHTHALATE
bIS(2-ETHYLHEXYL) PHTHALAIE
CHRYSENE/BENZCiAI ANTHRACENE
3,3»-DICHLOROBENZ10INE
01-N-OCTYL PHTHALATE
BENZOCBI/BENZOIKlFLUGRANTHENEi
BENZOIAIPYRENE
INOENOJIt 2.3-COJPYRENE
01BENZO(AH»ANTHRACENE
BENZOIGHIJPERYLENE
ADDED
N0_l
N0_2
N0_3
N0.4
N0_5
MEAN
RSD
1.71
2.19
2
2
2
2
2.05
2.01
2
2.2
2.02
2
2.02
1.92
2.02
2.02
2.01
2.01
2.01
2.01
2.03
2
2.01
2.02
2
1.61
2.07
4.04
2.01
2.01
2.02
2.01
2.02
2.01
2.02
2.01
2.03
4.42
2.08
0
0
2.02
<0.5
0.82
1.1
0.98
1.5
1.8
1
1.9
1.3
0.75
2.2
2.6
<0.5
1.4
1.8
1.3
1.2
0.8
0.72
1. 1
1.3
1.8
1.2
1.8
<0.5
1.2
1.8
3.4
2
2
2.4
<0.5
1 .9
1.8
1.8
1.9
<0.5
3
2.2
0.6
<0.5
1.1
<0.5
0.52
0.99
1.5
1.8
0.75
1.7
1.3
0.73
2
0.84
<0.5
1.4
1.7
1.4
1.2
0.71
0.69
1.1
0.75
1.6
1 «6
<0.5
0.62
2
3.9
1.9
1.8
2.1
<0.5
1.6
1.6
1.6
2
<0.5
3.5
2.4
0.53
<0.5
1.3
0.52
0.8
1.1
1.2
(2.2}
2.2
0.63
2.9
1.6
0.89
2.6
1.6
<0.5
2
2.3
1.7
1.5
0.71
1.2
1.3
1.1
2.3
2
<3.5
0.85
1.7
3.4
2.3
1.8
2.2
<0.5
2
1.8
2.3
<0.5
3.2
2.5
0.51
<0.5
1.7
<. 506667
0.713333
1.06667
1.05667
1.5
1.93333
0.793333
2.16667
1. 4
0.79
2.26667
1.68
<0.5
1.6
1.93333
1.46667
1.3
0.74
0.87
1.16667
1.05
1.9
1.13333
1.8
<0.5
0.89
1.83333
3.56667
2.06667
1.86667
2.23333
<0.5
1.86667
1.8
1.73333
2.06667
<0.5
3.23333
2.36667
0.546667
<0.5
1.36667
0.01
0.17
0.36
0.12
0.00
0.23
0.19
0.64
0.17
0.09
0.31
0.88
Z
0.35
0.32
0.21
0.17
0.05
0.29
0.12
0.28
0.36
0.06
0.20
Z
0.29
0.15
0.29
0.21
0.12
0.15
Z
0.25
0.20
0.12
0.21
Z
0.25
0.15
0.05
Z
0.31
2.3
23.5
5.4
11.8
0.0
23*1
29*7
12.4
13*5
52.5
*
21.7
16.6
14.2
13.3
7.0
32.9
9.9
26.5
1 1 • i
32.8
8.3
8.1
10.1
6.2
6.8
13 5
llll
6.7
10.1
7 8
6*5
8.6
22*4
RECOVERY
30
33
53
53
75
97
39
108
70
36
25
83
96
73
65
37
43
58
II
56
89
II
89
88
103
93
111
25
92
16
61
103
25
58
60
68
-------
TABLE IV-41.
BASE/NEUTRAL EXTRACTABLE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL II
KJ
-P-
ro
COMPOUND
1,3-D1CHLORGBENZENE
It 4-DICHLORCBENZENE
1,2-DlCHLORGBENZENE
HEXACHLORGETHANE
BlSJZ-CHLORliETHYL) ETHER
BIS12-CHLUROISOPROPYL) ETHER
HEXACHLOROBUTAOIENE
NITROBENZENE
NAPHTHALENE
1,2,4-TRICHLORGBENZENE
BIS12-CHLQROETHOXY)METHANE
N-N1TROSOOI-N-PROPYLAMINE
HEXACHLOROCYCLGPENTAOIENE
2-CHLGRONAPHTHALENE
ISGPHORONE
ACENAPHTHYLENE
ACENAPHTHENE
DIMETHYL PHTHALATE
2t6-OINtTKOTOLUENE
FLUORENE
2,4-01 MITROTOLUENE
1,2-OIPHENYLHYDRAZINE
4-CHLOROPHENYL PHENYL ETHER
01ETHYL PHTHALATE
N-N1TROSODIPHENYLAMINE
HEXACHL6ROBENZENE
4-BR&HOPHENYL PHENYL ETHER
PHENANTHRENE/ANTHRACENE
DI-N-BUTYL PHTHALATE
FLUORANTHENE
PYRENE
BENZ101NE
BUTYL6ENZYL PHTHALATE
B1S(2-ETHVLH£XYLI PHTHALATE
CHRYSENE/BENZC«AJANTHRACENE
3.3'-DtCHLORQBENZIDINE
DI-N-OCTYL PHTHALATE
BENZOtB)/BENZG«K)FLUORANTHENES
BENZCi(A) PYRENE
INOEN01 l.Zf 3-COJPYRENE
OIBEiMZO(AH) ANTHRACENE
BENZOIGH1JPEKYLENE
ADDED
8.54
10.96
10.02
10.0<>
10
10.02
10.23
10.03
10.01
11
10.09
10.02
10.12
9.6
10.08
10.08
10.06
10.07
10.05
10.04
10.16
10.02
10.04
10.11
10
8.07
10.33
20.18
10.05
10.04
10.09
10.04
10.09
10.06
10. 08
10.04
10.13
10.12
N0_l
5.6
8.4
10
5.7
11
4.3
3.7
1.6
5.7
17
9.2
6.2
6.8
8.9
7.2
6.2
7.8
6.2
4.9
7.8
11
5.2
6.8
7.7
8.6
8.8
8.2
8.3
4.4
3.3
7.4
3
<0.5
34
18
0.5
<0.5
N3_2
7
8.0
11
6.6
11
9.2
17
10
6.1
9.1
9.2
8.4
11
4.8
10
9.8
5.8
8.7
10
8.7
8.3
9.7
9.9
4.7
3.8
3.4
8.4
4.7
<0.5
44
24
<0.5
<0.5
N0_3
N0_4
N0_5
MEAN
6.26667
10.1333
11.6667
8.53333
9.33333
11.3333
o'.i
1.36667
5.66667
14.2333
2.13333
9.26667
5.43333
8
8.76667
7.83333
6.8
9.56667
6.8
4.8
9.6
10.2667
5.7
8.26667
9.23333
8.93333
8.96667
9.3
9.4
3.86667
4.23333
3.33333
8.6
4.13333
<0.5
40.3333
21.3333
<.513333
<0.5
14.6667
0.23
0.70
RSO
11.2
14.8
13.1
4.4
22.3
2:
33.7
10.8
7.6
22.9
14.4
fc?
7.8
17.0
27:?
17.1
6.3
t,0
.8
14.4
5.5
8.5
10.4
10.1
22.0
8.9
1.7
15.2
23.7
14.3
4.5
RECOVERY
145
-------
n
l
i
1—r
T—i—r
"i—r
Figure XV-25. GC/MS chromatogram of base/neutral extractables
Coke Oven Biological Sludge, spiked
-------
TABLE IV-42.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL 0
COMPOUND
2-CHLGROPHENCL
2-NiTROPHENOL
PHENOL
2,4-OIMETHiaPHENCL
2,A-01CHLORCPHENOL
2,
-------
Figure IV-26. GC/MS chromatogram of acid extractables—
Coke Oven Biological Sludge, unspiked
-------
TABLE IV-43.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL I
COMPOUND
2-CHLOROPHENCL
2-NITROPHENOL
PHENUL
2,4-OINETHYLPHENOL
2,4-OICHtOROPHENOL
2i4t6-TRICHLOROPHENOL
4-CHLORQ-3-METHYLPHENOL
2,4-01NITROPHENOL
4,6-OlNlTRO-O-CRESOL
PENTACHLOROPHENOL
4-NITROPHENOL
ADDED
N0_l
N0_2
N0_3
N0_4
N0_5
4.01
4.02
4.02
4.04
4.02
4.01
4^01
4.6
5.1
5.7
1
I
4*1
3?8
6.3
6.4
8.1
1.2
6.2
6.7
6.2
7.2
6.3
5.3
6.8
4.6
5
5.8
0.78
4.9
5.3
4.3
7.5
5.6
4.4
5.5
MEAN
RSO
RECOVERY
5.16667
5.5
6.53333
0.993333
5.36667
5.66667
4.86667
6.4
5.23333
4.6
5. 76667
0.98
0.78
1.36
0.21
0.72
0.91
1*65
1.29
0.62
0.93
19.0
14.2
20.8
21.1
13.5
23«i 0
25.8
24.6
13.6
16.1
129
137
151
25
133
12 1
160
130
61
144
-------
TABLE IV-44.
ACID EXTRACTABLE SEMIVOLATILE ORGANICS DATA-
COKE OVEN BIOLOGICAL SLUDGE, SPIKE LEVEL II
ro
COMPOUND
2-CHLORCPHENOL
2-NITROPHENOL
PHENOL
2i4-OIMEIHlTLPHENOL
214-01CHLOROPHENOL
2i4,6-TRICHLOROPHENOL
4-CHLORO-3-METHYLPHENOL
2,4-DINlTROPHENOL
4i 6-0 INITRO-0-CRESOL
PENTACHLOROPHENOL
4-NITROPHENOL
ADDED
N0_l
N0_2
N0_3
N0_4
N0_5
10.03
10.05
10
10.04
10.11
10.06
10.02
10
10.04
10.02
10.02
9.7
14
8
1.8
13
9
9.7
9
8.7
5.1
6.8
9.5
12
9.6
2.3
12
11
11
7.6
6
6.9
10
9.3
13
9.9
l.l
11
9.6
8.2
5.1
7.2
6.5
11
MEAN
9.5
13
9.16667
1.73333
9.86667
9.63333
7.3
7.3
6.16667
9.26667
S
9.20
1.00
1.02
0.60
K03
U40
2.00
1.3$
0.95
2.19
RSO
2.1
7.7
11.1
34.8
Ht',5
27.4
18.5
15.3
23.7
RECOVERY
95
129
87
90
73
40
92
-------
NJ
-O
TI
I
5
I
10
I
15
50
Figure IV-27.
GC/MS chromatogram of acid extractables-
Coke Oven Biological Sludge, spiked
-------
G- Electroplating Sludge
249
-------
TABLE IV-45.
METALS DATA-
ELECTROPLATING SLUDGE, SPIKE LEVEL 0
r-o
-------
TABLE IV-46.
METALS DATA-
ELECTROPLATING SLUDGE, SPIKE LEVEL I
tsi
Ui
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
ADDEO
16.3
16.3
16.3
16.3
651
0
651
16.3
1950
16.3
16.3
33
977
N0_i
16
14
11
17
3250
25000
1900
14
6160
9.1
<0.5
28
3010
N0_2
t!
10
16
3173
25900
1890
13
5810
11
<0.5
26
2960
N0_3
16
14
11
16
3230
24100
1930
13
5240
-------
H. Electric Furnace Baghouse Dust
252
-------
TABLE IV-47.
METALS DATA-
ELECTRIC FURNACE BAGHOUSE DUST, SPIKE LEVEL 0
tsj
Ui
ELEMENT
ADDED
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
0
3
Q
0
3
0
0
0
0
8
0
0
N0_l
9.4
38
<0.2
9.4
1670
424
1400
1.4
525
0*8
73500
N0_2
8.1
32
<0.2
a. i
1610
416
1280
1.2
547
0.6
65300
N0_3
8.6
32
<0.2
10
1520
429
1280
1.2
571
0.9
65500
N0_4
N0_5
MEAN
RSD
RECOVERY
8.7
-34
<0.2
9.16667
1600
iffi
fc£58
<1
0.833333
<1
68100
0.66
3.46
I
0.97
75.50
6.56
69.28
0.12
23.01
I
0.06
I
4677.61
7.5
10.2
l&
i:J
9.1
4.2
6l9
6^9
-------
TABLE IV-48.
METALS DATA-
ELECTRIC FURNACE BAGHOUSE DUST, SPIKE LEVEL I
ELEMENT
ANTIMONY
ARSENIC
BERYLLIUM
CADMIUM
CHROMIUM
COPPER
LEAD
MERCURY
NICKEL
SELENIUM
SILVER
THALLIUM
ZINC
ADDED
12. 5
12.5
12.5
12.5
125
125
500
12.5
250
12.5
12.5
25
0
N0_l
17
tl
11
18
1760
532
1830
13
812
8
0.9
19
68300
N0_2
19
37
11
18
1 710
548
1620
18
784
9.5
0.6
18
64100
N0_3
18
34
11
16
1760
543
1840
15
786
8
0.9
19
61600
NO 4
N0_5
MEAN
RSO
18
37.3333
11
17.3333
1743.33
541
1763.33
15.3333
8.5
0.8
18.6667
64666. 7
1.00
3.51
0.00
1.15
28.87
8.19
124.23
2.52
15.62
0.87
0.17
0.58
3385.75
5.6
9.4
0.0
6.7
1.7
1.5
7.0
l!:J
21 * 7
1:4
RECOVERY
74
27
86
65
115
94
89
113
99
60
N
71
-------
Appendix V. Text of Methods for Total Content
255
-------
A. Proposed Method for Purgeable
Organics in Residual Waste
256
-------
PROPOSED METHOD FOR PURGEABLE ORGANICS
IN RESIDUAL WASTE
(January 1981)
1. Scope and Application
1.1 Scope—This method is used for the determination of purgeable
organic compounds. A selected list of compounds that may be
determined by this method is provided in Table V-l.
1.2 Application—The method is applicable to the measurement of
purgeable organics in commercial residual wastes. It is
designed to be used to meet the survey requirements of the
Office of Solid Waste (OSW). The method uses a purge-and-trap
apparatus for isolation and concentration of purgeable organic
compounds and a GC/MS system for qualitative and quantitative
determination of these compounds. Because of the diverse nature
and complexity of residual waste, the method described below is
recognized as broad in scope; nevertheless, it was written with
a priority of simplicity in mind. Of course, no single method
is applicable to all waste matrices and some method modification
may be necessary for unusual waste types.
