December 1988
SINGLE-LABORATORY EVALUATION
OF METHOD 8120
CHLORINATED HYDROCARBONS
by
Viorica Lopez-Avila, Nikhil Shah Dodhiwala,
and June Milanes
Acurex Corporation
Environmental Systems Division
485 Clyde Avenue
P.O. Box 7044
Mountain View, California 94039
EPA Contracts 68-03-3226, 68-03-3511
Project Officer
Dr. Werner F. Beckert
Quality Assurance Division
Environmental Monitoring Systems Laboratory
944 East Harmon Avenue
Las Vegas, Nevada 89193-3478
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89193-3478
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December 1988
SINGLE-LABORATORY EVALUATION OF
METHOD 8120 — CHLORINATED HYDROCARBONS
by
Vlorica Lopez-Av 11 a, N1kh1l Shah Dodhlwala,
and June M1lanes
Acurex Corporation
Environmental Systems Division
485 Clyde Avenue
P.O. Box 7044
Mountain View, California 94039
EPA Contracts 68-03-3226, 68-03-3511
EPA Project Officer: Dr. Werner F. Beckert
U.S. Environmental Protection Agency
Environmental Monitoring Systems Laboratory
944 East Harmon Avenue
Las Vegas, Nevada 89109
ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
LAS VEGAS, NEVADA 89109
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PREFACE
This 1s the final report for Work Assignments 2-13 and 3-15, EPA
Contracts No. 68-03-3226 and 68-03-3511, entitled, "Single-Laboratory
Evaluation of Method 8120 — Chlorinated Hydrocarbons," conducted at Acurex
Corporation, Project Nos. 8006 and 8008. These projects were directed by Dr.
V1or1ca Lopez-Avlla.
This report was written by Dr. V1or1ca Lopez-Avlla. Technical support
for both projects was provided by Mr. N1kh1l Shah Dodhlwala and Mr. June
M1lanes.
111
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TABLE OF CONTENTS
Section
Page
Preface 111
Figures v11
Tables xi
1 INTRODUCTION 1
2 CONCLUSIONS 4
3 RECOMMENDATIONS 5
4 LITERATURE REVIEW 6
5 EXPERIMENTAL PROCEDURES 7
5.1 Sample Acquisition 7
5.2 Evaluation of Gas Chromatography 9
5.3 Extraction and Spiking Techniques 11
5.3.1 Sample Extraction 11
5.3.2 Soil Spiking Studies 11
5.4 Extract Cleanup Techniques 13
5.4.1 Gel Permeation Chromatography (GPC) 13
5.4.2 Removal of Elemental Sulfur 13
5.4.3 Florisil Chromatography 13
5.5 Sample Preservation 14
5.6 GC/MS Methodology 14
6 RESULTS AND DISCUSSION 16
6.1 Evaluation of Gas Chromatography 16
6.1.1 Packed Column Studies 16
6.1.2 Capillary Column Studies 25
6.2 Extraction Techniques 25
6.3 Extract Cleanup Techniques 51
6.3.1 Gel Permeation Chromatography (GPC) 51
6.3.2 Sulfur Removal 52
6.3.3 Florlsil Cleanup 52
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TABLE OF CONTENTS (Concluded)
Section Page
6.4 Preservation Study 66
6.5 Revised Method 8120 Protocol 84
6.5.1 Reproducibility of the GC Technique 84
6.5.2 Instrument Calibration 84
6.5.3 Method Accuracy and Precision 90
6.5.4 Method Detection Limits 139
6.5.5 Ruggedness Test for Method 8120 139
6.5.6 Confirmation by GC/MS 145
6.5.7 Changes Suggested for Incorporation in
Method 8120 Protocol L49
REFERENCES 152
APPENDICES
A Literature Review A-l
B Method 8120 — Chlorinated Hydrocarbons (revised) . . B-l
C Preparation of Spiked Soil Samples C-l
v1
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LIST OF FIGURES
Page
1 GC/ECD chromatogram of Method 8120 composite standard
(concentration 0.1 to 20 ng/uL) analyzed on a 1-percent
SP-1000 packed column, isothermal at 65°C 18
2 GC/ECD chromatogram of Method 8120 composite standard
(concentration 0.1 to 20 ng/pL) analyzed on a 1-percent
SP-1000 packed column, isothermal at 150°C 19
3 GC/ECD chromatogram of Bloody Run Creek sediment extract
(10-fold dilution) analyzed on a 1-percent SP-1000 packed
column, isothermal at 65°C 20
4 GC/ECD chromatogram of Bloody Run Creek sediment extract
(10-fold dilution) analyzed on a 1-percent SP-1000 packed
column, isothermal at 150°C 21
5 GC/ECD chromatogram of Method 8120 composite standard
analyzed on a 1-percent SP-1000 packed column, temperature
programmed from 65°C to 175°C (hold 28 min) at 5°C/min . . 22
6 GC/ECD chromatogram of Bloody Run Creek sediment extract
(10-fold dilution) analyzed on a 1-percent SP-1000 packed
column, temperature programmed from 65°C to 175°C (hold
28 min) at 5°C/m1n 23
7 GC/ECD chromatogram of a hexane blank analyzed immediately
after the Bloody Run Creek sediment extract was analyzed
at 65°C, isothermal 24
8 GC/ECD chromatogram of Method 8120 compounds analyzed on
a SPB-5 fused-silica capillary column 26
9 GC/ECD chromatogram of Method 8120 compounds analyzed on
a SPB-35 fused-sillca capillary column 27
10 GC/ECD chromatogram of Method 8120 compounds analyzed on
a DB-210 fused-silica capillary column; standards in 28
isooctane at concentrations between 0.05 and 10 ng/yL . . .
11 GC/ECD chromatogram of Method 8120 compounds analyzed on
a DB-210 fused-silica capillary column; standards in
isooctane at concentrations between 0.01 and 2 ng/pL ... 29
vii
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LIST OF FIGURES (Continued)
Figures Page
12 GC/ECD chromatogram of Method 8120 compounds analyzed on
a DB-1301 fused-s1!1ca capillary column; standards 1n
Isooctane at concentrations between 0.1 and 20 ng/pl_ ... 30
13 GC/ECD chromatogram of Method 8120 compounds analyzed on
a DB-WAX fused-silica capillary column (No. 52861);
standards 1n Isooctane at concentrations between
0.1 and 20 ngM 31
14 GC/ECO chromatogram of Method 8120 compounds analyzed on
a OB-WAX fused-sH1ca capillary column (No. 130906);
standards in Isooctane at concentrations between
0.1 and 20 ng/yL 32
15 GC/ECD chromatogram of Method 8120 compounds analyzed on
a Supelcowax 10 fused-silica capillary column; standards
in Isooctane at concentrations between 0.1 and 20 ng/pL. . 33
16 GC/ECD chromatogram of a Method 8120 composite standard
containing elemental sulfur 55
17 Recovery as a function of time at pH 7 for:
hexachloroethane, 1,3-dichlorobenzene, 1,4-dichlorobenzene,
1,2-dichlorobenzene, benzyl chloride, and
1,3,5-trichlorobenzene 70
18 Recovery as a function of time at pH 7 for:
hexachlorobutadiene, 1,2,4-trichlorobenzene, benzal
chloride, benzotrichloride, 1,2,3-trichlorobenzene,
and hexachlorocyclopentadiene 71
19 Recovery as a function of time at pH 7 for:
1,2,4,5-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene,
1,2,3,4-tetrachlorobenzene, 2-chloronaphthalene,
pentachlorobenzene, and hexachlorobenzene 72
20 Recovery as a function of time at pH 7 for: alpha-BHC,
ganraa-BHC, beta-BHC, and delta-BHC 73
viii
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LIST OF FIGURES (Continued)
Figures Page
21 Recovery as a function of time at pH 2 for:
hexachloroethane, l,3-d1chlorobenzene, 1,2-dichlorobenzene,
1,4-dichlorobenzene, benzyl chloride, and
1,3,5-trichlorobenzene 74
22 Recovery as a function of time at pH 2 for:
hexachlorobutadiene, 1,2,4-trichlorobenzene, benzal
chloride, benzotrichloride, 1,2,3-trichlorobenzene,
and hexachlorocyclopentadiene 75
23 Recovery as a function of time at pH 2 for:
1,2,4,5-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene,
1,2,3,4-tetrach1orobenzene, 2-chloronaphthalene,
pentachlorobenzene, and hexachlorobenzene 76
24 Recovery as a function of time at pH 2 for: alpha-BHC,
gamma-BHC, beta-BHC, and delta-BHC 77
25 Recovery as a function of time at pH 9 for:
hexachloroethane, 1,3-dichlorobenzene, 1,4-dichlorobenzene,
1,2-dichlorobenzene, benzyl chloride, and
1,3,5-trichlorobenzene 78
26 Recovery as a function of time at pH 9 for:
hexachlorobutadiene, 1,2,4-trichlorobenzene, benzal
chloride, benzotrichloride, 1,2,3-trichlorobenzene,
and hexachlorocyclopentadiene 79
27 Recovery as a function of time at pH 9 for:
1,2,4,5-tetrachlorobenzene, 1,2,3,5-tetrachlorobenzene,
1,2,3,4-tetrachlorobenzene, 2-chloronaphthalene,
pentachlorobenzene, and hexachlorobenzene 80
28 Recovery as a function of time at pH 9 for: alpha-BHC,
gamma-BHC, beta-BHC, and delta-BHC 81
29 Recovery as a function of matrix for hexachloroethane . . 109
30 Recovery as a function of matrix for 1,3-dichlorobenzene . 110
31 Recovery as a function of matrix for 1,4-dichlorobenzene . Ill
1x
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LIST OF FIGURES (Continued)
Figures
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
Recovery as a function of matrix for 1,2-dichlorobenzene .
Recovery as a function of matrix for benzyl chloride . . .
Recovery as a function of matrix for 1,3,5-trichloro-
benzene
Recovery as a function of matrix for hexachlorobutadiene .
Recovery as a function of matrix for 1,2,4-trichloro-
benzene
Recovery as a function of matrix for benzal chloride . . .
Recovery as a function of matrix for benzotrlchloride . .
Recovery as a function of matrix for 1,2,3-trichloro-
benzene
Recovery as a function of matrix for hexachlorocyclo-
pentadlene .
Recovery as a function of matrix for 1,2,4,5-tetrachloro-
benzene
Recovery as a function of matrix for 1,2,3,5-tetrachloro-
benzene
Recovery as a function of matrix for 1,2,3,4-tetrachloro-
benzene
Recovery as a function of matrix for 2-chloronaphthalene .
Recovery as a function of matrix for pentachlorobenzene .
Recovery as a function of matrix for hexachlorobenzene . .
GC/ECO chromatogram of EPA WP-281 Sample 4 before
Florisll cartridge chromatography
GC/ECD chromatogram of EPA WP-281 Sample 4 after
Flor1s1l cartridge chromatography
Page
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
130
131
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LIST OF FIGURES (Concluded)
Figures Page
49 GC/MS chromatogram of 1 ng of Method 8120 composite
standard 150
50 GC/MS chromatogram of 5 ng of Method 8120 composite
standard 151
x1
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LIST OF TABLES
Table Page
1 Compounds Listed in Revised EPA Method 8120 3
2 Identification of the NBS Standard Reference Materials
Used in the Method Evaluation 8
3 Reference Values for Chlorobenzenes and
Hexachlorobutadiene in EC-2 10
4 GC Operating Conditions for the Fused-Silica Capillary
Column Analyses 12
5 Retention Times (min) of the Method 8120 Compounds on a
2 m x 2 mm ID Glass Column Packed with 1 percent SP-1000
on Supelcoport (100/120 mesh) 17
6 Retention Times (min) of the Method 8120 Compounds on a
15 m x 0.53 mm 10 SPB-5 Fused-Silica Capillary Column . . 34
7 Retention Times (min) of the Method 8120 Compounds on a
30 m x 0.53 mm ID SPB-35 Fused-Silica Capillary Column . . 35
8 Retention Times (min) of the Method 8120 Compounds on a
30 m x 0.53 mm ID DB-210 Fused-Silica Capillary Column . . 36
9 Retention Times (min) of the Method 8120 Compounds on a
30 m x 0.32 mm ID DB-1301 Fused-Silica Capillary Column . 37
10 Retention Times (min) of the Method 8120 Compounds on a
30 m x 0.53 mm ID DB-WAX Fused-Silica Capillary Column . . 38
11 Retention Times (min) of Other Chlorinated Aromatic
Compounds on a 15 m x 0.53 mm ID SPB-5 Fused-Silica
Capillary Column 39
12 Retention Times (min) of Other Chlorinated Aromatic
Compounds on a 30 m x 0.53 mm ID SPB-35 Fused-Silica
Capillary Column 41
13 Retention Times (m1n) of Other Chlorinated Aromatic
Compounds on a 30 m x 0.53 mm ID DB-210 Fused-Silica
Capillary Column 42
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LIST OF TABLES (Continued)
Table
14
15
16
17
18
19
20
21
22
23
24
25
26
27
Retention Times (min) of Other Chlorinated Aromatic
Compounds on a 30 m x 0.53 mm ID DB-WAX Fused-SiUca
Overall Percent Recoveries for Methods 3510 and 8120 . . .
Results of Method 8120 Analyses for Bloody Run Creek
Recoveries of the Method 8120 Compounds as a Function
of pH
Concentrations (ng/pL Extract) of the Method 8120
Compounds Identified 1n the Bloody Run Creek Sediment . .
Concentrations (ng/pL Extract) of the Method 8120
Compounds Identified in the Detroit River Sediment ....
Results of the Method 8120 Analysis for EC-2
GPC Elution Profile for Corn Oil
GPC Elution Profiles for the Method 8120 Compounds ....
Recovery of the Method 8120 Compounds Using the TBA
Procedure for Removal of Elemental Sulfur
Elution Patterns of the Method 8120 Compounds from
the Florisil Column by Elution with Petroleum Ether . . .
Elution Patterns of the Method 8120 Compounds from
the Florisil Column by Elution with Petroleum Ether
(Fraction 1) and Petroleum Ether/Diethyl Ether 1:1
(Fraction 2)
Elution Patterns of Other Chlorinated Aromatic Compounds
from the Florisil Column by Elution with Petroleum Ether
(Fraction 1) and Petroleum Ether/Diethyl Ether 1:1
/Fraction 2)
Recoveries of the Method 8120 Compounds from Florisil . .
Page
43
45
46
47
48
49
50
53
54
56
57
58
60
61
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LIST OF TABLES (Continued)
Table Page
28 Recoveries of the Method 8120 Compounds Using F1or1s1l
Disposable Cartridges (Elution with Hexane and
Hexane/Dlethyl Ether 1:1) 1 62
29 Recoveries of the Method 8120 Compounds Using Fieris1l
Disposable Cartridges as a Function of Analyte
Concentrations 63
30 Recoveries of the Method 8120 Compounds Using Florisil
Disposable Cartridges (Elution with Hexane/Acetone 9:1) . 64
31 Elution Profiles of Corn 011 from Florlsil Disposable
Cartridges 65
32 Concentration (ng/^L of Extract) as a Function of Time
at pH 7 67
33 Concentration (ng/yL of Extract) as a Function of Time
at pH 2 68
34 Concentration (ng/yL of Extract) as a Function of Time
at pH 9 69
35 Homogeneity of Spiked Soil Samples Prepared by Blending
and Kept Frozen for 5 Months 82
36 Homogeneity of Spiked Soil Samples Prepared by Blending
and Kept Frozen for 6 Months 83
37 Reproduc1b1l1ty of Retention Time and Absolute Peak Area
for 1,3,5-Trlbromobenzene Spiked as Internal Standard
1n Isooctane Blanks 85
38 Reproduc1bil1ty of Absolute Response and Retention Time
for a,a'-D1bromo-m-xylene 86
x1v
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LIST OF TABLES (Continued)
Table Page
39 Relative Retention Times (RRT) of the Method 8120
Compounds on the DB-210 Fused-S1l1ca Capillary Column ... 87
40 Relative Retention Times (RRT) of the Method 8120
Compounds on the DB-WAX Fused-S1lica Capillary Column ... 88
41 Response Factors for the Single-Level Calibration Data
for the Method 8120 Compounds Analyzed on the DB-210 Fused-
Silica Capillary Column 89
42 Multilevel Calibration Data for Standards Analyzed
on 5/27/87 91
43 Multilevel Calibration Data for Standards Analyzed
on 6/4/87 92
44 Multilevel Calibration Data for Standards Analyzed
on 6/18/87 93
45 Multilevel Calibration Data for Standards Analyzed
on 6/30/87 and 7/1/87 94
46 Multilevel Calibration Data for the Method 8120 Compounds
Analyzed on the DB-WAX Fused-S1l1ca Capillary Column .... 95
47 Accuracy and Precision Data for Methods 3510 and 8120
(Without Cleanup) 96
48 Accuracy and Precision Data for Methods 3550 and 8120
(Without Cleanup) 97
49 Method Precision and Accuracy for the Love Canal Soil
(Matrix 10) 98
50 Method Precision and Accuracy for the PCB-Contaminated
Soil (Matrix 11) 99
51 Recoveries of the Method 8120 Compounds Found in the
Spiked Loam Soil Extract After Florisil Cartridge
Cleanup (Matrix 1) 100
xv
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LIST OF TABLES (Continued)
Table Page
52 Recoveries of the Method 8120 Compounds Found 1n the Spiked
P6N-1B Shell Sample Extract After Flor1s1l Cartridge
Cleanup (Matrix 2) 101
53 Recoveries of the Method 8120 Compounds Found 1n the Spiked
P1ne Needle NBS SRM-1575 Sample Extract After Florisll
Cartridge Cleanup (Matrix 3) 102
54 Recoveries of the Method 8120 Compounds Found in the Spiked
River Sediment NBS SRM-1645 Sample Extract After Florlsil
Cartridge Cleanup (Matrix 4) 103
55 Recoveries of the Method 8120 Compounds Found 1n the Spiked
Citrus Leaves NBS SRM-1572 Sample Extract After Florisll
Cartridge Cleanup (Matrix 5) 104
56 Recoveries of the Method 8120 Compounds Found in the Spiked
Coal NBS SRM-1632a Sample Extract After Florisll
Cartridge Cleanup (Matrix 6) 105
57 Recoveries of the Method 8120 Compounds Found in the Spiked
Coal Flyash NBS SRM-1633a Sample Extract After Florlsil
Cartridge Cleanup (Matrix 7) 106
58 Recoveries of the Method 8120 Compounds Found in the Spiked
Detroit River Sediment Sample Extract After Florisll
Cartridge Cleanup (Matrix 8) 107
59 Recoveries of the Method 8120 Compounds Found in the Spiked
Bloody Run Creek Sediment Sample Extract After Florisll
Cartridge Cleanup (Matrix 9) 108
60 Compounds Identified 1n EPA Sample WP-485 — Polynuclear
Aromatlcs II 127
61 Compounds Identified 1n EPA Sample WP-281 Sample 2 .... 128
62 Compounds Identified 1n EPA Sample WP-281 Sample 4 .... 129
63 Results of GC/ECO Analyses for EPA Check Sample WP-685 . . 132
64 Results of GC/ECO Analyses for EPA Check Sample WP-186 . . 133
xv 1
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LIST OF TABLES (Concluded)
Table Page
65 Compounds Identified in EPA WP-1082 Sample 1 134
66 Compounds Identified in EPA WP-1082 Sample 2 135
67 Compounds Identified in EPA WP-482 Sample 3 136
68 Compounds Identified in EPA WP-482 Sample 4 137
69 Compounds Identified in EPA WP-482 Sample 1 138
70 Concentrations of the Method 8120 Compounds in Water Samples
for the MDL Study (Subjected to Florisil Cleanup) 140
71 Concentrations of the Method 8120 Compounds in Water Samples
for the MDL Study (No Florisil Cartridge Cleanup) 141
72 Concentrations of the Method 8120 Compounds Detected in
Method Blanks 142
73 List of Conditions Altered and Assigned Values for Gas
Chromatographic Analysis (Method 8120) 143
74 Design for Test of Experimental Conditions 144
75 Ruggedness Test for Method 8120 — Recovery Data for the
22 Test Compounds 146
76 Ruggedness Test for Method 8120 ~ Group Differences for
the 22 Test Compounds 147
77 Retention Times (Scan Numbers) and Three Most Intense
Ions of the Method 8120 Compounds Analyzed by GC/MS Using a
30 m x 0.25 mm ID (0.25 vm Film Thickness) DB-5
Fused-Silica Capillary Column 148
xvii
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NOTICE
This document is a preliminary draft. It has not been formally released by
the U.S. Environmental Protection Agency and should not at this stage be
construed to represent Agency policy. It is being circulated for comments on
its technical merit and policy implications. Mention of trade naires or
commercial products does not constitute endorsement or recommendation for
use.
SECTION 1
INTRODUCTION
Regulation of hazardous waste activities under the Resource Conservation
and Recovery Act (RCRA) of 1976 and its elements requires use of analytical
methodologies that provide reliable data. The document "Test Methods for
Evaluating Solid Waste," Office of Solid Haste Manual SW-046, revised
recently (1), provides a compilation of irethods for evaluating RCRA solid
wastes for environmental and human health hazards. One of the methods in
this document, Method 8120, addresses the determination of chlorinated
hydrocarbons. This method provides sample extract cleanup and gas
chromatographic conditions for the determination of 15 compounds in a variety
of environmental samples, including groundwater, liquids, and solids.
Analyses are done on packed columns at various temperatures, and compounds
are detected with an electron capture detector.
Problems with the current Method 8120 include the following:
o The primary column specified in the method is a 1.8 m x 2 mm ID
glass column packed with 1 percent SP-1000 on Supelcoport (100/120
mesh) which needs to be operated at two temperatures (65°C and
150°C) in order to chromatograph 8 of the 15 compounds; no
information is included in the method about the other 7 compounds.
• The confirmatory column specified in the method is a 1.8 m x 2 mm ID
glass column packed with 1.5 percent OV-1/2.4 percent OV-225 on
Supelcoport (80/100 mesh) which needs to be operated at three
temperatures (75°C, 100°C, and 165°C) in order to chromatograph 9 of
the 15 compounds.
o The current Method 8120 does not specify isorers for
trlchlorobenzenes, tetrachlorobenzenes, and BHCs.
o Method detection limits are given for only 9 of the 15 compounds
listed in the method, and their values are given only for the water
matrix.
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o Surrogate compounds are required to be spiked in the sample matrix
prior to extraction, yet no compounds are suggested for this
purpose. Likewise, internal standards are required whenever
internal standard calibration is used for quantification purposes,
yet no internal standards are recommended.
o Extract cleanup is performed according to Method 3620, yet no
recovery data are included in the method to indicate that the 15
compounds are recovered quantitatively from the Florisil column by
elution with petroleum ether.
The purpose of this study was to conduct a single-laboratory
evaluation of Method 8120. The range of compounds of interest was expanded
to include all the trichlorobenzenes, tetrachlorobenzenes, and the BHC
isomers. Twenty-two compounds shown in Table 1 were used in the evaluation
studies. Since the analysis with packed column did not give satisfactory
results, five fused-silica capillary columns were evaluated for their
suitability for this type of compounds. The results of the fused-silica
capillary columns evaluation were published in the journal of
High-Resolution Chromatography and Chromatography Communications in February
1988. The gas chromatographic procedure selected for incorporation in the
revised Method 8120 was subjected to ruggedness testing.
Florisil cartridges were evaluated for sample extract cleanup in order
to simplify and standardize the Florisil cleanup procedure. Possible
interferences from other chlorinated compunds such as chlorinated phenols,
toluenes, xylenes, polynuclear aromatic hydrocarbons, and other compounds
were investigated. Method detection limits were established and the modified
method was tested on a variety of sample matrices which included reagent and
San Francisco Bay water, two leachates, a sandy loam soil, five NBS Standard
Reference Materials (SRM-1572, SRM-1575, SRM-1632a, SRM-1633a, and SRM-1645),
sediments from the Detroit River and the Bloody Run Creek, a soil from the
Love Canal area, a RGB-contaminated soil, and a standard reference material
obtained from the Canada Centre for Inland Waters.
A revised protocol was prepared and is included as Appendix 8. The
final evaluation of the revised method was conducted at three concentrations,
each in triplicate. The precision and accuracy results indicate that the
revised Method 8120 could be reliably applied to the determination of
chlorinated hydrocarbons in liquid and solid matrices.
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TABLE 1. COMPOUNDS LISTED IN REVISED EPA METHOD 8120
Compound CAS no.
Benzal chloride 98-87-3
BenzotrlchloMde 98-07-7
Benzyl chloride 100-44-7
2-Chloronaphthalene 91-58-7
l,2-D1chlorobenzene 95-50-1
1,3-01chlorobenzene 541-73-1
l,4-D1chlorobenzene 106-46-1
Hexachlorobenzene 118-74-1
Hexachlorobutadlene 87-68-3
alpha-Hexachlorocyclohexane (alpha-BHC) 319-84-6
beta-Hexachlorocyclohexane (beta-BHC) 319-85-7
gamma-Hexachlorocyclohexane (gamma-BHC) 58-89-9
delta-Hexachlorocyclohexane (delta-BHC) 319-86-8
Hexachlorocyclopentadlene 77-47-4
Hexachloroethane 67-72-1
Pentachlorobenzene 608-93-5
1,2,3,4-Tetrach1orobenzene 634-66-2
1,2,4,5-Tetrachlorobenzene 95-94-2
1,2,3,5-Tetrachlorobenzene 634-90-2
1,2,4-Trlchlorobenzene 120-82-1
1,2,3-Tr1chlorobenzene 87-61-6
1,3,5-Trlchlorobenzene 108-70-3
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SECTION 2
CONCLUSIONS
Based on the results presented In Section 6 of this report, the
following conclusions were drawn concerning the determination of chlorinated
hydrocarbons.
o EPA Method 8120, revised as presented in Appendix B, can be used for
the determination of 22 chlorinated hydrocarbons in complex
environmental matrices. Use of a megabore DB-210 fused-silica
capillary column for primary analysis has been found to be
advantageous over the packed column specified in the original
Method 8120. A megabore JB-HAX fused-silica capillary column is
recommended for confirmatory analysis since it can resolve the
1,2,3,5-and 1,2,4,5-tetrachlorobenzene isomers.
• The cleanup procedures recommended in the original Method 8120 have
been evaluated. The use of gel permeation chromatography (Method
3640) and Method 3660 for elemental sulfur removal as options were
found to be appropriate. When Florlsil chromatography (Method 3620)
is used with petroleum ether as the eluant as specified in the
original method, not all compounds are recovered. Therefore,
Method 3620 was modified to allow quantitative recovery of 20
compounds. At the same time, a procedure using 1-g Florisil
disposable cartridges and hexane/acetone (9:1) as the eluant was
developed. This procedure gave quantitative recoveries of all test
compounds, regardless of the matrix used.
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SECTION 3
RECOMMENDATIONS
The revised Method 8120 presented in this report has been evaluated in a
single laboratory using a few relevant environmental samples. However, the
method should be evaluted in a number of laboratories and with additional
samples. This process could help to determine the range of applicability of
the methods and would serve to define its interlaboratory performance.
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SECTION 4
LITERATURE REVIEW
In the Initial phase of this study, a literature review covering
analytical methods for the determination of the chlorinated hydrocarbons in
water, soil, and sediment samples was performed. For this review, the
Computerized Chemical Abstracts search was used, as well as several reports
dealing specifically with the analysis of organic compounds in water.
Furthermore, recent issues of Analytical Chemistry, the Journal of
Chromatography, the Journal of Chromatographic Science, the Association of
the Official Analytical Chemists Journal, and the Environmental Science and
Technology were searched to gather recent references that had not yet been
entered in the computer database.
The computer searches were performed by using DIALOG. Chemical
Abstracts files were searched back to 1977 for all references containing
"chlorinated benzenes," "gas Chromatography," "extraction," and "cleanup."
Approximately 50 articles were judged to be scientifically relevant to the
objectives of this study and were retrieved from the literature.
The literature review summary is included as Appendix A and presents the
material in the following order:
• Sample preservation techniques
• Extraction techniques for water, sediment, and soil
e Cleanup techniques
o Gas Chromatographic analysis (columns, retention time information,
Chromatographic problems)
• Compound confirmation.
-------
SECTION 5
EXPERIMENTAL PROCEDURES
The method development tasks included evaluation of gas chromatographic
procedures with fused-silica capillary columns and electron capture
detection, sample extraction, extract cleanup, sample preservation,
determination of method precision, accuracy, and detection limits , and
confirmation of the chlorinated hydrocarbons by gas chromatography/mass
spectrometry.
5.1 SAMPLE ACQUISITION
The following samples were used in this study:
San Francisco Bay water (pH 8.0), collected close to Leslie Salt Hill
(off Seaport Blvd., South San Francisco). The sample was refrigerated at 4°C
until analyzed.
Leachate samples prepared from the Detroit Sediment and the Bloody Run
Creek sediment (specified below) as follows: 100 g (wet weight) of each
sediment were mixed with 1,600 mL deionized water, adjusted to pH 5.2 with
0.5 N acetic acid, and shaken for 24 hours on a mechanical shaker. Details
of the procedure are given in Method 1310 of the SW-846 Methods manual (1).
Each leachate was filtered through an 0.45 urn Millipore filter (Fischer
Scientific) prior to extraction with methylene chloride.
Sandy Loam soil (Matrix 1), obtained from Soils Incorporated, Puyallup,
Washington, and characterized as follows: pH 5.9 to 6.0; 89 percent sand,
7 percent silt, 4 percent clay, cation exchange capacity 7 meq/100 g, and
total organic carbon content 1290 ± 185 mg/kg.
Sediment sample (Matrix 2) of unknown origin, contaminated with
petroleum hydrocarbons.
NBS Standard Reference Materials (Matrices 3 through 7) used in the
methods development are identified in Table 2.
Detroit River sediment (Matrix 8), collected from the Detroit River at
Station 30CR by Indiana University staff. It was reportedly highly
contaminated with PCBs, chlorinated naphthalenes and terphenyls (1- to 3-ppir
levels). Ed Furlong of Indiana University, who has been working on the
organic chemical characterization of this sediment, will publish his findings
at a later date in the Journal of Great Lakes Research (2).
-------
TABLE 2. IDENTIFICATION OF THE NBS STANDARD REFERENCE MATERIALS USED
IN THE METHOD EVALUATION
Material
Description
SRM-1575
SRM-1645
SRM-1572
SRM-1632a
SRM-1633a
Pine needles obtained from Manistee State Park (Muskegon,
Michigan). The material was air-dried, ground, dried again at
85"C, mixed in a feed blender, and sterilized by irradiating with
Cobalt 60.
River sediment dredged from the bottom of Indiana Harbor Canal
near Gary, Indiana. The material was freeze-dried, sieved through
a 180-ym screen, mixed in a blender, and sterilized by irradiating.
Total organic carbon content is 30,000 mg/kg.
Citrus leaves from the Lake Alfred area of central Florida. The
material was air-dried, ground to pass through a 425-ym screen,
dried at 85°C, mixed in a feed blender, and sterilized by
irradiating with Cobalt 60.
Coal obtained from the Humphrey No. 7 mine and coal preparation
plant of the Consolidation Coal Co., Osage, West Virginia.
Contains approximately 1.8 to 1.9 percent sulfur and was ground
to pass through a 60-mesh sieve.
Coal flyash, obtained from a coal-fired power plant that uses
Pennsylvania and West Virginia coals. The material was sieved
pass through a 90-ym screen.
to
-------
Bloody Run Creek sediment (Matrix 9), a grab sample from the creek
downstream of the lOZnd-Street dump site in the Love Canal area. Jaffe and
Kites reported ppm concentrations of dichloroUrifluoromethyl Jbenzophenone,
dichloro(trifluoromethyl)difluorodiphenylmethane, and various chlorinated
trifluoromethyl-substituted biphenyls (3).
Love Canal soil (Matrix 10), obtained from the Environmental Research
Center of the University of Nevada in Las Vegas, Nevada.
PCB-contaminated soil sample (Matrix 11), obtained from Dr. William
Budde of EPA-Cincinnati.
EC-2 Standard Reference Material obtained from Alfred S. Y. Chau of
Canada Centre for Inland Waters, Ontario, Canada. This material was
collected from Lake Ontario near Niagara River in 1980. It was freeze-dried
in 25-kg lots, ground and sieved to give a 200- to 325-mesh dry sediment. The
bulk sample was blended until homogeneous and then subsampled in 25-g amber
bottles. The reference values for chlorobenzenes and hexachlorobutadiene
present in EC-2 are given in Table 3. In addition, this sediment was found
to contain polynuclear aromatic hydrocarbons: fluoranthene,
benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene,
indeno[l,2,3-c,d]pyrene, benzo[g,h,i]perylene, and PCBs at 1 to 3 ppm (4).
Standards: High-purity benzyl chloride, 2-chloronaphthalene,
1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene,
hexachlorobenzene, hexachlorobutadiene, alpha-BHC, beta-BHC, gamma-BHC, and
1,2,4-trichlorobenzene were obtained from the U.S. EPA Pesticides and
Industrial Chemicals Repository. Benzal chloride, 1,2,3,5-tetrachloro-
benzene, and the bromihated compounds were obtained from Aldrich Chemical
Company, Inc. The remainder of the compounds listed in Table 1 and the other
chlorinated compounds listed in other tables of this report were obtained
from Ultrascientific Inc. Stock solutions of each test compound were
prepared in isooctane (Burdick & Jackson Lab, Inc.) at concentrations of
1 mg/mL. Working calibration standards were prepared in isooctane by serial
dilution of a composite stock solution prepared from the individual stock
solutions.
5.2 EVALUATION OF GAS CHROMATOGRAPHY
Gas chromatography with electron capture detection was evaluated with
both packed and capillary columns. The gas chromatographs used throughout
these evaluations were a Varian 3400 gas chromatograph equipped with a
constant current pulsed frequency electron capture detector (ECO) and
interfaced to a Spectra Physics 4290 integrator and a Varian 6000 gas
chromatograph also equipped with a constant current pulsed frequency ECO and
interfaced to a Vista 402 data station. All injections were performed with
an autosampler Varian Model 8000.
-------
TABLE 3. REFERENCE VALUES FOR CHLOROBENZENES AND
HEXACHLOROBUTAOIENE IN EC-2a
Concentration
Compound (ng/g)
1,3,5-Trichlorobenzene 34.3 ± 2.6
1,2,4-Trichlorobenzene 80.7 ± 5.4
1,2,4,5-Tetrachlorobenzene 84.0 ± 4.9
1,2,3,4-Tetrachlorobenzene 36.5 ± 2.4
Pentachlorobenzene 48.6 ± 2.4
Hexachlorobenzene 200.6 ± 13.2
Hexachlorobutadiene 21.3 ±1.6
aData taken from Reference 4.
Packed Column Studies
For the packed column work, the instrumental parameters were as
follows:
• Column dimensions -- 2 m x 2 mm ID glass column
• Liquid phase — 1 percent SP-1000 on Supelcoport (100/120 mesh)
o Carrier gas -- nitrogen at 20.5 mL/min
o Injection volume — 2 yL (on-column)
o Injector temperature -- 150°C
o Detector temperature ~ 200°C
o Temperature — 65°C isothermal
-- 150°C isothermal
— 65°C to 175°C (28 min hold) at 58C/min
Capillary Column Studies
For the capillary column work, the instrumental parameters are
summarized in Table 4. Five fused-silica capillary columns coated with
various liquid phases have been investigated.
10
-------
5.3 EXTRACTION AND SPIKING TECHNIQUES
5.3.1 Sample Extraction
The extraction efficiencies for the Method 8120 compounds from reagent
water at pH 2, 7, and 9, were determined by using separatory funnel
extraction with methylene chloride (Method 3510). The compounds were spiked
into each water sample at 0.1 to 20 pg/L or 1 to 200 yg/L; analysis of the
extracts was performed by GC/ECD using the OB-210 fused-silica capillary
column and external standard calibration.
Soil or sediment samples were extracted either with hexane/acetone (1:1)
in a Soxhlet extractor (Method 3540) or with methylene chloride/acetone (1:1)
by using a sonic probe (Heat Systems Ultrasonics, Inc., Model W-375)
following the procedures specified in Method 3550.
5.3.2 Soil Spiking Studies
The following procedures were used for spiking soil samples:
Spiking and Blending was performed in a Waring laboratory blender
(Waring Products Division, Dynamics Corporation of America, New Hartford,
Connecticut). Five hundred grams sandy loam (Puyallup, Washington) were
mixed with 200 mL deionized water and blended at full speed for 2 minutes.
Twenty milliliters of an isooctane solution containing Method 8120 comoounds
at concentrations of 1 to 200 ug/mL were added and blending was continued for
another 10 minutes, cooling intermittently, to obtain a smooth slurry.
Immediately after blending, the slurry was separated into 35-g portions.
Stirring was done for very short times (10 sec) after each portion was
removed from the blender. The various portions were serially labeled in the
order in which the removal was done. Only those carrying the even number
were analyzed immediately. The portions carrying odd numbers were kept
frozen for up to 6 months at -10°C.
Spiking and Tumbling was performed In a tumbler from Norton Chemical
Products Division, Akron, Ohio. The amount of soil, deionized water, and the
volume of the spiking solution were the same as for blending. Before the
spiking solution was added, the soil was mixed with deionized water and
equilibrated for 1 hour. Tumbling was maintained for 12 hours following
spiking. The spiked soil was then split Into 35-g portions.
Spiking and Overnight Equilibration; 500 g sandy loam soil (Puyallup,
Washington) were mixed with 200 ml deionized water. The slurry was allowed
to equilibrate for 1 hour and then the spiking solution was added. The
spiked slurry was maintained at room temperature for 17 hours. Before
splitting Into 35-g portions and 1n between the removal of the 35-g portions,
the slurry was mixed with a glass rod.
11
-------
TABLE 4. GC OPERATING CONDITIONS FOR THE FUSEO-SILICA
CAPILLARY COLUMN ANALYSES
Instrument
Column dimensions
Type of liquid phase
Film thickness (PR)
Carrier gas
Carrier flow (nt/mln)
Temperature program
Injector
temperature CO
Detector
temperature (*C)
Injection
volume (iiL)
Type of Injection
Column 1
Varlan 6000
equipped
with ECD
15 m x 0.53 mm ID
SPB-5
(methylphenyl
s1 11 cone)
1.5
Helium
10
50*C to 175*C
(hold 20 mln)
at 4*C/m1n
220
300
1.5
On-column
Column 2
Varlan 3400
equipped
with ECD
30 m x 0.53 mm ID
SPB-35
(phenyl methyl
silicone)
1.0
Helium
10
50*C to 240*C
(hold 10 mln)
at 4*C/m1n
220
250
1.5
On-column
Column 3
Varlan 3400
equipped
with ECD
30 m x 0.53 mm ID
DB-210
(trlfluoropropyl
methyl silicone)
1.0
Helium
10
65*C to 175*C
(hold 20 mln)
at 4'C/min
220
250
1.5
On-column
Column 4
Varlan 3400
equipped
with ECD
30 m x 0.32 mm ID
06-1301
(cyanopropyl
methyl silicone)
1.5
Helium
1.5
100'C to 250*C
(hold 20 min)
at 5*C/min
220
250
1.5
Splitless (splitless
time 60 sec; split
flow 60 mL/min)
Column 5
Varian 6000
equipped
with ECD
30 m x 0.53 mm ID
DB-WAX
(polyethylene
glycol)a
1.0
Helium
10
60*C to 170'C
(hold 30 min)
at 4*c.'m1n
200
230
1.5
On-column
aTwo OB-MAX fused silica capillary columns have been evaluated in this study.
They are Identified as columns No. 52B61 and 130906.
-------
5.4 EXTRACT CLEANUP TECHNIQUES
5.4.1 Gel Permeation Chromatography (GPC)
The GPC conditions were as follows:
o Instrument -- HPLC Perkin Elmer Series 4
o Column -- 25 mm ID x 650 mm glass, packed with Bio-Beads SX-3
(-70 g)
o Flowrate — 5 mL/min
o Mobile phase -- methylene chloride
o Injection volume — 5 ml
o Detector — Perkin Elmer variable wavelength UV detector operated1 at
254 nm and 0.05/AUFS
The procedure given in Section 7.3.3 of the revised Method 8120 which is
included in Appendix B of this report was followed.
5.4.2 Removal of Elemental Sulfur
Two milliliters of a working standard of known concentration (in hexane)
were shaken with 1 ml 2-propanol and 1 ml tetrabutylammonium sulfite reagent
for at least 1 min. Sodium sulfite crystals (100 mg) were then added. If
the sodium sulfite crystals disappeared, more sodiuir sulfite was added in
100-mg portions until a solid residue remained after repeated shaking.
Finally, 5 mL reagent water were added and the test tube was shaken for
another minute. Centrifugation was employed to promote phase separation;
following centrifugation, the hexane layer was separated for gas
chromatbgraphic analysis.
5.4.3 Florisil Chromatography
Florisil (J. T. Baker Chemical Co., 60/80 mesh size, lot no. 442707) was
activated at 130°C for at least 16 hours before use. Calibration of the
Florisil was performed by the lauric acid method (5). Glass columns (20 mm
ID x 500 mm length) were packed with 12.3 g activated Florisil and prewashed
with 200 ml petroleum ether (Matheson, Coleman & Bell) before use. The test
compounds were eluted from the Florisil first with 200 ml petroleum ether and
then with 200 mL petroleum ether/diethyl ether (1:1). The fractions were
concentrated to 10 mL by Kuderna-Danish evaporation.
Florisil disposable cartridgeso(Supelco, Inc.) containing LC-Floris1l
(particle size 40 wm, pore size 60 A) were prewashed with 4 mL
pesticide-grade hexane prior to use. They were eluted in sets of 12 on a
specially designed vacuum manifold (SPE vacuum manifold, Supelco Inc.) that
provided increased sample throughput while the volume of the elutlng solvent
13
-------
was kept to a minimum. The eluting solvents evaluated with the Florisil
disposable cartridges were hexane, hexane/diethyl ether (1:1), and
hexane/acetone (9:1).
5.5 SAMPLE PRESERVATION
Sample preservation studies were carried out for both water and soil
samples. Fourteen one-liter reagent water samples were spiked with the test
compounds at one concentration and were stored at 4°C for up to 21 days. Two
samples were extracted immediately; the other samples were removed at day 1,
3, 7, 10, 14, and 21 and analyzed for the 22 test compounds. Duplicate
measurements were performed at each time event. In addition, six one-liter
reagent water samples were spiked with the test compounds at one
concentration, adjusted to pH 2 with 6N ^$04 and stored at 4eC. Two samples
were extracted immediately; the other samples were analyzed at day 7 and 14.
This experiment was repeated at pH 9.
Spiked soils samples were kept frozen at -10°C for 5 months and
6 months.
