PB87-227286
POHC (Principal Organic Hazardous Constituent)
Analysis Methods for Hazardous Waste
incineration. Volume 1, Part 1
Southern Research Inst., Birmingham, AL
Prepared for
Environmental Protection Agency
Research Triangle Park, NC
Aug 87
U.S. DEPARTMENT OF COMMERCE
National Technical Information Service
»
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NOTICE
This document has been reviewed in accordance with
U.S. Environmental Protection Agency policy and
approved for publication. Mention of trade names
or commercial products does not constitute endorse-
ment or recommendation for use.
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FOREWORD
This report has been prepared by Southern Research Institute as part of
ongoing studies in support of regulatory programs of Environmental Protection
Agency's (EPA's) Air and Energy Engineering Research Laboratory, Research
Triangle Park, North Carolina. This report contains criteria for the analysis
methods for determination of principal organic hazardous constituents (POHCs)
from the combustion of hazardous waste. The data in this report are intended
as a reference to be used by laboratories that are monitoring the hazardous-
waste streams of incineration facilities. Because of subtle differences among
laboratories and analytical instrumentation, analysts who participate in simi-
lar studies should generate data that will establish their own criteria for the
analysis of POHCs.
ABSTRACT
As part of the Resource Conservation and Recovery Act of 1976, the
U.S. Environmental Protection Agency has proposed regulations for owners
and operators of facilities that treat hazardous wastes by incineration
to ensure that these incinerators will be operated in an environmentalTy
responsible manner. The primary criterion upon which the operational
specifications are based is the destruction and removal efficiency (ORE)
of the incinerator. The ORE value, defined in"terms of waste-input and
stack-output levels of designated principal organic hazardous constituents
(POHCs), must be equal to or greater than 99.99%.
In support of the ORE requirement, we evaluated and, when necessary,
modified generalized GC/FID, GC/MS, and HPLC/UV analysis methods for the
determination of approximately 70 candidate POHCs. These candidate POHCs
represent a variety of compound types, including alcohols, esters, chlori-
nated aliphatics and aromatics, carboxylic acids, aliphatic and aromatic
amines, nitrated aromatics, nitrosamines, hydrazines, nitriles, - organo-
sulfur compounds, and polynuclear aromatics and heterocyclics.
The developed generalized GC/MS and HPLC/UV methods are suitable for
inclusion in the POHC Method Manual, Sampling and Analysis Methods for
Hazardous Waste Combustion (EPA-600/8-84-002). The methods were applied
to the determination of candidate organic compounds over concentration
ranges of interest and demonstrated acceptable precision in the determin-
ation of most of the compounds.
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TABLE OF CONTENTS
Foreword iii
Abstract iii
Figures vii
Tables xviii
Abbreviations and Symbols xx
Acknowledgments xxi
1. Introduction I
Regulatory Requirements for the Incineration of
Hazardous Wastes 1
Sampling and Analytical Methods for Hazardous-
Waste Incineration. 1
Modification of Directed-Analysis Methods 2
.2. Conclusions 4
3. Recommendations 5
4. Technical Approach in the Development of
Generalized Analysis Methods . 6
General Considerations 6
Selection of Candidate POHCs 6
Preparation of Stock Standard Solutions 7
GC Analysis Procedures 8
Description of instruments and
general operating conditions 8
Optimization of the GC/FID and GC/MS procedure . . 8
GC quality-control procedures 9
HPLC/UV Analysis Procedures 10
Optimization and calibration
of the HPLC/UV procedures 11
HPLC/UV quality-control procedures 12
5. Results and Discussion of the Development
of Generalized Analytical Methods 13
GC/FID and GC/MS analysis 13
General considerations 13
POHCs not amenable to GC/FID and GC analysis ... 15
HPLC Analysis 19
6. Description of Supplementary Methods
Development and Other Tasks 24
7. Quality-Assurance Summary 25
References 26
Preceding page blank
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TABLE OF CONTENTS
(continued)
Appendices
Chromatograms and calibration curves for
GC/FID determinations 27
Chromatograms, mass spectra, and calibration
curves for GC/MS determinations 65
Chromatograms, UV spectra, and calibration
curves for HPLC/UV determinations 159
Description of supplementary method development
and other tasks. . . 230
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FIGURES
Figure Page
A-l Chromatogram by GC/FID for
(A) 1,3-dichloro-2-propanol(tR =3.8 rain),
(B) pentachloroethaneCtR =5.0 min),
(C) benzyl chloride(tR =5.6 min),
(D) 1,2,4,5-tetrachlorobenzene(tR = 10.5 min), and
(E) pentachlorobenzene(tR = 13.1 min) 28
A-2 Calibration curve for the determination of
1,3-dichloro-2-propanol by GC/FID 29
A-3 Calibration curve for the determination of
pentachloroethane by GC/FID.' 30
A-4 Calibration curve for the determination of
benzyl chloride by GC/FID 31
A-5 Calibration curve for the determination of
1,2,4,5-tetrachlorobenzene by GC/FID 32
A-6 Calibration curve for the determination of
pentachlorobenzene by GC/FID 33
A-7 Chromatogram by GC/FID for
(A) dimethyl sulfate(tR = 3.4 min),
(B) 1,4-naphthoquinoneOtR = 11.7 min),
(C) 9,10-dimethyl-l,2-benzanthracene(tR = 26.0 min), and
(D) dibenz[a,j]acridine(tR = 31.5 min) 34
A-8 Calibration curve for the determination of
dimethyl sulfate by GC/FID 35
A-9 Calibration curve for the determination of
1,4-naphthoquinone by GC/FID 36
A-10 Calibration curve for the determination of
.9 ,10-dimethyl-l.2-benzanthracene by GC/FID 37
A-ll Calibration curve for the determination of
dibenz[a,jlacridine by GC/FID 38
A-12 Chromatogram by GC/FID for
(A) methanesulfonic acid ethyl ester(tR = 4.6 min), and
(B) alpha-naphthylamine(tR = 13.6 min) 39
(continued)
vii
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FIGURES
(continued)
Figure Page
A-13 Calibration curve for the determination of
methanesulfonic acid ethyl ester by GC/FID . 40
A-14 Calibration curve for the determination of
alpha-naphthylamine by GC/FID . 41
A-15 Chromatogram by GC/FID for
(A) methyl hydrazine,
(B) ethylene diamine,
(C) N-nitroso-N-methylethylamine,
(D) malononitrile,
(E) 2,6-diaminotoluene,
(F) £-dinitrobenzene, and
(G) £-nitroaniline 42
A-16 Calibration curve for the determination of
ethylene diamine by GC/FID 43
A-17 Calibration curve for the determination of
JJ-nitroso-N-methylethylamine by GC/FID ....... 44
A-18 Calibration curve for the determination of
malononitrile'by GC/FID 45
A-19 Calibration curve for the determination of
2,6-diaminotoluene by GC/FID 46
A-20 Calibration curve for the determination of
j>-di nitrobenzene by GC/FID 47
A-21 Calibration curve for the determination of
_p-nitroaniline by GC/FID 48
A-22 Chromatogram by GC/FID for
(A) Jtf-nitrosodiethylamine,
(3) ^-nitrosopyrrolidine,
(C) 4-chloroaniline,
(D) ^~nitrosodibutylamine,
(E) 3 ,4-diaminotoluene,
(F) 2,4-diaminotoluene, and
(G) m-dinitrobenzene 49
A-23 Calibration curve for the determination of
N-nitrosodiethylamine by GC/FID 50
(continued)
viii
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FIGURES
(continued)
Figure . Page
A-24 Calibration curve for the determination of
JY-nitrosopyrrolidine by GC/FID 51
A-25 Calibration curve for the determination of
4-chloroaniline by GC/FID 52
A-26 Calibration curve for the determination of
^-nitrosodibutylamine by GC/FID 53
A-27 Calibration curve for the determination of
3,4-diaminotoluene by GC/FID 54
A-28 Calibration curve for the determination of
2,4-diaminotoluene by GC/FID 55
A-29 Calibration curve for the determination of
m-dinitrobenzene by GC/FID 56
A-30 Chromatogram by GC/FID for
(A) _N-nitroso-N-methylurethane,
(B) 2 ,6-dichlorophenol, and
(C) 2,4,5-trichlorophenol 57
A-31 Calibration curve for the determination of ~ -
2,6-dichlorophenol by GC/FID 58
A-32 Calibration curve for the determination of
2,4,5-trichlorophenol by GC/FID 59
A-33 Chromatogram by GC/FID for
(A) safrole,
(B) nicotine, and
(C) 2-acetamidof luorene . 60
A-34 Calibration curve for the determination of
safrole by GC/FID 61
A-35 Calibration curve for the determination of
nicotine by GC/FID 62
A-36 Calibration curve for the determination of
2-acetamidof luorene by GC/FID 63
A-37 Chromatogram by GC/FID for all candidate POHCs 64
(continued)
ix
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FIGURES
(continued)
Figure Page
B-l Chromatogram by GC/MS for
(A) 1,3-dichloro-2-propanol,
(B) pentachloroethane,
(C) benzyl chloride,
(D) 1,2,4 ,5-tetrachlorobenzene, and
(E) pentachlorobenzene 66
B-2 Mass spectrum for 1 ,3-dichloro-2-propanol 67
B-3 • Calibration curve for the determination of
1,3-dichloro-2-propanol by GC/MS 69
B-4 Mass spectrum for pentachloroethane 70
B-5 Calibration curve for the determination of
pentachloroethane by GC/MS .... 72
B-6 Mass spectrum for benzyl chloride 73
B-7 Calibration curve for the determination of
benzyl chloride by GC/MS 75
B-8 Mass spectrum for 1,2 ,4 ,5-tetrachlorobenzene 76
B-9 Calibration curve for the determination of • "
1 ,2 ,4 ,5-tetrachlorobenzene by GC/MS 78
5-10 Mass spectrum for pentachlorobenzene 79
ti-H Calibration curve for the determination of
pentachlorobenzene by GC/MS. ... 81
B-12 Chromatogram by GC/MS for
(A) dimethyl sulfate,
(B) 1,4-naphthoquinone,
(C) 9 ,10-dimethyl-l,2-benzanthracene, and
(D) dibenzfa,j]acridine 82
B-13 Mass spectrum for dimethyl sulfate 83
B-14 Calibration curve for the determination of
dimethyl sulfate by GC/MS 85
B-15 Mass spectrum for 1 ,4-naphthoquinone 86
(continued)
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FIGURES
(continued)
Figure • Page
B-16 Calibration curve for the determination of
1,4-naphthoquinone by GC/MS 88
B-17 Mass spectrum for 9,10-dimethyl-l,2-benzanthracene 89
B-18 Calibration curve for the determination of
9,10-dimethyl-l ,2-benzanthracene by GC/MS 91
B-19 Mass spectrum for dibenzfa,jJacridine 92
B-20 Calibration curve for the determination of
dibenzfa,j]acridine by GC/MS 94
B-21 Chromatogram by GC/MS for
(A) methanesulfonic acid ethyl ester and
(B) alpha-naphthylamine 95
B-22 Mass spectrum for methanesulfonic acid ethyl ester 96
B-23 . Calibration curve for the determination of
methanesulfonic acid ethyl ester by GC/MS. 98
B-24 Mass spectrum for alpha-naphthylamine : 99
B-25 Calibration curve for the determination of
alpha-naphthylamine by GC/MS 101
B-26 Chromatogram by GC/MS for
(A). JJ-nitrosodiethylamine,
(B) jtf-nitrosopyrrolidine,
(C) 4-chloroaniline,
(D) j^-nitrosodibutylamine,
(E) 3,4-diaminotoluene,
(F) 2,4-diaminotoluene, and
(G) m-dinitrobenzene 102
B-27 Mass spectrum for j^-nitrosodiethylamine 103
B-28 Calibration curve for the determination of
jj-nitrosodiethylatnine by GC/MS , 104
B-29 Mass spectrum for j4-nitrosopyrrolidine 106
B-30 Calibration curve for the determination of
jf-nitrosopyrrolidine by GC/MS 107
(continued)
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FIGURES
(continued)
Figure
B-31 Mass spectrum for 4-chloroantline 109
B-32 Calibration curve for the determination of
4-chloroaniline by GC/MS Ill
B-33 Mass spectrum for ^-nitrosodibutylamine 112
B-34 Calibration curve for the determination of
J^-nitrosodibutylamine by GC/MS 114
B-35 - Mass spectrum for 3,4-diaminotoluene 115
B-36 Calibration curve for the determination of
3,4-diaminotoluene by GC/MS 117
B-37 Mass spectrum for 2,4-diaminotoluene 118
B-38 Calibration curve for the determination of
.2,4-diaminotoluene by GC/MS 120
B-39 Mass spectrum for m-dinitrobenzene 121
B-40 Calibration curve for the determination of
m-dinitrobenzene by GC/MS. . 123
B-41 Chromatogram by GC/MS for
(A) _N-nitroso-|J-methylethylamine,
(B) .2 ,6-diaminotoluene,
(C) j)-dinitrobenzene,
(D) ja-nitroaniline, and
(E) malononitrile 124
B-42 Mass spectrum for ^-nitroso-N-methylethylamine 125
B-43 Calibration curve for the determination of'
j4-nitroso^N-methylethylamine by GC/MS 127
C-44 Mass spectrum for 2 ,6-diaminotoluene 128
B-45 Calibration curve for the determination of
2,6-diaminotoluene by GC/MS 130
B-46 Mass spectrum for p-dinitrobenzene 131
(continued)
xii
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FIGURES
(continued)
Figure' Page
B-47 Calibration curve for the determination of
2~dinitrobenzene by GC/MS 133
B-48 Mass spectrum for p-nitroaniline 134
B-49 Calibration curve for the determination of
£-nitroaniline by GC/MS 136
B-50 Mass spectrum for malononitrile 137
B-51 Chromatogram by GC/MS for
(A) Jl-ni troso-N-methylurethane,
(B) 2 ,6-dichlorophenol, and
(C) 2,4,5-trichlorophenol 139
B-52 Mass spectrum for ^~nitroso-N-methylurethane 140
B-53 Calibration curve for the determination of
£-nitroso-N-methylurethane by GC/MS 142
B-54 Mass spectrum for 2,6-dichlorophenol 143
B-55 Calibration curve for the determination of • -
2,6-dichlorophenol by GC/MS 145
B-56 Mass spectrum for 2,4,5-trichlorophenol. . ". 146
B-57 Calibration curve for the determination of
2,4,5-trichlorophenol by GC/MS 148
B-58 Chromatogram by GC/MS for
(A) safrole,
(B) nicotine, and
(C) 2-acetamidofluorene 149
B-59 Mass spectrum for safrole 150
B-60 Calibration curve for the determination of
safrole by GC/MS 152
B-61 Mass spectrum for nicotine 153
B-62 Calibration curve for the determination of
nicotine by GC/MS 155
(continued)
Xlll
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FIGURES
(continued)
Figure Page
B-63 Mass spectrum for 2-acetamidofluorene 156
B-64 Chromatogram by GC/MS for all candidate POHCs 158
C-l Chromatogram by HPLC/UV for streptozotocin 160
C-2 UV spectrum of streptozotocin 161
C-3 Calibration curve for the determination of
streptozotocin by HPLC/UV 162
C-4 Calibration curve for the determination of
streptozotocin by HPLC/UV(280nm) ' . 163
C-5 Chromatogram by HPLC/UV for phenol . 164
C-6 UV spectrum of phenol 165
C-7 Calibration curve for the determination of
phenol by HPLC/UV. 166
C-8 Calibration curve for the determination of
phenol by HPLC/UV( 280nm) 167
C-9 Chromatogram by HPLC/UV for 4-nitrophenol 168
C-10 UV spectrum of 4-nitrophenol 169
C-ll Calibration curve for the determination of
4-nitrophenol by HPLC/UV 170
C-12 Calibration curve for the determination of
4-nitrophenol by HPLC/UV( 280nm) 171
C-13 Chromatogram by HPLC/UV for o-chlorophenol 172
C-14 UV spectrum of £-chlorophenol 173
C-15 Calibration curve for the determination of
£-chlorophenol by HPLC/UV 174
C-16 Calibration curve for the determination of
£-chlorophenol by HPLC/UV(280nm) 175
C-17 Chromatogram by HPLC/UV for acetophenetidinec 176
(continued)
xiv
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Figure
C-18
C-19
C-20
C-21
C-22
C-23
C-24
C-25
C-26
C-27
C-28
C-29
C-30
C-31
C-32
C-33
C-34
C-35
FIGURES
(continued)
UV spectrum of acetophenetidine
Calibration curve for the determination of
acetophenetidine by HPLC/UV
Chromatogram by HPLC/UV for 5-nitro-o-toluidirie
UV spectrum of 5-nitro-o-toluidine
Calibration curve for the determination of
5-nitro-o-toluidine by HPLC/UV
Chromatogram by HPLC/UV for
tetramethylthiuram disulfide
UV spectrum of tetramethylthiuram disulfide
Calibration curve for the determination of
tetramethylthiuram disulfide by HPLC/UV
Chromatogram by HPLC/UV for 4-chloro-m-cresol
UV spectrum of -4-chloro-m-cresol
Calibration curve for the determination of
4-chloro-m-cresol by HPLC/UV
Calibration curve for the determination of
4-chloro-m-cresol by HPLC/UV(280nm)
Chromatogram by HPLC/UV for 2 ,4-dichlorophenol
UV spectrum of 2 ,4-dichlorophenol
Calibration curve for the determination of
2 ,4-dichlorophenol by HPLC/UV. .
Calibration curve for the determination of
2,4-dichlorophenol by HPLC/UV(280nm)
Chromatogram by HPLC/UV for
3-( alpha-acetonylbenzyl)-4-hydroxycoumarin
UV spectrum of 3-(alpha-acetonylbenzyl)-4-hydroxycoumarin. .
Page
177
178
179.
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
(continued)
xv
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FIGURES
(continued)
Figure " Page
C-36 Calibration curve for the determination of
3-(alpha-acetonylbenzyl)-4-hydroxycoumarin by HPLC/UV. . . . 195
C-37 Chromatogram by HPLC/UV for 2,4,6-trichlorophenol 196
C-38 UV spectrum of 2,4,6-trichlorophenol 197'
C-39 Calibration curve for the determination of
2,4,6-trichlorophenol by HPLC/UV " 198
C-40 Calibration curve for the determination of
2,4,6-trichlorophenol by HPLC/UV(280nm) 199
C-41 . Chromatogram by HPLC/UV for 2,3,4,6-tetrachlorophenol. . . . 200
C-42 UV spectrum of 2 ,3 ,4 ,6-tetrachlorophenol 201
C-43 Calibration curve for the determination of
2,3,4,6-tetrachlorophenol by HPLC/UV 202
C-44 Calibration curve for the determination of
2,3,4,6-tetrachlorophenol by HPLC/UV(280nm). . . 203
C-45 Chromatogram by HPLC/UV for reserpine 204
C-46 UV spectrum of reserpine 205
C-47 Calibration curve for the determination of
reserpine by HPLC/UV . . 206
C-48 Chromatogram by HPLC/UV for chlorambucil 207
C-49 UV spectrum of chlorambucil 208
C-50 Calibration curve for the determination of
chlorambucil by HPLC/UV 209
C-51 Chromatogram by HPLC/UV for
2,4-dichlorophenoxyacetic acid 210
C-52 UV spectrum of 2 ,4-dichlorophenoxyacetic acid 211
C-53 Calibration curve for the determination of
2,4-dichlorophenoxyacetic acid by HPLC/UV 212
(continued)
xvi
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FIGURES
(continued)
Figure
C-54 Chromatogram by HPLC/UV for
2 ,4 ,5-trichlorophenoxyacet ic acid 213
C-55 UV spectrum of 2 ,4,5-trichlorophenoxyacetic acid 214
C-56 Calibration curve for the determination of
2,4,5-trichlorophenoxyacetic acid by HPLC/UV 215
C-57 Chromatogram by HPLC/UV for
2-(2 ,4 ,5-trichlorophenoxy)propionic acid 216
C-58 UV spectrum of 2-(2,4 ,5-trichlorophenoxy)propionic- acid . . . 217
C-59 Calibration curve for the determination of
2-(2',4,5-trichlorophenoxy)propionic acid by HPLC/UV 218
C-60 Chromatogram by HPLC/UV for 4,6-dinitro-o-cresol and
methyl yellow T 219
C-61 UV spectrum of 4,6-dinitro-o^-cresol 220
C-62 Calibration curve for the determination of
4,6-dinitro-£-cresol by HPLC/UV( 378nm) 221
C-63 UV spectrum of methyl yellow 222
C-64 Calibration curve for the determination of
methyl yellow by HPLC/UV(400nm) 223
C-65 Chromadogram by HPLC/UV for JN-nitroso-N-methylurea. 224
C-66 UV spectrum of ^-nitroso-J>J-methylurea 225
C-67 Calibration curve for the determination of
^-nitroso-jtt-tnethylurea by HPLC/UV 226
C-68 Chromatogram by HPLC/UV for saccharin 227
C-69 UV spectrum of saccharin 228
C-70 Calibration curve for the determination of
saccharin by HPLC/UV 229
xvn
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TABLES
Table Page
1 SUMMARY OF GC/FID DETERMINATIONS OF CANDIDATE POHCs 14
2 SUMMARY OF GC/MS DETERMINATIONS OF CANDIDATE POHCs 16
3 PRECISION OF GC/FID DETERMINATIONS 17
4 PRECISION OF GC/MS DETERMINATIONS 18
5 SUMMARY OF HPLC/UV DETERMINATIONS OF CANDIDATE POHCs 20
6 POTENTIAL CANDIDATES FOR ANALYSIS BY HPLC/UV 22
7 PRECISION OF HPLC DETERMINATIONS ....... 23
B-l KEY IONS AND RELATIVE ABUNDANCES FOR
l,3-DICHLORO-2-PROPANOL 68
B-2 KEY IONS AND RELATIVE ABUNDANCES FOR PENTACHLOROETHANE .... 71
B-3 KEY IONS AND RELATIVE ABUNDANCES FOR BENZYL CHLORIDE ...... 74
B-4 KEY IONS AND RELATIVE ABUNDANCES FOR
1,2,4,5-TETRACHLOROBENZENE ' 77
B-5 KEY IONS AND RELATIVE ABUNDANCES FOR PENTACHLOROBENZENE. ... 80
li-6 KEY IONS AND RELATIVE ABUNDANCES FOR DIMETHYL SULFATE 84
B-7 , KEY IONS AND RELATIVE ABUNDANCES FOR 1,4-NAPHTHOQUINONE. .... 87
3-8 KEY IONS AND RELATIVE. ABUNDANCES FOR 9,10-DIMETHYL-l,2-
BENZANTHkACENE 90
B-9 KEY IONS AND RELATIVE ABUNDANCES FOR DIBENZ[a,j]ACRIDINE ... 93
B-10 KEY IONS AND RELATIVE ABUNDANCES FOR METHANESULFON1C ACID
ETHYL ESTER 97
P,-11 KEY IONS AND RELATIVE ABUNDANCES FOR alpha-NAPHTHYLAMINE ... 100
B-12 KEY IONS AND RELATIVE ABUNDANCES OF ^-NITROSODIETHYLAMINE. . . 105
B-13 KEY IONS AND RELATIVE ABUNDANCES OF J4-NITROSOPYRROLIDINE ... 108
B-14 KEY IONS AND RELATIVE ABUNDANCES FOR 4-CHLOROANIHNE 110
(continued)
xvi 11
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TABLES
(continued)
Table Page
B-15 KEY IONS AND RELATIVE ABUNDANCES FOR JJ-NITROSODIBUTYLAMINE . . 113
B-16 KEY IONS AND RELATIVE ABUNDANCES FOR 3,4-DIAMINOTOLUENE. ... 116
B-17 KEY IONS AND RELATIVE ABUNDANCES FOR 2,4-DIAMINOTOLUENE. ... 119
B-18 KEY IONS AND RELATIVE ABUNDANCES OF m-DINITROBENZENE 122
B-19 KEY IONS AND RELATIVE ABUNDANCES FOR N-NITROSO-
_N-METHYLETHYLAMINE 126
B-20 KEY IONS AND RELATIVE ABUNDANCES FOR 2,6-DIAMINOTOLUENE. ... 129
B-21 KEY IONS AND RELATIVE ABUNDANCES FOR £-DINITROBENZENE 132
B-22 KEY IONS AND RELATIVE ABUNDANCES FOR £-NITROANILINE 135
B-23 KEY IONS AND RELATIVE ABUNDANCES FOR MALONONITRILE ....... 138
B-24 KEY IONS AND RELATIVE ABUNDANCES FOR £-NITROSO-
_N-METHYLURETHANE . 141
B-25 KEY IONS AND RELATIVE ABUNDANCES FOR 2,6-DICHLOROPHENOL. ... 144
B-26 KEY IONS AND RELATIVE ABUNDANCES FOR 2,4,5-TRICHLOROPHENOL . . 147
B-27 KEY IONS AND RELATIVE ABUNDANCES FOR SAFROLE .......... 151
E-28 KEY IONS .AND RELATIVE ABUNDANCES FOR NICOTINE 154
B-29 KEY IONS AND RELATIVE ABUNDANCES FOR 2-ACETAMIDOFLUORENE ... 157
D-l PROPOSED AIR SAMPLING AND ANALYSIS
METHODS FOR SELECTED P.OHCs 236
D-2 EVALUATION OF RECOMMENDED DIGESTION AND ANALYSIS
PROCEDURES FOR BERYLLIUM, STRONTIUM, AND
VANADIUM IN SPIKED WATER SAMPLES 304
D-3 EVALUATION OF RECOMMENDED DIGESTION AND ANALYSIS
PROCEDURES FOR BERYLLIUM, STRONTIUM, AND
VANADIUM IN SPIKED SOIL SAMPLES ' 305
xix
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ABBREVIATIONS AND SYMBOLS
amu
Appendix VIII
CFR
DFTPP
DNPH
ORE
El
EPA
g
GC
GC/FID
GC/MS
h
HI
HPLC
HPLC/UV
ID
is
Mg
pL
mg
mL
mm
MM5
mol wt
ins
m/z
r-S
nm
PAHs
I'OHCs
PICs
QA
QC
RCRA
. RRF
KSD
SASS
SIM
s
SD
SoRI
TCDD
cr
UV
VOST
Atomic Mass Unit
Hazardous Constituents List (Part 261,
40 CFR)
Code of Federal Regulations
Decafluorotriphenylphosphine
Dinitrophenylhydrazine
Destruction and Removal Efficiency
Electron Impact lonization Mode
"U.S. Environmental Protection Agency
Gram
Gas Chromatography
Gas Chromatography/Flame-Ionizat ion
Detection
Gas Chromatography/Mass Spectrometry
Ho.ur
Hydroiodic Acid
High-Performance Liquid Chromatography
High-Performance Liquid Chromatography/
Ultraviolet Spectrometry Detection
Internal Diameter
Internal Standard
Microgram (10~6 g)
Microliter (10"6 L)
Milligram (10"3 g)
Milliliter (10"3 L)
Millimeter (10~3 m)
Modified Method 5 Sampling Train.
Molecular Weight -
Millisecond
Mass to Charge Ratio
Nanogram (10~9 g)
Nanometer (10~~9 m)
Polynuclear Aromatic Hydrocarbons
Principal Organic Hazardous Constituents
Products of Incomplete Combustion
Quality Assurance
Quality Control
Resource Conservation and Recovery Act
Relative Response Factor
Relative Standard Deviation
Source Assessment Sampling System
Selected-Ion Monitoring
Second
Standard Deviation
Southern Research Institute
Tetrachlorodibenzo-£-dioxin
Retention Time
Ultraviolet Spectroscopy
Volatile Organic Sampling Train
xx
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ACKNOWLEDGMENTS
We are especially grateful for Che individual efforts of the professional
staff of the Analytical Chemistry Division of Southern Research Institute and
Battelle-Columbus Laboratories who participated in the performance of this work
assignment. We are indebted to the following people from SoRI: Merry B.
Emory, Lucy M. Rose, Donna L. lozia, Marynoel M. Graham, Cathy R. Abroms, Linda
A. Burford, M. Susan Duncan, Linda K. First, Kathy S. Gray, Judy G. Riley,
Cathy E. Rowe, Christine G. Richards, Lee Ann Wallace, and Arnetta McGowan for
the organic analyses. We are grateful to the following people from
Battelle-Columbus: Martin P. Miller, Paula M. Chinn, Moira C. Landers, and J.
Scott Warner for organic analyses.
xxi
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SECTION 1
INTRODUCTION
REGULATORY REQUIREMENTS FOR THE INCINERATION OF HAZARDOUS WASTES
As part of the Resource Conservation and Recovery Act (RCRA), the U.S.
Environmental Protection Agency (EPA) has promulgated proposed, interim, and
final regulations for the owners and operators of facilities that treat hazard-
ous wastes by incineration. The purpose of the regulations is to ensure that
such incinerators are operated in an environmentally responsible manner. The
regulations cover a range of activities, including operational performance
standards, waste analysis, trial burns, monitoring and inspections, record-
keeping and reporting, and the establishment of emission-control criteria (_1) .
The specific details for each incinerator facility are authorized by facility
permits.
The primary criterion upon which all operational specifications are based
is the destruction and removal efficiency (DRE) of the incinerator. This
value, which is defined in terms of waste-input levels and stack-output levels
of the potentially hazardous substances, must be greater than 99.99% for proper
incineration. The substances from the list in Appendix VIII, Part 261, 40 CFR
have been designated principal organic hazardous constituents (POHCs), although
many inorganic substances have also been included.
SAMPLING AND ANALYTICAL METHODS FOR HAZARDOUS-WASTE INCINERATION
As part of the supporting documentation for the permit writer and for the
incinerator facility's'owners and operators, the EPA has compiled a manual of
methods for sampling and analysis for use in measuring the levels of POHCs in
the various streams of an incinerator facility, including inlet wastes, stack
gas,process waters, fly ash, and bottom ash (2). This manual is entitled
"Sampling and Analysis Methods for Hazardous Waste Combustion" and shall be
referred to as the Methods Manual hereafter. This manual expands upon and
augments the information in the "Guidance Manual for Evaluating Permit Applica-
tions for the Operation of Hazardous Waste Incineration Units" (_3) .
This Methods Manual is intended to be a resource document for the prepara-
tion and execution of a sampling-and-analysis plan for hazardous-waste inciner-
ators. The specific procedures described are primarily in the form of brief
descriptions with reference to other documents that contain highly detailed
description methods. Existing collections of sampling and analysis methods
documentation such as "Test Methods for Evaluating Solid Waste" (SW-846) or
"Samplers and Sampling Procedures for Hazardous Waste Streams" (EPA-600/2-80-
018) have not been directly incorporated into the manual but are incorporated
by reference (4,5).
-------
During trial burns at an incineration facility, the sampling and analysis
methods will allow measurement of those POHCs expected to be present in the
waste and products of incomplete combustion (PICs) . Also during trial burns,
the waste samples may be characterized with "the methods to establish limits on
the waste composition that may be incinerated. During routine facility opera-
tion, the incoming wastes will be analyzed periodically to ascertain whether
the composition of the waste has changed. Some gaseous species such as carbon
monoxide will be monitored continuously, as specified in the Methods Manual, as
an indicator of the combustion efficiency of the process. Periodically, at the
frequency not specified in the current regulations, the influent and effluent
streams are to be tested to monitor compliance with the DRE criteria.
Although the Methods Manual includes test procedures for proximate,
survey, and directed (or specific-compound) analysis, our brief discussion here
is limited to directed analysis because the modification of analytical methods
applicable to the identification and quantification of POHCs is currently of
primary interest to us (see Sections 4 and 5).
The directed-analysis portion of the waste-characterization scheme pro-
vides qualitative confirmation of compound identity and quantitative data with
appropriate quality control for the'potentially hazardous constituents that
might reasonably be expected to be present in the waste, based on engineering
judgment and on the results of proximate and survey analysis. Directed analy-
sis does not involve screening every waste sample against the complete hazard-
ous component list. A preliminary judgment is made as to the compounds or
types of compounds that are likely to be present. The directed analysis then
consists of the minimum set of analytical techniques that can be applied to the
waste for qualitative identification and quantitative determination of the
components that are actually present.
In practice, the results of the directed analysis will establish whether
the waste contains the suspected pollutant and will demonstrate the concentra-
tion range at which the pollutant may be expected to be found. Directed analy-
sis will also be used to confirm and quantify unexpected hazardous components
identified in the survey analysis. These data on quantitative analysis of
confirmed, identified contaminants of documented toxicity are essential for
selection of appropriate POHCs to be monitored for the prediction of hazardous
combustion by-products.
MODIFICATION OF DIRECTED-ANALYSIS METHODS
The Methods Manual recommends a variety of analytical techniques for the
determination of the list of POHCs given in Appendix VIII, Part 261, 40 CFR.
Whenever documentation was available to support the practice, the methods for
the determination of organic compounds were written to incorporate a high-
resolution analytical technique—fused-silica capillary gas chromatography—
and a highly specific detection technique—mass spectrometry. Also, whenever
-------
possible, high-performance liquid chromatography (HPLC) was recommended for the
determination of organic compounds that could not be determined by gas chroma-
tography with mass spectrometric detection (GC/MS). Many compounds are amen-
able to analysis by either procedure. The application of these two approaches
to the determination of as many of the POHCs as possible was"designed to pro-
vide satisfactory qualitative analyses on a cost-effective basis for a variety
of waste types and process chemistries.