2. Summary of Method
2.1 An appropriate weight of sludge (determined by preliminary
screening of the extractable organic content of the sample) is
diluted to 10 mL with organic-free water. The diluted sample
is purged at room temperature (^25 °C) with an inert gas for
12 min. Water-insoluble compounds boiling below 200 °C are
transferred from the aqueous phase to the gaseous phase. The
gaseous phase is passed through a sorbent trap where the organic
compounds are concentrated. The contents of the trap are then
desorbed into the GC/MS by heating and backflushing the trap.
Because variations in recovery efficiencies for the individual
purgeable organics can be affected by the sample matrices,
extensive quality control is required for accurate measurements.
The total analysis time is less than 1 h. This method is
recommended for use only by experienced analysts or by experi-
enced technicians under the close supervision of a qualified
analyst.
3. Apparatus and Reagents '
3.1 For sample preparation.
3.1.1 Purge-and-trap system—Assemble the system depicted in
Figures V-l and V-2. If desired, a commercial version of
this system, such as the Tekmar Liquid Sample Concen-
trator Model LSC-1, or its equivalent, may be used.
257
-------
Details of the purging device in Figures V-l and V-2 are
shown in Figure V-3. Details of the trap in Figures V-l
and V-2 are shown in Figure V-4. The trap may be pur-
chased commercially (Supelco 2-0293) or packed with
the individual elements in the following order:
Place the glass wool plug in the inlet end of the
trap. Follow this with the 3% OV-1, Tenax-GC, silica
gel, activated charcoal, and the second glass wool
plug. This order must be followed if the trap is to
perform properly. Reversing the packing order (i.e.,
placing the charcoal in the trap first) will cause
the silica gel and Tenax-GC layers to become con-
taminated with charcoal dust and will cause poor
desorption efficiencies. Install the trap so that
the effluent from the purging device enters the
Tenax end of the trap.
3.1.2 Glassware.
a. Screw-cap vials—40 mL with Teflon-lined caps.
b. Graduated pipets—1, 5, and 10 mL with tips cut
off. Disposable macropipets such as Fisher
No. 21-164-4E may also be used.
c. Volumetric flasks—10 mL.
3.1.3 Analytical balance.
3.1.4 Roller mill and 1/8 in. stainless steel ball bearings
(or equivalent mixing apparatus).
3.1.5 Catalytic gas purifier (optional).
3.1.6 Purging gas—helium or nitrogen, high-purity grade.
3.1.7 Syringes—10 uL, 100 yL, and 5 mL; gas tight for
quality control spiking.
3.1.8 Water free of purgeable organics (see Section 5).
3.1.9 Packing materials for sorbent trap.
a. 3% OV-1 on Chromosorb W, 100/110 mesh.
b. Tenax-GC—60/80 mesh.
c. Silica gel—Davison Grade 15, 35/60 mesh or
equivalent.
d. Coconut charcoal—Barnebey-Cheney #CA-580-26,
26 mesh or equivalent.
258
-------
3.1,10 Glass wool—Cleaned by thorough rinsing with hexane,
dried in a 110 °C oven, and stored in a hexane-rinsed
glass jar with a Teflon-lined cap.
3.2 For quantitation and identification.
3.2.1 Gas chromatograph/mass spectrometer/data system—
Capable of scanning from 35 to 350 a.m.u. every
4 sec or less at 70 volts (nominal) and producing
a recognizable mass spectrum (background corrected)
at unit resolution from 50 ng of decafluorotriphenyl-
phosphine (DFTPP) when the sample is introduced through
the inlet of the chrotnatograph (Reference 1). Evaluate
the system performance each day by examining the
spectrum of DFTPP or p-bromofluorobenze (BFB) . Inject
50 ng of DFTPP and compare with the performance criteria
listed in Table V-2. To use BFB, inject 50 ng of BFB and
compare with the performance criteria listed in Table V-3.
The mass spectrometer must be interfaced with a gas
chromatograph equipped with an injector system designed
for all-glass on-column injection on packed columns or,
alternatively, equipped with a capillary injector system
designed for splitless injection and glass capillary
columns. All sections of the transfer lines must be
glass or glass-lined and must be deactivated. (Use
Sylon-CT, Supelco, Inc., or equivalent to deactivate.)
Note: Systems utilizing a jet separator for the GC
effluent are required since membrane separators may
cause loss of sensitivity to small molecules.
3.2.2 The GC/MS should be fitted with a 6-ft glass column
(1/4 in. OD x 2 mm ID) packed with 1% SP 1000 on
Carbopack B, 60/80 mesh, preceded by a 5-cm precolumn
packed with 1% SP-1000 on Chromosorb W, 60/80 mesh.
The precolumn is only necessary during conditioning.
An alternate packing to the SP-1000 on Carbopack B is
0.2% Carbowax 1500 on Carbopack C, 60/80 mesh. An 8-ft
stainless steel column can be substituted for the
6-ft glass column.
3.2.3 A computer system must be interfaced to the mass
spectrometer to allow acquisition of continuous mass
scans for the duration of the chromatographic program.
The computer system should also be equipped with mass
storage devices for saving all data from GC/MS runs.
There must be computer software available to allow
searching any GC/MS run for specific ions and plotting
the intensity of the ions with respect to time or scan
number. The ability to integrate the area under any
specific ion plot peak is essential for quantification.
259
-------
3.2.4 Reference materials—These materials consist of assayed,
authentic samples of all of the compounds to be deter-
mined and in addition the following standards—(1)
internal standards (Section 6.3), (2) surrogate standards
(Section 6.4), (3) decafluorotriphenylphosphine (a cali-
bration standard for the MS), (4) p-bromofluorobenzene
(also a calibration standard for the MS).
4. Sample Collection and Preservation
4.1 Container preparation—Samples must be collected in 40-mL screw-
cap vials with zero head space and sealed with Teflon-lined caps
(larger wide-mouth bottles with Teflon-lined caps may be used).
Wash all sample bottles in detergent before use; rinse with tap
water and finally with distilled water. Rinse the Teflon seals
with distilled water and allow the bottles and seals to air dry
at room temperature. Heat in a 100 °C oven for 1 h; then
allow to cool in an area known to be free of organics. Do not
heat the Teflon seals for extended periods of time (more than
1 h) because the silicone layer slowly degrades at 100 °C.
4.2 Sampling—Samples are collected at discrete time intervals by
grab sampling. When data for relatively long time intervals,
such as 24 h, are necessary or desirable, compositing of several
grab samples must be performed. To do this, collect six grab
samples (i.e., one 40-mL grab sample collected every 4 h over a
24-h period) and composite the six grab samples.
4.3 Preservation—As a general guideline, ice samples immediately
after collection, refrigerate at 4 °C, and purge within 10 days.
4.4 Sample handling—The chilled samples are mixed by gentle swirling
in a 250-mL wide-mouth flask. (Vigorous mixing must be avoided
to prevent analyte losses.) Analysis should be performed
immediately after compositing. When this is impossible or
sample material is to be retained for future reference, aliquots
of the composite sample should be returned to cleaned vials with
zero head space and stored at 4 °C.
5. Preparation of Reagent Water Free of Purgeable Organics
Reagent water is generated by passing tap water through a carbon filter
bed containing about 1 Ib of activated carbon. The water is purged
overnight with prepurified nitrogen. A Milliport Super-Q Water System
or its equivalent may be used to generate reagent water. Alternatively,
reagent water can be prepared by boiling distilled water for 15 min.
Transfer the water while it is still hot to a glass-stoppered bottle.
Cool to room temperature. Test the reagent water daily by analyzing it
according to the method in Section 9.1.
260
-------
6. Preparation of Standards
The following protocol assumes the preparation of stock solutions from
the pure compounds. Commercially available mixed stock solutions, if
they are shown to be satisfactory, may be used instead.
6.1 Analytical standards (solutions of authentic samples of the
compounds to be determined)—Prepare standard stock solutions
of liquid compounds (at approximately 20 Ug/UL) by adding, from
a 100-uL syringe, 1 to 2 drops (%0.2 mL) of the 99+% pure
reference standard to methyl alcohol (9 mL) contained in a
tared 10-mL volumetric flask (weighed to nearest 0.1 mg). Add
the component so that the drops fall into the alcohol and do
not make contact with the neck of the flask. Prepare standards
of gaseous compounds (e.g., vinyl chloride) in a similar manner
using a 50-mL valved gas-tight syringe with a 2-in. needle.
Fill the syringe with the gaseous compound. Weigh a 10-mL
volumetric flask containing 9 mL of methyl alcohol to the
nearest 0.1 mg. Lower the syringe needle to about 5 mm below
the methyl alcohol meniscus and slowly inject the standard
into the flask. The gas rapidly dissolves in the methyl
alcohol. Reweigh the flask, and use the weight gain to cal-
culate the concentration of the standard. Dilute the volume,
mix, and transfer to a 10-mL screw-cap vial and seal with a
Teflon-lined cap. Gas stock standards are generally stable
for at least 1 wk when maintained below 0 °C. Stock standards
of compounds that boil above room temperature, with the
exception of 2-chloroethyl vinyl ether, are generally stable
for at least 4 wk when stored at 4 °C. (Safety caution:
Because of the toxicity of most organohalides, precaution
should be taken by weighing and making dilutions of standards
in a fume hood.)
6.2 Solution for sample spiking (a solution of authentic samples
of the compounds to be determined)—Prepare the spiking solution
from appropriate stock solutions in accordance with the spiking
procedures given in the QA/QC protocol.
6.3 Internal standards spiking solution—From a neat compound, weigh
out 5 mg of d8-toluene or de-benzene in a 50-mL volumetric flask
with 45 mL of methyl alcohol in the container; mix and dilute to
volume (0.10 ug/yL). Add 5 to 10 yL (depending on background
interference) of this internal standard spiking solution to every
sample and analytical standard. The 50-mL volume of the internal
standard solution can be transferred to 10-mL serum vials and
sealed with Teflon-lined septa and crimp-on caps. Keep the
internal standard solution below 4 °C until use. Let the vial
reach room temperature and rinse off the outer surface before
removing aliquots.
261
-------
6.4 Surrogate standard spiking solution—From stock solutions prepared
as in Section 6.1, add 1 mg each of bromochloromethane and 1,4-
dichlorobutane to 45 mL of reagent water contained in a 50-mL
volumetric flask; mix and dilute to volume. Add 10 yL of this
surrogate spiking solution to every sample and analytical standard.
Prepare a fresh surrogate standard spiking solution on a weekly
basis. Surrogate standards can be attained commercially (Supelco
4-8823).
7. Sample Preparation and Purging
7.1 Weigh an appropriate sample into a pretared 10- to 15-mL Teflon-
lined, screw-capped vial.
Dilute the sample to 10 mL with reagent water. Transfer the total
sample or an aliquot of the purge device using a syringe with an
1/8-in. gauge Teflon needle. Seal the sample in the purge device.
Add an appropriate volume of surrogate and internal standard
solutions. With a gas flow of 40 mL/min (nitrogen or helium),
purge the sample 12 min at room temperature. If the sample
foams excessively, stop purging. Place a glass wool plug in the
top of purge tube to disperse the foam, seal the purge device,
and continue to purge (with excessive foam, smaller sample sizes
may be desired).
7.2 Weigh a second sample into a vial. Add the method recovery
spiking solution (Section 6.2) underneath the surface of the
sample; also add the surrogate and internal standard solutions.
Analyze as in Section 7.1.
8. Analysis of the Sample Purge
8.1 Heat the trap to 200 °G. Backflush it for 4 min in the desorb
mode into the gas chromatograph. Analyze the sample purge by
GC/MS using the 1% SP-1000 on Carbopack B column operated with a
helium carrier gas flow of 30 mL/min. Hold at 50 °C for 4 min,
and then program at 10 °C/min to 220 °C. Hold at this temperature
until all compounds have been eluted. The MS should be repeti-
tively scanned over the range m/e equal to 20 to 275 in 4 sec or
less. (A representative chromatogram is shown in Figure V-5.)
8.2 The purging device must be thoroughly rinsed with reagent water
between successive samples. Thoroughly clean the purging device
by flushing 10 mL of water into the purge device and removing
the water; do this several times before leaving the desorb mode.
Upon returning to the purge mode, the trap must be conditioned
at 200 °C with gas flow for 10 min between successive samples.
Let the trap cool 10 min before the next sample is added. For
dirty samples, longer conditioning may be required.
262
-------
9. Analytical Quality Assurance
9.1 System blanks—Analyze daily a reagent water blank spiked with
50 ng of p-bromofluorobenzene prior to the analysis of samples.
Check the spectrum obtained for p_-bromofluorobenzene and adjust
„ the MS tuning parameters as required to meet the ion abundance
criteria specified in Table V-3. The intensities of Extracted
Ion Current Profiles (EICP's) for the internal standards give
an overall check of the system sensitivity.
9.2 Analytical standards—Analyze standard solutions of low and
high concentrations of each day that sample analyses are
conducted. Response factor data obtained from these standards
are used to determine the concentrations of compounds identified
in the samples.
9.3 For the first sampling of each site within an industrial sub-
category, the method recovery must be determined.
9.4 Spiked and duplicate samples—Analyze spiked and duplicate
samples according to procedures in the QA/QC protocol.
9.5 All samples and analytical standards shall be spiked with
internal standard and surrogate spiking solutions at concen-
trations of the same order of magnitude as the concentrations
of spike recovery compounds.
10. Data Handling
Using the characteristic retention times and ions listed in Tables V-4
and V-5, obtain Extracted Ion Current Profiles (EICP's) of the character-
istic ions for each compound. Verify the presence of compounds of inter-
est on the basis of retention times and intensities of the characteristic
ions. Calculate the concentrations of compounds identified by comparing
the areas of the primary (highest abundance) ion peaks with the areas of
the corresponding standard peaks. If the sample matrix produces a signi-
ficant interference with the primary ion EICP, a secondary ion plot may be
used for quantitation. Calculate the concentrations in the sample as
follows:
in wet sludge.
whe re :
A = area of peak in the sample.
B = rea of peak in the analytical standard.
IS = area of internal standard peak in the sample.
263
-------
B = area of internal standard peak in the analytical standard.
J_ j
N = micrograms in the analytical standard .
W = weight of wet sludge analyzed (g) .