5.6 GC/MS METHODOLOGY
A Finnigan 4510B GC/MS system interfaced to a Finnigan Nova 4X data
system was used in this study. The GC was equipped with a split/splitless
injector. The column was a 30 m x 0.25 mm ID DB-5 fused-silica capillary
column (0.25 urn film thickness) supplied by J£W Scientific, Inc. The GC
instrumental conditions were as follows:
• Temperature program ~ 40°C to 300°C at 8°C/min
o Injector temperature — 250°C
o Transfer line temperature — 260°C
o Injection volume --1 uL
« Injection solvent — methylene chloride
o Carrier gas — helium at 10 psi at 40*C
The MS conditions were as follows:
• Ion source tuning ~ as per EPA DFTPP requirement
• Ion source temperature — 190°C
• Scanning mass range — 45 to 450 amu
• Scan rate —1 sec/cycle
14
-------
0
Electron energy —70 eV
Multiplier voltage —1,400 eV,
15
-------
SECTION 6
RESULTS AND DISCUSSION
6.1 EVALUATION OF GAS CHROMATOGRAPHY
6.1.1 Packed Column Studies
Results of the analyses performed on packed columns are presented in
Table 5. GC/ECD chromatograms of working standards and sample extracts are
shown In Figures 1 through 6. Both isothermal and temperature-programmed
conditions were evaluated. At 65°C, which is the temperature specified in
the current Method 8120, only 11 compounds elute from the 1-percent SP-1000
column within 30 minutes. At 150°C, 6 compounds elute within 4 minutes, but
hexachlorocyclopentadlene, beta-BHC, and delta-BHC still do not elute from
the gas chromatographic column. Resolution is so poor at 150°C that the
compounds cannot be identified. When temperature-programmed conditions were
used, the separation of the early eluting peaks was acceptable, but the late
eluting components give broad peaks, and the background from column bleed is
excessive. A GC/ECD chromatogram of a composite standard containing the
22 test compounds and obtained under temperature-programmed conditions is
presented in Figure 5. A GC/ECD chromatogram of the Bloody Run Creek
sediment extract was obtained under the same temperature-programmed
conditions (Figure 6). No peaks could be Identified because of poor
resolution. It is interesting to note that a hexane blank, analyzed
immediately after the Bloody Run Creek sediment extract had been analyzed at
65°C isothermally, showed a very high background (Figure 7) because many of
the compounds from the previous analysis had not eluted from the gas
chromatographic column at 65°C (isothermal).
The following conclusion can be drawn from these data: when analyzing
complex environmental samples by GC/ECD the sample column temperature must be
programmed from a low temperature (e.g., 50"C to 65°C) to about 20°C below
the maximum operating temperature of the column and maintained at that
temperature for 15 to 30 minutes, depending on the complexity of the sample.
The Isothermal analysis of environmental sample extracts on packed
columns was ruled out, and no further effort was put into developing a
temperature-programmed analysis for the packed column because of Inadequate
resolution.
16
-------
TABLE 5. RETENTION TIMES (MIN) OF THE METHOD 8120 COMPOUNDS
ON A 2 M X 2 MM ID GLASS COLUMN PACKED WITH
1 PERCENT SP-1000 ON SUPELCOPORT (100/120 MESH)
Compound
Benzyl chloride
Benzal chloride
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2,4-Trichlorobenzene
1 ,2,3-Trichlorobenzene
1 ,3,5-Trichlorobenzene
1,2,3,4-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
1,2,3,5-Tetrachlorobenzene
Pentachl orobenzene
Hexachlorocyclopentadiene
Benzotrichloride
2-Chloronaphthalene
Hexachloroethane
Hexachl orobutadiene
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
Hexachl orobenzene
65°C
Isothermal
6.60
22.00
5.42
3.64
4.31
12.90
20.26
6.30
a
a
a
a
a
18.42
a
3.93
6.15
a
a
a
a
a
150°C
Isothermal
b
b
b
b
b
b
b
b
1.47
1.03
1.00
1.87
a
b
^97
b
b
10.05
a
20.65
a
3.94
aCompound did not elute under the specified conditions.
bNot analyzed at that temperature.
17
-------
Figure 1. GC/ECO chromatogram of Method 8120 composite standard
(concentration 0.1 to 20 ng/uL) analyzed on a 1-percent
SP-1000 packed column, Isothermal at 65*C.
18
-------
Figure 2. GC/ECD chromatogram of Method 8120 composite standard
(concentration 0.1 to 20 ng/uL) analyzed on a 1-percent
SP-1000 packed column, Isothermal at 150'C.
19
-------
Figure 3. GC/ECO chromatogram of Bloody Run Creek sediment extract
(10-fold dilution) analyzed on a 1-percent SP-1000 packed
column, Isothermal at 65*C.
20
-------
Figure 4. GC/ECD chromatogram of Bloody Run Creek sediment extract
(10-fold dilution) analyzed on a 1-percent SP-1000 packed
column, Isothermal at 150'C.
21
-------
I
Figure 5. GC/ECD chromatogram of Method 8120 composite standard
analyzed on a 1-percent SP-1000 packed column, temperature
programmed from 65*C to 175*C (hold 28 mln) at 5*C/m1n.
22
-------
Figure 6. GC/ECO chromatogram of Bloody Run Creek sediment extract
(10-fold dilution) analyzed on a 1-percent SP-1000 packed
column, temperature programmed from 65°C to 175°C (hold
28 rain) at 5°C/m1n.
23
-------
Figure 7. GC/ECO chromatogram of a hexane blank analyzed Immediately after
the Bloody Run Creek sediment extract was analyzed on a 1-percent
SP-1000 packed column at 65°C, Isothermal. The column was held at
65°C for 40 m1n, then clean hexane was Injected and the
temperature was programmed from 65°C to 175°C (hold 28 m1n) at
5°C/m1n.
24
-------
6.1.2 Capillary Column Studies
GC/ECD chromatograms of a composite standard containing the 22 compounds
analyzed on five fused-silica capillary columns are shown in Figures 3
through 15. Tables 6 through 10 summarize the retention times of the 22 test
compounds for each fused-silica capillary column and Tables 11 through 14
summarize the retention times of other chlorinated compounds such as
chlorinated toluenes, xylenes, naphthalenes, styrenes, etc. The coeluting
compounds among the 22 test compounds are:
SPB-5: benzyl chloride/1,4-dichlorobenzene
benzotrichloride/hexachlorobutadiene
hexachlorocyclopentadiene/l,2,3,5-tetrachlorobenzene
2-chloronaphthalene/l,2,3,4-tetrachlorobenzene
beta-BHC/gamma-BHC
SPB-35: 2-chloronaphthalene/l,2,3,4-tetrachlorobenzene
1,2,3,5-/l,2,4,5-tetrachlorobenzene
DB-210: benzal chloride/1,2,4-trichlorobenzene
1,2,3,5-/1,2,4,5-tetrachlorobenzene
DB-1301: benzotrichloride/1,2,3-trichlorobenzene
hexachlorocyclopentadlene/1,2,3,5-71,2,4,5-tetrachlorobenzene
DB-WAX: benzal chloride/1,2,3-tr1chlorobenzene
2-chloronaphthalene/pentacnlorobenzene
Additional discussion of the fused-silica capillary column evaluation
can be found in Reference 6.
Of six bromoaromatics tested for suitability as internal standards,
a.a'-dibromo-m-xylene is best suited with retention times of 18.41 min for
the DB-210 column and 35.94 min for the DB-WAX column. 1,3,5-Tribromobenzene
(11.67 min on the DB-210 column and 22.60 min on the DB-WAX column) is also
suitable, however, it coelutes with o,2,6-tr1chlorotoluene, and incomplete
separation from 1,2,3,4-tetrachlorobenzene 1s found when the latter 1s
present at >1 ng/wL. Of 35 chlorinated aromatics tested for suitability as
surrogates, a,2,6-tr1chlorotoluene, l,4-d1chloronaphthalene and
2,3,4,5,6-pentachlorotoluene are recommended. Their retention times on the
DB-210 column are 12.96, 17.43, and 18.96 min, respectively, and on the
DB-WAX column 23.34, 26.33, and 27.66 nvin, respectively.
6.2 EXTRACTION TECHNIQUES
The results of the single-laboratory evaluation of the Methods 3510 and
3550 are summarized 1n this section. In the case of Method 3510, 800 ml to
1,000 mL of liquid sample (spiked with the three surrogate compounds
a,2,6-trichloro-toluene, l,4-d1chloronaphthalene, and
2,3,4,5,6-pentachlorotoluene) was extracted at neutral pH in a separatory
funnel with 60 rt methylene chloride. The extraction was repeated twice;
25
-------
SPB-5 FSCC
LU
Z
i
9 H 17 a 12
15 21 2 19 4 10811 13
I
I
r
i
7
3
J 6
Lu--
i
>
wi
22
—
2
-
0
^
i
18
I
-
1(
— J
S
i
^
^
I
JJLA_A^
0 5 10 15 20 25 30 35
TIME (min)
Figure 8. GC/ECO chromatogram of Method 8120 compounds analyzed on a SPB-5
fused-silica capillary column; the GC operating conditions are
given In Table 4. For peak Identification refer to Table 6.
Standards In Isooctane at concentrations between 0.05 and
10 ng/yL.
26
-------
SPB-35 FSCC
3 15 12
L
10 12 13
n 11
8
UL-.
10 15 20 25 30
TIME (min)
35
40
Figure 9. GC/ECD chromatogram of Method 8120 compounds analyzed on a SPB-35
fused-silica capillary column; the GC operating conditions are
given In Table 4. For peak Identification refer to Table 7.
Standards In Isooctane at concentrations between 0.05 and
10 ng/wL.
27
-------
DB-210 FSCC
17
10 12 11 13
8
16
0
10 15 20
TIME (min)
25
30
Figure 10. GC/ECO chromatogram of Method 8120 compounds analyzed on a
DB-210 fused-slllca capillary column; the GC operating
conditions are given In Table 4. For peak Identification,
refer to Table 8. Standards In Isooctane at concentrations
between 0.05 and 10 ng/yL.
28
-------
DB-21O FSCC
CM
• •
r-
0?
Figure 11. GC/ECO chromatogram of Method 8120 compounds analyzed on a
DB-210 fused-sllica capillary column; the GC operating
conditions are given In Table 4. For peak Identification,
refer to Table 8. Standards in Isooctane at concentrations
between 0.01 and 2 ng/vL. Internal standard 1s a,a'-d1bromo-
m-xylene at 0.5 ng/uL (retention time 17:00 m1n).
29
-------
DB-13O1 FSCC
10 12 11 13
d
IU
z
mm \
0
is
5
3
. , .1
22
u
1
9
20
a
16
18 '
19
1
4
_
4
*^- —
8
I i i i i i
5 10 15 20 25 30
TIME (min)
Figure 12. 6C/ECO chromatogram of Method 8120 compounds analyzed on a
DB-1301 fused-silica capillary column; the GC operating
conditions are given In Table 4. For peak Identification,
refer to Table 9. Standards In Isooctane at concentrations
between 0.1 and 20 ng/uL.
30
-------
DB-WAX FSCC
15 9
12
10
20 30
TIME (min)
40
50
Figure 13. 6C/ECD chromatogram of Method 8120 compounds analyzed on a
DB-WAX fused-silica capillary column (No. 52861); the GC
operating conditions are given In Table 4. For peak
Identification, refer to Table 10. Standards In Isooctane at
concentrations between 0.1 and 20 ng/yL.
31
-------
rs>
N
CO
ir.
01
o
UJ
"->
z:
a.
DB-WAX FSCC
Figure 14. GC/ECD chromatogram of Method 8120 compounds analyzed on a
DB-WAX fused-silica capillary column (No. 130906); the GC
operating conditions are given in Table 4. For peak
identification, refer to Table 10. Standards in isooctane at
concentrations between 0.1 and 20 ng/uL.
-------
C*>
CO
Figure 15. GC/ECD chromatogram of Method 8120 compounds analyzed on a
Supelcowax 10 fused-slUca capillary column; the GC operating
conditions are given In Table 4. Standards'In Isooctane at
concentrations between 0.1 and 20 ng/uL. The order of elutlon
Is the same as for the DB-WAX column.
-------
TABLE 6. RETENTION TIMES (MIN) OF THE METHOD 8120 COMPOUNDS ON A
15 M X 0.53 MM ID SPB-5 FUSED-SILICA CAPILLARY COLUMN
Retention time
Compound
No.
6
3
7
5
15
22
1
20
21
9
2
19
14
18
4
17
16
10
8
11
12
13
Compound
1 , 3-D 1 ch 1 orobenzene
Benzyl chloride0 .
1,4-Dlchlorobenzene
1 , 2-D 1 ch 1 orobenzene
Hexach loroethane
1,3, 5-Tr1chl orobenzene
Benzal chloride
1 , 2 , 4-Tr 1 ch 1 orobenzene
1,2,3-THchlorobenzene
Hexach 1 orobut ad 1 enee
Benzotrlchlorlde f
1,2,3, 5-Tetrachl orobenzene
Hexach 1 orocyc 1 opent ad 1 ene
1,2,4,5-Tetrachlorobenzene
2-Chloronaphthalene9
1,2,3, 4-Tetrach 1 orobenzene9
Pent ach 1 orobenzene
alpha-BHC
Hexach 1 orobenzene
beta-BHC".
gamma-BHC"
delta-BHC
k
8°C/m1nD
4.45
4.58
4.60
4.91
5.58
6.62
6.64
7.38
7.95
7.98
8.00
9.82
9.85
9.88
10.40
10.64
12.69
15.18
15.20
15.92
16.06
16.84
8°r /
i/
4.46
4.57
4.57
4.93
5.58
6.57
6.67
7.32
7.91
8.09
8.09
9.82
9.82
9.82
10.57
10.57
12.73
15.20
15.36
16.04
16.04
16.82
4.45
4.56
4.56
4.92
5.56
6.55
6.64
7.30
7.88
8.06
8.06
9.78
9.78
9.78
10.56
10.56
12.67
15.15
15.15
15.98
15.98
16.78
6°C/m1n
5.16
5.61
5.61
6.41
7.68
7.82
8.64
9.41
9.55
9.66
9.66
11.88
11.88
12.04
12.89
12.89
15.68
18.91
18.91
19.98
19.98
20.88
(min)a
4°C/m1n
5.90
6.08
6.08
6.66
7.76
9.52
9.76
10.90
12.00
12.36
12.36
15.56
15.56
15.82
17.04
17.04
21.15
25.96
26.21
27.56
27.56
28.89
3°C/m1n
6.39
6.61
6.61
7.30
8.62
10.85
11.14
12.60
13.98
14.44
14.44
18.59
18.59
18.96
20.52
20.52
25.89
32.26
32.58
34.38
34.38
36.20
2°C/m1n
7.79
7.57
7.57
8.46
10.18
13.18
13.59
15.58
17.50
18.19
18.19
24.16
24.16
24.72
26.92
26.92
34.81
44.25
44.64
47.37
47.37
50.14
aTemperature program: 50°C to 175°C; hold 20 m1n at 175°C; Injector temperature
220°C; detector temperature 300°C. Helium as carrier gas at 10 n>L/m1n; nitrogen
as makeup gas at 30 mL/m1n.
"Individual standards.
^Composite standard; duplicate determinations.
d,e,r,g,nThese pa^rs cannot be resolved on the
SPB-5 fused-sllica capillary column.
-------
TABLE 7. RETENTION TIMES (WIN) OF THE METHOD 8120 COMPOUNDS ON A
30 M X 0.53 MM IP SPB-35 FUSED-SILICA CAPILLARY COLUMN
Compound Retention timea»b
number Compound (min)
6
7
3
5
15
22
1
20
9
21
2
14
19
18
17
4
16
8
10
12
11
13
1,3-Dichlorobenzene
l,4-D1chlorobenzene
Benzyl chloride
1,2-Dichlorobenzene
Hexachloroethane
1, 3, 5-Trichl orobenzene
Benzal chloride
1, 2 , 4-Tri chl orobenzene
Hexachlorobutadiene
1,2,3-Trichlorobenzene
Benzotri chloride
Hexachlorocyclopentadiene
1,2,3,5-TetrachlorobenzeneC
l,2,4,5-Tetrachlorobenzenec
l,2,3,4-Tetrach1orobenzened
2-Chloronaphtha1ened
Pentachl orobenzene
Hexachloro benzene
alpha-BHC
gamma- BHC
beta-BHC
delta-BHC
9.35
10.16
10.67
11.05
11.80
14.00
15.15
15.96
16.53
17.43
17.72
20.60
20.93
21.01
22.91
23.00
27.08
32.48
33.06
34.97
35.41
37.11
aTemperature program: 50*C to 240°C (hold 10 min at
240aC) at 4°C/m1n; injector temperature 220°C;
detector temperature 250*C. Helium as carrier gas at
10 ml/min; nitrogen as makeup gas at 30 mL/min.
Composite standard.
c»dTnese pairs cannot be resolved on the SPB-35
fused-silica capillary column.
35
-------
co
TABLE 8. RETENTION TIMES (MIN) OF THE METHOD 8120 COMPOUNDS ON A
30 M X 0.53 MM ID DB-210 FUSED-SILICA CAPILLARY COLUMN
Retention time
(min)
65"C to 175°C (hold 20 min)
at 4«C/min
Compound
number
15
6
7
5
3
22
9
20
1
2
21
14
19
18
17
4
16
8
10
12
11
13
Compound
Hexachloroethane
1 ,3-DlcM orobenzene
1 . 4-01 chl orobenzene
1.2-Olchlorobenzent
Benzyl chloride
1.3,5-Trlchlorobenzene
He xachl orobutad iene
1 ,2.4-Tr1chl orobenzeM°
Benzal chloride"1
Benzotrichlorlde
1 , 2 . 3-T r i c hi orobenzene
Hexachlorocycl open tad ten*
1.2. 3. 5-Tetrachl orobenzene*
1.2. 4 ,5-Tetrachl orobenzene*
1.2.3,4-TetracMorobcnzene
2 -Chi oronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
al pha-BHC
9M»a-BHC
beta-BHC
delta-BHC
65°C to 175°C
(hold 20 oin)
at 2*C/nin)»
3.82
4.38
5.26
5.26
5.26
6.71
5.SO
7.21
7.21
8.86
8.86
10.14
10.83
10.43
14.31
17.32
17.32
31.00
36.84
40.43
43.39
44.51
65"C to 175°C
(hold 15 oln)
at 3°C/nlna
3.59
3.94
4.11
4.11
4.83
5.02
5.02
6.42
6.42
7.74
8.96
10.22
9.30
8.96
11.75
14.03
14.03
23.58
27.52
29.98
31.93
32.73
b
3.41
3.74
3.88
4.55
4.70
5.57
5.86
6.96
6.98
7.92
8.27
8.94
10.19
10.31
12.07
13.57
14.99
19.36
22.37
24.22
25.66
26.30
5-9
11:42°
3.47
3.78
3.93
4.58
4.74
5.61
5.93
7.04
7.04
8.04
8.33
9.06
10.39
10.29
12.11
13.66
15.06
19.45
22.42
74.30
25.76
26.38
5-10
11:44<:
3.44
3.75
3.90
4.55
4.71
5.58
5.90
6.99
6.99
7.98
8.27
8.99
10.24
10.24
12.07
13.62
15.02
19.42
22.40
24.28
25.73
26.36
5-11
11:03*
3.44
3.76
3.90
4.55
4.70
5.58
5.90
6.99
6.99
7.98
8.27
8.99
10.24
10.24
12.06
13.60
15.09
19.39
22.38
24.24
25.68
26.32
5-12
11:03=
J.43
3.74
3.89
4.53
4.68
5.55
5.87
6.96
6.96
7.98
8.27
8.99
10.22
10.22
12.06
13.60
15.02
19.40
22.38
24.26
25.70
26.32
65°C to 175°C
(hold 1$ min)
at S'C/min*
3.32
3.60
3.73
4.11
4.32
5.?2
5.49
6.43
6.43
7.28
7.55
8.13
9.25
9.25
10.67
13.10
14.70
19.02
20.54
21.71
22.2?
22.70
75°C to 175°C
(hold ?0 min)
at S'C/min*
2.61
3.38
3.46
3.65
4.18
4.3f>
4.30
5.09
5.09
5.84
6.08
6.58
7.60
7.55
8.94
11.80
11.24
17.08
18.58
19.72
20.24
20.47
85 "C to 17S°C
(hold '25 min)
at 6°C/min«
2.04
2.58
2.61
2.78
3.09
3.21
3.21
3.79
3.79
4.35
4.35
5.70
4.91
4.55
6.75
H.6P
R.60
11.43
11.38
14.64
15.61
16.12
'Composite standards, single determinations.
bIndividual standards.
cCoeposite standards; replicate analyses done over four consecutive days.
' ~ pairs cannot be resolved on the 08-210 fused-sillca capillary column.
-------
TABLE 9. RETENTION TIMES OF THE METHOD 8120 COMPOUNDS ON A
30 M x 0.32 MM ID DB-1301 FUSED-SILICA CAPILLARY COLUMN*
Retention time (min)b
Compound
number
6
7
3
5
15
22
1
20
9
2
21
14
18
19
17
4
16
8
10
12
11
13
Compound
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Benzyl chloride
1,2-Dichlorobenzene
Hexachloroethane
1 ,3,5-Trichl orobenzene
Benzal chloride
1, 2, 4-Tri chl orobenzene
Hexachl orobutad iene
Benzotrichloridec
1, 2, 3-Trichl orobenzene0
Hexachl orocycl opentadiene
l,2,4,5-Tetrachlorobenzened
1,2,3,5-Tetrachlorobenzened
1,2,3, 4-Tetrachl orobenzened
2-Chl oronaphthal ene
Pent achl orobenzene
Hexachl orobenzene
alpha-BHC
gamma -BHC
beta-BHC
delta-BHC
Individual
standard
5.61
5.74
5.93
6.30
6.78
8.24
8.91
9.55
10.04
10.80
10.72
13.37
13.44
13.44
15.01
15.23
18.51
23.31
24.16
25.84
27.79
28.99
Composite
standard
5.58
5.58
5.92
6.32
6.78
8.22
8.91
9.55
10.03
10.78
10.78
13.40
13.40
13.40
15.01
15.21
18.54
23.32
24.18
25.86
27.79
29.00
Composite
standard
5.59
5.73
5.93
6.33
6.78
8.23
8.91
9.56
10.04
10.80
10.68
13.39
13.45
13.45
15.00
15.20
18.54
23.31
24.18
25.86
27.79
29.00
Composite
standard
5.61
5.74
5.94
6.34
6.80
'8.24
8.93
9.58
10.05
10.81
10.70
13.40
13.40
13.40
15.01
15.?1
18.53
23.31
24.17
25.85
27. 78
29.00
aTemperature program: 100°C to 250°C (hold 20 min) at 5°C/min; injector
temperature 220°C; detector temperature, 250°C; helium as carrier gas at
1.5 mL/min; nitrogen as makeup gas at 40 mL/min.
bSingle determination for Individual standards. Three replicate determinations for
composite standard.
c«dThis pair/group cannot be resolved on the DB-1301 fused-silica capillary
column.
37
-------
TABLE 10. RETENTION TIMES (WIN) OF THE METHOD 8120 COMPOUNDS ON A
30 M X 0.53 MM ID UB-WAX FUSEO-SILICA CAPILLARY COLUMN
OJ
CO
Retention time (min)
Compound
Hunter
6
15
7
5
9
22
3
20
2
1
21
19
18
17
4
16
14
8
13
10
12
11
Compound
1,3-Dlchlorobenzene
Hexachloroethane
1 . 4-Ui chl orobenzene
1. 2-D1chl orobenzene
Hexachlorobutadlene
1. 3. 5-Trl chl orobenzene
Benzyl chloride
l.2,4-Tr1chlorobenzene
Benzotrichlorlde
Benzal chloride^
1.2. 3-Tr i chlorobenzened
1.2.3.5-Tetrachlorobenzene
1.2,4, 5-Tetrachl orobenzene
1.2.3,4-Tetrachlorobenzene
2-C hi oro naphthalene*
Pentachlorobenzene*
Hexachlorocyclopentadiene
Hexachl orobenzene
delta-BHC
alpha-BHC
gamma -BHC
beta-BHC
60'C to 170*C
(hold 30 min)
at 4'C/mlnB
7.84
8.26
8.53
9.60
9.98
10.41
10.51
13.63
15.10
15.59
15.70
17.07
17.20
20.40
22.54
22.76
c
27.44
30.54
36.43
45.52
c
60*C
(hold
at 4
7.99
8.37
8.71
9.75
10.11
10.45
10.45
13.63
15.20
15.64
15.64
17.07
17.36
20.43
22.80
22.80
c
27.55
30.96
37.10
46.59
c
to 170*C
30 min)
•C/minb
7.95
8.33
8.68
9.72
10.08
10.41
10.41
13.57
15.12
15.56
15.62
17.00
17.28
20.33
22.70
22.70
c
27.44
30.82
36.86
46.24
c
70*C to 185*C
(hold 10 min)
at 3'C/min
6.83
7.23
7.58
8.73
9.12
9.50
9.50
13.21
15.14
15.74
15.74
17.48
17.84
21.74
24.80
24.80
C
30.94
35.22
38.94
44.10
c
70*c to no'c
(hold 2 min)
at 3'C/tnin;
130*C to 185*C
(hold 10 min)
at 5'C/min
6.84
7.22
7.59
8.71
9.10
9.48
9.48
13.20
15.12
15.73
15.73
17.48
17.84
21.90
25.18
25.18
c
30.30
33.22
36.48
41.56
c
70*C to 130*C
(hold ? min)
at 3*C/min;
130*C to 185*C
(hold 20 min)
at 8'C/min
6.89
7.27
7.64
8.77
9.15
9.54
9.54
13.25
15.17
15.78
15.78
17.53
17.89
21.95
24.82
24.84
c
28.62
30.88
34.04
c
c
Individual standards.
^Composite standard.
°Not able to determine.
d«eThese pairs cannot be resolved on the DB-HAX fused-silica capillary column.
-------
TABLE 11. RETENTION TIMES (MIN) OF OTHER CHLORINATED AROMATIC
COMPOUNDS ON A 15 M X 0.53 MM ID SPB-5 FUSED-SILICA
CAPILLARY COLUMN
Compound Retention time
2-Chloro-p-xylene 8.00
a-Chloro-o-xylene 8.89
a-Chloro-m-xylene 8.97
a-Chloro-p-xylene . 9.09
a,3-Dich1oroto1uene 11.48
a,4-Dichloroto1uene 12.00
2,6-Dichlorostyrene 12.17
2,5-Dichlorostyrene 12.54
3,4-Dichlorostyrene 13.21
2,4,5-Trichlorotoluene 14.67
a,a'-D1chloro-o-xy1ene 15.36
0,2,4-Trichlorotoluene 15.80
o,2,6-Trichlorotoluene 15.95
a,o'-Dichloro-m-xylene 16.84
a,a'-D1chloro-p-xylene 16.96
a,3,4-Trichlorotoluene 17.38
a,a*,2,6-Tetrachlorotoluene 19.48
1,4-Dichloronaphthalene 22.17
2,7-Dichloronaphthalene 22.36
1,5-Dlchloronaphthalene 22.37 and 28.70
1,2-Dichloronaphthalene 22.86
2,4,5,6-Tetrachloro-rc-xylene 23.36
2,3,4,5,6-Pentachlorotoluene 24.94
a,a,a,a',a',a'-Hexachloro-p-xylene 26.73
a,a,o,a1,a',a'-Hexachloro-m-xylene 28.00
1,2,3,4-Tetrachloronaphtnalene 31.97
0,0',2,3,5,6-Hexachloro-p-xylene 34.78
0,0',2,4,5,6-Hexachloro-m-xylene 34.81
(confTnued)
aAnalysis was performed on a 15 m x 0.53 mm ID SPB-5
fused-slHca capillary column; 50°C to 175°C (hold 20 min)
at 4°C/min; Injector temperature 220*C; detector
temperature 300*C.
39
-------
TABLE 11.. (concluded)
Compound
Retention time (min)a
Octachloronaphthalene
4-Chloro-p-terphenyl
2,4-D1chloro-p-terphenyl
2,5-Di chloro-p-terpheny1
2,5-Dichloro-m-terphenyl
2,5-Dichloro-o-terphenyl
b
b
b
b
b
b
aAnalysis was performed on a 15 m x 0.53 mm ID SPB-5
fused-sillca capillary column; 50°C to 175°C (hold 20 min)
at 4°C/min; injector temperature 220°C; detector
temperature 300°C.
&No response; compound does not elute from the GC
column under the conditions specified above.
40
-------
TABLE 12. RETENTION TIMES (MIN) OF OTHER CHLORINATED AROMATIC COMPOUNDS
ON A 30 M X 0.53 MM ID SPB-35 FUSED-SILICA CAPILLARY COLUMN
Compound Retention tirre (min)a
a-Chloro-m-xylene 14.12
a-Chloro-p-xylene .14.25
a-Chloro-o-xylene 14.31
a,3-Dichlorotoluene 17.34
2,6-Dichlorostyrene 17.42
a,4-Dichlorotoluene 17.45
2,5-Dichlorostyrene 17.46
3,4-Dfchlorostyrene 18.67
2,4,5-Trichlorotoluene 19.77
a.a'-Dichloro-o-xylene 21.98
a,2,4-Tn"chlorotoluene 22.29
a,2,6-Trichlorotoluene 22.47
a.a'-Dichloro-m-xylene 23.68
a,3,4-Trichlorotoluene 23.92
a.a'-Dichloro-p-xylene 23.93
1,4-Dlchloronaphthalene 28.61
1,5-Dichloronaphthalene 28.81 and 35.82
2,7-Dichloronaphthalene 28.82
1,2-D-fchloronaphthalene 29.37
2,4,5,6-Tetrachloro-m-xylene 29,63
2,3,4,5,6-Pentachlorotoluene 31.44
ct,a,a,a' ,a' ,a'-Hexachloro-m-xylene 33.07
a,a,a,a1,a',a'-Hexach1oro-p-xylene 34.42
1,2,3,4-Tetrachloronaphthalene 39.37
o,a',2,3,5,6-Hexachloro-p-xylene 41.95
a,a1,2,4,5,6-Hexachloro-m-xylene 41.95
a,a',2,6-Tetrachlorotoluene 12.46 and 15.04
2-Chloro-p-xylene b
aAna1ysis was performed on a 30 m x 0.53 mm ID SPB-35
fused-silica capillary column; 50°C to 240°C (hold
10 min) at 4°C/m1n; injector temperature 2208C; detector
temperature 250°C.
bNot analyzed.
41
-------
TABLE 13. RETENTION TIMES (MIN) OF OTHER CHLORINATED AROMATIC COMPOUNDS
ON A 30 M X 0.53 MM ID DB-210 FUSED-SILICA CAPILLARY COLUMN
Compound Retention time (min)a
a-Chloro-p-xylene 6.66
a-Chloro-m-xylene 6.86
2,6-Dichlorostyrene 7.52
2,5-Dichlorostyrene 8.11
a,3-pichlorotoluene 8.99
ci,4-Dichlorotoluene 9.10
3,4-Dichlorostyrene 9.55
2-Chloro-p-xylene 9.71
2,4,5-Trichlorotoluene 9.90
a,2,4-Trichlorotoluene 12.14
a-Chloro-o-xylene 12.88
a,a'-Dichloro-o-xylene 12.94
a,2,6-Trichlorotoluene 12.96
a,3,4-Trichlorotoluene 14.22
a.a'-Dichloro-m-xylene 14.65
a.a'-Dichloro-p-xylene 14.86
a,a',2,6-Tetrachlorotoluene 15.04
2,4,5,6-Tetrachloro-m-xylene 17.26
1,4-Dichloronaphthalene 17.43
1,5-Dichloronaphthalene 17.62 and 23.72
2,7-Dichloronaphthalene 18.29
1,2-Dichloronaphthalene 18.62
2,3,4,5,6-Pentachlorotoluene 18.96
a,a,a,a',a',a'-Hexachloro-m-xylene 19.87
a,a,a,a',a',a'-Hexachloro-p-xylene 21.38
1,2,3,4-Tetrachloronaphthalene 26.32
a,a',2,4,5,6-Hexachloro-m-xylene 29.57
o,a',2,3,5,6-Hexachloro-p-xylene 29.58
Analysis was performed on a 30 m X 0.53 mm ID DB-210
fused-silica capillary column; 1 ym film thickness; 65eC to
175°C (hold 20 min) at 4°C/min; injector temperature 220°C;
detector temperature 250*C.
42
-------
TABLE 14. RETENTION TIMES (MIN) OF OTHER CHLORINATED AROMATIC
COMPOUNDS ON A 30 M X 0.53 MM ID DB-WAX FUSED-SILICA
CAPILLARY COLUMN
Compound Retention time
a-Chloro-m-xylene
a-Chloro-o-xylene
2,6-Dichlorostyrene
2,5-Dichlorostyrene
2,4,5-Trichlorotoluene
3,4-Dichlorostyrene
a,3-Dichloroto1uene
a,4-0i chl orotol uene
a,2,4-Trichlorotoluene
0,2,6-Trichlorotoluene
a.a'-Dichloro-o-xylene
2,4,5,6-Tetrachloro-ro-xylene
o-Chloro-p-xylene
2-Chloro-p-xylene
a, a' , 2, 6-Tetrachl orotol uene
a, 3 ,4-Tri chl orotol uene
2,7-Dichloronaphthalene
1,5-Dlchloronaphthalene
l,4-L)ichloronaphthalene
a,a'-Dichloro-m-xylene
a,a-0ichloro-p-xy1ene
2,3,4,5,6-Pentachlorotoluene
1,2-Dlchloronaphthalene
a, a, a, a1 ,a' ,a'-Hexachloro-m-xylene
0,0,0,0' ,o',a'-Hexachloro-p-xylene
a, a1 ,2,4,5,6-Hexachloro-m-xylene
1,2,3,4,-Tetrachloronaphthalene
0,0' ,2,3,5,6-Hexachloro-p-xylene
12.09
12.58
14.53
14.60
15.98
17.18
18.12
18.34
22.98
23.34
25.09
25.79
26.06
26.08
26.11
26.26
26.28
26.32 and 28.57
26.33
27.07
27.26
27.66
29.28
29.63
31.41
32.94
39.84
b
Analysis was performed on a 30 m x 0.53 mm ID DB-WAX
fused-slllca capillary column; 1 wm film thickness;
708C to 130°C (hold 2 min) at 38C/min; 130°C to 185°C
(hold 20 min) at 8*C/min; injector temperature 2208C;
detector temperature 250°C.
bNo response; compound does not elute from the GC column
under the conditions specified above.
43
-------
the methylene chloride extracts were combined, exchanged to hexane and then
analyzed by gas chromatography with electron capture detection. The results
for Method 3510 for two sediment leachates, two reagent waters (identified in
Table 15 as method blanks for leachates 1 or 2) and one surface water are
presented in Table 15. All compounds were recovered quantitatively (recovery
>75 percent) regardless of the matrix. Only in the case of the Bloody Run
Creek sediment leachate, recoveries were either too low or too high because
the target compounds were spiked at approximately 0.1 to 20 yg/l and some of
the compounds were present in the sample at mg/L concentrations (Table 16).
All test compounds were recovered quantitatively from water by
extraction with methylene chloride regardless of sample pH. Table 17 shows
the recovery data at pH 7, 2, and 9 for each of the 22 compounds.
Evaluation of the extraction techniques for soil samples was performed
with environmental samples, either unspiked or spiked with the 22 target
compounds. The extraction was performed either with hexane/acetone (1:1) in
a Soxhlet extractor (Method 3540) or with methylene chloride/acetone (1:1)
using a sonicator probe (Method 3550). The amount of soil or sediment used
for Soxhlet extraction was 10 g and for sonication extraction 30 g. In each
case, the material was mixed with an equivalent amount of anhydrous sodium
sulfate prior to extraction, and the extracts were cleaned up by Florisil
chromatography (Method 3620). Tables 18 and 19 summarize the results for the
Bloody Run Creek sediment and the Detroit River Sediment extracts,
respectively. Although it is very difficult to draw a conclusion about the
efficiency of the extraction technique from the individual measurements for
the target analytes, the Soxhlet extraction seems to be more exhaustive than
the sonication. Of course, two factors need to be taken into consideration
when analyzing the data presented in Tables 18 and 19: the weight of sample
and the extraction solvent.
Additional effort is needed to optimize the Soxhlet extraction
technique. Although sediment samples are usually extracted for 8 to 16 hours
by the Soxhlet method, Chau et al. (4) found no difference 1n the recoveries
of chlorobenzenes and hexachlorobutadiene when using varying extraction
times. However, Chau et al. (4) reported that recoveries of chlorobenzenes
from standard reference material EC-2 by sonication with acetone/hexane (1:1)
were about 80 percent for penta- and hexachlorobenzene, 70 percent for
hexachlorobutadiene and tetrachlorobenzenes, and 50 percent for
dichlorobenzenes. We have extracted this standard reference material using
Method 3550 (sonication with 1:1 methylene chloride/acetone) and analyzed the
extract following the conditions In the revised Method 8120. The results of
our analyses are given In Table 20. The only two compounds for which the
certified values agree with our measured values were 1,3,5-trichlorobenzene
and hexachlorobenzene. For the remainder of compounds, our results were
either lower (for 1,2.4-trlchlorobenzene, 1,2.4,5-tetrachlorobenzene, and
hexachlorobutadiene) or higher (for 1,2,3.4-tetrachlorobenzene and
44
-------
TABLE 15. OVERALL PERCENT RECOVERIES FOR METHODS 3510 AND 8120
~
Compound
Hexachloroethane
1,3-Dichlorobenzene
1 ,4-Dichl orobenzene
1,2-Dichlorobenzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachlorobutadiene
Benzal chloride13
1 ,2,4-TMchlorobenzeneb
Benzotrichloride
1 ,2,3-Tnchl orobenzene
Hexachlorocyclopentadiene
1,2, 4, 5-Tetrachl orobenzene0
1 ,2,3,5-Tetrachlorobenzene0
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachl orobenzene
alpha -BMC
gamma-BHC
beta-BHC
delta -8HC
Volume extracted (ml)e
Sample pH
Amount
spiked
(u9)
0.1
10
10
• 10
10
1.0
0.1
2.0
2.0
1.0
0.1
2.0
1.0
20
0.1
0.1
1.0
1.0
1.0
1.0
Leachate 1
(Detroit
sediment)
92
82 •
82
91
150a
83
91
96
96
96
100
93
98
92
75
98
97
100
99
100
800
5.14
Method
Slank for
Leachate 1
100
98
99
101
163a
98
100
104
104
108
107
102
105
103
86
110
108
105
- 106
107
800
5.10
Leachate 2
(Bloody Run
Creek
sedinent)f
130
39
53
d
d
30
d
110
270
40
200
150
130
149
300
160
510
240
150
170
800
5.12
Method
Blank for
Leachate 2
88
69
72
86
144*
79
89
94
97
95
93
107
96
84
68
93
107
96
97
96
800
5.10
San
Francisco
Bay water
92
75 '
79
9?
l?,5a
92
97
99
102
105
100
100
103
97
79
110
105
104
106
104
1,000
8.03
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene
1 ,4-Dichloronaphthalene
2,3,4 ,5 ,6-Pentachl orotol uene
1.0
10
1.0
81
82
80
94
110
90
101
151
55
77
90
75
97
95
89
aUnable to explain the high recovery. Spiking solution has been verified and found to contain
10 ng/uL.
b«cThese pairs cannot be resolved on the 08-210 fused-sil ica capillary column.
dNot able to determine recovery because the spike level was below the background level.
eVextract 1s 10 ml for each sample.
fHigh recoveries are due to high concentrations of the Method 8120 compounds in the leachate
(see Table 16).
45
-------
TABLE 16. RESULTS OF METHOD 3120 ANALYSES FOR
BLOODY RUN CREEK LEACHATE (UNSPIKED)
Concentration*
Compound (wg/L)
Hexachloroethane 1.
1,3-Dichlorobenzene 340"
1,4-Dichlorobenzene 340
1,2-Dichlorobenzene 2,600
Benzyl chloride 3,600
1,3,5-Trichlorobenzene 120
Hexachlorobutadiene 11
Benzal ch1orideb
l,2,4-Trich1orobenzeneb
Benzotrichloride 6.2
1,2,3-Trichlorobenzene 69
Hexachlorocyclopentadiene 2.5
l,2,4,5-Tetrachlorobenzenec
1,2,3,5-Tetrachlorobenzenec
1,2,3,4-Tetrachlorobenzene 140
2-Chloronaphthalene 1,100
Pentachlorobenzene 14
Hexachlorobenzene 1.8
alpha-BHC 250
gamma-BHC 26
beta-BHC 18
delta-BHC 44
aFinal volume of extract is 10 mL. Volume
of leachate extracted by Method 3510 is
800 nt (pH 5.12). Extract was diluted
10-fold prior to GC/ECD analysis.
b»cThese pairs cannot be resolved on the
DB-210 fused-silica capillary column.
46
-------
TABLE 17. RECOVERIES OF THE METHOD 8120 COMPOUNDS AS A FUNCTION OF pH
Compound
Hexachl oroethane
1 ,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachl orobutad iene
Benzalch1orideb
l,2,4-Trichlorobenzeneb
Benzotrichloride
1,2, 3-Tri chl orobenzene
Hexachl orocycl o pentad i ene
1,2,4, 5-Tetrachl orobenzene0
1,2, 3, 5-Tetrachl orobenzene0
1,2,3, 4-Tetrachl orobenzene
2-Chloronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
al pha-BHC
gamma -BHC
beta-BHC
delta-BHC
Spike
level
(yg/L)
1.0
100
100
ino
100
10
1.0
20
10
10
1.0
20
10
200
1.0
1.0
10
10
10
10
Percent
PH
108
106
118
113
111
117
113
108
109
113
81
117
114
119
118
121
108
108
109
105
7
93
85
82
87
89
89
87
96
100
93
66
94
95
95
98
100
99
99
93
95
PH
105
101
109
107
105
109
107
105
108
109
80
112
109
113
113
116
106
106
106
103
Recovery3
2
107
105
114
111
109
116
112
105
107
114
87
118
115
120
117
121
108
108
109
105
PH
106
104
113
109
108
112
109
107
109
111
82
114
111
114
114
116
106
107
108
104
9
105
101
109
107
106
109
108
106.
108
109
81
112
110
112
112
115
106
106
107
103
Duplicate experiments were performed at each pH.
b»cThese pairs cannot be resolved on the OB-210 fused-silica capillary
column.
47
-------
TABLE 18. CONCENTRATIONS (ng/yL EXTRACT) OF THE METHOD 8120 COMPOUNDS
IDENTIFIED IN THE BLOODY RUN CREEK SEDIMENT*
Method 3540
(Soxhlet extraction)
Method 3550
(Sonicatlon extraction)
Compound
Hexachloroethane
1,3-Dichlorobenzene
1,4-Di chl orobenzene
1,2-01 chl orobenzene
Benzyl chloride
1,3,5-Trichlorobenzene
Hexachlorobutadiene
Benzal chloride0 .
1 , 2 , 4-Tr 1 ch 1 orobenzene0
Benzotrichloride
1,2,3-Trlchlorobenzene
Hexachl orocyc 1 opentad 1 ene
1,2,3, 5-Tetrachl orobenzene6
1 , 2 , 4 , 5-Tetrach 1 orobenzene6
1,2,3, 4-Tetrach 1 orobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC°
gamma-BHC
beta-BHCB.
delta-BHCD
f
(rain)
3.39
3.70
3.85
4.49
4.64
5.51
5.83
6.92
7.91
8.20
8.92
10.24
11.96
13.50
14.92
19.29
22.24
24.14
25.60
26.22
A
<0.
116*
<0.
0.
0.
0.
0.
0.
<0.
-------
TABLE 19. CONCENTRATIONS (ng/yL EXTRACT) OF THE METHOD 8120 COMPOUNDS
IDENTIFIED IN THE DETROIT RIVER SEDIMENT*
Method 3540 Method 3550
(Soxhlet extraction) (Sonicatlon extraction)
Compound (ml
Hexachloroethane
l,3-D1chlorobenzene
1 , 4-D 1 ch 1 orobenzene
l,2-D1chlorobenzene
Benzyl chloride
1,3,5-THchlorobenzene
Hexachlorobutadlene
Benzal chlor1dec
1,2, 4-Tr 1 ch 1 orobenzenec
Benzotr1chlor1de
1,2,3-Trlchlorobenzene
Hexachlorocyclopentadlene .