For some of the compounds on the Appendix VIII list, there were limited
references that recommended either GC/MS or HPLC analyses. For some compounds,
the only analytical methods readily available were colorimetric or thin-layer
chromatographic techniques. Other compounds required chemical derivatization
to produce a product suitable for chromatographic analysis. For yet other
compounds, no acceptable analytical method was found for inclusion in the
Methods Manual. Furthermore, GC/MS or HPLC methods were documented for some
compounds for which the operating conditions given for analysis were peculiar
to the compounds and not readily adaptable to the determination needed to
reduce the number or complexity of analytical methods in the Methods Manual,
generalized GC/MS and HPLC techniques were developed for the determination of
as many of the chemicals on the list of hazardous wastes as possible. Our
effort was concentrated on a select number of POHCs (approximately 70) which
are discussed later.
The subsequent sections of this report describe the efforts by Southern
Research Institute to evaluate and, when necessary, modify GC/MS and HPLC/UV
generalized analysis procedures for POHCs. This work is presented in
Sections 4 and 5.
Battelle-Columbus Laboratories in a joint effort with Southern Research
Institute undertook specific tasks to.supplement the development of generalized
test procedures. Specific analysis methods for brucine and 2-fluoroacetamide
were developed. These compounds were not determined by the generalized proce-
dures. Potentially useful air-sampling, sample-preparation, and analysis pro-
cedures for various POHCs including aldehydes, acids, esters, alcohols, and
thiols were recommended. Many of these compounds were not included in the
evaluation of the developed analysi-s procedures. Existing preparative and '
analysis methods for the determination of metals in wastes and incinerator
effluents were refined and supplemented. Because this material is now largely
historical and has been superseded by approaches in the final revision of the
Methods Manual, we included the information in the Appendix D of our report.
-------
SECTION 2
CONCLUSIONS
Generalized GC/FID, GC/MS, and HPLC/UV methods were developed for the
determination of approximately 70 POHCs. The candidate POHCs were a variety of
compound types, including alcohols, esters, chlorinated aliphatic and
aromatics, carboxylic acids, aliphatic aromatic amines, nitrated aromatics,
nitrosamines, hydrazines, nitriles, organosulfur compounds, and polynuclear
aromatics and heterocyclics.
The developed generalized methods were suitable for inclusion in the POHC
Methods Manual. The methods were applied to the determination of candidate
organic compounds over concentration ranges of interest and have demonstrated
acceptable precision in the determination of most of the compounds.
The ultimate utility of the methods in the determination of POHCs in
incinerator wastes and effluent will of course depend on the prudent choice of
appropriate sampling procedures and sample-preparation procedures. As part of
our work, therefore, we have compiled proposed overall air-sampling, sample-
preparation, and analysis procedures for a variety of POHCs. The evaluation of
the accuracy and precision of these total sampling and analytical methods
should be the emphasis of future investigation.
Also under this work assignment, other tasks have been performed.
• Specific GC analysis methods were developed for two compounds, •
brucine and 2-fluoroacetamide. These compounds could not be
determined by the generalized GC method.
• Existing generalized digestion procedures and specific analysis
procedures for the determination of metals in wastes and
incinerator effluent were also revised. The generalized
digestion procedures were found suitable for the determination
of three metal-s, beryllium, strontium, and vanadium, for which
the procedure had not been evaluated previously.
-------
SECTION 3 .
RECOMMENDATIONS
Several recommendations for future investigations are as follows:
• SoRI will continue to apply the general survey methods to those
POHCs not yet evaluated.
• Based on SoRI's findings, the proposed screening program should
be evaluated with incinerator-effluent samples, extracts, and
sorbent media.
• In those cases where a generalized method was not sufficient to
quantify a POHC, then more specific analytical techniques should
be developed and evaluated on a priority basi_s.
-------
SECTION 4
TECHNICAL APPROACH IN THE DEVELOPMENT
OF GENERALIZED ANALYSIS METHODS
GENERAL CONSIDERATIONS
The primary focus of our experimental work was to develop two generalized
analytical methods for the determination of POHCs in appropriate organic sol-
vents. One analytical technique involved GC/MS with the use of a capillary
column, and the other involved HPLC with ultraviolet/visible spectrophotometric
detection (HPLC/UV).* During the optimization of the GC methods, flame-
ionization detection (FID)—in addition to MS—was employed to aid in estab-
lishing operating conditions. The HPLC method was' developed for use with
reversed-phase C.R columns primarily because reversed-phase columns are less
apt than normal-phase columns to adsorb organic analytes -irreversibly. HPLC
detection systems, other than ultraviolet/visible (UV/VIS) detection, were not
considered because UV/VIS detection was judged to be more suitable for the
development of a generalized,HPLC test method. Because the UV/VIS detector can
measure absorbances at selected wavelengths over a fairly broad range (190 to
600 nm), the detector offers selectivity and versatility in determining a
variety of compound types.
The laboratory work was structured to lead systematically to the deter-
mination of the feasibility of developing generalized test methods. The
resulting methods were applied to the determination of selected POHCs. First,
we selected.a variety of POHCs for preliminary investigation and performed
analyses of standard solutions of mixtures of these POHCs (in appropriate sol-
vents) "~o optimize instrumental operating conditions. Once suitable operating
conditions had been established, an individual chromatogram for each of these
POHCs was generated. Finally, we analyzed a series of standard solutions of
each of the selected POHCs to estimate detection limits and to establish cali-
bration curves. Also, multiple determinations were made on specific concentra-
tions of selected POHCs to define the precision of the test methods..
SELECTION OF CANDIDATE POHCs
Several criteria were used in compiling the list of organic POHCs to be
included in our investigations. First, some of the organic compounds listed in
Appendix VIII, Part 261, 40 CFR, were eliminated from consideration in the
method-development work. We excluded over 70 priority pollutants in the list
because generalized analytical methods were available for their determination.
*Although the detector is capable of measuring absorbances in both the
ultraviolet and visible regions (190 to 600 nm), we use the acronym
HPLC/UV, which is conventional for describing HPLCs with variable-
wavelength detectors.
-------
Several extremely hazardous compounds—including aflatoxins, cyanogen
bromide, diisopropylfluorophosphate, mustard gas, and others—were not investi-
gated for the following reasons: First, special handling procedures would
likely have to be incorporated into methods for the determination of these
compounds to eliminate the possibility of the analyst's being exposed to them.
Second, the lability of some of the compounds would necessitate their trans-
formation to stable analytes, a complication that would preclude the applica-
tion of a straightforward GC/MS or HPLC/UV analytical procedure. Other
compounds such as formaldehyde and other volatile aldehydes were not considered
because derivatization schemes would be required to determine these compounds
by GC/MS or HPLC/UV methods. Other less reactive volatile compounds including
acetonitrile , br onto ace tone, carbon disulfide, 1,2-dibr omoe thane , methyl eth-y.l
ketone, and others were not investigated because thei'r determination along with
many of the less volatile compounds was impractical and because many can likely
be determined by the EPA's generalized analytical method for volatile organic
compounds. —
From the remaining POHCs on the hazardous-compound list, we selected about
70 candidate compounds, largely on the basis of commercial availability.
Included in this selection were a variety of compound types including alcohols,
esters, chl.orihated aliphatics and aromatics, carboxylic acids and acid
anhydrides, aliphatic and aromatic amines, nitrated aromatics, nitrosamines,
hydrazines, nitriles, organosulfur compounds, and polynuclear aromatics and
heterocyclics. The candidate compounds were chosen from such a wide variety in
an attempt to represent most of the compound types of the organic POHCs in the
hazardous-compound list (i.e., Appendix VIII, Part 261, 40 CFR). The specific
compounds selected are presented in Section 5 along with the analytical
results.
Once we had selected the candidate POHCs, we divided the compounds into
two primary groups—one groups for GC/MS investigations, the other for HPLC/UV
studies. In general, thermally stable compounds that.were -expected to be
vaporized at temperatures typical of gas-chromatographic operating conditions
were selected for GC/MS work. Of course, compounds that were expected to"be
irreversibly adsorbed on GC columns were excluded from GC/MS work. We analyzed
relatively nonvolatile compounds with molecular electronic absorption bands in
the ultraviolet/visible wavelength ranged by HPLC/UV; these compounds included
some materials such as saccharin and epinepherine for. which the analytical
methods recommended by the Methods Manual involved derivitization to produce
products suitable for GC analysis. Other candidate POHCs that we investigated
by HPLC/UV were compounds for which no chromatographic procedure was recom-
mended in the Methods Manual, such as 5-nitro-o-toluidine and Trypan blue.
PREPARATION OF STOCK STANDARD SOLUTIONS
We prepared stock standard solutions of the candidate compounds in appro-
priate solvents at a concentration of either about 1 mg/mL or about 10 mg/mL.
These stock solutions were serially diluted as required to prepare working
standards.
-------
We used primarily methylene chloride as the solvent in the preparation of
standards ..for GC/MS studies. Several different polar solvents—acetonitrile,
methanol, and water—were used in preparing solutions of POHCs determined by
HPLC. A few candidate compounds required ionic solutions to effect dissolu-
tion. For instance, we dissolved epinephrine in dilute hydrochloric acid and
melphalan in a 1:1 combination of 0.01 H NaH PO and methanol.
GC ANALYSIS PROCEDURES •
Description of Instruments and General Operating Conditions
We developed the GC/MS generalized test method on the Hewlett-Packard
Model 5895 gas chroitfatograph/mass spectrometer-data system. The components of
the instrument include a hyperbolic quadrapole mass filter with a convertible
electron-impact (El) and positive-ion chemical-ionization source, a capillary
and jet separator GC/MS interface, and a data system that includes an HP2113
computer, a high-speed printer, a magnetic tape system, a 50-megabyte HP.7920M
disk-drive system, a communications interface, GC/MS operating software, and an
unabridged NBS spectral library. The supplemental GC/FID work was performed on
a Hewlett-Packard Model 5840 gas chromatograph that was equipped for use with
capillary columns.
The work with both GC/MS and GC/FID involved capillary chromatography with
matched, fused-silica SE-54 wallcoated capillary columns 25 m long, 0.31-mm ID.
The initial operating conditions were chosen as a compromise of the conditions
given for several capillary GC methods in the Methods Manual. The initial
starting column temperature was 40 °C; the temperature was then programmed at
10 °C/min to 280 °C and maintained at 280 °C for 15 min. Injection and detec-
tion temperatures were 250 °C. The carrier gas was helium and was maintained
at a volume flow rate through the column of about 2 mL/min. In the GC/FID
work, the carrier-gas flow was split downstream from the injection port in the
conventional manner at a.ratio of about 1:40. Thus, only a small percentage of
an injected sample was actually passed onto the column. In the GC/MS work, the
"splitless" injection technique was employed. Consequently, we assumed that
essentially all of the injected sample reached the column in GC/MS
determinations.
Optimization of the GC/FID and GC/MS Procedure
GC operating conditions were optimized by analyzing solutions containing a
variety of the candidate POHCs by the GC/FID technique. The column-head pres-
sure was adjusted appropriately to maximize the FID response to test mixtures.
We used these adjustments to pinpoint the optimum carrier-gas velocity, which
in turn defined the splitting ratio.
Having established GC operating conditions by the GC/FID procedure, we
then applied the method to the determination of the candidate POHCs by GC/MS.
We also established reference mass spectra for the identification of the indi-
vidual POHCs. The mass spectrometer was operated in a full-mass-scanning range
(41 to 350 or 450 amu) in the El mode. The scan time was maintained at <1 s to
enable the collection of enough scans to characterize each capillary GC peak.
-------
GC Quality-Control Procedures
. We calibrated the GC/FID and GC/MS procedures with external standard solu-
tions of the candidate POHCs. Five-point calibration curves were prepared for
each candidate POHC determined by gas chromatography. Each curve was a plot of
the FID or MS response (relative to anthracene-d ) as a function of the
quantity of the particular POHC injected on the GC column. The detection limit
for each candidate POHC was estimated as the quantity (ng) of POHC on the GC
column that gave rise to a signal approximately twice the background noise
level. We also established reference mass spectra for the identification of
the individual POHCs.
In addition to the use of external standards for the'calibration of both
GC/FID and GC/MS methods, other quality-control measures were implemented. The
performance of the GC/MS system was checked daily with decafluorotriphenylphos-
phene (DFTPP) according to the requirements given in EPA Method No. 625 (6).
The precision of determinations by GC/FID and GC/MS was estimated by
triplicate injections of at least one standard solution of each POHC investi-
gated by gas chromatography. The estimate of precision of the replicate
measurements is expressed as the relative standard deviation (RSD) calculated
from Equation 1.
' . RSD (%)„ = (fM 10° (1)
Standard Deviation (SD) was calculated from Equation 2.
(2)
(n - 1)
Mean relative response (X) was calculated from Equation 3
n
x = t I x: (3)
i = 1
where
n = number of replicate measurements, and
X£ = relative response of the POHC standard.
-------
Furthermore, we used anthracene-d as an internal standard in the GC
methods. Along with the analytes we injected anthracene-d to minimize the
effect of injection volume and instrument performance upon the precision of
determinations. Also, the anthracene-d internal standard was used to calcu-
late the relative response factor (RRF) tor each POHC from Equation 4.
RRF = (AsCis)/(AigCg) (4)
where
Ac = area of the characteristic ion for the POHC to be measured,
O
A- = area of the characteristic ion for the internal standard,
L S
C- - = concentration of the internal standard (pg/mL), and
Cg = concentration of the POHC (yg/mL) to be measured.
Recovery data were not applicable for this phase of the project because
our analyses were done with neat solutions and standard mixtures of POHCs. We
did not.collect, prepare, or analyze field samples that required spiking of the
matrix with surrogate standards or specific POHCs.
HPLC/UV ANALYSIS PROCEDURES
For the development of a generalized HPLC/UV analysis procedure, we used
the Hewlett-Packard Model 1084B high-performance liquid chromatograph equipped
with a variable-wavelength UV/VIS detector (190 to 600 nm) and an automatic
sampling system. The following two reversed-phase columns were used with an
acetonitrile/water eluent:
• Perkin-Elmer HC-ODS-SIL-X-1,"10-um particle size, 25 cm long,
2.6-mm ID..
• Waters Associates yBondapak C , lO-ym particle size, 30 cm
long, 3.9-tnm ID.
The pBondapak C.g column was employed only after we found that a few of the
candidate POHCs either were not retained by or did not chromatograph well on
the HC-ODS-SIL-X-1 column. In practice, the performance of a column from one
source to another may vary. In addition, interlaboratory differences may occur
that are attributed to the handling and history of the column. Once a column
is selected, its performance should be monitored throughout the study.
Rather than attempt to establish one rigid set of HPLC operating condi-
tions, our strategy was to identify various procedural options that would allow
determination of a broad range of compound types. Thus, we investigated
numerous isocratic and gradient elution programs with acetonitrile/water mobile
10
-------
phase. In the determination of several POHCs (including the phenoxyacetic
acids), the eluent was acidified. The wavelength of UV detection was also
varied to optimize sensitivity.
Optimization and Calibration of the HPLC/UV Procedures
The POHCs were grouped into classes of compounds and submitted for HPLC
analysis. Initially, we analyzed standard mixtures of candidate POHCs to
establish solvent programs suitable for the determination of a variety of
compounds. At that time the UV detector was set to monitor absorbances at
254 nm. Various chromatographic conditions were evaluated and modified until
the elution rate and the resolution were optimized. The various procedures
(options) are:
Option 1—Perkin-Elmer HC-ODS-SIL-X-1, 10-um particle size, 25 cm
long x 2.6-mm ID
Option 1A—Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent Program: 10% B, 5 min; 10 to 100% B in
35 min; 100% B, 10 min
Solvent Flow Rate: 1.0 mL/min
Option IB—Solvent A: 1% (v/v) acetic acid in distilled,
deionized water
Solvent B: Acetonitrile
Solvent Program: 20% B, 10 min; 20 to 50% B in
10 min; 50% B, 5 min
Solvent Flow Rate: 2 mL/min
Option 1C—Solvent A: 1% (v/v) acetic acid in distilled,
deionized water
Solvent B: Acetonitrile
Solvent Program: 10% B, 2 min; 10 to 100% B in
18 min
Solvent Flow Rate: 2 mL/min
Option 2—Waters Associates yBondapak C , 10-pm particle size, 30 cm'
long x 3.9-mm ID
Option 2A—Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent Program: 2% B, isocratic
Solvent Flow Rate: 1 mL/min
Option 2C—Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent Program: 20% B, 0 min; 20 to 100% B in
20 min; 100% B, 10 min
Solvent Flow Rate: 1 mL/min
11
-------
Option 2E—Solvent A: Distilled, deionized water
Solvent B: Acetonitrile
Solvent Program: 10% B, isocratic
Solvent Flow Rate: 1 raL/min
In subsequent work, the UV spectra of the candidate POHCs were determined
on a Gary Model 17 spectrophotometer to establish an absorption maximum in the
range from 190 to 400 nm that would be a suitable alternate wavelength for
quantifying each POHC by HPLC/UV.
As in the GC/FID and GC/MS analyses, calibration curves were prepared for
each compound by plotting the absorbance as a function of the injected quantity
of the compound.
HPLC/UV Quality-Control Procedures
As in the GC investigations, we determined the precision of determinations
with replicate injections of standard solutions of the analytes. The precision
of analysis was determined for only a representative group of the compounds
investigated by HPLC. An internal standard was not used in the HPLC/UV
determinations. In practice, not all POHCs will be found in a sample. Thus,
after the POHCs in the sample are identified, an appropriate internal standard
can be selected and then added to improve the quantification of POHCs.
12
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SECTION 5
RESULTS AND DISCUSSION OF THE DEVELOPMENT
OF GENERALIZED ANALYTICAL METHODS
GC/FID AND GC/MS ANALYSIS
General Considerations
In Table 1 we present the GC/FID results. The retention time and on-
column detection limit are given for each compound. The compounds are listed
in the order of their elution from the GC column. Retention times are relative
to that observed for the internal standard, anthracene-d . The on-column
detection limit is the quantity of each analyte that was estimated to yield an
FID response of about twice the background signal; about three-fourths of the
detection limits were in the subnanogram range. Reference chromatograms and
calibration curves, which appear in Appendix A, have also been cited in
Table 1. •
Appendix A contains chromatograms of seven different POHC mixtures (the
chromatograms cited in Table 1) and a chromatogram of a mixture of all of the
candidate POHCs investigated by GC/FID (Figure A-37). The chromatograms
demonstrate the observed absolute retention times, the peak shapes, and any
shifts in the base line that occurred. Although no two of the candidate POHCs
may coexist in a field situation and, therefore, may not require simultaneous
determination, the chromatogram of the compound mixture demonstrates the
resolving power of the capillary column in general.
Each reference calibration curve given in Appendix A and cited in Table I
is a point-to-point plot (solid line) of FID response as a function of the
quantity of the analyte on the GC column. Each plot can be used to estimate
the sensitivity expected in the determination of a particular analyte. In
"generating these curves, we made no attempt to determine the upper limit of the
Linear range of determinations. However, each plot serves to demonstrate the
linearity of FID response within the range of quantities investigated. A
laboratory that uses these methods will have to generate its own calibration
curves, which may differ slightly from the ones given in this report. Our
calibration curves will serve as a guide.
Also, with each calibration curve is the least-squares plot (a broken
line) based on the linear-regression analysis of FID response versus
concentration of analyte. Linear-regression analysis of the data typically
gave correlation coefficients of >0.9900.
13
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IABLL 1. SUMMARY OF GC/fID DLILRMiNATIONS OF CANDIDAFL POHCs
Appendix A
Compound
Methylhydrazine
Lthylenediamine
N-Nitroso-N-methyiethylamine
Malononitrile
Dimethyl sulfate
1 ,3-Dichloro-2-propanol
N-Nitrosodiethylamine
Methanesulfonic acid ethyl ester
N-Nitroso-N-methy lure thane
Pent achloroe thane
Benzyl chloride
N-Nitrosopyrrolidine
2 ,6-Dichlorophenol
4-Chloroaniline
N-Nitrosodibutylamine
Saf role
5 ,4-Diaminotoluene
1 ,2 ,4 ,!>-Tetrachlorobenzene
•Nicotine
1 ,4 ,5- I richlorophenol
2 /i-DLaminotoluene
2 ,6-Oiaminotoluene
1 ,4-Naphthoquinone
.£-Oinitrobenzene
m-Dinitrobenzene-
Pen1: ach lo robe nzene
aipha-Naphthy lamine
g-Nitroani line
2- Acetamidof luorene
'.• , 10-Uimethy 1-1 ,2-benzanthracene
ljibenz[a, jjacridine
Relative
retention
time8
0.0645
0.0842
0.181
0.200
0.207
0.233
0.241
0.265
0.266
0.306
0.343
0.411
0.526
0.528
0.585
0.606
0.626
0.643
0.658
0.666
0.691?
0.697
0.716
0.7J4
0.748
0.807
0.812
0.880
1.38
1 .60
1.95
On-column
detection
limit, ng
. 0.4
0.4
0.6
0.6
5.0
0.6
0.2
0.7
2.0
1.0
0.2
0.2
2.0
0.2
0.2
0.3
0.4
0.5
'0.4
2.0
2.0
0.1
0.4
0.5
0.1
0.7
0.2
0.5
0.4
1.0
0.8
Reference
chroma-
togram
A-15
A- 15
A-15
A-15
A-7
A-1
A-22
A- 12
A- 30
A-1
A-1
A-15
A- 30
A-22
A-22
A- 33
A-22
A-1
A-33
A- 30
A-22
A-15
A-7
A-15
A-22
A-1
A-12
A-15
A-33
A-7
A-7
Reference
calibration
curve
_.b
A- 16
A-17
A- 18
A-8
A- 2
, A-23
A-13 .
__b
A- 3
A-4
A-17
A-31
A- 25
A- 26
A- 34
A- 27
A- 5
A- 35
A- 32
A- 28
A- 19
A-9
A- 20
A- 29
A-6
A-14
A-21
A- 56
A- 10
A-11
aRelative to the retention time of anthracene-d ; =16 rain.
K ^ *^
"Calibration curve was not included in the appendix because of poor resolution
of the compound.
14
-------
Table 2 summarizes the GC/MS determinations. As in Table 1, the retention
times are given relative to the internal standard, anthracene-d . Table 2
also lists the five most abundant mass fragments of each compouna and, more-
over, specifies" the mass of the ion of each compound that was used for the
establishment of detection limits and for the generation of calibration curves.
The detection limits are the quantities of the analytes that were estimated to
yield ion currents (of the selected ions) corresponding to about twice the
background ion currents. Typical values of the detection limits were 1 to
5 ng.
Reference ion chromatograms, calibration curves, and mass spectra are
cited in Table 2. The mass spectra are presented in Appendix B along with the
reference chromatograms and calibration curves. One reference chromatogram
(Figure B-64) is for the determination of a mixture of all of the compounds
investigated by GC/MS.
In Table 3 we present the results of triplicate GC/FID determinations of
approximately 0.05-yg quantities of all of the candidate PORCs listed in
Table 1 except the hydrazines. The calculated values of the SD and RSD in
Table 3 indicate that most GC/FID .determinations gave acceptable precision.
RSDs greater than about 5% were, however, obtained for several of the
compounds—N-nitrosodiethylamine, _N-nitroso-N-methylurethane, methanesulfonic
acid ethyl ester, pentachloroethane, benzyl chloride, 2,6-dichlorophenol, and
1,2,4,5-tetrachlorobenzene. The less precise determinations were the result of
anomalously low responses obtained with the first in the series .of three deter-
minations for each of these compounds. Perhaps at least one injection was
required to condition the GC column and thereby to prevent loss of the
compounds in subsequent injections.
In Table 4 we present the results of triplicate GC/MS determinations of
about 0.1-pg quantities of selected POHCs listed in Table 2. In general, the
GC/MS determinations were less precise than the GC/FID determinations. About
two-thirds of the compounds were, however, determined with an RSD of about <5%.
Several of the compounds for which we obtained relatively imprecise determina-
tions by GC/FID were also found to yield RSDs >5% by GC/MS; these included
tetrachlorobenzene, pentachloroethane, and benzyl chloride.
POHCs Not Amenable to GC/FID and GC/MS Analysis
Several compounds determined by GC/FID were not determined by GC/MS.
These compounds—methylhydrazine, dimethylhydrazine, and ethylenediamine—were
volatile enough to be partially swept from the splitless injector of the GC/MS
system along with the solvent and thus could not be determined. It is likely
that these compounds could be determined, with some loss of sensitivity, by
GC/MS with split injection techniques.
15
-------
IAULL 2. SUMMAKY Ul IIC/'MS ULILKMINAI 1UNS 0( CANUIDAIL POHCs
Compound
^-Nitroso-^-methylethylamine
Mdlonoiutri le
1 ,3-Dichloro-2-propanol
N-Nitrosodiethylamine
Dimethyl sulfate
N-Nitroso-N-methylurethmie
Pentachloruethane
Methanesulfonic acid ethyl ester
Beiiz yl chloride
N-Nitrosopyrrolidiiie
4-Chlorouni I iiie
N-Nitrosodibutylamine
2,6-Dichlorophenol
3,4-Ditjminotoluene
Safrole
1 ,2 ,4,5-1 etrachiorobenzene
Nicotine
2 ,4-Diaminotoluene
2 ,6-Diaminotoluene
p_-Diiiitrobenzene
m-Oinitroberizerke
2,4,5-lrichlorophenol .
1 ,4-Naphthoquinone
Pentachlorobenzene
alpha-Naphthy lafliine
£-Nitroaniline
2-Acetamidof luoreite
9, 10-Dimethyl-1,2-benz anthracene
Oiben2[a,j]acridine
Relative
retention
time3
0.148
0.187
0.200
0.206
0.25i
0.259
0.277
0.298
U.M6
0.374
0.505
0.568
0.582
0.600
0.620
0.6S2
0.673
0.677
0.696
0.723
0.735
0.735
U.741
0.787
0.824
0.871
1.41
1.55
1.96
On-column
detection
limit, ng
4.8
5.6
6.1
2.7
4.0
23
1.2
5.2
0.72
1.9
1 .1
4.8
1.7
10
O.U92
1.3
4.2
10
2.4
1.5
1.5
2.2
3.6
1.0
0.33
5.1
3.7
4.9
12
Mol
wt
88
66
129
102
126
1S2
202
124
126
100
128
154
163
122
162
216
162
122
122
168
168
197
158
250
• 143
138
225
256
279
Masses of characteristic LI ions
(relative abundance)
1
88(100)
66(100)
' 79(100)
102(100)
95(100)
43(100)
117(100)
79(100)
91(100)
100(100)
127(100)
84(100)
162(100)
122(100)
162(100)
216(100)
84(100)
121(100)
122(100)
168(100)
168(100)
198(100)
158(100)
250(100)
143(100)
158(100)
1U1(100)
256(100)
279(100)
2
42(93)
65(12)
81(38)
42(68)
96(76)
96(76)
119(87)
109(78)
126(16)
41(61)
65(51)
>7(73)
164(62)
121(71)
104(7B)
214(85)
133(38)
122(90)
121(63)
76(82)
76(92)
196(96)
102(67)
252(62)
115(51)
65(85) .
180(82)
241(54)
280(38)
3
43(46)
64(9)
43(27)
44(60)
66(28)
66(28)
167(82)
97(26)
65(16)
42(58)
129(38)
41(61)
63(58)
94(42)
77(62)
218(52)
42(21)
94(29)
104(36)
50(80)
50(82)
97(58)
104(66)
.248(62)
116(29)
108(84)
223(62)
239(36)
277(19)
4
56(24)
67(5)
49(20)
56(56)
79(20)
79(20)
165(65)
80(19)
63(11)
68(16)
92(29)
42(40)
98( 34)
77(22)
131(60)
74(37)
162(19)
77('19)
94(33)
75(78)
75(75)
200(31)
76(62)
108(41)
144(12)
92(40)
152(37)
240(36)
125(14)
5
71(1i)
50(5)
42(8)
57(36)
65(16)
65(10)
169(41)
65(14)
89(9)
43(14)
1IJU(3U)
99(25)
99(15)
106(21)
135(36)
181(24)
161(18)
105(16)
106(20)
122(34)
122(32)
132(29)
130(45)
• 54(21)
89(11)
80(24)
. 153(19)
257(19)
139(11)
Reference
chromato-
gram
B-41
B-41
B-1
B-26
B-12
B-51
B-1
B-21
B-1
fr-26
B-26
B-26
B-51
B-26
B-58
B-1
B-58
B-26
B-41
B-41
B-26
B-51
B-12
B-1
B-21
B-41
B-58
B-12
B-12
Appendix B
Reference
mass
spectrum
B-42
B-50
B-2
B-27
B-13
B-52
B-4
B-22
B-6
B-29
B-31
B-53
B-54
B-55
B-59
B-8
B-61
B-37
B-44
B-46
B-59
B-56
B-15
B-10
B-24
B-48
B-63
B-17
B-19
Reference
t.a I ibrat ioii
curve
B-4 3
__b
B- J
B-28
B-14
B-53
B-5
B-2 3
B-7
B-.SU
b-)2
B-J4
B-55
8-36
B-6U
B-9
B-62
B-58
B-45
B-47
B-4U
B-57
B-1fa
B-11
B-25
B-49
__b
B-1B
B-2U
8Rclative to the retention time of anthraceie-d ^, =16 mm.
''Calibration curve was not included in the appendix because of poor resolution of the compound.
-------
TABLE 3. PRECISION OF GC/FID DETERMINATIONS
Compound
2-Acetamidof luorene
Benzyl chloride
4-Chloroaniline
2 ,4-Diaminotoluene
2 ,6-Diaminotoluene
3 ,4-Diaminotoluene
Dibenzta, j ]acridine
2 ,6-Dichlorophenol
1 ,3-Dichloro~2-propanol
9 ,10-Dimethyl-l ,2-benzanthracene
Dimethylsulfate
m-Dinitrobenzene
p-Dinitrobenzene
Ethylenediamine
Malononitrile
Methanesulfonic acid ethyl ester
Methylhydrazine
1 ,4-Naphthoquinone
alpha-Naphthylaraine
Nicot ine
p-Nitroaniline
N-Nitrosodibutylamine
N-Nitrosodiethylamine
N-Nitroso-N-methylethylamine
N-Nitroso-N-rae thy lure thane
N-Nitrosopyrrolidine
Pentachlorobenzene
Pentach lor oe thane
Safrole
1 , 2 ,4 ,5-Tetrachlorobenzene
2 ,4 ,5-Trichlorophenol
Quantity
on column,
47.1
51.1
57.6
65.0
60.5
64.0
43.7
53.1
55.6
48.6
62.5
46.7
63.5
64.5
66.0
56.1
67.4
44.2
49.6
56.6
66.0
61.0
59.6
60.5
43.2
78.4
51.6
69.5
48.6
48.6
51.1
Mean
0.698
0.864
0.657
0.691
0.618
0.705
0.801
0.396
0.234
1.06
0.0476
0.554
0.328
0.0387
0.828
0.243
0.202
0.438
1.10
0.618
0.561
0.695
0.609
0.467
0.182
0.558
0.359
0.161
0.722
0.427
0.414
RRFa
SD
0.011
0.059
0.027
0.0085
0.0035
0.012
0.0070
0.026
0.013
0.0000
0.0019
0.0036
0.0000
0.0012
0.0037
0.026
0.011
0.025
0.021
0.0083
0.0092
0.027
0.050
0.020
0.012
0.024
0.021
0.012
0.0093
0.0300
0.0050
-
RSD, %
1.6
6.8
4.1
1.2
0.57
1.7
0.87
6.6
5.5
0.00
4.0
0.65
0.00
3.1
4.5
11
5.4
5.7
1.9
1.3
1.6
3.9
8.2
4.3
6.6
4.3
5.8
7.5
1.3
7.0
1.4 .
JRRF
17
-------
TABLE 4. PRECISION OF GC/MS DETERMINATIONS
Compound
2-Acetamidof luorene
Benzyl chloride
4-Chloroaniline
2 ,4-Diaminotoluene
2 ,6-Diaminotoluene
3 ,4-Diaminotoluene
Dibenz[a, j Jacridine
2 ,6-Dichlorophenol
1 ,3-Dichloro-2-propanol
9 , 10-Dimethyl-l ,2-benzanthracene
Dimethyl sulfate
m-Dinitrobenzene
p-Dinitrobenzene
Methanesulfonic acid ethyl ester
1 ,4-Naphthoquinone
alpha-Naphthylamine
Nicotine
p-Nitroaniline
N-Nitrosodibutylamine
N-Nitroso-N-methylethylamine
N-Nitroso-N-me thy lure thane
N-Nitrosopyrrolidine
Peiitachlorobenzene
P en tach lor oe thane
Safrole
1 ,2 ,4 ,5-Tetrachlorobenzene
2 ,4 ,5-Trichlorophenol
Quantity
injected,
ng
95.3
103
116
131
122
129
88.2
107
112
97.6
126
94.5
128
113
88.8
100
114
133
123
122
86.9
158
104
140
98.1
97.6
103
Mean
0.151
0.445
0.101
0.227
0.128
0.110
0.252
0.199
0'.144
0.0293
0.138
0.157
0.0490
0.216
0.316
0.660
0.257
0.0931
0.214
0.0820
0.118
0.144
0 . 184
0.0970
0.152
0.211
0.288
RRFa
SD
0.012
0.057
0.010
0.0044
0.0000
0.0040
0.023
0.0060
0.0067
0.0048
0.0080
0.0085
0.00067
0.0081
0.011
0.011
0.024
0.0057
0.020
0.0018
0.0047
0.013
0.0053
0.0085
0.0032
0.011
0.010
RSD, %
7.9
13
9.9
1.9
0.00
3.6
9.1
3.0
4.7
16
5.8
5.4
1.4
3.8
3.5
1.7
9.3
6.1
9.3
2.2
4.0
9.0
2.9
8.8
2.1
5.2
3.5
aRRF = (AisCig)/(AisCs)
18
-------
Some other compounds investigated could not be determined reliably by the
GC/FID or GC/MS survey methods. These included maleic anhydride, thiophenol,
cyclophosphamide, and o-toluidine. Apparently, these compounds were
irreversibly adsorbed by the GC column or were decomposed in solution, on the
column, or in the injection port.