11. References
11.1 "Reference Compound to Calibrate Ion Abundance Measurement in
Gas Chromatography—Mass Spectrometry Systems," J. W. Eichel-
berger, L. E. Harris, and W. L. Budde, Anal. Chem. 47, 995-1000
(1975).
11.2 "Development of Analytical Test Procedures for the Measurement
of Organic Priority Pollutants in Sludge and Sediments,"
Midwest Research Institute, Final Report EPA Contract No. 68-
03-2695, June 26, 1979.
11.3 "Method for Purgeable Organics," (Unpublished), Personal
Communication with MERL-EPA, Cincinnati, Ohio 45268,
March 1980.
11.4 "Interim Methods for the Measurement of Organic Priority
Pollutants in Sludges," U. S. Environmental Protection Agency
Environmental Monitoring and Support Laboratory, Cincinnati,
Ohio 45268, September 1979.
264
-------
TABLE V-l. SELECTED PURGEABLE ORGANICS DETECTABLE
WITH THE PURGE-AND-TRAP METHOD
A. Fluoro-, Chloro-, and Bromomethanes
Methylene chloride (dichloromethane)
Chloroform (trichloromethane)
Carbon tetrachloride (tetrachloromethane)
Bromoform (tribromomethane)
Chlorodibromomethane
Bromod ichlo rome thane
Trichlorofluoromethane
B. Chlo roe thanes
1,1-Dichloroethane
1,2-Dichloroethane
1,1,1-Trichloroethane
1,1,2-Trichloroethane
1,1,2,2-Tetrachloroethane
C, Benzenes and Chlorobenzenes
Benzene
Chlorobenzene
Toluene
Ethylbenzene
D. Chloroethylenes, -propanes, and -propenes
1,1-Dichloroethylene (1,1-dichloroethene)
Trans-l,2-dichloroethylene
(Trans-1,2-dichloroethene)
Trichloroethylene (trichloroethene)
Tetrachloroethylene (tetrachloroethene)
1,2-Dichloropropane
Trans-1,3-dichloropropene
Cis-1,3-dichloropropene
265
-------
TABLE V-2. IONS AND ION ABUNDANCE CRITERIA
OF DECAFLUORQTRIPHENYLFHOSPHINE (DFTPP)
M/E Ion abundance criteria
51 30 to 60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40 to 60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5 to 9% of mass 198
275 10 to 30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17 to 23% of mass 442
266
-------
TABLE V-3. IONS AND ION ABUNDANCE CRITERIA
OF 2.-BROMOFLUOROBENZENE (BFB)
M/E Ion abundance criteria
50 20 to 40% of mass 95
75 55 to 75% of mass 95
95 base peak, 100% relative
abundance
174 75 to 98% of mass 95
175 5 to 9% of mass 174
176 75 to 98% of base peak and
93 to 99% of mass 174
177 0 to 5% of mass 176
267
-------
TABLE V-4. ELUTION ORDER AND DETECTABILITIES
OF SELECTED PURGEABLE ORGANICS
BY THE GC/MS METHOD3
Compound
Methylene chloride
Trichlorof luorome thane
1 ,1-Dichloroethylene
Bromochlorome thane
1 ,1-Dichloroethane
Trans -1 , 2 -dichlo roe thylene
Chloroform
1 ,2-Dichloroethane
1 ,1 ,l-Tr±chloroethane
Carbon tetrachloride
Bromodichloromethane
1 ,2-Dichloropropane
Trans-l,3-dlchloropropene
Tri chloroe thylene
Dibromochlorome thane
Cis-1 ,3-dichloropropene
1 ,1 , 2-Trichloroethane
Benzene
2-Bromo-l-chloropropane
Bromoform
1,1 ,2 ,2-Tetrachloroethene
1,1,2 ,2-Tetrachloroethane
1 ,4-Dichlorobutane
Toluene
Chlo r obenzene
Ethylbenzene
Relative
retention
timeb
0.38
0.39
0.46
0.47
0.48
0.52
0.53
0.56
0.61
0.62
0.64
0.69
0.70
0.73
0.75
0.76
0.76
0.76
0.80
0.86
0.95
0.95
0.96
1.00
1.05
1.15
Limit of
*g
injected
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
£•
detection '
yg/g of
sample
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
a. These data were obtained under the following conditions:
GC column, 6 ft x 2 mm ID glass column packed with 1% SP-1000
coated on Carbopack B, 60/80 mesh; carrier flow—30 mL/min;
temperature program—50 °C held for 4 min, programmed
10 °C/min to 220 °C and held until all compounds have been
eluted.
b. Relative to Toluene at 22.1 min.
c.
This is a minimum level at which the entire analytical system
must give recognizable mass spectra (background corrected) and
acceptable calibration points. The overall level of detection
is based on purging 0.1 gram of sample and desorbing total
volatiles to the MS system. This level may be difficult to
achieve depending on the nature of the sample.
268
-------
TABLE V-5. CHARACTERISTIC IONS OF PURGEABLE ORGANICS
Compound
Methylene chloride
Trichloro flurome thane
1 ,1 ,-Dichloroethylene
Bromochlorome thane
1 ,1-Dichlo roe thane
Trans -1 , 2-dichloroethylene
Chloroform
1 ,2-Dlchloroe thane
1 ,1,1-Trichloroethane
Carbon tetrachloride
B romodi chlorome thane
1 ,2-Dichloropropane
Trans-1 , 3-dichloropropene
Trichloroethylene
Dibromo chlorome thane
Cis-1 , 3-dichloropropene
1 ,1 ,2-Trichloroethane
Benzene
2-Bromo-l-chloropropane
Bromoform
1,1,2, 2-Tetrachloroethene
1 ,1,2 ,2-Tetrachloroethane
1 ,4-Dichlorobutane
Toluene
Chlorobenzene
Ethylbenzene
Ion used to
El ions (relative intensity) quantify
49(100);
101(100);
61(100) ;
49(100) ;
63(100) ;
64(100);
83(100) ;
62(100);
97(100);
117(100);
83(100) ;
63(100) ;
75(100);
95(100);
129(100) ;
75(100) ;
83 (95);
78(100);
77(100);
171 (50);
129 (64);
83(100);
55(100);
91(100) ;
112(100);
91(100) ;
51
103
96
130
65
96
85
64
99
119
85
65
77
97
127
77
85
39
79
(33);
(66);
(80);
(88);
(33);
(90);
(66)
(33);
(66);
(96);
(66);
(33);
(33)
(66);
(78);
(33)
(60);
(13);
(33);
173(100);
131
85
90
92
114
106
(62);
(66);
(30);
(78)
(33)
(33)
84
98
128
83
98
98
117
121
127
112
130
208
(86)
(53)
(70)
(3)
(57)
(23)
(17)
(30)
(13)
(4)
(90)
(13)
97(100)
51
156
175
164
131
92
(18)
(5)
(50)
(78)
(7)
9
9
9
9
9
9
9
9
9
•
9
9
9
9
86
51
98
100
119
129
114
132
206
99
250
(55)
(33)
(7); 100(4)
(15)
(16)
(17)
(3)
(85)
(10)
(63); 132 (9); 134(8)
(4); 252(11)
166(100);
133
(7); 166 (5); 168(6)
(10)
84
101
96
128
63
96
83
98
97
117
127
112
75
130
127
75
97
78
77
173
164
168
55
92
112
106
-------
NO
•^1
O
CARRIER GAS FLOW CONTROL
PRESSURE REGULATOR
LIQUID INJECTION PORTS
PURGE GAS
FLOW CONTROL \
13X MOLECULAR
SIEVE FILTER
OPTIONAL 4-PORT COLUMN
SELECTION VALVE
TRAP INLET (TENAX END)
RESISTANCE WIRE
COLUMN OVEN
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
PURGING DEVICE
HEATER CONTROL
Figure V-l. Purge-trap system (purge-sorb mode)
-------
PRESSURE REGULATOR
CARRIER GAS FLOW CONTROL
3
PURGE GAS .
FLOW CONTROL X
}3X MOLECULAR
SIEVE FILTER
LIQUID INJECTION PORTS
' [~| f| P] fl L
I U U U U
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CONFIRMATORY COLUMN
TO DETECTOR
'*"-- ANALYTICAL COLUMN
OPTIONAL 4-PORT COLUMN
SELECTION VALVE
TRAP INLET (TENAX END)
6-PORT VALVE I RESISTANCE WIRE
TRAP
200°C
PURGING DEVICE
HEATER CONTROL
Figure V-2. Purge-trap system (desorb mode)
-------
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MEDIUM POROSITY
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1/4 IN. O.D.
1/16 IN. O.D.
STAINLESS STEEL
13X MOLECULAR
SIEVE PURGE
GAS FILTER
PURGE GAS
FLOW CONTROL
Figure V-3. Purging device
272
-------
PACKING PROCEDURE
CONSTRUCTION
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CLASS WOOL JMM
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Figure V-5. Chromatogram of purgeable organics by purge and trap,
GC/MS
-------
B. Proposed Method for Base/Neutral and Acid
Extractable Semivolatile Organics
in Residual Waste
275
-------
PROPOSED METHOD FOR BASE NEUTRAL AND ACID
EXTRACTABLE SEMIVOLATILE ORGANICS
IN RESIDUAL WASTE
(January 1981)
1. Scope and Application
1.1 This method covers the determination for those semivolatile
organic pollutants that are solvent extractable and amenable
to analysis by gas chromatography/mass spectrometry. At a
minimum, the compounds listed in Table V-6 may be determined.
by this method.
1.2 This method is applicable to the determination of these compounds
in a variety of residual wastes. It is designed to be used to
meet the survey requirements of the Office of Solid Waste (OSW).
Because of the potential complexity of residual wastes, the method
described below is recognized as being broad in scope; neverthe-
less, it was written with a priority of simplicity in mind. Of
course, no single method is applicable to all waste materials and
some method modification may be necessary for unusual waste types.
1.3 The detection limit of this method is usually dependent upon the
level of interferences rather than instrumental limitations.
The limits listed in Tables V-7 and V-8 represent levels that can
be achieved in residual wastes in the absence of interferences.
These levels were determined by the minimum quantity required
for confirmation by the mass spectrometric method described
below.
1.4 This method is recommended for use only by experienced residue
analysts and persons experienced with GC/MS or under the close
supervision of such qualified persons.
2. Summary of Method
2.1 A 40-g sample of wet residual waste is extracted with methylene
chloride with the aid of a high-speed homogenizer. The sample
is extracted at pH >.!! and again at pH <2 to extract base/neutral
and acidic compounds, respectively. Each extract is dried over
sodium sulfate and concentrated to a volume of 5 mL or less by
use of a Kuderna-Danish (K-D) evaporator. The GC/MS conditions
described allow separation, identification, and quantitation of
the compounds in the extracts.
2.2 The method provides a general-purpose, gel permeation chromatography
(GPC) cleanup procedure to minimize interferences if they are
encountered.
276
-------
2.3 Identification of a compound (qualitative analysis) is performed
by an analysis of the full, background-corrected mass spectrum.
To identify a compound qualitatively, an Extracted Ion Current
Profile (EICP) is obtained for the primary ion and at least two
other ions (if available).
2.4 Quantitative analysis is performed by GC/MS with either the
internal standard or the external standard technique.
2.5 A flow diagram summarizing the method is given in Figure V-6.
3. Interferences
3.1 Solvents, reagents, glassware, and other sample processing hard-
ware may yield discrete artifacts causing misinterpretation. All
of these materials must be demonstrated to be free from inter-
ferences under the conditions of the analysis by running method
blanks. Specific selection of reagents or purification of solvents
by distillation in all-glass systems may be required.
3.2 Interfering substances coextracted from the samples will vary
considerably from source to source, depending upon the diversity
of the residual wastes being sampled. Although general cleanup
techniques are provided as part of this method, unique samples
may require additional cleanup approaches to isolate the compounds
of interest from interfering substances and to achieve the sensi-
tivities stated in Tables V-7 and V-8.
3.3 Glassware must be scrupulously clean. Clean glassware as soon
as possible after use by rinsing with the last solvent used.
Glassware should be sealed/stored in a clean environment immedi-
ately after drying to prevent any accumulation of dust or other
contaminants.
3.4 The recommended analytical procedure may not afford sufficient
resolution to differentiate between certain isomeric pairs.
Examples are anthracene and phenathrene, chrysene and benzo(a)-
anthracene , and benzo(b)fluoranthene and benzo(k)fluoranthene.
The GC retention times and mass spectral data are not sufficiently
different to provide an unambiguous distinction between these
compounds. Resolution may be improved with GC capillary columns.
Alternative techniques should be used to identify these specific
compounds.
4. Apparatus and Materials
4.1 Sampling equipment, for discrete or composite sampling.
277
-------
4.1.1 Grab sample bottle—Amber glass, 1-liter or 1-quart
volume, minimum. Bottle with a wide-mouth design is
recommended. The container must be washed, rinsed
with solvent, and dried before use to minimize inter-
ferences.
4.1.2 Bottle caps—Threaded to fit sample bottles. Caps
must be lined with Teflon. Aluminum foil may be
substituted if the sample is not corrosive.
4.1.3 Compositing equipment—Automatic or manual compositing
system that incorporates glass sample containers for
the collection of a minimum of 1000 mL. Sample con-
tainers must be kept refrigerated during sampling. No
plastic or rubber tubing other than Teflon may be used
in the system.
4.2 Extracting equipment.
4.2.1 SDT Tissumizer (Tekmar SDT 182 EN or equivalent).
4.2.2 Centrifuge (IEC CU-5000 or equivalent).
4.2,3 Screw-capped centrifuge bottles—200 mL (Scientific
Products C4144) with Teflon-lined screw caps.
4.2.4 Fleakers (or beakers)—300 mL.
4.2.5 Glass syringe—50 mL equipped with a 150 mm x 5 mm ID
Teflon tube.
4.3 Drying column—A 400 mm x 20 mm ID Chromaflex Column equipped
with a glass wool plug (Kontes Glass K-420300 or equivalent).
4.4 Kuderna-Danish (K-D) apparatus.
4.4.1 Concentrator tube—10 mL, graduated (Kontes K-570050-
1025 or equivalent). Calibration must be checked.
Ground glass stopper (size 19/22 joint) is used to
prevent evaporation of extracts.
4.4.2 Evaporative flask—500 mL (Kontes K-57001-0500 or
equivalent). Attach to concentrator tube with springs
(Kontes K-662750-0012).
4.4.3 Snyder column—Three-ball macro (Kontes K503000-0121 or
equivalent).