1,2,3, 5-Tetrach 1 orobenzene^
l,2,4,5-Tetrachlorobenzenea
1,2,3, 4-Tetr ach 1 orobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC?
gamma-BHCD
beta-BHCD.
delta-BHC6
3.39
3.70
3.85
4.49
4.64
5.51
5.83
6.92
7.91
8.20
8.92
10.24
11.96
13.50
14.92
19.29
22.24
24.14
25.60
26.22
<0
0
3
0
1
0
0
0
0
0
0
<0
<0
0
0
0
0
<0
0
0
.001
.35
.88
.02
.64
.012
.002
.009
.012
.008
.002
.01
.01
.10
.002
.003
.003
.005
.005
.007
<0.001
0.33
6.07
0.02
1.82
0.036
0.002
0.019
0.031
0.005
0.003
0.017
<0.01
0.11
0.002
0.003
0.010
<0.005
0.038
0.028
<0
<0
0
0
0
0
0
0
0
0
0
0
<0
0
0
0
0
0
0
.001
.1
.04
.05
.04
.004
.001
.011
.005
.005
.001
.002
.01
.14
.004
.004
.012
.005
.009
0.029
<0
0
<0
0
2
0
0
0
0
0
0
0
<0
0
0
0
0
0
0
0
.001
.91
.01
.03
.2
.007
.002
.012
.005
.003
.001
.006
.01
.40
.004
.007
.009
.007
.008
.015
<0
<0
0
0
<0
0
0
0
0
0
<0
0
<0
0
0
0
0
0
0
0
.001
.1
.04
.03
.01
.005
.001
.009
.007
.005
.001
.012
.01
.72
.001
.004
.008
.007
.013
.018
<0.001
<0.1
0.05
0.05
0.03
0.007
0.002
0.016
0.006
0.004
0.001
0.016
<0.01
1.14
0.002
0.005
0.012
0.008
0.013
0.021
aEach extract was subjected to Flor1s1l chromatography (Method 3620) prior to
GC/ECD analysis on the DB-210 fused-s1!1ca capillary column. Fraction 1 was
eluted with 200 ml petroleum ether; Fraction 2 with 200 ml petroleum ether/dlethyl
ether (1:1). Final voluiie of Fraction 1 or Fraction 2 1s 10 ml. Each fraction
was diluted 1,000-fold prior to analysis. Weight of sediment sample 1s 10 g for
Soxhlet extraction and 30 g for son1cation. To convert to concentrations 1n ng/g
of sediment, multiply the values given 1n ngM extract by 1,000 for Soxhlet
.extraction and 333 for sonlcation extraction.
''Found 1n Fractions 1 and 2 (Flor1s1l chromatography).
c»aThese pairs cannot be resolved on the DB-210 fused-sH1ca capillary column.
49
-------
TABLE 20. RESULTS OF THE METHOD 8120 ANALYSIS FOR EC-2
Certified value3 Value determined by
Compound (ng/g) revised Method 8120b
1,3, 5-Tr i chl orobenzene
1,2, 4-Tr i chl orobenzene
1,2, 4, 5-Tetrachl orobenzene
1,2,3,4-Tetrachlorobenzene
Pentachlorobenzene
Hexachl orobenzene
Hexachlorobutadiene
34
80
84
36
48
200
21
.3
.7
.0
.5
.6
.6
.3
±
±
±
±
±
±
±
2
5
4
2
2
13
1
.6
.4
.9
.4
.4
.2
.6
32.
7.
29.
78.
92.
167.
11.
7
1
8
0
6
9
8
aData taken from Reference 4.
^Height of sample is 10 g. Extraction was performed by Method 3550.
The1 extract was cleaned up by Florisil chromatography. 1-g Florisil
disposable cartridges and elution with hexane/acetone (9:1) were
employed.
50
-------
pentachlorobenzene) than the certified values. No other experiments were
attempted to solve the discrepancy.
A method to prepare reference materials from soils is described in Appendix C.
6.3 EXTRACT CLEANUP TECHNIQUES
Fractionation or cleanup of sample extracts prior to instrumental
analysis (e.g., gas chromatography) is used to remove-coextracted materials
that often interfere with the determination of target analytes. Such
fractionations are usually accomplished by column chromatography (e.g., on
Florisil, alumina, silica gel), gel permeation chromatography, or acid/base
partitioning. More elaborate fractionation schemes that involve a
combination of such cleanup procedures can be quite tedious, and experienced
analysts are required for their successful application.
Standardized cleanup procedures such as Methods 3610 and 3620 published
in EPA SV,'-846(1) specify amounts of alumina and Florisil in excess of 10 g
and large volumes of eluting solvents (e.g., a 12-g Florisil column and
200 mL of petroleum ether are recommended for cleanup of sample extracts
containing chlorinated hydrocarbons). Such large volumes of solvents
increase the likelihood of sample contamination by impurities in solvents.
Furthermore, the adsorbent materials and the solvents are not recycled, and
although such materials are not overly expensive, the time required for the
preparation of the adsorbent, for the packing of the chromatographic columns,
and the evaporation of solvents contributes to the overall cost of analysis.
Use of disposable Florisil cartridges known as Supelclean™, Quick-Sep™,
Sep-Pak™, and Bond-Elut1" for sample extract cleanup has been investigated.
When using disposable cartridges, the elution conditions are typically chosen
to retain the target analytes on the adsorbent while the coextracted
materials are washed from the cartridge with the eluant. Alternatively, the
coextracted materials are retained while the target analytes are eluted from
the cartridge.
This section presents the results of the gel permeation chromatography
experiments, sulfur cleanup experiments, and the Florisil cleanup
experiments.
6.3.1 Gel Permeation Chromatography (GPC)
Due to time and budgetary constraints, It was not possible to develop
and then evaluate a GPC procedure for Method 8120. Instead, the current GPC
procedure given 1n Method 3640 was chosen and evaluated with the target
analytes.
A Bio-Beads SX-3 GPC column and methylene chloride were used to separate
the target compounds from corn oil interferents. To determine the elution
profile of corn oil (which is representative of lipid materials), a solution
of corn oil in methylene chloride was injected Into the GPC column and 10-rt
fractions were collected at 2-min intervals for 36 min. Each fraction was
51
-------
evaporated to dryness and the residue was determined gravimetn'cally.
Table 21 presents the results of the gravimetric analyses. It can be seen
that the elution of corn oil begins with Fraction 9 and over 94 percent of
the corn oil is removed in the first 150 ml of solvent (Table 21). The GPC
elution volumes of the chlorinated hydrocarbons are greater than 150 ml, thus
complete separation of these compounds from lipid materials is achieved by
GPC.
To establish the elution profiles of the chlorinated hydrocarbons, a
composite solution of the 22 chlorinated hydrocarbons (in isooctane) was
injected onto the Bio-Beads SX-3 column which was subsequently eluted with
methylene chloride at 5 mL/min. Fifteen 20-mL fractions were collected over
60 minutes. Methylene chloride was exchanged to hexane following
Kuderna-Danish evaporation, and each fraction was analyzed by GC/ECD on the
DB-210 fused-silica capillary column. Table 22 shows the amounts of various
chlorinated hydrocarbons that were recovered in fractions F-10 through F-13.
The elution profiles are reproducible for the two duplicate experiments,
However, the overall recoveries of the chlorinated hydrocarbons are somewhat
low. Additional experimental work is needed to determine why the recoveries
are low and what can be done to improve them.
6.3.2 Sulfur Removal
Presence of elemental sulfur in sample extracts is undesirable
especially when chlorinated hydrocarbons need to be determined because sulfur
gives large peaks that interfere with the analysis of half of the target
compounds (Figure 16 as compared to Figure 10). Method 3660 is recommended
by EPA for cleanup of sample extracts containing elemental sulfur; however,
the current procedure does not specify how well the procedure works for the
chlorinated hydrocarbons.
We have used the procedure by Jensen et al. (7), which is the procedure
from which Method 3660 was derived, and determined the recoveries of the
target compounds when subjected to the TBA reagent. All recoveries were
quantitative and removal of sulfur is complete (Table 23). Thus, Method 3660
is adequate for incorporation in Method 8120.
6.3.3 Florisil Cleanup
Cleanup of the sample extracts was performed initially according to the
procedure given in EPA Method 3620 (1). In this procedures, Florisil (60/80
mesh), activated (prior to use) at 1308C for at least 16 hours, is used, and
the target compounds are eluted with 200 rnL petroleum ether. Under these
conditions, most of the chlorinated hydrocarbons listed in Table 24 were
recovered quantitatively (recovery >78 percent), except for the BHC isoirers,
benzal chloride, and benzotrichloride. When a second fraction was collected
by eluting the Florisil column with 200 ml petroleum ether/diethyl ether
(1:1), the BHC isomers were recovered quantitatively; however, benzal
chloride and benzotrichloride were not recovered at all (Table 25). It was
then concluded that the Florisil procedure given in Method 3620 needs to be
modified by requiring collection of an additional fraction in order to
52
-------
TABLE 21. GPC ELUTION PROFILE FOR CORN OIL
Fraction
No.
F-l
F-2
F-3
F-4
F-5
F-6
F-7
F-8
F-9
F-10
F-ll
F-12
F-13
F-14
F-15
F-16
F-17
F-18
Total
Weight of residue3
(mg)
<0.0001
< 0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
<0.0001
0.0013
0.0059
0.0564
0.2458
0.3392
0. 2328
0.0590
0.0028
0.0026
0.0021
0.9479 g
(95 percent
recovery)
a5 mL of a 200-mg/mL corn oil
solution in methylene chloride
were loaded to a Bio-Beads SX-3
column; 18 fractions, 10-mL
each, were collected over
36 min. The procedure is given
in Section 7.3.3 of the revised
Method 8120 which is included in
Appendix 3 of this report.
53
-------
TABLE 22. GPC ELUTION PROFILES FOR THE METHOD 8120 COMPOUNDS3
in
Compound
Hexachloroethane
1 ,3-Di chl orobenzene
1 ,4-01 chl orobenzene
1,2-Di chl orobenzene
Benzyl chloride
1,3, 5-TH chl orobenzene
Hexachl orobutad 1 ene
Benzal chloride1*
1,2,4-Trlchlorobenzene''
Benzotrlchlorlde
1 ,2,3-THchlorobenzene
Hexachl orocycl opentad 1 ene
1, 2, 4,5-Tetrachl orobenzene0
1,2, 3, 5-Tetrachl orobenzene0
1,2, 3, 4-Tetrachl orobenzene
2-Chl orona phthal ene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
gamma -BHC
beta-BHC
delta-BHC
Amount
spiked
5
500
500
500
500
50
5
100
50
50
5
50
50
1000
5
5
50
50
50
50
Amount recovered tug)
F-10
<0.1
-------
Figure 16. GC/ECD chromaitogram of a Method 8120 composite standard
containing elemental sulfur. Analysis was done on a
30 m x 0.53 mm ID DB-210 fused-s1!1ca capillary column.
The GC operating conditions are given 1n Table 4. Peaks
labeled A, B,, C, D represent elemental sulfur (Sn- where
n 1s 2,4,6.8).
55
-------
TABLE 23. RECOVERY OF THE METHOD 8120 COMPOUNDS USING THE TBA
PROCEDURE FOR REMOVAL OF ELEMENTAL SULFUR*
Percent recovery
Compound
Hexachloroethane
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1,3,5-Trichlorobenzene
Hexach lorobutadiene
Benzal chlorided
l,2,4-Trichlorobenzened
Benzotri chloride
1,2,3-Trichlorobenzene
Hexach 1 orocy cl opentad iene
1,2,4,5-Tetrachlorobenzene6
1 , 2, 3 ,5-Tetrachlorobenzenee
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexach lorobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Amount
spiked
(wg)
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
ib
101
106
105
106
103
106
104
103
103
106
110
106
105
104
88
107
104
103
104
104
2b
100
105
104
104
101
103
102
103
103
105
108
102
104
102
. 86
106
104
104
102
104
3'
101
104
104
103
102
103
102
103
104
105
110
102
105
103
87
106
104
104
102
105
4C
100
106
105
105
102
104
102
103
104
106
110
104
105
103
86
106
105
105
102
106
Procedure by S. Jensen et al. (Reference 7).
bDuplicate determinations with standards only.
cDuplicate determinations with standards spiked with sulfur
(300 yg/irtj.
d»eThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
56
-------
TABLE 24. ELUTION PATTERNS OF THE METHOD 8120 COMPOUNDS FROM
THE FLORISIL COLUMN BY ELUTION WITH PETROLEUM ETHER
Amount Recovery
Compound (ug) (percent)
Hexachloroethane
1,3-Dlchlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachlorobutadiene
Benzal chloridea»c
1 , 2 ,4-Tri chl orobenzene3
Benzotri chloride0
1,2 ,3-Trichlorobenzene
Hexachlorocycl open tad iene
1 ,2,4,5-Tetrachlorobenzeneb
l,2,3,5-Tetrachlorobenzeneb
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexachlorobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
1.0
100
100
100
100
10
1.0
10
10
10
10
1.0
4 A
10
10
200
1.0
1.0
10
10
10
10
95
84
83
89
62
88
91
0
17
0
90
85
89
93
84
90
86
3
0
2
1
a»bThese pairs cannot be resolved on the DB-210
fused-silica capillary colurm.
cSeparate experiments were performed with benzal
chloride and benzotrichloride to verify that
these compounds are not recovered from Florisil
by elution with petroleum ether.
57
-------
TABLE 25. ELUTION PATTERNS OF THE METHOD 8120 COMPOUNDS FROM THE FLORISIL
COLUMN BY ELUTION WITH PETROLEUM ETHER (FRACTION 1) AND
PETROLEUM ETHER/DIETHYL ETHER 1:1 (FRACTION 2)
Recovery (percent)
Compound
Hexachloroe thane
1 , 3-Di chl orobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1, 3, 5-Trich1 or benzene
Hexachlorobutadiene
Benzal chloridea»c
l,2,4-Trichlorobenzenea
Benzotrichloride0
1,2,3-Trichlorobenzene
Hexachlorocyclopentadiene
l^^.S-Tetrachlorobenzeneb
l,2,3,5-Tetrachlorobenzeneb
1,2, 3, 4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachlorobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Amount
(ug)
1.0
100
100
100
100
10
1.0
10
10
10
10
1.0
10
10
200
1.0
1.0
10
10
10
10
Fraction 1
99
101
101
100
78
99
98
0
59
0
95
93
100
96
111
126
113
0
0
0
0
102
106
108
105
86
106
104
0
60
0
98
94
106
112
119
132
120
0
0
0
0
Fraction 2
0
0
0
0
21
0
0
0
0
0
0
0
0
0
0
0
0
93
106
108
70
0
0
0
0
12
0
0
0
0
0
0
0
0
0
0
0
0
97
105
109
73
a»bThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
°Separate experiments were performed with benzal chloride and
benzotrichloride to verify that these compounds are not recovered
from Florisil in either fraction.
53
-------
recover quantitatively 20 of the 22 target analytes. An additional 8
chlorinated hydrocarbons that were subjected to this Florisil procedure were
found to behave similarly (Table 26).
Table 27 summarizes the recoveries of the 22 target compounds and their
distribution profiles in the absence of interferents ([Samples 2 and 3) and in
the presence of interferents such as corn oil material (Samples 4 and 5),
diesel fuel type hydrocarbons (Samples 6 and 7), and phthalate esters
(Samples 8 and 9). The data shown in Table 27 indicate that 18 compounds are
recovered quantitatively from the Florisil column with 5 irL hexane. The BHC
isomers cannot be recovered with hexane only; therefore, a more polar solvent
(e.g., diethyl ether) is needed to elute the apalytes from the Florisil
column. However, the distribution profiles of the BKC isomers are not
reproducible when hexane and hexane/diethyl ether (1:1) are used as the
eluants. It is interesting to note that when the solution that was applied
to the Florisil cartridge contained 10 percent acetone, then the BHC isorrers
were eluted quantitatively with 5 ml hexane.
To verify that all compounds can be recovered quantitatively from the
Florisil cartridge by elution with 5 ml hexane followed by 10 ml of hexane/
diethyl ether (1:1), we conducted an experiment in which the Florisil
cartridges were loaded with the target compounds at three different levels.
The amounts of the analytes were ranging from 0.02 yg to 2.0 yg for those
compounds that give large signals on the electron capture detector (e.g.,
hexachloroethane, hexachlorobenzene) and from 4 yg to 400 yg for
2-chloronaphthalene. Two and five replicates were performed, depending on
concentration (Tables 28 and 29). Improved reproducibilities and excellent
recoveries were achieved when the eluting solvent was a mixture of hexane/
acetone (9:1). Although hexane/acetone (9:1) elutes the test compounds from
the Florisil cartridge very efficiently (Table 30), at the same time it also
removes the corn oil materials (Table 31). In contrast to hexane, this
solvent mixture is somewhat less desirable; nonetheless, it proved to give
reproducible and quantitative recoveries for the 22 target analytes.
The Florisil procedure was tested with nine environmental materials
including relatively clean matrices such as a sandy loam soil, and highly
contaminated samples, such as the Detroit River Sediment and the Bloody Run
Creek sediment. With very few exceptions, all of the target compounds were
recovered satisfactorily when spiked into sample extracts at known
concentrations. These results are presented in a subsequent section that
addresses method performance.
Use of disposable cartridges reduces solvent usage and labor cost in
sample preparation. Because cartridges are prepackaged and ready for use,
there is no need for adsorbent calibration, activation, or deactivation.
Furthermore, sets of 12 or 24 extracts, depending on the capacity of the
vacuum manifold, can be cleaned up simultaneously with no danger of sample
contamination, thus sample throughput is increased significantly. In
addition, a significant error factor resulting from operator and material
variables that may affect the quality of the results can be eliminated.
59
-------
TABLE 26. ELUTIUN PATTERNS OF OTHER CHLORINATED AROMATIC COMPOUNDS FROM
THE FLORISIL COLUMN BY ELUTION WITH PETROLEUM ETHER (FRACTION 1)
AND PETROLEUM ETHER/DIETHYL ETHER 1:1 (FRACTION 2)
Recovery (percent)
Amount
Compound (ug) Fraction 1 Fraction 2
a-Chloro-o-xylene 10 88 96 00
a,a,4-Tricmoroto1uene 10 96 112 0 0
a,a'-Dich1oro-m-xylene 10 0 0 94 96
1,2,3,4-Tetrachloronaphthalene 10 80 77 00
2,7-Dlchloronaphthalene 10 91 96 00
a,3-Dich1orotoluene 10 93 94 00
a,a',2,4,5,6-Hexachloro-m-xy1ene 10 100 100 0 0
a,2,6-Trichlorotoluene 10 57 54 31 38
60
-------
TABLE 27. RECOVERIES OF THE METHOD 8120 COMPOUNDS FROM FLORISIL
a,b
Compound
Fraction 1 (5 *. hexane) Fraction 2 (5 *. hexane)
Aaount
spiked
Jug) 2k 3A 4A 5A 6A 7A 8AC 9AC 28 38 48 SB 6B 78 88 98
Fraction 3 (5 ri. di ethyl ether/hexane 1:1)
2C 3C 4C 5C 6C ,7C 8C 9C
Hexach loroethane
V , J-0 1 ch lorobenzene
1 ,4-Olchlorobenzene
1.2-Olchlorobenzene
Benzyl chloride
1 ,3.5-Trichlorobenzene
Hexach lorobutadiene
Benzal chloride6
1 , 2 , 4 -T r i ch 1 or o benzene*
Benzotrlchlortde
1. 2, 3-Trlch lorobenzene
Hexach lorocyc lopentad tene
1,2.4. S-Tttrach lorobenzene"
1 . 2 , 3 . 5-Tetrach lorobenzene'
1,2,3,4-Tetrachtorobenzene
2-Ch loronaphtha lene
Pentach lorobenzene
Hexach lorobenzene
alpha-BHC
gaaM-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
90
77
91
74
62
91
89
93
92
93
87
81
126
67
80
110
95
60
0
0
80
75
88
73
55
86
84
90
82
89
80
76
122
63
80
97
56
3
1
0
90
80
95
77
63
96
90
96
94
97
90
85
130
70
90
110
93
50
8
1
90
81
96
78
64
97
93
96
94
97
90
85
131
69
90
no
94
53
9
1
80
62
80
62
52
260*
60
76
80
65
70
54
93
62
70
70
77
53
2
2
75
61
78
62
S3
270<>
70
76
82
67
70
57
97
65
70
76
82
68
3
3
87
78
93
76
64
89
80
84
95
92
87
78
125
66
85
100
99
88
87
85
89
81
97
79
66
94
90
96
98
95
93
83
129
69
86
110
102
89
94
92
2
2
3
3
3
3
2
4
3
3
2
3
3
4
5
4
18
64
40
2
1
1
2
2
5
2
1
3
1
2
0
0
2
3
4
3
63
45
4
0.5
2
2
2
2
3
3
1
3
2
2
2
3
3
3
4
3
35
66
33
2
3
3
3
3
4
4
2
4
3
3
2
4
4
5
5
5
30
63
35
2
3
3
4
3
4
13
3
S
3
4
3
2
4
9
6
4
14
SS
40
2
2
1
1
1
2
5
1
2
1
1
0
2
2
5
4
2
4
26
53
2
2
2
2
2
2
2
2
3
3
2
2
3
3
3
4
3
4
5
3
4
3
0
0
0
4
0
0
0
2
3
0
0
0
9
0
0
0.9
0.3
0.4
6
0
0
0
0
0
0
0
0
3
0
0
0
0
9
8
2
0
8
62
100
0
0
0
0
0
0
0
0
0
0
0
0
0
11
8
3
7
80
95
100
0
0
0
0
0
0
0
0
0
0
0
0
0
4
9
1
2
37
45
95
0
0
0
0
0
0
0
0
0
0
0
0
0
4
2
11
2
J7
41
104
0
f.
V
0
0
0
0
0
0
0
0
0
0
14
929
3
0
5
42
109
0
i °
0
0
0
0
0
0
0
0
0
0
0
15
789
1
0
2
25
108
0
0
0
0
0
0
0
0
0
0
0
0
0
S
459
2
0
1
0
13
0
0
0
0
0
0
0
0
3
0
0
0
0
3
4
2
2
3
2
3
•Florist 1 disposable cartridges (1 9) were used. Fraction 1 *as eluted with 5 *. hexane. Fraction 2 with S M. hexane. and Fraction 3 *ith S «L dlethy)
ether/hexane (1:1).
°Sa*ples 2.3 are standards In hexane. Staples 4.5 are standards in hexane containing corn oil at 20 mg/tL. Saaples 6,7 are standard in hexane
containing diesel fuel at 20 axjM.. Saaples 8,9 are standards in hexane containing the Method 8060 phthalate esters at 20 wg/«L.
'Solution applied to the Florist! cartridge contained 10 percent acetone. It Is very likely that this caused the elution of beta-BHC and delta-BHC in
Fraction 1.
°H1gh recovery due to Mtrix interference. • •
••'These pairs cannot be resolved on the 08-210 fused-silica capillary coluin.
9H1gh recovery of pentachlorobenzene in Fraction 3 is likely due to Mtrix interference since pentachlorobenzene elutes In Fraction 1.
-------
IVJ
TABLE 28 RECOVERIES OF THE METHOD 8120 COMPOUNDS USING FLORISIL DISPOSABLE
* CARTRIDGES (ELUTION WITH HEXANE AND HEXANE/DIETHYL ETHER 1:1)
Percent recovery3
Compound
Hexachloroethane
1 ,3-Dichlorobenzene
1,4-Dichl orobenzene
1 , 2-D1 chl orobenzene
Benzyl chloride
1,3, 5-TH chlorobenzene
Hexachl orobutadi ene
Benzal chloride°
l,2,4-Trichlorobenzeneb
Benzotrlchlorlde
1 ,2,3-Trlchlorobenzene
Hexachl orocyclopent ad iene
1,2, 4, 5-Tetrachl orobenzene0
l,2,3,5-Tetrachlorobenzenec
1,2,3 ,4-Tetrachl orobenzene
2-Chloronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
gamna-BHC
beta-BHC
delta-BHC
Amount
spiked
(.9)
0.1
10
10
10
10
1
0.1
1.0
1.0
1.0
0.1
1.0
1.0
20
0.1
n.i
1.0
1.0
1.0
1.0
Re p.l
Fr.l
76
68
68
69
69
73
71
70
70
73
72
73
80
65
61
110
46
0
0
0
Rep.l
Fr.2
0
0
0
0
11
0
0
0
0
0
0
0
0
0
0
0
60
97
86
89
Rep. 2
Fr.l
65
55
57
59
65
61
57
67
67
66
59
62
73
61
54
102
57
0
0
0
Rep. 2
Fr.2
0
0
0
0
9
0
0
0
0
0
0
0
0
0
0
0
46
95
86
88
Rep. 3
Fr.l
88
83
82
84
85
87
87
80
89
89
87
90
93
77
71
129
94
78
0
0
Re p. 3
Fr.2
0
0
0
0
9
0
0
0
0
0
0
0
0
0
6
0
0
33
81
85
Rep. 4
Fr.l
92
87
87
89
88
94
94
83
92
95
94
97
98
82
76
140
97
81
0
0
Rep. 4
Fr.2
0
0
0
0
16
0
0
0
0
0
0
0
0
5
0
0
9
49
119
114
Rep.S
Fr.l
89
84
82
85
77
88
89
78
69
84
78
86
89
81
65
123
41
0
0
0
Rep. 5
Fr.2
0
0
0
0
24
0
0
0
0
0
0
3
4
6
0
0
72
102
94
03
Average
recovery
(percent)
•
R?
75
75
77
91
81
80
76
77
81
78
82
87
75
67
121
104
107
93
94
RSD
(percent )
14
18
16
16
14
17
19
9.0
16
15
17
18
12
16
15
13
6.6
13
16
12
aFlor1sil disposable cartridges (1 g) were used. Fraction 1 was eluted with 5 ml hexane. Fraction 2 with 10 ml
hexane/dlethyl ether (1:1)- Final volume of each fraction is 2 ml.
D>cThese pairs cannot be resolved on the DB-210 fused-silica capillary column.
-------
TABLE 29. RECOVERIES OF THE METHOD 8120 COMPOUNDS USING FLORISIL DISPOSABLE
CARTRIDGES AS A FUNCTION OF ANALYTE CONCENTRATIONS*
Percent recovery
,.
Compound
9
Hexachloroethane
1,3-Dichlorobenzene
1 ,4-Dichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1,3,5-Trichlorobenzene
Hexachl orobutadi ene
Benzal chloride^
1 , 2,4-Trichl orobenzeneb
Benzotrichloride
1.2,3-TMchlorobenzene
Hexachlorocycl opentadiene
1,2,4, 5-Tetrachl orobenzenec
1 . 2, 3, 5-Tetrachl orobenzenec
1 ,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexachl orobenzene
alpha-BHC
gantna-BHC
beta-BHC
delta-BHC
Amount
spiked
(ug)
2.0
200
200
200
200
20
2.0
20
20
20
2.0
20
20
400
2.0
2.0
20
20
20
20
Rep.l
Fr.l
80
98
129
100
88
120
100
80
70
93
135
103
86
109
90
no
76
63
2.0
0
Rep.l
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
6
37
100
88
Rep. 2
Fr.l
80
100
133
103
90
124
103
79
70
95
140
105
88
116
92
115
75
40
0
0
Rep. 2
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
13
63
no
94
Amount
spiked
(u9)
0.02
2.0
2.0
2.0
2.0
0.2
0.02
0.2
0.2
0.2
0.02
0.2
0.2
4.0
0.02
0.02
0.2
0.2
0.2
0.2
Percent
Rep.l
Fr.l
70
63
81
67
62
85
70
89
121
58
80
78
74
98
80
120
97
53
2.0
0
Rep.l
Fr.2
0
P
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2.0
24
4?
58
recovery
Rep. 2
Fr.l
60
54
70
57
52
74
60
75
98
57
80
67
64
83
70
100
82
58
0
n
Rep. 2
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
14
41
55
aFlorisil disposable cartridges (1 g) were used. Fraction 1 was eluted with 5 ml hexane, Fraction 2
with 10 ml hexane/diethyl ether (1:1).
pairs cannot be resolved on the DB-210 fused-sllica capillary column.
63
-------
Ok
TABLE 30. RECOVERIES OF THE METHOD 8120 COMPOUNDS USING FLORISIL DISPOSABLE
CARTRIDGES (ELUTION WITH HEXANE/ACETONE 9:1)
Compound
Hexachl oroethane
1,3-Oichlorobenzene
1,4-Dichlorobenzene
1.2-D1ch1orobenzene
Benzyl chloride
1, 3. 5-Trichl orobenzene
Hexachl orobutad 1 ene
Benzal chloride^
1,2. 4-Tr 1 c hi or oben zene5
Benzotrichloride
1.2,3-Trlchlorobenzene
Hexachlorocyclopentadiene
1 .2,4 ,5-Tetrachl orobenzenec
1 ,2 ,3 ,5-Tetrachl orobenzenec
1 , 2,3 ,4-Tetrachl orobenzene
2-Chl oronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
al pha-BHC
gatnma-BHC
beta-BHC
delta-BHC
Amount
spiked
(M9)
l.Q
100
100
100
100
10
1.0
10
10
10
1.0
10
10
200
1.0
1.0
10
10
10
10
Percent recovery3
Rep.l
Fr.l
92
99
98
100
100
95
92
99
91
96
100
95
98
94
102
77
100
99
95
95
Rep.l
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3.0
3.0
0
0
Re p. 2
Fr.l
96
102
101
102
101
99
95
99
88
97
104
98
99
95
105
79
100
99
96
99
Rep. 2
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3.0
3.0
3.0
3.0
Rep. 3
Fr.l
96
103
103
103
101
99
96
100
94
98
105
99
100
94
105
79
100
99
94
94
Rep. 3
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4.0
4.0
3.0
3.0
Rep. 4
Fr.l
97
104
102
104
103
101
97
100
96
100
108
101
101
97
106
79
100
100
98
100
Rep. 4
Fr.2
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Re p. 5
Fr.l
96
99
98
101
99
98
94
98
81
95
100
97
98
94
104
78
99
98
94
%
Rep. 5
Fr.2
0
C
0
0
0
0
0
0
0
0
0
0
0
0
0
- JO
0
0
0
0
Average ,
recovery
(percent)
' 1 ^
95
101
100
102
101
98
95
99
90
97
103
98
9f)
95
104
78
100
99
95
97
RSD
(percent)
2.0
2.3
2.3
1.6
1.5
2.2
2.0
0.8
6.5
2.0
3.3
2.2
1.3
1.4
1.5
1.1
0.4
0.7
1.8
2.7
4Florisi1 disposable cartridges (1 g) were used. Fraction 1 was eluted with 5 ml of hexane/acetone 9:1. Fraction 2 with an
additional 5 ml of hexane/acetone 9:1. Final volume of each fraction is 10 ml.
D>cThese pairs cannot be resolved on the DB-210 fused-silica capillary column.
-------
TABLE 31. ELUTION PROFILES OF CORN OIL FROM FLORISIL DISPOSABLE
CARTRIDGES
Percent recovery*
Percent recovery3
Amount
spiked
(mg)
10
200
500
Fraction 1
(5 tnL
hexane)
0
63
72
Fraction 2
(5 mL
hexane)
0
4.8
2.7
Fraction 3
(5 mL
hexane/
di ethyl
ether
(1:1))
102
32
20
Amount
spiked
(mg)
10
20
500
Fraction 1
(5 mL
hexane/
acetone
(9:1))
101
91
91
Fraction 2
(5 mL
hexane/
acetone
(9:1))
0
0.8
0.9
aFlorisil disposable cartridges (1 g) were used; 1 nt of a corn oil
solution in hexane (concentration 10 mg/mL, 200 mg/mL, 500 mg/mL) was
used in each case.
65
-------
An additional advantage of the Flor1s1l procedure 1s the complete
removal of phenolic compounds by the Flor1s1l material. If chlorinated
hydrocarbons are to be determined 1n the presence of the phenolic compounds,
then this Flor1s1l cleanup 1s a must, because the 12 chlorinated hydrocarbons
elute 1n the retention window of the phenolic compounds when the gas
chromatographlc analysis 1s performed on the DB-210 fused-sH1ca capillary
column.
6.4 PRESERVATION STUDY
Tables 32 through 34 summarize the results of the preservation
experiments for water samples. The same results are presented in Figures 17
through 28. Tables 35 and 36 summarize the results for spiked soil samples
that were kept frozen at -10°C for 5 and 6 months, respectively. At pH 7,
recoveries were >80 percent at day 1 for all compounds when spiked 1n reagent
water. BHCs appeared to be stable for up to 21 days while compounds such as
benzyl chloride, benzal chloride, and benzotrichloride were found to degrade
rapidly. Recovery of benzal chloride at day 21 was slightly above 10 percent
and the recoveries of benzyl chloride and benzotrichloride were about
20 percent. Hexachlorobutadlene and hexachlorocyclopentadlene also degraded
quite rapidly. The latter was reported to be very photosensitive to sunlight
or long wave UV light (8). Its half-life 1s less than 3.5 m1n in aqueous
solution and less than 1.6 m1n and 2.5 min in hexane and methanol,
respectively (8). At pH 2 benzyl chloride, benzotrichloride,
hexachlorobutadiene, and hexachlorocyclopentadlene appeared to be slightly
more stable. Recoveries of the rest of the compounds were not much different
from those obtained at pN 7.
At pH 9, benzal chloride disappeared much faster than benzyl chloride or
benzotrichloride, and delta BHC was the only BHC compound that degraded. It
1s Interesting to note that at pH 9 recovery of pentachlorobenzene was about
250 percent at day 7 and about 230 percent at day 14. Additional work is
needed 1n order to determine whether the apparent Increase 1n the
concentration of pentachlorobenzene is due to pentachlorobenzene being formed
in the sample from other chlorinated benzenes or to an interferent that might
be coeluting with pentachlorobenzene on the DB-210 fused-sllica capillary
column.
Data on the preservation of soil samples by freezing at -10°C Indicate
that only half of the compounds can be preserved (e.g., tetrachlorobenzenes,
2-chloronaphthalene, pentachlorobenzene, hexachlorobenzene, and the four BHC
isomers) since the other compounds have either disappeared completely (e.g.,
benzotrichloride and hexachlorocyclopentadlene) or only small percentages
were recovered after 5 and 6 months (e.g., recovery of benzal chloride is
4.3 percent and recovery of benzyl chloride 1s 10 percent).
66
-------
TABLE 32. CONCENTRATION (ng/pL OF EXTRACT) AS A FUNCTION OF TIME AT PH
Compound
Hexachloroethane
1,3-Dichlor obenzene
1 ,4-Uichlorobenzene
1 . 2-Di chl or obenzene
Benzyl chloride
1.3.5-Trichlorobenzene
Hexachl orobutadl ene
Benzal chloride^
1.2.4-Tetrachlorobenzene>>
Benzotrichloride
1 .2. 3- Tetrachlor obenzene
Hexachlorocyclopentadlene
1,2. 4. 5-Tetrachlor obenzene'
l,2.3.5-Tetrachlorobenzenec
1,2,3 ,4-Tet rachl orobenzene
2-Cnloronapnthalene
PentacMorobenzene
Hexachlorobenzene
alpha-flHC
g«MU-BHC
bet«-6HC
delU-BHC
Surrogate recovery (percent)
a.2.6-Trich1orotoluene
1,4-Dichloronaphthalene
2.3,4,5.6-Pentichlorobenzene
Spike
Level
(ng/uU
0.1
10.0
10.0
10.0
10.0
1.0
0.1
2.0
1.0
1.0
0.1
2.0
1.0
20.0
0.1
0.1
1.0
1.0
1.0
1.0
0.1
1.0
0.1
Day
0.108
10.6
11. 8
11.3
11.1
1.17
0.113
2.17
1.09
1.13
0.162
2.35
1.14
23.8
0.118
0.121
1.08
1.08
1.09
l.OS
89
98
95
0
0.093
8.51
8.82
8.69
8.90
0.890
0.087
1.92
1.00
0.926
0.132
1.39
0.949
19.1
0.098
0.100
0.990
0.989
0.933
0.945
75
87
83
Day
0.088
7.08
8.24
8.40
9.05
0.647
0.080
1.67
0.888
0.872
0.104
1.82
0.903
18.1
0.096
0.101
1.02
1.02
1.09
1.02
83
87
92
1
0.082
6.27
7.35
7.41
8.18
0.799
0.075
1.58
0.840
0.829
0.103
1.74
0.874
17.7
0.094
0.100
1.02
1.03
1.10
1.02
85
90
91
Day
0.073
5.51
6.70
6.60
7.73
0.702
0.065
1.37
0.779
0.732
0.096
1.56
0.795
16.3
0.087
0.093
1.01
1.02
1.14
1.04
88
91
97
3
0.045
3.06
4.21
3.68
4.96
0.432
0.037
0.871
0.585
0.397
0.058
0.87
0.435
10.3
0.059
0.061
0.783
0.807
0.775
0.800
68
72
77
Day
0.074
5.57
6.08
6.39
6.26
0.622
0.059
1.08
0.693
0.695
0.062
1.38
0.727
13.9
0.073
0.076
0.901
0.902
0.895
0.900
86
76
86
7
0.066
4.71
5.29
5.50
5.65
0.557
0.053
0.943
0.626
0.631
0.057
1.25
0.671
13.2
0.069
0.070
0.892
0.884
0.895
0.890
84
74
85
Day 10
0.024
2.02
2.98
2.65
3.99
0.240
0.019
0.362
0.265
0.247
0.032
0-475
0.251
6.47
0.041
0.041
0.683
0.732
0.870
0.850
96
86
92
Day
0.03S
2.86
3.90
3.77
3.43
0.302
0.022
0.271
0.118
0.326
0.038
0.578
0.306
7.88
0.043
0.042
0.761
0.799
0.852
0.862
94
86
90
14
0.043
2.90
3.85
3.79
2.91
0.378
0.033
0.326
0.30S
0.424
0.055
0.491
0.452
10.1
0.056
0.050
0.772
0.795
0.767
0.809
79
73
77
Day
0.066
5.47
5.64,
f.»?
2.19
0.538
O.OSO
0.351
0.380
0.612
0.055
1.185
0.645
12.8
0.065
0.066
0.881
0.883
0.820
0.868
72
66
75
21
0.051
4.91
5.31
5.48
2.32
0.447
0.031
0.300
0.094
0.548
0.038
0.998
0.575
12.5
0.058
0.060
0.899
0.905
0.894
0.913
78
71
80
•To convert to ng/l of water. Multiply the values given by a factor of 2.
"•'These pairs cannot be resolved on the 08-210 fused-silica capillary column.
-------
TABLE 33. CONCENTRATION (ng/uL OF EXTRACT) AS A FUNCTION OF TIME AT pH 2*
Compound
Hexachloroethane
1 , 3-Uichl orobenzene
1,4-Dichlorobenzene
1,2-Ui chl orobenzene
Benzyl chloride
1, 3, 5-Tri chl orobenzene
Hexachlorobutadi ene
Benzal chloride^
l,2,4-Trichlorobenzeneb
Benzotrichloride
1 , 2 , 3-Tri chl orobenzene
Hexachlorocyclopentadiene
l,2,4,5-Tetrachlorobenzenec
1,2. 3, 5-Tetrachl orobenzene0
1 , 2, 3, 4-Tetrach! orobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexa chl orobenzene
alpha-BHC
gamroa-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
0,2,6-Trichlorotoluene
1,4-Dichloronaphthalene
2,3,4,5,6-Pentachlorobenzene
Spike
Level
(ng/nL)
0.1
10.0
10.0
10.0
10.0
1.0
0.1
2.0
1.0
1.0
2.0
2.0
1.0
20.1
0.1
0.1
1.0
1.0
1.0
1.0
Day
0.105
10.1
10.9
10.7
10.5
1.09
0.107
2.10
1.08
1.09
0.160
2.24
1.09
22.6
0.113
0.116
1.06
1.06
1.06
1.03
91
95
94
0
0.107
10.5
11.4
11.1
10.9
1.16
0.112
2.10
1.07
1.14
0.173
2.36
1.15
23.9
0.117
0.121
1.08
1.08
1.09
1.05
93
100
98
Day
0.088
7.18
7.6-1
8.23
7.81
0.778
0.079
1.48
0.837
0.860
0.081
1.77
0.892
16.9
0.086
0.087
0.962
0.957
0.987
0.962
96
82
94
7
0.071
5.24
5.72
5.98
5.60
0.581
0.056
1.09
0.674
0.658
0.062
1.32
0.698
13.5
0.071
0.072
0.898
0.897
0.907
0.905
86
75
86
Day
0.089
7.12
8.09
8.51
4.41
0.818
0.079
0.459
0.605
0.926
0.103
1.74
0.878
17.7
0.094
0.087
0.969
0.981
0.969
0.967
99
100
102
14
0.084
6.55
7.47
7.84
4.18
0.739
0.072
0.452
0.597
0.852
0.102
' 1.67
0.846
16.9
0.091
0.084
0.954
0.965
0.944
0.954
96
98
99
aTo convert to yg/L of water, multiply the values given by a factor of 2.
c«dThese pairs cannot be resolved on the 08-210 fused-sH1ca capillary column.
68
-------
TABLE 34. CONCENTRATION (ng/uL OF EXTRACT) AS A FUNCTION OF TIME AT pH 9*
Compound
Hexachloroe thane
1,3-Dichl orobenzene
1,4-Di chl orobenzene
1 , 2-Di chl orobenze ne
Benzyl chloride
1, 3, 5-Tricnl orobenzene
Hexachlorobutadiene
Benzal chloride3
1 . 2. 4-Tr i chl orobenzene*
Benzotrichloride
1, 2, 3-Trichloro benzene
Hexachlorocyclopentadiene
1 .2.4, S-Tetrachlorobenzeneb
1.2,3,5-Tetrachlorobenzene0
1.2.3 ,4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexa chl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
cL.2,6-Tr1cn1orotoluene
1,4-Di chloronaphthalene
2,3,4,5.6-Pentachlorobenzene
Spike
Level
(ng/wL)
0.1
10.0
10.0
10.0
10.0
1.0
0.1
2.0
1.0
1.0
0.1
2.0
1.0
20.0
0.1
1.0
1.0
1.0
1.0
1.0
Day
0.106
10.4
11.3
10.9
10.8
1.12
0.109
2.15
1.09
1.11
0.164
2.28
1.11
22.9
0.114
0.116
1.06
1.07
1.08
1.04
90
93
93
0
0.105
10.1
10.9
10.7
10.6
1.09
0.108
2.13
1.08
1.09
0.161
2.24
1.10
22.4
0.112
0.115
1.06
1.06
1.07
1.03
85
94
91
Hay
0.099
9.25
9.36
9.99
7.44
0.994
0.096
0.958
0.809
1.05
0.158
2.15
1.09
22.4
0.278
0.113
1.04
1.03
1.09
0.710
96
101
100
7
0.089
8.09
8.07
8.62
6.83
0.819
0.079
0.793
0.754
0.895
0.137
1.79
0.939
18.8
0.234
0.094
0.961
0.957
1.02
0.644
90
97
96
Day
0.081
6.38
7.02
7.64
4.14
0.706
0.067
0.452
0.578
0.823
0.100
1.59
0.835
16.3
0.213
0.086
0.934
0.940
0.981
0.684
99
98
103
14
0.086
6.53
7.15
7.91
4.18
0.792
0.079
0.438
0.606
0.914
0.116
1.84
0.941
18,1
0.255
0.096
0.958
0.959
0.988
0.642
100
99
104
aTo convert to ug/L of water, multiply the values given by a factor of 2.
c»dThese pairs cannot be resolved on the DB-210 fused-silica capillary column.