HPLC ANALYSIS
A summary of HPLC/UV determinations is given in Table 5. A.description of
the generalized HPLC/UV analysis method including the various procedural
options is presented in Section 4.
In Table 5, the option used in the determination of each compound is
specified. Over half of the listed compounds were determined by Option 1A.
Option IB, which involved the acidification of the eluent, was instituted
primarily for the determination of the phenoxyacetic acids. We observed that
4,6-dinitro-£-cresol and methyl yellow chromatographed very poorly without the
inclusion of acid in the eluent; thus, Option 1C was established for the deter-
mination of these two compounds. Option 2A was suitable for the determination
of .N-nitroso-N-methylurea, and Option 2B was suitable for saccharin.
(Option 2C was used for the determination of other compounds discussed later.)
For some of the compounds, it is likely that another option—either one of the
other options listed here or a new set of operating -conditions—would have
given results comparable to those presented in Table 5.
The application of the specified procedures yielded the retention times
and detection limits given in Table 5. For most of the compounds listed, the
initial determinations were made at a detector wavelength of 254 nm, the wave-
length of maximum absorbance for the phenyl functional group. After we had
selected optimum wavelengths for analysis, we redetermined some of the
compounds to establish lower detection limits. The limits established for the
optimum wavelengths were typically <10 ng and usually about a factor of 10
lower than the limits at 254 nm.
Table 5 cites the reference chromatograms, UV spectra, and calibration
curves generated for the compounds listed. The chromatograms were obtained for
2- to lO-yg quantities of each analyte injected onto the appropriate HPLC
column. The calibration curves were plotted with the GC/MS data system as
described previously for the GC determinations. Correlation coefficients were
typically >0.999, with a few exceptions. For some exceptions, such as phenol,
we obtained calibration curves that were nonlinear. Because these curves none-
theless appeared to be useful in determining the substance with reasonable
accuracy, we did not consider it necessary to determine these substances on
other HPLC columns or with alternative solvent programs.
19
-------
TABLE 5. SUMMARY OF HPLC/UV DETERMINATIONS OF CANDIDATE POHCs
Procedural
Compound option3
Streptozotocin
Phenol
4-Nitrophenol
o-Chlorophenol
Acetophenetidine
5-Nitro-o-toluidine
Tetramethylthiuram disulfide
4-Chloro-m-cresol
2 , 4-Dichlorophenol
3-(alpha-Acetonylbenzyl)-4-
hydroxycoumarin
2,4, 6-Trichlorophenol
2 , 3 , 4 , 6-Tetrachlorophenol
Reserpine
Chlorambucil
2,4-Dichlorophenoxyacetic acid
2,4, 5-Trichlorophenoxyacetic
acid
2- (2 , 4 , 5-Trichlorophenoxy )-
propionic acid
4 , 6-Dinitro-o-cresol
Methyl yellow
N-Nitroso-N-methylurea
Saccharin
1A
1A
1A
1A
1A
1A
1A
1A
1A
I
1A
1A
1A
1A
1A
IB
IB
IB
1C
1C
2A
2B
Retention
time,
min
1.
5.
9.
12.
12.
14.
16.
16.
17.
19.
20.
21.
22.
23.
7.
14.
16.
7.
13.
8.
3.
4
4
5
4
6 ,
3
3
8
6
8
0
5
7
9
6
2
5
6
1
4
2
Wavelength
of
detection,
nm
254 /
254 /
254 /
254 /
254 /
254 /
254 /
254 /
254 /
254 /
254 /
254. /
254 /
254 /
254 /
254 /
254 /
378.
400
254 /
254 /
' 230
' -280
' 280
' 280
1 248
' 253
' 280
1 280
' 280
1 280
280
280
267
258
284
287
1 287
234
' 224
On-column
detection
limit,
ng
2
80
50/6
70/6
1,
1
1
80/4
100 / 2
2
50/7
20 / 20
30
1
70
60
40
20
3
10
2
Appendix C
Reference
chromat-
ogram
C-l
C-5
C-9
C-13
C-17
C-20
C-23
C-26
C-30
C-34
C-37
C-41
C-45
C-48
C-51
C-54
C-57
C-60
C-60
C-65
C-68
Reference
UV
spectrum
C-2
C-6
C-10
C-14
C-18
C-21
C-24
C-27
C-31
C-35
C-38
C-42
C-46
C-49
C-52
C-55
C-58
C-61
C-6 3
C-66
C-69
Reference
calibration
curve
C-3
C-7
C-ll
C-15
C-19
C-22
C-25
C-28
C-32
C-36
C-39
C-43
C-47
C-50
C-53
C-56
C-59
C-62
C-64
C-67
C-70
/
/
/
/
/
/
/
/
C-4
C-8
C-12
C-16
C-29
C-3 3
C-40
C-44
•
'See Section 4, p. 11 for description of procedural options.
-------
In addition to the compounds cited in Table 5, we found others that may
be determined by the generalized HPLC/UV test procedure. Because of time
constraints, the investigation of these substances was not completed; neverthe-
less, compounds are presented in Table 6 as potential candidates for analysis
by the HPLC/UV procedure. Retention times and approximate detection limits
were determined for the compounds on the basis of a limited number of injec-
tions of standard solutions. The retention times of several of the compounds—
thiourea, thioacetamide, and ethylene thiourea—were uncertain because several
major peaks were observed in their chromatograms. The presence of more than
one major peak in the chromatogram was interpreted as an indication of gross
contamination of the sample or as an indication of the decomposition of the
analyte on the HPLC column. Thus, the feasibility of the application of the
method to the determination of these four compounds is uncertain.
The precision of HPLC determinations for a representative group of the
candidate POHCs is demonstrated by the data in Table 7. All but two compounds
gave <5% RSD for triplicate determinations. The precision of the determination
of acetophenetidine was biased by one value that was 15% higher than the other
two. Perhaps additional determinations would have proved the high result to be
a statistical outlier. The determinations of 5-nitro-o-toluidine yielded
increasing responses with each subsequent determination; such a trend is
usually indicative of column conditioning. Perhaps the response would reach a
stable value after repeated injections.
21
-------
TABLE 6. POTENTIAL CANDIDATES FOR ANALYSIS BY HPLC/UV
. Procedural
Compound option3
Trypan blue
Epinephrine
Thiosemicarbazide
Thiourea
Thioacetamine
Ethylene thiourea
Crotonaldehyde
Diethylstilbestrol
Mitomycin C
Melphalan
'!• , 3 ' -Dimethyoxybenzidine
dihydrochloride
Daunomycin
Azaserine
2C
2C
2C
2C
2C
2C
2C
2C
1A
1A
1A
IB
2A
Retention
time, min
3
3
3
=3C
s4c
- =4C
5
14
5
14
= 19 ..
8
4
Approximate
on-column
detection
limiting
20
60
5
6
2
8
1
4
17
10
9
75
2
Wavelength
of
detection ,
nm
315
279
254
254
254
254
230
240
254
254
254
254
254
aSee Section 4, page 11 for description of procedural options.
^Quantity injected that should yield a response of 1000 counts on the
integrator.
cThe presence of several major peaks in the chromatogram made the
assignment of a retention time difficult.
22
-------
TABLE 7. PRECISION OF HPLC/UV DETERMINATIONS
Compound
Quantity
injected,
US
Area counts x
Mean SD
10-3
RSD, %
3-(alpha-AcetonyIbenzyl)-
4-hydroxycoumarin
Acetophenetidine
Chlorambucil
5-Nitro-o-toluidine
^-Nitroso-N-methy1urea
Reserpine
Saccharin
Tetramethylthiuram disulfide
9.39
52
76
48
96
50
0.977
9.45
894
962
452 .
747
108
58.8
42.7
264
8.0
85
4.0
56
1.0
2.5
0.66
10
0.9
8.9
0.9
7.4
0.8
4.2
1 .5
0.4
23
-------
SECTION 6
DESCRIPTION OF SUPPLEMENTARY METHODS
DEVELOPMENT AND OTHER TASKS
In addition to the work that was performed at Southern Research Institute,
other specific tasks were carried out by Battelle-Columbus Laboratories. These
tasks are listed below:
• Development of analysis methods for brucine and 2-fluoroaceta-
mide.
• Recommendation of potentially useful air-sampling, sample-
preparation, and analysis procedures for various POHCs.
• Revision of the general sample digestion procedure and specific
analysis methods for the determination of metals.
'O Evaluation of digestion and analysis procedures for beryllium,
strontium, and vanadium.
Most of this information is historical and has been superseded by
approaches' in the Methods Manual. Nevertheless, we have included the results
of these tasks in Appendix D.
24
-------
SECTION 7
QUALITY-ASSURANCE SUMMARY
The work that was done at SoRI and presented in this report was performed
under Contract 68-02-2685, Work Assignment 111. Although the project includes
environmentally related measurement activities, no field samplings were
analyzed. Thus, sampling procedures, chain-of-custody procedures, and
spiked-sample matrixes were considered as inapplicable in the systematic review
of this project. • The major efforts of SoRI were to evaluate and, when
necessary, modify GC/MS and HPLC/UV generalized analysis procedures for
candidate POHCs. This task was accomplished with individual POHCs and mixtures
of POHCs.
An internal audit of the project revealed no deficiencies in the internal
quality-control checks and data processing. The relative retention times,
on column detection limits, chromatograms, calibration curves, relative ion
abundances, spectra, and relative standard deviations in this report will be.a
guide for other analytical laboratories. Because of subtle differences among
laboratories and analytical instrumentation, analysts who participate in
similar studies should generate data that will establish their own criteria for
the analysis of POHCs.
25
-------
REFERENCES
1. Resource Conservation and Recovery Act, Subtitle C SS3001-3013, 42 U.S.C.
-SS6921-6934, 1976, and Supplement IV, 1980.
2. Harris, J.C.; Larsen, D.J.; Rechsteiner, C.E.; and Thrun, K.E. Sampling
and analysis methods for hazardous waste combustion. EPA-600/8-84-002,
NTIS PB 84-155-845; 1984 February.
3. Vogel, G.; Brooks, K.; Cross, J.; Frankel, I.; Haus, S.; and Jacobsen, W.
Guidance manual for evaluating permit applications for the operation of
hazardous waste incinerator units. Final Report, EPA Contract 68-01-6092,
U.S. Environmental Protection Agency, Washington, D.C.; 1981 April.
4. U.S. Environmental Protection Agency. Test methods for evaluating solid
waste: physical/chemical methods. EPA Report No. SW-846, U.S. Environ-
mental Protection Agency, Cincinnnati, OH: 1980.
5. de Vera, E.R.; Simmons, B.P.; Stephens, R.D.; Storm, D.L. Samplers and
sampling procedures for hazardous waste streams. EPA-600/2-80-018, NTIS
PB 80-135-353, U.S. Environmental Protection Agency, Cincinnati, OH;
1980.
6. Federal Register 44(23): 69540-59; 1979.
26
-------
APPENDIX A
CHROMATOGRAMS AND CALIBRATION CURVES
FOR GC/FID DETERMINATIONS
Index
Compound
Reference
chromatogram
Figure No.
Reference
calibration curve
Figure No.
2-Acetamidof luorene
Benzyl chloride
4-Chloroaniline
2 ,4-DiaminoColuene
2 ,6-Diaminotoluene
3 ,4-Diamino toluene
Dibenzfa, j ] acrid ine
2 ,6-Dichlorophenol
1 , 3-Dichloro-2-propanol
9 , 10-Dimethyl-l ,2-benzanthracene
Dimethyl sulfate
m-Dinitrobenzene
p-Dinitrobenzene
Ethylene diamine
Malononitrile
Methanesulfonic acid ethyl ester
Methylhydrazine
1 ,4-Naphthoquinone
alpha-Naphthylamine
Nicotine
p-Nitroaniline
N-Ni trosodibutylamine
N-Nitrosodiethylamine
N-Ni troso-N-me thy lethylamine
N-Nitroso-N-me thy lure thane
N-Nitrosopyrrolidine
Pentachlorobenzene
Pe n t achl or oe thane
Safrole
1 ,2 ,4 ,5-Tetrachlorobenzene
2 ,4 ,5-Trichlorophenol
A-33
A-l
A-22
A-22
A-15
A-22
A-7
A- 30
A-l
A-7
A-7
A-22
A-15
A-15
A-15
A-12
A-15
A-7
A-12
A-33
A-15
A-22
A-22
A-15
A- 30
A-15
A-l
A-l
A-33
A-l
A- 30
A-36
A-4
A-25
A- 28
A-19
A-27
A-ll
A-31
A- 2
A-10
A-8
A-29
A-20
A-16
A-18
A-13
a
A- 9
A-14
A- 3 5
A-21
A-26
A-23
A-17
a
A-17
A- 6
A- 3
A- 34
A- 5
A-32
Calibration curve not available.
27
-------
IS
Ul
in
2
Ul
-------
Reproduced from
best available copy.
UJ
CO
Z
O
Q.
CO
LU
cc
x>
x/
2 O 0
400
6 0 0
1 0 O O
1200
1400
QUANTITY ON COLUMN, ng
Figure A-2. Calibration curve for the determination of
1,3-dichloro-2-propanol by GC/FID.
Range: 21 - 1000 ng
Correlation coefficient: 0.997
Slope: 4.4 x 10~3
y-Intercept: 2 .4 x 10~2
29
-------
4 . 0
2
O
o.
«/>
UJ
2 . 0 I-
QC -
UJ
>
p
< 1.51-
_l
UJ
CC
1 .0
_.•
409 600 S00 1000
QUANTITY ON COLUMN, ng
1200
1403
Figure A-3. Calibration curve for the determination of
pentachloroethane by GC/FID.
Range: 65 - 1300 ng
Correlation coefficient: 0.999
Slope: 2.8 x 10~3
y-Intercept: 2.9 x 10~2
30
-------
CO
O
a.
a.
UJ
1 0 0
2 0 0
jyy
4 @ £1 5 0 0
600
r' U t'
S 0 0 9 0 0
QUANTITY DIM COLUMN, ng
Figure A-4. Calibration curve for the determination of
benzyl chloride by GC/FID.
Range: 48 - 720 ng
Correlation coefficient:
Slope: 1 .4 x 1U"1
y-Intercept: 1 .6 x 10" !
0.999
31
-------
6 '-
to
I 4
CO
01
tr
Ui
UJ
DC
20Q
4 0 0 6 6 0
QUANTITY ON COLUMN, ng
800
1000
Figure A-5. Calibration curve for the determination of
1,2,4,5-tetrachlorobenzene by GC/FID.
Range: 18-910 ng
Correlation coefficient: 0.999
Slope: 7.2 X 10"3
y-Intercept: 4 .6 x. 10~2
32
-------
Ul
in
Z
o
a.
CO
01
oc
<
LU
cr
1 -•
490 609 30
QUANTITY ON COLUMN, ng
1000
1200
Figure A-6. Calibration curve for Che determination of
pentachlorobenzene by GC/FID.
Range: 19 - 970 ng
Correlation coefficient: 0.999
Slope: 6.4 x 10~3
y-Intercept: 1.0 x 10~2
33
-------
01
e/»
O .
0.
tr
Q
iZ
6
15 20 25
RETENTION TIME, min
30
35
40
Figure A-7. Chromatogram by GC/FID for
(A) dimethyl sulfate(tn = 3.4 min),
(B) 1,4-naphthoquinonettR = 11.7 min),
(C) 9,10-dimethyl-l,2-benzanthracene(tR
(D) dibenzfa,j]acridine(CR = 31.5 rain).
Temperature program:
40 °C, 0 min isothermal
40 CC to 280 °C at 10 °C/min
280 °C, 15 min isothermal
26.0 min), and
34
-------
2 .0
1 .5
00
O
a.
CO
LU
0 .0
y-
490 600 . 300'
QUANTITY ON COLUMN, ng
1000
1 2 0 0
Figure A-8. Calibration curve for the determination of
dimethyl sulfate by GC/FID.
Range: 120 - 1200 ng
Correlation coefficient: 0.999
Slope: 1.1 x 10~3
y-Intercept: -2.0 x 10~2
35
-------
LU
CO
z
O
Q.
in
UJ
cc
<
_!
CC
14
13 -
12
1 1
10 h
2 3 3
4 @ 0 t- 0 0
QUANTITY ON COLUMN, ng
300
1000
Figure A-9. Calibration curve for Che determination of
1 ,4-naphthoquinone by GC/FID.
Range: 20-830 ng
Correlation coefficient: 0.999
Slope: 1.6 x 10~2
y-Intercept: 4.0 x 10~2
36
-------
CO
Z
o
a.
CO
LLI
OC
10. -
,L
>•
x
X
x
X
2 Q 0 4 0 0 6 0 0
QUANTITY ON COLUMN, ng
S0.0
Figure A-10.
Calibration curve for the determination of
9,10-dimethyl-l,2-benzanthracene by GC/FID.
Range: 46 - 680 ng
Correlation coefficient: 0.998
Slope: 1.9 x 10~2
y-Intercept: -2.9 x. 10" 1
37
-------
14
13
12
1 1
10
U)
O
a.
(/»
m
cc
"'
200
4 @ 0 f. 0 0 8 0 O
QUANTITY ON COLUMN, ng
lOOO
Figure A-l1.
Calibration curve for the determination of
dibenz[a,j]acridine by GC/FID.
Range: 41 - 820 ng
Correlation coefficient: 0.999
Slope: 1.6 x 10~2
y-Intercept: 3 .b x. 10~2
38
-------
B
IS
UJ
ta
O
a.
tu
oc
u
O
_L
10 15
RETENTION TIME, min
20
25
Figure A-12. Chroraatogram by GC/FID for
(A) methanesulfonic acid ethyl esCer(tR = 4.6 min) and
(B) alpha-naphthylamineCtp = 13.6 min).
Temperature program:
40 °C, 0 min isothermal
40 CC to 280 °C at 10 3C/min
280 °C, 15 min isothermal
39
-------
UJ
CO
O
a
at
cc
ui
>
P
400 see see
QUANTITY ON COLUMN, ng
Figure A-13.
Calibration curve for the determination of
methanesultonic acid ethyl ester by GC/FID.
Range: 56 - 1100 ng
Correlation coefficient: 0.999
Slope: 5.2 x 10~3
y-Intercept: 1.6 x 10~2
40
-------
24
CO
O 14
Q.
CO
LJJ
oc 12
01
Z 10
X
ii 0 tf
400
QUANTITY ON COLUMN, ng
S 0 0
1000
Figure A-14.
Calibration curve for Che determination of
alpha-naphthylamine by GC/FID.
Range: 20 - 990 ng
Correlation coefficient: 0.999
Slope: 2.3 x 10~2
y-Intercept: b.2 x 10~2
41
-------
Z
o
cc
o
iZ
u
o
IS
A C
B
I
I
10 15
RETENTION TIME, min
20
25
Figure A-15. Chromatogram by GC/FID for
(A) methyl hydrazine(tR = 1.1 min),
(B) ethylene diamine(tR =1.4 min),
(C) J^-ni troso-^N-methylethylamine( tR =3.0 min),
(D) malononitrileCtR = 3.3 min),
(E) 2,6-diaminotoluene(tR = 11.4 min),
(F) j)-dinitrobenzene( tR = 12.0 min), and
(G) 2.-nitroaniline( tR = 14.3 min).
Temperature program:
40 °C, 0 min isothermal
40 °C to 280 CC at 10 °C/min
280 CC,-15 min isothermal
42
-------
I
00
HI
cc
UJ
>
<
.X'
£ 0 0
4 y O 6 u 6
QUANTITY ON COLUMN, ng
S 9 0
1000
Figure A-16-.
Calibration curve for the determination of
ethylene diamine by GC/FID.
Range: 97 - 970 ng
Correlation coefficient: 0.997
Slope: 7.4 x 10~3
y-Intercept: I.1 x ID"1
43
-------
LU
cc
CO
Z
O
a.
4 0 0 6 6 @
QUANTITY ON COLUMN, ng
S00
1000
Figure A-17.
Calibration curve for Che determination of
N-nitroso-N-methylethylamine by GC/FID.
Range: 57 - 910 ng
Correlation coefficient: 0.998
Slope: 8.5 x 10"3
y-lntercept: 1.8 x 10"l
44
-------
C/5
Z
o
Q.
CO
200
400
QUANTITY ON COLUMN, ng
800
1000
Figure A-18. Calibration curve for the determination of
malononitrile by GC/FID.
Range: 99 - 990 ng
Correlation coefficient: 0.998
Slope: 8.9 x 10~3
y-Intercept: -8.1 x 10 2
45
-------
Ul
40
O
a.
CO
LU
oc
ID
<
UJ
tr
3 h
x
X
X"
400 660
QUANTITY ON COLUMN, ng
1000
Figure A-19. Calibration curve for the determination of
2,6-diaminotoluene by GC/FID.
Range: 5.7 - 910 ng
Correlation coefficient: 0.999
Slope: 1.5 x 10~2
y-Intercept: -1.0 x 10~2
46
-------
z
o
Q.
t/i
Ol
CC
> 4 .
1 •
2 o 0
460 66@
QUANTITY ON COLUMN, ng
see
1000
Figure A-20.
Calibration curve for the determination of
p-dinitrobenzene by GC/FID.
Range: 24 - 950 ng
Correlation coefficient: 0.999
Slope: 8.9 x 10~3
y-Intercept: -4.4 x 10~2
47
-------
11
10
Lti 7
v> '
I . <-
LU
DC
LU C
200
400 600
QUANTITY ON COLUMN, ng
see
looe
Figure A-21.
Calibration curve for the determination of
j>-nitroaniline by GC/FID.
Range: 6.0 - 990 ng
Correlation coefficient: 0.999
Slope: 1.1 x 10~2
y-Intercept: -5.9 x 10~2
-------
IS
B
LU
c/j
O
%
LU
cc
O
o
_L
J_
Figure A-22.
0 5 10 15
RETENTION TIME, min
Chromatogram by GC/FID for
20
25
(A)
(B)
(C)
(D)
(E)
(F)
(G)
^J-nitrosodiethylamineC tR =3.9 min) ,
= 6.8 min),
4-chloroaniline( tR =8.8 min),
J^-nitrosodibutylamine(tR = 9.7 min),
3 ,4-diaminotoluene( tR = 10.4 min),
2 ,4-diaminotoluene( tn = 11.6 min), and
m-dinitrobenzene( tD = 12.4 min).
— K
Temperature program:
40 °C, 0 min isothermal
40 °C to 280 "C at 10 cC/min
280 "C, 15 min isothermal
49
-------
11
10
LU
CO
1
UJ
cc
SJ
1:00
400 600 . 800 1000
QUANTITY ON COLUMN, ng
1200
Figure A-23.
Calibration curve for the determination of
N-nitrosodiethylamine by GC/FID.
Range: 110 - 1100 ng
Correlation coefficient: 0.997
Slope: 8.6 x 10~3
y-Intercept: 2.U x 10~1
50
-------
16
14
10
O
Q.
(/>
LU
cc
uj
..•-X"
UJ
cc
200 4@0"' 600 300 1000
QUANTITY ON COLUMN, ng
1200 1400
Figure A-24.
Calibration curve for the determination of
Jtf-nitrosopyrrolidine by GC/FID.
Range: 15 - 1500 ng
Correlation coefficient: 0.998
Slope: 1.0 x 10~2
y-Intercept: 7.6 x 10~2
51
-------
14 -
12 1-
ui
CO
1
CO
LLJ
cc
X
2 @ 8
488
600
8*0
1000
1200
QUANTITY ON COLUMN, ng
Figure A-25.
Calibration curve for the determination of
4-chloroaniline by GC/FID.
Range: 11 - 1100 ng
Correlation coefficient: 0.999
Slope: 1.2 x 10~2
y-Intercept: 1.3 x 10" l
52
-------
14 L
o
a.
CO
LU
(C
2 0 0
too see
QUANTITY ON COLUMN, ng
1000
1200
1400
Figure A-26.
Calibration curve for the determination of
N-nitrosodibutylamine by GC/FID.
Range: 110 - 1100 ng
Correlation coefficient: 0.999
Slope: 1.3 x 10~2
y-Intercept: I.9 x 10"l
53
-------
C/5
I
V)
Ui
oc
LU
CC
200
400
see
1600 1200 1400
QUANTITY ON COLUMN, ng
Figure A-27.
Calibration curve for the determination of
3,4-diaminotoluene by GC/FID.
Range: 12 - 1400 ng
Correlation coefficient: 0.996
Slope: 1.2 x 10~2
y-Intercept: 2.0 x 10~2
-------
16
14
12
UJ
V)
\ 10
LU
cc
UJ
'
_,,"•">
.- ^...
""
j_
2 8 0
400
606
300
1 O 0 O
1200
1400
QUANTITY ON COLUMN, ng
Figure A-28.
Calibration curve for the determination of
2,4-diaminotoluene by GC/FID.
Range: 12 - 1400 ng
Correlation coefficient: 0.996
Slope: 1.2 * 10~2
y-Intercept: b.Q x 10 2
55
-------
UJ
CO
I
V)
LLJ
CC
_l
LLJ
CC
10 r
1 @ 0
£ 0 0
300
400
500
600
700
800
900
QUANTITY ON COLUMN, ng
Figure A-29.
Calibration curve for the determination of
m-dinitrobenzene by GC/FID.
Range: 120 - 880 ng
Correlation coefficient: 0.999
Slope: 1.1 x 10~2
y-Intercept: 6.1 x 10~2
56
-------
LU
CO
I
CO
ci
a
IS
B
I
I
10 15
RETENTION TIME, min
20
25
Figure A-30. Chromatogram by GC/FID for
(A) ^J-nitroso-N-methylurethaneCt,, = 4.4 min),
(B) 2,6-dichlorophenoKtp = 8.7 min), and
(C) 2,4,5-trichlorophenoHtR = 11.0 min).
Temperature program:
40 CC, 0 min isothermal
40 °C to 280 °C at 10 °C/min
280 °C, 15 min isothermal
57
-------
I;.
Ill
CO
1 5
CO
UJ
oc
> 4
K
<
£90
400 600
QUANTITY ON COLUMN, ng
see
Figure A-31.
Calibration curve for the determination of
2,6-dichlorophenol by GC/FID.
Range: 20 - 900 ng
Correlation coefficient: 0.998
Slope: 8.9 x 10~3
y-Intercept: 1.4 x 10'1
58
-------
t r
o
Q.
c/j
408
QUANTITY ON COLUMN, ng
800
Figure A-32.
Calibration curve for the determination of
2,4,5-trichlorophenol by GC/FID.
Range: 20 - 860 ng
Correlation coefficient: 0.998
Slope: 5.9 x 10*3
y-Intercept: 1.1 x 10"*
59
-------
o
a.
V)
UJ
cc
u
o
IS
B
Figure A-33.
0 5 10 15
RETENTION TIME, min
Chromatogram by GC/FID for
(A) safrole(tR = 9.9 min),
(B) nicotine(tR = 10.7 min), and
(C) 2-acetamidofluorene(tR = 22.5 min).
Temperature program:
40 °C, 0 min isothermal
40 °C to 280 °C at 10 °C/min
280 °C, 15 min isothermal
20
25
60
-------
12
v>
Z
o
Q.
V)
UJ
408 6Q0 880
QUANTITY ON COLUMN, ng
1088
Figure A-34.
Calibration curve for the determination of
safrole by GC/FID.
Range: 46 - 910 ng
Correlation coefficient: 0.999
Slope: 1.4 x 10~2
y-Intercept: 2.8 x 10"!
61
-------
16
14
12
CO
O 10 I-
Q.
CO
LU
OC
#
#-••"
..-• ,•••
.,-• ..-•••'"
,x
-•%•••
200
400 600 see
QUANTITY ON COLUMN, ng
ieee
1200
Figure A-35. Calibration curve for the determination of
nicotine by GC/FID.
Range: 53 - 1100 ng
Correlation coefficient: 0.998
Slope: 1.5 x 10~2
y-lntercept: -3.1 x 10"l
62
-------
1 4
12
2
CO
UJ
oc
200
4(36 600
QUANTITY ON COLUMN, ng
S00
Figure A-3b.
Calibration curve for the determination of
2-acetamidofluorene by GC/FID.
Range: 18 - 890 ng
Correlation coefficient: 0.999
Slope: 1.5 x 10~2
y-Intercept: -5.3 x 10~2
63
-------
z
o
Q.
00
UJ
cc
u
o
IS
I
1
1
1
UL
u<
- - __
1
.JJoj
|
>-
1 1 1 1
RETENTION TIME, min
Figure A-37. Chromatogram by GC/FID for all candidate POHCs,
Temperature program:
40 CC, 0 min isothermal
40 CC to 280 CC at 10 cC/min
280 CC, 15 min isothermal
64
-------
APPENDIX B
CHROMATOGIIAMS, MASS SPECTRA, AND CALIBRATION
CURVES FOR GC/MS DETERMINATIONS
Index
Compound
2-Acetamidof luorene
Benzyl chloride
4-Ghloroaniline
2 ,4-Diaminotoluene
2 ,6-Diaminotoluene
3 ,4-Diaminotoluene
Dibenzfa, j ] acridine
2 ,6-Dichlorophenol
1 , 3-Dichloro-2-propanol
9,10-Dimethyl-
1 ,2-benzanthracene
Dimethyl sulfate
m-Dinitrobenzene
p-Dinitrobenzene
Mai ononit rile
Methanesulfonic acid
ethyl ester
1 ,4-Naphthoquinone
alpha-Naphthylamine
Nicotine
p-Nitroaniline
N-Nitrosodibutylamine
N-Ni trosodiethylamine
N-Nitroso-N-
me t hy 1 ethyl ami ne
N-Nitrosopyrrolidine
Peatachlorobenzene
Pen tachloroe thane
Safrole
1,2,4, 5-Tetrachlorobenzene
2 ,4 ,5-Trichlorophenol
Reference
chromatogram
Figure No.
B-58
B-l
3-26
B-26
B-4.1
B-26
B-12
B-51
B-l
B-12
B-12
B-26
B-41
B-41
B-21
B-12
B-21
B-58
B-41
B-26
B-26
B-41
B-26
B-l
B-l
B-58
B-l
B-51
Reference
mass
spectrum
Figure No.
" B-63
B-6
B-31
B-37
B-44
B-35
B-19
B-54
B-2
B-17
B-13
B-39
B-46
B-50
B-22
B-15
B-24
B-61
B-48
B-33
B-2 7
B-42
B-29
B-10
B-4
B-59
B-8
B-56
Reference
calibration
curve
•Figure No.
— a
B-7
B-32
B-38
B-4 5
B-36
B-20
B-55
B-3
B-18
B-14
B-40
B-47
— a
B-23
B-16
B-25
B-62
B-49
B-34
B-28
B-43
B-30
B-ll
B-5
B-60
B-9
B-5 7
Calibration curve not available.
65
-------
B
IS
11
12
14
15
16
17
IS
Figure B-l. Chromatogram by GC/MS for
(A) 1,3-dichloro--2-propanol(tn = 4.6 min) .
(B) pentachloroethane(tR =5.7 min),
(C) benzyl chloride(tR =6.4 min),
(D) 1,2,4,5-tetrachlorobenzene(tR = 11.2 min), and
(E) pentachlorobenzeneCtR = 13.8 min).
Temperature program:
40 °C, 0 min isothermal
40 °C to 280 °C at 10 °C/min
280 rC, 15 min isothermal
66
-------
Reproduced from
best availaole copy.
LfiRGST 4 : 79.1,1 OO . 0 3 1.0, 38 .4 43.2,26.7 49.1,20.2
LflST 4: 139.3, .1 163.2, .1 179.3, .1 130.3, .1
100.
60;
40!
20!
•0"
100.
30!
60!
40.
20
0
, |
20 40
• -
'•'•"• 1S\3 '""20Vi
I..I, ||m. i|., Kill- nmtn'tti
60 30 100 120 140 160
220 240 260 230 306 32S
Figure B-2. Mass spectrum for 1,3-dichloro-2-propanol
67
-------
TABLE B.I KEY IONS AND RELATIVE ABUNDANCES
FOR 1.3-DICHLORO-2-PROPANOL
M/Z
41
42
43
44
45
47
49
SO
51
52
53
55
56
57
60
61
62
63
65
63
72
73
75
76
Abundance
2 . :::
3 .' 1
26.7
4.1
• •"•
3 . 5
20.2
2.5
5.9
1 .0
.9
1 .2
.7
1 .5
.7
1 .6
§ •?
1 .*7
1 .O
.1
..5-
1.1
3 . 3
1 .2
M/Z
f' (''
79
SI
32
36
33
91
92
93
94
96
97
102
110
112
115
117
127
123
129
133
1413
Abundance M/Z Abundance
1.3 163 .1
100.0
33.4 179 .1
•7 139 .1
.4
.2
1 .1
.4 .