4.4.4 Snyder column—Two-ball micro (Kontes K-569001-0219 or
equivalent).
278
-------
4.4.5 Teflon boiling stones (Chemplast or equivalent).
4.4.6 Tube heater/concentrator (K720001) with heating block
(K720003).
4.5 Water bath for Kuderna-Danish concentrators. The bath should
be used in a hood.
4.6 Gel permeation chromatography cleanup apparatus.
4.6.1 Chromatography column—500 mm x 19 mm ID (Scientific
Products C-4670-106 or equivalent).
4.6.2 Bio-Beads S-X3, 200/400 mesh (Bio-Rad Laboratories
152-2750).
4.6.3 Glass wool.
4.6.4 Graduate cylinders—100 mL.
4.6.5 GPC Autoprep (Analytical Biochemistry Labs, Inc. 1002
or equivalent with 25-mm ID column containing 50 to 60 g
of Bio-Beads S-X3) (optional).
4.7 Gas chromatograph—Analytical system complete with gas chromato-
graph capable of on-column injection. All required accessories
including column supplies, gases, etc.
4.7.1 Column 1—For base/neutrals, a 6-ft glass column
(1/4 in. OD x 2 mm ID) packed with 1% SP-2250 coated on
100/120 Supelcoport (or equivalent).
4.7.2 Column 2—For acids, a 6-ft glass column (1/4 in. OD x
2 mm ID) packed with 1% SP-1240 DA coated on 100/120
Supelcoport (or equivalent).
4.8 Mass spectrometer—Capable of scanning from 35 to 350 a.m.u. every
4 sec or less at 70 volts (nominal) and producing a recognizable
mass spectrum (background corrected) at unit resolution from 50 ng
of decafluorotriphenylphosphine (DFTPP) when the sample is intro-
duced through the GC inlet (Reference 2). The mass spectrometer
must be interfaced with a gas chromatograph equipped with an
injector system designed for all-glass on-column injection on
packed columns or, alternatively, equipped with a capillary
injector system designed for splitless injection and capillary
columns. All sections of the transfer lines must be glass or
glass-lined and must be deactivated. (Use Sylon-CT, Supelco, Inc.,
or equivalent to deactivate.) Note: Systems utilizing a jet
separator for the GC effluent are required since membrane separators
may cause loss of sensitivity to small molecules, and glass frit
separators may inhibit the elution of polynuclear aromatics.
279
-------
4.9 A computer system must be interfaced to the mass spectrometer
to allow acquisition of continuous mass scans for the duration
of the chromatographic program. The computer system should also
be equipped with mass storage devices for saving all data from
GC/MS runs. There must be computer software available to allow
searching any GC/MS run for specific ions and plotting the
intensity of the ions with respect to time or scan number. The
ability to integrate the area under any specific ion plot peak
is essential for quantification.
5. Reagents
5.1 Sodium hydroxide—(ACS) 10 N in distilled water.
5.2 Hydrochloric acid—(ACS) concentrated, 12 N.
5.3 Sodium sulfate—(ACS) granular anhydrous; conditioned at 400 °C
for 4 h and rinsed with methylene chloride (20 mL of solvent
per gram of sodium sulfate).
5.4 Methylene chloride—Pesticide quality (Burdick and Jackson or
equivalent).
5.5 Reference materials—These materials consist of assayed, authentic
samples of all of the compounds to be determined and the following
standards in addition: (1) internal standards, (2) surrogate
standards, and (3) decafluorotriphenylphosphine (a calibration
standard for the MS). Internal standards may be selected from
the following list of compounds:
Deuterated compounds. For aromatics: de-benzene,
ds-toluene, and d 10-anthracene. For amines:
d$-pyridine and ds-aniline. For phenols: de-phenol.
For nitroaromatics: ds-nitrobenzene.
Surrogate standards are taken from this list of alternate compounds:
Fluorinated compounds: For aromatics: pentafluorobenzene,
2-fluoronaphthalene, and 1,2,3,4,5-pentafluorobiphenyl.
For phenols: pentafluorophenol, ot,a,a-trifluoro-m-cresol,
and 2-fluorophenol.
5.6 GPC calibration solution—Prepared as a 1:1 mixture of the following:
5.6.1 Corn oil-200 mg/mL in methylene chloride.
5.6.2 Bis(2-ethylhexyl phthalate) and pentachlorophenol—4.0 mg/mL
in methylene chloride.
280
-------
6. Calibration Standards
6.1 Prepare calibration standards that contain samples of the authentic
compounds to be determined, either singly or mixed together. The
standards should be prepared at concentrations that will completely
bracket the working range of the chromatographic system (two or
more orders of magnitude are suggested). If the limit of detection
of a given compound (Table V-7 or V-8) can be calculated as 20 ng
injected, for example, prepare standards at 10 yg/mL, 100 yg/mL,
1000 yg/mL, etc., so that injections of 1 to 5 yL of the calibra-
tion standards will define the linearity of the detector in the
working range.
6.2 Assemble the necessary gas chromatographic apparatus and establish
operating parameters equivalent to those indicated in Tables V-7
and V-8. By injecting calibration standards, establish the linear
range of the analytical system and demonstrate that the analytical
system meets the limits of detection requirements of Tables V-7
and V-8. If the sample gives peak areas above the working range,
dilute and reanalyze.
6.3 The internal standard consists of adding one or more of the
selected compounds (Section 5.5) to each sample to be analyzed.
This approach is acceptable for all of the extractable semi-
volatile organics when internal standards meeting the following
criteria can be selected:
6.3.1 No interference with other components in the sample.
6.3.2 Structural similarity to the compound to be determined.
6.3.3 The amount added approximates the concentration of the
compound to be determined.
6.4 Internal standard method—The utilization of the internal standard
method requires the periodic determination of response factors
(RF) which are defined in Equation 1.
RF - (AsCls)/(AisCs) (1)
where: As is the integrated area of peak height of the character-
istic ion for the calibration standard (an authentic sample
of the compound being determined).
Aj[s is the integrated area or peak height of the character-
istic ion for the internal standard.
C±s is the amount (yg) of the internal standard.
Cs is the amount (yg) of the calibration standard.
281
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The response factor (RF) must be determined over all concentra-
tion ranges of the calibration standard (Cs) which are being
determined. Generally, the amount of the internal standard
added to each extract is the same—20 or 40 yg/mL—so that Cis
remains constant. Use a minimum of three concentrations over
the range of interest. Once this relative response factor has
been determined, it should be verified daily by injecting at
least one standard solution containing an internal standard.
If a significant change has occurred, a new response factor must
be established. If significant changes in individual response
factors have occurred, a new calibration standard solution should
be analyzed. To quantify, add the internal standard to the con-
centrated sample extract no more than a few minutes before
injecting into the GC/MS. To minimize the possibility of losses
due to evaporation, adsorption or chemical reaction, calculate
the concentration by using Equation 2 in Section 17.2 with an
appropriate response factor from Equation 1. (Ideally, the
response factor will not change with concentration.)
6.5 The external standard method can be used at the discretion of
the analyst and is recommended when the criteria for use of the
internal standard cannot be met. Prepare a master calibration
curve using a minimum of three standard solutions of each of
the compounds that are to be measured. Plot concentrations
versus integrated areas or peak heights (selected characteristic
ion for GC/MS). One point on each curve should approach the
limit of detection in Table V-7 or V-8. After the master instrument
calibration curves have been established, they should be verified
daily by injecting at least one standard solution. If signifi-
cant drift has occurred, a new calibration curve must be
constructed. Calculate the concentration by using the equation
in Section 17.3.
7. Quality Control and Quality Assurance^
7.1 Before processing any samples, demonstrate through the analysis
of a method blank that all glassware and reagents are interference-
free. Each time a set of samples is extracted or there is a change
in reagents, a method blank should be processed as a safeguard
against chronic laboratory contamination.
7.2 Standard quality assurance practices should be used with this
method. Field replicates should be collected to determine the
precision of the sampling technique. Laboratory replicates
should be analyzed to determine the precision of the analysis.
Fortified (spiked) samples should be analyzed to determine the
accuracy of the analysis. Field blanks should be analyzed to
check for contamination introduced during sampling and transpor-
tation.
282
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7.3 GC/MS system performance evaluation is required each day the
system is used for samples or reagent blanks. A sample of
50 ng of decafluorotriphenylphosphine is injected into the
system, the mass spectrum is acquired, and the background-
corrected spectrum is plotted. Criteria established in
Reference 2 must be met. The analyst should also demonstrate
that the analytical conditions employed result in sharp total
ion current peaks for 100 ng of benzidine on the SP-2250
column when this column is used for base/neutrals, and 250 ng
of pentachlorophenol on the SP-1240 DA column when it is used
for acids. All plots from the performance evaluation must be
retained as proof of valid performance (Reference 3).
7.4 Further details on quality control and quality assurance are
given in the QA/QC protocol.
8. Sample Collection, Preservation, and Handling
8.1 Grab samples must be collected in glass containers. Conventional
sampling practices should be followed (Reference 5). Composite
samples should be collected in glass containers maintained at
4 °C and in accordance with the specific requirements of a given
sampling and analysis problem. Automatic sampling equipment
must be free of Tygon and other potential sources of contamina-
tion.
8.2 The samples must be iced or refrigerated from the time of col-
lection until the time of extraction. Chemical preservatives
should not be used in the field unless more than 24 h will
elapse before delivery of samples to the laboratory. If the
samples will not be extracted within 24 h of the time of
collection, preservation techniques should be considered to
prevent deterioration of the samples.
8.3 All samples must be extracted within 2 d of sample receipt and
within 5 d of sample collection. The analyses must be completed
within 7 d of collection.
9. Sample Extraction (Base/Neutrals)
9.1 Thoroughly mix the residual waste sample by homogenizing it in
the sample bottle. Weigh several 40-g aliquots into 250-mL
centrifuge bottles; spike the aliquots with the surrogate spikes
according to the QA/QC protocol. Add 40 mL of deionized,
'distilled water. Aqueous samples may not require the addition
of water.
283
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9.2 Adjust the pH of the sample with 10 N sodium hydroxide to a pH
of 11 or greater. Mix briefly with the homogenizer to ensure
uniform sample pH.
9.3 Add 60 mL of methylene chloride to each centrifuge bottle and
homogenize briefly. Rinse the homogenizer with a minimum
volume of water and then with about 5 to 10 mL of methylene
chloride. An additional amount of methylene chloride may be
added until the total liquid level is near the top of the
centrifuge bottle.
9.4 Centrifuge the sample aliquots at 1400 R.C.F. for 15 min. The
mixture will separate into an aqueous layer over the methylene
chloride extract. A solid cake or emulsion may form at the
water-methylene chloride interface. If the emulsion interface
between layers has more than one-half the volume of the solvent
layer, the analyst may employ a smaller sample aliquot to com-
plete the phase separation. The optimum technique will depend
upon the total solid content of the sample. Withdraw the organic
extract from the centrifuge bottle with a 50-mL glass syringe
that has been equipped with a 150 mm x 5 mm ID Teflon tube.
Discharge the extract into a 300-mL fleaker.
9.5 Add a second 60-mL volume of methylene chloride to the centrifuge
bottle and complete the extraction procedure a second time,
combining the extracts in the fleaker.
9.6 Perform a third extraction in the same manner. Pour the com-
bined methylene chloride extracts through a drying column
containing a 60-mm layer of anhydrous sodium sulfate and into
a 500-mL K-D flask equipped with a 10-mL concentrator tube.
Rinse the fleaker with 20 to 40 mL of methylene chloride.
Pour the rinse solvent through the drying column. Seal the
combined extracts and rinse solvent, label the base/neutral
fraction, and proceed with the acid extraction.
10. Sample Extraction (Acids)
10.1 Adjust the pH of the water, previously extracted for base-neutrals,
with hydrochloric acid to a pH of 2 or less. The acid must be
added slowly and with instant mixing to minimize foaming of the
sample.
10.2 Extract the sample again by procedures described in Sections 9.3
to 9.6. Discard the extracted residual wastewater aliquots.
Seal the combined extracts, label as the acid fraction.
284
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11' Extract Concentration (Base/Neutrals and Acids)
11,1 Add one Teflon boiling stone to the 500-mL K-D flask equipped with
a 10-mL concentrator tube and attach a three-ball macro-Snyder
column. Prewet the Snyder column by adding about 1 mL of methylene
chloride through the top. Place the K-D apparatus on a warm water
bath (60 to 65 °C) so that the concentrator tube is partially
immersed in the water and the entire lower rounded surface of the
flask is bathed with water vapor. Adjust the vertical position
of the apparatus and the water temperature as required to complete
the concentration in 15 to 20 min. At the proper rate of
distillation the balls of the column actively chatter but the
chambers do not flood. When the liquid has reached an apparent
volume of 1 mL, or when distillation appears to cease, remove the
K-D apparatus from the water bath and allow the solvent to drain
for at least 10 min while cooling. Remove the Snyder column and
rinse the flask and its lower joint into the concentrator tube
with 1 to 2 mL of methylene chloride from a Teflon squeeze bottle.
Reserve the concentrated extract for analysis or additional concen-
tration as in Section 11.2.
11.2 If additional concentration is required, add a clean boiling
stone and attach a two-ball micro-Snyder column to the concentrator
tube referred to in Section 11.1. Prewet the column by adding
about 0.5 mL of methylene chloride through the top. Place the
K-D apparatus in the tube heater that is preset at a temperature
required to complete the concentration in 5 to 10 min. At the
proper rate of distillation the balls of the column actively
chatter but the chambers do not flood. When the liquid reaches
an apparent volume of about 0.5 mL, remove the K-D from the tube
heater and allow the solvent to drain and cool for at least 10 min.
Remove the micro-Snyder column and rinse its lower joint into the
concentrator tube with approximately 0.2 mL of methylene chloride.
Adjust the final volume to 5.0 mL. This final volume adjustment
will depend on the concentrations of compounds being determined
as well as the nature of the residual wastewater. Reserve the
concentrated extract for analysis or cleanup as described in
Section 12. Cleanup will be required on all samples containing
interference.
12. Extract Cleanup
12.1 Place 20 to 25 g of Bio-Beads S-X3 in a 200-mL beaker. Cover the
beads with methylene chloride and allow the beads to swell over-
night before packing a 500 mm x 19 mm ID chromatographic column.