69
-------
a
UJ
o
u
a
H
U
O
a:
UJ
a.
110
100 -
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
/\
/\
/
/
/
/
Y.
i
HCE
/
/
/\
/
/
/
/\
DCB 1.3
DCB 1.4
DCB 1.2
BENZYLCL
X X
TRICB 1.3.5
T=0
COMPOUNDS
T=3 1^3 T = 7
IXXI T=14
T = 21
Figure 17. Recovery as a function of time at pH 7 for: hexachloroethane.
1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene,
benzyl chloride, and 1,3,5-trichlorobenzene.
-------
u.
u
I
o
u
LJ
O
a
u
a.
I3U —
140 -
130 -
120 -
110 -
100 -
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
n -
7
/
/
/
/
/
/
/
/
/
X
X
X
X
X
X
X
X
X
X
x
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Y/////////////////.
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y
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vS
X
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(I
HCBu
TRICB 1,2.4
BENZALCL
BENZOTRICL
T-0
COMPOUNDS
T=7
TRICB 1.2.3
T=14
HCCP
T=21
Figure 18.
Recovery as a function of time at pH 7 for: hexachlorobutadlene,
1,2,4-trlchlorobenzene, benzal chloride, benzotrlchlorlde.
1,2,3-trlchlorobenzene, and hexachlorocyclopentadiene.
-------
K
u
o
UJ
tK
UJ
O
CC
UJ
Q.
120
110 -
/ \
\
I
TETCB 1,2.4.5 TETCB 1.2.3.5 TETCB 1.2.3.4
CN-2
T=0
T=1
COMPOUNDS
T=7
QCB
T=14
HCB
T = 21
Figure 19. Recovery as a function of time at pH 7 for: 1,2,4,5-tetrachloro-
benzene, 1,2,3,5-tetrachlorobenzene, 1,2,3,4-tetrachlorobenzene,
2-chloronaphthalene, pentachlorobenzene, and hexachlorobenzehe.
-------
UJ
K.
Id
o
u
a.
i-
z
u
o
T=0
ALPHA-BHC
GAMMA-BHC
BETA-BHC
DELTA-BHC
COMPOUNDS
T=1
T=3
T=14
T=21
Figure 20.
Recovery as a function of time at pH 7 for: alpha-BHC,
gamma-BHC, beta-BHC, and delta-BHC.
-------
120
110 -
100 -
90 -
80 -
70 -
60 -
50
40 -
30 -
20 -
10 -
0
I
I
I
I
I
TRICB 1.3.5
HCE
DCB 1.3
DCB 1.4
COMPOUNDS
T = 7
DCB 1.2
BENZYLCL
T=14
Figure 21. Recovery as a function of time at pH 2 for: hexachloroethane,
1,3-dichlorobenzene. 1,2-dichlorobenzene, 1,4-dichlorobenzene,
benzyl chloride, and 1,3,5-trichlorobenzene.
-------
en
tt
u
s
o
LJ
(T
I-
LJ
O
ft
170
160 -
150 -
140 -
130 -
120 -
110
100 -
90 -
80 -
70 -
60 -
50 -
40 -
30 -
20 -
10 -
0
/\
HCBu
1
TRICB 1.2.4
T=0
BENZALCL
BENZOTRICL TRICB 1.2.3
HCCP
COMPOUNDS
T = 7
T=14
Figure 22. Recovery as a function of time at pH 2 for: hexachlorobutadlene,
1,2.4-trlchlorobenzene, benzal chloride, benzotrlchloride,
1,2,3-trlchlorobenzene, and hexachlorocyclopentadlene.
-------
IE
U
o
Ul
(T
I-
LJ
O
120
110
100
90
80
70
60
50
40
30
20
10
0
/\
r r " r
TETCB 1.2.4.5 TETCB 1.2.3.5 TETCB 1.2.3.4
I
T
CN-2
T=0
COMPOUNDS
T = 7
I
QCB
HCB
T-14
Figure 23. Recovery as a function of time at pH 2 for: 1,2,4,5-tetrachloro-
benzene, 1,2,3,5-tetrachlorobenzene, 1,2,3,4-tetrachlorobenzene,
2-chloronaphthalene, pentachlorobenzene, and hexachlorobenzene.
-------
8
u
u
-------
00
o:
LJ
s
o
u
a:
H-
Z
u
o
a:
u
a.
120
110 -
100 -
90 -
80 -
70 -
60 -
50 -
40 -
30 -i
20 -
10 -
0
HCE DCB 1.3 DCB 1.4 DCB 1.2 BENZYLCL
COMPOUNDS
I77I T=0 r\\] T = 7 VTTZk T=14
TRICB 1.3.5
Figure 25. Recovery as a function of time at pH 9 for: -hexachloroethane,
1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene,
benzyl chloride, and 1,3,5-trichlorobenzene.
-------
170
VO
o:
o
u
a
o
a.
u
a
HCBu
TRICB 1.2.4
ZZ1
BENZALCL
BENZOTRICL TRICB 1.2.3
HCCP
COMPOUNDS
\Xl T = 7
T=14
Figure 26. Recovery as a function of time at pH 9 for: hexachlorobutadiene.
1,2,4-trichlorobenzene. benzal chloride, benzotrichloride.
1,2,3-trichlorobenzene, and hexachlorocyclopentadiene.
-------
CD
O
K
LJ
O
111
a:
H
LJ
O
a
260
240
220
200
180
160
140
120
100
80
60
40 -
20
TETCB 1.2.4.5 TETCB 1.2.3.5 TETCB 1.2.3.4 CN-2
COMPOUNDS
T-0
OCB
HCB
T=14
Figure 27. Recovery as a function of time at pH 9 for: 1,2,4,5-tetrachloro-
benzene, 1,2,3,5-tetrachlorobenzene, 1,2,3,4-tetrachlorobenzene,
2-chloronaphthalene, pentachlorobenzene, and hexachlorobenzene.
-------
00
8
o
u
a
ALPHA-BHC
GAMMA-BHC
T-0
COMPOUNDS
T-7
DELTA-BHC
Figure 28. Recovery as a function of time at pH 9 for: alpha-BHC,
gamma-BHC. beta-BHC, and delta-BHC.
-------
TABLE 35 HOMOGENEITY OF SPIKED SOIL SAMPLES PREPARED BY BLENDING AND KEPT
FROZEN FOR 5 MONTHS
Concentration
Compound
Hexachloroethane
1 . 3-0 1 ch 1 orobenzene
1 , 4-0 1 ch 1 orobenzene
1 , 2-D 1 ch 1 orobenzene
Benzyl chloride
l,3,5-Tr1ch1orobenzene
Hexach 1 orobutad J ene
Benzal chloride0 h
1 ,2,4-Tr1chlorobenzeneD
Benzotrlchlorlde
1,2.3-Trlchlorobenzene
Hexachlorocyclopentadlene
1,2,4, 5-Tetrach 1 orobenzene;
l,2,3,5-Tetrachlorobenzenec
1,2,3, 4-Tetrach 1 orobenzene
2-Chloronaphthalene
Pentach 1 orobenzene
Hexach 1 orobenzene
alpha-BHC
gana-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
o,2,6-Tr1chlorotoluene
l,4-D1chloronaphthalene
2,3,4,5,6-Pentachlorotoluene
Spike
Level
0.1
10.0
10.0
10.0
10.0
1.0
0.1
2.0
1.0
1.0
0.1
2.0
1.0
20.0
0.1
0.1
1.0
1.0
1.0
1.0
0.1
1.0
0.1
-1
0.
0.
3.
1.
1.
0.
0.
0.
0
0.
0
0.
0.
12.
0.
0.
0.
0.
0.
0.
104
100
100
02
27
68
54
16
41
025
075
22
51
43
8
042
033
64
71
37
60
-2
0.
0.
2.
1.
1.
0.
0.
0.
0
0.
0
0.
0.
15.
0.
0.
0.
0.
0.
0.
114
104
103
02
19
34
59
30
38
026
086
29
69
61
0
052
041
73
82
57
78
-3
0
0
2
1
0
0
0
0
0
0
0
0
0
16
0
0
0
0
0
0
100
91
92
.02
.18
.74
.37
.93
.39
.029
.090
.32
.84
.72
.8
.058
.047
.79
.88
.74
.88
-4
0.02
0.07
2.74
1.61
1.00
0.36
0.027
0.091
0
0.30
0
0.81
0.69
16.0
0.058
0.052
0.78
0.86
0.69
0.85
105
96
109
(ng/gL extract)'
-5
0.02
0.06
2.93
1.44
0.90
0.37
0.031
0.094
0
0.36
0
0.89
0.79
17.5
0.063
0.051
0.82
0.91
0.80
0.92
110
104
107
Average
0.02
0.15
2.89
1.51
1.06
0.38
0.028
0.087
0
0.30
0
0.75
0.65
15.6
0.055
0.044
0.75
0.84
0.63
0.81
107
99
104
Percent
RSD
0
59.0
17.1
6.8
15.9
5.1
8.6
8.5
._
17.1
20.3
21.2
11.7
14.6
16.4
9.4
9.2
27.0
15.6
4.7
5.1
7.4
?To convert to ng/g of soil. Multiply the values given 1n ngM extract by 400.
D'cThese pairs cannot be resolved on the OB-210 fused-silica capillary column.
82
-------
TABLE 36. HOMOGENEITY OF SPIKED SOIL SAMPLES PREPARED BY BLENDING AND KEPT
FROZEN FOR 6 MONTHS
Compound
Hexachloroethane
1.3-D1chloroben2ene
1,4-Olchlorobenzene
l,2-01chlorobenzene
Benzyl chloride
1,3,5-Trlchlorobenzene
HexachlorobutadJene
Benzal chloride" .
1.2.4-Tr1ch1orobenzeneD
Benzotrl chloride
1 , 2 , 3-Tr 1 ch 1 orobenzene
Hexachlorocyclopentadlene
1 . 2 . 4 . 5- Tetrach 1 orobenzene^
1.2,3. 5-Tetrach 1 orobenzene
1,2.3,4-Tetrachlorobenzene
2-Ch 1 oronaphtha 1 ene
Pentach 1 orobenzene
Hexachl orobenzene
alpha-BHC
gam-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
0,2,6-Trlchlorotoluene
1 , 4-0 1 ch 1 oronaphtha 1 ene
2.3.4.5,6-Pentachlorotoluene
Spike
level
(ng/uL)
0.1
10.0
10.0
10.0
10.0
1.0
0.1
2.0
1.0
1.0
0.1
2.0
1.0
20.0
0.1
0.1
1.0
1.0
1.0
1.0
0.1
1.0
0.1
Concentration (ngM extract)*
-6
0.01
0.12
2.36
1.13
0.53
0.34
0.021
0.09
0
0.31
0.011
0.96
0.80
20.75
0.07
0.044
0.81
0.86
0.75
0.84
98
91
78
-7
0.
0.
1.
0.
0.
0.
0.
0.
0
0.
0.
0.
0.
8.
0.
0.
0.
0.
0.
0.
91
91
96
008
10
05
80
40
21
on
05
15
006
37
31
14
039
025
58
63
34
57
-8
0
0
2
1
0
0
0
0
0
0
0
0
0
11
0
0
0
0
0
0
90
100
79
.012
.17
.97
.09
.52
.28
.016
.06
.20
.006
.51
.45
.02
.048
.029
.69
.73
.51
.70
-9
0
0
2
0
0
0
0
0
0
0
0
0
0
14
0
0
0
0
0
0
90
95
95
.016
.10
.16
.87
.42
.26
.018
.07
.18
.01
.51
.43
.24
.047
.035
.68
.73
.48
.69
Average
0.
0.
2.
0.
0.
0.
0.
0.
0
0.
0.
0.
0.
13.
0.
0.
0.
0.
0.
0.
92
94
88
012
12
14
97
47
27
017
07
21
008
59
50
54
051
033
69
74
52
70
Percent
RSD
28.5
26.9
37.5
16.7
14.3
19.7
24.7
24.4
__
33.2
32.9
43.7
42.4
40.0
26.0
25.0
13.7
12.8
32.8
15.8
3.6
3.9
9.8
"To convert to ng/g of soil. Multiply the values given 1n ng/uL extract by 400.
D>cThese pairs cannot be resolved on the 08-210 fused-slllca capillary column.
83
-------
6.5 REVISED METHOD 8120 PROTOCOL
The revised Method 8120 was evaluated in terms of the reproducibility of
the injection technique, the linearity of response over several orders of
magnitude in_concentration, the precision of the identification and
measurement of the gas chromatographic technique, and the minimum detectable
levels for the target analytes were established. Subsequent subsections
address the reproducibility of the injection technique, the instrument
calibration, and the method detection limit. Furthermore, a ruggedness test
of the ?as chromatographic procedure was performed and is described in this
section.
6.5.1 Reproducibility of the GC Technique
To establish the reproducibility of the GC technique, 10 consecutive
injections of isooctane blanks, spiked with 10 uL of a 1,3,5-tribromobenzene
solution at 100 ng/wL (nominal concentration of 1,3,5-tribromobenzene that
was analyzed is 1 ng/wL), were performed with an autosampler.
The results are presented in Table 37 as the retention time (minutes)
and the absolute response of the 1,3,5-tribromobenzene, the average values of
the two parameters, and their corresponding standard deviations (SO) and
relative standard deviations (RSD). The reproducibility of the retention
time and detector response for the 10 consecutive injections are 0.67 percent
and 0.8 percent, respectively. When actual samples were analyzed over a
24-hour period (Table 38), the reproducibility of retention time on three
different days for 9 to 25 injections ranged from 0.066 to 0.13 percent.
Similarly, the reproducibility of detector response ranged from 14 to
28 percent. The internal standard that was tested in this case was
a,ct'-dibromo-m-xylene.
Tables 39 and 40 present the retention times of the Method 8120
compounds relative to a,a'-d1bromo-m-xylene and 2,5-d1bromotoluene,
respectively. Table 41 shows the reproducibility of the detector response
for each target analyte over a period of five days for six injections. With
the exception of l,4-d1chlorobenzene, the target analytes exhibited percent
RSDs better than 15 percent, with 72 percent of the values under 10 percent.
6.5.2 Instrument Calibration
Quantification of the target analytes is typically performed using two
types of calibration: external standard calibration and internal standard
calibration. In the former case, working solutions containing the target
analytes are"analyzed prior to samples to determine the linear dynamic range
of the detector. Quantification of compounds in an unknown sample is
performed by comparing the detector responses obtained for the unknown sample
to that measured for a calibration standard that is within the linear range
of the instrument. In the latter case, the linear dynamic range of the
instrument needs to be established the same way. In addition, an internal
standard is spiked into every calibration standard and unknown sample. After
the sample is analyzed, the ratio of detector responses of each test compound
84
-------
TABLE 37. REPRODUCIBILITY OF RETENTION TIME AND ABSOLUTE
PEAK AREA FOR 1,3,5-TRIBROMOBENZENE SPIKED AS
INTERNAL STANDARD IN ISOOCTANE BLANKS3
Injection
number
1
2
3
4
5
6
7
8
9
10
Average
SO
RSO (percent)
Retention time
(m1n)
11.70
11.69
11.70
11.68
11.70
11.69
11.70
11.69
11.69
11.68
11.69
0.0079
0.067
Detector response
5093338
4982222
4978096
5013383
4996981
5052108
5000252
5033607
5074277
5025909
5025017
38687
0.8
Analyses were performed using an autosampler. the DB-210
column, and the operating conditions given 1n Table 4.
Each Isooctane blank was spiked with 10 »L of a
1,3,5-trlbromobenzene solution 1n Isooctane (concentration
100 ng/pL).
85
-------
TABLE 38. REPRODUCIBILITY OF ABSOLUTE RESPONSE AND RETENTION TIME
FOR a.a'-niBROMO-M-XYLENE3
Retention time (min)
Detector response
Date
November
November
November
13,
17,
20,
1987
1987
1987
Average
value
16.601
16.65
16.70
SD
0.011
0.020
0.020
RSD
(percent)
0.066
0.102
0.130
nb
25
11
9
Average
value
283,621
284,484
305,529
38
68
86
SO
,746
,100
,467
RSD
(percent) n&
14
24
28
25
11
q
Analyses were performed using an autosampler, the DB-210 column, and the
operating conditions given in Table 4. Each standard or sample extract was
spiked with 10 uL of a ot,ct'-dibromo-m-xylene solution in isooctane
(concentration 100 ng/uL).
Number of determinations.
86
-------
TABLE 39. RELATIVE RETENTION TIMES (RRT) OF THE METHOD 8120 COMPOUNDS
ON THE DB-210 FUSED-SILICA CAPILLARY COLUMN*
RRT
Compound
HexacHloroethane
1,3-Dichlorobenzene
1 ,4-Di chlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1, 3, 5-Tri chlorobenzene
Hexachlorobutadlene
Benzal chlorideb
l,2,4-Trichlorobenzeneb
Benzotrichloride
1, 2, 3-Tri chlorobenzene
Hexachlorocyclopentadiene
l,2,4,5-Tetrachlorobenzenec
1,2,3, 5-Tet rach 1 or obe nzenec
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachlorobenzene.
Hexa chlorobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Std. 1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
.1574
.1723
.1795
.2117
.2206
.2648
.2826
.3399
.3399
.3942
.4091
.4502
.5224
.5224
.6208
.7090
.7913
.0459
.2200
.3298
.4186
.4538
Std. 2
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
1.
1565
1720
1792
2115
2198
2640
2820
3393
3393
3931
4086
4498
5221
5221
6207
7091
7921
0478
2204
3321
4194
4546
Std. 3
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
1.
1564
1719
1791
2113
2197
2645
2818
3391
3391
3928
4084
4484
5224
5224
6203
7087
7916
0460
2215
3313
4203
4555
Averaoe
RRT'
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
1.
1568
1721
1793
2115
2200
2644
2821
3394
3394
3934
4087
4495
5223
5223
6206
7089
7917
0466
2206
3311
4194
4546
Percent
RSD
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
35
12
12
09
22
15
15
12
12
19
09
21
03
03
04
03
05
10
06
09
06
06
alnternal standard is a.a'-dibromo-m-xylene; analyses were
performed on December 4, 1987.
b»cThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
87
-------
TABLE 40. RELATIVE RETENTION TIMES (RRT) OF THE METHOD 8120 COMPOUNDS
ON THE DB-WAX FUSED-SILICA CAPILLARY COLUMN4
RRT
Compound ~
Average Percent
Std. 1 Std. 2 Std. 3 Std. 4 Std. 5 Std. 6 RRT RSD
Hexachloroethane
1 ,3-D1chlorobenzene
1,4-Dlchlorobenzene
1,2-Dlchl orobenzene
Benzyl chloride^
l,3,5-Tr1chlorobenzenec
Hexachlorobutadlene
Benzal chloride
1 , 2.4-Tr Ichl orobenzene
Benzotri chloride
1 ,2. 3-Trl chl orobenzene
Hexachlorocyclopentadlene
1,2,4,5-Tetrachlorobenzene
1 , 2. 3 ,5-Tetrachl orobenzene
1 , 2, 3,4-Tetrachlorobenzene
2-Chloronaphthalened
Pentachlorobenzened
Hexac hi orobenzene
alpha-BHC
gama-BHC
beta-BHC
delta-BHC
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
.4383
.4167
.4577
.5164
.5590
.5590
.5380
.8577
.7407
.8318
.8625
.5380
.9601
.9434
.1412
.2803
.2803
.5720
b
b
b
b
0.4377
0.4167
0.4571
0.5164
0.5585
0.5585
0.5375
0.8577
0.7396
0.8323
0.8631
0.5375
0.9590
0.9429
1.1412
1.2798
1.2798
1.5720
b
b
b
b
0.4377
0.4167
0.4577
0.5164
0.5580
0.5580
0.5375
0.8577
0.7407
0.8323
0.8625
0.5375
0.9596
0.9429
1.1407
1.2803
1.2803
1.5714
b
b
b
b
0.4377
0.4167
0.4577
0.5164
0.5590
0.5590
0.5375
0.8577
0.7407
0.8318
0.8620
0.5375
0.9596
0.9429
1.1407
1.2803
1.2803
1.5709
b
b
b
b
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
.4377
.4167
.4577
.5164
.5585
.5585
.5375
.8571
.7407
.8318
.8625
.5375
.9596
.9429
.1407
.2803
.2803
.5720
b
b
b
b
0.4380
0.4169
0.4579
0.5162
0.5593
0.5593
0.5378
0.8581
0.7411
0.8323
0.8630
0.5378
0.9601
0.9439
1.1419
1.2816
1.2816
1.5728
b
b
b
b
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
1.
1.
4379
4167
4576
5164
5587
5587
5376
8577
7406
8321
,8626
5376
9597
9432
1411
2804
2804
5719
b
b
b
b
0.06
0.02
0.06
0.02
0.08
0.08
0.04
0.04
0.07
0.03
0.05
0.04 •
0.04 '
0.04
0.04
0.05
0.05
0.04
b
b
b
b
Internal standard Is 2.5-dlbromotoluene; analyses were performed on November 25, 1987.
"Not able to chromatograph the BHCs on the DB-NAX fused-silica capillary column.
pairs cannot be resolved on the OB-MAX fused-silica capillary column.
88
-------
CO
TABLE 41. RESPONSE FACTORS FOR THE SINGLE-LEVEL CALIBRATION DATA FOR THE
METHOn 8120 COMPOUNDS ANALYZED ON THE DB-210 FUSED-SILICA
CAPILLARY COLUMN
Concentration 11-13-87 11-14-87 11-14-87 11-14-87 11-17-87 11-18-87 RSO
Co^Mund (ng/uL) 06:55 pm 01:04 «• 09:22 a* 05:40 p» 10:35 p* 06:08 an (percent)
Hexachloroethane 0.001 14.2
1.3-D1chlorobenzene 0.1 4.1
1.4-Oichlorobenzene 0.2 1.9
1.2-01chlorobenzene 0.1 4.6
Benzyl chloride 0.1 7.6
1.3.5-Trichlorobenzene 0.01 4.3
Hexachlorobutadlene 0.001 10.3
Benzal chloride" 0.001 3.1
l.2.4-Tr1chlorobenzene* 0.05 3.1
Benzotrlchlorlde 0.005 3.4
l.2.3-Tr1ch1orobenzene 0.1 7.4
Hexachlorocyclopentadlene 0.1 9.3
1.2.4.5-Tetrachlorobenzeneb 0.01 8.0
1.2,3.5-Tetrachlorobenzeneb 0.01 8.0
1.2.3,4-Tetrachlorobenzene 0.01 11.7
2-Chloronaphthalene 0.5 12.1
Pentachlorobenzene 0.01 19.9
Hexachlorobenzene 0.005 6.5
alpha-BHC 0.01 7.3
ga«u-BHC 0.01 7.2
beta-BHC 0.01 2.5
delta-BHC 0.01 5.8
10' 14.1 x 10' 14.2
105 4.1
105 1.9
105 4.6
105 7.6
106 4.3
10' 10. 1
10« 3.1
106 3.1
10' 3.4
10^ 7.4
105 9.2
10« 8.0
10« 8.0
106 12.2
10* 12.6
106 19.9
10' 6.7
10' 7.3
10' 7.2
10' 2.5
10' 5.8
105 4.1
10s 1.9
105 4.6
105 7.5
106 4.3
10' 10.3
10« 3.0
106 3.0
10' 3.5
10« 7.4
10s 9.6
10« 8.1
106 8.1
10« 12.4
104 12.7
Ifl6 19.9
10' 6.6
10' 7.3
10' 7.2
10' 14.1 x 10' 12.2
105 4.1 x 10s 3.5
10s 2.0 x 10s 3.4
10s 4.6 x IflS 4.1
105 7.6 x 105 6.8
106 4.3 x 10« 3.8
10' 10.3 x 10' 9.0
106 3.1 x 106 2.8
106 3.1 x 10^ 2.8
10' 3.6 x 10' 3.9
106 7.4 x IflC 6.7
10s 10.2 x IflS 9.9
106 8.0 x 10^ 8.8
106 8.0 x 106 8.8
106 12.5 x 10* 11.4
104 12.1 x 104 11.9
106 19.9 x 106 18.4
10' 6.5 x 10' 6.0
10' 7.2 x 10' 5.5
10' 7.2 x 10' 5.3
10' 2.5 x 10' 2.5 x 10' 1.7
10' 5.8 x 10' 5.8 x 10' 3.9
10' 13.4
10s 3.8
10s 3.7
10s 4.4
105 7.3
106 4.1
10' 9.4
106 2.9
106 2.9
10' 4.4
Ifl6 7.3
10* 9.3
106 9.5
106 9.5
10^ 11.4
104 11.7
10^ 19.9
10' 7.2
10' 6.2
10' 6.4
10' 2.1
10' 4.6
107 5.8
105 6.4
105' ' *34.3
105 .6
105 .3
Ifl6 .9
10' .7
106 .2
106 .2
10' 10.5
106 3.9
105 4.1
Ifl6 7.4
106 7.4
106 4.2
104 3.2
10« 3.1
10' 5.9
10' 11.3
10' 11.5
10' 14.6
10' 15.7
*»DThese pairs cannot be resolved on the DB-210 fused-silica capillary colum.
-------
to the internal standard 1s compared to that 1n the calibration standard to
determine the concentration of the target analyte.
During the course of this project, we performed four sets of multilevel
calibrations for Jthe 06-210 fused-sH1ca capillary column and one set for the
OB-WAX fused-s1l1-ea capillary column. Initially, we analyzed standards
ranging from O.orng/yL to 0.5 ng/yL for compounds such as hexachloroethane,
hexachlorobenzene, and from 1.0 ng/uL to 100 ng/uL for 2-chloronaphthalene.
The remainder of the compounds were at concentrations in between those
values. From the data in Table 42, we concluded that the linear range
extends only from 0.01 ng to 0.1 ng for hexachloroethane and correspondingly
for the remainder of compounds. The data presented 1n Tables 43 through 46
give the individual response factors, the average response factors, and the
percent RSDs for four sets of multilevel calibrations.
6.5.3 Method Accuracy and Precision
To establish method accuracy and precision, we spiked reagent water
samples, sandy loam samples, and highly contaminated river sediment samples
with the target analytes at concentrations ranging from 1.0 to 200 ug/L (for
water), 330 to 66,000 ng/g (for sandy loam soil), and 1.3 to 260 ng/g and 5.4
to 1,080 ng/g (for Love Canal and RGB-contaminated soil), and processed them
according to the analytical scheme. Furthermore, extracts of nine
environmental matrices (Including some of the samples listed above) and NBS
standard reference materials were spiked with the target analytes and
processed according to the method. Table 47 presents the recovery and precision
data for water samples and Table 48 presents recovery and precision data for
a sandy loam soil. Tables 49 and 50 present the results from two
(contaminated) soil samples spiked at four concentrations, each 1n triplicate
or quadruplicate. Tables 51 through 59 present recovery data (using the
DB-210 and the OB-WAX columns) for the nine environmental sample extracts
that were spiked with the target compounds and processed according to the
method. Figures 29 through 46 show how recovery of each target compound
varies with matrix.
In the case of the water samples, method precision was better than
9 percent and compound recoveries (method accuracy) were greater than
87 percent (Table 47).
In the case of the contaminated soil samples, method precision was
better than 22 percent (except for l,4-d1chlorobenzene, l,2-d1chlorobenzene,
and hexachlorocyclopentadlene), and for most compounds, the recoveries were
greater than 70 percent. Furthermore, method recovery does not seem to be a
function of .analyte concentration or matrix.
In addition to the spiked samples and extracts , we have also analyzed a
series of EPA performance evaluation samples to determine 1f the target
analytes can be Identified and quantified accurately in the presence of other
organic compounds of environmental significance. Tables 60 through 69
summarize the results of these analyses.
90
-------
TABLE 42. MULTILEVEL CALIBRATION DATA FOR STANDARDS ANALYZED ON 5/27/87
Response factor
Compound
Hexachloroe thane
1.3-Dichlorobenzene
1.4-D1chlorobenzene
1 .2-01 chl orobenzene
Benzyl chloride
1 . 3, 5-TMchl orobenzene
Hexachl orobutad 1 ene
Benzal chloride'
1 ,2 ,4-Tr 1 chl orobenzene'
Benzotrlchlorlde
1 ,2 , 3-Tr 1 chl orobenzene
Hexachl orocycl o pent ad 1 ene
l,2,4.5-Tetrachlorobenzeneb
1.2,3 ,5-Te trachl orobenzeneb
1 ,2, 3,4-Tetrachl orobenzene
2 -CM oronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
al pha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.01 to
ng/ul
26.20 x
9.75 x
2.33 x
7.19 x
6.50 x
4.93 x
14.48 x
17.14 x
17.14 x
11.55 x
11.94 x
4.99 x
8.95 x
8.95 x
23.50 x
2.05 x
4.34 x
8.33 x
11.43 x
10.25 x
2.97 x
9.95 x
2.0
106
103
10*
10*
104
105
106
105
105
106
105
106
10*
105
105
10j
in6
106
10«
106
106
106
0.02 to 4.0
ng/nL
30.70 x 106
9.50 x 103
2.33 x 10*
7.83 x 10*
6.97 x 10*
5.02 x 1Q5
15.43 x 106
19.40 x 105
19.40 x HP
9.88 x 106
12.82 x 105
5.45 x 106
9.07 10*
9.07 105
25.99 105
2.18 10*
4.26 106
8.81 106
11.06 106
10.06 106
3.40 x 106
10.40 x 106
0.05 to
ng/pl
28.60 x
9.50 x
2.53 x
9.54 x
8.30 x
5.41 x
18.42 x
16.96 x
16.96 x
6.55 x
15.33 x
6.27 x
10.40 x
10.40 x
27.98 x
2.19 x
4.38 x
9.21 x
7.91 x
7.55 x
4.00 x
7.90 x
10.0
106
103
10*
10*
10«
105
10«
105
105
106
105
106
10*
105
105
10*
106
106
106
106
106
106
0.1 to
ng/ul
22.70 x
10.90 x
3.12 x
10.20 x
9.27 x
6.56 x
17.70 x
13.20 x
13.20 x
4.60 x
15.30 x
8.50 x
11.85 x
11.85 x
23.60 x
2.78 x
5.26 x
13.30 x
5.74 x
5.60 x
3.50 x
5.95 x
?0.0
106
103
10*
10*
10*
105
10^
105
lOf
106
105
106
10*
105
105
10*
10*
10*
106
Ifl6
106
106
0.2 to 40.0
ng/pL
15.84 x 106
12.40 x 103
3.45 x 10*
8.30 x 10*
10.70 x 10*
6.13 x 105
13.50 x 106
9.13 x 105
9.13 x 105
2.93 x 106
11.80 x 10*
8.31 x 10^
9.50 x 10*
9.50 x 105
16.90 x 105
2.88 x 10*
6.10 x 106
12.40 x 106
3.90 x 106
3.78 x 106
2.58 x 106
4.05 x 106
0.5 to 100.0
ng/pL
9.15 x 106
14.30 x 10s
2.80 x 10*
5.27 x 10*
6.40 x 10*
4.30 x 105
8.30 x 106
5.18 x 105
5.18 x 105
1.52 x Ifl6
7.34 x 10*
6.14 x 106
5.69 x 10*
5.69 x 105
9.97 x 105
2.26 x 10*
5.04 x 106
8.56 x 106
2. 10 x 106
2.09 x 106
1.58 x 106
2.43 x 106
Average
22.28 K HO*
11.06 x 103
2.76 x 10*
8.06 x 10*
8.02 x 10*
5.39 x 105
14.60 x 106
13.50 x 105
13.50 x 10s
6.17 x 10fi
12.42 x 105
6.61 x 106
9.24 x 105
9.24 x 105
21.32 x 105
2.39 x 10*
4.90 x 106
10.10 x 106
7.02 x 106
6.56 x 106
3.01 x 106
6.78 x 106
Percent
RSD
37.2
17.6
16.4
21.8
21.5
15.4
?4.8
40.4
40.4
63.8
23.7
22.2
22.1
22.1
31.4
14.6
14.7
21.5
54.1
50.8
28.2
47.3
«bThese pairs cannot be resolved on the DB-210 fused-slllca capillary column.
-------
TABLE 43. MULTILEVEL CALIBRATION DATA FOR STANDARDS ANALYZED ON 6/4/87
Response factor
Compound
0.01 to 2.0
ng/pL
0.02 to 4.0
ng/iiL
0.04 to 8.0
ng/pL
0.05 to 10.0
ng/pL
0.07 to 14.0
ng/pL
0.08 to 16.0
ng/pL
0.1 to 20.0
ng/pl Average
Percent
RSO
Hexachloroethane
1 , 3-P1 chl orobenzene
1,4-Dichl orobenzene
1,2-Oichl orobenzene
Benzyl chloride
1, 3, 5-TMchl orobenzene
Hexachlorobutadlene
Benzal chloride*
1 ,2, 4-TMchl orobenzene*
Benzotrlchlorlde
1. 2. 3-Tri chl orobenzene
Hexachlorocyclopentadlene
1 ,2.4, 5-Tetrachl orobenzene0
1 ,2. 3,5-Tetrachl orobenzeneb
1,2,3, 4-Tetrachl orobenzene
2 -Chl or ona pht hal ene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
24.1 x 106
9.9 x 103
2.3 x 104
6.8 x 104
6.2 x 104
4.1 x 105
12.2 x 106
14.8 x 105
14.8 x 105
10.2 x 10«
10.7 x 105
5.2 x 10*
6.8 x 10s
6.8 x 10s
18.8 x 105
2.3 x 104
4.1 x 106
7.9 x 106
9.2 x lO6
14.5 x 106
4.3 x 106
12.8 x 106
28.7 x 106
9.4 103
2.3 104
7.5 104
6.8 104
4.4 in5
12.9 106
17.1 105
17.1 105
9.4 106
11.4 105
5.6 x 106
7.1 x 105
7.1 x 105
20.1 x Ifl5
2.3 x 104
4.1 x 106
7.9 x 106
9.6 x 106
12.7 x 106
4.0 x 106
12.0 x 106
29.2 x 106
9.3 x 103
2.4 x 104
8.7 x 104
7.7 x 104
4.6 x 105
14.1 x 106
17.3 x 105
17.3 x 105
7.2 x 106
12.5 x 105
5.9 x 106
7.0 x 105
7.0 x 105
21.9 x 105
2.4 x 104
4.1 x 106
8.3 x If*
7.8 x 106
9.9 x 106
4.9 x 10^
9.8 x 106
28.0 x
9.4 x
2.5 x
9.2 x
. 8.1 x
4.7 x
14.7 x
16.2 x
16.2 x
6.4 x
13.1 x
6.2 x
7.1 x
7.1 x
22.3 x
2.4 x
4.1 x
8.6 x
7.1 x
8.8 x
4.3 x
8.7 x
106
103
104
104
104
105
106
105
105
100
105
106
105
105
105
104
10"
106
106
106
106
106
25.1 x 106
9.6 x 103
2.6 x 104
9.6 x 104
fl.5 x 104
4.8 x 105
15.1 x 106
14.5 x 105
14.5 x 105
5.4 x 106
13.6 x 105
6.6 x 106
7.3 x 105
7.3 x 105
21.7 x 105
2.5 x 104
4.2 x 106
9.2 x 106
6.2 x 106
7.4 x 106
3.Q x 106
7.4 x 106
23.9 x 106
9.8 x 103
2.7 x 104
9.7 x 104
8.7 x 104
4.9 x 105
15.2 x 106
13.8 x 105
13.8 x 105
5.1 x 106
13.fi x 105
6.8 x 106
7.4 x 105
7.4 x 105
21.2 x 105
2.6 x 104
4.2 x 10*
9.7 x 106
5.7 x 106
7.0 x 106
3.8 x 106
6.9 x 106
22.4 x
10.6 x
3.0 x
9.9 x
9.0 x
5.5 x
15.4 x
12.9 x
12.9 x
4.5 x
13.8 x
7.7 x
7.7 x
7.7 x
?0.6 x
2.7 x
4.5 x
10.9 x
5.3 x
6.3 x
3.7 x
6.4 x
106 «
103
in4
is\4
10^
10*
106
105
105
106
105
106
10*
105
105
10*
106
106
106
106
106
106
,24.5 x 106
9.6 x m3
2.5 x 104
8.8 x 104
7.9 x 104
4.7 x 105
14.2 x 106
15.2 x 105
15.2 x 105
6.9 x 106
12.7 x 105
6.3 x 106
7.? x 105
7.2 x 105
20.9 x 105
2.5 x 104
4.2 x 106
8.9 x 106
7.3 x 106
9.5 x 106
4.1 x 106
9.1 x 106
9.1
2.5
6.5
13.5
13.1
Q.3
8.7
11.0
11.0
31.7
9.5
13.2
4.1
4.1
5.8
6.0
3.5
12.2
23.1
32.0
10.0
27.4
*>DThese pairs cannot be resolved on the DB-210 fused-sllica capillary column.
-------
TABLE 44. MULTILEVEL CALIBRATION DATA FOR STANDARDS ANALYZED ON 6/18/87
Response factor
0.01 to 2.0 0.02 to 4.0 0.04 to 8.0 0.06 to 10.0 0.07 to 14.0 0.08 to 16.0 0.1 to 20.0
Compound ng/pl ng/wL ng/pL ng/ML ng/nL nq/uL ng/pl Average t RSO
1 i
Hexacbloroethane 24.8
1.3-Dlchlorobenzene 9.8
1.4-Dichlorobenzene 2.4
1.2-Oichlorobenzene 7.0
Benzyl chloride 6.2
1.3,5-Trlchlorobenzene 5.4
Hexachlorobutadlene 14.9
Benzal chloride* 17. 5
1.2.4-THchlorobenzene* 17. 5
Benzotrtchlortde 11.6
1.2,3-Trichlorobenzene 18.3
Hexachlorocyclopentadlene 5.6
1.2.4.5-Tetrachlorobenzeneb 8.4
1.2.3.5-Tetrachlorobenzeneb 8.4
1.2.3.4-TetriChlorobenzene 23.0
2-Chloronaphthalene 2.1
Pentachl orobenzene 4.2
Hexacnl orobenzene 12.7
alptia-8HC 8.3
9MM-BHC 11.0
beU-BHC 3.3
delU-BHC 9.8
106 29.9 « 106 30.5
103 9.8 x 103 10.0
104 2.4 x 10* 2.6
10* 7.7 x 10* 9.2
104 6.7 x 10* 7.9
10* 5.5
106 15.9
10s 20.3
10* 20.3
106 10.1
10* 14.8
10s 7.6
10* 9.S
10s 9.5
10* 26.2
104 2.5
Ifl6 4.3
106 8.9
106 9.4
106 11.1
10s 3.5
106 10.7
105 5.9
Ifl6 18.4
10* 19.1
10* 19.1
106 7.6
10* 16.1
10« 7.5
10* 10.3
10% 10.3
10s 29.7
104 2.5
106 4.4
106 9.1
10s 8.2
106 9.2
10« 4.2
106 9.1
106 29.0
103 9.9
10* 2.6
10* 9.7
10* 8.3
10* 5.8
10s 18.8
105 17.6
10* 17.6
106 6.8
10s 16.1
106 7.4
10* 10.1
10s 10.1
10* 29.3
10* 2.5
106 4.4
10^ 8.8
106 7.5
106 8.4
106 4.2
10* 8.3
10« 25.9
103 10.2
10* 2.8
10* 10.1
10* 8.8
10* 6.3
106 18.8
10s 15. «
10s 15.8
10* 5.7
10s 16.8
10* 8.1
10* 11.8
10s 11.8
10* 27.5
10* 2.7
106 4.8
106 10.2
10« 6.5
106 7.3
106 4.0
106 7.2
10s 24.8
in3 in. a
104 2.9
104 10.2
104 10.2
in* 6.4
10* 18.9
105 14.8
10s 14.8
10* 5.3
10s 16.6
106 7.9
10* 11.4
10* 11.4
10s 26.7
10* 2.7
10* 4.6
10« 10.9
I0« 6.2
106 6.9
106 3.9
in6 22.8
lO1 10.9
10* ?.l
in* 10.2
10* 9.1
10* 6.8
106 17.8
10* 13.4
10* 13.4
106 4.7
10* 15.6
10s 8.7
10* 11.8
10* 11.8
10* 24.8
10* 5.6C
106 5.0
106 12.1
10" 5.7
106 6.2
10« 3.S
106 6.9 x 106 6.2
106 26. «
in3 ID.)
10* 2.7
in4 9.2
10* 8.2
in* e.n
in* 17.6
in* 16.9
10* 16.9
10* 7.4
10* 16.3
10* 7.5
10* 10.5
10* 10.5
10s 26.7
10* 2.9
10s 4.5
in« 10.4
106 7.4
Ifl6 8.6
106 3.8
10s 9.7
in* 11.1
103 4.0
»"\4f 9-7
10* 14.1
10* 16.9
10* 8.5
10* 9.1
105 14.3
10* 14.3
10* 34.9
10* 6.7
10* 12.9
10s 12.2
in* 12.2
10* 8.9
104 40.4
106 6.4
106 15.2
106 17.9
10s 22.6
106 9.3
106 37.6
'•''These pain cannot be resolved on the 08-210 fused-sllica capillary col ion.
cPeak not Integrated correctly.