.5
.4
.2
' .2
•">
m w
.2
.1
- .0
.1
.1
.1
.2
.1
.1
68
-------
CO
Z
O
Q.
tO
LU
30 40 50 66
QUANTITY ON COLUMN, ng
Figure B-3. Calibration curve for the determination of
1,3-dichloro-2-propanol by GC/MS.
Range: 9.0-86 ng
Correlation coefficient: 0.996
Slope: 6.7 x 10
y-Intercept: -1.5 x 10"1
69
-------
LflRGST
LflST 4
L 0 0
30.
60!
40
0'
1 0 0
60!
40.
0
4: 117.0,100.
207. T,
I
,
20! 4I0U '
130 200
0'
II
1
"iJ" '"60
'•!•••• i;::'
>:
1:3.9, 37.1 167.0, 31.3 164.9, 64.9
0:5.0, .2 219.4, .2 236.0, .2
-
30
24'0
!,,,!
-
1
li,
, II
l&Q 120 140 160
2 6 0 280 300 320
Figure B-4. Mass spectrum for pentachloroethane.
70
-------
TABLE B-2. KEY IONS AND RELATIVE ABUNDANCES
FOR PENTACHLOROETHANE
M/Z
42
44
47
48
49
50
52
56
57
60
61
62
6 3
65
KI*,
67
70
72
74
75
73
32
83
34
Abundance
32
1 1
1 1
4
55
6
17
1
1
2
. l
16
39
12
.4
i4
?
. 6
'.3
.3
i3
.3
.7
'*'
•
-------
3 .0
2.0
z •
o
d.
-------
LflRGST 4: 91.1,109.13 126.2, 16.1 65.0, 15.5 63.2, 11.3
LOST 4: 184.0, .9 191.5, .0 199.3, .0 297.1, .1 .
100.
30.
60!
48.
20!
0"
1 0 0
36.
60!
40.
20
0
[T1 n . , . . , ., T -r rri M ' 1 1 1 1 1 1 1 1 1 i M J 1 1 1 1 1 1 1 ' 1 1 1 1 1 1 1 1 1 ' 1 1 1 1 1
20 40 60 30
100 120 14'0 160
-
'
'"" iW' "•''•'•' 20y " ''"'"" 22'0 '"" 24^ '"" 26'0' '"" £S^ '"" 30'fe' '"" 32'0
Figure B-6. Mass spectrum for benzyl chloride.
73
-------
TABLE B-3. KEY IONS AND RELATIVE ABUNDANCES
FOR BENZYL CHLORIDE
M/Z
41
43
44
45
47
43
49
50
51
52
53
61
62
63
65
66
67
69
71
73
74
75
76
r r
Abundance M/Z
1
6
I
2
g£
5
11
15
1
1
1
.6
.2
.4
. 6
.3
.4
.3
• €•
. -"!
.5
.3
.4
. 6
.3
. 5
.9
.1
.1
.1
•?
.2
• 2
. 6'
.4
? O
79
30
31
32
34
35
36
•I- r
39
91
9 2
93
95
97
99
131
106
1 11
113
1 14
117
1 19
121
Abundance M/Z
.1
. 0
.1
.1
. 1
.4
1 . 0
1 .3
• r
9.4
100.0
7.3
. 3
.1
, ^
1 .1
.4
.0
.0
.0
.0
.0
.1
.0
126
127
123
129
130
132
134
154
155 '
153
163
134
191
199
207
Abundance
16.1
2.0
5 .6
.5
.0
.0
.0
.0
.0
.0
• 0
.0
.0
.0
. 1
-------
11
r
o
a.
CO
UJ
-------
LflRGST 4:
LflST 4:
100.
80.
60
40.
20!
0"
100.
30.
60.
40.
20
o
'' ' ' ' j;:
I
,\
215.9,100.0 213.9. 35.1 217.9, 52.3 74.2, 36.3
219.1, 3.3 219.3, 10.2 220.3, .6 221.3, .7
i
.11 llll|llll IIII|MII llll|lll
il,
60 30 ' 100 ' 120 14B 160
i ..
Figure B-b. Mass spectrum for 1,2,4,5-Cetrachlorobenzene.
76
-------
TABLE B-4. KEY IONS AND RELATIVE ABUNDANCES
FOR 1,2,4,5-TETRACHLOROBENZENE
M/Z
41
43
44
45
47
43
49
50
51
54
55
57
60
61
62
6 3
64
66
67
6 S
72
-r ••.
i .'
74-
75
Abundance
•-•
••.
10
4
1
6
9
4
14
26
3 6
---
.1
• liL
.2
.4
.0
.7
.3
.9
.3
.3
. 8
. i
.3
. 2
.3
.5
. 2
. 3
, ^J
•"•'
t ;5
];•;
• '!<
M/Z
76
77
73
r o
'I- w
34
35
36
37
39
90
91
92
'93
94
95
96
Cl 7
9 :-l
99
107
103
109
110
1 11
Abundance
13
4
6
2
3
2
2
4
3
1
3
C '"•
24
9
"'
.1
. 2
-i
.0
. 9
.5
.0
.3
. 5
.'7
.0
• I'
. 2
'"!
7
.0
. 6
. 6
.5
.3
. 7
. 8
'"'
. 4
M/Z
112
113
119
120
121
122
123
124
129
131
132
134
13S
143
144
145
146
147
143
149
153
154
155
156
Abundance
. 6
3 . 3
2.5
3.0
1 .6
.':3
.1
.1
1 .1
•7
m 2
.0
18.9
S.6
13.5
5.5
2.6
.9
"T*
" -^
\ 7
•*•
. 6
M/Z
153 '
165
167
169
170
171
179
130
131
132
133
134
135
214
216
213-
219
2 2 0
221
Abundance
.2
.3
. 6
. 1
22 .''<
5.3
23.5
2 . -
6 . 0
. 6
. !:i
35. 1
' 100.0
52.3
3.3
10.2
. 6
I Reproduced from
1 best available copy.
77
-------
v . H -
LU
CO
Z
O
a. I
00 I
UJ
cc 1 .5 r
LU
1 .0
10
20 . 30 40
QUANTITY ON COLUMN, ng
Figure B-9.
Calibration curve for the determination of
1,2,4,5-tetrachlorobenzene by GC/MS.
Range: 2.0 - 59 ng
Correlation coefficient: 0.991
Slope: 4.3 x 10'2
y-Intercept: -1.3 x 10
78
-------
LflRGST 4 :
LflST 4 :
103.
30"
60."
40^
20"
0
100
30^
60.
40.
20
0
249.3,100. 0
256.0, 4.1
"
1,1.
' 20 ' 4'0 ' .
ill
''''"' 13
•
l!n ill i ii
0 ' '" 20'0 ' '"
ii
251.. 3,
256.9,
|i< njl
60
.1
;j(ii"' ' "i"
62.4 247.3, 61.3 1US.0, 40.3
.4 £57.9, .5 269.0, .2
II 1
i , ,| 'h I1 ''•• '1 1' •'-- '!' • • I"'
30
.. „„,„.. ..
100 ' 120 140 160
-
•In i
Figure B-10. Mass spectrum for pentachlorobenzene.
79
-------
TABLE B-5. KEY IONS AND RELATIVE ABUNDANCES FOR PENTACHLOROBENZENE
M/Z Abundance M/Z
1 I
41 .2 90
42 • .6 91
43 .3 94
47 10.1 95
96
43 3r3 97
49 5.6 9*
50 .9 101
51 .0
52 .1
53 .7
54 1.1 104
55 .6 106
56 .4 107
60 6.9 103
61 9.4 109
1 10
62 1.6 111
67 .4 116
67 .1
69 .1 113
71 10.6
72 11.8 '
7 ''•'• 2 7 . O
74 2.7 11'?
120
79 .1 12 1
32 1.4 124
33 5.0 125
34 10.2 . 126
35 2.7 127
36 2.6 123'
3 7 .3 1 3 0
39 5.0 131
Abundance M/Z Abundance
4.7 132 .3
1.3 133 1.5
2.3 134 .4
4.4 135 .1
6.7 142 9.7
1.4 143 15.5
1.3 144 7.0
.2 145 9.9
.5 146 1.3 '
4.3 147 1.4
13.5 143 .2
40.3 153 .*
7.7 154 .8
13.2 155 .4
1.1
"^ 156 .6
•5 f, 1 •-' '" • 4
153 .2
1 6 5 . 6
1.3 167 .6
6.2 ' 169 _ .3
1.1
.3 177 3.0
3.1 173 11.7
5.9 179 3.6
4.2 ISO 10.7
.9 131 3,2
.3 132 3,6
1.0 133 .r-
1 .9 134 .4
Reproduced Irorn /'
-------
CO
Z
O
a.
<.
tu
CC
0.0 L
19 £0 30 40 50 60
QUANTITY ON COLUMN, ng
70
SO
Figure B-ll.
Calibration curve for the determination of
pentachlorobenzene by GC/MS.
Range: 8.3 - SO ng
Correlation coefficient:
Slope: 2.3 x 10"2
y-Intercept: 1 .0 x 10~ *
0.993
81
-------
•• v,.
IS
B
,J
D
-,»•••'•• "•-.>.,„
~T 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 \ 1 1 1 1 1 1 1 1 [—
45673-5 1011 12 1314 15 1617 18 192S21 £2232425262728293031 323334
Figure B-12. Chromatogram by GC/MS for
(A) dimethyl sulfate(tR = 4.0 min),
(B) 1 ,4-naphthoquinone(t|j = 12.3 min),
(C) 9,10-dimethyl-l,2-benzanthracene(tR
(D) dibenz[a,j]acridine(to = 31.6 min).
Temperature program:
40 CC, 0 min isothermal
40 to 280 CC at 10 cC/min
280 °C, 15 min isothermal
26.2 min), and
82
-------
LfiRGST 4: 95.0,106.
LfiST 4: 136.6,
100.
30!
60.
20!
0"
100.
80!
60,
40.
20.
0
,1
2'0 ' 4^
-
1 8 6 2 0 0
0 96
6 139
I i |l
' 6!0
' 22'0
.0, 76.2 65.9, 27.8 79 . 1 , 20 . 1
.1, .5 1S3.0, .5 209.6, .6
(
^
il_. -_.,_,
li 1,
30 100 120 140 160
i'0" " '""26i3 '""2Si3 '""30i3 '1""3210
Figure B-13. Mass spectrum for dimethyl sulfate.
83
-------
TABLE B-6. KEY IONS AND RELATIVE
ABUNDANCES FOR
DIMETHYL SULFATE
M/Z
43
45
43
49
50
51
52
54
59
61
62
64
65
66
67
63
75
76
73
79
SO
81
Abundance
1 .3
10.7
17.2
6.1
2.4
. 9
1 .0
1 .0
.9
1 .0
. 7
13.6
15.9
27.3
1 .4
2.S
1 .0
1 .0
9.0
26.1
1 .6
3.0
M/Z
95
•36
97
93
99
111
115
126
125
126
127
129
133
134
136
139
133
299
Abundance
100.0
76.2
9.3
4.7
.3
.6
.5
.5
6.1
4.2
1 .0
.5
.5
.4
.6
.5
.5
.6
91 .5
84
-------
1 .0
CO
2 .6
O
CL
CO
LLJ
.4
tu
IT
40 68 SO
QUANTITY ON COLUMN, ng
100
120
Figure B-14.
Calibration curve for the determination of
dimethyl sultate by GC/MS.
Range: 16 - 120 ng
Correlation coefficient: 0.985
Slope: 7.2 x 10~3
y-Intercept: 1 .0 x 10"!
85
-------
Reproduced (rom
best available copy.
LflRGST 4: 153.0', 130.0
LflST 4: 193.2, .3
100.
30
60"
40^
£0!
0"
1 3 0
30"
20.
3
„„ ,.,,.,,,, ,„,.,,,, ,,,,.,, ,.,„, ,,,|
20 40
'""18& '"' 20'y
102.1 ,
209.5,
ill nnilll, liniii
60
2 2'0 '
66.5 104
.3 244
||
......iiii., ...i...
80 1 00
.0 , 65 .5 76 .9 , 6.1 .6
.3, .3 343.3, .3
1 i ii
1 12'y
1 4 '0 ' 1 6!0
-
240 260 230 300 32y
Figure B-15. Mass spectrum for 1,4-naphthoquinone.
86
-------
TABLE B-7. KEY IONS AND RELATIVE ABUNDANCES
FOR 1,4-NAPHTHOQUINONE
M/Z Abundance M/Z Abundance M/Z Abundance
44 .1
47 .5
43 1 .3
4'? 4.1
50 34.0
51 1 0 . fi
52 3.9
53 6.5
54 5.1
55 .3
56 .5
60 .2
61 2.9
62 3.7
63 2.3
64 .2
65 .2
66 1 .3
67 .4
68 ' .4
73 5.3
74 22.8
75 . 21.3
76 61.6
77
r' y
79
si
ft 2
84
35
86
37
S3
96
97
93
99
102
104
105
106
103
109
110
11 1
113
1 14
115
7
1
2
•".
•_<
1
1
66
65
5
1
.3
.3
-.
.*4
. I''
•^
• 1'
.1
.2
.9
.4
.4
.5
.9
.3
.5
.5
.5
.5
.3
.0
.4
.4
.4
.4
.4
119
121
122
123
130
131
• 132 •
135 .
141
147
149
153
159
'160
192
193
209
245
343
. .1
.4
.3
.4
45.4
4.7
1 .1
.5
.2
.4
•5
. •— '
100 .0
11 .5
1 .5
.4
^i
.3
.3
.-i
• -'
87
-------
1 .0
V) ,-,
O
o.
"» . 7
LU
cc
> -t'
§ .5
01
,
40 • 60
QUANTITY INJECTED, ng
Figure B-16.
Calibration curve for the determination of
1,4-naphthoquinone by GC/MS.
Range: 7.1 - 89 ng
Correlation coefficient: 0.975
Slope: 1.4 x 10~2
y-Intercept: 9.8 x 10~2
88
-------
LfiRGST 4: 256.0,100.0 241.1, 53
LflST 4: 2:35.8, .1 290.0,
100.
8 0
60
40
20
0
1 0 0
:? 0
60.
40.
20
0
i
.7 23'?. 9, 36.1 240.2, 35.7
.1 295.2, .0 327.2, .1
1
i ,..iii... .11 ....II!
'• £&' ' 4ft 6# '' 30 '
.
„,, ,„„„ ., .,,, „ ...I,,,., .,
""'" is&" l- ' 20'0 ""' '22'0 '"'24
!, • It
L00 12Q . 140 160
II. ..1. .11. ••jjy •."( 'J','11'" ""1 '.".'11'" I"Ir¥" '."_'|_
O 2frO 2S0 300 320
Figure B-17. Mass spectrum for 9,10-dimethyl-l,2-benzanthracene.
89
-------
TABLE B^8. KEY IONS AND RELATIVE ABUNDANCES FOR
9,10-DIMETHYL-l,2-BENZANTHRACENE
M/Z
41
43
44
46
47
49
50
51
C2
53
59
59
61
62
63
65
66
67
63
69
• 74
75
7 f.
TT
7*
79
3 1
34
•I* t'
,-, •-,
3 9
90
91
94
94
96
M ~
93
ClC|
Abundance
.-,
| 7
.2
.3
. i
.5
t Q
1 .2
. 4
. O
.3
.4
.4
.9
1 .3
.3
.1
.4
.5
. 1
.8
1 .4
1 .1
1 .3
.4
. 1
.5
. i
• 6
1 .6
1 .9
. 3
'.-'
.1
1 .5
2 .3
.5
.-,
• w
.4
1 .7
M/Z
100
101
103
104
107
103
i 0 9
i 10
1 1 3 '
115
116
120
122
125
126
127
123
133
137
139
140
145
143
149
150
151
152
153
154
159
160
161
162
163
164
165
166
170
Abundance
3.0
3 . 6
.4
c;
'~: "-11
fci . ••'
.-,
. 6
11 .7
.3
. 3 .
21 .3'
.3
4 .7
7.7
5.5 .
5.4
.1
.0 •
.4
. 0
. 1
.1
". 1
1 .0
1 .0
•7
•~J
. 3
. 2
• IL!
•-,
.4
• '"'
. 5
.4
1
--I
M/Z
171
173
174
175
176
177
.173
179
135
186
187
133
189
1^0
192
194
1 93
199
200
201
202
203
204
211
212
213
214
215
£16
217
•T" '• ''•
223
224
225
226
227
223
229
Abundance
.1
.1
.6
.6
1 .4
.6
.8
^2
!4
.5
1 .6
.1
1 .1
.2
.2
.1
.6
7
1 .5
.8
1 .7
.3
. 1
• l'
• " . £
'"* '."*
,-.
• '!•
3 .2
-7
n 2
• •-'
.5
.-, .-,
i. * •.'
2. 1
7 . 6
•i* . ta.
2.1
3 . 0
M/Z
230
231
2^'*
235
237
239
240
241
242
243
243
250
252
253
256
257
253
259
282
233
235
290
295
327
Abundance
. 6
. 2
.2
c;
4 .0
36. 1
:•:£ 7
53 ! 7
10.3
1 . 1
• O
4 .3
3 .4
4.4
100.0
19.1
1 .7
.2
. •-•
!T
. i
.1
.0
. 1
j Ropioducod from
hcs: .-w;>i!;ibte copy..
90
-------
UJ
t/5
O
a.
v>
UJ
K
tu
<
UJ
oc
15
..-•••
"
.05
0 .0 0
Figure B-18.
26 48 60
QUANTITY INJECTED, ng
Calibration curve for the determination of
9,10-dimethyl-l,2-benzanthracene by GC/MS.
100
Range: 22 - 110 ng
Correlation coefficient: 0.994
Slope: 2.4 x 10"3
y-Intercept: 8.b x 10~3
91
-------
..HKiST 4: 279.2,100.0
LflST 4: 234.0, 1 .6
100_
so"
60.
40]
20]
0.
ISO.
30]
60]
40.
£0
0
,,.. ,, ,.,.,.., ,,,.,..,. ....... . ,|..|,
' 2\a ' 4V '•
1 • 1 1 1 1 ' 1 III
ISO ' 200
230.1. 22.9 277.1, 20 .'1 273.2, 11.6
327.1, .3 341.1, 2.0 345.1, 3.2
' rl - 1 lhfrllj+lf n t 11 1 1 tHlll il 1 littm 1 ' ^ — ^ -^- A ^
60 30 ' 1010 12
III 1 till ' 1 '1
.0 140 1 60
22k ' 24'0 ' 26'6 ' ' 28'0 ' :?o'o ' 32ti
Figure B-19. Mass spectrum for dibenz[a,j]acridine
92
-------
TABLE B-9. KEY IONS AND RELATIVE ABUNDANCES FOR DIBENZ[a,j]ACRIDINE
M/Z Abundance
43
47
49
50
51
C2
52
55
57
59
o T
69
79
71
73
74
75
7 1'
r? t-i
i •_'
7 '^
33
36
'•T* 2
94
96
97
93
'3 ;-;
•va
1 0 0
101
1 0 3
c;
4
4
.;.
5
7
3
'•?
3
2
5
6
1
ii
'";
--.
•-i
•"'
3
2
2
2
5
•"•
.2
.8
.8
.4.
.3
.0
.2
. 6
.4
1 2
.3 .
.4
_ 2
is
. 2
.4
. 6
.0
.4
'"•
.4
.0
.0
.0
.4
. 6
.0
.4
.-,
f £_
.0
.4
M/Z
104
196
1
1
1
1
1
1
1
1
1
1
1
1
1
A
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
03
1
1
1
1
1
1
1
'"•
•~«
^|
.7,
V
il*
•-.
;T;
•o
•^'
3
;T;
4
0
1
2
•••
4
l'
Q
9
1
•-;
4
5
6
i'
4
£,
7
3
9
1
43
Abundance
4
T
i
^'
£;
4
1
i
i
.1
•*•
7
3
6
1
4
1
-7
1
1
44 2
4
4
c;
5
1;,
1;,
r,
6
T"
l'
y
!^
'i
1
.-!
•I-
!;!
9
1
2
--i
2
•-,
4
£
•~-
. 4
.4
. 6*
. 6
.9
.4
.9
. 6
.9
. 6
. 6
.4
.4
•-•
. 6
.4
.4
.3
. 6
.4
.6
• *
. 6
. 6
.9
. 6
.8
.4
.9
•-•
. 9
.9
. 3
M/Z Abundance M/Z Abundance
133
191
193
198
290
205
297
209
210
211
221
223
225
233
243
250
251
252
253
265
267
275
276
277
273
279
230
4
3
1
1
2
3
1
1
o
to
2
.-.
7
5
6
•*'
2
1
6
t-
29
11
.3 231 5.6
.0 232 • .4
.2 233 1.2
.6 234 1 .6
. 6
327 .3
.0
.6 341 2.0
.4
.6 345 3.2
.4
.6
.0
.4
.0
.0
.2
.-.
• h_
.0
.0
.0
.6
.3
.4
. 1
. 6
1 9 9 . 0
22
.9
["Reproduced from p'**, ^
1 best availaoln ropv. ^liis^
93
-------
.30
O
a.
LU
.15
>
K
<
M
cc . ly
0 . 0 0
_X..
X
40
100
120
QUANTITY INJECTED, ng
Figure B-20. Calibration curve for the determination of
dibenz[a,jJacridine by GC/MS.
Range: 24 - 120 ng
Correlation coefficient: 0.974
Slope: 1.8 x 10~3
y-Intercept: 1.5 x 10~2
94
-------
IS
E
;
X"V
"'"•"••••••'•..-.
\
L
"^•-^-,
•'•"•"-'•'•'-—• '-*-'--~— ••."rt-».^,.,_.\,....^.....^--..«.w....s..^Vv'''-...v.^
J
JLj
a
1 1 1 1 1 1 1 1 1 " I ' 1 ~ • 1 — •
4 5 6 7 8 9 10 11 12 1314 15 16 17
>gure B-21. Chromatogram by GC/MS for
(A) methanesulfonic acid ethyl ester(tR =5.2 rain) and
(B) alpha-naphthylamine(tp = 14.1 min).
Temperature program:
40 :C, 0 min isothermal
40 to 280 'C at 10 °C/min
280 °C. 15 min isothermal
95
-------
LPRGST 4: 79.8,100.0 189.0, 77.3 97.1, 25.9 30.1, 19.1
LflST 4: ' 195.8, .2 19S.4, .2 207.2, .0 23 1.1, .1
100.
30!
60]
40'
20'
0"
188.
30!
60!
40.
20"
0
ill 'it till 1 1 ill TMrtfii. trr
1
1 • " 'i
28 40 ' 60 SB ' 190 ' 120 148 16'0
'' 13'0 '' 20'fc ''"' 22'0 ""'""2410 '""2610 '"" 23i3 '"" 30' ti '"" 32\3
Figure B-22. Mass spectrum for methanesulfonic acid ethyl ester,
96
-------
TABLE B-10. KEY IONS AND RELATIVE ABUNDANCES FOR
METHANESULFONIC ACID ETHYL ESTER
M/Z
1
41
42
43
45
46
47
43
49
SO
51
52
56
59
62
63
64
65
67
70
71
74
76
79
83
Abundance
.6
2.6
5.7
14.9
1 .3
1 .0
8.6
1 .5
.9
.8
.5
.4
2.2
.7
3 .6
6 .0
14.1
.3
.3
.3
.3
.3
130.3
19.1
M/Z
31
32
84
33
39
90
92
93
93
95
97
98
99
101
107
199
110'
111
117
123
124
125
126
123
Abundance
6.0
.5
.3
.4
.2
.3
.1
.3
.3
1.6
25.9
.4
1 .3
.2
.4
77.3
3.2
3.1
.0
2.3
4.1
.3
.2
.2
M/Z
136
139
150
166
163
193
195
198
207
281
Abundance
.2
.2
.1
.2
.2
.1
.2
.2
.0
.1
97
-------
.16
. 14
HI
O
Q.
.10 h
.08
.04
.62
19
3Q 48 56
QUANTITY INJECTED, ng
Figure B-23. Calibration curve for the determination of
methanesulfonic acid ethyl ester by GC/MS.
Range: 13 - 64 ng
Correlation coefficient: 0.992
Slope: 2.4 x 10~3
y-Intercept: 8.8 x 10~3
98
-------
LflRGST 4: 143.1,100.0 115.2, 51.0
LOST 4: 138.5, .1 267.2, .1
100.
30!
60!
40"
20"
0"
100.
30!
60"
40.
20
0
ii i iiiilllii HI ill I'm i I'lli ii rill
20 40 60 80
116.0, 29
231 .0,
I
'"'^
.4 144.0, 12.0
.0 232.2, .1
T is'a ''''' "20'0 I""22I0 '""24^ I""26I0' '""2sfr '"" 3013 '"" 32'0
Figure B-24. Mass spectrum for alpha-naphthylamine.
99
-------
TABLE B-ll. KEY IONS AND RELATIVE ABUNDANCES FOR alpha-NAPHTHYLAMINE
M/Z
41
42
44
46
47
43
49
59
51
52
53
54
55
56
57
S3
60
61
62
63
64
65
66
67
63 '
Abundance
.3
.9
.3
.3
.2
.3
.3
4.1
4.5
3.1
.4
.3
.3
.3
.5
.9
.3
1 .4
4.9
7.0
1 .9
3.2
.5
.1
.3
M/Z
71
71
74
75
76
77
73
31
i-:'.-1
34
85
36
37
33
39
99
91
•sc;
96
97
93
•3 M
1 0 6
101
102
Abundance
1 .3
1 .3
. 3.7
2.9
2.9
2.9
' 1 .3
.1
.0
.5
1 .4
2..0
2.9
3.1
10.3
2.6
1 .0
. 1
.1
.3
.3
.6
-9
• r
1 .1
.9
M/Z
193
104
105
107
108
109
Ml
113
115
116
117
113
119
120
121
122
123
126
127
123
129
135
140
143
Abundance
1 .0
.3
.3
.1
^2
!T
.3
3.5
51 .0
29.4
5.5
.5
.1
.1
.1
.2
.1
1 .3
.7
.3
.1
.1
2.7
100.0
M/Z
144
149
159
170
133
267
23l"
232
Abundance
12.0
.1
.1
.1
.1
.1
.0
. 1
100
-------
.50 r
.45 -
UJ
CO
o
a.
cc
UJ
>
UJ
cn
40
Figure B-25.
QUANTITY INJECTED, ng
Calibration curve for the determination of
alpha-naphthylamine by GC/MS.
Range: 4.5 - 56 ng
Correlation coefficient: 0.998
Slope: 8.2 x 10~3
y-Intercept: -9.0 x 10~5
101
-------
B
\. ,
IS
••>-._,_.v..l'.
456
3 •=>
12 ib
IS
Figure B-26. Chromatogram by GC/MS for
(A)
(B)
(C)
(D)
(E)
(F)
(G)
^J-nitrosodiethylamineC
Jsl-nitrosopyrrolidine(
4-chloroaniline(t
= 4.7 min) ,
7.2 min),
R
9.4 min),
n = 10.1 min).
3 ,4-diaminotoluene( t^ = 10.9 min),
2 ,4-diaminotoluene( tp = 12-. 1 min), and
m-dinitrobenzene( tD = 12.9 min).
— K
Temperature program:
40 °C , 0 min isothermal
40 ^C to 280 °C at 10 °C/min
280 °C, 15 min isothermal
102
-------
LflRGST 4 : 102. 1 . 160.0
LflST 4 : 141.0, .2
100.
36.
60"
40^
20"
0"
1 0 0
so"
60.
40.
20
0
' 2!0 ' 4'0
' 1S'0" ''"' 20i3
-
""'"'
»
4ii.i, 67.7 44.1, 59.6 56.3. 56.0
166 .0, .2 167.3, .1 177. 1 , .2
,„ n,|| ,,,,1,1,,. ,,,
1
60 30 100 120 140 160
;2'0' '"" 24^ '"" 26'0 '"" 23'fe '"" 30'o '" ' 32'o
Figure B-27. Mass spectrum for N-nitrosodiethylamine
103
-------
4 .0
ID
g
2
-------
TABLE B-12. KEY IONS AND RELATIVE
ABUNDANCES OF
N-NITROSODIETHYLAMINE
M/Z
41
42
44
45
SO
52
53
54
56
57
53
59
64
67
63
76
71
72
73
74
76
77
3!
32
Abundance
14.3
K ,' m f
59.6
3 . 4
.1
1 .6
.9
5.1
56.3
35.6
1 .1
.9
.3
.4
.2
4 .0
2.5
.6
..7
.5
.2
'.2
.3
.1
M/Z
34
35
36
87
83
91
99
192
103
104
105
141
166
163
177
Abundance
1 .2
7.3
.5
S.2
.1
.2
.2
100.0
5.0
.4
.2
.2
.2
.1
.2
105
-------
Reproduced from
best available copy.
LflRGST 4: 199.1 ,199.9 41 .
LflST 4: 133.6, .1 154.
199.
39.
60!
40!
20]
0"
190.
80.
40.
20.
0
1 lull!
.,,, ,...,,,,, ""I'"' I.M|llll ll.l| . ....{., ,|,,M ,.
20 40 b0
' is'0 ' '20'0 . ' 22''0
2, 61.4 42.2, 58.5 68.1, 16.2
•3, .2 198.5, .1 267.9, .1
Ilillt ilmllit-mmtii-tm
I
89 190 ' 129 149 160
' 2 4*0 ' 26'0 ' 28'0 ' 3913 ' 32'o
Figure B-29. Mass spectrum for j^-nitrosopyrrolidine
106
-------
.X'
UJ
CO
I
(/>
LLJ
QC
01
>
4 I-
'•£
.xx-
-^
11-3
33 40 50 60 70
QUANTITY ON COLUMN, ng
Figure B-30.
Calibration curve for the determination of
N-nitrosopyrrolidine by GC/MS.
Range: 13 - 100 ng
Correlation coefficient:
Slope: 5.7 x 10"2
y-Intercept: -1.9 x 10"
0.998
107
-------
TABLE B.13. KEY IONS AND RELATIVE
ABUNDANCES OF
N-NITROSOPYRROLIDINE
M/Z
41
42
43
44
45
46
58
51
52
53
54
55
56
57
5'?
61
63
64
65
63
69
70
72
73
74
Abundance M/Z
61
• ES
.13
•?
2
1
-'
3
•-t
4
16
4
1
.4
.5
.9
.3
.7
.3
.3
.9
• -J
.8
is
.9
.4
.2
<-j
.6
.6
.4
.2
.5
.5
m 2
-~i
• o
.2
77
31
82
84
85
92
95
96
100
101
102
1 17
i21
126 '
138
154
198
267
Abundance
.1
.2
.1
.3
.2
.2
.2
.1
100.0
• 4 .9
.4
.1
.1
.1
.1
.2
.1
.1
108
-------
LflRGST 4: 127.1,100.0 65.1, 51.3
LftST 4: 141.0, .0 143.2, .0-
-901 +• 91 0
100.
30
40.
20]
0"
100.
S0.
60.
49.
20
0"
' 20' ' 40
' " 1S'0 '""201
lilii III
60
' '22y '
]hlll|||llmi nil
30
""'""240' ''
129.0, 37.7 92.1 , 29.1
145.2, .0 149.1, .1
l-rrrr
II
100 120 140 160
"
"260 '""2S'0" ' "J"" :3i/i'0" "'"" 320
Figure B-31. Mass spectrum for 4-chloroaniline.
109
-------
TABLE B-14. KEY IONS AND RELATIVE ABUNDANCES
FOR 4-CHLOROANILINE
M/Z
41
42
44
45
47
43
49
50
51
52
53
54
55
57
69
61
62
63
64
65
66
67
68
72
73
Abundance M/Z
5
1
1
1
1
1
5
.-.
•I-
c;
10
i
i
2
i
10
13
14
51
n
1
-."•
9
.4
!0
.9
.5
.0
.0
.— 1
. o
.3
.1
.6
•?
. r
.1 .
.1
.3
B '.*'
B '5
.5
.1
;•}
.1
.4
. 1
.3
. 3
74
75
76
77
73
79
30
•I' tl
34
36
37
S3
3 9
99
91
92
93
94
95
96
97
99
130
101
162
Abundance M/Z
5
6
1
1
1
1
5
10
29
"2
10
20
5
6
.5
.9
.3
.3
.6
.1
.2
.1
, 9
•;
is
.3
.4
•5
• i''
.1
.1
.1
.1
•-•
.4
. ft
!s
.4
.4
103
103
110
111
112
113
114
1 22
127
129
130
133
139
141
143
145
149
Abundance
..7
.
o
• t_
• .6
.4
.3
.1
.1
.0
100.0
37.7
2.1
.0
.0
.0
.0
.0
.1
110
-------
IU
to
Z
O
.a.
-------
LPRGST 4 : 34.1.100.5 57.1,73.3 41.1,61.0 42.3,40.0
LflST 4: 159.1, 1.3 160.6, .2 163.9, .1 131.4, .1
100.
SO.
60!
40.
20^
0'
100.
so]
69.
40!
20
0
' 2'0 ' 4h
••' i"" '":ii" i"" - - :
1 y o ;i o y
•"iiihll
,.II|IMI
l|mlnll|,|
^,,,,,,.lll,w
,1
' , i 1
100 120 140 160
'-" 22'* '"" £4'£ '"" 26& '"" 2S& '"" 30^ '"" 32^
Figure B-33. Mass spectrum for N-nitrosodibutylamine. •.