Put a glass wool plug in the bottom of the column. Transfer the
swelled beads to the column and continue to rinse the packed
column with methylene chloride. Add to the top of the packed
285
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column a glass wool plug followed by a layer of glass beads that
will prevent the Bio-Beads from floating to the top of the eluting
solvent. Wash the column with about 200 mL of methylene chloride.
Just prior to exposure of the GPC packing, stop the elution with
methylene chloride by closing the stopcock on the chromatography
column. Discard the eluted solvent.
12.2 Transfer 5 mL of the GPC calibration solution to the Bio-Beads
S-X3 column. Drain the column into a 12-mL graduated centrifuge
tube until the liquid is just above the surface of the GPC packing.
Wash the calibration solution on the column with several 1-mL
aliquots of methylene chloride. Elute the column with 200 mL of
methylene chloride and collect 10-mL fractions. Analyze the
fractions for bis^2-ethylhexyl) phthalate and pentachlorophenol
by GC/FID on a 1% SP-1240 DA column. Determine the corn oil
elution pattern by evaporation of each fraction to dryness
followed by gravimetric determination of the residue. Plot the
concentration of each component in each fraction versus the total
eluent volume. Determine the range of eluent volumes following
>85% of the corn oil, including all of the phthalate and all of
the pentachlorophenol, and including 50 mL beyond the pentachloro-
phenol. This range of eluent volumes dictates the range in which
all of the cleaned sample extract will be recovered in Section 12.3.
A typical calibration may result in the following procedure: dis-
card the first 60 mL and retain the next 110 mL for sample analysis.
12.3 Apply the above GPC separation procedure to an aliquot (1 to 4 mL)
of the base/neutral or acid concentrate from Section 11.2 The
volume of concentrate submitted to GPC is determined by the total
material in the concentrate. Determine a residue weight of the
concentrate by placing a 1-mL aliquot on a tared aluminum foil
pan, allowing the solvent to evaporate, and reweighing the pan.
The volume of extract submitted to GPC should not exceed the
capacity of the column—approximately 200 mg.
12.4 Collect the GPC-cleaned sample extract by the procedure determined
in Section 12.2, by allowing the correct range of column effluent
to pass through a 60-mm layer of sodium sulfate into a 500-mL
K-D flask equipped with a 10-mL concentrator tube. Rinse the
drying column with 10 to 20 mL of methylene chloride into the
K-D flask.
13. GPC-Cleaned Extract Concentration
13.1 Concentrate the GPC-cleaned extract as described in Section 11.
13.2 Transfer the cleaned, concentrated extract to a 6-mL serum Teflon-
capped bottle and store at 4 °C for GC/MS analysis.
286
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14. Gas Chromatography-Mass Spectrometry of Base/Neutrals Fraction
14.1 Table V-7 summarizes the recornmended gas chromatographic column
materials and operating conditions for the instrument. Included
in this table are estimated retention times and sensitivities
that can be achieved by this method for base/neutral extractable
semivolatile organics . An example of the separations achieved
is shown in Figure V-7.
14.2 Calibrate the system daily with a minimum of one injection of
calibration standards . Insure that the GC/MS system meets the
criteria in Reference 2 by injecting 50 ng of DFTPP through the
GC inlet system.
14.3 Transfer the sample extract (from Section 11.1, 11.2, or 12.4)
into a solvent-tight container. Do not add the internal standard
at this time. The recommended container is a standard 2-mL serum
vial equipped with a Teflon-lined rubber septum and crimp cap.
When the sample extract is not being used for analysis, it is
stored in a serum vial with an unpierced septum and in the dark
below 4 °C.
14.4 Internal standard—Add 40 yg of the internal standard (20 yL of
a solution having a concentration of 2 yg/yL) to 1 mL of the
sample extract just prior to analysis. Mix thoroughly.
14.5 Inject 2 to 5 yL of the sample extract into the GC/MS. The
solvent-flush technique is preferred. Smaller (1.0-yL) volumes
can be injected if automatic devices are employed. Record the
volume injected to the nearest 0.05 yL, and the resulting peak
size in area units.
14.6 If the peak area exceeds the linear range of the system, dilute
the extract and reanalyze.
14.7 At the beginning of each day that base/neutral analyses are to
be performed, inject 100 ng of benzidine either separately or as
a part of a standard mixture that may also contain 50 ng of DFTPP.
The tailing factor for benzidine should be less than three.
Calculation of the tailing factor is given in Reference 2 and
described in Figure V-9.
15. Gas Chromatography/Mass Spectrometry of Acid_Fraction
15.1 Table V-8 summarizes the recommended gas chromatographic column
materials and operating conditions for the instrument. Included
in this table are retention times and sensitivities that can be
achieved by this method for acid extractable semivolatile organics.
The limits of detection given in Table V-8 refer to the amounts
required to obtain MS confirmation by the methods described below.
Chromatography of nitrophenols is poor. An example of the sepa-
rations achieved is shown in Figure V-8.
287
-------
15.2 At the beginning of each day that acid fraction analyses are to
be performed, inject 250 ng of pentachlorophenol either separately
or as part of a standard mixture that may also contain DFTPP.
The tailing factor for pentachlorophenol should be less than
five. Calculation of the tailing factor is given in Reference 2
and described in Figure V-9.
15.3 After acceptable instrumental response is demonstrated, proceed
with the analysis as described for the base/neutral fraction.
(Sections 14.1 through 14.6).
16. Reduction of Data from the Mass Spectrometer
16.1 The complete background-corrected mass spectrum is compared to a
reference mass spectrum, from either an authentic sample or a
library spectrum, to provide qualitative identification. All of
the following criteria must be met:
16.1.1 The retention time relative to that of the internal
standard at the experimental mass spectrum must be
within ±60 sec of the relative retention time of the
authentic compound.
16.1.2 The ratios of the three EICP peak heights must
agree within ±20% with the ratios of the relative
intensities for these ions in a reference mass spectrum.
The reference mass spectrum can be obtained from either
a standard analyzed through the GC/MS system or a
reference library.
16.1.3 Structural isomers that have very similar mass spectra
(phenanthrene and anthracene; benzo(a)pyrene and benzo(e)-
pyrene, etc.) can be explicitly identified if the
resolution between the isomers in a standard mixture is
acceptable. Acceptable resolution is achieved if the
valley height between isomers is less than 25% of the
sum of the two peak heights. Otherwise, structural
isomers are identified as isomeric pairs.
16.2 In samples that contain an inordinate number of interferences,
the chemical ionization (CI) mass spectrum may make identification
easier. The use of chemical ionization MS to support El is
encouraged but not required.
17. Calculations (Base/Neutrals and Acids)
17.1 When a compound has been identified, the quantification of that
compound will be based on the integrated area from the specific
ion plot of the first-listed characteristic ion in Table V-9 or V-10.
If the sample produces an interference for the first-listed ion,
use a secondary ion to quantify. Quantification will be done by
the internal or external standard method.
288
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17.2 Internal standard method — By addition of a constant known amount
of internal standard (C^s in micrograms) to every sample extract,
the concentration of a pollutant (Co) in micrograms per gram of
the sample is calculated by use of Equation 2.
(Cis>
° (Ais) (RF)(W0)
where: W0 is the weight of the original sample in grams.
DF is the dilution factor.
Other terms are defined in Section 6.4.
17.3 External standard method — The concentration of a pollutant in
the sample is determined by use of Equation 3.
(A) (V.)
0 (Vi) (Ws)
where: A = mass of compound from calibration curve (yg) .
Vi = volume of extracted injected (UL).
Vt = volume of total extract (ML).
Ws = weight of sample extracted (g) .
17.4 Report all final results to at least two significant figures.
Report results in micrograms per gram without correction for
recovery data. When duplicate and spiked samples are analyzed,
all data obtained should be reported. Recovery data, relative
response ratios, and response factors from MS analysis should
be included in the data.
17.5 In order to minimize unnecessary GC/MS analysis of method blanks
and field blanks, the field blank may be run on a GC/FID equipped
with an appropriate SP-2250 or SP-1240 DA column. If no peaks
are seen of intensities equal to or greater than that of the
internal standard, then it is not necessary to do a GC/MS
analysis of the blank. If such peaks are seen, then the field
blank must be submitted for complete analysis.
18. References
18.1 Method 610, Polynuclear Aromatic Hydrocarbons, U.S. EPA, EMSL,
Cincinnati, Ohio 45268, 1979.
289
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18.2 "Reference Compound to Calibrate Ion Abundance Measurement in
Gas Chromatography—Mass Spectrometry Systems," J. W. Eighel-
berger, L. E. Harris, and W. L. Budde, Anal. Chem. 47_,
995-1000, 1975.
18.3 "Quality Assurance and Quality Control Procedures for Screening
and Verification of Industrial Effluents for Priority Pollutants,
U. S. EPA, EMSL, Cincinnati, Ohio 45268, 1979.
18.4 "Development of Analytical Test Procedures for the Measurement
of Organic Priority Pollutants in Sludges and Sediments,' MRI
Project No. 4583-A, EMSL, Cincinnati, Ohio 45268, 1979.
18.5 "Samplers and Sampling Procedures for Hazardous Waste Streams,"
EPA-600/2-80-018, January, 1980.
18.6 "Development of Analytical Test Procedures for the Measurement
of Organic Priority Pollutants in Sludge and Sediments,"
Midwest Research Institute, Final Report EPA Contract No. 68-03-
2695, June 26, 1979.
290
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TABLE V-6. BASE/NEUTRALS AND ACID EXTRACTABLES
DETERMINED BY THE PROPOSED METHOD
Base/Neutrals
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Hexachloroethane
Bis(2-chloroethyl) ether
Bis(2-chloroisoporpyl) ether
Hexachlorobutadiene
Nitrobenzene
Naphthalene
1,2 ,4-Trichlorobenzene
Bis(2-chloroethoxy)methane
N-nitrosodi-n-propylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Acenaphthene
Dimethyl phthalate
2,6-Dinitrotoluene
Fluorene
2,4-Dinitrotoluene
1,2-Diphenylhydrazine
4-Chlorophenyl phenyl ether
Diethyl phthalate
N-ni t ro so diphenylamine
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanth rene/anth racene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Benzidine
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Chrysene/benzo(a)anthracene
3,3'-Dichlorobenzidine
Di-n-octyl phthalate
Benzo(b)fluoroanthrene/
benzo(k)fluoranthene
Benzo(a)pyrene
Indeno(l,2,3-cd)pyrene
Dibenzo (ah)anthracene
Benzo(ghi)perylene
(Continued)
291
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TABLE V-6. BASE/NEUTRALS AND ACID EXTRACTABLES
DETERMINED BY THE PROPOSED METHOD
(CONTINUED)
Acids
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethylphenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-3-methylphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
Pentachlorophenol
4-Nitrophenol
292
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TABLE V-7. ELUTION ORDER AND DETECTABILITIES
OF BASE/NEUTRAL EXTRACTABLES BY THE
GC/MS METHOD3
Compound
1 , 3-Dichlorobenzene
1 ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
Hexachloroe thane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
Nitrobenzene
Naphthalene
1 ,2 ,4-Trichlorobenzene
Bis (2-chloroethoxy)methane
N-nitrosodi-n-propylamine
Hexachlorocyclopentadiene
2 -Chlor onaphthalene
Isophorone
Acenaphthylene
Acenaphthene
Dimethyl phthalate
2 ,6-Dinitrotoluene
Fluorene
2 , 4 -Dinitro toluene
1 ,2-Diphenylhydrazine*
4-Chlorophenyl phenyl ether
Diethyl phthalate
N-nitrosodiphenylamine**
Hexachlorobenzene
4-Bromophenyl phenyl ether
Phenanthrene / anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Benzidine
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Chrysene/benzo (a) anthracene
393'-Dichlorobenzidine
Relative
retention
timeb
0.19
0.21
0.24
0.24
0.35
0.35
0.44
0.46
0.47
0.49
0.53
0.58
0.58
0.66
0.68
0.73
0.76
0.83
0.83
0.83
0.87
0.87
0.88
0.89
0.89
0.90
0.95
1.00
1.12
1.19
1.22
1.36
1.37
1.41
1.42
1.49
Limit of detection
ng
injected
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
20
Ug/g of
sample
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0 .3
0.3
0.3
0.3
0.3
0.3
0.3
0«5
.3
0.3
Or\
.3
OQ
. j
0*^
.3
(Continued)
293
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TABLE V-7. ELUTION ORDER AND DETECTABILITIES
OF BASE/NEUTRAL EXTRACTABLES BY THE
GC/MS METHODa (CONTINUED)
Compound
Di-n-octyl phthalate
Benzo(b) fluoranthene/
benzo (k) fluoranthene
Benzo(a)pyrene
Indeno(l ,2 ,3-cd)pyrene
Dibenzo(ah) anthracene
Benzo ( ghi) perylene
Relative
Retention
time6
1.51
1.58
1.58
1.86
1.87
1.94
Limit of detection0
ng
injected
20
20
20
50
50
50
Vg/g of
sample
0.3
0.3
0.3
0.8
0.8
0.8
* Detected as azobenzene.
** Detected as diphenylamine .
a. Six-foot glass column (1/4 in. OD x 2 mm ID) packed with 1%
SP-2250 coated on 100/120 mesh Supelcoport. Carrier gas:
nitrogen at 30 mL/min. Temperature program: isothermal for
4 min at 50 °C, then 8° per minute to 270 °C. Hold at
270 °C for 15 min. If desired, capillary columns may be used.
b. Relative to dio-anthracene (internal standard) at 19.7 min.
c. This is a minimum level at which the entire analytical system
must give recognizable mass spectra (background corrected)
and acceptable calibration points. The overall level of detec-
tion is based on a 2-yL injection of the extract from a 40-g
sample of residual waste that has been extracted and concentrated
to a volume of 2.0 mL.