-------
TABLE 45. MULTILEVEL CALIBRATION DATA FOR STANDARDS ANALYZED ON
6/30/87 AND 7/1/87
Response factor
Compound
Hexachl oroethane
1 t 3-01 c hi orobenzene
1,4-Dichl orobenzene
1,2-Dichl orobenzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachl orobut ad lene
Benzal chloride'
1 , 2 , 4-Tr i chl or obenzene*
Benzotrlchlorlde
1.2,3-Trlchlorobenzene
Hexachl orocycl opentad 1 ene
1 ,2,4 ,5-Tetrachl orobenzene0
10 1.2, 3. 5-Tetrachl orobenzene0
*• 1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachl orobenzene
alpha -BHC
beta-BHC
gamma -BHC
delta-BHC
0.01 to 2.0
ng/pL
29.7 x
9.9 x
2.4 x
7.5 x
7.1 x
4.6 x
13.7 x
18.4 x
18.4 x
13.3 x
13.3 x
8.2 x
8.1 x
8.1 x
21.1 x
2.3 x
4.6 x
15.1 x
12.0 x
6.2 x
16.8 x
13.3 x
106
103
104
104
104
105
106
105
105
105
106
105
105
105
106
106
Ifl6
106
106
106
0.02 to 4.0
ng/pL
36.3 x 106
10.1 x 103
2.5 x 104
8.9 x 104
8.2 x 104
4.9 x 105
15.4 x 106
21.0 x 10s
21.0 x IflS
10.7 x 106
14.0 x 105
7.6 x 106
8.2 x 105
8.2 x 105
23.9 x 10*
2.4 x 104
4.7 x 106
10.4 x 106
10.6 x 106
5.3 x 106
14.0 x 106
12.7 x 106
0.04 to 8.0
ng/pL
34.4 x
10.1 x
2.7 x
10.8 x
9.84 x
5.2 x
17.4 x
19.8 x
19.8 x
7.9 x
15.5 x
7.6 x
8.4 x
8.4 x
25.9 x
2.6 x
4.8 x
11.1 x
8.6 x
5.6 x
10.9 x
10.4 x
106
103
104
104
104
105
106
105
105
106
105
105
105
105
104
10"
106
106
106
106
0.05 to 10.0
ng/pL
32.6 x 106
10.5 x 103
2.9 x 104
11.6 x 104
10.6 x 104
5.5 x Ifl5
18.3 x 106
18.4 x 105
18.4 x 105
7.1 x 106
16.5 x 105
8.0 x 106
8.9 x 105
8.9 x 105
26.2 x 105
2.8 x 104
5.0 x 106
10.5 x 106
8.6 x 106
5.3 x 106
9.7 x 106
9.6 x 106
0.07 to ]4.0
ng/pL
28.6 x 106
11.4 x 103
3.2 x 104
11.6 x 104
10.8 x 104
5.8 x 105
18.4 x 106
16.3 x 105
16.3 x 105
5.9 x 106
16.3 x 105
8.7 x 106
9.1 x 105
9.1 x 105
24.8 x 105
2.9 x 104
5.2 x 106
12.1 x 106
6.7 x 106
4.9 x 106
8.3 x 106
8.4 x 106
0.08 to 16.0
ng/pL
27.1 x 106
11.8 x in3
3.4 x ID4
11.5 x 104
10.7 x 104
6.0 x 105
18.3 x 106
15.4 x 105
15.4 x 105
5.5 x 106
16.1 x 105
9.1 x 106
9.2 x 105
9.2 x 105
24.0 x 105
3.0 x 104
5.3 x Ifl6
12.1 x 106
7.1 x 106
4.9 x If*
7.9 x 106
8.3 x 106
0.1 to 20.0
ng/pL
26.5 x 106 '
12.8 x lO3
3.9 x 104
12.3 x 104
11.7 x 104
6.7 x 10$
19.2 x Ifl6
15.0 x 105
15.0 x 105
5.1 x 106
17.4 x 105
10.3 x 106
10.1 x 105
10.1 x 10*
24.6 x 105
3.4 x 104
5.6 x 106
14.1 x 106
- 6.5 x 106
4.5 x 106
/.I x 106
7.5 x 106
Average
3d. 7 x 106
10.9 x Ifl3
3.0 x 104
10.6 x 104
9.8 x 104
5.5 x 10*
17.2 x 106
17.8 x 105
17.8 x 105
7.9 x 106
15.6 x 105
8.5 x 106
8.9 x 105
8.9 x 105
24.4 x 105
?.B x 104
5.1 x 106
12.2 x 106
8.6 x 106
5.2 x 106
10.7 x 106
10.0 x 106
Percent
RSD
12.?
9.9
17.8
16.4
16.6
12.9
11.5
12.7
12.7
38.4
9.3
9.1
7.9
7.9
6.9
13.5
7.0
14.7
24.1
10.6
33.2
22.4
a>bThese pairs cannot be resolved on the DB-210 fused-silica capillary column.
-------
TABLE 46. MULTILEVEL CALIBRATION DATA FOR THE METHOD 8120 COMPOUNDS
ANALYZED ON THE OB-WAX FUSED-SILICA CAPILLARY COLUMN
RRT
Average Percent
Compound Std .1 Std. 2 Std. 3 Std .4 Std. 5 Std. 6 RRT RSD .
Hexachloroethane
1, 3- Di chl orobenzene
1 ,4-Dichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride0
1 , 3 ,5-Tr i chl orobenzenec
Hexachlorobutadiene
Benzal chloride
1,2,4-Trichlorobenzene
Benzotrichloride
1 ,2,3-Tri chl orobenzene
Hexachlorocyclopentadiene
1,2,4,5-Tetrachlorobenzene
1,2. 3. 5-Tetrachl orobenzene
1,2, 3, 4-Tetra chl orobenzene
2-Chl orona phthal ened
Pentachlorobenzened
Hexachl orobenzene
alpha-BHC
gamma -BHC
beta-BHC
delta -BHC
0.4383
0.4167
0.4577
0.5164
0.5590
0.5590
0.5380
0.8577
0.7407
0.8318
0.8625
0.5380
0.9601
0.9434
1.1412
1.2803
1.2803
1.5720
b
b
b
b
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
.4377
.4167
.4571
.5164
.5585
.5585
.5375
.8577
.7396
.8323
.8631
.5375
.9590
.9429
.1412
.2798
.2798
.5720
b
b
b
b
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
.4377
.4167
.4577
.5164
.5580
.5580
.5375
.8577
.7407
.8323
.8625
.5375
.9596
.9429
.1407
.2803
.2803
.5714
b
b
b
b
0.4377
0.4167
0.4577
0.5164
0.5590
0.5590
0.5375
0.8577
0.7407
0.8318
0.8620
0.5375
0.9596
0.9429
1.1407
1.2803
1.2803
1.5709
b
b
b
b
0.4377
0.4167
0.4577
0.5164
0.5585
0.5585
0.5375
0.8571
0.7407
0.8318
0.8625
0.5375
0.9596
0.9429
1.1407
1 .2803
1.2803
1.5720
b
b
b
b
0.4380
0.4169
0.4579
0.5162
0.5593
0.5593
0.5378
0.8581
0.7411
0.8323
0.8630
0.5378
0.9601
0.9439
1.1419
1.2816
1.2816
1.5728
b
b
b
b
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
1
1
.4379
.4167
.4576
.5164
.5587
.5587
.5376
.8577
.7406
.8321
.8626
.5376
.9597
.9432
.1411
.2804
.2804
.5719
b
b
b
b
0.06
0.02
0.06
0.02
0.08
0.08
0.04
0.04
0,07
0.03
0.05
0.04
0.04
0.04
0.04
0.05
0.05
0.04
b
b
b
b
alnternal standard is 2,5-dibromotoluene; analyses were performed on November 25, 1987.
°Not able to chromatograph the BHCs on the OB-MAX fused-sillca capillary column.
pairs cannot be resolved on the DB-WAX fused-silica capillary column.
95
-------
TABLE 47. ACCURACY AND PRECISION DATA FOR METHODS 3510 AND 8120
(WITHOUT CLEANUP) USING SPIKED REAGENT WATER
Compound
Hexachl oroethane
1,3-Dichl orobenzene
1,4-Dichl orobenzene
1 , 2-Dichl orobenzene
Benzyl chloride
1, 3, 5-Trichl orobenzene
Hexachl orobutadi ene
Benzal chloridec
l,2,4-Trichlorobenzenec
Benzo trichloride
1, 2, 3-Trichl orobenzene
Hexachl orocycl opentadiene
1 ,2,4,5-Tetrachlorobenzened
l,2,3,5-Tetrachlorobenzened
1,2, 3, 4-Tetrachl orobenzene
2-Chl oronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
gamma -BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
a , 2 ,6-Tri chl orotol uene
1,4-Dichl oronaphthal ene
2 , 3 ,4 ,5 ,6-Pentachl orotol uene
Spike
level
(ug/L)
1.0
100
100
100
100
10
1.0
10
1.0
10
10
« /\
10
10
200
1.0
1.0
10
10
10
10
1.0
10
1.0
Average
recovery3 »b
(percent)
96
87
89
92
90
93
95
95
97
95
97
f\ M
94
96
91
89
92
96
96
103
103
85
78
80
Precision
(percent
RSD)
4.0
8.7
8.9
5.7
6.2
6.2
3.6
3.0
2.1
4.4
5.1
6*
.0
3.4
6.5
6.5
7.1
2.6
2.8
3.6
2.7
6.5
6.1
5.9
aNumber of determinations is 5.
bFinal volume of extract is 10 ml.
c,dThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
96
-------
TABLE 48. ACCURACY AND PRECISION DATA FOR METHODS T550 AND 8120
(WITHOUT CLEANUP) USING SPIKED SANDY LOAM SOIL
Compound
Spike
level
(ng/g)
Average
recoverya.b
(percent)
Precision
(percent
RSD)
Hexachloroethane 330 83
1,3-Dichlorobenzene 33,000 81
1,4-Dichlorobenzene 33,000 89
1,2-Dichlorobenzene 33,000 84
Benzyl chloride 33,000 121
1,3,5-Trichlorobenzene 3,000 75
Hexachlorobutadiene 330 83
Benzal chlorideC
l,2,4-Trichlorobenzenec <3
Benzotrichloride 3,300 90
1,2,3-Trichlorobenzene 3,300 79
Hexachlorocyclopentadiene 330 44
l,2,4,5-Tetrachlorobenzened _
l,2,3,5-Tetrachlorobenzened J
1,2,3,4-Tetrachlorobenzene 3,300 88
2-Chloronaphthalene 66,000 100
Pentachlorobenzene 330 81
Hexachlorobenzene . 330 81
alpha-BHC 3,300 100
gamma-BHC 3,300 99
beta-BHC 3,300 92
delta-BHC 3,300 97
Surrogate recovery (percent)
a,2,6-Trichlorotoluene 330 86
1,4-Dichloronaphthalene 3,300 88
2,3,4,5,6-Pentachlorotoluene 330 98
4.6
12.6
11.0
7.1
5.9
5.3
4.7
2.7
2.9
4.3
25.9
4.4
2.9
6.4
3.5
3.2
2.9
4.1
2.4
1.5
2.7
4.5
11.7
aNumber of determinations is 5.
bFinal volume of extract is 10 mL.
c»dThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
97
-------
TABLE 49. METHOD PRECISION AND ACCURACY FOR THE LOVE CANAL SOIL (MATRIX 10)
V0
00
Compound
Hexachloroethane
1.3-D1chlorobtnztne
1.4-01chlorobenze*e
1.2-01chlorobenzem
Benzylchlorldt
1% C Tvtf^ljMMR^MYMM
,j,5-Tricnioraoenztnt
Hexachlorobutadltne
Benzal chloride'
l,2.4-Tr1chlorobenztnte
Benzotrlchlorlde
1 .2.3-Trlchlorobenzene
Hexachlorocyclopentadtene .
\ ,2 .4 .S-Tetrachlorobtnzene'
1.2.3.5-TetrachlorobenztntT
1.2.3.4-TetrachlorabmztM
2-Chloronaphtnalene
rented! lorooefizene
Hexachlorobenztne
alpha-BHC
gaMM-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
a.2.6-Tr1chlorotoluene
1 .4-Olchloronaphthalene
2.3.4.S.6-Pentachlorotoluene
Spike
level*
(ng/g)
5.4
540
540
540
540
54
5.4
54
54
54
5.4
54
54
1.080
Sj
• 1
5.4
54
54
54
54
54
540
54
Average*
93.0
75,0
202*
87.7
61.0
123
97.0
97.3
68.7
132
94.3
89.3
88.7
72.3
ItQ
11V
68.7
87.7
87.0
86.7
104
82.0
76.3
79.7
RSO
(percent)
3.9
4.8
61
36
2.8
6.6
3.6
6.8
3.0
22
11
9.3
5.6
0.8
15
5.7
8.1
6.4
10
3.2
5.5
10.2
Spike
level*
(ng/g)
27
2.700
2.700
2.700
2.700
270
27
270
270
270
27
270
270
5.400
27
270
270
270
270
54
540
54
Average*
57.3
50.7
69.3
62.7
68.3
67.3
62.7
77.0
67.3
84.7
74.3
76.0
79.0
73.0
M4
. 3
86.7
74.3
81.7
82.0
75.0
79.7
81.7
87.7
RSO
(percent)
1.0
1.0
22
4.9
14
12
6.0
6.7
9.6
11
4.1
5.3
5.8
4.1
57
. /
15
8.9
10
6.3
8.7
5.7
9.9
5.9
Spike
level*
(ng/g)
54
5.400
5.400
5.400
5.400
540
54
540
540
540
54
540
540
10.800
54
540
540
540
540
54
540
54
Average*
47.0
37.3
65.7
58.0
63.3
56.0
55.7
62.0
60.0
47.0
63.7
42.3
72.3
70.3
DI n
Of .U
82.0
87.0
83.7
74.0
71.0
80.7
81.7
87.7
RSO
(percent)
4.3
5.6
17.0
4.6
11
1.8
7.3
3.2
4.4
4.3
7.4
5.5
3.2
0.8
37
• /
2.4
3.0
2.5
16
9.9
1.4
4.9
0.6
Spike,
level*
(ng/g)
110
10.800
10.800
10.800
10.800
1.080
110
1.080
1.080
1.080
110
1.080
1.080
21.600
110
1.080
1.080
1.080
1.080
Average0
71.3
49.3
100
63.8
62.8
67.0
62.5
62.8
69.5
59.0
62.0
70.5
74.3
63.8
Mil
•u
80.8
90.5
92.5
83.5
90.3
RSD
(percent)
14
20
21
17
21
16
« ,18
11
10
20
11
15
19
9.0
64
. 3
8.1
8.7
5.6
10
10
•Concentrations are given on • dry Might basis.
"Thirty graw of wet soil (Moisture content Is 38.4 percent) Mere spiked Individually tilth 100 »l. 500 yl. or 1.000 pL or • solution containing
1 to 200 wg/M. of the Method 8120 compounds. Three replicates were performed at each concentration. Each extract Mas cleaned up by florlsll
with hexane/acetone (9:1).
cNurt>er of replicates Is four. Two replicates were done with 30 g wet soil, the other two replicates were done with 15 g wet soil; the final
voluws of the Florlsll fractions were 20 mi and 10 at. respectively, to compensate for the fact that the concentrations of Method 8120 o«pounds In
.the extracts were different.
"High recovery because 1.4-dlchlorobenzene was present In the staple at 1.900 ng/y.
'These pairs cannot be resolved on the 08-210 fused-stllca capillary coluan.
-------
\o
to
TABLE 50. METHOD PRECISION AND ACCURACY FOR THE PCB-CONTAMINATED SOIL
(MATRIX 11)
Compound
HexacMoroethane
1.3-Dtchlorobenzene
1.4-Dlchlorobenzene
I .2-Dlchlorobenzenc
Benzyl chloride
1.3.5-Trlchlorobeuene
Hexachlorobutadlene .
BZft*v-iriCniorontnitfie
Benzal chloride0^
Benzotrlchlorlde
1.2.3-Trtchlorobenzene
Htxachlorocyclopentadlene
1 ,2.4.5-Tttrachlorobtnzene'
1 ,2.3.5-Tttrachlorobenzene'
1 .2.3.4-Tetrachlorobtnztne
2-ChloronapfcthaUne
Pentachlorobenzene
Hexachlorobenztne
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent 1
o.2.6-Tr1chlorotoluene
1 .4-01chloronaphthalene
2.3.4, 5.6-Fentachlorotoluene
Spike
level*
(ng/g)
1.3
130
130
130
130
13
1.3
13
13
13
1.3
13
13
260
1.3
1.3
13
13
13
13
13
130
13
Average1*
60.0
60.0
79.3
86.3
70.0
62.0
71.0
58.0
72.3
48.7
71.0
80.7
70.7
95.3
72.3
c
c
c
c
79.3
79.3
85
USD
(percent)
17
22
23
21
22
19
16
17
11
34
8.5
8.4
9.6
8.2
13
13.5
9.6
10.5
Spike
level*
(ng/g) Average"
6.5
650
650
650
650
65
6.5
65
65
65
6.5
65
65
1.300
6.5
6.5
13
130
13
59.7
56.7
107
79.3
77.0
73.3
65.7
78.3
81.0
80.7
70.3
69.0
77.3
76.3
81.3
78.3
76.7
69.7
78.3
USD
(percent)
5.4
5.4
72
4.4
5.7
3.4
3.2
6.4
12
6.8
4.6
5.0
2.7
0.76
3.6
3.2
3.3
3.3
3.2
Spike.
level*
(ng/g)
13
1.300
1.300
1.300
1.300
130
13
130
130
130
13
130
130
2.600
13
13
13
130
13
Average**
97.0
65.7
90.0
100
106
81.7
76.0
119
113
103
71.7
99.3
104
88.3
96.0
99.7
95.3
90.0
98.3
RSO
(percent)
6.3
19
8.4
17
20 ..
8.0 ^
11
6.6
19
IS
15
14
11
0.7
8.3
7.8
0.6
11.1
6.5
{Concentrations are given on a dry weight basis.
"Thirty graM of wet soil (moisture content Is 38.4 percent) were spiked Individually with 100 wL. 500 uL, or
1,000 uL or a solution containing 1 to 200 vg/mL of the Method 8120 compounds. Three replicates were
performed at each concentration. Each extract was cleaned up by Florist! with hexane/acetone (9:1).
CBHC tsomers could not be determined because Matrix 11 was highly contaminated with PCBs which overlap with the
.BHC Isowrs on the 08-210 fused-si 1 tea capillary column.
"••These pairs cannot be resolved on the 06-210 fused silica capillary column.
( «
-------
TABLE 51. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
LOAM SOIL EXTRACT AFTER FLORISIL CARTRIDGE CLEANUP (MATRIX 1)
Recovery (percent)'
Spike level
Compound (ngM of extract)0 DB-210 DB-WAX
Hexachloroethane
1,3-01 chlorobenzene
l,4-D1chlorobenzene
1 , 2-0 1 ch 1 orobenzene
Benzyl chloride
1,3,5-Trlchlorobenzene
Hexachlorobutadlene
Benzal chloride
1,2, 4-Tr 1 ch 1 orobenzenec
Benzotr1chlor1de
1,2, 3-Tr 1 ch 1 orobenzene
Hexachlorocyclopentadlene .
1 , 2 , 4 , 5-Te tr ach 1 orobenzene0.
1,2,3, 5-Tetrach 1 orobenzene0
1,2,3,4-Tetrachlorobenzene
2-Chl oronaphthal ene
Pentachlorobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
X
1
20
0.1
0.1
1
1
1
1
88
86
93
98
96
92
83
140
88
103
36
86
oo
104
90
90
99
102
105
95
110
77
79
78
79
74
74
74
82
76
96
74
03
OO
84
87
87
89
a
a
a
a
Surrogate recovery (percent)
o,2,6-Tr1chlorotoluene 0.1 106 80
1,4-01chloronaphthalene 1 e 74
2,3,4,5,6-Pentachlorotoluene 0.1 87 66
?Not able to chromatograph the BHC Isomers on the DB-WAX column.
bThe sandy loam soil sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds
and the surrogates and subjected to Florlsll cartridge cleanup.
c»dThese pairs cannot be resolved on the DB-210 fused-s1!1ca
capillary column.
Recovery not determined because of matrix Interference.
100
-------
TABLE 52. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
P6N-1B SHELL SAMPLE EXTRACT AFTER FLORISIL CARTRIDGE CLEANUP
(MATRIX 2)
Recovery (percent)'
Spike level
Compound (ng/ML of extract)0 DB-210 DB-WAX
Hexachloroethane
l,3-01chlorobenzene
1 , 4-D 1 ch 1 orobenzene
1 , 2-D 1 ch 1 orobenzene
Benzyl chloride
1, 3, 5-Tr1chl orobenzene
Hexachlorobutadlene
Benzal chloride0
1,2,4-Trlchlorobenzene
Benzotr1chlor1de
1,2,3-Trlchlorobenzene
Hexachlorocyclopentadlene
1,2, 4, 5-Tetrachl orobenzene*!
1,2,3, 5-Tetrachl orobenzene0
1 , 2 , 3 , 4-Tetr ach 1 orobenzene
2-Chloronaphthalene
Pentach 1 orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
0.1
1
1
0.1
1
20
0.1
0.1
1
1
1
1
79
71
78
84
96
75
65
1 rt *>
102
84
89
31
in
/(j
80
78
76
76
98
98
85
114
70
71
70
72
70
70
66
TO
78
70
82
66
"7 A
/A
75
82
82
83
a
a
a
a
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene 0.1 82 73
l,4-D1chloronaphtha1ene 1 e 67
2,3,4.5.6-Pentachlorotoluene 0.1 70 62
*Not able to chromatograph the BHC 1sowers on the DB-WAX column.
DThe PGN-1B Shell sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds
and the surrogates and subjected to Flor1s1l cartridge cleanup.
c>aThese pairs cannot be resolved on the DB-210 fused-slUca
capillary column.
Recovery not determined because of matrix Interference.
101
-------
TABLE 53. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
PINE NEEDLE NBS SRM-1575 SAMPLE EXTRACT AFTER FLORISIL
CARTRIDGE CLEANUP (MATRIX 3)
Recovery (percent)'
Spike level
Compound (ngM of extract)0 DB-210 DB-WAX
Hexachloroethane
l,3-D1chlorobenzene
1 , 4-D 1 ch 1 orobenzene
l,2-D1chlorobenzene
Benzyl chloride
1,3,5-Trlchlorobenzene
Hexach 1 orobutad 1 ene
Benzal chloride0
1,2, 4-Tr 1 ch 1 orobenzenec
Benzotr1chlor1de
1,2,3-THchlorobenzene
Hexachlorocyclopentadlene .
1,2,4, 5-Tetrachl orobenzene0.
1,2,3, 5-Tetrachl orobenzene0
1,2,3, 4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexach 1 orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
72
68
65
79
83
67
59
95
76
81
46
76
78
100
85
78
93
91
65
114
73
81
80
84
77
77
71
109
68
64
71
85
88
94
94
92
a
a
a
a
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene
1,4-01 chl oronaphthal ene
2,3,4,5,6-Pentachlorotoluene
0.1
1
0.1
98
e
86
85
85
81
?Not able to chromatograph the BHC Isomers on the DB-WAX column.
"The pine needle NBS SRM-1575 sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to Flor1s1l cartridge cleanup.
c>dThese .pairs cannot be resolved on the DB-210 fused-sH1ca
capillary column.
eRecovery not determined because of matrix Interference.
102
-------
TABLE 54. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
RIVER SEDIMENT NBS SRM-1645 SAMPLE EXTRACT AFTER FLORISIL
CARTRIDGE CLEANUP (MATRIX 4)
Recovery (percent)'
Spike level
Compound (ngM of extract)0 DB-210 DB-WAX
Hexachloroethane
1,3-Oichlorobenzene
l,4-D1chlorobenzene
1 , 2-D 1 ch 1 orobenzene
Benzyl chloride
1,3,5-THchlorobenzene
Hexachlorobutadlene
Benzal chloride
I,2t4-Tr1chlorobenzenec
Benzotrl chloride
1,2,3-Trlchlorobenzene
Hexachlorocyclopentadlene .
1,2,4, 5-Tetrachl orobenzene^
1,2,3, 5-Tetrach 1 orobenzene0
1,2, 3, 4-Tetrachl orobenzene
2-Chloronaphthalene
Pent achl orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
70
57
59
67
84
63
60
85
80
74
23
59
b
b
70
190
99
107
105
73
60
66
65
67
68
68
64
73
67
75
64
70
71
81
81
136
a
a
a
a
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene
l,4-D1chloronaphthalene
2,3,4,5,6-Pentachlorotoluene
0.1
1
0.1
e
e
e
76
86
66
*Not able to chromatograph the BHC Isomers on the DB-WAX column.
DThe river sediment NBS SRM-1645 sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to F1or1s1l cartridge cleanup.
CfdThese pairs cannot be resolved on the DB-210 fused-sH1ca
capillary column.
eRecovery not determined because of matrix Interference.
103
-------
TABLE 55. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
CITRUS LEAVES NBS SRM-1572 SAMPLE EXTRACT AFTER FLORISIL
CARTRIDGE CLEANUP (MATRIX 5)
Compound
Spike level
(ngM of extract)5
Recovery (percent)'
DB-210 DB-WAX
Hexachloroethane
1,3-01chlorobenzene
l,4-D1chlorobenzene
1,2-01chlorobenzene
Benzyl chloride
1,3,5-THchlorobenzene
Hexachlorobutad1ene
Benzal chloride0
l,2,4-THchlorobenzenec
Benzotr1chlor1de
1,2,3-THchlorobenzene
Hexachlorocyclopentadlene .
1,2,4,5-Tetrach1orobenzene^
1,2,3,5-Tetrach1orobenzene
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentach1orobenzene
Hexachlorobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
78
67
120
80
112
46
57
96
90
70
123
50
69
84
58
61
99
101
85
98
129
142
139
148
140
140
128
133
117
169
128
134
135
156
156
165
a
a
a
a
o,2,6-Tr1chlorotoluene
l,4-D1chloronaphthalene
2,3,4,5,6-Pentachlorotoluene
0.1
1
0.1
88
78
88
76
71
103
*Not able to chromatograph the BHC Isomers on the DB-WAX column.
DThe citrus leaves NBS SRM-1572 sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to Flor1s1l cartridge cleanup.
CfdThese pairs cannot be resolved on the DB-210 fused-slUca
capillary column.
104
-------
TABLE 56. RECOVERY OF METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
COAL NBS SRM-1632a SAMPLE EXTRACT AFTER FLORISIL CLEANUP
(MATRIX 6)
Compound
Recovery (percent)4
Spike level .
(ngM of extract)5 DB-210 DB-WAX
Hexachloroethane
1 , 3-0 1 ch 1 orobenzene
1 , 4-D 1 ch 1 orobenzene
1,2-Dichlorobenzene
Benzyl chloride
1,3,5-Trichlorobenzene
Hexachl orobutad i ene
Benzal chloride0
l,2,4-Tr1chlorobenzenec
Benzotrichlorlde
1,2,3-Trlchlorobenzene
Hexachlorocyclopentadiene
1,2,4, 5-Tetrachl orobenzene*!
1,2,3, 5-Tetrachl orobenzened
1 , 2 , 3 , 4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
0.1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
70
58
59
73
85
59
54
94
75
73
28
63
75
80
74
67
98
100
90
75
58
67
60
71
68
68
59
101
55
86
59
70
85
80
80
76
a
a
a
a
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene
l,4-D1chloronaphthalene
2,3,4,5,6-Pentach1oroto1uene
0.1
1
0.1
104
48
75
71
67
65
*Not able to chromatograph the BHC isomers on the DB-WAX column.
"The coal NBS SRM-1632a sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to Florisil cartridge cleanup.
c*°These pairs cannot be resolved on the DB-210 fused-silica
capillary column.
105
-------
TABLE 57. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
COAL FLYASH NBS SRM-1633a SAMPLE EXTRACT AFTER FLORISIL
CARTRIDGE CLEANUP (MATRIX 7)
Recovery (percent)'
Spike level .
Compound (ng/uL of extract)0 DB-210 DB-WAX
Hexachloroethane
1 , 3-D 1 ch 1 orobenzene
1,4-Dichlorobenzene
1 ,2-D1chlorobenzene
Benzyl chloride
1,3, 5-Tr 1 ch 1 orobenzene
Hexachlorobutadlene
Benzal chloride0
l,2,4-Tr1chlorobenzenec
BenzotH chloride
1,2,3-Trlchlorobenzene
Hexachlorocyclopentadlene .
1,2,4, 5-Tetrach 1 orobenzene j:
1,2,3, 5-Tetrach 1 orobenzene
1,2, 3, 4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
0.1
10
10
10
10
1
1
1
1
1
0.1
1
1
20
0.1
0.1
1
1
1
1
76
69
39
83
96
68
65
103
82
91
35
61
83
78
71
78
101
102
97
100
65
72
69
73
74
74
66
75
61
79
66
70
72
77
77
82
a
a
a
a
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene
l,4-D1ch1oronaphthalene
2,3,4,5,6-Pentachlorotoluene
0.1
1
0.1
89
e
65
70
62
60
*Not able to chromatograph the BHC Isomers on the DB-WAX column.
"The coal flyash NBS SRM-1633a samples was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to Flor1s1l cartridge cleanup.
c»aThese pairs cannot be resolved on the DB-210 fused-sH1ca
capillary column.
eRecovery not determined because of matrix Interference.
106
-------
TABLE 58. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
DETROIT RIVER SEDIMENT SAMPLE EXTRACT AFTER FLORISIL
CARTRIDGE CLEANUP (MATRIX 8)
Recovery (percent)'
Spike level
Compound (ng/pL of extract)b DB-210 DB-WAX
Hexachloroethane
l,3-D1chlorobenzene
1 , 4-D 1 ch 1 orobenzene
l,2-D1ch1orobenzene
Benzyl chloride
1,3,5-THchlorobenzene
Hexachl orobutad 1 ene
Benzal chloride0
1,2, 4-Tr 1 ch 1 orobenzene0
Benzotr1chlor1de
1,2,3-Trlchlorobenzene
Hexachlorocyclopentadlene .
1,2,4, 5-Tetrachl orobenzene^
1,2,3, 5-Tetrachl orobenzene0
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
10
1,000
1,000
1,000
1,000
100
10
100
100
100
10
100
100
2,000
10
10
100
100
100
100
93
122
111
97
97
152
80
113
100
113
272
125
65
94
115
90
98
98
92
125
70
79
80
78
77
77
69
114
86
91
69
89
87
88
88
87
a
a
a
a
Surrogate recovery (percent)
a,2,6-Tr1chlorotoluene 10 101 83
l,4-D1ch1oronaphthalene 100 e 74
2,3,4,5,6-Pentachlorotoluene 10 92 69
*Not able to chromatograph the BHC Isomers on the DB-WAX column.
DThe Detroit River sediment sample was first extracted with methylene
chloride/acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to Flor1s1l cartridge cleanup.
Ct(1These pairs cannot be resolved on the DB-210 fused-s1!1ca
capillary columns.
eRecovery not determined because of matrix Interference.
107
-------
TABLE 59. RECOVERIES OF THE METHOD 8120 COMPOUNDS FOUND IN THE SPIKED
BLOODY RUN CREEK SEDIMENT SAMPLE EXTRACT AFTER FLORISIL
CARTRIDGE CLEANUP (MATRIX 9)
Recovery (percent)'
Spike level
Compound (ng/wL of extract)0 DB-210 OB-WAX
Hexachloroethane
1 , 3-D 1 ch 1 orobenzene
1 , 4-D 1 ch 1 orobenzene
l,2-D1chl orobenzene
Benzyl chloride
1,3,5-Trlchlorobenzene
Hexachlorobutadlene
Benzal chloride0
1,2,4-Trlchlorobenzene
Benzotr1chlor1de
1, 2, 3-THchl orobenzene
Hexachlorocyclopentadlene .
1,2,4, 5-Tetrach 1 orobenzene J
1,2,3, 5-Tetrach 1 orobenzene0
1,2, 3, 4-Tetrachl orobenzene
2-Ch 1 oronaphthal ene
Pent achl orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
100
10.000
10,000
10.000
10,000
1,000
100
1,000
1,000
1,000
100
1,000
1,000
20,000
100
100
1.000
1,000
1,000
1.000
82
57
87
100
91
59
85
104
94
110
83
77
115
85
107
181
99
99
96
99
66
74
76
77
78
78
85
73
80
89
85
82
69
63
63
78
a
a
a
a
Surrogate recovery (percent)
a.2,6-Tr1chlorotoluene 100 106 78
l,4-D1chloronaphthalene 1,000 176 103
2,3,4,5,6-Pentachlorotoluene 100 126 57
j*Not able to chromatograph the BHC Isomers on the DB-WAX column.
"The Bloody Run Creek sediment sample was first extracted with methylene
chloride/Acetone (1:1) using Method 3550. A portion of the extract,
after solvent exchange, was spiked with the Method 8120 compounds and
the surrogates and subjected to Flor1s11 cartridge cleanup.
c'"These pairs cannot be resolved on the DB-210 fused-siI1ca
capillary columns.
108
-------
o
vo
UJ
o
o
u
o
a
130
120
110
100
90
80
70
60
50
40
30
20
10
0
7
X
XX
I
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
PR-WAX COLUMN
Figure 29. Recovery as a function of matrix for hexachloroethane
-------
(t
u
o
Ul
a;
»-
z
u
o
UJ
a
150
140
130
120
110
100
90
BO
70
60
50
40
30
20
10
0
1
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
\7~7\ DB-210 COLUMN
DO-WAX COLUMN
Figure 30. Recovery as a function of matrix for 1,3-dichlorobenzene.
-------
a:
u
o
u
a:
K
U
(J
a:
140
130 -
120 -
110 -
100 -
90 -
80
70 -
60 -
50 -
40 -
30 -
20 -
10 -
I
XX
XX
XX
XX
XX
XX
XX
X
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
COLUMN
Figure 31. Recovery as a function of matrix for 1,4-dichlorobenzene.
-------
r\i
UJ
O
o
u
o
ft
150
140 -
130 -
120 -
110 -
100 -
90 -
80
70 -
60 -
50 -
40 -
30 -
20 -
10 -
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
V/\ DB-210 COLUMN
1XM DP-WAX COLUMN
Figure 32. Recovery as a function of matrix for 1,2-dichlorobenzene,
-------
LJ
3
O
u
LJ
O
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
i.
y\
I
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
\7~~A DB-210 COLUMN
DB-WAX COLUMN
Figure 33. Recovery as a function of matrix for benzyl chloride.
-------
ft:
UJ
3
o
UJ
o
a:
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
1
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
-1 OB-WAX COLUMN
Figure 34. Recovery as a function of matrix for 1,3,5-trichlorobenzene.
-------
en
a
(J
ui
a
o
a
LJ
a
130
120 -
110 -
100 -
90 -
80
70 -
60 -
50 -
40 -
30 -
20 -
10 -
fc
/xOs
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
08-210 COLUMN
IX\l nn-wAx COLUMN
Figure 35. Recovery as a function of matrix for hexachlorobutadiene.
-------
u
o
o
u
a:
z
u
o
a:
u
a.
,140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
X
I
y\
I
X
y\
17
\
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
V/\ 08-210 COLUMN
IX\| OB-WAX COLUMN
Figure 36. Recovery as a function of matrix for 1,2,4-trlchlorobenzene.
-------
o:
LJ
O
o
UJ
o:
^-
u
o
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
I
\
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
DB-WAX COLUMN
Figure 37. Recovery as a function of matrix for benzal chloride.
-------
00
a:
u
o
u
a:
i-
U)
o
a:
u
a.
120
7
y\
/\
X
X\
x\
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
|\NJ DB-WAX COLUMN
Figure 38. Recovery as a function of matrix for benzotrichloride.
-------
tt
U)
U
LJ
o
a:
UJ
a
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
y\
y\
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
[771 DB-210 COLUMN
DB-WAX COLUMN
Figure 39. Recovery as a function of matrix for 1,2,3-trlchlorobenzene.
-------
o:
I
o
u
UL
\-
z
u
o
CL
U
0.
280
260
240
220
200
180
160
140
120
100
80
60
40
20
0
I
y\
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
\7~7\ DB-210 COLUMN
DB-WAX COLUMN
Figure 40. Recovery as a function of matrix for hexachlorocyclopentadiene.
-------
O
u
LJ
a:
z
ui
O
a:
LJ
a.
'140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
Z
MATRIX-1 MATRIX-2 MATRlX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
\7~/\ DB-210 COLUMN
DB-WAX COLUMN
Figure 41. Recovery as a function of matrix for 1,2,4,5-tetrachlorpbenzene.
-------
rs>
ro
DC
UJ
I
(E
H
Z
til
enzene.
-------
ro
o
u
a
o
a:
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
vv
\
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
DB-WAX COLUMN
Figure 43. Recovery as a function of matrix for 1,2,3,4-tetrachlorobenzene.
-------
ro
u.
LJ
O
O
u
cr
\-
u
O
tc
UJ
Q.
0
V,
/00\ 17
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
DB-210 COLUMN
DB-WAX COLUMN
Figure 44. Recovery as a function of matrix for 2-chloronaphthalene.
-------
en
or
u
o
u
o:
z
UJ
o
a:
160
150 -
140 -
130 -
120 -
110 -
100 -
90
80
70
60
50
40
30
20 -
10 -
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
\7~7\ 08-210 COLUMN
|\\| DB-WAX COLUMN
Figure 45. Recovery as a function of matrix for pentachlorobenzene.
-------
ro
a:
u
o
LJ
(t
K
UJ
O
190
180
170
160
150
140
130
120
110
100
90
80
70
60
50
40
30
20
10
0
I
XX
XX
1
,
MATRIX-1 MATRIX-2 MATRIX-3 MATRIX-4 MATRIX-5 MATRIX-6 MATRIX-7 MATRIX-8 MATRIX-9
MATRIXES
V~7\ DB-210 COLUMN
DB-WAX COLUMN
Figure 46. Recovery as a function of matrix for hexachlorobenzene.
-------
TABLE 60. COMPOUNDS IDENTIFIED IN EPA SAMPLE WP-485 —
POLYNUCLEAR AROMATICS II
Compounds
known to Compounds
be present found by
in the sample Method 8120
at pg/L at
Acenaphthylene 100 Hexachlorobutadiene 0.034
Phenanthrene 100
Fluoranthene 10.0
Benzo(a)anthracene 10.0
Benzo(a)pyrene 10.0
Benzo(b)fluoranthene 10.0
D1benzo(a,h)anthracene 10.0
Benzo(g,h,1)pery1ene 10.0
127
-------
TABLE 61. COMPOUNDS IDENTIFIED IN EPA SAMPLE WP-281 SAMPLE 2
Compounds
known to
be present
In the sample
at ug/L
Compounds
found by
Method 8120
at ug/L
Phenol 15.0
2,4-D1methylphenol 12.5
2-Chlorophenol 8.3
4-Chloro-3-methylphenol 20.0
2,4-D1chlorophenol 10.0
2,4,6-TMchlorophenol 12.5
Pentachlorophenol 10.0
2-N1tropheno1 20.0
4-N1trophenol 15.0
None
128
-------
TABLE 62. COMPOUNDS IDENTIFIED IN EPA SAMPLE WP-281 SAMPLE 4a
Compounds
known to
* be present
r 1n the sample
at ug/L
Phenol
2, 4-D1methyl phenol
2,Chlorophenol
4-Chloro-3-Methylphenol
2,4-D1chlorophenol
2,4,6-Trlchlorophenol
Pentachlorophenol
2-N1trophenol
4-N1trophenol
100
83.3
110
175
70
125
90
175
130
Compounds
?ound by
Method 8120
at yg/L
None
aGC/ECD chromatograms of the EPA WP-281 Sample 4
before and after Florlsll cartridge chromatography
are shown 1n Figures 47 and 48, respectively.
129
-------
Figure 47. GC/ECO chronatogram of EPA WP-281 Sample 4 before Flor1s1l
cartridge chromatography.
130
-------
Figure 48. GC/ECO chromatogram of EPA WP-281 Sample 4 after F1or1s1l
cartridge chrcmatography.
131
-------
TABLE 63. RESULTS OF GC/ECD ANALYSES FOR EPA CHECK
SAMPLE WP-685
Compound
alpha-BHC
gamma-BHC
True value
(ug/mL)
100
100
Found value
(ug/mL)
117
85
Bias
(percent)
+ 17
-15
aAnalyses were performed on the DB-210
capillary column; the GC operating
conditions are listed in Table 4; the
solution provided by EPA was not spiked
into water but it was diluted 100X and
analyzed directly. Other compounds
present in the sample include:
heptachlor, heptachlor epoxide, dieldrin,
endrin, and 4,4'-DDD.
132
-------
TABLE 64. RESULTS OF GC/ECD ANALYSES FOR EPA CHECK SAMPLE WP-186a
Compound
1,3,5-Trichlorobenzene
1,2,3-TMchlorobenzene
1,2,4,5-Tetrachlorobenzene
1,2,3,4-Tetrachlorobenzene
True value
(ug/mL)
100
100
100
100
Found value
(yg/nt)
107
85
105
96
Bias
(percent)
+7
-15
+5
-4
aAnalyses were performed on the DB-210 capillary column; the
GC operating conditions are listed in Table 4; the solution
provided by EPA was not spiked into water but it was
diluted 100X and analyzed directly. Other compounds
present in the sample include: 4-chlorobenzotri fluoride,
m-chlorotoluene, 2,4-dichlorotoluene,
2,4,5-trichloroaniline, pentachloronitrobenzene.
133
-------
TABLE 65. COMPOUNDS IDENTIFIED IN EPA WP-1082 SAMPLE la
Concentration
(ug/L)
Bias (percent)
1
Compounds known to be present
1n the sample (yg/L)
4-Chlorobenzotr1 fluoride
m-Chlorotoluene
2,4-Dlchlorotoluene
1,3,5-TMchlorobenzene
1, 2, 3-Tr1chl orobenzene
1,2,4, 5-Tetrach 1 orobenzene
1,2,3, 4-Tetrachl orobenzene
2,4,6-Tr1chloroan111ne
Pentachloronl trobenzene
62.4
38.3
49.8
62.5
75.5
50.7
70.3
59.4
74.5
Compounds found by
EPA Method 8120
1, 3, 5-Tr1chl orobenzene
1 , 2 , 3-Tr 1 ch 1 orobenzene
1,2,4, 5-Tetrach 1 orobenzene
1,2,3,4-Tetrachlorobenzene
Before After Before
F1or1s1l Florlsll Florisll
Cartridge Cartridge Cartridge
36.2
24.9
12.1
49.1
26.5
24.6
13.3
37.2
-42
-67
-76
-30
After
Flt>rts1l
Cartridge
-58
-67
-74
-47
&D1lut1on factor for extract 1s 100. 1 mL sample provided by EPA was spiked Into 1 L water; Vextract
10 mL; additional 10-fold dilution prior to GC/ECD.
-------
TABLE 66. COMPOUNDS IDENTIFIED IN EPA WP-1082 SAMPLE 2
u>
Concentration
Bias (percent)
Compounds known to be present
In the sample (vg/L)
Compounds found by
EPA Method 8120
Before After Before After
Florlsll Flor1s1l FloHsil Ftorlsll
Cartridges Cartridge6 Cartridge Cartridge
4-Chl orobenzotr 1 f 1 uor 1 de
m-Chlorotoluene
2 , 4-D 1 ch 1 oroto 1 uene
1,3,5-Trlchlorobenzene
1,2,3-Trlchlorobenzene
1,2,4, 5-Tetrach 1 orobenzene
1,2,3, 4-Tetrach 1 orobenzene
2,4,6-Tr1chloroan1 1 1ne
Pentachloronltrobenzene
249
201
177
250
205
231
200
301
351
1,3,5-Trlchlorobenzene
1,2,3-Trlchlorobenzene
1 ,2 ,4 ,5-Tetrachl orobenzene
1,2,3,4-Tetrachlorobenzene
198
78.5
72.5
145
134
88.5
73.5
136
-21
-62
-69
-28
-46
-57
-68
-32
?D1lut1on factor 1s 500.
Values given are the average determinations at dilutions of 10 and 100 fold.
-------
TABLE 67. COMPOUNDS IDENTIFIED IN EPA WP-482 SAMPLE 3
Compounds known to be present
1n the sample (vg/L)
Concentration
Bias (percent)
Compounds found by
EPA Method 8120
Before After Before After
Flor1s1l Flor1s1l Flor1s1l Flor1s1l
Cartridge Cartridge Cartridge Cartridge
<*>
CT»
l,4-D1chlorobenzene
B1s(2-chloro1sopropyl)ether
Hexachloroethane
Nitrobenzene
Naphthalene
Dimethyl phthalate
Acenaphthene
Fluorene
4-Chlorophenyl phenyl ether
4-Bromophenyl phenyl ether
Anthracene
Fluor ant hene
Butyl benzyl phthalate
Chrysene
Ethyl hexyl phthalate
Benzo ( b ) f 1 uoranthene
Benzo(a)pyrene
D 1 benzo ( a , h ) ant hracene
Benzo(g,h,1)perylene
24.8
38.8
30.0
76.5
24.8
40.0
19.5
51.2
76.7
41.5
40.0
29.8
51.3
69.9
29.1
40.0
24.9
40.7
80.4
l,4-D1chlorobenzene 68. 3a 26.1 +175 +5.2
u
Hexachloroethane 15. 0D 9.0 -50 -70
^Dilution factor 1s 10.