112
-------
TABLE B-15. KEY IONS AND RELATIVE ABUNDANCES FOR N-NITROSODIBUTYLAMINE
M/Z
41
42
43
44
45
46
47
48
49
59
51
52
53
54
55
56
S7
53
59
60
64
65
66
67
63
Abundance
61
43
22
23
1
1
1
2
4
9
17
73
5
1
.0
.0
.5
,C|
.2
!.3
. 7
.3
. 1
.3
.4
.1
. 6
.3
.9
.3
.3
.0
• )'
.5
.3
.2
.1
.3
• 6
M/Z
70
71 '
72
73
74
75
7* I*.
73
7?
3y
31
y bi!
84
35
36
37
33
' 92
94
96
" 99
1 0 0
101
102:
Abundance
3
4
^
6
100
3
14
25
2
T
•*'
.4
• y
.5
• I'
.7
.3
. 1
.1
.2
.3
.3
.7
.0
.9
.4
.9
.3
.1
.1
.3
.3
.1
. 1
. 3
~
M/Z
105
107
103
112
113
115
116
117
113
119
125
123
129
130
133
139
141
142
149
153
159
160
163
Abundance M/Z Abundance
.1 131 .1
.1
.2
1 .1
.2
15.1
21 .8
1 .5
.2
.1
.1
.1
.7
.1
.1
.1
10.3
1.0
.1
14.3
1 .3
.2
.1
113
-------
UJ
CO
I 4
CO
_l
01
cc
X.'
19 20 30 40 50 60
QUANTITY ON COLUMN, ng
70
Figure B-34.
Calibration curve for the determination of
^-nitrosodibutylamine by GC/MS.
Range: 2.5 - 79 ng
Correlation coefficient:
Slope: 8.8 x 10"2
y-Intercept: -3.0 x 10"
0.99b
114
-------
LPRGST 4: 122.1.100.0 121.1, 70
LflST 4: 326.0, .2 341.0, 1
100.
30.
60]
40]
20]
0"
1 0 0
30]
60.
40.
20.
0
1,
III, hill II 1 III 'ill M II' 1
• \
.3
20 40 ' 60 3©
1 3 0 2 0 0 ' 2 2 0 2 4 O
94.1 , 41.7 77.0. 21.7
342.3, .5 343.0, .2
| ||
i'o1©1 '''"" i's'e
.,..,,,..,,...,.... ......... ..^
' 26'g '"' 2's''0 ' '""30fr '" 32'0
Figure B-35. Mass spectrum for 3,4-diaminotoluene.
115
-------
TABLE B-16. KEY IONS AND RELATIVE ABUNDANCES FOR 3,4-DIAMINOTOLUENE
M/Z
41
42
43
44
45
47
48
49
50
51
52
53
54
55
56
61
62
63
65
66
67
68
70
71
73
Abundance
i
6
3
1
2
1
5
10
12
6
6
1
1
2
3
3
8
7?
2
2
•-.
( ^
.2
.4
. 1
.5
.4
.2
.4
.4
.6
.6
.1
.0
. 1
.3
.5
.0
. 1
.3
. '••
is
•7
!i
.2
.4
M/Z
74
75
77
78
79
80
81
32
84
86
87
38
89
90
91
92
93
94
95
96
99
100-
102
104
Abundance
1
2
21
17
4
8
2
1
4
13
41
7
17
.3 '
. 1
. 7
• •!•
.0
.3
.3
.6
.3
.3
.3
.1
. 6
.4
.2
.5
.3
• i''
.4 '
.6
.1
.0
.3
.4
M/Z
105
106
107
103
109
113
117
119
121
122
123
124
127
129
131
133
1 36
141
148
151
154
156
171
Abundance
18
21
3
1
70
100
8
.3
.1
.3
.3
.2
.1
.3
.9
.7
.0
.1
.6
.2
.1
.2
.3
.2
.2
.3
. 1
.1
.1
.2 .
M/Z
178
191
204
207
203
223
253
265
267
325
326
341
342
343
Abundance
.2
.1
.1
•?
f 2
.2
.2
.2
.1
.5
•?
1 .3
.5
Reproduced trom
best available copy.
116
-------
4.0
3 . Q
55 2.5
O
a.
«/>
UJ . .
ec -^ . y
< 1.5
UJ
CC
1 .6
25
53 75
QUANTITY ON COLUMN, ng
Figure B-36.
Calibration curve for the determination of
3,4-diaminotoluene by GC/MS.
Range: 26 - 83 ng
Correlation coefficient: 0.992
Slope: 4.0 x 10~2
y-Intercept: -3.3 x 10"l
117
-------
LflRGST 4: 121.1,100.0 122.1, 39.6
LflST 4: 153.0, .1 162.7, .1
100.
80.
60"
40"
20
0"
100.
8 0
60
40.
0
II 1
'in lllll-n iiiii'lliu ir
20 40 ' 60
' is'0 ' 20'0 ' 22'0 ' :
llln.i llimi
30
:4'o '
94.1 ,29.4 77.1 , 19.3
167.4, .1 177.0, .1
i III
10'0 ' 12'0 ' UVJ ' 16'0
-
26'0 ' 280 ' 30'b ' 32'0
Figure B-37. Mass spectrum for 2,4-diaminotoluene.
118
-------
EPA/600/8-87/037a
" August 1987
POHC ANALYSIS METHODS FOR PB87-2^72oo
HAZARDOUS WASTE INCINERATION
Volume 1, Part 1
by
Ruby H. James
Joe M. Finkel
H. Kenneth Dillon
Herbert C. Miller
SOUTHERN RESEARCH INSTITUTE
2000 Ninth Avenue South
P.O. Box 55305
Birmingham, AL 35255-5305
and
Afaf K. Wensky
1200
BATTELLE -COLUMBUS LABORATORIES ->"•'*• 2C'."-'
505 King Street
Columbus, OH 43201
Contract 68-02-2685
Work Assignment 111
EPA Project Officer: Larry D. Johnson
AIR AND ENERGY ENGINEERING RESEARCH LABORATORY
U.S. ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park, NC 27711
AIR AND ENERGY ENGINEERING RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NC 27711
REPRODUCED BY
U.S. DEPARTMENT OF COMMERCE
NATIONAL TECHNICAL
INFORMATION SERVICE
SPRINGFIELD. VA. 22161
-------
TABLE•B-17. KEY IONS AND RELATIVE ABUNDANCES FOR 2,4-DIAMINOTOLUENE
M/Z
41
42
43
44
49
50
51
52
53
54
55
56
57
60
61
ۥ2
63
64 '
65
66
67
6fi
69
7y
73
Abundance
i
5
3
1
1
4
'It
10
c;
c;
i
1
1
1
1
£
s
6
1
. 7
.3
.7
. 3
\7
.5
.3
.3
.8
.2
.6
.0
.3
.5
.2
.9
.3
.5
.0
.4
.5
.3
_ 2
'.3
M/Z
74
75
77
i" •!'
7 '"*
S 0
81
!-! '"'
34
8 6
37
•:• £
39
90
91
92
' 93
94
9 Pi
96
97
98
9 ?
1 00
102
Abundance
1
1
19
3
•-•
6
1
.-,
9
29
4
.0
.6
.3
.1
.3
.0
.9
. 7
.3
.4
.2
.2
.3
.5
. 7
.3
.6
.4
.9
.6
.2
.1
.2
.0
.6
M/Z
104
105
106
107
103
109
110
111
112
115
119
121
122
123
124
•129
135
135
149
153
163
167
Abundance M/Z Abundance
16.1 177 .1
15.9
9.3
1 .1
.1
.1
.1
.1
.1
. 1 -
1 .7
100.0
39.6
7.5
.3
.1
.1
.1
.0
.1
. 1
.1
119
-------
4.5 -
Z :l: . Q
O
Q.
V)
Ul
<
LU
£T
2 .0
'1.5
1 .0
QUANTITY ON COLUMN, ng
108
Figure B-38.
Calibration curve for the determination of
2,4-diaminotoluene by GG/MS.
Range: 10 - 84 ng
Correlation coefficient:
Slope: 5.7 x 10'2
y-Intercept: -1.8 x 10
0.999
120
-------
LflRSST
LOST 4:
100.
30.
601
40.
0"
100.
801
60
40.
20
0
1
1
4: 163.0,100
175.8,
2&1 ' 4^"
.0 7
.3 22
ll, ,1
^
6.1, 92.1 50.1, 82 . 3 75.1, 74.9
3.4, .3 263.1, .3 232.0, .4
-
1 &Q ' 100 ' 120 ' 14*0 . ' 160
1S'0 "'""lie1* ' '"'' 2"2M0 '""^'O '""26^ '""23'0 '"" 30'0 '"" 32o
Figure B-39. Mass spectrum for m-dinitrobenzene.
121
-------
TABLE B-18. KEY IONS AND RELATIVE ABUNDANCES
OF m-DINITROBENZENE
M/Z
41
42
46
59
51
52
53
54
55
57
61
62
63
64
65'
66
67
63
70
71
74
7£
76
•p?
Abundance M/Z
10
32
10
£.
1
1
c.
3
24
3 £
"2
1
1
46
74
92
6
. 2
• 3
• o
. 3
. 9
. I*
. 1
.3
is
.0
• 6
T?
•-:
.4
.0
•7 .
. 1
• c-
.1
• *i'
•J
. 1
. 1
73
7 ci
SO
31
32
33
36
37
33
. .;.Q
90
92
*:-:
95
96
97
• 99
100-
103
106
107
109
1 10
113
Abundance M/Z
1 .6
1 .3
1-.2
.5
.6
.3
2.2
1 .6
.5
.5
.5
33.4
3.7
.3
.1
.3
.4
.4
.4
1 .7
.3
.5
.4
.5
122
123
124
126
127
123
137
133
141
149
152
153
155
163
169
170
176
223
263
232
Abundance
32.0
2.7
.4
.3
.2
.3
.4
1 .9
.3
.1
4.1
.3
.5
100.0
3.2
1 .2
- .3
•~i
• •-'
.3
.4
122
-------
1 .4
1 .2
i .0
CO
O
a.
CO
ai
.cc
.4
10
70
QUANTITY DIM COLUMN, ng
Figure B-40. Calibration curve for the determination of
m-dinitrobenzene by GC/MS.
Range: 19 - 60 ng
Correlation coefficient: 0.999
Slope: 2.2 x 10"2
y-Intercept: -1.4 x 10~1
123
-------
IS
I
B
T
Q
18
T~
11
"Ti"
—i
13
— I
14
1
15
1
16
i
17
—1—
18
igure B-41. Chromatogram by GC/MS for
(A) N-nitroso-j4-methylethylamine(tn = 3.7 min)
(B) 2 ,6-diaminotoluene( tR = 11.9 mm),
(C) £-dinitrobenzene(tn = 12.6 min),
(D) p-nitroaniline(t^ = 15.0 min), and
malononitrile(not shown).
Temperature program:
40 °C, 0 min isothermal
40 "C to 280 °C at 10 °C/tnin
280 °C, 15 min isothermal
124
-------
LPRGST 4: 53.1,100.0 42.2, 92.9 43.2, 45.5 56.1, 23.7
LflST 4: 141.0, .3 155.6, .3 173.1, .3 183.9, .2
100.
30
60"
40.
2Y
0"
100.
•30"
60"
20]
0"
' '*® ' ^
1 Illlll lllll III 1
60 30.
1 10''0 ' 12'@ ' 14'0 ' 16U
•
Figure B-42. Mass spectrum for ^1-nitroso-^-meChylethylamine.
125
-------
TABLE B-19. KEY IONS AND RELATIVE
ABUNDANCES FOR
j^-NITROSO-
N-METHYLETHYLAMINE
M/Z
42
43
44
49
50
51
52
53
54
56
57
53
59
60
61
62
71
73
74
77
79
36
88
Abundance
92.9
45 is
3.7
2 .2
2 . 0
1 .4
3.3
1 .0
4 .4
23.7
9 . 8
. 7
3.3
. 6
• '.5
.4
13.4
' 3 . 1
.5
.1
.3
.3
100. 0
M/Z Abundance
140 .3
-141 .3
155 .3
173 .3
134 .2
126
-------
4.0
3 .5
3 .9
01
v>
Z 2.5
O
a.
C/9
LU
>
H
<
LU
IT
2.8
1 .5
1 .9
9 . 0
-x"
,::>-
10
30
40
QUANTITY ON COLUMN, ng
Figure B-43.
Calibration curve for the determination of
N-nitroso-N-methylethylamine by GC/MS.
Range: 24 - 78 ng
Correlation coefficient: 0.999
Slope: 5.7 x 10~2
y-Intercept: -5.2 x 10 !
127
-------
LflRGST 4: 122.1 ,100.0
LOST 4: 188.2, .4
100.
80^
60"
40"
20
0"
100
80'
60
40_
20
0
llll 1
20 40
180 20'0
121.1, 63.1
281.0, .4
llll' MI! 'Ill '
60
""22$ '"":
1
ll- ,1
^0 '
104.
233.
I
1 , 36.0 94.1 , 32. '?
2, .4 327.0, .1
il
100 120 140 160
\
26'0
' 280 ' 30'0 ' 32ti
Figure B-44. Mass spectrum for 2,6-diaminotoiuene.
128
-------
TABLE B-20. KEY IONS AND RELATIVE ABUNDANCES
FOR 2,6-DIAMINOTOLUENE
M/Z
41
42
43
44
45
45
47
59
51
52
53
54
55
59
60
61
62
63
65
66
67
6:3
70
73
74
Abundance
£
3
•-.
i.
1
1
•*•
-— ,
3
1 1
6
g
•-•
1
1
1
.— ,
3
6
5
1
1
. 6
-i
. 1
.S
.0
.;,
. l
.5
. 6
. 6
.4
. 1
.3
.7
. ft
. 7
.6
.9
.4
.4
•7
' .-.
T
. 6
. 0
M/Z
75
T* 7
73
7 ci
•30
81
32
36
ft 7
39
91
92
93
94
95
97
. 102
104
10;
106
107
1 17
1 13
Abundance M/Z
£
21
14
5
7
11
1
4
14
32
4
1
36
IS
19
1
.2
.0
, 2
.3
. 7
.4
.5
.2
.5
. 7
.8
.0
.7
t Q
.3
.4
.0
.0
.0
.9
. 5
.4
B Q
119
121
122
123
124
126
127
123
134
133
139
147
155
163
175
179
133
231
' 233
327
Abundance
2.0
63.1
100.0
3.3
.4
.4
.1
.3
3
is
.3
.7
.4
..4
• • J
.4
.4
.4
.4 •
. 1
129
-------
2 .5
UJ
CO
Z
O
Q.
"> 2 fi
ui "• • '-1
z
ai
cc
1 .5
1 .8
0. o
10
38 40 50
QUANTITY ON COLUMN, ng
80
Figure B-45.
Calibration curve for the determination ot
2,6-diaminotoluene by GC/MS.
Range: 24 - 78 ng
Correlation coefficient: 0.990
Slope: 4.6 x 10~2
y-Intercept: -2.8 x 10"!
130
-------
LflRGST 4:
LflST 4:
168 .9,100.3
169.0, 3.1
20;
.8
50.1, 7
242.3,'
.8
75.1, 7:3.3
243.9J .8
100.
SO.
6©!
40!
20!
100.
30!
60
40.
20
0
1111 Tl- 111 I IMT-TTTTTTrrr IIIITTTTT ITIIpTII MITIII
20 40' 60
"ffS
100 '"" 120
Figure B-46. Mass spectrum for £-dinitrobenzene.
131
-------
TABLE B-21. KEY IONS AND RELATIVE ABUNDANCES
FOR £-DINITROBENZENE
M/Z
41
42
43
44
46
47
49
59
51
52
53
54
57'
61
62
63
64
65
66
67
63
69
79
74
75
Abundance
1
1
O
79
12
3
3
5
1
6
1 1
30
31
1
3
1
2
1
51
73
.3 •
.3
.5
.6
.6
.3
.6
••"i
is
••}
• •-'
.5
.4
.9
.8
.0
'.3
^.
. 6
.1
.8
.4
.4
.3
M/Z
76
•7-r
79
30
31
82
34
87
S3
39
92
.93
94
95
96
.93
100
104 .
106
103
109
1 10
111
112
113
Abundance M/Z
82
3
2
T
i
i
i
35
2
T
i
i
i
i
i
i
• i
.1
.4
.4
.3
.5
.6
.4
.6
.8
.0
.1
.2
.4
< 2
is
.8
.0
'.0 '
.0
.8
.3
.0
.3
.0
.1
122
123
125
135
138
141
143
152
153
153
162-
163
163
169
207
242
243
Abundance
33
2
1
1
1
3
1
100
8
.5
.7
.0
• O
.3
.6
.3
.0
.3
.8
.8
.0
.0
.1
.3
.3
.3
132
-------
1 .4
1 .2
1 .0
QJ
V)
Z
o
Q.
V)
LU
CC
Ul
. .4
18 2S
30 40 50 60
QUANTITY ON COLUMN, ng
Figure B-47. Calibration curve for the determination of
p-dinitrobenzene by GC/MS.
Range: 26 - 82 ng.
Correlation coefficient: 0.992
Slope: 1.8 X 10~2
y-Intercept: -1.4 X. 10"1
133
-------
LflRSST 4
LflST 4:
133 .3 , 199 .9
225.4, 2.5
65.3, 35.2
230.5, 2.1
103.9, 73.8
253.9, . .4
•^.O, 49.5
313.9, 2.1
199.
39'
69
49.
I ll
lllilll Mllillll'llllminllJllll Ihmlll nlnili. nlllill. n.mlil InmiL M||| nllmrhln
60 39 109 129 14'0 169
199
50i
69
40
29
9
" '"" "2^"' ""'"" "4'9"
i i. I
20'9
24\3 '""26^ .-•^^-—r
Figure B-48. Mass spectrum for _p-ni.troaniline .
134
-------
TABLE B-22. KEY IONS AND RELATIVE ABUNDANCES FOR _p_-NITROANILINE
M/Z
41
42
43
44
46
43
49
50
52
53
54
53
59
61
62
63
64
65
66
67
•63
69
71
75
Abundance
8
3
3
•-'
7
' 4
7
4
22
13
3
3
4
-7
~8
16
21
85
11
5
;T|
1
.9
.3
.4
.1
.2
.6
.6
.2
.8
.1
.4
.4
.6
.2
.9
. 5
is
.2
.0
.5
.4
. 7
.4
.4
M/Z
1
1
77
73
30
81
82
33
34 '
86
37
92
93
94
94
97
98
99
02
06
103
109
1
1
1
*
12
13
15
Abundance
7
3
23
1
3
10
4
4
1
40
8
2
£
3
2
73
6
•>
2
T
..•
• £
.4
.6
.7
.0
. 5
m 2
.6
. t~
.5
.0
.5
.5
.3
.4
.4
.5
.3
.3
.7
.5
.1
.3
.•.
M/Z
124
126
133
133
139
140
149
15@
154
155
156
153
164
165
172
173
179
131
183
195
Abundance
3
2
4
190
3
3
2
2
2
2
2
2
3
2
4
3
.0
.1
.2
.0
.9
.3
.4
.1
.4
.4
.1
.5
.1
.1
.5
.4
.1
.6
.0
.4
M/Z Abundance
213 3.3
225 2.S
230 2 . 1
253 .4
313 2.1
122' 6.3 ' 205 .4
135
-------
UJ
l/V
z
o
Q.
(/)
LJJ
cc
01
.1
10 20 30 40 59 60
QUANTITY ON COLUMN, ng
Figure B-49. Calibration curve for Che determination of
p-nitroaniline by GC/MS.
Range: 10 - 90 ng
Correlation coefficient: O.y91
Slope: 8.3 X 10~3
y-Intercept: -5.6 X 10~2
136
-------
LfiRGST 4: 66.1,100.9 65.0, 11.5 64.4, 9.1 67.1, b.3
LflST 4: 133.3, .4 168.0, .4 207.0, .4 231.0, .4
100.
80.
60"
40]
20]
0"
100.
80^
60]
40]
£0.
0
II, I1
20 40 60
Inillli iliiiuli iiiiinii iliiiilii liliiiiiriiiiiil iiiii'iiiiiiiii IIIIIIIM inn
30 100 129 140 160
'"" i's'0 '"" 2W '' 22'0 '"" 24\3 '"" 26'0' '"" 2S& '"" 30'0 '"" 32^
Figure B-50. Mass spectrum for malononi.trile.
137
-------
TABLE B-23. KEY IONS AND RELATIVE
ABUNDANCES
FOR MALONONITRILE
M/Z
41
43
43
45
47
50
51
c,2
53
54
57
59
61
64
65
66
67
71
72
73
77
'83
Abundance
.4
.3
2.9
.4
2.1
4.6
2.9
1 .3
.5
.2
.3
1 .2
.5
9.1
11.5
109.0
5 . 3
.2
.3
.3
.6
2.3
M/Z
102
106
10:3
113
• 115
122 -
135
139
163
2@7
231
Abundance
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
.4
138
-------
IS
B
A
\,wU
V '*>*'.\'i V.*-.i
Vt
c
\
"•-^.^,^>A,,_.^__^j ^.,AA._.v_g
i | | | | 1 1 1 —
4 5 6 7 3 3 1011
\
V-^AA — _,X>J
— i 1 1 —
12 13 14
LJ
\
I -I '-~i
15 16
Figure B-51. Chromatogram by GC/MS for
(A) JN-nitroso-J>J-met:hylurethane( tR = 4.9 mih) ,
(B) 2,6-dichlorophenol(tR = 9.3 min), and
(C) 2,4,5-trichlorophenol(tR = 11.7 min).
Temperature program:
40 CC, 0 min isothermal
40 °C Co 280 °C at 10 °C/min
280 °C, 15 min isothermal
139
-------
WORK flREfl SPECTRUM FRH 11304 . PflGE 1 V = 1.00
LORGST 4: 43. 4, 199 :0 56.2, 32.3 . 60.1, 31.2 53.3, 25.9
LflST 4: 207.0, .5 208.9, 3.2 242.0, 6.4 249.0, 2.6
-73 + 76
199.
80.
60"
40'
20"
0
100.
so'
40.
20
0
' 2'0 ' 4'0
1 i' 1 1 ill I'll 1 1 1 1 III 1 i
60 :39 100 120 140 160
I i ' ,| | 1
' i?'0 ' 20'0 22'0 ' 24I0 ' 26!0 ' 28'0 ' 30'0 ' 32'o
Figure B-52. Mass spectrum for ^J-nitroso-N-methylurethane.
140
-------
TABLE B-24. KEY IONS AND
RELATIVE ABUNDANCES
FOR ^-NITROSO-
N-METHYLURETHANE
M/Z Abundance M/Z Abundance
41
43
44
45 '
49
50
51
54
cc;
56
Fl.-l
60
62
67
69
70
71
7" 3
75
79
52
86
37
14
1 0 0
6
12
5
19
('
1
1 1
-•C
31
•~,
3
4
5
6
'.3
3
4
3
6
21
.3
.0
•5
• .•
-?
. I1
.-.
• '.'
.0
Bfll
!i
.1
.3
t 'S
!2
. 2
^
. 2
.3
.4
. 2
.7
.2
.-i
• w
.9
• >*'
93
99
193
106
114
119
121
132
133
141
165
163
207
-20S
242
249
-
3
3
3
2
2
2
3
16
2
4
1
3
6
2
.2
,7
.7
.6
. 6
.6
.2
.4
.1
.5
.3
.6
.5
.2
.4
.6
141
-------
UJ
V)
Z
o
UJ
<
_l
LU
cc
.01
..X
OOQ0
40 60 8©
QUANTITY INJECTED, ng
100
120
Figure B--53.
Calibration curve for the determination of
N-nitroso-N-tnethylurethane by GC/MS.
Range: 18 - 130 ng
Correlation coefficient: 0.996
Slope: 5.8 x lO'1*
y-Intercept: -b.2 x 10~3
142
-------
LflRGST 4:
LUST 4:
162 .O , 100 .O
224.7, .6
164.0, 62.2
••»•?•? t; ' C
__'.•;•, . -j
63.2, 58.0
258.13, .4
98.1, 34.1
311.5, .5
100.
SO.
60'
40!
20!
0.
100.
se!
60!
40.
20.
0
Hi'.llllll
I'nniml'nnll,
.-.'A . '
Jtn-rtrt
60
SO
10
"'"" i'ii'o '"" 1413 '"" i't't
2 0 0
I"" _".!.
260
"]•••• v'Ji-
: j Q tj
Figure B-54. Mass spectrum for 2,6-dichlorophenol.
143
-------
TABLE B-25. KEY IONS AND RELATIVE ABUNDANCES FOR 2,6-DICHLOROPHENOL
M/Z Abundance M/Z
42 'l.2 7S
43 1 .9
45 1.6 77
47 3.6 83
81
4:3 3.4 22
49 7.3 S2
50 2.7 S4
51 6.0 35
52 1.7 *y
53 S.8 yy
54 .6
56 1.2 30
57 1.3 yl
59 1.2 1?2
69 4.S ??
61 12.3 y*
4Q
62 13.5 109
63 58.0 lyl
64 .5.5 ' -162
65 2.4
66 3.1 ly'"
67 .3 1°'?
72 7.1 11 *
73 13.0 I11
74 4.9 115
Abundance M/Z Abundance M/Z Abundance
6.3 118 .5' 311 .5
1.0 126 24.4
.9 12S 9.1
1.0. 129 1.0
1 .2
.6 133 4.2
3.4 135 2.5
3.3 136 .6
.1 136 .5
.9
147 1.2
1.7 151 .5
5.0
.7 162 100.0
.1 164 • 62.2
34.1 165 ' 4.6
14.9 166 10.1
10.4 167 .7
4.4
.6 207 .9
208 .5
1 .7
2.1 225 .6
.8 227 .5
.3
.2 251 .4
Reproduced from /P%
best available copy. fLjjp
144
-------
UJ
V)
I
CO
UJ
H
<
ill
DC
1 .5
1 .4
1 .3
1 .2
1 . 1
1 .0
.4
.
X
4© 66
QUANTITY ON COLUMN, ng
Figure B-55.
Calibration curve for the determination of
2,6-dichlorophenol by GC/MS.
Range: 21 - 80 ng
Correlation coefficient: 0.987
Slope: 1.8 x 10~2
y-Intercept: 6.2 x 10~2
145
-------
LflRGST 4: 197.9
LAST 4: 200.0
100
30.
60]
40
20]
0"
100.
80]
60.
0"
, 1 89 ;fi i it. . n , ^5 „ £ 97.1, 5ft . 0 200 . fl , 3fl . f.
,30.6 201.3, 4.4 216.2, 1.2 253.3, 1.2
||
. . iL , illl i. ..l.i . ll ii i.. . ,. . i ni.. .1.
' 2% '
H. in •
M|M,I .,.,,.„ ,,,,,„ , „ M ,,... MM,MI. ,,,,,,,,. MM^I MM|M ,,,,, MM@
' 13'0 . ' 200 ' 22'0 ' 240 ' 26'0 ' 2S*0 ' 30'o ' 32*0
Figure B-56. Mass spectrum for 2,4,5-trichlorophenol.
146
-------
TABLE B-26. KEY IONS AND RELATIVE ABUNDANCES FOR 2,4,5-TRICHLOROPHENOL
M/Z Abundance M/Z
43 .7 *4
45 1.0 y6
87
43 4.4 **
49 8.1
50 2.2 99
53 6.9 91
57 2.5 95
59 3.7 '?7
60 8.6 9S
61 If. .3 "
100
62 18.3 101
63 6.2 103
64 .5
66 3.0 I05
67 1.5 I07
70 2.0 I0y
71 1.5 109
72 6.9 II0
73 2.5 HI
74 3.7
120
77 2.0 121
30 3.7 125
81 1.0 129
83 9 . 1
1
Abundance M/Z Abundance M/Z Abundance
6.2 132 29
2.7 133 19
3.5 134 23
2.7 135 13
136 5
1 .7 137 . 1
.7 145 1
1..7 145 1
53.0
7.7 147 1
19.0 159 1
2.7
1.7 160 5
1.5 161 -3
162 6
2.7 163 1
3.7 167 4
3.5 163 2
4.4 169 3
2.0 171 2
1 .7
192 1
1.2 193 1
1.2 196 95
1 .2 198 100
.5 200 30
Reproduced from ff^%
besi available copy. \tfi'£jy
.1 202 4.4
.0
.2 216 1.2
.1
.4 259 1.2
.7
.7
.0
.2
• I*
.9
.9
.4
.0
.7
.5
.5
•:•
• h.
.2
. 5
. 6
. 0
. 6
147
-------
.7 i-
o
a.
in
UJ.
CC
UJ
ff
.4
. 1
40
60
QUANTITY ON COLUMN, ng
Figure B-57.
Calibration curve for the determination of
2,4,5-trichlorophenol by GC/MS.
Range: 21 - 84 ng
Correlation coefficient: 0.986
Slope: 1.1 x 10~2
y-Intercept: 4.9 x 10~2
148
-------
IS
/
'"--'- — „__._ .._,-.,._.,.,._,„_
B
i
LL~JLji
I
Figure B-58. Chromatogram by GC/MS for
(A) safrole(tR = 10.6 rain),
(B) nicotine(tR = 11.4 min) , and
(C) 2-acetamidof luorene(tD = 22.8 min)
, K
Temperature program:
40 °C, 0 min isothermal
40 °C to 280 °C at 10 °C/min
280 °C, 15 min isothermal
149
-------
4 :
LflST 4:
162.1 ,
137.9,
104.2, 78.5
1S9.3, .3
77.4, 62.0
211.1, .2
131.4, 60.2
322.0, .2
100.
30.
60.
40.
20.
.0.
100.
SO.
60'
40
l.
30
60
120
160
130 200 22'6 ''."" 2"4''0" ' 26I0 '"" 25^0
30'0
Figure B-59. Mass spectrum for safrole.
150
-------
TABLE B-27. KEY IONS AND RELATIVE ABUNDANCES FOR SAFROLE
M/Z
41
42
45
48
49
50
51
52
53
54
55
56
5:3
59
61
62
63
64
65
66
67
68
69
74
75
Abundance
•?
•_•
1
•-,
i.
19
33
1 1
9
1
3
.-,
•p
19
4
10
£
1
3
7
.2
.6
.0
.4
.4
.5
.0
.0
. 1
.0
.0
.4
. 6
. 1
.0
.6 •
.3 '
. 6
_ 2
. 3
1 2
.4
-~i
!!
M/Z
77
73
79
30
34
86
37
33
39
91
92
93
94
95
93
103
194
105
106
107
103
109
1 15
116
1 17
Abundance
*"• b
39
13
1
1
1
4
10
3
59
73
20
3
1
2
T
.0
.6
.2
.7
.1
.7
.6
.2
.4
.3
.3
.9
.3
.3
.6
.0
.5
T>
• 1
.7
.1
.6
_ 2
is
.0
. 6
M/Z
119
120
121
122
123
131
132
133
135
136
137
141
142
145
147
149
159
161
162
163
164
173
Abundance M/Z Abundance
3
1
2
60
21
'5
35
3
1
33
100
11
1
-
.5 183
.3 139
.3
.3 211
.4
.2 322
.4
.0
.9
.0
.4
.1
^.
• ••'
.4
.3
.2
.3
. 1
.0
.5
. 6
_2
.2
.3
.'2
.2
151
-------
to
z
o
a.
CO
UJ
cc
ui
LU
cc
• r
.4
. 1
15 2@ 36 48 50 66
QUANTITY ON COLUMN, ng
figure B-60.
Calibration curve for the determination of
safrole by GC/MS.
Range: 7.8-82 ng
Correlation coefficient: 0.983
Slope: 1.3 x 10~2
y-Intercept: 1.1 x 10"l
152
-------
LflRGST 4: 34.1,100.0 133.0, 33.4. 42.0, 21.1 162.0, 19.0
LflST 4: 168.5, .3 205 . 1 , .3 207.0, .3 223.1, .3
100.
30"
60"
40"
20"
0'
100.
30'
40.
20.
0
1
-
II
1-
1 lllll'iu i ll ilii mi llllllli
1 .,i , ..,.,. Ill, . i
' 22'0 '""24'0' '.'""2'ii'0 '"'"' 2'3i3 30'0" "'"' 32'0
Figure B-61. Mass spectrum for nicotine.
153
-------
TABLE B-28. KEY IONS AND RELATIVE ABUNDANCES FOR NICOTINE
M/Z
41
42
43
44
59
51
52
S3
54
55
56
57
58
61
63
64
65
66
67
68
63
71
72
73
74
Abundance
;*;
21
•-.'
4
Q
c;
1
1
4
1
c
4
!•'
I
2
I
i
.4
.1
.3
.0
_ 2
A
.1
.7
.9
.7
. 3
.9
.1
i
.6
. 7
.0
• i''
.-i
!!
.6
• 6
.3
.6
.3
. 1
M/Z
75
76
77
73
7*
89
SI
:-! ^'
34
85
8S
S9
99
91
9£
93
94
' 96
192
103
104
105
106
107
Abundance
1
2
i
2
2
2
3
100
7
1
1
2
4
10
2
1
2
1
1
1
.8
.7
,C|
.9
.2
.2
.6
.2
.0
^
> <•
.1
.4
.1
.4
.7
.3
.9
.4
.9
.0
.6
.6
.3 •
. 1
M/Z
199
119
115
117
113
119
120
121
124
123 .