294
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TABLE V-8. ELUTION ORDER AND DETECTABILITIES
OF ACID EXTRACTABLES BY THE
GC/MS METHOD3
Compound
2-Chlorophenol
2-Nitrophenol
Phenol
2 ,4-Dimethylphenol
2 ,4-Dichlorophenol
2 ,4 ,6-Trichlorophenol
4-Chloro-3-methylphenol
2 ,4-Dinitro phenol
2 ,6-Dinitro-o-cresol
Pentachlorophenol
4-Nltrophenol
Relative
retention
time5
0.70
0.79
1.00
1.19
1.24
1.54
1.73
2.11
2.14
2.44
2.86
Limit of detection1"
ng
injected
50
50
50
50
50
50
50
200
200
50
50
yg/g of
sample
0.8
0.8
0.8
0.8
0.8
0.8
0.8
3.1
3.1
0.8
0.8
a. Six-foot glass column (1/4 in. OD x 2 mm ID) packed with 1%
SP-1240 DA coated on 100/120 mesh Supelcoport. Carrier gas:
nitrogen at 30 mL/min. Temperature program: isothermal for
2 min at 70 °C, then 8° per minute to 190 °C. Hold at
190 °C for 8 min. If desired, capillary column may be used.
b. Relative to de-phenol (internal standard) at 7.0 min.
c. This is a minimum level at which the entire analytical system
must give recognizable mass spectra (background corrected) and
acceptable calibration points. The overall level of detection
is based on a 2-yL injection of the extract from a 40-g sample
of residual waste that has been extracted and concentrated to
a volume of 2.0 mL.
295
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TABLE V-9. CHARACTERISTIC IONS OF BASE/NEUTRAL EXTRACTABLES
Compound
1 ,3-Dichlorobenzene
I ,4-Dichlorobenzene
1 ,2-Dichlorobenzene
Hexachioroe thane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Hexachlorobutadiene
Nitrobenzene
Naphthalene
1,2 ,4-Trichlorobenzene
Bis(2-chloroethoxy)methane
N-nitrosodi-n-propylamine
Hexachlorocyclopentadiene
2-Chloronaphthalene
Isophorone
Acenaphthylene
Acenaphthene
Dimethyl phthalate
2 ,6-Dinitrotoluene
Fluorene
2 ,4-Dinitrotoluene
1 ,2-Diphenylhdyrazine
4-Chlorophenyl phenyl ether
Die thy 1 phthalate
N-nitrosodiphenylamine
Hexa chlo rob enzene
4-Bromophenyl phenyl ether
Phenanthrene/anthracene
Di-n-butyl phthalate
Fluoranthene
Pyrene
Benzidine
Butylbenzyl phthalate
Bis(2-ethylhexyl) phthalate
Chrysene/benzo (a) anthracene
3,3 '-Dichlorobenzidine
Di-n-octyl phthalate
Benzo (b) f luoranthene/
benzo(k) f luoranthene
Benzo (a) pyrene
Indeno (1,2, 3-cd ) pyrene
Dibenzo (ah) anthracene
Benzo (ghi)perylene
El ions
(relative intensity)
146(100), 148(64), 113(12)
146(100), 148(64), 113(11)
146(100), 148(64), 113(11)
117(100), 199(61), 201(99)
93(100), 63(99), 95(31)
45(100), 77(19), 79(12)
225(100), 223(63), 227(65)
77(100), 123(50), 65(15)
128(100), 127(10), 129(11)
74(100), 109(80), 145(52)
93(100), 95(32), 123(21)
130 (22), 42(64), 101(12)
237(100), 235(63), 272(12)
162(100), 164(32), 127(31)
82(100), 95(14), 138(18)
152(100), 153(16), 151(17)
154(100), 153(95), 152(53)
163(100), 164(10), 194(11)
165(100), 63(72), 121(23)
166(100), 165(80), 167(14)
165(100), 63(72) , 121(23)
77(100), 93(58), 105(28)
204(100), 206(34), 141(29)
149(100), 178(25), 150(10)
169(100), 168(71), 167(50)
284(100), 142(30), 249(24)
248(100), 250(99), 141(45)
178(100), 179(16), 176(15)
149(100), 150(27), 104(10)
202(100), 101(23), 100(14)
202(100), 101(26), 100(17)
184(100), 92(24), 185(13)
149(100), 91(50)
149(100), 167(31), 279(26)
228(100), 229(19), 226(19)
252(100), 254(66), 126(16)
149(100) , 167(41)
252(100), 253(23), 125(16)
252(100), 253(23), 125(16)
276(100) , 138(37), 277(25)
278(100), 139(24), 279(24)
276(100), 138(28), 277(27)
Ion used to
quantify
146
146
146
117
93
45
225
77
128
180
93
130
237
162
82
152
154
163
165
166
165
77
204
149
169
282
248
178
149
202
202
184
149
149
228
252
149
252
252
276
278
276
296
-------
TABLE V-10. CHARACTERISTIC IONS OF ACID EXTRACTABLES
Compound
El Ions
(relative intensity)
Ion used to
quantify
2-Chlorophenol
2-Nitrophenol
Phenol
2,4-Dimethylphenol
2,4-Dichlorophenol
2,4,6-Trichlorophenol
4-Chloro-3-methylphenol
2,4-Dinitrophenol
4,6-Dinitro-o-cresol
Pentachlorophenol
4-Nitrophenol
128(100),
139(100),
94(100),
122(100),
162(100),
196(100),
142(100),
184(100),
198(100) ,
266(100),
65(100),
64(54)
65(35)
65(17)
107(90)
164(58)
198(92)
107(80)
63(59)
182(35)
264(62)
139(45)
130(31)
109 (8)
66(19)
121(55)
98(61)
200(26)
144(32)
154(53)
77(28)
268(63)
109(72)
128
139
94
122
164
196
142
184
198
266
139
297
-------
SLUDGE
(40 gms)
AJUST TO p
WITH 10 N NaOH
I
EXTRACT 3X WITH CH2CI2
BY HOMOGENIZATION/
CENTRIFUGATION
SLUDGE
ADJUST TO pH<2
WITH 12 N HCI
1
1
EXTRACT
DRY WITH N32SO4
EXTRACT 3X WITH CH2Cl2
BY HOMOGENIZATION/
CENTRIFUGATION
I
DRY WITH Na2SO4
I
CLEAN UP BY GPC ON
BIO-BEADS S-X3 ELUTED
WITH CH2Cl2
I
DETERMINE BASE/NEUTRALS
BY GC/MS ON SP-2250
CLEAN UP BY GPC ON
BIO-BEADS S-X3 ELUTED
WITH CH2CI2
I
DETERMINE PHENOLS
BY GC/MS
ON SP-1240-DA
Figure V-6.
Summary of the proposed method for
extractable base/neutral and acid
organic compounds in residual waste
298
-------
o
c
•o
^J
3
0
Ll
o
.
0
i
OJ
c
ithrac
to
in
41(
ci at
c c
TI
I J3
C 4J
^ C
O 2
O
3
^H
Pb
e
>,
Xi V
i — i
25
Figure V-7. Chromatogram of extractable base/neutral semivolatile organico, GC/MS
-------
LO
O
O
TI
10
15
i I
es.
Figure V-8. Chromatogram of extractable acid semivolatile organics, GC/MS
-------
BC
TAILING FACTOR = —
Example calculation:
Peak Height = DE = 100 mm
10% Peak Height = BD = 10 mm
Peak Width at 10% Peak Height = AC = 23 mm
AB = 11 mm
BC = 12 mm
Therefore: Tailing Factor = -ry = 1.1
Figure V-9. Tailing factor calculation
301
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C. Proposed Method for the Determination of
of Metals in Residual Waste
302
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PROPOSED METHOD FOR THE DETERMINATION
OF METALS IN RESIDUAL WASTE
(January 1981)
1. Scope and Application
1.1 This method may be used for the determination of metals in residual
wastes. Although the method should be applicable to a wide range
of industrial wastes, it is recognized that low recoveries of certain
elements may be experienced with some types of waste materials and
that modifications in the method may be required in order to obtain
satisfactory results.
1.2 Total elemental concentrations are determined following a digestive
procedure. Since significant concentrations of elements other than
the elements of interest may also be dissolved by the digestive
step, each particular matrix, must be examined for potential inter-
ference problems.
1.3 Detection limits, sensitivity, optimum ranges, and recommended
wavelengths for the determination of selected metals by direct
aspiration, furnace, gaseous hydride, and cold vapor (mercury)
procedures may be obtained by consulting the instruction manual
for the particular instrument being used. Sensitivity values
may vary slightly with various makes and models of atomic
absorption spectrometers. Actual working detection limits,
however, are dependent on the sample matrix.
2. Summary of Method
2.1 This method describes a procedure for the determination of elements
in residual wastes, after acid digestion, by atomic absorption
spectroscopy.* The method of analysis may be by direct aspiration,
furnace, or gaseous hydride technique, dependent on the concentra-
tion of the metal in a particular matrix. Mercury should be
determined by the cold vapor procedure. A series of measurements
must be performed to evaluate potential spectral, physical, and
chemical interference problems as outlined in Section 4.1. Back-
ground correction should be employed for all analyses.
3. Definitions
3.1 Total metals—The concentration determined on an unfiltered sample
following acid digestion.
* An ICP spectrometer, if available, may also be used.
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3.2 Detection limit—The concentration equivalent to a signal due to
the analyte that is equal to three times the standard deviation
of a series of ten replicate measurements of a reagent blank
signal at the same wavelength. In an actual sample, however,
the detection limit may be influenced by the sample matrix.
3.3 Sensitivity—The concentration of an element which will produce
a signal of 0.0044 absorbance units.
3.4 Instrument check standard—A standard of known concentrations
prepared by the analyst. It should be included in the analytical
scheme with a frequency of 10%.
3.5 Reference standard—A solution obtained from an outside source
having known, verified values. It must be used initially to
verify the calibration standards and analyzed thereafter as a
blind sample on a weekly basis.
3.6 Calibration standards—A series of known standard solutions used
by the analyst for calibration of the instrument (i.e., prepara-
tion of the analytical curve).
3.7 Linear dynamic range—The concentration range over which the
analytical curve remains linear.
3.8 Reagent blank—A volume of deionized, distilled water containing
the same acid matrix as the calibration standards which is carried
through the entire analytical scheme.
3.9 Calibration blank—A volume of deionized, distilled water acidified
with nitric acid.
3.10 Method of standard addition—The standard addition technique
involves the use of the unknown and the unknown plus a known
amount of standard.
4. In te r f e r en ce s
4.1 Several types of interference effects may contribute to inaccuracies
in the determination of trace elements. They can be summarized as
follows:
4.1.1 Spectral interferences can be categorized as (1) overlap
of a spectral line with that from another element; (2)
unresolved overlap of molecular band spectra; and (3)
background contribution from continuous or recombination
phenomena. The first of these effects can be compensated
for by utilizing a computer correction of the raw data,
requiring measurement of the interfering element. The
second effect may require selection of an alternate wave-
length. The third can usually be compensated for by a
background correction adjacent to the analyte line.
304
-------
4.1.2 Physical interferences are generally considered to be
effects associated with the sample nebulization and
transport processes. Such properties as change in
viscosity and surface tension can cause significant
inaccuracies especially in samples that may contain
high dissolved solids and/or acid concentrations. If
these types of interferences are operative, they must
be reduced by dilution of the sample and/or utilization
of standard addition techniques.
4.1.3 Chemical interferences are characterized by molecular
compound formation, ionization effects and solute
vaporization effects. These, if observed, can be
minimized by careful selection of operating conditions,
by buffering of the sample, by matrix matching, and by
standard addition procedures. These types of inter-
ferences can be highly dependent on the matrix type and
the specific analyte element. Consult the manufacturer's
operating manual for specific details regarding procedures
to minimize chemical, interferences .
4.2 It is recommended that whenever a new or unusual sample matrix
is encountered, a series of tests be performed prior to reporting
concentration data for analyte elements. These tests, as outlined
in Sections 4.2.1 through 4.2.4, will assure the analyst that
neither positive nor negative interference effects are operative
on any of the analyte elements thereby distorting the accuracy of
the reported values.
4.2.1 Serial dilution—If the analyte concentration is suffi-
ciently high (minimally a factor of 10 above the instrumental
detection limit after dilution), an analysis of a diluted
sample should agree within 5% of the original determination
(or within some acceptable control limit that has been
established for that matrix). If not, a chemical or physi-
cal interference effect should be suspected.
4.2.2 Spike addition—The recovery of a spike added at a minimum
level of 10X should be within 90 to 110% or within the
established control limit for the matrix being analyzed.
If not, a matrix effect should be suspected. The use of
a standard addition analysis procedure can usually com-
pensate for this effect.
4.2.3 Comparison with an alternate method of analysis—When a
new sample matrix is investigated, comparison tests may be
performed with other analytical techniques such as ICP or
other approved methodology. (Caution: The standard
addition technique does not detect coincident spectral
overlap. If suspected, use of an alternate wavelength or
comparison with an alternate method is recommended.)
305
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4.2.4 Wavelength scanning of the analyte line region—If the
appropriate equipment is available, wavelength scanning
can be performed to detect potential spectral inter-
ferences.
5. Apparatus
5.1 Atomic absorption spectrometer.
5.1.1 Background corrector.
5.1.2 Furnace attachment.
5.1.3 Recorder, multi-range, 0-10 mV.
5.1.4 Argon gas supply, welding grade or better.
5.1.5 Acetylene gas supply, welding grade.
5.1.6 Nitrous oxide gas supply, C.P. grade.
5.1.7 Nitrogen gas supply, dry.
5.1.8 Hydrogen gas supply, C.P. grade.
5.1.9 Air supply: dry, oil-free, dust-free air from cylinders
or compressed air lines.
5.2 Operating conditions—Because of the differences between various
makes and models of satisfactory instruments, no detailed operating
instructions can be provided. Instead, the analyst should follow
the instructions provided by the manufacturer of the particular
instrument being used. Sensitivity, instrumental detection limit,
precision, linear dynamic range, and interference effects must be
investigated and established for each individual analyte line on
that particular instrument.
6. Reagents and Standards
6.1 The nitric acid used in the preparation of standards and for sample
processing and preservation must be ultra-high purity grade or the
equivalent. Redistilled acids are acceptable.
Nitric acid, concentrated (sp gr 1.41).
6.2 Deionized, distilled water—Prepare by passing distilled water
through a mixed bed of cation and anion exchange resins. Use
deionized, distilled water for the preparation of all reagents,
calibration standards and as dilution water.
306
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6.3 Standard stock solutions (1 mL containing 1000 Ug of the element
to be determined) may be purchased or prepared from ultra-high
purity grade chemicals or metals. If available, materials trace-
able to NBS Standards should be used.* All salts must be dried
for 1 h at 105 °C, unless otherwise specified, prior to preparation
of stock solutions.
6.4 Two types of blanks are required for the analysis. The calibration
blank (Section 3.9) is used in establishing the analytical curve.
The reagent blank (Sectio'n 3.8) is used to correct for possible
contamination resulting from varying amounts of acid used in the
sample processing.