DD1lut1on factor 1s 100.
-------
TABLE 68. COMPOUNDS IDENTIFIED IN EPA WP-482 SAMPLE 4
Compounds known to be present
In the sample (vg/L)
Concentration
Bias (percent)
Compounds found by
EPA Method 8120
Before After Before After
Flor1s1l Flor1s1l Flor1s1l Florlsll
Cartridge Cartridge Cartridge Cartridge
l,4-D1ch1orobenzene 251
B1s(2-chloro1sopropyl) ether 204
Hexachloroethane 303
Nitrobenzene 373
Naphthalene 250
Dimethyl phthalate 404
Acenaphthene 197
Fluorene 250
4-Chlorophenyl phenyl ether 374
4-Bromophenyl phenyl ether 373
Anthracene 200
Fluoranthene 301
Butyl benzyl phthalate 250
Chrysene 209
Ethyl hexyl phthalate 153
Benzo(b)fluoranthene 203
Benzo(a)pyrene 224
D1benzo(ath)anthracene 204
Benzo(g,h,1)perylene 300
l,4-D1chlorobenzene ND 195*
Hexachloroethane 168b 70b
-45
-22
-77
?D1lut1on factor 1s 100.
"Dilution factor 1s 1.000.
ND — Not detected because the sample was diluted too much.
-------
TABLE 69. COMPOUNDS IDENTIFIED IN EPA WP-482 SAMPLE 1
Concentration
(vg/L)
Bias (percent)
Compounds known to be present
1n the sample (vg/L)
Compounds found by
EPA Method 8120
Before After Before After
Flor1s1l Flor1s1l Flor1s1l Flor«1s1l
Cartridge Cartridge Cartridge Cartridge
B1s-2-chloroethyl ether
1, 3-D 1ch lorobenzene
l,2-D1chlorobenzene
Nltrosodlpropylamlne
Isophorone
B1s(2-ch1oroethoxy)methane
1,2,4-Trlchlorobenzene
Hexach 1 orobetad 1 ene
2-Chloronaphthalene
2,6-01n1trotoluene
2,4-Dlnltrotoluene
Dlethyl phthalate
Hexach lorobenzene
Phenanthrene
01 butyl phthalate
Pyrene
Benzo( a) anthracene
Dloctyl phthalate
Benzo ( k ) f 1 uoranthene
48.2
52.0
24.7
34.8
76.7
48.6
25.3
49.6
25.4
76.5
73.8
25.1
35.7
40.2
24.9
60.2
73.9
43.9
45.7
l,3-D1chlorobenzene
l,2-D1chlorobenzene
1,2,4-Trlchlorobenzene
Hexach 1 orobutad 1 ene
2-Ch 1 oronaphtha 1 ene
Hexach lorobenzene
1
»
32. 6a
9.8a
a
6.2?
23.0b
19. 9a
K
45. 7b
A
16.2a
10.8
^
2.9a
20.5b
20. 7a
K
49. 4b
-37
-60
-75
-54
-22
+28
-69
-56
-89
-59
-19
+38
?D1lut1on factor Is 10.
DD1lut1on factor 1s 100.
-------
The data in Tables 63 and 64 Indicate biases of -15 to +17 percent for
alpha-BHC, gamma-BHC, 1,3,5- and 1,2,3-trichlorobenzene, and 1,2,4,5- and
1,2,3,4-tetrachlorobenzene when no other compounds were present 1n the
sample. Biases as high as -76 percent for 1,2,4,5-tetrachlorobenzene were
encountered when other chlorinated compounds were present (Tables 65 and 66).
Fract1onat1on of samples extracts by Flor1s1l cartridge chromatography did
not help. Much higher biases (e.g., +175 percent) were encountered when
l,4-d1chlorobenzene and hexachloroethane were present 1n the sample, at the
same concentration, because the two compounds give such different detector
signals. Consequently, the sample extract had to be diluted to get the
signal within the detector's linear range (Table 67). Nonetheless, all
Method 8120 compounds can be determined 1n the presence of other EPA
base/neutral compounds and organochlorlne pesticides (Tables 68 and 69). If
the EPA's priority pollutant addle compounds are present, the Flor1s1l
procedure that utilizes a 1-g disposable cartridge and hexane/acetone (9:1)
as the elutlng solvent may be used to separate the Method 8120 compounds from
the EPA's priority pollutant phenols.
6.5.4 Method Detection Limits
The method detection limits (MDL) are presented 1n Tables 70 and 71.
They were determined by spiking seven or eight reagent-grade water samples
with the 22 chlorinated hydrocarbons and subjecting them to the entire
analytical process. Blank measurements were performed 1n triplicate
(Table 72). MDLs were determined from the standard deviations of the seven
or eight replicates and the Student's t value for a one-tailed test at the
99 percent confidence level (6 degrees of freedom). For water samples that
were subjected to FloHsIl, MOLs ranged from 1.4 to 1,300 ng/L. When a
1.5 yL aliquot of a 2-mL extract (after FloHsIl cleanup) obtained from 1 L of
water containing the test compounds was used, the amounts Injected onto the
GC column ranged from about 1 pg to 1,000 pg. These amounts are sufficient
for Identifying the compounds, since our lowest-level calibration standard
used for quantifying the samples contained 1 to 500 pg/yL, and we normally
Inject 1.5-yL allquots. Detection limits lower than those given 1n Tables 70
and 71 may be achievable by using larger samples and by concentrating the
extracts to 0.5 ml Instead of 2 ml. However, a minimum extract volume of
2 ml 1s suggested for Method 8120 as 1 ml 1s needed for the primary analysis
and another 1-mL aliquot 1s saved for the confirmatory analysis.
6.5.5 Ruqgedness Test for Method 8120
A ruggedness test was performed for Method 8120 to determine how
sensitive the method 1s to changes of seven specified conditions. The seven
variables are listed 1n Table 73 and Include: Injector temperature, detector
temperature, Injection volume, type of response factors used 1n calibration,
solvent, and presence or absence of two matrix Interferents (dlesel
hydrocarbons and organochlorlne pesticides). The seven variables are
assigned the letters A,a through G,g (Table 74). For example, the Injector
temperature 1s 230°C 1n experiments 1 through 4 and 210°C 1n experiments 5
through 8.
139
-------
TABLE 70. CONCENTRATIONS OF THE METHOD 3120 COMPOUNDS IN WATER SAMPLES FOR
THE HDL STUDY (SUBJECTED TO FLORISIL CARTRIDGE CLEANUP)
Compound
Hexachloroethane
1,3-01 chlorobenzene
1,4-Dlchlorobenzene
1,2-Dlchlorobenzene
Benzyl chloride
1, 3, 5-Trl chlorobenzene
Hexachlorobutad lene
Benzal chloride
1 ,2.4-THchl orobenzene
BenzotrlchYoMde
1. 2, 3-TM chlorobenzene
Hexachlorocyclopentadlene
1,2,4 ,5-Tetrachl orobenzenec
l,2,3,5-Tetrachlorobenzenec
1,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
del ta-BHC
Surrogate recovery (percent)
a ,2 ,6-Tr 1 chl orotol uene
1.4-Dlchloronaphthalene
2 ,3 ,4 ,5,6-Pentachl orotol uene
Spike
level
(PPt)
2
200
400
200
200
20
2
2
100
10
200
200
20
20
1.000
20
10
20
20
20
20
200
2,000
200
Concentration (ppt)
Rep.l
2.4
296
999
244
166
9.8
1.2
a
89.2
6.6
139
299
24.0
14.2
398
20.0
11.8
18.2
25.0
27.6
29.0
62
66
58
Rep. 2
1.9
312
1,240
466
308
22.4
2.6
a
72.8
3.9
134
271
18.6
14.2
262
18.8
8.8
19.6
30.4
31.8
26.6
61
57
51
Rep. 3
1.3
146
648
262
229
13.4
2.2
a
91.6
8.8
142
362
23.4
14.6
380
31.8
12.6
22.4
32.0
41.8
31.6
63
90
69
Rep. 4
0.8
124
384
192
130
16.6
2.0
a
90.0
6.0
118
216
15.8
9.2
720
14.4
12.6
10.2
12.2
12.8
12.2
41
45
36
Rep. 5
1.3
130
712
188
168
14.8
1.9
a
119
1.1
138
118
19.0
21.8
1,550
52.4
13.4
18.2
23.4
21.8
21.0
63
85
45
Re p. 6
0.9
210
784
258
158
14.2
2.2
a
200
5.6
140
262
19.8
13.8
830
14.6
11.2
14.8
15.0
14.6
16.4
49
50
31
Rep. 7
1.2
80
572
204
122
10.0
1.4
a
54.0
3.7
126
136
19.2
14.6
1,240
18.6
10.8
14.4
14.6
15.2
17.4
56
60
52
Rep. 8
1.8
142
376
236
166
16.4
2.0
a
73.0
8.4
162
226
15.0
17.0
840
22.8
15.0
16.2
17.2 .
16.8
19.6
71
75
68
Average
(PPt)
1.26
IPO
714
?50
180
14.7
1.94
--
98.7
4.64
137
236
19.4
14.9
780
24.2
12.0
16.8
20.2
21.3
21.7
sn
(ppt)
0.54
'»4.45
295
90
61
4.0
0.45
--
45.1
2.0
12.8
81
3.2
3.5
450
12.7
1.85
3.72
7.56
10.2
6.73
MDLb
(PPt)
1.6
250
890
270
180
12
1.4
—
140
6.0
39
240
9.5
11
1,300
38
5.6
11
23
31
20
aNo concentration given because benzal chloride coelutes with 1,2,4-trichlorobenzene. Estimated MDL is 2-5 ppt.
bMDL is the method detection limit was determined from the analysis of eight replicate aliquots processed through the entire
analytical method (extraction, Florisil cleanup, and GC/ECD analysis). MDL = tfn.^o ^gjxSO where tfn.j^o.qQ) 's the
Student's value appropriate for a 99 percent confidence interval and a standard deviation with n-1 degrees of freedom, and
SD is the standard deviation of the eight replicate measurements.
cThis pair cannot be resolved on the DB-210 fused-silica capillary column.
-------
TABLE 71. CONCENTRATIONS OF THE METHOD 8120 COMPOUNDS IN WATER SAMPLES FOR
THE MDL STUDY (MO FLORISIL CARTRIDGE CLEANUP)
Compound
Hexachloroethane
1.3-01chlorobenzene
1 . 4-D1 chl orobenzene
1 ,2-Dlchlorobenzene
Benzyl chloride
1 ,3.5-TrlcW orobenzene
Hexachl orobutadl ene
Benzal chloride
1.2,4-Trichlorobenzene
Benzotrichloride
1.2.3-Trichlorobenzene
Hexachl orocyclopentadiene
1.2,4.5-Tetrach1orobenzenec
1.2.3. 5-Tetrachlorobenzenec
1 ,2,3,4-Tetrachlorobenzene
2-Chloronaphthalene
Pent achl orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
a . 2 , 6-Tr 1 chl orotol uene
1 ,4-Oichloronaphthalene
2.3,4,5.6-Pentachlorotoluene
Spike
level
(ppt)
2
200
400
200
200
20
2
2
100
10
200
200
20
20
1.000
20
10
20
20
20
20
200
2,000
200
Concentration (ppt)
Rep.l
1.8
162
344
262
186
14.2
2.2
a
102
8.6
156
277
18.2
17.2
624
18.0
9.0
17.4
18.2
15.8
13.4
73
87
71
Rep. 2
1.2
202
370
256
188
12
1.8
a
84
5.2
146
218
17.8
20.0
742
17.8
9.4
16.4
18.0
15.2
14.4
69
68
57
Rep. 3
1.6
164
358
274
204
15.8
2.4
a
100
10.6
170
348
20.0
22.0
732
19.2
10.4
17.2
18.0
15.8
14.6
71
84
77
Rep. 4
1.4
236
296
172
110
9.8
2.1
a
74
6.0
126
230
22.8
18.4
1.270
10.4
10.3
13.4
13.6
15.4
15.0
52
58
44
Rep .5
1.4
124
324
192
150
13.2
1.7
a
81
9.8
150
142
23.0
20.8
920
14.6
11.9
18.4
19.8
18.6
18.4
74
79
65
Rep. 6
1.2
174
332
208
176
14.6
1.8
a
77
9.0
162
190
28.4
20.0
760
17.2
10.5
19.2
17.4
18.0
18.0
75
86
80
Rep. 7
2.3
312
372
170
130
12.6
1.8
a
64
7.1
138
160
19.2
19.4
1,080
14.4
12.2
15.0
16.0
14.6
14.8
60
69
62
Averaoe
(ppt)
1.4
196
342
219
163
13.2
1.9
—
83
5.0
150
224
21.3
19.7
875
15.9
9.5
16.7
17.3
-16.2
15.5
SO
(ppt)
0.39
61.8
27.3' '
44.2
34.3
1.96
0.26
—
13.7
2.0
14.8
71.0
3.73
1.57
229
3.0
1.18
2.0
2.0
1.5
1.9
(ppt)
1
1.3
1,90
86
140
110
6.2
0.8
—
43
6.3
46
220
12
4.9
720
9.4
3.7
6.3
6.3
4.7
6.0
aNo concentration given because benzal chloride coelutes with 1.2,4-trichlorobenzene.
bHDL is the method detection limit. MDL was determined from the analysis of seven replicate aliquots processed
through the entire analytical method (extraction and GC/ECO analysis). MDL = tjp.^o.ggjxSO. where t(n-l,0.99)
Is the Student's t value appropriate for a 99 percent confidence Interval and a standard deviation with n-1
degrees of freedom, and SO is the standard deviation of seven replicate measurements.
cThis pair cannot be resolved on the DB-210 fused-silica capillary colurm.
-------
TABLE 72. CONCENTRATIONS OF THE METHOD 8120 COMPOUNDS DETECTED IN
METHOD BLANKS
Compound
Concentration (ppt)
Without Florisil Cleanup With Florisil Cleanup
Rep.l Rep.2 Rep.3 Rep.4 Rep.l Rep.2 Rep.3 Rep.A
Hexachloroethane
1,3-Oi chl orobenzene
1,4-Oichlorobenzene
1,2-Dichlorobenzene
Benzyl chloride
1,3,5-Trichl orobenzene
Hexachlorobutadiene
Benzal chloride
1,2,4-Trichiorobenzene
Benzotrichloride
1,2,3-Trichlorobenzene
Hexachlorocyclopentadiene
1,2,4,5-Tetrachl orobenzene
1,2,3,5-Tetrachlorobenzene
1,2,3,4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachlorobenzene
Hexachl orobenzene
alpha -BHC
gamma-BHC
beta-BHC
delta-BHC
Surrogate recovery (percent)
ct,2,6-Trichlorotoluene 76
1,4-Oichloronaphthalene 75
2,3,4,5,6-Pentachlorotoluene 70
0.14 0.16 0.15 0.17 0.15 0.20 0.20 0.21
80
77
72
80
81
81
84
81
74
76
130
77
1
2
68
70
66
72
78
77
68
72
62
142
-------
TABLE 73. LIST OF CONDITIONS ALTERED AND ASSIGNED VALUES FOR GAS
CHROMATOGRAPHIC ANALYSIS (METHOD 8120)
Condition
Injector temperature (°C)
Detector temperature (°C)
Injection volume (yL)
Calibration
Solvent
Interferences from matrix
No.
1
2
3
4
5
6
Letter
A, a
B,b
C,c
D,d
E,e
F,f
Value
for capital
letter
230
260
3
Using
average
RF
Hexane
With diesel
Val
for 1
case 1
210
240
1
Using
single
RF
Hexane-
acetone
Without
ue
ower
etter
(50:50)
(diesel hydrocarbons)
Interferences from matrix
(chlorinated pesticides)
hydrocarbons
G,g With organo-
chlorine
pesticides
Without
143
-------
TABLE 74. DESIGN FOR TEST OF EXPERIMENTAL CONDITIONS
Values of conditions in determination
Experimental
condition
No.
12345578
1 AAAAaasa
2 BBbbBBbb
3 CcCcCcCc
4 DDddddDD
5 EeEeeEeE
6 FffFFffF
7 GggGgGGg
144
-------
The analytical results are presented as percent recovery of each test
compound in each of the eight experiments (Table 75). Table 76 shows the
group differences VA through VQ which were calculated from equations 1
through 7.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
For example, V^ for hexachloroethane represents the average for the /\
determinations minus the average for the ^ determinations
(e.g., VA = 1/4 (93 + 114 + 78 + 89) -1/4 (68 + 101 + 85 + 119) = 0.25 which
means that an injection temperature of 230°C gave a slightly higher response
than at 2108C.
The results showed that the GC method is reasonably rugged. Of course,
the results for individual compounds vary, but overall it was found that:
o Raising the injector temperature from 210°C to 230°C had essentially
no effect.
o Raising the detector temperature had a clear positive
effect.
o Increasing the injection volume had a clear negative effect, mainly
because of column overloading.
o Use of the average RF in calibration is significantly more
advantageous than use of single RF.
o There was essentially no difference between hexane and
hexane/acetone (1:1) as solvents.
• The presence of diesel fuel hydrocarbons resulted in lower
responses.
o In the presence of chlorinated pesticides, the BHCs went off scale
although they could still be identified, whereas the determination
of the other 18 compounds was essentially not affected.
6.5.6 Confirmation by GC/MS
Table 77 gives the retention times (as scan numbers) and the three most
intense ions 1n the mass spectra of the 22 target compounds, the three
internal standards, and the three surrogate compounds proposed in the revised
Method 8120. GC/MS chromatograms of a composite standard containing the 22
target compounds at 1 ng/yL and 5 ng/yL (in methylene chloride) are given in
145
-------
TABLE 75. RUGGEDNESS TEST FOR METHOD 8120 -- RECOVERY DATA FOR THE
22 TEST COMPOUNDS
Percent recovery
12345678
Compound (s) (t) (u) (v) (w) (x) (y) (z)
Hexachloroethane
1,3-Dichlorobenzene
1 , 4-Di chl orobenzene
1 , 2-Di chl orobe nzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachlorobutadiene
Benzal chlorideb
l,2,4-Trichlorobenzeneb
Benzotri chloride
1, 2, 3-Trichloro benzene
Hexachlorocyclopentadiene
l,2,4,5-Tetrachlorobenzenec
1 ,2 , 3, 5-Tetra chl orobenzene0
1,2, 3, 4-Tetrachl orobenzene
2-Chl oronaphthalene
Pentachl orobenzene
Hexachlorobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
93
132
149
143
128
140
115
94
94
78
118
125
124
124
112
129
120
76
a
a
a
a
114
116
115
119
121
118
103
138
138
139
125
119
131
131
136
146
128
96
137
137
126
158
78
108
99
115
109
94
119
73
73
60
103
108
99
99
98
82
82
104
59
58
109
69
89
78
82
83
89
83
94
93
93
99
79
100
78
78
80
92
121
100
a
a
a
a
68
117
126
132
111
119
106
70
70
56
110
93
117
117
105
128
92
86
56
56
108
66
101
134
128
130
122
122
107
113
113
105
132
117
136
136
135
127
146
101
a
a
a
a
85
97
84
96
101
78
101
83
83
73
89
111
88
88
87
90
102
90
a
a
a
a
119
82
82
80
94
83
97
119
119
130
81
119
80
80
81
86
97
94
126
127
107
128
aNot able to quantify compound because of interference from the
other organochlorine pesticides.
b»cThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
146
-------
TABLE 76. RUGGEDNESS TEST FOR METHOD 8120 ~ GROUP DIFFERENCES FOR THE
22 TEST COMPOUNDS
Group differences
Compound
Hexachloroethane
l,3-D1ch1orobenzene
l,4-D1chlorobenzene
l,2-D1chlorobenzene
Benzyl chloride
1, 3, 5-Tr1chl orobenzene
Hexach 1 orobutad iene
Benzal chloride
l,2,4-Tr1chlorobenzenea
Benzotr1chlor1de
1,2, 3-Tr 1 ch 1 orobenzene
Hexach lorocyclopentadlene
1,2,4,5-Tetrachlorobenzenef*
1,2,3, 5-Tetrachl orobenzene0
1,2,3, 4-Tetr ach 1 orobenzene
2-Ch 1 oronaphthal ene
Pentach 1 orobenzene
Hexach 1 orobenzene
alpha-BHCc
gamma-BHCc
beta-BHCc
delta-BHCc
Statistics*1
Mean
Standard deviation
Standard error
Lower limit of mean
Upper limit of mean
VA
0
i
6
5
4
8
5
3
3
3
3
3
2
2
4
4
3
1
3
3
5
8
3
1
0
2
4
.2
.0
.2
.5
.7
.2
.0
.2
.2
.0
.2
.0
.7
.7
.5
.5
.5
.2
.5
.0
.0
.2
.6
.9
.5
.7
.6
VB
1.2
33.5
42.7
37.5
22.2
40.2
5.0
11.7
11.7
4.0
33.2
4.0
40.7
40.7
35.5
45.0
21.0
-7.2
2.0
2.0
4.5
6.7
23.5
17.3
4.1
14.9
32.1
VC
-24
11
12
18
5
6
10
-35
-35
-51
0
-4
0
0
-7
-5
-24
-8
-37
-37
-4
-37
-7
19
4
-17
2
.7
.0
.7
.5
.7
.2
.0
.7
.7
.5
.7
.5
.7
.7
.5
.5
.0
.7
.0
.5
.0
.7
.3
.4
.6
.0
.3
VD
18.7
-2.5
-1.2
-5.5
3.2
0.2
-2.5
21.2
21.2
25.0
-2.7
14.0
-1.7
-1.7
-0.5
5.5
1.5
-8.7
37.0
37.5
4.0
37.7
4.6
10.5
2.5
-0.6
9.8
VE
8.
12.
12.
9.
7.
10.
8.
3.
3.
1.
7.
11.
6.
6.
4.
-8.
0.
0.
-2.
-2.
-4.
-6.
6.
5.
1.
3.
8.
7
0
7
5
7
2
5
7
7
5
7
5
2
2
5
0
5
7
0
0
5
7
0
1
2
4
5
VF
-2.
-11.
3.
-5.
-7.
3.
-4.
-7.
-7.
-3.
-15.
-4.
-13.
-13.
-19.
-2.
-7.
-8.
-3.
-3.
-5.
-8.
-7.
6.
1.
-10.
-4.
2
5
2
5
7
2
5
7
7
5
2
5
7
7
5
5
0
7
5
0
0
2
1
0
4
1
2
VG
-2.7
4.5
5.2
1.5
1.2
2.2
-2.0
-4.2
-4.2
-7.5
-0.2
3.5
-0.2
-0.2
-1.5
-1.0
22.5
-3.2
-94.5
-94.5
-112.5
-105.2
0.8
6.3
1.5
-2.4
3.9
a«bThese pairs cannot be resolved on the DB-210 fused-s1!1ca capillary
column.
cTo calculate group differences for these compounds, values of 0 were
used for the missing data 1n Table 75.
dStudent t value 1s 2.11. The BHC isomers were excluded from the
statistics.
147
-------
TABLE 77. RETENTION TIMES (SCAN NUMBERS) AND THREE MOST INTENSE IONS OF
THE METHOD 8120 COMPOUNDS ANALYZED BY GC/MS USING A
30 M X 0.25 MM ID (0.25 wm FILM THICKNESS) DB-5 FUSE0-SILICA
CAPILLARY COLUMN*
r
Compound
1,3-Dichlorobenzene
l,4-D1chlorobenzene
Benzyl chloride
1,2-Dichlorobenzene
Hexachloroethane
1,3,5-Trlchlorobenzene
Benzal chloride
1,2,4-Trlchlorobenzene
1,2,3-Trichlorobenzene
Hexach 1 orobu tad 1 ene
Benzotr1chlor1de
1,2,4, 5-Tetrachl orobenzene
1,2,3 , 5-Tetr ach 1 orobenzene
Hexachlorocyclopentadlene
2-Chloronaphthalene
1,2,3,4-Tetrachlorobenzene
Pentachl orobenzene
alpha-BHC
Hexach 1 orobenzene
beta-BHC
gamma-BHC
delta-BHC
2,5-Dibromotoluene (IS)
1,3,5-Trlbromobenzene (IS)
a,a'-D1bromo-m-xylene (IS)
a,2,6-Tr1chlorotoluene (SU-1)
l,4-D1chloronaphtha1ene (SU-2)
2,3,4,5,6-Pentachlorotoluene (SU-3)
Scan
No.
598
606
612
644
703
786
794
845
891
897
904
1031
1029
1035
1078
1081
1229
1393
1407
1436
1448
1486
968
1129
1228
1050
1265
1376
Ions at m/z
(relative intensity)
146 (100), 148 (63), 111 (38)
146 (100), 148 (62), 111 (36)
91 (100), 126 (25), 65 (12)
146 (100), 148 (62), 111 (41)
117 (100), 119 (96), 201 (76)
180 (100), 182 (95), 184 (30)
125 (100), 127 (31), 63 (17)
180 (100), 182 (95), 184 (30)
180 (100), 182 (96), 145 (31)
225 (100), 227 (66), 190 (41)
159 (100), 161 (63), 89 (18)
216 (100), 214 (76), 218 (46)
216 (100), 214 (76), 218 (46)
237 (100), 239 (67), 235 (62)
162 (100), 127 (36), 164 (32)
216 (100), 214 (78), 218 (47)
250 (100) . 252 (61), 248 (61)
183 (100), 181 (98), 219 (85)
284 (100), 286 (81), 282 (51)
109 (100), 181 (83), 111 (80)
181 (100), 183 (97), 219 (82)
109 (100), 181 (97), 183 (97)
250 (100), 169 (68), 89 (66)
314 (100), 316 (100), 74 (96)
183 (100), 104 (99), 185 (96)
159 (100), 161 (64), 194 (18)
196 (100), 198 (63), 126 (31)
229 (100), 227 (81), 264 (67)
aThe GC/MS operating conditions are as follows: 40°C to 300°C at 8°C/m1n;
Injector temperature 250°C; transfer line temperature: 260°C; 1on source
temperature: 190°C; scanning mass range, 45 to 450 amu; electron energy,
70 eV; multiplier voltage, 1,400 eV; scan rate, 1 sec.
IS — Internal standards.
SU -- surrogate compound.
148
-------
Figures 49 and 50, respectively. The sensitivity of the GC/MS
Instrument 1s estimated to be approximately 0.5 to 1 ng per compound.
6.5.7 Changes Suggested for Incorporation 1n Method 8120 Protocol
The following Items were Incorporated 1n a proposed revision of
Method 8120 which 1s Included 1n Appendix B.
• The 11st of target compounds was expanded to Include 22 target
compounds.
• Extract cleanup using Flor1s1l cartridges was Included as an
option.
• A GPC step for removal of waxes and I1p1ds from municipal sludges
and other h1gh-Hp1d matrixes was Included.
• Spiking levels for each Individual analyte were suggested.
• A procedure for spiking soil samples was Included.
• Internal standards and surrogates were specified.
• The use of fused-silica open tubular columns 1n place of the packed
columns was specified.
• The GC retention times of the 22 compounds, the surrogates and the
Internal standards on the specified columns and at the specified
conditions were Included.
• A table suggesting the five concentration levels for multl level
calibration (Method 8000) was Included.
• Tables with MDLs and precision and accuracy data for a water and a
soil matrix were Included.
149
-------
•1/22/tt 9i49i«t
s«»LEi mat sro ue/u.
CONK. I PIWM9H
MHKi G t.aM LMB.I H t. 4.11
•IMSTOI n
• t. 1.9 J • MKl U
Saws 4MTO
we.
1 I
UK.
13tt
ttra
[^r'||i^-4^>
12M I4M 1C«
2»tM 23i» 2«:4t
SOW
Figure 49. GC/MS chroraatograw of 1 ng of Method 8120 composite standard
Injected on colunn. GC/MS conditions are given 1n Table 77,
Footnote a.
150
-------
RR.
«C OMTIH •12HTD5 11 SCONS 9H TO 2W*
•1/22'W Cl42lM CM.Ii (120105 tt
SMPlf i (121 STO MOsUL
COKJS.I FMM9N
MHKi G 1.3M UHLl H •. 4.« OMHi « •. !.• J | MCi U 21. 3
net
i
3
7
*
i
*
Mi
T
kg
«
•
_»
.
1
lip
8 1«
T
w
14V
1*21 1(14
12H
3*t« 33191TW
Figure 50. GC/MS chroMtogram of 5 ng of Method 8120 composite standard
Injected on col mm. GC/MS conditions are given 1n Table 77,
Footnote a.
151
-------
REFERENCES
1. Test Methods for Evaluating Solid Waste; Laboratory Manual ~
Physical/Chemical Methods, Volume IB. U.S. Environmental Protection
Agency, Washington, O.C., 1986.
2. Furlong, E., Indiana University, private communication, 1988.
3. Jaffe, R., and R. A. Hites, "Fate of Hazardous Waste Derived Organic
Compounds 1n Lake Ontario," Environ. Sc1. Technol. 20:267-274, 1986.
4. Lee, H. B., R. L. Hong-You, and A. S. Y Chau, "Analytical Reference
Materials Part V — Development of a Sediment Reference Material for
Chlorobenzenes and Hexachlorobutadlene," Analyst 111:81-85, 1986.
5. Mills, P. A, "Variation of Florlsil Activity: Simple Method for
Measuring Adsorbent Capacity and Its Use 1n Standardizing Florlsil
Columns," J. Assoc. Off. Anal. Chem. 51: 29 (1968).
6. Lopez-Av1la, V., N. Dodhlwala, and W. F. Beckert, "Evaluation of
Fused-S1l1ca Capillary Columns for GC/ECD Analysis of Chlorinated
Hydrocarbons Listed 1n EPA Method 8120," J. High Resol. Chrom. & Chrom.
Communlc. 11:234-241, 1988.
7. Jensen, S. L., L. Renberg, and L. Reutergardh, "Residue Analysis of
Sediment and Sewage Sludge for Organochlorlnes 1n the Presence of
Elemental Sulfur," Anal. Chem. 49:316-318, 1977.
8. Chou, S-F. J., R. A. Griff1n, and M-I. M. Chou, "Effect of Soluble Salts
and Caustic Soda on Solubility and Adsorption of Hexachlorocyclo-
pentadlene," 1n: Land Disposal of Hazardous Waste, Proceedings of the
8th Annual Research Symposium, Fort Mitchell, Kentucky, PB 82-173022,
137-149, 1982.
152
-------
APPENDIX A
LITERATURE REVIEW
A-l
-------
CONTENTS
Figures A-4
Tables A-5
Abbreviations A-8
1 Introduction • A-9
2 Chemical Structures, Physlco-Chemical Properties, Manufacture, and
Industrial Uses A-10
2.1 Chemical Structures and Physico-Chemical Properties A-10
2.2 Manufacture and Industrial Uses A-10
2.3 Occurrence A-17
3 Analytical Methodologies for Chlorinated Hydrocarbons A-23
3.1 Sample Preservation A-23
3.2 Extraction A-27
3.2.1 Extraction of Water Samples A-27
3.2.2 Extraction of Sediment and Soil Samples A-32
3.3 Cleanup A-34
3.3.1 Liquid-Solid Chromatography A-34
3.3.2 Gel Permeation Chromatography A-41
3.3.3 Sulfur Removal A-41
3.4 Solvent Concentration A-44
3.5 GC Analysis A-44
3.5.1 Gas Chromatographic Columns A-45
3.5.2 Gas Chromatographic Detectors A-64
3.5.3 Confirmation of Compound Identity A-70
References A-73
A-3
-------
FIGURES
Number Page
1 Fractionalion scheme for chlorinated benzenes, PCBs, PCTs,
PCDPEs, PCNs using alumina chromatography A-40
2 Chromatogram of chlorobenzene mixture in pentane on
Carbowax 20M capillary column A-49
3 Chromatogram of chlorobenzene mixture in pentane on SP-2100
capillary column A-50
4 GC/FID chromatograms of chlorinated hydrocarbons analyzed
on a OB-1301 fused-silica capillary column A-51
5 GC/ECD Chromatogram of chlorinated hydrocarbons on a
SPB-5 15 m x 0.53 mm ID fused-silica capillary column .... A-52
6 GC/ECD chromatograms of chlorinated hydrocarbons on a
DB-210 30 m x 0.53 mm ID fused-silica capillary column and
DB-210 30 m x 0.25 mm ID fused-silica capillary column . . . A-53
7 Comparison of high-performance column packings for the
separation of chlorobenzenes A-63
8 GC/ECD Chromatogram of chlorinated hydrocarbons analyzed on
a 2 m x 2 mm ID glass column packed with 1 percent SP-1000
on Supelcoport A-68
A-4
-------
TABLES
Number Page
1 CAS numbers, chemical structures, molecular formulae, and
nomenclatures of 22 chlorinated hydrocarbons proposed for
evaluation of Method 8120 A-ll
2 Physico-chemical properties of the Method 8120 compounds. . . . A-15
3 Median concentrations of the chlorinated hydrocarbons for
Industrial effluents (pg/L), ambient water (wg/L),
sediments (pg/Kg), and biota (pg/Kg) for the United States
from all STORET stations A-18
4 Wastes dumped at Hyde Park, the S and N areas, and
Love Canal A-19
5 Chlorobenzene concentrations 1n the Niagara River A-20
6 Organic compounds Identified 1n the Niagara River Watershed . . A-21
7 Amounts (Kg) of chlorobenzenes 1n Lake Ontario compartments . . A-22
8 Summary of analytical methodologies for chlorinated
hydrocarbons A-24
9 Preservation of water samples containing BHCs at 4°C
and 24°C A-26
10 Effect of long-term cold storage on levels of chlorobenzenes
and hexachlorobutadlene 1n freeze-drled sediment samples. . . A-28
11 Summary of extraction techniques for water samples A-29
12 Accuracy and precision measurements of substituted benzenes
with EPA Methods 625 and 625.1 A-31
13 Summary of extraction techniques for soils and sediments. . . . A-33
14 Summary of cleanup procedures A-35
A-5
-------
TABLES (CONTINUED)
Number Page
15 Elution patterns of some chlorinated hydrocarbons from a
semlmlcro Flor1s1l column A-36
16 Elution patterns of some chlorinated hydrocarbons from a
combined Florisil-silicic acid column A-38
17 Effect of increased solvent polarity on separation of
chlorinated hydrocarbons from a combined Florisil-silicic
acid column A-39
18 GPC elution volumes for some chlorinated benzenes and
organochlorine pesticides A-42
19 Recoveries (percent ± SO, duplicate determinations) of
organochlorine contaminants A-43
20 GC columns and conditions reported for the analysis of
chlorinated hydrocarbons A-46
21 Retention times and response factors for chlorobenzenes .... A-54
22 Retention times of chlorinated benzenes, organochlorine
pesticides and PCBs on OB-17 and DB-5 fused-silica
capillary columns A-55
23 Retention times of halogenated benzenes on a 15 m SE-52
capillary column A-57
24 Retention indices of chlorobenzene isomers on a
25 m x 0.22 mm ID SE-30 fused-silica capillary column .... A-58
25 Retention indices of chlorobenzene Isomers on a
22 m x 0.30 mm ID Carbowax 20M glass capillary column. . . . A-59
26 Incremental effect of chlorine substitution and temperature
on retention indices on a 25 m x 0.22 mm ID SE-30
fused-s1!1ca capillary column A-61
27 Incremental effect of chlorine substitution and temperature
on retention indices on a 22 m x 0.30 mm ID Carbowax 20M
glass capillary column A-62
28 GC of chlorobenzenes on a Dexsil 410 packed column A-65
A-6
-------
TABLES (CONCLUDED)
Number Page
29 GC relative retention times of chlorinated benzenes on an
OV-101 and an OV-101/OV-210 column, both operated at 130°C. . A-66
30 Retention times relative to pentachlorobenzene for various
columns at 130°C and 150°C A-67
31 Relative sensitivities (HCB = 10.0) and characteristic ions of
chlorobenzenes and hexachlorobutadiene A-69
32 Comparison of detection limits for chlorobenzenes A-71
33 Chemical confirmation of BHC isomers A-72
A-7
-------
LIST OF COMPOUND ABBREVIATIONS USED IN THIS REPORT
Abreviation
Complete Name
CBs
2-CN
DCB
HCB
HCE
HCBu
BHC
HCCP
OCPs
OPPs
QCB
PCBs
PCDPEs
PCDBFs
PCDBDs
PCNs
PCTs
TeCB
TCB
Chlorobenzenes
2-Chloronaphthalene
Dlchlorobenzene
Hexachlorobenzene
Hexachloroethane
Hexachlorobutadlene
Hexachlorocyclohexane
Hexachlorocyclopentadiene
Organochlorlne Pesticides
Organophosphorus Pesticides
Pentachlorobenzene
Polychlorlnated Blphenyls
Polychlorlnated Dlphenyl Ethers
Polychlorlnated Dlbenzofurans
Polychlorlnated D1benzod1ox1ns
Polychlorlnated Naphthalenes
Polychlorlnated Terphenyls
Tetrachlorobenzene
Trlchlorobenzene
A-8
-------
SECTION 1
INTRODUCTION
The Resource Conservation and Recovery Act (RCRA) of 1976 and its
elements require the Environmental Protection Agency (EPA) to regulate
hazardous waste activities. Implementation and enforcement of RCRA requires
analytical methodologies that will provide reliable data. The document "Test
Methods for Evaluating Solid Waste," Office of Solid Waste Manual SW-846,
revised recently, provides a compilation of methods for evaluating RCRA solid
wastes for environmental and human health hazards. SW-846 Method 8120 for
chlorinated hydrocarbons requires evaluation as part of an ongoing program of
EPA-Las Vegas. To assist EPA-Las Vegas in this evaluation, Acurex was asked
to perform a literature review and recommend approaches for sample
extraction, cleanup, analysis, and compound confirmation.
This report presents the literature review pertinent to this study.
This literature review was performed using the computerized Chemical
Abstracts search and several EPA reports dealing with the analysis of organic
compounds in water. Furthermore, recent issues of Analytical Chemistry, the
Journal of Chromatography, the Journal of ChromatographTc Science, the
Journal of the Association of Official Analytical ChemisTs, and
Environmental Science and Technology were searched to gather recent
references that were not in the computer data base.
The computer searches were done using DIALOG. Chemical Abstracts files
were searched back to 1977, for all references containing "chlorinated
hydrocarbons," "gas chromatography," "extraction," and "cleanup."
Approximately fifty articles that were judged to be scientifically relevant
to the objectives of this study were retrieved from the literature.
The literature review summary that is presented in this report addresses
the following:
• Sample preservation techniques
• Extraction techniques for water, sediment, and soil
• Cleanup techniques
• Gas chromatographic analysis (columns, retention time information,
chromatographic problems)
o Compound confirmation.
A-9
-------
SECTION 2
CHEMICAL STRUCTURES, PHYSICO-CHEMICAL PROPERTIES,
MANUFACTURE, AND INDUSTRIAL USES
2.1 CHEMICAL STRUCTURES AND PHYSICO-CHEMICAL PROPERTIES
The Chemical Abstracts Registry (CAS) numbers, chemical structures,
molecular formulae, and the nomenclatures for 22 chlorinated hydrocarbons
that are proposed for evaluation in this study are given in Table 1. Their
physico-chemical properties are listed in Table 2.
2.2 MANUFACTURE AND INDUSTRIAL USES
Benzyl Chloride, Benzal Chloride, and Benzotrichloride
Benzyl chloride, benzal chloride, and benzotrichloride are manufactured
by the chlorination of toluene and are converted to various chemical
intermediates or products. Benzyl chloride is utilized in the manufacture of
butyl-benzyl phthalate; benzal chloride is hydrolyzed to .benzaldehyde, and
benzotrichloride is converted to benzoyl chloride (1). Small amounts of
benzotrichloride are used in the manufacture of benzotrifluoride, an
intermediate in the manufacture of dyes, and in the synthesis of
hydroxybenzophenone ultraviolet light stabilizers (1).
Chlorinated Benzenes
Chlorinated benzenes, with the exception of 1,3-dichlorobenzene,
1,3,5-trichlorobenzene and 1,2,3,5-tetrachlorobenzene, are produced by
chlorinating benzene in the presence of a Friedel -Crafts catalyst (ferric
chloride) (1). Each compound, except hexachlorobenzene, can be further
chlorinated to produce various higher-chlorinated benzenes. Pure compounds
are obtained by distillation and crystallization.
1,2-Dichlorobenzene is used in the manufacture of toluene diisocyanates
and 3,4-dichloroaniline, and it has found some limited use as a heat transfer
fluid. 1,4-01 chlorobenzene is used in mothballs and room deodorant blocks.
1,2,4-Trichlorobenzene has limited uses as a solvent and as a dye carrier in
the textile industry. 1,2,4,5-Tetrachlorobenzene is used exclusively as the
raw material for 2,4,5-triacid and its esters, and for hexachlorophene. The
other chlorinated benzenes have no significant industrial applications.
A-10
-------
TABLE 1. CAS NUMBERS, CHEMICAL STRUCTURES, MOLECULAR FORMULAE, AND
NOMENCLATURES OF 22 CHLORINATED HYDROCARBONS PROPOSED FOR
EVALUATION OF METHOD 8120
CoMon naae
Cheatcal
Abstracts
Registry No.
Chemical
structure
Molecular
formula
(molecular
weight)
Nomenclature
1. Benzal chloride
98-87-3
5
HcClz (Dlchloromethyl)benzene or
160) alpha,alpha-Olchlorotoluene
2. Benzotrlchloride
98-07-7
jfc
0
CiHi;Cl3 (Trichloromethyl)benzene or
(194) alpha .alpha .alpha-Trlchlorotoluene
3. Benzyl chloride
100-44-7
CHjCl
C7H7C1
7H7UI
(1*6)
alpha-Chlorotoluene or (Chloronethyl)
benzene
4. 2-Chloronaphthalene 91-58-7
ci
Cl 2-Chloronaphthalene
5. 1,2-Olchlorobenzene
95-50-1
ci
ci
CfiHdCl
(146)
Cl2 1.2-Olchlorobenzene
6. 1.3-D1ch1orobenzene 541-73-1
ci
ci
1.3-Oichlorobenzene
-------
TABLE 1. (continued)
Molecular
Chemical formula
Abstracts Chemical (molecular
QOMKXI naive Registry No. structure weight)
7. 1,4-Dlchlorobenzene 106-46-7 Jk. C6H4C12
[^ rue)
Cl
8. Hexachlorobenzene 118-74-1 ,, JL ,, CgCU
Yi *28^
*• 9. Hexachlorobutadlene 87-68-3 CJ c| ^ ci CdClg
~ / = C~C= \ 25)
ci ci
10. alpha-BHC 319-84-6 . C6H6C16
H (288)
1 H H
H Cl
f H H
11. heta-HHC 319-8S-7 C1"V4 J, ri r.r,HfC.\<
Nomenclature
1 ,4-01 chl orobenzene
Hexachlorobenzene
Hexachl orobutadl ene
a 1 pha- 1.2.3.4 ,5 ,6-Hexachl orocyc 1 ohexane
beta-1.2.3»4.5.6-Hexachlorocyclohexane
-------
TABLE 1. (continued)
CoMon naae
Chemical
Abstracts
Registry No.