130
131
133
134
135
' 141
141
143
144
145
146
147
143
149
Abundance
.4
.4
.3
5.4
6.2
9.6
2.2
.3
.3
.5
7.2
1 .5
33.4
4.2
.3
.4
.1
.4
. .9
.6
.3
•7
• 1
.4
.4
M/Z
157
153
159
161
162
163
165
163
205
20?
223
Abundance
.4
.4
1 .5
13.2
19.9
1 .7
.3
-".
• •-'
.3
.3
.3 '
154
-------
1 .8
to
O
a.
CO
UJ
oc
1G £0 38 40 50 60
QUANTITY ON COLUMN, ng
70
SO
90
Figure B-62.
Calibration curve for the determination of
nicotine by GC/MS.
Range: 9.1 - 87 ng
Correlation coefficient: 0.980
Slope: 1.1. x 10~2
y-Intercept: 7.2 x 10~2
155
-------
LflRGST 4: 1 3 1 . 1 , 1 OO .0 180.1, 32.2 223.1, 62.3 1S2.U, 37.2
LflST 4: 263.0, 1 .6 281.9, 2.6 232.2, 1.0 326.'?, i ."••
1 9 0_
so"
• 60!
40!
20"
0"
100.
80!
60"
40.
20.
0
h nil!, i, hi , M., i iJ.Mil.i iiililii. i.,.., in. M. ii I.IH.I . . .. iili. .1 i . i, i . ...
' 2.
till'lm i ill
''"is
3 4!0 60 80 100 .120 14y 160
iii".
H ' 20'@ ' £2'0 ' 24'0 '''"'26'e '"'''"" 2S'0 ' 30'o" ' 32'o
FLgure B-63. Mass spectrum for 2-acetamidofluorene.
156
-------
TABLE B-29; KEY IONS AND RELATIVE ABUNDANCES FOR 2TACETAMIDOFLUORENE
M/Z
41
42
43.
44
47
43
49
50
51
52
53
54
54
55
56
57
59
62
63
64
AF.
67
f, '3
70
71
72
73
•74
75
76
77
73'
79
30
31
. 3 2
33
34
35
Abundance
i.i
•-•
25
c;
::'
5
6
2
•-•
7
4
7
3
i
2
3
3
2
f.
1
7
C,
4
•7
1
i
4
2
3
7
4
..,
!•?
.1
!i
.4
1 2
!s
.6
.1
.3
.3
.0
.4
.5
.3
.1 .
.1
.6
. 6
.1
. 6
. 6
f
.3
!0
.4
2
.9
.0
. 6
.6
. 7
. 6
!i
. 2
. 3
M/Z
36
•"• 7
33
39
91
92
93
94
95
96
97
93
99
'100
101
102
103
104
105
103
109
1 10
1 1 1
112
1 1 3
114
115
117
119
120
• 122
123
125
126
127
123
Abundance M/Z
c,
2
4
1
3
1
I
1
~j
3
1
O
2
T
^
2
T
2
1
3
2
^1
1
3
1
1
1
1
1
2
' 4
5
2
.4
• y
.9
.6
. 1
.6
.3
.3
. 6
• 6«
.'6
.4
. 3
. 1
.3
.6
.3
.1
.3
.3
.3 '
.4
. 1
.3
. 3
. 1
.0
.6
.3
.3
.3
. 6
. 1
.4
. 1
129
131
133
135
136
137
139
140
. 141
147
149
150
151
152
153
154
155
157
153
159 •
161
162
163
164
165
166
167
. 163
169
'171
176
177
173
ISO
131
132
133
134
Abundance
1
1
2
'V
T
i
3
1
1
1
*
2
5
14
37
19
3
1
1
1
1
1
1
4
4
10
2
T
1
1
1
1
• 3
3
32
1 00
16
'"'
I
.0
.%
.1
.1
is
.9
.6
.0
• o'
.4
.2
.2
.4
.6
.6
.3
.3
.0
.3
.6
.4
.4
.3
.3
. 6
.3
.0
.3
. 6
. 6
2
!o
.5 '
.1
.6
M/Z
137
1 O >'•
1 O O
191
193
195
1O *7
' f
205
207
203
2 O 9
.-, ... .-,
224
•"• •"• ~.
*"""""
254
263
23 1
327
Abundance
1
,.
O
1
1
1
1
1
1
\'
2
1
.• .— ,
12
2
1
1
2
1
1
.6
.
!0
.0
. 3
.0
. 3
.*.
.:,
...
.1
.3
.0
• 1""'
. 3
157
-------
.. ,,
___
[ill
4567
i T I r I I I i I I I I I I I I I I I I I r riii
9 101112131415161718 1929 £1 22 232425 2627 23 29 30 3 1 32 33'34
Figure B-64. Chromatogram by GC/MS for all candidate POHCs,
Temperature program:
40 °C, 0 min isothermal
40 °C to 280 °C at 10 °C/min
280 °C, 15 min isothermal
158
-------
APPENDIX C
CHROMATOGRAMS, UV SPECTRA, AND CALIBRATION
CURVES FOR.HPLC/UV DETERMINATIONS
Index
Reference
chroraatogram
Compound Figure No.
3-( alpha-Acetonylbenzyl)
-4-hydroxycoumarin
Acetophenetidine
Chlorambucil
4-Chloro-m-cresol
o-Chlorophenol
2 ,4-i)ichlorophenol
2 ,4-Dichlorophenoxyacetic acid
4 ,6-Dinitro-o-cresol '
Methyl yellow
4-Nitrophenol .
N-Nitroso-N-methylurea
5-Nitro-o-toluidine
Phenol
Reserpine
Saccharin
SCreptozotocin
2 ,3 ,4 ,6-Tetrachlorophenol
Tetraraethylthiuram disulfide
2 ,4 ,6-Trichlorophenol
2 ,4 ,5-Trichlorophenoxyacetic acid
C-34
C-17
C-48
C-26
C-13
C-30
C-51
C-60
C-60
C-9
C-65
C-20
C-5
C-45
C-68
C-l
C-41
C-23
C-37
C-54
Reference
UV
Figure No.
C-35
C-18
C-49
C-27
C-14
C-31
C-52
C-61
C-63
C-10
C-66
C-21
C-6
C-46
C-69
C-2
C-42
C-24
C-38
C-55
Reference
calibration
curve
Figure No.
C-36
C-19
C-50
C-28,
C-15,
C-32,
C-53
C-62
C-64
C-ll,
C-67
C-22
C-7,
C-47
C-70
C--3,
C-43,
C-25
C-39,
C-56
C-2
C-12
C-3
C-l
C-8
C-4
C-44
C-40
159
-------
OJ
at
O
a.
in
I
_L
10
15 20
RETENTION TIME, min
25
30
35
Figure C-l. Chromatogram by HPLC/UV for
streptozotocin.
160
-------
01
o
<
co
oc
O
210
250 300
WAVELENGTH, nm
350
400
Figure C-2. UV spectrum of streptozotocin.
161
-------
166
146
_ 100
b
1^
J< 30 -
tu
ce
60 i-
,^X
QUANTITY INJECTED. M9
Figure C-3. Calibration curve for the determination of
streptozotocin by HPLC/UV.
Range: 0.064 - 6.4 ug
Correlation coefficient:
Slope: 2.4 x 10+1
y-Intercept: -5.4
0.993
162
-------
LU
QC
506 >
450 f-
I-
460 j-
i-
3 5 0
X
QUANTITY INJECTED,
Figure C-4. Calibration curve for the determination of
streptozotocin by HPLC/UV(280nm).
Range: 0.64 - 9.2 pg
Correlation coefficient:
Slope: 7.4 x 10+1
y-Intercept: -4.9
0.999
163
-------
Ui
CO
O
a.
cc
>
T
T
10
IS 20
RETENTION TIME, min
28
30
33
Figure C-5. Chromatogram by HPLC/UV for
phenol.
164
-------
01
u
CO
CO
210
250 300
WAVELENGTH, nm
350
400
Figure C-6. W spectrum of phenol.
165
-------
x
3Q0
2S0
200
150
160
5 a
4- • 5 6
QUANTITY INJECTED,
10 11
Figure C-7. Calibration curve for the determination of
phenol by HPLC/UV.
Range: 2.5 - 10 ug .
Correlation coefficient: 0.995
Slope: 3.0 x 10+1
y-Intercept: -1.7 x 10+1
166
-------
LU
cc
148 r
9.0 .5 1.0 1.5. 2.0 2.5 3.0 3.5 4.0 4.5 5 .0
QUANTITY INJECTED, M9
Figure C-8. Calibration curve for the determination of
phenol by HPLC/UV.(280nm) .
Range: 1.0 - 5.0 ug
Correlation coefficient: 0.985
Slope: 2.2 x 10+1
y-Intercept: -1.6 x 10+1
167
-------
O
Q.
X
3
I
I
10
15 20
RETENTION TIME, min
25
30
35
Figure C-9. Chromatogram by HPLC/UV for
4-nitrophenol.
168
-------
ui
o
<
m
E
O
in
oo
—r I i—!—^~
210
250
300
WAVELENGTH,
350
400
nm
Figure C-10. UV spectrum of 4-nitrophenol.
169
-------
CTI
b
til
tr
459
499
350
300
250
200
150
100
50
456
QUANTITY INJECTED, M9
10
Figure C-ll. Calibration curve for the determination of
4-nitrophenol by HPLC/UV.
Range: 0.52 - 10 yg
Correlation coefficient:
Slope: 4.3 x 10+1
y-Intercept: -1.1 x 10*
0.999
170
-------
1688
1408
til
OC
1288
I
1888
4 8 8
2 8 6
X'"
456
QUANTITY INJECTED,M9
18 11
Figure C-12.
Calibration curve for the determination of
4-nitrophenol by HPLC/UV(280nm).
Range: 0.52 - 10 pg
Correlation coefficient: 0.999
Slope: 1.6 x 10+2
y-Intercept: -2.9 x 10+1
171
-------
z
o
a.
in
15 20
RETENTION TIME, min
25
Figure C-13. Chromatogram by HPLC/UV for
o-chlorophenol.
172
-------
LU
u
<
CO
IT
O
VI
CD
__LZ_I ! L_H1__
_pzi._...;—r_.^—
210
250 300
WAVELENGTH, nm
350
400
Figure C-14. UV spectrum of £-chlorophenol
173
-------
*?
b
UJ
cc
140
- 100
SO
40
3456
QUANTITY INJECTED./j
Figure C-15. Calibration curve for the determination of
o-chlorophenol by HPLC/UV.
Range: 0.47 - 9.4 pg
Correlation coefficient:
Slope: 1.6 x 10+1
y-Intercept: -2.6
0.999
174
-------
UJ
K
60©
soo
400
see
200
1 Q 0
3456
QUANTITY INJECTED, M9
Figure C-16.
Calibration curve for the determination of
o-chlorophenol by HPLC/UV(280nm).
Range: 0.47 - 9.4 yg
Correlation coefficient:
Slope: 6.3 x 10+1
y-Intercept: -6.5
0.999
175
-------
LU
CO
O
0.
CO
UJ
-------
o
z
<
03
CC
O
V)
CO
— I-V -_—! h-4 1
210
250 300
WAVELENGTH, nm
350
400
Figure C-18. IN spectrum of acetophenetidine.
177
-------
2000
1400
1200
- 1 9 0 0
x
400
200 r
nL
X
1.0 1.5 2.0
4.0 4.5
Figure C-19.
QUANTITY INJECTED. M9
Calibration curve for the determination of
acetophenetidine by HPLC/UV.
Range: 0.050 - 5.0 pg
Correlation coefficient:
Slope: 3.6 x 10+2
y-Intercept: -5.3
0.999
178
-------
u>
O
a.
tSI
I
10
15 20
RETENTION TIME, min
25
30
3S
Figure C-20. Chromatogram by HPLC/UV for
5-nitro-o-toluidine.
179
-------
Reproduced frorp
best nvailanie copy.
-------
CO
b
14QO
12Q8
1000
800
6 0 0
400
£00
y. y
,x
,X'
X'
X
1.0. 1.5 2.0 2.5 3.0
QUANTITY INJECTED,Mg
Figure C-22. Calibration curve for the determination of
5-nitro-o-toluidine by HPLC/UV
Range: 0.050 - 5.0 pg
Correlation coefficient:
Slope: 3.0 x 10+2
y-Intercept: -6.0
0.999
181
-------
LU
V)
O
Q.
in
10
15 20
RETENTION TIME, min
25
30
35
Figure C-23. Chromatogram by HPLC/UV for
tetramethylthiuram disulfide.
182
-------
UJ
u
<
CO
cc
o
CO
m
210
250 300
WAVELENGTH, nm
350
400
Figure C-24. UV spectrum of tetramethylthiuram disulfide.
183
-------
2500
X
cc
2 0 0 0
1500
0 0 0
P. M f 1
X
X
0 1 234 5.6
QUANTITY INJECTED, M9
Figure C-25. Calibration curve for the determination of
tetramethylthiuram disulfide by HPLC/UV.
Range: 0.047 - 9.4 ug
Correlation coefficient:
Slope: 2.& -x. 10+2
y-Intercept: -2.7
0.999
184
-------
o
a.
tsi
UJ
ac
I
10
15 20
RETENTION TIME, min
25
30
35
Figure C-26. ChromaCogram by HPLC/UV for
4-chloro-m-cresol.
185.
-------
01
(J
<
CD
ff
o
CO
00
210
250 300
WAVELENGTH, nm
350
400
Figure C-27. UV spectrum of 4-chloro-m-cresol.
186
-------
o
X-
UJ
BE
120
iee
40
4567
QUANTITY INJECTED, ^9
1 1
Figure C-28. Calibration curve for the determination of
4-chloro-m-cresol by HPLC/UV.
Range: 0.57 - 12 pg
Correlation coefficient:
Slope: 8.6
y-Intercept: -1.3
0.999
187
-------
700
x
UJ
cc
4 8 6
3 8 8
203
1 8 8
4567
QUANTITY INJECTED, M9
18 11
Figure C-29. Calibration curve for the determination of
4-chloro-m-cresol by HPLC/UV(280nm).
Range: 0.57 - 12 pg
Correlation coefficient:
Slope: 5.7 x 10+1
y-Intercept: -1.1
0.999
188
-------
z
o
0
10
15 20
RETENTION TIME, min
25
30
35
Figure C-30. Chromatogram by HPLC/UV for
2 ,4-dichlorophenol.
189
-------
o
<
so
oc
o
CO
CD
:.c~ --•>-— t—a—_-
250
300
WAVELENGTH, nm
350
400
Figure C-31. UV spectrum of 2,4-dichlorophenol
190
-------
o
X
UJ
cc
30 h
£0 h
456
QUANTITY INJECTED,/
10
1 1
Figure C-32. Calibration curve for the determination of
2,4-dichlorophenol by HPLC/UV.
Range: 0.55 - 11 yg
Correlation coefficient; 0.999
Slope: 5.9
y-Intercept: -8.3 x 10"1
191
-------
ijj 0 £1
500
^ 4130
b
x
2i 3 e o
100
4 5 b
QUANTITY INJECTED, M9
10
1 1
Figure C-33.
Calibration curve for Che determination of
2,4-dichlorophenol by HPLC/UV(280nm).
Range: 0.55 - 11 pg
Correlation cpefficient:
Slope: 6.3 x 10+1
y-Intercept: -4.2
0.999
192
-------
z
o
Q.
_L
10
15 20
RETENTION TIME, min
25
30
35
Figure C-34.
Chromatogram by HPLC/UV for
3-(alpha-acetonylbenzyl)-4-hydroxycoumarin.
193
-------
o
<
m
cc
O
CO
oo
210
250
300
WAVELENGTH.
350
400
nm
Figure C-35. UV spectrum of 3-(aLpha-acetonylbenzyl)-4-hydroxycoumari.n.
194
-------
01
cc
'300 f
S 0 0
700
b 0 0
5 0 0
400
2 0 0
103 -
JL.
X
V"
'
0 1 ' 2 3 4 S 6
QUANTITY INJECTED, fig
Figure C-3fa. Calibration curve for the determination of
3-(alpha-acetonylbenzyl)-4-hydroxycoumarin
by HPLC/UV.
Range: 0.47 - 9.4 pg
Correlation coefficient:
Slope: 9.5 x 10+1
y-lntercept: -7.8
0.999
195
-------
us
Z
O
rft
10
15 20
RETENTION TIME, min
25
30
35
Figure C-37. Chromatogram by HPLC/UV for
2 ,4 ,6-trichlorophenol.
196
-------
Reproduced fr;.-"'->
best available copy
O
m
c
o
CD
_-.^ .... I - -I.-.- _l |.._. |_J..j__.l. _-„:.__,„_!__ j . ...
——13__J_ii_i - \ ^7ir;z"i_z.;IriT' i~- hn~.!'zr.ti^nil~!."
210
250 300
WAVELENGTH, nm
350
400
Figure C-38. UV spectrum of 2,4,6-trichlorophenol.
197
-------
o
X
120
too
40
QUANTITY INJECTED,
Figure 039.
Calibration curve for the determination of
2,4,6-trichlorophenol by HPLC/UV.
Range: 0.48 - 9.6 Mg
Correlation coefficient:
Slope: 1.1 x 10+1
y-Intercept: 2.0
0.999
198
-------
400
350
30u
250 - .
£00 -
DC
< 150
1 0 0
QUANTITY INJECTED,/
Figure C-40.
Calibration curve for the determination of
2,4,6-trichlorophenol by HPLC/UV(280nm).
Range: 0.48 - 9.6 ug
Correlation coefficient:
Slope: 4.0 y. 10+1
y-Intercept: -6.2
0.999
199
-------
O
cc
>
10
15 20
RETENTION TIME, min
25
30
35
Figure C-41. Chromatogram by HPLC/UV for
2,3,4 ,6-tetrachlorophenol.
200
-------
I
<
03
er
s
00
~_i .'j ". r /."
250
300
WAVELENGTH, nm
350
400
Figure C-42. UV spectrum of 2,3,4,6-tetrachlorophenol
201
-------
300
o
^»
X
iu
x.
250
200
150
100
4 6
QUANTITY INJECTED. M9
10
Figure C-43. Calibration curve for the determination of
2,3,4,6-tetrachlorophenol by HPLC/W.
Range: 0.55 - 11 pg
Correlation coefficient: 0.990
Slope: 2.3 x 10+1
y-Intercept: 3.6 x 10*1
202
-------
b
^
UJ
ce
240
220
200
ISO
160
140
120
100
3 0
60
40
20
i ' : ' i ' t ' i • i ' i • i ' i ' i ' i
^ ,^""
: ' ,/
-..--/^
....,
X ,-• """
-.•••"''
x""... ""
.••"' -*1"
.-•*".-••'
-.
_.••"
.,,/
~ ••'".-•'*
! , 1 , 1 , 1 . 1 , I , 1 . 1 , 1 , 1 , 1
10 11
QUANTITY INJECTED,/jg
Figure C-44. Calibration curve for the determination of
2,3,4,6-tetrachlorophenol by HPLC/UV(280nm).
Range: 1.1 - 11 yg
Correlation coefficient:
Slope: 2.2 x 10+1
y-Intercept: 1.6
0.995
203
-------
to
O
Q.
I
15 20
RETENTION TIME, min
25
30
35
Figure C-45. Chromatogram by HPLC/UV for
reserpine.
204
-------
o
00
cc
3
CO
250
300
WAVELENGTH,
350
400
nm
Figure C-46, UV spectrum of reserpine.
205
-------
LU
cc
19
345
QUANTITY INJECTED,/J9
Figure C-47.
Calibration curve for the determination of
reserpine by HPLC/UV.
Range: 0.37 - 7.5 yg
Correlation coefficient:
Slope: 8.0
y-Intercept: -4.6 x 10"
U.998
206
-------
O
Q.
>
_L
10 15 20
RETENTION TIME, min
25
30
35
Figure C-48. Chromatogram by HPLC/UV for
chlorambuci1.
207
-------
u
z
<
ca
cc
o
«/>
00
210
250 300
WAVELENGTH, nm
350
400
Figure C-49. UV spectrum of chlorambucil.
208
-------
1000
O
X
UJ
QC
6 9 0
400
£00
y .O
1 .Q ..1-5 2..S 2.5
QUANTITY INJECTED, /jg
:S . 0
3:5
Figure C-50. Calibration curve for the determination of
chlorambucil by HPLC/UV.
Range: 0.35 - 3.5 ug
Correlation coefficient: 0.999
Slope: 2.6 x lO+2
y-Intercept: -2.0 K 10"1"1
209
-------
C/J
a
CL
V)
UJ
OC
10
15
20
25
30.
35
RETENTION TIME, min
Figure C-51. Chromatogram by HPLC/UV for
2 ,4-dichlorophenoxyacetic acid.
210
-------
LU
U
z
<
00
cc
o
CO
00
-I1 J0.3F" """
t:_.. rb."r-_:
210
250 300
WAVELENGTH, nm
350
400
Figure C-52. UV spectrum of 2,4-dichlorophenoxyacetic acid.
211
-------
200
150
"?
b
LU
QC
4 6
QUANTITY INJECTED, M9
10
Figure C-53. Calibration curve for the determinatipn of
2,4-dichlorophenoxyacetic acid by HPLC/UV.
Range: 1.2 - 9.7 yg
Correlation coefficient:
Slope: 2.0 x 10+1
y-Intercept: 7.3
0.998
212
-------
o
a.
10
J l__
15 20
RETENTION TIME, min
25
30
35
Figure C-54. Chromatogram by HPLC/UV for
2,4,5-trichlorophenoxyacetic acid.
213
-------
u
z
<
CO
cc
o
U)
to
210
250 300
WAVELENGTH, nm
350
400
Figure C-55. UV spectrum of 2,4,5-trichlorophenoxyacetic acid.
214
-------
200
ISO
160
CO
b
12o
100
SO
60
40
.X
4 5 6
QUANTITY INJECTED,
10
Figure C-56.
Calibration curve for the determination of
2,4,5-trichlorophenoxyacetic acid by HPLC/UV,
Range: 1.5 - 9.9 pg
Correlation coefficient: 0.999
Slope: 1.7 x 10+1
y-Intercept: -4.1 x 10""*
215
-------
U)
Z
O
a.
vt
LLJ
X
T
I
10
15 20
RETENTION TIME, min
25
30
35
Figure C-57. Chromatogram by HPLC/UV for
2-(2,4,5-1rich lorophenoxy)prop ionic acid.
216
-------
LU
o
<
00
cc
o
OQ ~ "* _ ~ I " ' I •- '' —-- •
h.--.i -
!- - -0.2!
Ee:^^.^.:-:!
210
250 300
WAVELENGTH, nm
350
400
Figure C-58. UV spectrum of 2-(2,4,5-Crichlorophenoxy)propionic acid.
217
-------
120
100
b
x
UJ
tr
40
3 4.5
QUANTITY INJECTED,
Figure C-59.
Calibration curve for the. determination of
2-(2,4,5-trichlorophenoxy)propionic acid by HPLC/UV.
Range: 1.1 - 7.2 yg
Correlation coefficient: 0.998
Slope: 1.6 x 10+1
y-Intercept: -5.5 x 10"1
218
-------
C/l
Z
o
a.
GO
L c±
10
I I
15 20
RETENTION TIME, min
25
30
35
Figure C-60. Chromatogram by HPLC/UV for
(A) 4,6-dinitro-o-cresol(t,, = 7.5 min) and
(B) methyl yellow(tR = 13.0 min).
219
-------
o
z
<
00
cc
o
CO
CO
210
250 300
WAVELENGTH, nm
350
400
Figure C-61. UV spectrum of 4 ,6-dinitro-o-cresol.
220
-------
148
1 28
1QS J--
i
n
b
QUANTITY INJECTED,
Figure C-62.
Calibration curve for the determination of
4,6-dinitro-o-cresol by HPLC/UV( 378nm) .
Range: 0.50 - 5.0 Mg
Correlation coefficient:
Slope: 2.9 x 10+1
y-Intercept: -5.3
0.998
221
-------
IU
o
2
<
CD
CC
O
CO
CO
-I- 4-f-
T3EE
i I
—-j—
-p-
U.9.
Eg
4-H—-}— |—i-
iihiicd—'—'-
—j—-1—i:
—I—j—•——i— —|—i—
K/.u: —
-|.-
--i_1-id—h~
-4—I—-i-
P
7—f-
10.7r
tdm
-»--
-10.5
=;=zhEZ
l^f
i—(--•
^^m.
w^
r t i
rj:
d:
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^^F^-
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"J -~~.
EE£
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nf—
4=t=
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i j__
—in:
-»;
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—[-—|—-
—-h—*—
-~r—1
._)._._ — i—j—.
zE;
_i
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-t"
—!._•.. lirq_'^_!~_.:.
r _J 1 _;_L
^~~£~
"ZZHI~L—r~ ]~~~\ '• ~ i i"
i riii i i _.
•/-
210
250 300
WAVELENGTH, nm
350
400
Figure C-63. UV spectrum of methyl yellow.
222
-------
1408
1200
1000
o
X
4 0 0
3 . 4
QUANTITY INJECTED, M9
Figure C-64.
Calibration curve for the determination of
methyl yellow by HPLC/UV(400nm).
Range: 0.60 - 6.0 pg
Correlation coefficient: 0.995
Slope: 2.4 x 10+2
y-Intercept: -3.0 x 10+1
223
-------
z-
o
0.
-------
u
<
CD
CC
o
V)
CO
~-h=i--!---!»- i
_!.. . i
—LI. .1—i—n.—
!- — — —i—• o.i;-—
' r :
— t — -t 4 —
—; I L .. -I.
210
250 300
WAVELENGTH, nm
350
400
Figure C-66. UV spectrum of N-nitroso-N-methylurea.
225
-------
o
f—
X
UJ
cc
£400
2 3 8 0
1200
4 ft ft
3 ' 4 5 6
QUANTITY INJECTED, pg
10
Figure C-67.
Calibration curve for the determination of
^-nitroso-^J-methylurea by HPLC/UV.
Range: 0.50 - 9.9 yg
Correlation coefficient: 0.999
Slope: 2.4 x 10+2
y-Intercept: -2.0 x 10+1
226
-------
V)
O
0.
V)
Ul
IT
_L
15 ' 20
RETENTION TIME, .mm
25
30
35
Figure C-68.
Chromatogram by HPLC/UV for
saccharin.
227
-------
LU
o
<
00
-------
m
o
LU
ce
70.
'."' I-
1 .00 1 .5>j
QUANTITY INJECTED, /ng
Figure C-70. Calibration curve for the determination of
saccharin by HPLC/UV.
Range: 0.49 - 2.4 gg
Correlation coefficient: 0.960
Slope: 2.4 x 10+1
y-Intercept: 1 .4 x It)"1"1
229
-------
APPENDIX D
DESCRIPTION OF SUPPLEMENTARY METHOD DEVELOPMENT
'AND OTHER TASKS
INTRODUCTION
Battelle-Columbus Laboratories, Columbus, Ohio, in a joint effort with
Southern Research Institute, undertook specific tasks to supplement the
development of generalized test procedures. Specific analysis methods for
brucine and 2-fluoroacetamide were developed. Also, potentially useful
air-sampling, sample-preparation, and analysis procedures for various POHCs
were recommended. Existing preparative and analysis methods for the
determination of metals in wastes and incinerator effluents were refined and
supplemented. These tasks are reported in the following sections of this
appendix.
DEVELOPMENT OF ANALYSIS METHODS FOR BRUCINE AND 2-FLUOROACETAMIDE
Because spectrophotometric analysis methods are given in the Methods
Manual for these two compounds, gas chromatographic analysis procedures were
sought for their determination. The developed generalized GC procedures
described previously, however, were not entirely suitable for these two
compounds. Consequently, GC conditions were modified to accommodate the
determination of the compounds. The conditions found optimum for brucine are
given on page 231. Under the specified conditions, the detection limit was
estimated to be between 5 and 20 ng in a single injection. A chromatogram of
brucine i.s presented as Figure D-l.
The optimum conditions found for the determination of 2-fluoroacetamide
are given on page 233. The detection limit was about 20 ng of
2-fluoroacetamide in a single injection. A chromatogram of the compound is
presented as Figure D-2.
230
-------
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
Brucine
GC/FID
Organic solvent extract of waste sample
or sampling medium
Brucine
GC/FID
GC:
FID:
Column — Fused-silica capillary, 30 m long,
0.25-mm ID, wall^coated with SE-52
Carrier gas — He at 2 mL/min
Temperature program — 120 to 300 °C at 8 °C/min;
300 °C, 32 min isothermal
Injector temperature — 300 CC
Detector temperature — 300 °C
Detection limit — 5 to 20 ng
^This method was developed by Battelle-Columbus Laboratories, Columbus,
Ohio.
231
-------
w
c/3
o
u
Cd
Q
I—I
fa
u
u
01
c
•H
u
3
10 15 20 25 30 35 40
RETENTION TIME, min
45 50
Figure D-l.
Chromatogram by GC/FID for brucine (200 ng)
232
-------
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
GC:
2-Fluoroacetamide"
GC/FID
Organic solvent .extract of waste sample
or sampling medium
2-Fluoroacetamide
GC/FID
FID:
Column — Chromosorb 101 (100/120 mesh),
1.8 m x 2-mm ID
Carrier gas — He at 30 mL/min
Temperature program — 155 °C isothermal
Detector temperature —
Detection limit — =20 ng
References :
1. Warner, J. S., and M. C. Landes, Internal Communication, Battelle-
Columbus Laboratories, November 10, 19811
"This method w.as developed by Battelle-Columbus Laboratories. Columbus,
Ohio.
233
-------
ft
c/:
c/:
PL.
oS
C
b
U
CJ3
n
1.5 3.0 4.5 6.0
RETENTION TIME, min
7.5
Figure D-2. Chromatogram by GC/FID for 2-fluoroacetamide (100 ng)
234
-------
RECOMMENDATION OF POTENTIALLY USEFUL AIR-SAMPLING,
SAMPLE-PREPARATION, AND ANALYSIS PROCEDURES FOR
VARIOUS POHCs
As part of the work performed in the initial phase of this contract
assignment, overall air-sampling and analysis methods were proposed for the
determination of particular chemical classes of POHCs. On the basis of profes-
sional judgment and information found in literature references, these methods
were suggested as refinements of and additions to the methods already given in
the Methods Manual.
The classes of compounds that were considered included those listed in
Table C.4 of the Methods Manual—aldehydes, acids, and esters—and those listed
in .Table C.4—alcohols and thiols. The specific compounds given consideration
are listed in Table D-l of this appendix along with their corresponding Chemi-
cal Abstracts Service (CAS) Registry numbers, chemical structures and formulas,
molecular weights, boiling points (or flash points or melting points), and
brief summary statements describing the proposed air-sampling, sample-
preparation, and analysis procedures. The compounds in Table D-l have been
separated into groups according to the following scheme:
Group n.otation Chemical class or chemical name
C-5-B Alcohols
C-5-C Epinephrine
C-5-A Thiols
C-4-C Aldehydes
C-4-B Organophosphorus compounds
C-4-E Organosulfur compounds
C-4-F " Trifluoroacetic acid, sodium salt
C-4-D Methyl methacrylate
C-4-A Carboxylic acids
The air-sampling methods given in Table D-l require the use of two sam-
pling trains. For the collection of most of the compounds, a modified version
of the EPA Method 5 train is appropriate. This modified train was developed by
Battelle-Columbus Laboratories; a diagram of its components is given as
Figure D-3. Another sampling train was recommended for the collection of alde-
hydes in air; this device is presented in Figure D-4. The collection media for
aldehydes is sodium bisulfite in aqueous solution. The collected aldehyde is
then derivatized with dinitrophenylhydrazine or 2,3,4;5,6-pentafluorobenzyl-
hydrazine for determination by GC.
Detailed descriptions of the proposed methods for each group of compounds
shown in Table D-l are presented on pages 243 through 281.
235
-------
TABLE D-l. PROPOSED AIR SAMPLING AMD ANALYSIS METHODS FOR SELECTED POHCs
CAS
Registry No.
107-18-6
a
Name Structure Formula Mol wt bp, C
(Allyl alcohol) CH =CH-CH -OH C H 0 58 96-98
Air sampling and
sample preparation
methods Analysis method
Modified Method 5 (MM5) GC/FID (glass column
2-Propen-l-ol . " « (extraction with water packed with 0.8% THEED"
107-19-7
57-55-6
U
1 of sorbent and filter) on Carbopak) or GC/MS
2-Propyn-l-ol HCHC-CH2-OH C3H,,0 56 114-115 6 (capillary glass column
1,2-Propanediol CH3-CHOH-CH2OH C3H802 76 187
1 wall-coated with SE-52)
51-43-4
108-98-5
594-42-3
75-70-7
Epinephrine
Benzenethiol
Tetrachloromethane-
thlol
Trichloromethane-
thiol
CH,HN-CH,CHOH C.H, ON 183
3 *• i 9133
CC13SH
C6H5SH 110
CC1..S
186
CHC13S 152
mp
21JT]
212 u Modified Method 5 (MM5)
10 (extraction with 1% HC1
<-> of sorbent (alumina) and
filter)
168-169
147-148
LCEC or GC/MS (capillary
glass column wall-coated
with SE-52)
^ Modified Method 5 (MM5) GC/ECD or GC/MS (glass
i (extraction with methylene capillary column wall-
chloride of XAD-2 sorbent coated with SE-52)
and filter)
(continued)
-------
TABLE D-l (continued)
CAS
Registry No. Name
75-07-0 Acetaldehyde
4170-30-3 Crotonaldehyde
765-34-4 Glycidylaldehyde
107-20-0 Chloroacetaldehyde
3288-58-2 0,0-Diethyl-j>-raethyl-
ester phosphorodi-
thioic acid
NJ
LO
vj 311-45-5 0-£-Nitrophenyl ester,
0,0-diethyl phosphoric
acid
297-97-2 0,0-Diethyl-0-(2-
pyrazinyl) phosphoro-
thioate
55-91-4 Diisopropyl
fluorophosphate
Structure
CH3CHO .