6.4.1 The calibration blank must contain the same concentration
of nitric acid as that present in the standards used to
define the calibration curve.
6.4.2 The reagent blank must contain nitric acid in the same
volume as that used in the processing of the samples.
The reagent blank must be carried through the complete
procedure and contain the same acid concentration in the
final solution as the sample solution used for analysis.
6.5 In addition to the calibration standards, an instrument check
standard (Section 3.4) and a reference standard (Section 3.5)
are also required for the analyses.
6.5.1 The instrument check standard is prepared by the analyst
to contain elemental concentrations equivalent to the
midpoints of the corresponding calibration curves. This
standard should be included in the analytical scheme
with a frequency of 10%.
6.5.2 The reference standard should be prepared according to
the instructions provided by the supplier. Following
initial verification of the calibration standards,
analyze weekly.
7. Sample Handling and Preservation
7.1 For the determination of trace elements, contamination and loss
are of prime concern. Dust in the laboratory environment,
impurities in reagents, and impurities in laboratory apparatus
which the sample makes contact with are all sources of potential
contamination. Sample containers can introduce either positive
or negative errors in the measurement of trace elements by (1)
contributing contaminants through leaching or surface desorption
and (2) by depleting concentrations through adsorption. Thus,
* Caution: Many metal salts are extremely toxic and may be fatal if
swallowed. Wash hands thoroughly after handling.
307
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the collection and treatment of the sample prior to analysis
requires particular attention. Laboratory glassware including
the sample bottle (whether linear polyethylene, polypropylene,
or Teflon) should be thoroughly washed with detergent and tap
water; rinsed with 1:1 nitric acid, tap water, 1:1 hydrochloric
acid, tap water, and finally deionized, distilled water in that
order.*
7.2 For the determination of total elements, known volumes of
representative samples of liquid residual wastes should be
acidified to pH <2 with concentrated nitric acid as soon as
possible after collection. The volume of acid used for the pH
adjustment may vary considerably for various types of industrial
waste and may result in significant dilution of the sample. The
volume of nitric acid used for preservation must be recorded to
allow calculation of a dilution factor. Dry, solid residual
wastes should be stored in clean, capped plastic or glass con-
tainers .
8. Sample preparation
8.1 For the determination of total elements, take an approximate
volume (previously determined by a preliminary screening of
the sample) of the liquid waste sample and transfer it to a clean
pretared 50-mL glass ampul. Reweigh the ampul and record the
weight of the sample. Add 2 mL of concentrated nitric acid,
dilute to about 20 mL, if necessary, with deionized, distilled
water, and gently warm the sample until any gas evolution subsides,
Seal the tip of the ampul with a torch making certain that a
leak-free seal is obtained. Place the ampul in a 125 °C oven and
digest for 1 h. For solid wastes, accurately weigh out a sample,
not to exceed approximately 5 g, and quantitatively transfer it
to a clean 50-mL ampul. Add 20 mL of 10% nitric acid, warm until
gas evolution subsides, and seal. Digest for 1 h at 125 °C. Cool
the ampul, wrap with a towel, and snap off the tip.** All samples
should be at pH <2 after digestion.
* Chromic acid may be useful to remove organic deposits from glassware;
however, the analyst should be cautioned that the glassware must be
thoroughly rinsed with water to remove the last traces of chromium. This
is especially important if chromium is to be included in the analytical
scheme. A commercial product, NOCHROMIX, available from Godax Laboratories,
6 Varick St., New York, NY 10013, may be used in place of chromic acid.
Chromic acid should not be used with plastic bottles.
If it can be documented through an active analytical quality control program
using spiked samples and reagent blanks that certain steps in the cleaning
procedure are not required for routine samples, those steps may be eliminated
from the procedure.
** Caution: Significant pressure buildup may occur in the ampul during the
digestion step; therefore, the analyst should wrap the ampul in
a towel in case shattering should occur during opening.
308
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If not, repeat the digestion using a sufficient volume of concen-
trated nitric acid to maintain acidic conditions. Quantitatively
transfer samples containing no solid residue to a 50-mL volumetric
flask with deionized, distilled water and dilute to volume. For
samples containing solid residue, suction filter the sample through
a prewashed Whatman No. 42, or equivalent, filter paper. Rinse the
ampul several times with deionized, distilled water and filter the
rinsings through the residue. Wash the residue with deionized,
distilled water and dilute the filtrate to a final volume of 50 mL.
The sample is now ready for the analysis of total metals.
9. Procedure
9.1 Set up the instrument with proper operating parameters established
in Section 5.2 for direct aspiration, furnace, gaseous hydride, or
cold vapor analysis. Allow at least 30 min for the instrument
to stabilize prior to analysis.
9.2 Develop linear calibration curves for each element according to
the instrument manufacturer's recommended procedures, using
appropriate standards prepared from stock solutions described in
Section 6.3.
9.3 Before beginning a sample run, reanalyze the reference standard
(Section 6.5.2) to ensure that no changes in instrument sensitivity
have occurred.
9.4 Begin the sample runs. For flame analysis, flush the system with
the calibration blank (Section 6.4.1) between each sample. Analyze
the reference standard (Section 6.5.2) every 10 samples.
9.5 If it has been found that methods of standard addition are required,
the following procedure is recommended:
9.5.1 The standard addition technique involves preparing new
standards in the sample matrix by adding known amounts of
standard to one or more aliquots of the processed sample
solution. This technique compensates for a sample consti-
uent that enhances or depresses the analyte signal, thus
producing a different slope from that of the calibration
standards. It will not correct for additive interference,
which causes a baseline shift. The simplest version of
this technique is the single-addition method in which two
identical aliquots of the same solution, each of volume Vx,
are taken. To the first (labeled A) is added a small
volume Vs of a standard analyte solution of concentration
Cg- To the second aliquot (labeled B) is added the same
volume Vx of the solvent. The analytical signals of
A and B are measured and corrected for nonanalyte signals.
The unknown sample concentration Cx is calculated:
309
-------
c
s
r -
x "
where SA and SB are analytical signals (corrected for
the blank) of solutions A and B respectively. Ve and Cs
should be chosen so that SA is roughly twice 85 on the
average . It is best if Vs is made much less than Vx and
thus Cs is much greater than Cx to avoid excess dilution
of the sample matrix. If a separation or concentration
step is used, the additions are best made first and
carried through the entire procedure. For the results
for this technique to be valid, the following limitations
must be taken into consideration:
a. The analytical curve must be linear.
b. The chemical form of the analyte added must respond
the same as the analyte in the sample.
c. The interference effect must be constant over the
working range of concern.
d. The signal must be corrected for any additive
interference.
10. Calculation
10.1 Analytical signals for reagent blanks (Section 6.4.2) should be
subtracted from signals for all samples. This is particularly
important for digested samples requiring large quantities of
acids to complete the digestion.
10.2 If dilutions are performed, the appropriate factor must be applied
to sample values.
10.3 Results should be reported in yg/g of undiluted residual waste.,
For concentrations below 1 yg/g, report as <1 yg/g; for concentra-
tions above 1 yg/g, report up to three significant figures.
11. Quality Control (Instrumental)
11.1 Analyze the instrument check standard (Section 6.5.1) at a frequency
of 10%. This check standard is used to determine instrument drift.
If agreement is not within ±2% of the expected values or within the
established control limits, the analysis is out of control.
310
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11.2 For the purpose of verifying interelement and/or background
correction factors, analyze a second check standard prepared
by spiking a representative sample with the analytes of interest
at either 10 times the detection limit for samples containing
low concentrations of analyte, or 2 times the concentration
for samples containing high concentrations of analyte. Values
should fall within the established control levels of 1.5 times
the check standard.
11.3 A reference standard (Section 6.5.2) from an outside source,
but having known concentration values, should be analyzed as a
blend sample on a weekly frequency. Values should be within
the established quality control limits. If not, prepare new
stock standards.
12. Quality Control (Method)
12.1 The precision of the analyses should be determined by analyzing
a minimum of five replicates of each type of residual waste.
12.2 The accuracy of the method should be determined from the spike
recovery data obtained by the analysis of a minimum of five
replicates of the same residual waste, spiked prior to digestion
of the sample, and carried through the same sample preparation
method used in Section 12.1.
13. References
13.1 "Procedures of Analysis of Heavy Metals and Other Elements in
Sewage or Sludge," University of Washington, Laboratories of
Radiation Ecology Research Report, February 21, 1980.
311
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D. Quality Assurance and Quality Control Procedures for
Determination of Purgeable Organics and Base/Neutral
and Acid Extractable Organies in Residual Waste
312
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Quality Assurance and Quality Control Procedures for
Determination of Purgeable Organics and Base/Neutral
and Acid Extractable Organics in Residual Waste*
1. Scope and Application
1.1 These procedures are provided for use by laboratories performing
analyses by the proposed methods for purgeable and semivolatile
organics in residual waste. To provide data with a known degree
of reliability, a strong Quality Assurance and Quality Control
program is presented. The procedures are designed to produce
data with known precision and accuracy so that a determination
of confidence can be placed in the data. Quality Assurance
(QA) is the total program for ensuring the reliability of the
monitoring data. Quality Control (OC) is the routine applica-
tion of procedures for controlling the measurement process.
1.2 The Quality Assurance plan'includes the following elements:
1.2.1 Spiked reagent water samples.
1.2.2 Daily use of reference compounds to verify ion abundance
measurements: decafluorotriphenylphosphine (DFTPP) for
semivolatiles and p-bromofluorobenzene (BFB) for purge-
ables.
1.2.3 Daily use of a Quality Control sample to establish GC
instrument performance: benzidine at the 100-ng level
for base/neutrals and pentachlorophenol at the 250-ng
level for acids.
1.2.4 Spike recovery and duplicate analyses to establish
precision and accuracy.
1.2.5 Routine use of surrogate spikes for quality control and
internal standards for quantitation.
1.2.6 Method blanks with every sample set.
1.3 Initially, the methodology must be validated for each industrial
subcategory being measured by the laboratory. The requirement
for validation of each subcategory is based on the assumed unique
The quality control and the quality assurance procedures for metals are
similar to those for purgeable and semivolatile organics. For those
instances where there are very specific differences, the quality control
and quality assurance procedures are given in detail in the proposed
method for metals in residual waste.
313
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nature of the residual waste associated with each subcategory.
The Quality Assurance data are used to define the performance
of the specified methodology on the individual waste matrices.
2. Quality Assurance Requirements
2.1 Field blank—The field blank is defined as an appropriate volume
of reagent water that is sent to the sampling site and back to
the analytical laboratory in a container and bottle identical
to the type used to collect the samples. Field blanks and
samples must be shipped in separate containers. An appropriate
field blank is provided to the analyst by the sampling crew.
When received in the laboratory, the field blank is spiked
with surrogates, extracted, and concentrated as if it were an
actual sample.
2.1.1 For the semivolatile organics (base/neutrals or acids),
the minimum requirement is to provide an appropriate
volume of blank water that has been processed through
the sampling equipment in the same manner as a sample.
The field blank is then analyzed in the laboratory as
if it were a sample. The field blank may be screened
by GC/FID. Full GC/MS analysis is to be performed if
the screening analysis gives any peaks larger than the
internal standard peak. When contamination of the field
blank occurs, the analytical results must be discarded
or flagged so as not to result in the reporting of
false positives in the authentic samples.
2.1.2 Field blanks for the purgeable organics consists of
"organic-free" water that is sent from the laboratory
to the sampling site and retained with the samples.
The purpose is to check on possible contamination of
the sample by permeation of volatiles through the
septum seal. Sample blanks should be protected during
transit and in the laboratory by storage of the sample
bottles in a sealed container with activated carbon.
2.2 Method blank—The method blank is defined as an appropriate
volume of "organic-free" water that is processed exactly as a
sample is processed (same glassware, reagents, solvents, etc.).
A method blank must be processed for each set of field samples
extracted at a given time (at least one method blank per 20
field samples analyzed) and whenever a new source of reagent
or solvent is introduced into the analytical scheme. The
method blank can be screened by the GC/FID. Analysis by GC/MS
is required only if GC/FID analysis of the field blank gives
314
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any peaks larger than the internal standard peak. Reagents or
solvents having background levels that interfere with the com-
pounds to be determined must be purified and shown to be
acceptable or replaced with some that are acceptable before
proceeding with the analyses. Problems encountered and
corrective actions taken shall be documented and reported for
the record.
2.2.1 For the extractable semivolatile organics (base/neutrals
or acids), the method blank requires extraction of 40 mL
of reagent water.
2.2.2 For the purgeable organics, 10 mL of reagent water
should be analyzed by the purge-and-trap methodology
only if positive interferences are noted during the
analysis of a field blank. If positive interferences
still occur, repeat the method blank analysis. If
interference persists, dismantle the system, thoroughly
clean all parts that make contact with the sample,
purge gas, and carrier gas. Replace or repack the
sorbent trap and change the purge and carrier gas.
2.3 Analytical standards—The proposed methods for purgeable and
semivolatile organics in residual waste assume the preparation
of stock solutions from pure, authentic samples of the compounds
to be determined. Commercially available mixed stock solutions,
if they are shown to be satisfactory, may be used to prepare
standard solutions and spiked samples. Reagents and standards
should carry a well-affixed label providing identification and
concentration, preparation date, name of responsible person and
identification numbers that allow the solutions to be traced to
the analytical records for their preparation. A minimum three-
point calibration curve should be prepared for each compound
determined. The calibration curve should bracket the concentra-
tion for that particular compound in the sample to be analyzed.
Standards should be kept refrigerated in serum bottles with
Teflon-lined caps and the liquid level marked on the bottles.
Stock solutions of most standard compounds that boil above room
temperature are generally stable for at least four weeks when
stored at 4 °C; however, the stability should be checked on a
periodic schedule.
2.4 Surrogate spikes—Surrogate spikes are defined as standards that
are added to every sample prior to sample processing and analysis.
The standards chosen should be chemically similar to compounds in
the fraction being analyzed. Also, the standards should be
compounds that would not likely be found in environmental samples.
The purpose of the surrogate spikes is to provide quality control
on every sample by constantly monitoring for unusual matrix
effects, gross sample processing error, etc. The surrogate spikes
should not be used as internal standards for quantitation purposes
315
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2.5 Internal standards—Internal standards are defined as compounds
that are added to the sample no more than a few minutes before
its injection into the GC/MS to minimize the possibility of
losses due to evaporation, adsorption, or chemical reaction.