Chemical
structure
Molecular
formula
(molecular
weight)
Nomenclature
12. gawa-BHC
(llndane)
13. delta-BHC
58-89-9
319-86-8
CI
gaDna-1.2,3,4,5.6-Hexachlorocyclohexane
C6H6C16 delta-1.2.3,4,5,6-Hexachlorocyclohexane
(288)
14. Hexachlorocyclopentadlene 77-47-4
0
ci ci
CcCl6 Hexachlorocyclopentadlene
c6
(270)
15. Hexachloroethane
67-72-1
C) CI
-
C?C1<; Hexachloroethane
?<;
(231)
16. 1,2,3.4-Tetrachlorobenzene 634-66-2
tl
CfiHoCl
(214)
1.2.3.4-Tetrachlorobenzene
-------
TABLE 1. (concluded)
COMOII name
Chemical
Abstracts
Registry No.
Chemical
structure
Molecular
formi 1 a
(molecular
weight)
Nomenclature
17. 1,2,4,5-Tetrachlorobenzene 95-94-2
1,2,4,5-Tetrachlorobenzene
18. 1,2,3,5-Tetrachlorobenzene 634-90-2
1,2,3, 5-Tet rach 1 orobenzene
19. 1.2.4-Trlchlorobenzene 120-82-1
20. 1,2,3-Trlchlorobenzene 87-61-6
ci
ci
1 , 2 , 4-Tr 1 ch 1 orobenzene
1 , 2 , 3-Tr 1 ch 1 orobenzene
21. 1,3,5-Trlchlorobenzene
108-70-3
1,3, 5- Trl ch 1 orobenzene
22. Pentachlorobenzene
608-93-5
Cl
Cl
Pent ach 1 orobenzene
-------
TABLE 2. PHYSICO-CHEMICAL PROPERTIES OF THE METHOD 8120 COMPOUNDS
I
H-«
cn
Compound name
Benzal chloride
BenzotHchloHde
Benzyl chloride
2 -Chi oronaphthal ene
1 ,2-D1ch1 orobenzene
1.3-Dichl orobenzene
1 ,4-Dlchl orobenzene
Hexach 1 orobenzene
Hexachlorobutadlene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachl orocycl opentadlene
Hexachl oroethane
1 ,2,3,4-Tetrachlorobenzene
1 ,2,4,5-Tetrachlorobenzene
1 ,2,3,5-Tetrachlorobenzene
1 ,2,4-Trlchl orobenzene
1,2,3-Trlchlorobenzene
1, 3, 5-Trlchl orobenzene
Pentachl orobenzene
Melting
point9
(°C)
-16.4
-4.75
-39.2
61.0f
-16.97
-24.76
53.04
228.7
-21. tie
159.2
311.7
112.9
140.8
11.34
185.0
479; 46.0
1409; 139.5
549;51.0
259;17.15
539;53.5
639;63.5
869;85.0
Boiling
point*
(°C)
205.2
220.6
179.4
259.0
180.4
173.0
174.1
319.3
215.0*
288. 06 0
60.0°-5e
323. 4e „
6000.36e
239.0
186.0
254.9
248.0
246.0
213.8
218.5
208.5
276.0
Density8
(Kg/L)
1.2560
1.3740
1.1135
1 .2656
1.3022
1.2828
1.2475
1.5960
1 .5542e
h
h
h
h
1.7100
2.0940
1.7000
1.8330
h
1.4483
h
n ,. «
1.B34216'5
Water
solubility
at 25°C
(mg/L)
h
h
h
6.74*
45?
123f
90^. 79f
0.005b
2f
1.63d;!. 21 to 2.03f
0.70^:0.13 to 0.7f
7.3 to lO.fldja.e to 31. 4f
h
l.§f
5.0;50f
4.3b;4.279
0.599
3.479
SO6; 349
319
6.59
0.56b
log
h
h
h
h
3.599
3.599
3.4b;
5.5«>;
3.4b
h
h
h
h
h
h
4.5b;
5.059
5.059
4.f)b;
.4.279
4.279
4.9b;
*o*C
3.599
6.539
5.059
4.279
5.799
aData taken from Reference I.
t>Data taken from Reference 2.
CKOW Is the octanol/water partition coefficient.
dData taken from Reference 3.
eData taken from Reference 4.
fData taken from Reference 5.
9Data taken from Reference 6.
"Information Is not available.
-------
BHCs
Benzene hexachloride (BHC) or hexachlorocyclohexane is the fully
saturated product formed by light-catalyzed addition of chlorine to benzene.
The reaction produces a number' of stereo-isomeric compounds of the
composition Ce^Clc. The composition of the various isomers in benzene
hexachloride depends on the conditions of manufacture but is commonly as
follows:
o alpha (65 percent)
o beta (7 percent)
o gamma (14 percent)
o all others (14 percent)
The physico-chemical properties of the four major isomers are included in
Table 2.
Lindane is one of the oldest chlorinated insecticides. It is used on
field crops, vegetable crops, fruit crops, viticulture, etc.
Hexachlorocyclopentadiene
Hexachlorocyclopentadiene is obtained by chlorination of cyclopentadiene
with alkaline hypochlorite solution at 40°C; the reaction product is
recovered by fractional distillation. Preparation of hexachloro-
cyclopentadiene by thermal dechlorination of octachlorocyclopentene at 470°C
to 480°C was also reported (1).
2-Chloronaphthalene
Ferric chloride-catalyzed chlorination of molten naphthalene at 10P°C to
110°C gives a crude product which, distilled at 259°C to 260°C, gives a
fraction containing 91 percent 1-chloronaphthalene and 9 percent
2-chloronaphthalene (1). Pure 2-chloronaphthalene can be prepared from
2-naphthylamine via the diazonium salt by the Sandmeyer reaction (1).
Hexachloroethane
Hexachloroethane Is obtained by chlorination of tetrachloroethylene, in
the presence of ferric chloride, at 100°C to 140°C (1). Minor amounts of
hexachloroethane are formed in many industrial chlorination processes of
saturated and unsaturated Cg hydrocarbons. Hexachloroethane is used in the
formulations of high-pressure lubricants, as a degasifier in the manufacture
of aluminum and magnesium metals, and also as a chain transfer agent in the
radiochemical emulsion preparation of propylene-tetrafluoroethylene
copolymer (1).
A-16
-------
2.3 OCCURRENCE
Table 3 summarizes the median concentrations of chlorinated hydrocarbons
or Industrial effluents, ambient water, sediments, and biota for stations
collectively maintained by EPA regions and other government agencies (e.g.,
U. S. Geological Survey) 1n a computerized water quality database called
STORE! (STOrage and RETrleval) (7). Only two of the chlorinated hydrocarbons
listed 1n Table 3 were detected 1n water samples 1n more than 10 percent of
the samples (7). Because not all of the STORET stations had measured
sediment and biota concentration, there are fewer values for these matrices.
The occurrence of the chlorinated benzenes 1n the environment seems to
be related to their high production (approximately 200,000 metric tons in the
U.S. 1n 1978) as well as to their uses which were described in
Section 2.2 (8). Those compounds that may have entered the environment are
not readily biodegraded, photolyzed, or hydrolyzed (5). Table 4 Identifies.
the wastes dumped at Hyde Park, the S and N areas, and Love Canal in New York
State from 1953 jntil 1979. Leachates from the disposal sites have
contaminated the Niagara River and, subsequently, Lake Ontario.
Chlorobenzene concentrations in the Niagara River were reported by Oliver and
N1col (10) and are given in Table 5. Chlorobenzene and chlorotoluene
concentrations 1n the Niagara River watershed were reported by Elder et al.
(11) and are presented in Table 6. A series of unexpected compounds which
were related to benzyl chloride and benzoyl chloride wastes were found at the
102nd Street bay and 1n the Bloody Run Creek (11). The benzyl derivatives
detected in samples collected from the 102nd Street area were attributed to
migration of organics from the Love Canal area because the 102nd Street dump
is not known to contain any benzyl chloride wastes and because the highest
concentration of benzyl derivatives in the bay was directly in front of the
storm sewer outfall from the Love Canal area (11). Elder et al. (11)
attributed the presence of various chlorinated benzyl alcohols,
benzaldehydes, and benzole adds to reaction of labile chlorine attached to
the carbon adjacent to the benzene ring. Thus, benzyl alcohol formed from
benzyl chloride and benzole acid formed from benzotrlchloride (11). Oliver
and Nicol (10) reported that the concentrations of all chlorinated benzenes
(except 1,4-and 1,2-dichlorobenzenes) were below 1 ppt in Lakes Ontario and
Huron. The mean concentrations for l,4-d1Chlorobenzene were 45 ppt for Lake
Ontario and 4 ppt for Lake Huron. l,2-D1chlorobenzene was detected only 1n
Lake Ontario at a mean concentration of 5 ppt. Drinking water samples
collected from three cities 1n the Lake Ontario vicinity contained mean
concentrations of 13 ppt for l,4-d1chlorobenzene, 3 ppt for 1,2-dichloro-
benzene, and 2 ppt for 1,2,4-tHchlorobenzene (10).
Chlorobenzene concentrations in the Great Lakes were also
Investigated (10). Concentrations are lowest 1n Lake Superior (- 10 ppb),
somewhat higher in Lakes Huron and Erie (- 26 ppb for Lake Huron and ~ 38 ppb
for Lake Erie) and much higher 1n Lake Ontario (~ 560 ppb). The values given
represent the sum of the dichloro- through hexachlorobenzenes. Because about
50 percent of the sediments in Lake Ontario come from the Niagara River, the
contamination of Lake Ontario was attributed to the chemical manufacturing
effluents and the waste disposal site leachates (10).
A-17
-------
TABLE 3. MEDIAN CONCENTRATIONS OF THE CHLORINATED HYDROCARBONS
FOR INDUSTRIAL EFFLUENTS (yg/L), AMBIENT WATER (ug/L),
SEDIMENTS (ng/Kg), AND BIOTA (Ug/Kg) FOR THE UNITED
STATES FROM ALL STORET STATIONS^
00
Effluents
Compound
alpha-BHC
beta-BHC
gauma-BHC
delta-BHC
Chloronaphthalene
Hexachl oroethane
Hexachl orobutadlene
Hexachl orocyc 1 opent ad 1 ene
l,2-Q1chlorobenzene
1 ,3-01chlorobenzene
1,4-Olchlorobenzene
Trlchlorobenzene
Hexachl orobenzene
Median
(ug/L)
<0.007
<0.007
<0.007
<0.050
< 10.000 1
<10.000 ]
<6.000
<10.000
<10.000
< 10.000
<10.000
< 10. 000
<10.000
nc
630
633
628
62
1.255
1.253
.190
.228
.311
.301
.306
.256
.267
Percent
detectable
4.1
2.0
1.4
d
1.4
2.0
1.6
0.9
2.5
1.5
1.7
2.1
2.2
Median
(ng/L)
<0.018
<0.050
<0.100
0.020
< 10. 000
<10.000
<10.000
<10.000
< 10. 000
<10.000
<0. 100
< 10. 000
0.020
Water
n
1,470
1.010
880
4.505
863
882
593
854
1.077
986
8.S76
882
1.786
Sediment
Percent
detectable
8.0
1.3
0.8
27.0
0.2
0.1
0.2
0.1
0.6
0.3
3.0
0.3
26.0
Median
(M9/K))
<3.0
d
<10.0
<2.0
<500
<500
<500
<500
<500
<500
-------
TABLE 4. WASTES DUMPED AT HYDE PARK, THE S
AND N AREAS, AND LOVE CANAL3
Loading (tons)
Type of Waste
Chlorobenzene
Benzyl chloride
BHCs
Benzotrichlorides
Chlorotol uenes
Hexachlorocyclo pentad iene
Hyde
Parkb
16,500
3,400
2,000
1,700
1,700
1,100
S and N
areas
18,900
1,600
17,400
Love
Canal
2,000
2,400
6,900
aData taken from Reference 9.
bThe Hyde Park area was used by Hooker Chemical
Company as a dump for approximately 160 million
pounds of toxic wastes from 1953 to 1979.
A-19
-------
TABLE 5. CHLOROBENZENE CONCENTRATIONS IN THE
NIAGARA RIVER (ppt)a
Compound
1,3-Dichlorobenzene
1 ,4-Dichl orobenzene
1 ,2-Oichl orobenzene
1 ,3,5-Trichlorobenzene
1, 2, 4-Trichl orobenzene
1, 2, 3-Trichl orobenzene
1,2, 3, 5-Tetrachl orobenzene
1,2, 4, 5-Tetrachl orobenzene
1,2,3,4-Tetrachl orobenzene
Pentachl orobenzene
Hexachlorobenzene
-------
TABLE 6. ORGANIC COMPOUNDS IDENTIFIED IN THE NIAGARA RIVER
UATERSHED
Bloody Run
Compound 102nd Street Creek Gill Creek
Chlorobenzenes
Chlorobenzene b c c
Dichlorobenzenes c c c
Trichlorobenzenes 40 8 c
Tetrachlorobenzenes 200 25 c
Pentachlorobenzene 100 10 d
Hexachlorobenzene 8 10 30
Chi or otol uenes
Dichlorotoluenes 20 90 d
Trichlorotoluenes 100 50 d
Tetrachlorotoluenes 40 10 d
Pentachlorotoluenes 40 5 d
Hexachlorotoluenes 40 d d
Heptachlorotoluenes 20 d d
BHCs 10 c d
aData taken from Reference 11.
bSamp1e was not analyzed for this compound.
GCompound was detected in water at a level of 0.1 to 1 ppb or
,in sediment at a level of 0.5 to 2 ppm but was not quantitated.
Compound was not detected in water or in sediment; lower limits
of sensitivity are about 0.1 ppb in water and 0.5 ppm in
sediment.
A-21
-------
Amounts of chlorobenzenes in Lake Ontario compartments reported by
Oliver (2) are presented in Table 7. The detection of chlorobenzenes in lake
trout at levels as high as 130 ppb for hexachlorobenzene is striking. This
indicates that such compounds are quite persistent in the environment, and
the fact that they were detected in fish samples shows that chlorinated
benzenes are bioconcentrated.
TABLE 7. AMOUNTS (Kg) OF CHLOROBENZENES IN LAKE ONTARIO COMPARTMENTS3
Compartment 1,2,4-TCB 1,2,3,4-TeCB QCB HCB
Bottom sediments 11,000 3,300 4,100 8,500
Lake water 700 210 90 90
Suspended sediments 10 4 49.
Biota 2 228
aData taken from Reference 2.
A-22
-------
SECTION 3
ANALYTICAL METHODOLOGIES FOR CHLORINATED HYDROCARBONS
A summary of published methods for the determination of chlorinated
hydrocarbons in water, wastewater, soils, etc., is presented in Table 8.
Examination of this table shows a wide range of detection methods (e.g., gas
chromatography with electron capture detection, Hall electrolytic
conductivity or photoionization detection, and gas chromatography/mass
spectrometry) that vary in sensitivity, selectivity, complexity, ease of
operation, etc. A detailed discussion of each of these techniques follows.
Sample preservation and the isolation of the chlorinated hydrocarbons from
water, soil, and sediments are discussed first. The sample extract cleanup
and the analysis techniques are discussed next and are followed by a
discussion of the compound confirmation techniques that were reported in the
1 iterature.
3.1 SAMPLE PRESERVATION
The importance of proper sample preservation cannot be overemphasized.
The choice of the preservation method depends on the type of sample, the
compound(s) to be determined in the sample, the duration of sample storage
prior to analysis, and the analytical procedure to be used (21). The method
chosen must not impair the analytical procedure to be used. Amber glass
bottles are the container of choice because of the protection from
photodegradation. The bottle must not be prerinsed with sample before
collection (12). Composite samples should be collected in glass containers
and refrigerated. When automatic sampling equipment is to be used, then it
must be free of any tygon tubing (12). Most investigators report that water
samples should be refrigerated at 4°C while soils and sediments should be
frozen until analysis. Oliver and Nicol (10) stored water samples in bottles
without headspace and with aluminum foil caps at 4°C until extraction
(<48 hrs).
Weil and Quentin (22) investigated the effect of container, temperature,
and light on the storage of water samples containing lindane at 10 ug/L and
reported substantial loss during a 2-week storage period for polyethylene
containers. In another study, Millar et al. (23) investigated the effects of
pH, temperature, and residual chlorine on the preservation of spiked water
samples conta-lning BHCs and other organochlorine pesticides in glass bottles
sealed with aluminum-foil-lined caps, for a period of 7 days. The results of
Millar's study are summarized in Table 9. It is evident from the data that,
at pH 10 and 24°C the losses were significant for alpha-, gamma-, and
A-23
-------
TABLE 8. SUMMARY OF ANALYTICAL METHODOLOGIES FOR CHLORINATED HYDROCARBONS
Method Matrix
EPA Netted 612 ttoter
EPA Method 625 Hater
EPA Method 162S Utter
EPA Method 8120 liquids
Solids
Con pounds
1.2-DCB
1 .3-OCB
1.4-TC8
1.2.4-TCB
2-CN
HCB
HCE
HCBu
1.2-DCB
1.3-flCB
1,4-OCB
1.2.4-TCB
HCB
alpha-BHC
beti-BHC
gaau-BHC
delt»-BHC
HCE
HCCP
HCBu
2-CN
.2-DCB
,3-OCB
,4-DCB
,2.3-TCB
,2.4-TCB
HCE
2-CN
HCB
HCCP
HCBu
1.2-DCB
1. 3-OCB
1.4-DCB
HCB
HCBu
BHCs
HCCP
HCE
TeCB
1,2.4-TCB
QCB
Bengal chloride
Benzotri chloride
Benzyl chloride
Extraction
procedure
Separatory funnel
nethylene chloride
(no pH adjustment)
Separatory funnel
continuous 1 (quid-
liquid extractor
•ethylene chloride
(pH > 11 and then
pH < 2)
Separatory funnel
continuous liquid-
liquid extractor
•ethylene chloride
(pH 12-13 and then
pH < 2)
EPA Method 3S10
EPA Method 1520
EPA Method 3540
EPA Method 3550
Cleanup Analysis
procedure procedure
12 g Florist! ; GC/ECD
20 mL petcoleua 1.8 m x 2 M ID glass column
ether packed with 1 percent SP-lOflO
on Supelcoport (100/120 nest))
l.fl • x 2 M ID glass column
packed with 1.5 percent
OV-1/2.4 percent OV-22S on
Supelcoport (BO/IHO nesh)
None GC/HS
1.8 • x 2 M ID glass column
packed with 3 percent SP-22SO
on Supelcoport (100/120 nesh)
None Isotope dilution GC/HS
30 • x 0.2S m ID DB-S
f used-silica capillary
coluwi or equivalent
EPA Method 3620 GC/ECD
l.fl • x 2 nun II) glass column
packed with 1 percent SP-1000
on Supelcoport (100/120 «esh)
1.8 in » 2 m 10 glass col urn
packed with l.S percent
OV-1/2.4 percent OV-72S on
Supelcoport (80/100 «esh)
MOL
(pg/l or
pg/Kg) Reference
0.03 - 1.34 12
0.9 - 4.4 13
10 14
"
0.03 - 1.34 IS
ICL - Method detection Unit.
-------
TABLE 8. (concluded)
Method
Matrix
Compounds
Extraction
procedure
Cleanup
procedure
Analysis
procedure
HIU
MA or
M9/*9)
Peference
EPA Method 8010
Liquids 1.2-OCB
Solids 1.3-OCB
1.4-OCB
EPA Method 5030
None
r,C/Hall
8 ft x 0.1 In ID glass col urn
packed with 1 percent SP-lflOO
on Carbopik-B (60/80 «esh)
6 ft x 0.1 In ID glass
col urn packed with
n-octine on Porastl C
0.15 - 0.3?
16
EPA Method 8020
liquids 1.2'OCB
Sol Us 1.3-OCB
1.4-DX8
EPA Method 5030
None
GC/PID
6 ft x 0.08 in ID glass
coition packed with S percent
SP-1200/1.75 percent Bentone
on Supelcoport (100/120 «esh)
8 ft x 0.1 In ID glass
col Mm packed with S percent
1.2,3-Trts(2-cyanoethoxy)'
propane on Chroaosorb
U-AW (60/80 «esM
0.3 - 0.4
17
I
ro
en
EPA Method 8080 Liquids alpha-BHC
Solids beta-BHC
gMM-BHC
delta-BHC
EPA Method 8250 Liquids alpha-BHC
8270 Solids beta-BHC
gaou-BHC
delU-BHC
2-CN
1.2-OCB
1.3-DCB
1.4-OCB
HCB
HCBu
HCCP
HCE
QCB
1.2,4.5-TeCB
1.2.4-TCB
EPA 3510
EPA 3520
EPA 3S40
EPA 3550
EPA 3510
EPA 3520
EPA 3540
EPA 3550
EPA Method GC/ECD 0.00 3-0. 009a
3620 1.8 • x 4 im ID glass coluoi
packed «1th 1.5 percent
SP-2250/1.9S percent SP-2401
on Supelcoport
1.8 • x 4 m ID glass
coluM packed with 3 percent
OV-1 on Supelcoport
None GC/MS inb; 66
-------
TABLE 9. PRESERVATION OF WATER SAMPLES CONTAINING
BHCs AT 4°C AND 24°C
Recovery3
(percent)
Compound
t = 4°C
al pha-BHC
beta-BHC
gamma -BHC
delta-BHC
t = 24°C
al pha-BHC
beta-BHC
gamma -BHC
delta-BHC
pH 2
64
86
100
80
65
84
94
lOQb (64)c
pH 7
60
98
100
108
68b
87
93
101b
pH 10
82
81
84
74
(25)c 19
95
15
(77)c 36b (26)C
aData taken from Reference 23. Average of four
replicates unless accompanied by parenthetical
values.
bAverage of two replicates.
cWhen residual chlorine was present; average of
two replicates.
A-26
-------
delta-BHC. Residual chlorine also contributes to the decrease in compound
concentration, expecially for delta-BHC (23).
Stability of the chlorinated hydrocarbons in soils has not been
systematically investigated. 'Storage of soil samples at room temperature
should be avoided since degradation of some chlorinated compounds does
occur (24). Losses of delta-BHC after incubation of soil samples at 25°C,
under aerobic conditions, were observed 7 days after initiation of
experiment, and only 35 to 40 percent of it was found at day 30 of the
experiment (24). Storage of freeze-dried sediment samples at 4°C, in the
dark, indicated no evidence of degradation or volatilization for some
chlorinated benzenes and hexachlorobutadiene (Table 10).
Deep freezing at -20°C appears to be the most suitable method for
storage of solid matrices since it has the widest range of application,
causes the least changes in the samples, and makes the addition of
preservatives unnecessary.
3.2 EXTRACTION
A number of methods have been reported for isolation of chlorinated
hydrocarbons from water, soil, and sediment. The extraction techniques that
have been used on water samples include liquid-liquid extraction by stirring,
separatory funnel extraction, and extraction in a continuous liquid-liquid
extractor, and adsorption onto polymeric materials such as XAD resins and
other 1iquid-chromatographic bonded stationary phases. The methods used for
extraction of soil and sediment samples with organic solvents include Soxhl et
extraction and sonication. Each of these techniques will be reviewed below.
3.2.1 Extraction of Water Samples
Table 11 is a summary of extraction methods for water samples published
in the literature for chlorinated hydrocarbons. The following describes in
detail some of these procedures.
3.2.1.1 Liquid-Liquid Extraction
Liquid-liquid extraction is the simplest and most widely used technique
for extraction of organic compunds from water. This technique consists of
mixing the sample with a water-immiscible solvent in the original sample
container, a separatory funnel, or a continuous liquid-liquid extractor. An
important parameter for the liquid-liquid extraction is the solvent. It must
be immiscible with water, it must extract the organics of interest from the
sample, and it must not interfere with the analysis procedure.
In the case of the separatory funnel technique, up to 1 liter of an
aqueous sample is extracted in a separatory funnel by shaking it with an
organic solvent. The layers are allowed to separate and the organic solvent
is drawn off. Solvents with a density greater than that of water are
preferred since the organic layer can be removed more easily.
A-27
-------
TABLE 10. EFFECT OF LONG-TERM COLD STORAGE ON LEVELS OF CHLOROBENZENES AND
HEXACHLOROBUTADIENE IN FREEZE-DRIED SEDIMENT SAMPLES*
Residue level after
storage (ng/g)
Compound
1,3,5-Trichlorobenzene
1, 2, 4-Trichl orobenzene
1,2 ,4, 5-Tetrachl orobenzene
1,2, 3, 4-Tetrachl orobenzene
Pentachl orobenzene
Hexachl orobenzene
Hexachlorobutadiene
Reference
value ± SO
(ng/g)b
34.3 ± 2.6
80.7 ± 5.4
84.0 ± 4.9
36.5 ± 2.4
48.6 ± 2.4
200.6 ± 13.2
21.3 ± 1.6
12
months
29
79
91
37
49
207
c
24
months
37
71
106
32
44
188
21
48
months
32
88
91
34
48
190
18
aData taken from Reference 25.
bTri plicate analyses.
clnformation is not available.
SO — Standard deviation.
A-28
-------
TABLE 11. SUMMARY OF EXTRACTION TECHNIQUES FOR WATER SAMPLES
i
ro
Method
Solvent extraction
(bottle/stlrbar)
Solvent extraction
(separatory funnel,
continuous liquid-
liquid extractor)
Solvent extraction
(separatory funnel ,
continuous liquid-
liquid extractor)
Solvent extraction
(separatory funnel )
Solvent extraction
(separatory funnel)
Solvent extraction
( separatory funnel )
Solvent extraction
(bottte/stlrbar)
Solvent extraction
(turbo-stirring)
Adsorption onto
Chronosorb 102
(100 ran x 1.5 mi ID;
60 «g)
Solvent
Pentane
Methyl ene
chloride
Methyl ene
chloride
Methyl ene
chloride
IS percent
•ethyl ene
chloride In
hexane
Methyl ene
chloride
Methyl ene
chloride
Cyclohexane
Hexane
Pentane
Compound
DCBs, TCBs. TeCBs.
QCB, HCB
DCBs. 1.2.4-TCB.
HCB. HCCP. HCBu.
HCE. 2-CH
OCBs. 1.2.4-TCB.
HCB. HCCP. HCBu.
HCE. 2-CN. BHCs
BHCs
BHCs
OCBs. TcBs. TeCBs.
QCB. HCB
OCBs. TCBs. TeCBs.
QCB. HCB. BHCs
HCB
PCBs
BHCs
HCB
OCBs. TCBs. TeCBs,
QCB.
HCB
Spiking
Recovery 1 evel
(percent) (ppb) Reference
AO to 96 0.0001 to 0.011 10. 26. 27
80 to 91 0.001 to 0.1
<160 10 to 100 12
<172 100 13. 14»
92 to 109 0.02 to 0.04 23
86 to 106 0.02 to 0.04 23
Table 12*> 28
c 11
c 29
quantitative ppt 30
86 to 97 0.0001 to 0.011 25
80 to 91 0.001 to 01
aRefer to EPA Method 1625 for compound recovery data.
bFor EPA Method 625. first partition was at pH 11. the second at pH 2. For EPA Method 625.1.
first partition Mas at pH 7, the second at pH 2.
cInformation 1s not available.
-------
Disadvantages of the separatory funnel extraction are:
• Limited sample size
• Emulsion formation during extraction of wastewaters.
To break emulsions, 1t has been recommended that the extract be passed
through a 25-mm-thick glass wool pad (31).
Several reports dealing with the determination of chlorinated
hydrocarbons 1n water samples Involve liquid-liquid extraction; however,
there appears to be little consensus as to the best organic solvent, the
extraction conditions (e.g., solvent-to-!1qu1d ratios, time, degree of
agitation, pH), or the use of salts to enhance partitioning Into the organic
layer. Table 11 lists the various systems used and the percent recoveries
reported. Among the solvents reported we found: pentane (10, 26, 27),
methylene chloride (11,12,13,14,23,28), 15 percent methylene chloride in
hexane (23), cyclohexane (29), and hexane (30). Most literature reports
Indicate that extraction at neutral pH gives quantitative recoveries for the
chlorinated hydrocarbons.
Elchelberger et al. (28) assessed the performance of the EPA Methods 625
and 625.1 for a series of organic compounds Including those of Interest to
our study. The basic difference 1n the two EPA methods 1s 1n the extraction
step. In EPA Method 625, the water sample 1s first adjusted to pH>ll and
extracted with methylene chloride to recover the neutral and the basic
compounds; the acidic compounds are then extracted at pH <1. In EPA Method
625.1, the extraction with methylene chloride 1s first performed at pH 7
followed by acidification and extraction of the acidic compounds at pH 2.
The pH 7 extraction minimizes the risk of base-catalyzed reactions of
analytes (28). Qualitatively, there appears to be no difference between the
two methods, except for alpha-BHC and gamma-BHC (Table 12). This was
attributed to the base-sen$1t1v1ty of the two compounds since each of them
chromatographs well on the packed column recommended 1n EPA Method 625. The
alpha- and gamma-Isomers of BHC have two chlorines in a transaxial
configuration with hydrogen which 1s a favorable arrangement for
base-catalyzed dehydroch1or1nation (28). The delta-1somer has a similar
configuration but apparently reacts much more slowly with the base (28).
Dlchlorobenzenes had somewhat low and variable recoveries when analyzed
by EPA Method 625; this was attributed partly to their volatility which
leads to losses during the extract concentration and partly to Imprecise peak
area measureaents caused by poor resolution from the solvent on the
fused-sH1ca capillary column (28).
The low recovery of hexachlorocyclopentadlene was attributed to
degradation during sample storage and processing (28). Hexachlorocyclo-
pentadlene was found to be highly photoreactlve, exhibiting a half-life of
less than 10 »1n 1n water (5); tetrachlorocyclopentadlene was
A-30
-------
TABLE 12. ACCURACY AND PRECISION MEASUREMENTS OF SUBSTITUTED BENZFNFS WITH
EPA METHODS 625 AND 625.1
i
CO
Compound
1,2-Dichl orobenzene
1,3-Dichlorobenzene
1 ,4-Dichl orobenzene
1 ,2, 4-Trichl orobenzene
1 ,2,3-Trichlorobenzene
1, 3, 5-Trichl orobenzene
1,2,3 ,4-Tetrac hi orobenzene
1 ,2,3,5-Tetrachlorobenzene
Pentachl orobenzene
He x ac hi or obe n zene
al pha-BHC
beta-BHC
gamma -BHC
delta -BHC
Hexachloroethane
Hexachlorobutadiene
Hexachlorocycl o pentad iene
2-Chl oronaphthal ene
Spike
level
(u9/L)
3.8
3.8
13.8
3.8
4
4
4
4
4
3.8
5
6
7
6
3.8
3.8
3.8
EPA Method
Mean
recovery
(percent)
105
50
37
86
58
40
59
50
55
73
0
91
0
72
76
74
b
78
625a
SD
(percent)
122
31
4.6
23
9.9
5.8
12
9.1
9.8
18
23
27
23
18
23
Spike
level
(ug/i;
10
10
10
10
b
b
b
b
b
10
10
10
10
10
10
10
10
10
EPA Method
Mean
recovery
) (percent)
61
58
68
76
98
90
95
87
92
55
64
?8
75
6?5.la
SD
(percent)
10
6.1
11
11
24
18
7.3
12
4.9
6.2
15
7.1
9.1
aThe number of determinations is 5 to 10 for the EPA Method 625 and 7 for the EPA
Method 625.1. Data taken from Reference 28.
^Not measured.
SD -- Standard deviation.
-------
reported to be the primary photolysis product (5). Hydrolysis of
hexachlorocyclopentadiene is also relatively fast (half-life is 14 days at
25°C) and is independent of pM in the ranqe of pH 5 to pH 9 (5).
One of the more recent devices introduced specifically for liquid-liquid
extractions is the Mixxor (Xydex Corp., Bedford, Massachusetts). This device
utilizes a piston-cylinder principle for extraction. It comes in various
sizes and can handle sample volumes up to 50 ml. The mixing is accomplished
by moving a piston up and down in the mixing chamber five or six times
(equivalent to 40 or more shakes in a separatory funnel). The system is
fast, precise, and safe (3?). The main disadvantage is the ease with which
emulsions are generated (32) and maybe the volume limitation.
3.2.1.2 Adsorption
Preconcentration of the chlorinated hydrocarbons from water onto a
macroreticular resin was reported by Oliver and Bothen (27). Approximately
60 mg of Chromosorb 102 resin, packed into a borosilicate glass tube (100-mm
long x 1.5 mm ID) was used for a 500-mL water sample, and the chlorobenzenes
were recovered quantitatively (recovery Q5 percent) from the resin using
300 uL pentane. The recovery efficiency of the preconcentration technique on
the Chromosorb 102 resin was compared with that of the pentane extraction
technique at two concentrations in the ppt range (27). The authors concluded
that both techniques recover more than 80 percent of the amounts spiked, and
excellent agreement between the resin column and the pentane extraction
technique was reported for two river water samples (?7).
3.2.2 Extraction of Sediment and Soil Samples
This section summarizes the extraction techniques reported in the
literature for soil and sediment samples. Examples of solvent and solvent
mixtures used for extraction, type of extraction, compounds investigated, and
recovery data are presented in Table 13.
Lee et al . (25) concluded that the Soxhlet extraction is the most
exhaustive method for the extraction of organics from solid samples. No
difference in the recoveries of chlorobenzenes and hexachlorobutadiene was
reported with Soxhlet extraction times ranging from 3 hrs to 16 hrs. When
using ultrasonication, recoveries of chlorobenzenes from a standard reference
material were approximately 80 percent for penta- and hexachlorobenzenes,
70 percent for hexachlorobutadiene and tetrachlorobenzenes, 50 to 70 percent
for trichlorobenzenes, and 50 percent for dichlorobenzenes.
The Soxhlet extraction technique is also recommended by £PA and has been
standardized as EPA Method 3540. A validation study of the Soxhlet procedure
was done by Michael et al. (33). Recoveries of 2-chloronaphthalene and
1,4-dichlorobenzene ranged from 87.1 to 93.4 and from 58.5 to 78.7,
respectively, for spike levels in the percent range.
Warner et al. (34) developed a solvent extraction method for solid
wastes that is applicable to a wide range of compounds, gives acceptable
A-32
-------
TABLE 13. SUMMARY OF THE EXTRACTION TECHNIQUES FOR SOILS AND SEDIMENTS
Type of
Solvent extraction Compound
Spiking
Recovery level
(percent) (ppb)
Reference
Hexane-acetone
(41:59)
Soxhlet
Methylene chloride Soxhlet
Hexane-acetone
(1:1)
Soxhlet
3*
I
CO
Hexane-acetone
(1:1).
Ultrasonlcation
I,3-DCB
1.4-DBC
1.2-OCB
1.3.5-TCB
1.2.3-TCB
1.2.3.5-TeCB
1.2.4.5-TeCB
1.2.3.4-TeCfl
QCB
HCB
HCE
HCBu
2-CN
1,4-OCB
1.2-DC8
1.3-DCB
1.4-KB
1.3.5-TCB
1.2.4-TCB
1.2.3-TCB
1.2.3.5-TeCB
1.2.4.5-TeCB
1.2.3.4-TeCB
QCB
HCB
1.3-DCB
1.4-DCB
1.2-OCB
1.3.5-TCB
1.2.3-TCB
1.2.3.S-TeCB
1.2.4.5-TeCB
QCB
HCB
HCE
HCBu
100
ppba
25
87.1 to 93.4
58.5 to 78.7
lxlO«; SxlO6; 1x107
1x10'; SxlO7; IxlO8
33
10
SO for DCBs
50 to 70 for TCBs
70 for HCBu and TeCB
80 for QCB ami HCB
ppb*
25
Methylene chloride
intrasonication HCE
1.4-DCB
QCB
HCB
1-CH
57 to 70
51 to 60
50. 000
250. POO
34
aNot specified.
bInformation is not available.
-------
recoveries and reprodudblHty, and 1s easily performed at a reasonable
cost. The waste matrices Include: aqueous sludges, dry solids, soils, tars,
oils, and oily sludges. This method 1s a dry neutral extraction procedure
with methylene chloride (one extraction only) and with anhydrous sodium
sulfate which 1s added to remove any water present. Ultrason1cat1on 1s used
to promote the Interaction of the solvent and the waste. Screening steps are
Incorporated 1n the method to determine the neutralization requirement of the
waste matrix, the residue weight of the extract, and the optimum
concentration of the extract for subsequent gas chromatographic
analysis (34).
3.3 CLEANUP
Several types of cleanup techniques are available for removal of
coextractants from a sample matrix. They are:
• Liquid-solid chromatography (Florlsll, alumina, silica gel)
• Gel permeation chromatography
• Sulfur removal
3.3.1 Liquid-Solid Chromatography
In the following discussions, the application of Florlsll, alumina, and
silica gel to the cleanup of sample extracts prior to gas chromatographlc
analysis 1s addressed. Table 14 1s a summary of the cleanup procedures
reported 1n the literature.
3.3.1.1 Florisil
Florlsll 1s a synthetic magnesium silicate manufactured by Floridin
company from magnesium sulfate and sodium silicate; magnesium silicate 1s
filtered, dried, and calcinated at 650°C. Examples of cleanup methods using
Florlsll are listed 1n Table 14.
Jan and Malnersic (35) used Florlsll to clean up fish extracts that were
contaminated with chlorinated benzenes. The hexane extract of a fish sample
was passed through a Florlsll column and eluted with 20 mL of 6 percent
d1ethyl ether 1n hexane. Additional cleanup of the collected fraction with
2-percent ethanollc KOH allowed detection of low ppb levels of chlorinated
benzenes 1n fish and mussel tissue (35).
The elutlon patterns of BHCs, penta- and hexachlorobenzenes,
hexachlorobutadiene, and hexachlorocyclopentadlene from Florlsll using hexane
and 20 percent methylene chloride 1n hexane were reported by Mes (36) and are
shown 1n Table 15. It 1s Interesting to note the different behavior of the
BHC Isomers: alpha-BHC elutes 1n Fraction I (35 mL hexane) while beta-,
delta-, and gamma-BHCs elute 1n Fraction II (40 mL of 20 percent methylene
chloride In hexane).
A-34
-------
TABLE 14. SUMMARY OF CLEANUP PROCEDURES
Ad sorbent
Florljll . activated
at 130 to UO'C
Flor1$1l
(7 cm x 1 cm ID)
and O.S cm
Na2S04 on top
Florlsll, activated
at 130'C. 20 g
Elutlng
solvent
6 percent, 15 percent,
50 percent dlethyl ether
1n hexane
6 percent dlethyl ether 1n
hexane
20 percent methyl en*
chloride In hexane;
50 percent methyl en*
chloride, 0.35 percent
Recovery
Compound (percent)
BHCs 97 to 100
1,4-DCB; 1.2-OCB; 1,3.5-TCB; a
1.2.4-TCB; 1.Z.3-TCB;
1.2.4,5-TeCB; 1.2.3.4-TeCB;
QCB; HCB
BHCs > 90
HCB
OCPj
OPPs
Reference
23
35
37
Florist), activated
at 130*C
FlorUtl
acetonltrlle. 49.65
percent hexane; 50 percent
methylen* chloride,
1.5 percent acetonltrlle,
48.5 percent hexane
6 percent dlethyl ether In
hexane
HCCP
gamna-BHC
100
90
6 percent dlethyl ether 1n BHCs. DCBs. HCB. HCBu. HCCP. > SO
petroleun ether HCE. TeCB. TCB
38
39
Florlsll and silicic
add
Alumina (deactivated
with 10 percent
water)
A-540 basic aluslna
(5 g per mg of
halogenated material)
Neutral alumina
activity grade I
deactivated with
5 percent water
Silica gel (100/200
mesh) activated at
300*C
Hexane; 20 to 80 percent
methylene chloride In
hexane; 20 percent ethyl
acetate 1n methyl ene
chloride
Hexane; 50 percent dlethyl
ether In hexane
Heptane
Hexan*
Hexane; IS percent
benzene In hexane
Tables 15. 16. 17
BHCs
CBs. PCfls. PCTs. PCNs.
PCDFEs. PCOBOs
HCCP
gam-BHC
HCCP
gama-SHC
Table 15, 16, 17 36, 40
23
41
100
100
99
100
38
38
Silica gel
GPC SX-3 (200/400
mesh). 60 g.
60 x 2.5 em ID
column (48 CM bed)
Hexan*; 10 percent
methyl ene chloride In
hexane; methylene
chloride, methane1
Methylene chlorlde-
cyclohexane (1:1)
OCBs, TCBs, TeCBs. QCB. HCB, a
BHCs
U
19
* In format ton It not available.
DGPC 1s recoMendcd for the elimination of llplds, polyners, copolyners, proteins.
natural resins, steroids, and other hlgh-molecular-welght compounds present In the sample extracts (19).
A-35
-------
TABLE 15. ELUTION PATTERNS OF SOME CHLORINATED HYDROCARBONS FROM A
SEMIHICRO FLORISIL COLUMN
Recovery3»b
(percent)
Conpound
(2.5 ug each)
Fraction I Fraction II Total
Hexachlorobenzene
Hexachloro-l,3-butadiene
alpha-BHC
Hexachl oropentad i ene
Pentachlorobenzene
beta-BHC
gamma -BHC
delta-BHC
85
86
85
85
80
0
0
0
0
0
0
0
0
103
99
102
85
86
85
85
80
103
99
102
j*Data taken from Reference 40.
^Fraction I was eluted with 35 ml hexane.
Fraction II was eluted with 40 ml 20 percent
methylene chloride 1n hexane.
A-36
-------
Mills et al. (37) also used 20 percent methylene chloride In hexane to
recover various pesticides Including alpha-, beta-, and delta-BHCs, and
hexachlorobenzene from fat extracts and reported that approximately 85 to
90 percent of the butterfat and 70 to 80 percent of the corn oil are retained
by Flor1s1l during elutlon with 20 percent methylene chloride 1n hexane,
while only 25 to 35 percent of the butterfat and 20 to 30 percent of the corn
oil are retained during elutlon with 6 percent and 15 percent d1 ethyl ether
1n petroleum ether.
McMahon and Burke (39) reported recoveries of >80 percent for the BHCs,
l,3-d1chlorobenzene, 1,4-dichlorobenzene, hexachlorobenzene,
hexachlorobutadlene, hexachlorocyclopentadlene, hexachloroethane, tetra- and
trlchlorobenzenes when elutlon of the Flor1s1l 1s done with 6 percent dlethyl
ether 1n petroleum ether.
A combined Flor1s1l-s1l1c1c acid column was used to separate chlorinated
hydrocarbons Into several fractions (36, 40). The elutlon patterns and
percent recoveries are shown 1n Table 16. Florisll retains the liplds and
prefractlonates the chlorinated hydrocarbons while the silicic acid provides
partial separation of chlorinated hydrocarbons from PCBs and organochlorine
pesticides. Florisll and silica gel were first activated to 300°C (7 hours)
and 130°C (overnight), respectively. Florisll was then deactivated with
2 percent water (v/w) and shaken for 2 to 3 hours, and the silicic add was
deactivated with 5 percent water (v/w), shaken for 15 min and then allowed to
equilibrate for 24 hours. The deactivated silicic acid is prepared fresh
every 5 days. Compounds are eluted from the Flor1s1l-s1lic1c add column as
follows: Fraction I, 35 ml hexane; Fractions II through V, 40 ml of 20, 40,
60, and 80 percent methylene chloride in hexane, respectively; Fraction VI,
40 ml of 20 percent ethyl acetate 1n methylene chloride. The effect of
increasing the polarity of the eluent on the elutlon pattern of the
chlorinated hydrocarbons from the combined Flor1s1l-s1lica gel column 1s
shown 1n Table 17.
If PCBs are not expected to be present in the matrix, then a Florisll
column alone can be used for the cleanup of chlorinated hydrocarbon residues.
However, it should be noted, that if toxaphene is present, 25 percent of the
toxaphene present is recovered 1n Fraction I, and this may cause problems in
identifying the other compounds (40).