CH3CH=CHCHO
A
H2C-CHCHO
CH2C1-CHO
OC2H5
1
H5C,0-P-SCH,
II
II
s
0-C2Hs
1 / — •y
HsC.O-P-O-^
If
0
OC2H5
|
H5c20-pr°-|''ol
s ^
F
H3C |
/CH-0-P=0
H3C |
0
1
CH
HP ^*T*
3 \* \j
Air sampling and
sample preparation
Formula Mol wt bp, °Ca methods Analysis method
C2H^O 44 21 1
Modified Method 5 (MM5) GC/ECD6 or MS (glass
C^H60 70 104 o (impinger with derivatiz- capillary column wall-
-i Ing agent such as DNPHf) coated with SE-52) or
o HPLC (Zorbax-ODS, 75%
C3H^02 72 112-113 1 methanol/25% H20)
C2H3OC1 78 85-86
C5H,302S2P 200 —
C10H,,.N06P 275 —
>-N02
c
Modified Method 5 (MM5) GC/AFID8 or GC/MS (glass
'^ (XAD-2 sorbent, extrac- capillary wall-coated
^ tion with methylene with SE-52 column)
C8Hi3N203PS 217 —
C6H,,.F03P 184 ' 62
(9 torr)
„ (continued)
chloride)
-------
TABLE D-l (continued)
CAS
Registry No.
Name
Structure
Formula
Mol wt bp, °Ca
Air sampling and
sample preparation
methods
Analysis method
3689-24-5
107-49-03
126-68-1
00 126-72-7
757-58-4
52-05-7
Tetraethyldithio- (C2H50)2P(S)OP(S)(OC2H5)2 CeH2005P2S2 ' 322 136-139
pyrophosphate
II cV, ~v/ ^
\ 0 0 s
Tetraethyl pyro- \p g /
phosphate P-O-P
\
\
0,0,0-Triethyl- H5C20—P-S
phosphorothioate /
CJH20°7P2 29° . 13
C6H1603PS 198 100 •" Modified Method 5 (MM5)
(16 torr) g (XAD-2 sorbent, extrac-
•^ tion with methylene
g chloride)
GC/AFID or GC/MS (glass
capillary column wall-
coated with SE-52)
\ «
Tris(2,3-dibromo- CII2Br-CHBr-CH2-0-P=0 C,H, jEr^F 218 fp >112 ^
propyl) phosphate
Hexaethyl tetra- 0=F
phosphate
/
I—P—O—P=0 C12HJ00,3P^ 506 decompo-
| I ses above
150 °C
Phosphorothioic H3CO g
aciJ-0,0-dimethyl \||
ester, 0-ester with P-0-(O}-SO2N
sulfonamide benzene /
CH3
325 mp 52-53
H3CO
CH,
(continued)
-------
TABLE D-l (continued)
CAS
Registry No.
77-78-1
62-50-0
66-27-3
62-74-8
80-52-6
53-86-1
145-73-3
Name • Structure Formula Mol wt
O
II
Dimethyl sulfate CH30-S-OCH3 C2H6O,,C1 126
II
0
Ethylmethane sul- CH3S03C2H5 C3He03S . 124
fonate
Methyl methane CH3S03CH3 C2!I603S 110
sulfonate
Trifluoroacetic CF3COO"Na+ C202F3Na 136
acid, Na salt
Methyl raeth- CH2C(CH3)COOCH3 C5He02 100
acrylate
0
l-(£-Chlorobenzoyl)- N CH3 C, 5Hi60,.NCl 357
5-methoxy-2-methyl- f-^^n lT
indole-3-acetic acid Y II II
H,«r**^ CH2COOH
0
|
7-Oxabicyclo[2.2.1] r-"T\_ CflH10Os 180
Air sampling and
sample preparation
bp, °Ca methods
—
188' (with
decom-
position)
Modified Method 5 (MM5)
(XAD-2 or Porapak Q or
silica gel sorbent and
— i acetone or water
extraction)
- J
— d Modified Method 5 (MM5)
-i (filter and impinger (10%
J1 HN03] and steam distilla-
tion)
101 1 Modified Method 5 (MM5)
, (XAD-2 sorbent, extraction
"f with methylene chloride)
Q
mp 155
,
Modified Method 5 (MM5)
(particulate and filter,
then diethyl ether
extraction)
I
i
Analysis method
CC/MS (glass capillary
column wall-Coated with'
SE-52)
CC/ECD or MS (glass
capillary column wall-
coated with SE-52)
GC/FIU or MS (glass
capillary column wall-
coated with SE-52)
Derivatization
(diazoroethane), GC/ECD
or MS (glass capillary
[SE-52] or packed [OV-1
on Gas-Chrom Q] column)
heptane-2,3-dicar-
boxylic acid
(continued)
-------
TABLE D-l (continued)
Air sampling and
CAS sample preparation
Registry No. Name Structure Formula Mol wt bp, °Ca methods Analysis method
94-75-7 2,4-dichloropheuoxy- C1-/Q) -0-C112-COOH C8H60:1C12 221
acetic acid
ci
1
93-76-5 .2,4,5-trichloro- Cl-/O)-°-cll2-COOH C8H5C1303 255 mp 151-153 c Modified Method 5 (MM5) Derivatization
phenoxyacetic acid '—( ' £ (partlculate and filter, (dlazomethane), GC/ECD
Cl < then diethyl ether or MS (glass capillary
Cl H . ^ extraction) [SE-52J or packed (OV-1
)—y | ' on Gas-Chrom Q] column)
93-72-1 2-(2,4,5-trichloro- C1-/O)-°"C~C0011 C9H7C1303 270 -rap 180-181
phenoxy)propionic o- ^—/ |
acid Cl CH3
-t>
O
aBoiling points (bp) are given except when flash points (fp) and melting points (mp) are indicated.
bTHEED = tetrahydroxyethylene amiue.
CLCEC = liquid chromatograpliy with electrochemical detection.
GC/FPD = gas chromatograpliy with flame photometric detection.
eGC/ECD = gas chromatography with electron capture detection.
fDNPH « 2,4-dlnitrophenylhydrazine.
8GC/AFID = gas chromatography with alkali flame ionization detection.
-------
TEMPERATURE
SENSOR
_
PROBE—~fs;
REVERSE-TYPE
PITOT TUBE
CHECK
VALVE
FILTER HOLDER
8ATTELLE
SORBENTTRAP
RECIRCULATION PUMP
THERMOMETERS
VACUUM LINE
DRY GAS METER AIR-TIGHT
PUMP
Figure D-3. Battelle Modified Method (MM5) Train.
241
-------
GLASS
CLASS WOOL PROSE
.
—
-
"V /
10% NaHSOj
SOLUTION
E
M
PF
^»
f
ICE BATH
\
aOWMETER
Figure D-4. Diagram of sampling train for aldehydes..
242
-------
EXAMPLE 1. POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Sampling-Method Parameters:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (particulate plus vapor-
phase material)
Alcohols (Allyl alcohol, 2-Propyn-l-ol,
1,2-Propanediol) (C-5-B)
GC/FID
Hardware: RAC or equivalent sampling train modified to include
sorbent module as shown in Figure 3
Filter — Glass-fiber filter
Sorbent — XAD-2 resin
Impinger reagent — Water
Deployment: Traverse and sample isokinetically as specified in
EPA Method 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate
Recovery Check:
References:
Spike filter/sorbent or impingers before
(or both) sampling with known quantity of
deuterated or fluorinated analog of target
compound.
243
-------
Method Number:
Method Name:
Basic Method:
Matrix:
EXAMPLE 1: POHC SAMPLE-PREPARATION METHOD
Extraction
20-min shaking of filter and XAD-2
sorbent in water
Sorbent and solid waste and filter
Liquid waste (organic)
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Alcohols (Allyl alcohol, 2-Propyn-l-ol ,
1 ,2-Propanediol) (C-5-B)
Apparatus — Standard Equipment
Solvent — Water
Time — 20 rain
Sample size — 20-200 g
244
-------
EXAMPLE 1. POHC ANALYSIS METHOD
Method Number:
Method Name: Alcohols
Basic Method: GC/FID, GC/MS
Matrix: Water (impinger and extract)
Liquid organic waste (neat and dilute)
Specific POHC from Appendix VIII
to which method may be applied: Alcohols (Allyl alcohol, 2-Propyn-l-ol. .
1,2-Propanediol) (C-5-B)
Apparatus: GC/MS/DS (gas chromatograph with mass
spectrometer and data system)
Analysis-Method Parameters:
GC: Column — Fused-silica capillary, 30 m long, 0.25-mm ID,
. ' wall-coated with SE-52
Carrier gas — He at 25 cm/s at 100 °C
or
Column— Carbopak C plus 0.8% THEED (tetrahydroxyethlene-
diamine) packed in 55 x 0.2-cm ID glass column
Carrier gas — He
Temperature program — 115 °C, isothermal
MS: Mass range — 42-450 amu
Scan range — 2 s/sean ~ '
lonization — El, 70 eV
Criteria for Qualitative
Identification: As defined in Section VI.E.S.b. (of the
Methods Manual).
Criteria for Quantitative
Analysis: As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily.
Detection Limits: 5-20 ng of each compound injected on column
or 1-4 yg/m3 of each compound in a 5-m3
stack-gas sample,
0.25-1 pg/g of each compound in a 20-g
waste sample,
0.25-1 pg/g of each compound in a 20-g
ash sample.
245
-------
EXAMPLE 1. POHC ANALYSIS METHOD (continued)
References:
1. DiCorcia, A.; Samperi, R. Gas chromatographic determination of
glycolo at the parts-per-million level in water by graphitized
carbon black. Anal. Chem. 51(5): 776-778; 1979.
246
-------
EXAMPLE 2. POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (particulate)
Specific POHC from Appendix VIII
to which method may be applied: Epinephrine (3.4-Dihydroxy-cc-[(methylamine)-
methyl]benzyl alcohol) (C-5-C)
Sampling-Method Parameters:
Hardware:
Deployment:
Recovery Check:
References:
RAC or equivalent sampling train modified to include
sorbent module as shown in Figure 3
Filter — Glass-fiber filter
Sorbent — Alumina (pH 8.5)
Impinger reagent — 1% HC1 solution
Traverse and sample isokinetically as specified in
EPA Methods 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate
Spike fiFter/sorbent or impingers (or both)
before sampling with known quantity of
deuterated or fluorinated analog of target
compound.
247
-------
EXAMPLE 2. POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Desorption
Desorption of adsorbed compound with
0.5 M
Sorbent material (alumina), filter
Solid waste
Fly Ash
Bottom Ash
Epinephrine (3,4-Dihydroxy-a~[(methylamine)
methyl]benzyl alcohol) (C-5-C) ..
Standard solid/liquid extraction
248
-------
EXAMPLE 2. POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:. Analyte concentration
Basic Method: Evaporation
Matrix: Salt solution of epinephrine
Specific POHC from Appendix VIII
to which method may be applied: Epinephrine (3,4-Dihydroxy-a-[(raethylamine)-
methyl]benzyl alcohol) (C-5-C)
Sampling-Method Parameters Evaporate slowly in water bath
Recovery Check: Add epinephrine to appropriate acid
solution and evaporate by heating
in water bath
References:
249
-------
EXAMPLE 2: POHC ANALYSIS METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
Epinephrine (catechol amine)
LCEC, Derivatization/GC/MS, or GC/FID
1% HC1 extract of liquid and solid
organic waste and sorbent
1% HC1 wash solution of filter in
sampling train
1% HC1 impinger solution
Epinephrine ( 3,4-Dihydroxy-a- [.(methy lamine) -
methylJbenzyl alcohol) (C-5-C)
LCEC (Liquid chromatography with electro-
chemical detection) or GC/MS/DS (Finnigan
4000 or equivalent)
HPLC:
Column — yBondapak C (Waters Associates)
Mobile phase — 6.8 g NaAc, 100 mg EDTA, 1 g
heptanesulfonic acid in 1 L,
pH adjusted to 4.8 with 2 M HC1
Flow rate — 1 mL/min
Detector type — electrochemical detection
Injector temperature — 250 °C
Criteria for Qualitative
Identification:
Criteria for Quantitative
Analysis:
Detection Limits:
As defined in Section VI.E.3.b.
As defined in Section VI.E.3.c; at least
two calibration standards to be run daily.
Unspecified
250
-------
EXAMPLE 2. POHC ANALYSIS METHOD (continued)
References:
1. Goldstein, D.S., et al. Validity and .reliability of liquid
chromatography with electrochemical detection for measuring plasma
levels of norepinephrine and epinephrine in man. Life Sci. 28:
467-475; 1981. •
2. Mefford, I.N., et al. Determination of plasma catecholamines and
free 3,4-dihydroxyphenylacetic acid in continuously collected human
plasma by high performance liquid chromatography with electrochemical
detection. Life Sci. 28: 477-483; 1981.
3. Davis, G.C.; Kissinger, P.T.; Shoup, R.E. Strategies for
• determination of serum or plasma norepinephrine by reverse-phase
liquid chromatography. Anal. Chem. 53: 156-159; 1981.
251
-------
EXAMPLE 3: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Sampling-Method Parameters:
Hardware:
Modified .Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Filter or sorbent material (or both)
from stack sampler and solid waste
Thiols (Benzenethiol, Tetrachloromethane-
thiol', and Trichlorotnethanethiol) (C-5-A)
RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 3
Filter — Glass-fiber filter
Sorbent — XAD-2 resin
Impinger reagent —
Deployment: Traverse and sample isokinetically as specified in
EPA Methods 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate
Recovery check:
References:
Spike filter/sorbent before sampling with known
quantity of deuterated or fluorinated analog of
target compound.
252
-------
EXAMPLE 3. POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied: -
Extraction-Method Parameters:
Soxhlet extraction
Continuous 24-h extraction with methylene
chloride
Solid wastes
Fly ash
Bottom ash
Particulate/sorbent from comprehensive
sampling train
Thiols (Benzenethiol, Tetrachloromethane-
thiol, and Trichloromethanethiol) (C-5-A)
Apparatus — Fisher Catalog No. 09-556
or equivalent
Solvent — Methylene chloride, 200 mL
Time — 24-h extraction
Sample size — 20-200.g
253
-------
EXAMPLE 3: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Method Parameters:
Recovery Check:
References:
Extraction concentration
Kuderna-Danish
Solvent extract
Thiols (Benzenethiol, Tetrachloromethane-
thiol, and Trichloromethanethiol) (C-5-A)
Use Kuderna-Danish evaporative concentrator
with three-ball-Snyder column to reduce
extract volume to OO mL. Use micro Snyder
to concentrate further if necessary to meet
detection limits.
Add these compounds to appropriate volume .
of solvent and concentrate using procedures
applied to samples.
254
-------
EXAMPLE 3: POHC ANALYSIS METHOD
Method Number:
Method Name: Thiols
Basic Method: GC/FID or GC/MS
Matrix: Organic solvent extract
Liquid organic waste (neat or diluted)
Specific POHC from Appendix VIII
to which method may be applied: Thiols (Benzenethiol, Tetrachloromethane-
thiol, and Trichloromethanethiol) (C-5-A)
Apparatus: GC/FPD (gas chromatography with flame-
photometric detection) or GC/MS
Analysis-Method Parameters:
GC: Column — Fused-silica capillary, 30 m long, 0.25 mm ID
wall-coated with SE-52
Carrier gas — He at 25 cm/s at 100 °C
or
Column — Aluminum packed with 30% tritolyl phosphate on
Chromosorb P support
MS: Mass range — 42-450 amu
Scan range — 2 s/scan
lonization — El, 70 eV - '
Criteria for Qualitative
Identification: As defined in Section VI.E.3.b.
Criteria for quantitative
Analysis: As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily.
Detection Limits: 5-20 ng of each compound injected on column
or 1-4 yg/m3 of each compound in a 5-m3
stack-gas sample,
0.25-1 yg/g of each compound in a 20-g
waste sample,
0.25-1 pg/g of each compound in a 20-g
ash sample.
References:
1. Kremer, L.; Spicer, L.D. Gas chromatographic separation of hydrogen
sulfide, carbonyl sulfide and higher sulfur compounds with a single
pass system. Anal. Chem. 45(11): 1973.
255
-------
EXAMPLE 4: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Sampling-Method Parameters:
Hardware:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-irapinger)
Stack gas (vapor-phase material)
Aldehydes (Acetaldehyde, Crotonaldehyde,
Glycidylaldehyde, and Chloroacetaldehyde)
(C-4-C)
Deployment:
Recovery Check:
References:
RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 3
Filter •— Not. applicable
Sorbent — Not applicable
Impinger reagent — DNPH in 2 _N HC1, or 2,3,4,5,6-
pentachlorobenzylhydrazine, or
10% NaHS03 (Figure 4)
Traverse and sample isokinetically as specified in
EPA Methods 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate . - -
Spike impingers before sampling with
known quantity of deuterated or
fluorinated analog of. target compound.
256
-------
EXAMPLE 4: POHC SAMPLE-PREPARATION METHOD
Method Number;
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Derivatize with DNPH and extract with
CH2Cl2 and pentane
3-batch liquid-liquid phase extraction
Solid wastes (derivatized)
Fly ash (derivatized)
Impinger solution (DNPH, 2 N HC1")
Aldehydes (Acetaldehyde, Crotonaldehyde,
Glycidylaldehyde, and Chloroacetaldehyde)
(C-4-C)
Apparatus '•— Standard equipment
Solvent — Methylene chloride, 100 mL, and
ti-pentane, 100 mL
Time —
Sample size — 20-200 g
257
-------
EXAMPLE 4: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Method Parameters:
Recovery Checks:
References:
Extraction concentration
Kuderna-Danish
Solvent extracts
Aldehydes (Acetaldehyde, Crotonaldehyde,
Glycidylaldehyde, and Chloroacetaldehyde)
(C-4-C)
Use Kuderna-Danish evaporative concentrator
with three-ball-Snyder column to reduce
extract volume to <10 mL. Use micro Snyder
to concentrate further if necessary to mee't
detection limits.
Add compound of interest to appropriate
volume of solvent and concentrate using
procedures applied to samples.
258
-------
EXAMPLE 4: POHC"ANALYSIS METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
GC:
Aldehydes
Derivatization (DNPH) and HPLC/UV or
GC/ECD or GC/MS
Organic solvent extract of derivative
Liquid organic waste (neat or diluted)
(derivatized)
Aldehydes (Acetaldehyde, Crotonaldehyde,
Glycidylaldehyde, and Chloroacetaldehyde)
(C-4-C)
HPLC/UV (254 nm or.370 nm), GC/ECD (gas
chromatography with electron-capture
detection), or GC/MS/DS (Finnigan 4000
or equivalent)
HPLC:
MS:
Column — Fused-silica capillary, 30 m long, 0.25-mm ID
wall-coated with SE-52
Carrier gas — He at 25 cm/s at 100 °C
Temperature program — 25 °C, 2 min isothermal
25-150 °C_at 4 °C/min
Injector temperature — 200 °C
Column — Zorbax-ODS 1250 x 4.6-mm ID
75% CH3OH/25% H20)
Mass range — 42-450 amu
Scan rate — 2 s/scan
lonization — El, 70 eV
Criteria for Qualitative
Identification:
Criteria for Quantitative
Analysis:
As defined in Section VI.E.S.b-.
As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily,
259
-------
Detection Limits: 5-20 ng of each compound injected on column
or 1-4 ug/m3 of each compound in a 5-m3
stack-gas sample,
0.25-1 Pg/g of each compound in a 20-g
waste sample,
0.25-1 yg/g of each compound in a 20-g
ash sample.
References:
1. Kobayashi, K., et al. Gas chromatography determination of low-
molecular-weight carbonyl compounds in aqueous solution as their
c)-(2,3,4,5,6-pentafluorobenzyl) oximes. J. Chromatogr. 187: 413-17;
1980.
260
-------
EXAMPLE 5: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Sampling-Method Parameters:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (vapor phase material)
Phosphate and thiophosphate esters
(0,£-Dlethyl-S_-methylester phosphoro-
dithioic acid; C^-j3-Nitrophenylester,
£,(D-Diethyl phosphoric acid; CsO_-
Diethyl-0-(2-pyrazinyl)phosphoro-
thioa.te; Diisopropyl fluorophosphate;
Tetraethyldithio pyrophosphate; Tetra-
ethyl pyrophosphate; £,(),0-Triethyl
phosphorothioate; Tris(2,3-dibromo-
propyl)phosphate; Hexaethyl tetra-
phosphate; and Phosphorothioic acid-
C),()-dimethylester, 0-ester with N^N-
dimethyl benzene sulfonamide)
Hardware:
Deployment:
Recovery Check:
References:
RAC or equivalent sampling train modified to include
sorbent module as shown in Figure 3
Filter — Glass-fiber filter
Sorbent — XAD-2 resin
Impinger reagent — Water
Traverse and sample isokinetically as specified in
EPA Methods 1-5
Collect 5-m sample at approximately 0.75-ft3/min
sampling rate
Spike sorbent or impingers (or both) before
sampling with known quantity of deuterated
or fluorinated analog of target compound.
261
-------
EXAMPLE 5: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Soxhlet extraction
Continuous 24-h extraction with methylene
chloride
Solid wastes
Fly ash
Particulate (glass fiber filter)
Phosphate and thiophosphate esters
(£,0-Diethyl-S_-methylester phosphoro-
dithioic acid; 0_-p_-Nitrophenylester,
0,0-Diethyl phosphoric acid; 0,0-
Diethyl-0_-(2-pyrazinyl)phosphoro-
thioate; Diisopropyl fluorophosphate;
Tetraethyldithio pyrophosphate; Tetra-
ethyl pyrophosphate; C),0_,0-Triethyl
phosphorothioate; Tris(2,3-dibromo-
propyl)phosphate; Hexaethyl tetra-
phosphate; and Phosphorothioic acid-
£,0-dimethylester, 0-ester with N..N-
dimethyl benzene sulfonamide)
Apparatus — Fisher Catalog No. 09-556
or equivalent
Solvent — Methylene- chloride, 200 mL
Time — 24-h extraction
Sample size — 20-200 g
262
-------
EXAMPLE 5. POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Method Parameters:
Recovery Check:
References:
Extraction concentration*
Kuderna-Danish
Solvent extracts
Phosphate and thiophosphate esters
(0,(D-Diethyl-S^methylester phosphoro-
dithioic acid; ()-£-Nitrophenylester,
£,0-Diethyl phosphoric acid; £,0_-
Diethy !-()-(2-pyrazinyl) phosphoro-
thioate; Diisopropyl fluorophosphate;
Tetraethyldithio pyrophosphate; Tetra-
ethyl pyrophosphate; jD,(),()-Triethyl
phosphorothioate; Tris(2,3-dibromo-
propyl)phosphate; Hexaethyl tetra-
phosphate; and Phosphorothioic acid-
jD^O.-dimethylester, 0-ester with ^I^N,-
dimethyl. benzene sulfonaraide)
Use Kuderna-Danish evaporative concentrator
with three ball-Snyder column to reduce
extract volume to <10 mL. Use micro Snyder
to concentrate further if necessary to meet
detection limits.
Add compound of interest to appropriate
volume of solvent and concentrate using
procedures applied to samples.
^Volatile components like tetraethyl pyrophosphate will be lost in this
extract concentration procedure. Lower recoveries resulting in higher
detection limits might have to be accepted in this case.
263
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EXAMPLE 5: POHC ANALYSIS METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
Phosphate and thiophosphate esters
GC/AFID or FPD or GC/MS
Methylene chloride extract
Liquid organic waste (neat or diluted)
Phosphate and thiophosphate esters
(Cs()-Diethyl^S_-methylester phosphoro-
dithioic acid; 0-£-Nitrophenylester,
(),0-Diethyl phosphoric acid; £,£-
Diethyl-£-(2-pyrazinyl)phosphoro-
thioate; Diisopropyl fluorophosphate;
Tetraethyldithio pyrophosphate; Tetra-
ethyl pyrophosphate; (),
-------
EXAMPLE 6: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VII]
to which method may be applied:
Sampling-Method Parameters:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (particulate plus vapor phase
material)
Sulfates and sulfonates (Dimethyl sulfate,
Ethyl methanesulfonate, Methyl methane-
sulfonate) (C-4-E)
Hardware:
Deployment:
Recovery Check:
RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 3
Filter — Glass-fiber filter (acid washed)
Sorbent — XAD-2 resin, Porapak Q, or silica
gel
Traverse and sample isokinetically as specified
in EPA Methods 1-5
Collect 5-m3 sample approximately 0.75~ft3/min
sampling rate
Spike filter or sorbent (or both) before
sampling with known quantity of deuterated
or fluorinated analog of target compound.
References:
1. Lee, M.L.; Later, D.W.; Rollin, D.L.; Eatough, D.J.; Hansen, D.L.
Dimethyl and monomethyl sulfate: Presence in fly ash and airborne
particulate matter. Science 207: 186-188; 1980.
265
-------
EXAMPLE 6: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Soxhlet extraction
Continuous 24-h extraction with acetone
(glass-fiber filter and Porapak Q) or
water (glass-fiber filter and silica gel)
Solid wastes
Fly ash
Bottom ash
Particulate and sorbent from comprehensive
sampling train
Sulfates and sulfonates (Dimethyl sulfate,
Ethyl methanesulfonate, Methyl methane-
sulfonate) (C-4-E)
Apparatus — Fisher Catalog No. 09-556
or equivalent
Solvent — Acetone (Porapak Q as sorbent)
Water (silica gel as sorbent)
Time — 25-h continuous extraction
Sample size — 20-200 g
266
-------
EXAMPLE 6: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name: Extract concentration*
Basic Method: Kuderna-Danish
Matrix: Solvent extracts
Specific POHC from Appendix VIII
to which method may be applied: Sulfates and sulfonates (Dimethyl sulfate,
Ethyl methanesulfonate, Methyl methane-
sulfonate) (C-4-E)
Method Parameters: Use Kuderna-Danish evaporation concentrator
with three ball-Snyder column to reduce
extract volume to <10 mL. Use micro Snyder
to concentrate further if necessary to meet
detection limits.
Recovery Check: Add compounds of interest to appropriate
volume of solvent and concentrate using
procedures applied to samples.
References:
*0nly for the acetone extract,
267
-------
EXAMPLE 6: POHC ANALYSIS METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
GC:
Sulfates and sulfonates
GC/MS
Organic solvent extract
Water extract
Liquid organic waste
Sulfates and sulfonates .(Dimethyl sulfate,
Ethyl methanesulfonate, Methyl methane-
sulfonate) (C-4-E)
GC/MS/DS (Finnigan 4000 or equivalent)
MS:
Column — Fused-silica capillary, 3 m long, 0.25-mm ID,
wall-coated with SE-52
Carrier gas — He at 25 cm/s at 100 °C
Temperature program — 50 °C, 8 min isothermal
50-150 °C at 8 "C/min
Injector temperature — 150 °C
Mass range — 42-450 amu
Scan rate — 2 s/scan
lonization — El, 70 eV
Criteria .for Qualitative
Identification:
Criteria for Quantitative
Analysis:
Detection Limits:
As defined in Section VI.E.S.b.
As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily.
5-20 ng of each compound injected on column
or 1.4 yg/m3 of each compound in a 5-m3
stack-gas sample,
0.25-1 Mg/g of each compound in a 20-g
waste sample,
0.25-1 Mg/g of each compound in a 20-g
ash sample.
268
-------
EXAMPLE 7: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Sampling-Method Parameters:
Hardware:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (particulate plus vapor-
phase material)
Trifluoroacetic acid, Na salt (C-4-F)
Deployment:
Recovery Check:
References:
RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 3
Filter — Glass-fiber filter
Impinger reagent — 1% HNOa solution
Traverse and sample isokinetically as specified
in EPA Methods 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate
Spike filter or impingers (or both) before
sampling with known quantity of acetic acid
analog of target compound.
269
-------
EXAMPLE 7: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Solvent extraction
3-batch extraction with 1% HNO$
Solid wastes
Fly ash
Bottom ash
Particulate (glass-fiber filter)
Trifluoroacetic acid, Na salt (C-4-F)
Apparatus — Flask and wrist shaker
Solvent — 1% HNOs, 200 mL
Time — 3 x 0.25 h
Sample size — 20-200 g
270
-------
.EXAMPLE 7: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Method Parameters:
Recovery Check:
Purge and trap or steam distillation
Purge or steam distillation
1% HN03
Trifluoroacetic acid, Na salt (C-4-F)
Purging device, trap and desorber
(15 cm of Tenax-GC, 60/80 mesh)
Add trifluoroacetic acid to 1% HNOa
solution to appropriate volume and purge
and trap or steam distillation
References:
1. EPA Method 624 (purge and trap).
271
-------
EXAMPLE 7: POHC ANALYSIS METHOD
•Method Number:
Method Name: Trifluoroacetic acid
Basic Method Derivatization with £.-bromobenzyl bromide
and GC/ECD or MS
Matrix: Acidified water extract
Specific POHC from Appendix VIII
to which method may be applied: Trifluoroacetic acid, Na salt (C-4-F)
Apparatus: " GC/ECD or GC/MS/DS (Finnigan 4000 or
equivalent
Analysis-Method Parameters:
GC: Column — Fused-silica capillary column, 30 m long,
0.25-mm.ID, wall-coated with SE-52
Carrier gas — He at 7.5 cm/s at 100 °C (linear velocity)
Temperature program — 25 °C, 2 min isothermal
25-100 °C at 8 °C/min
Injector temperature — 200 °C
MS: Mass range — 42-450 amu
Scan rage — 2 s/scan
lonization — El, 70 eV
Criteria for Qualitative
Identification: As defined in Section VI.E.S.b.
Criteria for Quantitative
Analysis: As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily.
Detection Limits: <5 ng of derivative injected on column
<1 ug/m3 in a 5-m3 stack-gas sample
<0.25 Mg/g in a 20-g waste sample
<5 Mg/L in a 1-L scrubber water sample
<0.25 yg/g in a 20-g ash sample
References:
272
-------
EXAMPLE 8: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Sampling-Method Parameters:
Hardware:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (vapor-phase material)
Methyl methacrylate (C-4-D)
Deployment:
Recovery Check:
References:
RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 3
Sorbent — XAD-2 resin
Traverse and sample isokinetically as specified
in EPA Methods 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate
Spike sorbent before sampling with known
quantity of deuterated or fluorinated
analog of target compound.
273
-------
EXAMPLE 8: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Extraction-Method Parameters:
Soxhlet extraction
Continuous 24-h extraction with n-pentane
(CH2C12 will also be effective)
Solid wastes
Sorbent from comprehensive sampling train
Methyl methacrylate (c-4-D)
Apparatus — Fisher Catalog No. 09-556
or equivalent
Solvent — n-pentane, 200 mL
Time — 24-h extraction
Sample size — 20-200 g
274
-------
EXAMPLE 8: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name: Extract concentration*
Basic Method: Kuderna-Danish
Matrix: Solvent extracts
Specific POHC from Appendix VIII
to which method may be applied: Methyl methacrylate (C-4-D)
Method Parameters: Use Kuderna-Danish evaporative concentrator
with three ball-Snyder column to reduce
extract volume to <10 mL. Use micro Snyder
to concentrate further if -necessary to meet
detection limits.
Recovery Check: Add methyl methacrylate to appropriate
volume of solvent and concentrate using
procedures applied to samples.
References:
Lower temperatures should be used in this step because of the relatively
low boiling point of methyl methacrylate.
275
-------
EXAMPLE 8: POHC ANALYSIS METHOD
Metho'd Number:
•Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which methodjnay be applied:
Apparatus:
Analysis-Method Parameters:
GC:
Methyl raethacrylate
GC/FID, GC/MS
Organic solvent extract
Liquid organic waste (neat or diluted)
Gas grab' sample
Methyl methacrylate (C-4-D)
GC/FID, GC/MS/DS (Finnigan 4000 or equivalent)
Column — Fused-silica capillary, 30-m-long,
0.25-mm ID, with SE-52
Carrier gas — He at 25 cm/s at 100 °C
Temperature program — 50 °C, 8 min isothermal
50-150 °C at 8 °C/min
Injector temperature — 150 °C
MS: Mass range — 42-450 amu
Scan rate — 2 s/scan
lonization — IE, 70 eV
Criteria for Qualitative
Identification:
Criteria for Quantitative
Analysis:
Detection Limits:
Refert nces:
As defined in Section VI.E.3.b.
As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily.
5^20 ng of each compound injected on column
or 1-4 ug/m3 of each compound in a 3-m3
stack-gas sample,
0.25-1 Mg/g of each compound in a 20-g
waste sample,
0.25-1 ug/g of each compound in a 20-g
ash sample.
Rygle, K.G. Trace residual monomer analysis by capillary gas
chromatography. J. Coat. Technol. 52: 47-52; 1980.