The standard compounds chosen should be chemically similar to
compounds in the fraction being analyzed. Compounds used as
internal standards are not to be used as surrogate standards.
The internal standards must be different from the surrogate
standards.
2.6 Replicates—To determine the precision of the method, a regular
program of analyses of replicate aliquots of environmental
samples must be carried out. At least three replicate aliquots
of a well-mixed sample must be analyzed with each set of
20 samples or less from an industrial subcategory that is analyzed
at a given time. For those compounds where a sufficient number of
positive results are accumulated over a period of time, precision
criteria should be developed. A minimum of 15 replicates at a
particular concentration or concentration range where linearity
exists is required to start an on-going program for QA and sub-
sequent estimates of precision.
2.7 Spiked samples—These are samples that contain additions of known
amounts of authentic analytical standards. These samples are
processed and analyzed in the same manner as a sample (including
addition of surrogate and internal standard solutions). The
spiked samples are analyzed along with each set of 20 samples
or less from each industrial subcategory. Spike data are obtained
for each compound to be determined.
2.8 Spiked method blanks—These are obtained by additions of known
amounts of authentic standards to the water blank before analysis.
These blanks are then processed and analyzed in the same manner
as a sample. The standards should be present at approximately
the concentrations found in routine samples. The percent recoveries
are determined as described later in this protocol. At least two
spiked method blanks must be analyzed along with each set of
20 samples or less.
2.9 GC performance evaluation.
2.9.1 For the base/neutral semivolatile organics, 100 ng of
benzidine is run daily either separately or as part of
a standard mixture that may also contain 50 ng of DFTPP.
The tailing factor for benzidine should be less than
three. Calculation of this factor is described in
Figure V-10.
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2.9.2 For the acid semivolatile organics, 250 ng of penta-
chlorophenol is run daily either separately or as part
of a standard mixture that may also contain 50 ng of
DFTPP. The tailing factor for pentachlorophenol should
be less than five. Calculation of this factor is
described in Figure V-10-
2.10 GC/MS calibration evaluation.
2.10.1 For the extractable semivolatile organics, 50 ng of
decafluorotriphenylphosphine (DFTPP) is run daily and
checked to ensure that the performance criteria listed
in Table V-ll are met. If the system performance criteria
are not met, the analyst must retune the mass spectrometer
and repeat the performance evaluation. The performance
criteria must be met before any samples or standards may
be analyzed.
2.10.2 For the purgeable organics, 100 ng of p-bromofluorobenzene
(BFB) is run daily and checked to ensure that the per-
formance criteria listed in Table V-ll are met. If the
system performance criteria are not met, the analyst must
retune the mass spectrometer and repeat the performance
evaluation. The performance criteria must be met before
any samples or standards may be analyzed.
3. Mathematical Calculations
3.1 Precision—For each compound, use the concentrations of compounds
in the samples or the spiked samples (Oi, Oz, 03,...,0n) to
calculate the standard deviation (S) of replicate analyses
according to Equation 1.
S =
1-1
n(n-l)
(1)
3.2 Accuracy.
3.2.1 For each compound, use the concentration values for the
samples or the spiked samples (Oi, 02, 03,..., On) to
calculate the mean value of replicate analyses (X)
according to Equation 2.
x = i=1
(2)
n
where n = number of replicates.
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3.2.2 For each compound, use the resulting mean concentration
values of the samples and of the spiked samples to cal-
culate the mean percent recovery (F) of the method
according to Equation 3.
- _\ -*Q (3)
P —
T
where X. = mean observed concentration of replicates
of the spiked sample at a given spike level.
XQ = mean observed concentration of replicates
of the sample not spiked.
T = true value or calculated concentration of
the spike added to the sample .
3.3 The precision and accuracy data shall be documented for the
record as evidence that the laboratory can properly process
the samples and perform chromatography essential for the
proposed methods for purgeable and semivolatile organics.
4. Preliminary Precision and Accuracy with Compounds in Clean Water
4.1 Before any work is begun on actual field samples, a laboratory
must demonstrate its ability to perform properly the liquid-
liquid extractions, the gas purge extractions, and the required
chromatography. Clean water spikes are analyzed to demonstrate
the laboratory's ability to implement the proposed methods for
purgeable and semivolatile organics.
4.2 Prepare reagent water for use in determining preliminary precision
and accuracy according to the procedure in the proposed methods
for purgeable and semivolatile organics.
\
4.3 Spike four replicates of reagent water with an authentic sample
of each compound to be determined at a concentration approximately
equal to 10 times the limit of detection. In addition, spike all
aliquots with a minimum of three surrogate standards. For semi-
volatile organics, each replicate must be 40 mL; each purgeable
sample requires at least 10 mL (do not dose purgeables with more
than 2 yL of an alcoholic standard per each 10 mL of water).
Analyze the spiked solutions according to the proposed methods for
purgeable and semivolatile organics.
4.4 Determine precision and accuracy according to Section 3.
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5. Method Validation
5.1 Semivolatile organics—The following procedures are to be applied,
separately, to samples being analyzed for the base/neutral and
acid groups of compounds. The analysis shall be performed
according to the procedures given in the proposed method for these
classes of organics. The validation studies must be performed
under the same conditions ordinarily applied to the samples of a
given subcategory.
5.1.1 Sample pretreatment—The laboratory should collect a
sample of adequate volume to carry out the validation
study described here and should collect one field blank
by the method described in the sampling protocol. Mix
the sample with some type of stirring device. Withdraw
aliquots, while stirring, and add them to a 250-mL
round-bottom centrifuge bottle, using a siphon made of
glass or Teflon. Measure and record the aliquot weights
precisely. Initially analyze the 40-g aliquots to deter-
mine the sample background so that proper spiking levels
can be selected for Section 5.1.2. The remainder of the
sample should be stored at 4 °C until the validation
study is begun. At the same time that the sample aliquot
is analyzed, analyze a 40-g aliquot of the field blank.
5.1.2 Spiking of aliquots—All sample aliquots are spiked with
surrogate standards. Five aliquots for each spiking
level are spiked with surrogate standards plus the
standard pollutant compounds of interest. Select the
three spiking levels (concentrations) for the compounds
of interest based on the results of the background
analysis obtained in Section 5.1.1. If the initial
background level for a particular pollutant is X, select
the spike levels to give final concentrations of 2X, 10X,
and 100X. If X equals 20 yg/g, spike with 20, 180, and
1980 yg/g. This gives final concentrations of the
pollutant of 40, 200, and 2000 Pg/g. Spike each 40-g
replicate with each surrogate at a level of 20 yg/g.
5.1.3 Prepare spiking standards in concentrations such that no
more than 1 mL of spiking solution is added for each 40 g
of sample. This will insure that the solubility of the
standard in water will not be significantly affected by
the added organic solvent. Add the spiking solution to
the sample aliquots in the round-bottom centrifuge bottle
by use of a transfer pipet or microsyringe. After adding
the spikes, thoroughly mix the samples and after 1 h
at room temperature proceed with the extraction.
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5.1.4 Use of the data from spiked samples in analyses—The
data obtained from the determination of semivolatile
organics of interest are used to calculate the precision
and accuracy of the method and to establish control
limits for the individual compounds of interest.
The addition of surrogate spikes provides a quality
control on every sample by monitoring for matrix effects
and gross sample processing errors. The surrogate is
not used as an internal standard for quantification
purposes. Suggested surrogate standards are 2-fluoro-
biphenyl, 2,2'-difluorobiphenyl, and 2-fluoronaphthalene
for base/neutral compounds and 2-fluorophenol, penta-
fluorophenol and a,a,a-trifluoro-m-cresol for the acid
compounds.
5.1.5 Internal standards are added to the concentrated sample
prior to GC/MS analysis to provide quality control on
every sample by monitoring the possibility of losses due
to changes in operating parameters. Internal standards
are used for quantification purposes. Suggested internal
standards are naphthalene-da, anthracene-dio, and
nitrobenzene-ds for the base neutral compounds and
phenol-de for the acid compounds.
5.2 Purgeable organics.
5.2.1 The validation of the method for purgeables requires a
minimum of 500 g of sample. The validation may be
performed on a grab sample or a composite sample prepared
from discrete grab samples.
Thirteen aliquots of each sample are required. They
should be treated and spiked according to Sections
5.2.2 d through 5.2.2 e and 5.2.6. The remaining
sample is transferred to a clean vial and sealed with
no headspace, as is done when the sample is first
collected. This sample should be held at 4 °C until
the determination is made that there is no further need
for the sample.
Caution: Prepare only as many sample aliquots as can be
analyzed in the working day. This may mean
that each of the three concentration levels
will be analyzed on different days.
5.2.2 Pretreatment of grab samples to be composited—Individual
grab samples should be composited according to the
following procedure:
320
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a. Composite only grab samples of equal volume.
b. Carefully pour the contents of all individual grab
samples collected from a given source during the
specified time period into a 1000-mL wide-mouth
flask, which is chilled in a wet ice bath.
c. Stir the mixture gently with a glass rod for
approximately 1 min while the mixture is in the
ice bath.
d. Carefully fill 13 clean 40-mL vials, or three
120-mL vials and four 40-mL vials, with the
composited sample.
e. Store the vials at 4 °C until the validation study
is begun.
5.2.3 Spiking levels for analytical standards and surrogate
standards—The spiking levels of the analytical standards
are determined by the background (X) in the sample. The
low level spike will give a final concentration that is
2 times the background level. The intermediate and high
level spikes will give final concentrations that are 10
and 100 times the background level. Concentrations in
excess of 1 ug/g are likely to exceed the linear range
of the method. Therefore, the total concentration (back-
ground plus spike) of each individual compound should not
exceed 1 ug/g. Even at this level, the solubility of the
compounds in the sample must be considered. The spiking
level for all surrogate standards should be 1 yg/sample
aliquot.
5.2.4 Preparation of spiking standards—Prepare methanolic stock
solutions of the analytical standards and the surrogate
standards according to the directions given in the proposed
method for purgeable organics in residual wastes.
5.2.5 Take one 40-mL vial for immediate analysis to determine
the background of the purgeable. Weigh an appropriate
sample into a pretared 10- to 15-mL Teflon-lined, screw-
capped vial. Dilute the sample to 10 mL with reagent
water. Transfer the total sample or an aliquot to the
purge device using a syringe with a 1/8-in. gauge Teflon
needle. Add an appropriate volume of surrogate and
internal standard solutions. Seal the sample in the purge
device. Analyze the sample aliquot according to the
proposed method for purgeable organics in residual waste.
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5.2.6 Spiking the sample aliquots—Weigh an appropriate
sample into a pretared 10- to 15-mL Teflon-lined,
screw-capped vial. Add an appropriate volume of
solution of the authentic compound to be determined.
Mix and proceed as in Section 5.2.5.
5.2.7 Calculation of precision and accuracy—The precision
and accuracy of the purgeable organics and the surro-
gate standards are calculated as directed for the
extractable organics in Section 3.
6. Reference
6.1 Appendix III—Example Quality Assurance and Quality Control
Procedures for Organic Priority Pollutants, FR 44 (233) ,
69553-69559, 1979).
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TAILING FACTOR
Example calculation:
Peak Height = DE = 100 mm
10% Peak Height = BD = 10 mm
Peak Width at 10% Peak Height
AB = 11 mm
BC « 12 mm
AC - 23 mm
12
Therefore: Tailing Factor = TT
Figure V-10. Tailing factor calculation
323
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TABLE V-ll. IONS AND ION ABUNDANCE CRITERIA
OF DECAFLUOROTRIPHENYLPHOSPHINE (DFTPP)
M/E Ion abundance criteria
51 30 to 60% of mass 198
68 Less than 2% of mass 69
70 Less than 2% of mass 69
127 40 to 60% of mass 198
197 Less than 1% of mass 198
198 Base peak, 100% relative abundance
199 5 to 9% of mass 198
275 10 to 30% of mass 198
365 Greater than 1% of mass 198
441 Present but less than mass 443
442 Greater than 40% of mass 198
443 17 to 23% of mass 442
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TABLE V-12. IONS AND ION ABUNDANCE CRITERIA
OF 2-BROMOFLUOROBENZENE (BFB)
M/E Ion abundance criteria
50 20 to 40% of mass 95
75 50 to 70% of mass 95
95 Base peak, 100% relative abundance
96 5 to 9% of mass 95
173 Less than 1% of mass 95
174 70 to 90% of mass 95
175 5 to 9% of mass 95
176 70 to 90% of mass 95
177 5 to 9% of mass 95
325
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TECHNICAL REPORT DATA
(Please read f*Unictioni on the reverse before completing/
REPORT NO,
2.
3. RECIPIENT'S ACCESSION-NO.
TITLE AND SUBTITLE
SATS Evaluated Methodology for the Analysis
of Residual Wastes
5. REPORT DATE
December 1980
6. PERFORMING ORGANIZATION CODE
7, AUTHOR1S)
8. PERFORMING ORGANIZATION REPORT
SORI-EAS-80-721
4097-8-IX-F
10. PROGRAM ELEMENT NOT
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Southern Research Institute
2000 Ninth Avenue South
Birmingham, Alabama 35255
II.CONfRACT/GRANtNO.
68-02-2685 WA-108
12. SPONSORING AGENCY NAME ANO ADDRESS
Industrial Environmental Research Laboratory
U. S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 1/80-2/81
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report presents the results of a program of evaluation and validation of
analytical methods for "Total Content" of residual wastes. Candidate methods were
first evaluated and modified, and then validated with the analysis of a variety of
residual waste samples and determination of a broad range of organic compounds and
metals. The results, based on statistical analysis of over 10,000 data points, are
quoted primarily in terms of observed accuracy and precision. The methods depend
on extraction, GPC clean-up, preconcentration, and GC/MS analysis for identification
and quantitation of semivolatile organics; purge-and-trap and GC/MS for purgeable
organics; and acid digestion combined with AAS or ICP determinations for metals.
An edited text of the validated methods is presented in the format specified by
EMSL-Cincinnati for standard methods as an appendix to this report.
Also, results of SoRI's contribution to the interlaboratory study (with BCL)
of Potential Mobility (Leachate) methods and Total Content methods are presented.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Analysis
Atomic Absorption
GC/MS
Method Development
Potential Mobility
Purge and Trap
Residual Waste
Solid Waste
Total Content
Toxic Pollutants
Analysis of Total
Content
Analysis of Potential
Mobility
19. SECURITY CLASS (This Report)
UNCLASSIFIED
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
21. NO. OF PAGES
345
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
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