276
-------
EXAMPLE 9: POHC SAMPLING METHOD
Method Number:
Method Name:
Basic Method:
Matrix: •
Specific POHC from Appendix VIII
to which method may be applied:
Modified Method 5 (MM5)
Comprehensive sampling train
(filter-sorbent-impinger)
Stack gas (particulate)
Carboxylic acids (l-£-chlorobenzyl)-5-
methoxyl-2-methylindone-3-acetic acid,
7-Oxabicyclo[2.2.1]heptane-2,3-dicar-
boxylic acid, 2,4-Dichlorophenoxyacetic
acid, 2,4,5-Trichlorophenoxyacetic acid,
and 2-(2,4,5-Trichlorophenoxy)propionic
acid)
Sampling-Method Parameters:
Hardware:
Deployment:
Recovery Check:
References:
RAC or equivalent sampling train modified to
include sorbent module as shown in Figure 3
Filter — Glass-fiber filter
Sorbent — Not applicable
Impinger reagent — Not applicable
Traverse and sample isokinetically as specified
in EPA Methods 1-5
Collect 5-m3 sample at approximately 0.75-ft3/min
sampling rate
Spike filter before sampling with known
quantity of deuterated or fluorinated
analog of target compound.
277
-------
EXAMPLE 9: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
Specific POHC from Appendix VIII
to which method.may be applied:
Extraction-Method Parameters:
Soxhlet extraction
Continuous 24-h extraction with diethyl
ether
Solid wastes
Fly ash
Bottom ash
Particulate from comprehensive sampling
train
Carboxylic acids (l-£-chlorobenzyl)-5-
methoxyl-2-methylindone-3-acetic acid,
7-Oxabicyclo[2.2.1]heptane-2,3-dicar- .
boxylic acid, 2,4-Dichlorophenoxyacetic
acid, 2,4,5-Trichlorophenoxyacetic acid,
and 2-(2,4,5-Trichlorophenoxy)propionic
acid)
Apparatus Fisher Catalog No. 09-556 or equivalent
Solvent — Methylene chloride, 200 mL
Time — 24-h extraction
Sample size — 20-200 g
278
-------
EXAMPLE 9: POHC SAMPLE-PREPARATION METHOD
Method Number:
Method Name: Extract concentration
Basic Method: Kuderna-Danish
Matrix: Solvent extracts
Specific POHC from Appendix VIII Carboxylic acids u-£-chlorobenzyl)-5-
to which method may be applied: methoxyl-2-methylindone-3-acetic acid,
7-Oxabicyclo[2.2.1]heptane-2,3-dicar-
boxylic acid, 2,4-Dichlorophenoxyacetic
acid, 2,4,5-Trichlorophenoxyacetic acid,
and 2-(2,4,5-Trichlorophenoxy)propionic
acid)
Method Parameters: Use Kuderna-Danish evaporative concentrator
with three ball-Snyder column to reduce
extract volume to <10 mL. Use micro Snyder
to concentrate further if necessary to meet
detection limits.
Recovery Check: Add components of this group (C-4-A) to
appropriate volume of solvent and concen-
trate using procedures applied to samples.
References:
279
-------
EXAMPLE 9: POHC ANALYSIS METHOD
Method Number:
Method Name:
Basic Method:
-Matrix:
Specific POHC from Appendix VIII
to which method may be applied:
Apparatus:
Analysis-Method Parameters:
Carboxylic acids
Derivatization* GC/ECD or GC/MS
Diethyl ether extract
Liquid organic waste (neat or diluted)
Carboxylic acids (l-£-chlorobenzyl)-5-
methoxyl-2-methylindone-3-acetic acid,
7-Oxabicyclo[2.2.1]hep tane-2,3-dicar-
boxylic acid, 2,4-Dichlorophenoxyacetic
acid, 2,4,5-Trichlorophenoxyacetic acid,
and 2-(2,4,5-Trichlorophenoxy)propionic
acid)
GC/ECD or GC/MS/DS (Finnigan 4000 or
equivalent)
GC:
MS:
Column — Fused-silica capillary, 30 m long,
0.25-mm ID, wall-coated with SE-52
Carrier gas — He at 25 cm/s at 100 °C (GC/MS)
5%.methane in argon
Temperature program — 40 °C, 2 min isothermal
40-250 °C at 20 °C/min
Injector temperature — 250 °C
Mass range — 42-450 amu
Scan rate — 2 s/scan
lonization — El, 70 eV
Criteria for Qualitative
Identification:
Criteria for Quantitative
Analysis:
As defined in Section VI.E.3.b.
As defined in Section VI.E.3.C.; at least
two calibration standards to be run daily,
'Derivatization with either diazomethane or an extractive alkylation
procedure is necessary to form the ester.
280
-------
EXAMPLE 9. POHC ANALYSIS METHOD (continued)
Detection Limits: 5-20 ng of each compound injected on column
or 1-4 pg/m3 of each compound, in a 5-m3
stack-gas sample,
0.25-1 yg/g of each compound in a 20-g
waste sample,
0.25-1 yg/g of each compound in a 20-g
ash sample.
References:
1. ASTM Method D3478-79, Chlorinated phenoxy acid herbicides in water.
2. Plazonnet, B.; Vandenheuval, W.J.A. Preparation, gas chromatography
and mass spectrometry of methyl and trimethyl silyl esters in
indomethacin. J. Chromatogr. 142: 587-596; 1977.
3. Ferry, D.G., et al. Indomethacin estimatioN IN plasma and-serum by
electron capture gas chromatography. J. Chromatogr. 89: 110-112;
1974.
4. Arbin, A. Three alkylation methods for the detemrination of
indomethacin in plasma by electron capture gas chromatography. J.
Chromatogr. 144: 85-92; 1977.
5. Jensen, J.M. Detemrination of indomethacin in serum by an extractive
alkylation tyechnique and gas-liquid chromatography. J. Chromatogr.
153: 195-202; 1978.
281
-------
In laboratory work performed,after the compilation of these proposed meth-
ods, we at SoRI developed several analysis methods that are believed to be more
suitable than the corresponding proposed procedures. For example, an HPLC/UV
analysis method was developed for the determination of phenoxyacetic acids that
does not require the derivatization step of the GC/MS technique proposed in
Table D-l. Many of the proposed analysis methods and all of the proposed sam-
pling procedures, however, still represent viable techniques that should be
considered for inclusion of the revised Methods Manual.
REVISION OF THE GENERAL SAMPLE DIGESTION PROCEDURE AND SPECIFIC
ANALYSIS METHODS FOR THE DETERMINATION OF METALS
An editorial and technical revision of sample operation and analysis meth-
ods for metals was undertaken as a refinement of those procedures given in the
Methods Manual. The resulting recommended revisions are present on pages 283
through 287. Comments on the digestion and specific analysis procedures are
given initially. Following these comments, revised methods, which include many
of the suggested changes, are given on pages 288 through 302 for antimony,
arsenic, barium, beryllium, cadmiun, chromium, lead, nickel, selenium,
strontium, silver, thallium, and vanadium.
EVALUATION OF DIGESTION AND ANALYSIS PROCEDURES FOR BERYLLIUM,
STRONTIUM, AND VANADIUM
The general digestion procedure delineating the preparation of water,
sludge, and solid samples for the subsequent determination of metals had not
previously been verified for beryllium, strontium, and vanadium. Consequently,
soil and water samples were spiked with salts of these metals and subjected to
the digestion procedure.
282
-------
GENERAL SAMPLE DIGESTION PROCEDURES
1. Pg VI-51 "Alicuots (100 g or 100 ml) from well mixed field samples... will
be used for the analysis of metals".
A. The methods cited state to use 3 ml of concentrated nitric acid on the
100 g of sample. If the sample is primarily solid, 3 ml of acid will
not wet the sample and will not adequately digest the sample. A smaller
aliquot (5-10 g) should be taken for samples that are primarily solids.
The referenced cited (SW-846) does state that 100 g or 100 ml aliquots
should be used for As, Cd, Ni, and Se. .These methods should be corrected
for cases where high solids samples are to be analyzed.
2. Pg VI-51 "Thorium (Th)"
A. I believe that thallium (Tl) should be. listed here in place pf thorium
(Th) . Thallium is a priority pollutant metal and is listed under RCRA,
whereas thorium is not. Furthermore, the individual methods included
in the manual include one for thallium, but not for thorium.
3. Pg VI-51 "Most samples will be prepared for analysis by general HN03 diges-
tion procedures as specified in the methods for each metal in SW-846,
section 8, methods 8.50 to 8.60".
A. No method exists in SW-846 for beryllium, osmium, strontium, thallium
(see No. 2) or vanadium, thus this reference is incomplete.
E. The methods given in SW-846 for arsenic and selenium involve HNO,- ^02
digestion, not just nitric acid.
4. Pg VI-51 "Pesticide waste samples containing high levels of organic materials,
such as oil, greases or waxes, will be prepared by dissolving the sample in
an appropriate organic solvent or digesting the sample in nitric acid,
sulfuric acid, hydrogen peroxide, and hydrochloric acid as specified in
SW-846, Section 8, pages 8.49-7 to 8.49-11".
A. As stated in SW-846, pages 8.49-7 to 8.49-11. .The
digestion is appropriate for As, Se, Hg, Cr, Cd, Ba, Pb, and Ag. If
a precipatate forms, special precautions are required for Ba, Pb, and
(continued)
283
-------
Ag since the formation of BaSO^,. PbSO^, or AgCl can occur if the cation
concentrations are high enough to exceed the solubility product con-
stant. However, this procedure is not listed for analysis of antimony,
beryllium, nickel, osmium, strontium, thallium (see No. 2), or vanadium.
Thus, no method is provided for analysis of these elements in samples
containing high levels of organics.
5. Pg VI-51 "Other sample preparation procedures are given in the references".
A. The only reference given is to "Methods for Chemical Analysis of Water
and Wastes", EPA-600/4-79-0200 (March 1979). These methods are not
applicable, in general, to samples containing high levels of organic
material.
INDIVIDUAL METHODS OF.ANALYSIS
1. Pg VI-139, Antimony
A. Under apparatus, hydride generator should be included since antimony
forms a hydride and this is a very sensitive method for antimony
analysis.
B.. Under AA wavelength, either 206.8 nm or 231.1 nm should be specified •
as alternate wavelengths if high concentrations of lead are present
since the lead line at 217.0 nn can interfere.
C. Background correction should be required for graphite furnace analysis.
D. For complex samples, the method of standard additions should be re-
quired for graphite furnace analysis.
E. From personal experience, the HN03 digestion does not provide quanti-
tative recovery of spikes in many cases. We have had much better luck
using the HN03-H202 digestion specified for arsenic and selenium.
F. The ICAP detection limits can be improved dramatically if hydride gen-
eration—ICAP is used.
G. References are missing.
2. Pg VI-141, Arsenic
A. There are many ways to form a hydride other than using SnCl2 and zinc
metal. The most common method is to add NaBH^. Other methods should
be included, if one is being specified.
B. The ashing temperature of 1100°C for arsenic should only be ussd if
nickel has been added to the sample to prevent atomization of arsenic.
This step should be included in the method write-up.
(continued)
284
-------
C. Arsenic can be analyzed by ICAP, and this method should be included,
along with the corresponding detection limits and working range.
D. Hydride generation—ICAP can also be used for arsenic.
E. Background correction is required for graphite furnace work.
. F. For complex samples, the method of standard additions should be re-
quired for graphite furnace analysis.
3. Pg VI-143, Barium
A. Background correction may prove useful in graphite furnace analysis,
if appropriate background corrector is available at 553.6 rim (Tungsten
Iodide lamp).
B. The method of standard additions is required for complex samples when
using graphite furnace analysis.
C. References are missing.
4. Pg VI-145, Beryllium
A. Background correction and standard additions is required for graphite
furnace work.
B. References are missing.
5. Pg VI-147, Cadmium
A. Same as 4A.
B. Reference 3, to ARL product literature, is inappropriate, particularly
since no indication is given as to what information was taken from
that source.
6. Pg VI-148, Chromium and Pg VI-153, Nickel
A. Same as 4A.
B. Same as 5B.
7. Pg VI-149, Lead
A. Same as 4A.
B. References are missing.
C. Lead can be determined by hydride generation—ICAP with detection limits
approximately one,-tenth of direct aspiration ICAP.
(continued)
285
-------
6. Pg VI-151, Mercury
A. Mercury can be determined by hydride generation ICAP with a detection
limit of approximately 2 vg/£. It does not form a hydride, but can be
reduced to the elemental form with NaBH^.
9. Pg VI-155, Osmium
A. Same as AA.
B. References required.
10. Pg VI-157, Selenium
A. There are many ways to form the hydride other than SnCl2-Zinc. Other
options should be specified.
B. The ashing temperature of 1200°C can only be used if nickel has been
added to the samples to prevent atomization of selenium. This step
should be included in the method write-up.
C. Selenium can be analyzed by ICAP, and this method should be included,
along with the corresponding detection limits and working range.
D. Hydride generation—ICAP can also be used for selenium.
E. For complex samples, background correction and standard additions
should be required for graphite furnace analysis.
F. References required.
11. Pg VI-159, Silver
A. Silver does not form a hydride, thus listing a hydride generator under
apparatus is incorrect.
B; Same as AA.
C. References required.
12. Pg VI-161, Strontium
A. Strontium does not form a hydride, thus no hydride generation should
be listed under apparatus.
B. Same as AA.
C. Same as 5B.
(continued)
286
-------
13. ?g VI-162i Thallium
A. Thallium does not form a hydride, thus no hydride generator should be
listed under apparatus.
B. Same as 4A.
C. Same as 5B.
D. Under furnace parameters, dry temperature is given as 1250°C, should
be 125eC. . •
14. Pg VI-164, Vanadium
A. Vanadium does not form a hydride, thus no hydride generator should be
listed, under apparatus.
£. Same as 4A.
C. References required.
The following pages correspond to the pages in the Methods Manual discussed in
the previous editorial and technical comments; appropriate revisions have been made
or indicated.
287
-------
Page VI-51
Method "Nuab'er: P032
hathoc Naae: Digestion Procedures for Metals
Basic Method: Acid Digestion
Matrix: Aqueous
Sludge
Solid
Specific POHC/PIC from Appendix VIII to which the method nay be applied:
Antimony (Sb)
Arsenic (As)
Bariiia (Ba)
Beryllium (Se)*
Caesium (.Cd)
__ Chromium (.Cr)
"Lead (Pb)
Mercury (Hg)
Nickel (Mi)
Osmium (.Qs)
Selenium (Se)
Silver (Ag)
Strontium (Sr)*
Thallium (Tl)*
Vanadium (V)*
Method Parameters:
Aliquots (lOOg or 100 mL or 5-10 g if sample is primarily solid)
from veil mixed field samples (Methods P001-P003; wastewater,
sludge, and solids) will be used for the analysis of metals.
Most samples will be prepared for analysis by general EN03 digestion
procedures as specifed in the methods for Sb, Ba, Cd, Cr, Pb, Hg, Ni,
and Ag in SW-846, Section 8, Methods 8.50 to 8.60 and by Hl^-^C^
for As, Se, and Sb. Pesticide waste samples containing high levels
of organic materials, such as oil, greases or waxes will be.
prepared by dissolving the sample in an appropriate organic solvent
or digesting the sample in nitric acid, sulfuric acid, hydrogen
peroxide and hydrochloric acid as specified in SW-846, Section 8,
pages 8.49-7 to 8.49-11. Special precautions, however, should be
taken if BaSOA, PbSO^, or AgCl precipitated.
These elements were not included in Method SW-846 list. However, Che
method was found to be applicable to them based on work in Battelle
laboratories.
288
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Page VI-39
Method Number: A221
Method Name: Antimony
Basic Method: Atomic Spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber waters
Specific POHC/PIC from Appendix VIII to which method may be applied:
Antimony
Antimony Compounds N.O.S.
Apparatus: ICAP Spectrometer
AA Spectrometer with burner and graphite furnace
Hydride generator
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of solution
Analytical Wavelengths - 206.8 and 187.1 nm
AA: Analytical Wavelength - 217.6 nm
206.8 nm or 231.1 nm if Pb is present
at high concentration
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 800°C for 30 sec
Atomize @ 2700°C for 10 sec
Argon gas purge
Background correction
Flame Conditions - Air - acetylene flame
flue lean
Detection Limits and Typical Working Range:
ICAP: 0.1 mg/L; 0.5-100 mg/L and less if hydride generator
is used
Furnace AA: 3 ug/L; 20-300 ug/L
Flame AA: 0.2 mg/L; 1-40 mg/L
289
-------
Page VI-1A1
Method Number: A222
Method Name: Arsenic
Basic Method: Atomic Spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
'Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Arsenic
Arsenic compounds N.O.S.
Arsenic acid
Arsenic pentoxide
Arsenic trichloride
Benzene arsonic acid
Dichloro phenyl arsine
Diethy1 arsine
Apparatus: AA spectrophotometer
Hydride generator
Graphite furnace
Analysis Method Parameters:
AA: Analytical Wavelength - 193.7 nm
Hydride Generation:
In generator add SnCl2 to form trivalent arsenic, then
add zinc metal to form hydride. NaBH^ can also be used
to generate the hydride.
Flame Conditions - Argon - hydrogen flame
Furnace Parameters - Dry @ 125°C for 30 sec
Ash @ 1100°C for 30 sec (if nickel has been
added to prevent atomization of arsenic)
Atomize @ 2700°C for 10 sec
Argon purge
Background correction
290
-------
Page VI-143
Method Number: A223
Method Name: Barium
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Barium
Barium compounds N.O.S.
Apparatus: ICAP spectrometer
AA spectrometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of solution
Analytical Wavelength - 455.4, 233.5 nm
AA:. Analytical Wavelength - 553.6 nm
Furnace Parameters - Dry 1258C - 30 sec
Ash 1200°C - 30 sec
Atomize 2800°C - 10 sec
Argon purge gas
Background correction (Tungsten Iodide lamp)
Flame Conditions - Nitrous oxide - acetylene
Fuel rich
Detection Limits:
ICAP: 2 ug/L; 0.010-10 mg/L
Furnace: 2 ug/L; 10-200 ug/L
Flame AA: 0.1 mg/L; 1-20 mg/L
291
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Page VI-145
Method Number: A224
Method Name: Beryllium
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Beryllium
Beryllium compounds N.O.S.
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters: . ,
ICAP: Sample input via direct aspiration of solution
Analytical Wavelengths - 313.0, 234.9 nm
- AA: Analytical Wavelength - 234.9 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 1000°C - 30 sec
Atomize 2800°C - 10 sec
Argon purge gas
Background correction
Flame Conditions - Nitrous oxide - acetylene
Fuel rich
Detection Limits:
ICAP: 0.5 vg/L; 0.005-5 mg/L
Furnace AA: 0.2 ug/L; 1-30 ug/L
Flame AA: 5 ug/L; 0.05-2 mg/L
292
-------
Page VI-47.
Method Number: A225
Method Name: Cadmium
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Cadmium
Cadmium compounds N.O.S.
Apparatus:
Analysis Method Parameters:
ICAP: Sample input via direct aspiration of solution
Analytical Wavelength - 226.5, 214.4 nm
AA: Analytical Wavelength - 228.8 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 500°C - 30 sec
Atomize 1900°C~- 10 sec
Argon purge gas
Background correction
Flame Conditions - Air - acetylene
Oxidizing
Detection Limits:
ICAP: 0.02 mg/L; 0.1-20 mg/L
Furnace AA: 0.1 yg/L; 0.5-10 pg/L
Flame AA: 5 pg/L; 0.05-2 mg/L
References:
1. U.S. Environmental Protection Agency, "Test Methods for
Evaluating Solid Waste - Physical/Chemical Methods,"
Report No. SW-846 (1980).
2. U.S. Environmental Protection Agency, "Methods for Chemical
Analysis of Water and Wastes," EPA-600/4-79-020 (March 1979),
293
-------
Page VI-148
Method Number: A226
Method Name: Chromium
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Chromium
Chromium compounds N.O.S.
Calcium chrornate
Apparatus: ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelength - 267.7, 294.9 nm
AA: Analytical Wavelength - 357.9 nm
Furnace Parameters - Dry 125°C --30 sec
Ash 1000°C - 30 sec
Atomize 2700°C - 10 sec
Argon purge gas
Background correction
Flame Conditions - Nitrous oxide - acetylene
Fuel rich
Detection Limits:
ICAP: 0.05 mg/L; 0.2-50'mg/L
Furnace AA: 1 pg/L; 5-100 pg/L
Flame AA: . 0.05 mg/L; 0.5-10 mg/L
References:
1. U.S. Environmental Protection Agency, "Test Methods for
Evaluating Solid Waste - Physical/Chemical Methods,"
Report No. SW-846 (1980).
2. U.S. Environmental Protection Agency, "Methods for Chemical
Analysis of Water and Wastes," EPA-600/4-79-020 (March 1979).
294
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Page VI-149
Method Number: A227
Method Name: Lead
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Lead
Lead compounds N.O.S.
Lead acetate
Lead phosphate
Lead subacetate
Tetraethyl lead
Apparatus: • ICAP spectrophotometer
AA spectrophotometer with burner and graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 220.3, 217.0 nm
AA: Analytical Wavelength - 217.0 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 500°C - 30 sec
Atomize - 2700°C - 10 sec
Argon purge gas
Background correction
Flame Conditions - Acetylene - air
Oxidizing
Detection Limits:
ICAP: 0.1 mg/L; 1-100 mg/L
Furnace AA: 1 ug/L; 5-100 ug/L
Flame AA: 0.1 mg/L; 1-20 mg/L
295
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Page VI-153
Method Number: A229
Method Name: Nickel
Basic Method: Atomic spectroscopy
Matrix: . Solid and liquid wastes
Solid effluents
Scrubber water
Specific POHC/PIC from Appendix VIII to which method may be applied:
Nickel
Nickel compounds N.O.S.
Nickel carbonyl
Apparatus: AA spectrophotometer with burner and graphite furnace
ICAP spectrophotometer
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelengths - 231.6, 227.0 nm
AA: Analytical Wavelength - 232.0 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 900°C - 30 sec
Atomize - 2700°C - 10 sec
Argon purge gas
Background correction
Flame Conditions - Air - acetylene
Oxidizing
296
-------
Page VI-157
Method Number: A231
Method Name: Selenium
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber waters
Specific POHC/PIC from Appendix VIII to which method may be applied:
Selenium
Selenium compounds N.O.S.
Selenious acid
Selenium sulfide
Selenourea
Apparatus: AA spectrometer with graphite furnace
Hydride generator
Analysis Method Parameters: •
AA: Analytical Wavelength - 196.0 nm
Hydride Generation:
Reduction with SnCl2 or
Zinc metal added to drive off hydride.
Flame - argon - hydrogen
Furnace Parameters - Dry 125°C - 30 sec
Ash 1200°C - 30 sec
Atomize 2700°C - 10 sec
Argon purge gas
Background correction
Detection Limits:
Hydride Generation - <1 ug/L; 2-20 ug/L
Furnace AA - 2 ug/L; 5-100 ug/L
297
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Page VI-159
Method Number: A232
Method Name: Silver
Basic Method: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber waters
Specific POHC/PIC from Appendix VIII to which method may be applied:
Silver
Silver compounds N.O.S.
Apparatus: AA spectrometer with graphite furnace
Analysis Method Parameters:
ICAP: Direct aspiration of sample solution
Analytical Wavelength - 328.1, 224.6 no
AA: Analytical Wavelength - 328.1 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 400°C - 30 sec
Atomize 2700°C .- 10 sec
Argon purge
Background correction
Flame Conditions - Acetylene - air
Oxidizing
Detection Limits:
ICAP: 0.01 mg/L; 0.1-50 mg/L
Furnace AA: 0.2 ug/L; 1-25 ug/L
Flame AA: 0.01 mg/L; 0.1-4'mg/L
298
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Page VI-161
Method Number: A233
Method Name: Strontium
Basic Method: Atomic-.spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber waters
Specific POHC/PIC from Appendix VIII to which method may be applied:
Strontium sulfide
Apparatus: AA spectrometer with graphite furnace
Analysis Method Parameters:
ICAP: Analytical Wavelengths - 407.8, 346.4 nm
AA: Analytical Wavelength - 460.7 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 10008G - 30 sec
Atomize 2500°C - 10 sec
Argon purge gas
Background -correction
Flame Conditions - Nitrous oxide/acetylene flame
Fuel lean
Detection Limits:
ICAP: 2 yg/L; 0.05-10 mg/L
Furnace AA: .2 yg/L; . 4-+20 yg/L
Flame AA: .08 mg/L; .2+5 mg/L
References:
1. U.S. Environmental Protection Agency, "Test Methods for
Evaluating Solid Waste - Physical/Chemical Methods,"
Report No. SW-846 (1980).
2. U.S. Environmental Protection Agency, "Methods for Chemical
Analysis of Water and Wastes," EPA-600/4-79-020 (March 1979)
299
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Page VI-169
POHC/PIC ANALYSIS METHOD
Method Number:
Method Name:
Basic Method:
Matrix:
A234
Thallium .
Atomic Spectroscopy
Solid and liquid wastes
Solid effluents
Scrubber waters
Specific'POHC/PIC from Appendix VIII to which method may be applied:
Thallium
Thallium compound, NOS
Thallic oxide
Thallium(I)acetate
Thallium(I)carbonate
Thallium(I)chlo rid e
Thallium(I)nitrate
Thallium selenite .
Thallium(I)sulfate
Apparatus:
AA spectrometer with graphite furnace
Analysis Method Parameters:
ICAP: Analytical Wavelengths --190.9, 351.9 nm
AA: Analytical Wavelength - 276.8 nm
Furnace Parameters - Dry 125°C - 30 sec
Ash 400°C - 30 sec
Atomize 2400"C - 10 sec
Argon purge gas
Background correction
Flame Conditions - Air - acetylene
Oxidizing
300
-------
Page VI-163
Detection Limits:
ICAP: 0.1 ng/L; 1-100 mg/L
Furnace AA: 1 ug/L; 5-100 ug/L
Flame AA: 0.1 mg/L; 1-20 mg/L
References:
1. U.S. Environmental Protection Agency, "Test Methods for
Evaluating Solid Waste - Physical/Chemical Methods,"
Report No. SW-846 (1980).
2. U.S. Environmental Protection Agency, "Methods for Chemical
Analysis of Water and Wastes," EPA-600/4-79-020 (March 1979)
301
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Page VI-164
Method Number: • A235
Mechod Name: Vanadium •
Basic Mechod: Atomic spectroscopy
Matrix: Solid and liquid wastes
Solid effluents
Scrubber waters
Specific POHC/PIC from Appendix VIII to which method may be applied:
Vanadic acid, ammonium salt
Vanadium pentoxide
Apparatus: AA spectrometer with graphite furnace
Analysis Method Parameters:
ICAP: Analytical Wavelengths - 309.3, 214.0 nm
.AA: Analytical Wavelengths - 318.4 nm
Furnace Parameters.- Dry 125°C - 30 sec
Ash 1400°C - 30 sec
Atomize 2800°C - 15 sec
Argon purge gas
Background correction
Flame Conditions - Nitrous oxide - acetylene
Fuel rich
Detection Limits:
ICAP: 0.01 mg/L; 0.1-150 mg/L
Furnace AA: 4 ug/L; 10-200 ug/L
Flame AA: 0.2 mg/L; 2-100 mg/L
302
-------
Digestion Procedure for Metals in Water
Transfer 250 mL of Che well-mixed acid-preserved sample Co a Griffin
beaker. Add 3 mL of concenCraCed HN03- Place Che beaker on a hoc plate and
evaporaCe Co approximately 5 mL cautiously, making cerCain Chat Che sample does
not boil. Cool the beaker with a watch glass and return to the hot plaCe.
Increase the temperature of the hot plate so that a gentle reflux action
occurs. Continue heating, adding addicional acid as necessary, uncil Che
digesCion is compleCe (generally indicaCed when Che digestate is lighc in color
or does not change in appearance with continued refluxing.) Again, evaporate
to near dryness (1 to 2 mL) and cool the beaker. Add 1.5 mL of concentrated
HC1 and 5 mL of deionized, distilled water and warm the beaker gently for
15 rain to dissolve and precipitate or residue resulting from evaporation.
Allow to cool, wash down the beaker walls and watch glass with deionized, dis-
tilled water, and filCer the sample to remove insoluble material that could
clog the nebuliz.er. Dilute to a final volume of 25 mL in a volumetric flask
with deionized, distilled water. The sample is now ready for analysis.
Aspirate the sample and calibration standards into the ICAP following the manu-
facturer's recommendations. Calibrate the instrument with calibration
standards and set readout for direct output of concentration units. Analyze
samples and the method blank (a distilled-water blank taken through the entire
procedure above for the samples). Concentrations so determined shall be
reported as "total."
Digesti-on Procedure for Metals in Soil
Weigh out 5.00 g of the dried soil sample into a 150-mL beaker. Add 10 mi.,
of deionized, distilled water and 5.0 mL of concentrated nitric acid. Digest
on a hot plate at 90 °C fir 3 h (do not boil). Filter into a 50-mL volumetric
flask through White Ribbon 589 paper, with pulp, and wash and dilute to volume
with deionized, distilled water. Shake well and remove a 5-mL aliquot, placing
the aliquot in another 50-mL volumetric flask. Add 4.5 mL of concentrated
nitric acid and dilute to the mark with deionized, distilled water. The sample
is now ready for analysis. Aspirate the samples and calibration standards into
the ICAP following the manufacturer's recommendations. Calibrate the instru-
ment with calibration standards and set to readout for direct output of concen-
tration units. Analyze samples and the method blank (a distilled-water blank
taken through the above acid digestion).
The results obCained wich Che digesCion and analysis procedure are pre-
sented in Tables D-2 and D-3. In general, the results obtained with spiked
,/ater samples were accurate and precise except for occasional high values
obtained with the unspiked water samples. The resulCs of the analysis of the
soil samples were generally precise, but were biased by high responses to
unspiked samples. Presumably the unspiked soil samples contained measurable
quantities of the three metals. These blank responses were especially high for
vanadium determinations. After correction for the average response to unspiked
soil samples, the determinations of beryllium and strontium were generally
acceptable, with recoveries ranging from 89 to 100%. The recoveries of vana-
dium calculated afcer correccion for Che blank responses were less accurate and
ranged from 70 to 87%.
303
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TABLE D-2. EVALUATION OF RECOMMENDED DIGESTION AND ANALYSIS
PROCEDURES FOR BERYLLIUM, STRONTIUM, AND
VANADIUM IN SPIKED WATER SAMPLES
Test
concn,
Element Mg/L
Be 0.
5.
10.
20
50
100
Sr 0.
5.
10.
20
.50
100
V . 0.
5.
10.
20
50
100
0
0
0
0
0
0
0
0 .
0
Observed
specified
0
4
9
20
49
99
1
4
9
19
48
95
0
5
9
19
47
93
1
.0
.8
;8
.2
.8
.6
.0
.3
.5
2
0.0
4.9
9.9
20
51
100
0.1
4.8
9.7
19
50
98
0.0
4.7
9.5
20
50
98
concn for
sample,3 pg/L
3
0.0
4.8
9.4
19
49
95
0.1
4.8
9.6
19
50
96
0.0
4.4
9.0
19
48
95
4
0.2
4.8
9.9
20
51
100
3.0
5.7
11.0
21
51
100
3.1
.5.8
11.0
21
50
99
Avg observed
concn," Mg/L
0
4
9
20
50
99
1
5
10
' 20
50
97
0
5
9
20
49
96
.0
.8
.8
.1 .
.0
.0
.8
.1
.8
RSD,
ey
1.
2.
2.
2.
2.
9.
6.
5.
2.
2.
12.
8.
4.
3.
2.
0
4
5
3
4
0
9
1
5
3
4
9
8
1
9
Avg
Recovery ,
—
96
98
100
100
99
—
100
100
100
100
97
—
102
98
100
98
96
Results have not been corrected for responses to unspiked water samples.
[(Avg observed concn)/(test concn)] x 100.
304
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TABLE D-3. EVALUATION OF RECOMMENDED DIGESTION AND ANALYSIS
PROCEDURES FOR BERYLLIUM, STRONTIUM, AND
VANADIUM IN SPIKED SOIL SAMPLES
Element
Be
Sr
V
Test
concn,
yg/L
0.0
5.0
10.0
20
50
100
0.0
5.0
10.0
20
50
100
0.0
5.0
10.3
20
50
100
Observed concn for
specified sample, a ug/L '
1
1.3
5.9
10.0
20
48
96
13
18
22
31
60
100
57
61
63
70
99
140
2
1.2
5.8
10.0
20
48
95
13
17
22
31
60
110
57
62
66
72
100
150
3
1.5
6.0
. .11.0
20
49
97
13
17
22
30
62
100
57
59
63
69
93
.,140
4
1.4
5.9
10.0
20
49
95
14
18
24
32
61
110
54
58
64
68.
98
140
Avg observed
concn, yg/L
1.4
5.9
10.3
20
49
96
13 -"
18
22
31
61
108
56
60
64
70
98
143
RSD,
9.6
1.4
4.5
0.0
1.2
1.0
3.8
3.3
4.4
2.6
1.6
4.5"
2.7
3.0
2.2
2.4
3.2
3.5
Avg
recovery,
-
90
89
93
95
95
- —
100
90
90
96
95
—
80
80
70
83
87
Results have not been corrected for responses to unspiked soil samples.
[(Avg observed concn)/(test concn)] x 100. This value has been corrected for
the responses to the unspiked soil samples.
305
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