3.3.1.2 Alumina
Use of basic alumina to fractionate complex mixtures of chlorinated
aromatic compounds was reported by Albro and Parker (41). The fractlonation
scheme Involving A-540 basic alumina is shown in Figure 1. The solvent
required to fractionate the compounds depends upon the composition of the
sample. In most cases, aliphatic hydrocarbons and chlorobenzenes are eluted
with heptane (3 to 4 mL heptane per gram of alumina); PCBs, PCNs, PCTs, and
PCDPEs are eluted with 2 percent methylene chloride 1n hexane, and PCDBOs and
PCDBFs are eluted with 20 percent methylene chloride 1n hexane (10 ml per
gram of alumina). Under these conditions, the phthalate esters are retained
A-37
-------
TABLE 16. ELUTION PATTERNS OF. SOME CHLORINATED HYDROCARBONS FROM A
COMBINED FLORISIL-SILICIC ACID COLUMN
Recovery3»b,c
(percent)
Compound
(2.5 yg each)
Fraction I Fraction II Fraction IV Fraction VI Total
Pentachlorobenzene
Hexachlorobenzene
alpha-BHC
beta-BHC
ganma-BHC
107
95
0
0
0
1
0
96
26
93
0
0
0
74
7
0
0
0
0
0
108
95
96
100
100
aData taken from Reference 40.
b4.5 g Deactivated Florisil (2 percent); 4.5 g silicic acid.
Fraction I was eluted with 35 mL hexane.
Fraction II was eluted with 40 ml 20 percent methylene chloride in hexane.
Fraction IV was eluted with 40 mL 60 percent methylene chloride in hexane.
Fraction VI was eluted with 40 mL 20 percent ethyl acetate in methylene
chloride.
fractions III and V were eluted with 40 mL 40 percent and 80 percent
methylene chloride in hexane, respectively. No results were reported for
Fractions III and V.
A-38
-------
TABLE 17. EFFECT OF INCREASED SOLVENT POLARITY ON SEPARATION OF CHLORINATED
HYDROCARBONS FROM A COMBINED FLORISIL-SIL 1C 1C ACID COLUMN
Recovery3»
(percent)
Compound
(2.5 ug each)
Fraction I Fraction II Fraction III Total
Hexachlorobenzene
Hexachl oro-1 ,3-butadiene
Pentachl orobenzene
1 ,2,4-Trichl orobenzene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
92
95
80
78
0
1
0
0
0
0
0
0
97
40
88
2
0
0
0
0
1
57
0
101
9?+
95
RO
7R
93
97
88
103
aData taken from Reference 36.
b4.5 g Deactivated Florisil (2 percent); 4.5 g silicic acid.
Fraction I was eluted with 2 percent methylene chloride in hexane.
Fraction II was eluted with 20 percent methylene chloride in hexane.
Fraction III was eluted with fiO percent methylene chloride in hexane.
A-39
-------
n-heptane
GC
Dexsil 410
Extract |
Alumi na
A-540
2 percent
methylene chloride
1n hexane
20 percent
methylene chloride
In hexane
PCBs, PCTs,
PCNs, PCDPEs
GC
OV-225
SbCl,
PCDBFs,
PCDBDs
Acidic alumina
Perchlorination products
GC, Dexsil 410
Figure 1. Fractionation scheme for chlorinated benzenes, PCBs, PCTs, PCDPEs,
PCNs using alumina chromatography (41).
A-40
-------
on the alumina column. They can be eluted with 50 percent methylene chloride
1n hexane using 10 mL of solvent per gram of alumina (41).
Law and GoerUtz (38) and Millar et al. (23) used neutral alumina to
clean up water sample extracts containing hexachlorocyclopentadlene and BHCs
as well as other organochlorlne pesticides. It was found that alumina was
more efficient than Flor1s1l and silica gel for the removal of naturally
occurlng organic adds and pigments (38).
3.3.1.3 Silica Gel
Silica gel used 1n combination with Flor1s1l was reported by
Mes (36, 40). Law and GoerUtz (38) and Elder et al. (11) used silica gel
alone for cleanup of environmental sample extracts suspected to contain
chlorinated hydrocarbons. Elutlon of hexachlorocyclopentadlene from the
silica gel column with hexane was quantitative (38). A more polar solvent
mixture (15 percent benzene 1n hexane) was required to elute gamma-BHC from
the silica gel column (38).
Oliver and N1col (10) used silica gel 1n combination with alumina and
Flor1s1l to clean up fish extracts. The cleanup was performed 1n two steps:
the hexane extract was first applied to a large column of Na2S04/alum1na/
silica gel/Flor1s1l; the eluate was then concentrated and applied to a small
column of 40 percent H2S04 on silica gel.
3.3.2 Gel Permeation Chromatoqraphy (GPC)
In gel permeation chromatography the separation mechanism 1s based on
differences in molecular size. Large molecules cannot diffuse into the pores
of the gel and elute first whereas the smaller molecules are retained longer
and elute later.
The use of GPC (Blobeads SX-3) with methylene chlorlde-cyclohexane (1:1)
allows separation of the chlorinated hydrocarbons from adipose tissue (42).
Table 18 gives the GPC elutlon volumes for the chlorinated benzenes and other
organochlorlne pesticides of environmental significance. Under the
conditions indicated in Table 18, 99.98 percent of the fat 1s removed by GPC.
Recovery studies were carried out on GPC-cleaned fat fortified prior to
extraction at concentrations of 10, 100, and 500 ng/g on extracted fat basis.
The overall recoveries of the chlorinated benzenes and BHCs were quantitative,
except for trichlorobenzenes and hexachlorobutadiene (Table 19).
3.3.3 Sulfur Removal
Sulfur and organosulfur compounds, 1f present, may give large peaks
which could mask the region from the solvent peak to the earliest eluting
chlorinated benzene if packed columns are used for the gas chromatographic
analysis.
A-41
-------
TABLE 18. GPC ELUTIOM VOLUMES FOR SOME CHLORINATED
BENZENES AND ORGANOCHLORINE PESTICIDES*
Compound GPC elution volume^ (mL)
1,4-Dichl orobenzene
1 ,3-Dichlorobenzene
1 ,2-Di chl orobenzene
1 ,3 ,5-Trichl orobenzene
Hexachlorobutadiene
1 ,2 ,3-Tr ichl orobenzene
2,4,5-Trichlorotoluene
1,2, 3, 5-Tetrachl orobenzene
1 ,2 ,3,4-Tetrachl orobenzene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
Chlordene
gamma -BHC
beta-BHC
Heptachlor
Aldrin
Octachlorostyrene
Oxychlordane
Heptachlor epoxide
gamma-Chlordane
trans-Nonachlor
alpha-Chlordane
alpha-Endosulfan
2,4'-DDE
4,4'-DDE
Dieldn'n
Endrin
cis-Nonachlor
4, 4' -ODD
4, 4' -DDT
Photomirex
Mi rex
Methoxychlor
Decachlorobiphenyl
Hexabromobi phenyl
Aroclor 1260
200 to 220
210 to 220
210 to 220
200 to 220
170 to 210
210 to 230
200 to 220
200 to 220
200 to 230
200 to 230
200 to 230
190 to 230
170 to 210
200 to 230
240 to 280
170 to 210
170 to 210
170 to 210
170 to 200
170 to 210
180 to 210
170 to 210
170 to 220
170 to 220
170 to 210
180 to 210
180 to 210
170 to 210
180 to 230
190 to 220
180 to 210
180 to 210
180 to 210
190 to 210
170 to 210
200 to 220
180 to 220
aData taken from Reference 42.
b-236 ml bed volume SX-3 gel with methylene chloride-
cyclohexane (1+1, v/v) eluant.
A-42
-------
TABLE 19. RECOVERIES (PERCENT ± SO, DUPLICATE DETERMINATIONS)
OF ORGANOCHLORINE CONTAMINANTS*
Fortification level (ng/g)
Compound
1,3,5-Trichlorobenzene
Hexachlorobutadiene
1,2,3-Trichlorobenzene
2,4,5-Trichlorotoluene
1,2,3,4-Tetrachlorobenzene
Pentachl orobenzene
Hexachlorobenzene
alpha-BHC
gamma -BHC
beta-BHC
10
63.
43.
62.
94.
82.
110.
102.
111.
88.
120.
1
3
1
5
6
5
3
5
4
1
+
±
±
+
±
±
±
+
+
±
1.2
1.6
1.7
4.6
1.4
2.9
3.1
4.9
2.9
4.7
100
64.2
• 60.1
68.9
79.9
84.4
91.2
87.3
89.2
96.2
91.6
+
±
±
+
±
±
±
±
±
±
3.9
10.7
2.9
3.2
0.5
1.6
1.8
3.7
7.8
11.2
57.
62.
65.
76.
83.
90.
92.
90.
125.
92.
500
7
1
7
0
9
5
5
5
6
7
±
±
±
±
±
±
±
±
+
±
16
5.1
0.8
0.7
1.9
1.2
0.4
2.4
0.4
4.6
aData taken from Reference 42.
A-43
-------
Sulfur may be removed as a discrete fraction by GPC (43).
Alternatively, several chemical methods are available for removal of sulfur:
reaction with metallic mercury (44), activated copper (45), Raney nickel
(46), tetrabutylammonlum sulfHe (47), and potassium cyanide (48).
Lopez-Avlla et al. (49) reported quantitative recoveries for BHCs using the
tetrabutylammonlum sulfite procedure, and Jensen et al. (47) reported for the
same procedure recoveries of 94 and 79 percent for hexachlorobenzene and
gamma-lindane, respectively.
3.4 SOLVENT CONCENTRATION
Because of the volatility of chlorinated benzenes, procedures for the
concentration of solutions containing nanogram levels of these compounds were
reported. Lee et al. (25) Investigated rotary evaporation and the use of a
three-stage macro-Snyder column. In both cases, 200 mL hexane-acetone
(41:59) spiked with known amounts of chlorinated benzenes were evaporated in
the presence of 3 mL isooctane as keeper. Recoveries were lower for the
rotary evaporation (e.g., 50 to 70 percent for dlchlorobenzenes and 70 to
85 percent for tri-, tetra, penta-, and hexachlorobenzenes) than for the
macro-Snyder column. In the latter case, recoveries were always >90 percent.
Experiments with Kuderna-Danish evaporation techniques and equipment
conducted by Burke et al. (50) have shown that losses do occur when solutions
are concentrated to volumes of less than 0.5 mL by a stream of air. Use of a
micro-Snyder column with two bubbles allows concentration of a 10-mL solution
to 0.1 to 0.3 mL without loss of pesticides (50). The three-bubble
micro-Snyder column did not permit a great reduction in volume while the
one-bubble micro-Snyder column showed significant losses of pesticides during
solvent evaporation.
Kuderna-Danish, rotary evaporation, hot-plate evaporation, and nitrogen
blowdown were also evaluated by Erickson et al. (51). Mean recoveries of
l,3-d1chlorobenzene for the macro-evaporation techniques were 85 percent for
Kuderna-Danish evaporation, 78 percent for rotary evaporation, 77 percent for
hot-plate evaporation, and 83 percent for nitrogen blowdown with methylene
chloride as solvent. Use of 15 percent methylene chloride in hexane did not
affect the mean recoveries. However, when the micro-evaporation techniques
were Investigated, problems were encountered in m1cro-Kuderna-Dan1sh
concentrations. The solvent volume could not be reduced to a 0.2-mL volume
even after 25 to 30 m1n. The nitrogen blowdown with column was superior to
the nitrogen blowdown without column or to the micro-Kuderna-Danlsh
technique (51).
3.5 GC ANALYSIS
This section addresses the gas chromatographic analysis techniques
including gas chromatography/mass spectrometry. Basically, the chlorinated
hydrocarbons are separated on the packed or capillary column at elevated
temperatures, and the compounds are detected with an electron capture
detector (ECD), photoionizatlon detector (PID), Hall electrolytic
conductivity detector (HECD) or a mass spectrometer. Section 3.5.1 addresses
the separation of the chlorinated benzenes, toluenes, BHCs, etc., on gas
chromatographic columns (capillary and packed) and Section 3.5.2 addresses
A-44
-------
their Identification using various gas chromatographlc detectors. A brief
summary of compound confirmation techniques 1s presented 1n Section 3.5.3.
3.5.1 Gas Chromatoqraphic Columns
Open tubular glass and fused-slUca capillary columns have been reported
1n the literature for the separation of chlorinated benzenes, toluenes, BHCs, .
etc. Table 20 summarizes the GC columns, conditions, and the detectors
reported 1n the literature. Representative chromatograms of chlorinated
hydrocarbons obtained on various open tubular capillary columns and packed
columns are shown 1n Figures 2 through 6. None of the literature reports
that we were able to retrieve addressed all compounds listed 1n Table 1.
Most reports addressed the chlorinated benzenes and the chlorinated BHCs.
Figures 2 and 3 show chromatograms of a mixture of 12 chlorinated
benzenes that were separated on a Carbowax 20M capillary column and a SP-2100
capillary column. The analytical conditions and the retention times of the
12 compounds are given 1n Table 21. The Carbowax 20M column separates all
compounds; the SP-2100 column separates all but the 1,2,3,5- and
1,2,4,5-tetrachlorobenzenes. Use of a DB-17 and DB-5 fused-slUca capillary
columns was reported by LeBel and Williams (42). In addition to the
chlorinated benzenes and hexachlorobutadlene, LeBel and Williams (42) also
reported retention times for other chlorinated pesticides which are Included
1n Table 22. The DB-17 column was chosen as the primary column because most
of the organochlorlne pesticides could be resolved using a relatively short
column. Thirteen chlorinated hydrocarbons of Interest to our study were
resolved on the DB-17 fused-slUca capillary column. Furthermore, 1t appears
that the organochlorlne pesticides do not Interfere with the analysis of the
13 chlorinated hydrocarbons. The DB-5 fused-slUca capillary column resolves
fewer compounds than the DB-17 column. l,4-D1chlorobenzene coelutes with
l,3-d1chlorobenzene and hexachlorobutadlene coelutes with
1,2,3-trlchlorobenzene (Table 22).
Separation of 12 chlorinated benzenes and 7 bromlnated benzenes on a 15 m
SE-52 capillary column was reported by Crow et al. (52). l,3-D1ch1orobenzene
coelutes with l,4-d1chlorobenzene and 1,2,3,5-tetrachlorobenzene coelutes with
1,2,4,5-tetrachlorobenzene on the SE-52 capillary column (Table 23).
Furthermore, 1,2,3-trlchlorobenzene coelutes with l,2-d1bromobenzene (52).
The effect of Increasing chlorine substitution on retention time was
reported by Haken and Korhonen (53). The retention Indices of the
chlorobenzene Isomers on a 25 m x 0.22 mm ID SE-30 fused-slUca capillary
column and & 22 m x 0.30 mm ID Carbowax 20H glass capillary column were
determined at 120, 140, 160, and 180°C, and are shown 1n Tables 24 and 25.
The elutlon order 1s similar to that reported for the SP-2100 (26) and
SE-52 (52) columns, the various Isomers elutlng 1n the order of their boiling
points. The 1,2,3,5- and 1,2,4,5-tetrachlorobenzenes were not resolved on
the SE-30 column (Table 24). The 1,3- and l,4-d1chlorobenzenes were resolved
A-45
-------
TABLE 20. GC COLUMNS AND CONDITIONS REPORTED FOR THE ANALYSIS OF
CHLORINATED HYDROCARBONS
Column
GC conditions
Detector
Detection limit
Reference
i
*»
cn
30 • x 0.25 *m ID glass capillary
column coated with Carbowax 20H
(0.08 v» HI" thickness)
30 • x 0.25 MI ID glass capillary
colwm coated with SP-2100 (0.20
MM flla thickness)
15 • x 0.25 m ID DB-17
fused-si I lea capillary col urn
15 • x 0.25 MI ID DB-5
fused-sllica capillary column
15 m x 0.25 MI 1008-17
fused-sllica capillary coluan
15 • SE-52 glass capillary coluwi
22 m x 0.3 ram ID glass capillary
coluMi coated with Carbowax 20M
25 M x 0.22 on ID vitreous silica
coated with SE-30
33°C (3 min hold) to 180°C at
at 10°C/m1n
33°C (3 min hold) to 180°C at
at 10*C/«1n
80°C (2 Bin hold) to 220°C
(1 nin hold) at 20°C/nin
then to 280*C (6 Bin hold) at
5'C/nln
SOeC (2 min hold) to 22n°C
(1 sin hold) then to 275*C
(5 Bin hold) at 5*C/Mln
116°C (1 min hold) to 276°C
(9 *1n hold) at 16°C/Bin
60°C to 280'C at
4*C/n1n
ECD
Isothermal at 120°C,
140°C. 160°C. 180eC
Isothermal at 130°C. 140°C.
160°C. 180°C
0.01 ppt for QCB. HCB
0.05 ppt for TeCB
0.1 ppt for TCB
1.0 ppt for OC8
(concentration factors
1.000 to 2.500)
27
ECO
ECO
ECD
GC/HS (SIM) Table 22
GC/MS
(•ethane CD
5 ng for positive CI;
OCBs not detected in
negative CI; TCBs and
TeCB 5 to 50 tines
less sensitive In
negative CI than
positive CI. QCB and
HCB 5 to 20 times acre
sensitive In negative
CI than positive CI
27
42
4?
42
52
50 m x 0.35 M ID glass capillary 100°C to 250°C at 3°C/m1n
column coated with SE-S4
ECD
53
53
29
a$ame detection limits as for the Carbowax 20M column.
bOetector not specified.
cNot specified.
dOetection Units are given for air and biological samples.
-------
TABLE 20. (continued)
Coluwi
GC conditions
Detector
Detection limit
Reference
50 • x 0.26 MI ID glass capillary
coluwt coated with SE-S4 (0.26 u«
fttm thickness)
60 • x 0.32 MI ID fused-silica
capillary coluwi chemically bonded
with 08-1 (\ w» ftln thickness)
30 • x 0.2S MI ID fused-silica
capillary col urn bonded with
SupelcoMax-10 (0.25 M« fll«
thickness)
30 • x 0.32 MI 10 fused-silica
capillary coluwi coated with
06-1301 (1 vm film thickness)
30 • x 0.25 MI ID fused-silica
capillary coluwt bonded with
DB-519 (0.25 M* fH« thickness)
30 • x 0.53 MI 10 fused-silica
capillary coluwi bonded with
SPB-35 (O.S vm flla thickness)
1.8 • x 0.2 MI ID glass coluwi
packed with OV-1 on Gas-Chro» Q
(100/120 wish)
12 • x 0.2 M ID fused-silica
capillary coluwi coated with
Carbowax 20M and cross-linked
with OV-1
10 ft x 1/8 in sllanized glass
coluwi packed with (A) 0.5 percent
Carbowax E-20M over bonded E-20H
on SO/100 Mesh Chronosorb W-AU
and 5 percent Synerg C; (B) 0.2
percent Carbowax E-40H and 0.5
percent Synerg C on GLC-110
(130/MO *esh)
40°C to 250°C (programing ECO
rate not specified)
60°C to 200°C at 2"C/min ECD
105°C (7 »in hold) to 245°C at FID
5'C/nln
70°C to 200°C at 20°C/*in. then ECD
to 240*C at 3*C/«in
60*C (5 Bin hold) to 170°C FID
(20 Bin hold) at 5'C/*1n
50*C (1 «1n hold) to 220°C at ECD
8'C/nln; 50°C (1 din/hold) to
240°C at 4«C/»in or 6°C/«in;
70*C (1 min hold) to 220'C
at fl'C/Htn; 70*C (1 «1n hold)
to 240*C at 4*C/«in or 6'C/nin
105*C (4 uln hold) to 140"C ECO
(R «in hold) at 16'C/«in
40"C (0.5 Bin hold) to 80°C ECO
(5 min hold) at 30"C/«in. then to
140°C (5 Bin hold) at 8'C/nin
50"C (2 min hold) to 200°C PID
(6 min hold) at 10°C/Min 60°C (10.2 eV)
(2 nin hold) to 190°C at 12°C/n1n
30
0.9 pg for 1.2-DCB
8-17 Mg/g
56
57
58
Table 31
Table 31
25
25
59
aSane detection Units as for the Carbowax 20H column.
bOetector not specified.
cNot specified.
d Detect ion Units are given for air and biological samples.
-------
I
£k
00
TABLE 20. (concluded)
Column GC conditions Detector Detection limit Reference
2 m x 2 mm ID glass column packed 80°C (3 min hold) to 150°C at FID c 4)
with 3 percent Dexsil 410 on 2°C/min ECO
Anakrom AS (90/100 mesh)
1.8 M x 4 m ID glass column Isothermal at 130°C ECO (3H) 29 60
packed with 10 percent OV-101 on ECD (63N1)
ChroMSorb U (80/100 mesh)
3 m x 2 MI ID glass column 100°C to 200°C at 8°C/inin ECD c fil
packed with 0.5 percent Silar IOC
Chromosorb UAM (80/100 mesh)
•Same detection Units as for the Carbowax 20N column.
^Detector not specified.
cHot specified.
''Detection Units are given for air and biological samples.
-------
r
20
TMC.
Figure 2. Chromatogram of chlorobenzene mixture in pentane on Carbowax 20M
capillary column. Chlorobenzene concentration in yg/L;
CB (30,000); 1,3-DCB (74); 1,4-DCB (132); 1,2-DCB (72);
1,3,5-TCB (13); 1,2,4-TCB (8.1); 1,2,3-TCB (7.4);
1,2,3,5-TeCB (1.3); 1,2,4,5-TeCB (8.9); 1,2,3,4-TeCB (2.9);
QCB (1.4); HCB (1.2). Refer to Table 21 for gas chromatographic
conditions (Reference 26).
A-49
-------
a
u
ii
20
TO*, mm.
Figure 3. Chromatogram of chlorobenzene mixture in pentane on SP-2100
capillary column (chlorobenzene concentrations are the same as
for Figure 2). Refer to Table 21 for gas chromatographlc
conditions (Reference 26).
A-50
-------
Chlorinated Hydrocarbon* (Mcgibor*)
Carn«r:
Own.
ln|«clion:
D*t«clor:
0*-1M1
30m X 053mm 1.0.
1.0 micron Mm nduwu
HtKamia 11 mLiM
WO 5 mm
lO'Cminlo210*C
0 5 »L dirtct
FID
1 t.3-0ienioro6«nztn*
2. 1.4-0«niarae*n»n*
3. 1.2-OwrHoroMnztfl*
4. Hcuenierotawnt
S. t.
2-CMoronienihMn*
HmetiwroMnniw
2 3
• 17min •
Column:
Owner:
Ov«n:
M-1301
30m XOiSmm 10.
0-29 (MCfOn Mni t
Hydragtn <• 40 envue
tVC.4 men
1(TCiT»n n 21
-------
1 1.3-OicM«»ob««u«n« (20ng)
2. t.4-OieNenitannn«(20ngl
3 1.2-Oichlaratannn«(20ng)
4 HmcMorMthMwIOtngl
5 1.2.4-TricW,
6 HWKhd
I (01
HmKlilorocvcloiMnudiwwIO tng)
8 2-ChtororapMtialm (4Ong)
9 HcuchkxolMnzmlOIng)
. 1_
I I I
024
I I I I I
10 12
Figure 5. GC/ECD chromatogram of chlorinated hydrocarbons on a SPB-5
15 m x 0.53 mm ID fused-silica capillary column (1-5 urn film
thickness). Column temperature: 50°C to 175°C at 8°C/min. and
hold; Injector temperature: 220°C; detector temperature: 250°C;
flowrate: 10 mL/min, helium; makeup gas flow: 20 mL/min,
n1trogen;detect1on: ECD, sens.: 128 x 10-H AFS, sample: 1 pL
chlorinated hydrocarbons standard in isooctane, amounts
(0.1-40 ng) (Reference 63).
A-52
-------
Column:
DB-210
30m X 0.53mm I.D.
Film Thickness: 1.0 micron
Helium at 10ml/min.
85"Cto1750Cat10c'/min.
Direct 1 »il
Varian 3400 E.C.D.
Carrier:
Oven:
Injection:
Detector:
DB-210
Bonded (trifluoropropylmethlysilicone)
30 meters x .25mm I.D.
0.25 micron film
Split injection
H.. carrier @ 43cm/sec.
Program: 80°C/3 min.
6°C/min. to 180°C
Attn: 2|2
J>
i
in
1. Chtorobenzene
2. Hexachloroethane
3. m-Dwhlorobenzene
4. o-Dichtorobenzene
5. Hexachlorobutadiene
6. Hexachtorocyclopentadiene
7. 2-Chlcronaphthalene
8. Hexachlorobenzene
1. Chlorobenzene
2. Hexachloroethane
3. m-Oichlorobenzene
4. p-DiChlorobenzene
5. 0-Dkhlorobenzene
6. 4-Chlorostyrene
7. Hexachlorobutadiene
8. Hexachlorocyclopentadiene
9. 2-Chloronaphthalene
10. 1-Chloronaphthalene
11. Hexachlorobenzene
•10 min.
Figure 6. GC/ECD chromatogratns of chlorinated hydrocarbons on a DB-210
^n U X 2'oc mm !D fused-s1n'« capillary column (left) and 08-210
?Refere£f 62) fuscd-$111ca "P^'^y column (right)
-------
TABLE 21. RETENTION TIMES AND RESPONSE FACTORS FOR CHIOROBENZENES3
Compound
Retention time (sec)
Response factors
Carbowax 20Mb»c SP-2100c«d (counts/pg)
Chlorobenzene
1,3-Dichlorobenzene
1,4-Dichl orobenzene
1,2-Dichlorobenzene
1 ,3,5-Trichlorobenzene
1, 2, 4-Trichl orobenzene
1,2,3-Trichlorobenzene
1,2, 3, 5-Tetrachl orobenzene
1 ,2 ,4, 5-Tetrachl orobenzene
1,2,3,4-Tetrachlorobenzene
Pentachl orobenzene
Hexachl orobenzene
311
493
519
550
576
675
737
111
785
867
934
1,059
303
486
496
521
625
670
704
813
814
853
967
1,111
0.17
103
48
94
770
680
1,220
1,720
980
2,040
3,920
5,150
aData taken from Reference 26.
b30 m x 0.25 mm ID Carbowax 20M coated glass capillary column (-0.08 ym
film thickness).
cTemperature program: 33°C (hold 3 min) to 180°C at 10°C/min; nitrogen
flow rate at 1.3 mL/min; splitless injection: 5 uL (pentane).
Detector and injector temperatures 275°C.
d30 m x 0.25 mm ID SP-2100 coated glass capillary column (0.2 ym film
thickness).
eThe authors did not specify the capillary column. It appears that
response factors were determined on the Carbowax 20M column because only
this column can resolve 1,2,3,5- and 1,2,4,5-tetrachlorobenzene.
A-54
-------
TABLE 22. RETENTION TIMES OF CHLORINATED BENZENES, ORGANOCHLORINE
PESTICIDES AND PCBs ON DB-17 AND DB-5 FUSEO-SILICA CAPILLARY
COLUMNS
Retention t1mea
Compound
1 ,4-Dichlorobenzene
1,3-Dichlorobenzene
1,2-Di chl orobenzene
1,3,5-TMchlorobenzene
Hexachlorobutadlene
1 , 2, 3-Tr 1 chl orobenzene
2 , 4 ,5-TM chl orotol uene
1,2, 3, 5-Tetrachl orobenzene
1,2,3,4-Tetrachlorobenzene
Pentachl orobenzene
He xac hi orobenzene
alpha-BHC
Chlordene
gamma -BHC
beta-BHC
Heptachlor
Aldrin
Octachlorostyrene
Oxychlordane
Heptachlor epoxlde
gamma -Chl ordane
OB-17b
2.55
2.69
3.05
3.73
4.38
4.86
5.32
5.36
6.18
7.09
8.30
8.54
8.85
9.04
9.16
9.49
10.00
10.52
10.73
11.00
11.32
OB-5C
2.79
2.80
3.12
4.10
4.84
4.82
5.49
5.74
6.12
7.09
8.26
8.17
8.79
8.56
8.50
9.50
10.00
10.55
10.65.
10.65
11.06
MDLd
e
e
e
11.0
1.2
5.9
14.3
13.1
4.8
1.9
1.4
1.2
e
1.4
3.0
e
e
e
e
e
e
Relative to aldrln (RRT » 10.00): retention time
10.41 m1n (OB-17); 10.90
-------
TABLE 22. (concluded)
Retention time3
Compound DB-17b DB-5C
trans-Nonachlor
alpha-Chlordane
alpha-Endosulfan
2,4'-DDE
4,4' -DDE
Dieldrin
Endrin
cis-Nonachlor
4, 4' -ODD
2,4'-DDT
4, 4' -DDT
Photomirex
Mi rex
Methoxychl or
Decachlorobiphenyl
Hexabromobiphenyl
11.38
11.64
11.69
11.70
12.24
12.34
13.18
13.26
13.56
13.56
14.32
14.80
16.73
16.94
20.55
23.20
11.44
11.29
11.33
11.15
11.73
11.79
12.26
12.72
12.63
12.68
13.45
14.18
15.85
14.90
19.60
20.50
aRelative to aldrin (RRT = 10.00): retention time
10.41 min (DB-17); 10.90 min (DB-5). Data taken
from Reference 42.
b!5 m x 0.25 mm ID DB-17 fused-silica column (J&W
Scientific); oven temperature: 80°C (2 min hold)
at 20°C/min to 220°C (1 min hold) then program at
5°C/min to 280°C (6 min hold). Helium gas at
1.5 mL/min with nitrogen makeup at 30 mL/min;
injector temperature 260°C; detector
temperature 325°C.
C15 m x 0.25 mm ID DB-5 fused-silica capillary
column (J&W Scientific); oven temperature: 80°C
(2 min hold) at 20°C/min to 220°C (1 min hold)
then program at 5°C/min to 275°C (5 min hold).
Helium carrier gas at 1 mL/min with nitrogen
makeup gas at 30 mL/min; injector temperature
260°C; detector temperature 325°C.
A-56
-------
TABLE 23. RETENTION TIMES OF HALOGENATED
BENZENES ON A 15 M SE-52 CAPILLARY
COLUMNStb
Retention time
Compound (min)
Chi orobenzene 2.38
Bromobenzene 2.53
1,4-Dichl orobenzene 3.38
1,3-Dichlorobenzene 3.43
l,?.-Dichl orobenzene 4.0?
1,3,4-Trichlorobenzene 5.42
1,2,4-Trichlorobenzene 6.41
1,4-Dibromobenzene 6.51
1,3-Dibromobenzene 6.52
1,2-Dibromobenzene 7.77
1,2,3-Trichl orobenzene 7.30
1,2,3,5-Tetrachlorobenzene in.23
1,2,4,5-Tetrachlorobenzene 10.23
1,2,3,4-Tetrachlorobenzene 11.^3
1,3,5-Tribromobenzene 12.50
Pentachiorobenzene 15.30
Hexachlorobenzene 20.31
Tetrabromobenzene 21.06
Hexabromobenzene 36.31
aGC conditions were as follows: injector
temperature, 280°C; transfer line
temperature, 280°C; GC carrier gas,
methane; split ratio, 10/1; column
temperature, 60 to 280°C at 4°C/min; flow
rate, 25 cm/s. Methane was employed as a
carrier gas because it was found that
helium or hydrogen tended to disturb the
CI reagent ion pi asma.
bData taken from Reference 52.
A-57
-------
TABLE 24. RETENTION INDICES OF CHLOROBENZENE
ISOMERS ON A 25 M x 0.22 MM ID SE-30
FUSED-SILICA CAPILLARY COLUMN*
Temperature (°C)
Compound 120 140 160 180
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichlorobenzene
1 ,3, 5-Trichl orobenzene
1,2,5-Trichlorobenzene
1, 2, 3-Trichl orobenzene
1 ,2,3,5-Tetrachl orobenzene
1,2, 4, 5-Tetrachl orobenzene
1 ,2 ,3,4-Tetrachl orobenzene
Pentachl orobenzene
Hexachl orobenzene
964
970
1,005
1,131
1,177
1,211
1,326
1,326
1,366
1,496
1,656
1,013
1,015
1,038
1,144
1,183
1,217
1,329
1,329
1,371
1,505
1,673
1,016
1,016
1,050
1,150
1,193
1,228
1,344
1,344
1,388
1,525
1,695
1,021
1,021
1,057
1,159
1,207
1,247
1,367
1,367
1,412
1,552
1,723
aData taken from Reference 53.
A-58
-------
TABLE 25. RETENTION INDICES OF CHLOR08ENZENE
ISOMERS ON A 22 M x 0.30 MM ID
CARBOWAX 20M GLASS CAPILLARY COLUMN*
Temperature (°C)
Compound
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Dichl orobenzene
1, 3, 5-Trichl orobenzene
1 ,2 , 5-Trichl orobenzene
1,2, 3-Trichl orobenzene
1 ,2,3,5-Tetrachl orobenzene
1,2,4,5-Tetrachlorobenzene
1 ,2, 3, 4- Tetrachl orobenzene
Pentachl orobenzene
Hexachl orobenzene
140
1,415
1,438
1,447
1,515
1,630
1,705
1,754
1,764
1,871
1,956
2,124
160
1,434
1,471
1,514
1,545
1,653
1,735
1,786
1,793
1,908
1,999
2,178
180
1,509
1,529
1,575
1,590
1,698
1,775
1,824
1,830
1,941
2,027
2,204
!CW 20Mb
ISE-30
1.41
1.44
1.44
1.34
1.39
1.41
1.33
1.33
1.37
1.31
1.28
aData taken from Reference 53.
bRatio determined at 160°C; for values on SE-30 column
see Table 24.
A-59
-------
at 120°C; higher temperatures caused the two compounds to overlap. The
retention on the more polar Carbowax 20M is increased, as expected, although
the elution order is not altered. Complete separation of the 1,2,3,5- and
1,2,4,5-tetrachlorobenzenes was achieved on the Carbowax 20M column at 120
and 140°C (Table 25).
The incremental effect of chlorine addition is shown in Tables 26
and 27. For both stationary phases the incremental differences increase with
temperature. Furthermore, the effect is dependent upon the position of the
chlorines (53). For example, in the case of the 1,3-d'ichlorobenzene,
1,3,5-trichlorobenzene, and 1,2,3,5-tetrachlorobenzene, which are the lowest
retention isomers at 160°C on the SE-30 column, the retention index increases were
88, 103, and 126 index units, whereas in the case of 1,2-dichlorobenzene,
1,2,3-trichlorobenzene, and 1,2,3,4-tetrachlorobenzene, which are the highest
retention isomers at 160°C on the SE-30 column, the retention index increases
were 105, 129, and 137, respectively. The same trend is observed on the
Carbowax 20M column (Table 27). However, in the case of the Carbowax 20M
column, the highest retention isomers exhibit significantly larger retention
increases. The relative polar and steric effects are indicated by increments
shown in Tables 26 and 27, and by retention index ratios on the two columns
determined at 160°C (Table 25). It appears that the polar effects are
maximized with the 1,2,3,4-tetrachlorobenzene (53), and with further
substitution the polar effects are reduced due to steric constraints.
Other open-tubular capillary columns reported for the analysis of
chlorinated benzenes include: OV-1 (25), DX-4 (25), SE-54 (29,30),
DB-1 (54), Supelcowax-10 (55), DB-1301 (56), DB-519 (57), SPB-35 (58), and
Carbowax 20M cross-linked with OV-1 (25).
Packed column analysis of the chlorinated benzenes and other chlorinated
hydrocarbons was reported by Langhorst and Nestrick (59) on some specially
prepared column packings. Chromatograms are shown in Figure 7.
Three gas chromatographic column packings were employed for these
analyses. Column packing A, consisting of 0.50 percent Carbowax E-20M over
bonded E-20M on 80/100 mesh Chromosorb W-AW and 5 percent Synerg C, is a
specially prepared packing available from HNU Systems, Inc. Its design
provides high efficiency, high solvent capacity, isomer resolution
characteristics, and minimum liquid phase bleed (59).
Column packing B consists of 0.20 percent Carbowax E-40M and
0.50 percent Synerg C on 130/140 mesh GLC-110. Its design characteristics
are essentially the same as those described for column packing A, and it is
also available from HNU Systems. However, this packing is a surface-coated
glass bead packing and provides certain unique performance characteristics;
it is especially useful for high-sensitivity determinations using the i
photoionization detector. In particular, the optimum carrier velocity (vopt)
for this packing, as determined from the Van Deemter plot for hydrocarbon
elution, is unusually low for 2-mm ID columns. This particular packing
demonstrates a vgnt of approximately 8 cm^/min for helium carrier when tested
in a 2 mm ID x 180 cm glass column. This combination of high capacity, high
A-60
-------
TABLE 26. INCREMENTAL EFFECT OF CHLORINE SUBSTITUTION
AND TEMPERATURE ON RETENTION INDICES ON A
25 M x 0.22 MM ID SE-30 FUSEO-SILICA CAPILLARY
COLUMN*
Temperature (
120 140 160 180
Compound
1, 3- Pic hi orobenzene
1,4-Dichl orobenzene
1,2-Dichl orobenzene
1 ,3,5-Trichl orobenzene
1, 2, 4-Trichl orobenzene
1, 2, 3-Trichl orobenzene
1,2, 3, 5-Tetrachl orobenzene
1 ,2,4,5-Tetrachlorobenzene
1,2,3, 4-Tetr ac hi or oben zene
Pentachl orobenzene
Hexachl orobenzene
IA!D
132
138
173
299
345
379
494
494
534
664
824
A 1C
66
69
87
100
115
126
124
124
134
133
137
Lib
177
179
202
308
347
381
493
493
535
550
837
A 1C
89
90
101
103
116
127
123
123
134
134
140
I*.b
176
176
?10
310
353
388
504
504
548
685
«55
A 1C
88
88
105
103
118
120
1?6
126
137
I?7
143
1Mb
174
174
215
317
365
405
525
525
570
710
881
AIC
07
87
108
10K
122
135
131
ni
143
142
147
aData taken from Reference 53.
^Total retention index increase.
CRetention index increase per chlorine atom.
A-61
-------
TABLE 27. INCREMENTAL EFFECT OF CHLORINE SUBSTITUTION
AND TEMPERATURE ON RETENTION INDICES ON A
22 M x 0.30 MM ID CARBOWAX 20M GLASS
CAPILLARY COLUMN*
Temperature (°C)
140 160 180
Compound ^Alb &lb ^b Ajb ^^\b Ajb
1,3-Dichl orobenzene
1,4-Dichl orobenzene
1 ,2-Di chl orobenzene
1, 3, 5-Trichl orobenzene
1,2, 4-Tri chl oroben zene
1 ,2 ,3-Trichl orobenzene
1,2, 3, 5-Tetrachl oroben zene
1,2, 4, 5-Tetrachl orobenzene
1 ,2, 3, 4-Tetrachl orobenzene
Pentachl orobenzene
Hexachl orobenzene
158
181
190
258
373
448
497
507
614
699
867
79
91
95
86
124
149
124
127
154
140
145
164
201
244
275
383
465
516
523
638
729
908
82
101
122
92
128
155
129
131
160
146
151
220
240
286
301
409
486
535
541
652
738
915
110
120
143
100
136
162
134
135
163
148
153
aData taken from Reference 53.
bTotal retention index increase.
A-62
-------
1
Smimitv •
JS4.1CT"
2. 1.3-*-
1 1.4-*
4 1.2-*-
0 4
I 12
Minuw
51J > I?"
I 10
V
I I I I I I
4 t
Smrtivity •
si? > i
-------
efficiency, short retention times, and low carrier gas flow rates gave
improved sensitivity when used with the photoionization detector.
Column packing C in Figure 7 was a combination of the first two column
packings. The first 9 in. of column B described above were unpacked and
replaced with the packing described for column A. This front end packing
moved the monochlorobenzene peak away from the solvent front and protected
the packing B from stripping of the liquid phase during injection.
Eleven chlorinated benzenes were completely resolved on any of the three
packing materials. Mo data were reported for the 1,2,3,5-tetrachloro-benzene
isomer; therefore, we cannot conclude whether or not all the chlorinated
benzenes can be resolved.
Chromatography of various chlorinated benzenes on Dexsil 410 (41),
OV-101 (60,64), OV-101/OV-210 (60), OV-225 mixed (64), OV-105 (64), and
Silar IOC (61) are presented in Tables 28, 29, and 30. A GC/ECD chromatogram
of eight chlorinated hydrocarbons analyzed on a glass column packed with
1 percent SP-1000 is shown in Figure 8 (65).
3.5.2 Gas Chromatographic Detectors
Gas Chromatographic detectors reported in the literature for the
analysis of chlorinated hydrocarbons include the electron capture detector,
the photoionization detector, the electrochemical detector, the Hall
electrolytic conductivity detector, and the mass spectrometer. Lee et
al. (25) used a mass-selective detector in the selected ion monitoring mode
to improve the detector sensitivity. Table 31 summarizes the sensitivities
to various chlorinated benzenes relative to hexachlorobenzene of both the
electron capture detector and the mass spectrometer. The characteristic ions
for each chlorinated benzene are also shown. Quantitation by mass
spectrometry was performed using anthracene-dig as internal standard (25).
Since dichlorobenzenes were approximately 50 times less sensitive to the
electron capture detector than hexachlorobenzene, the levels reported for
dichlorobenzenes using the electron capture detector are less reliable than
those reported for higher chlorinated benzenes. It can be seen in Table 31
that the much higher relative sensitivity of the mass spectrometer detector
for the dichlorobenzene make such a detector more desirable for the analysis
of environmental samples.
To increase the sensitivity of the electron capture detector for those
chlorinated hydrocarbons that have few chlorine atoms, Miller and
Grimsrud (66) proposed the doping of the carrier gas with oxygen (up to
3.5 parts per thousand). The dichlorobenzene isomers show small, but
measurable, differences in their enhancements in the order 1,2-, 1,4-, and
1,3-dichlorobenzene having enhancement values of 1.5, 2.0, and 2.4,
respectively, at 300°C.
A new electrochemical detector for gas Chromatography that uses the same
pyrolysis furnace as the Hall electrolytic conductivity detector, but where
the analysis is based on the potentiometric determination of the chloride,
A-64
-------
TABLE 28. GC OF CHLOROBENZENES ON A
DEXSIL 410 PACKED COLUMN3
Retention
Compound time (min)D
Chlorobenzene
1,3- + 1,4-Dichlorobenzene
1,2-Dichlorobenzene
1,3,5-Trichlorobenzene
1 ,2 ,4-Tr ichl orobenzene
1,2,3-TMchlorobenzene
1,2,3,5-Tetrachlorobenzene
1,2, 3, 4-Tetrachl orobenzene
Pentachl orobenzene
Hexac hi orobenzene
0.86
2.44
3.20
6.32
7.10
8.60
11.82
12.90
17.80
23.68
aData taken from Reference 41.
bCo1umn 2 m x 2 mm ID glass column
packed with 3 percent Dexsil 410 on
Anakrom AS 90/100 mesh. Initial
temperature 80°C, 3 min hold, to 150°C
at 2°C/min. Helium flow rate is
35 mL/min.
A-65
-------
TABLE 29. RELATIVE RETENTION TIMES OF CHLORINATED BENZENES ON
AN OV-101 AND AN OV-101/OV-210 COLUMN, BOTH OPERATED
AT 130°Ca
Relative retention
time
Compound
1 ,3-Dichl orobenzene
1,4-01 chl orobenzene
l,2-D1chl orobenzene
Hexachl oroethane
1 , 3 ,5-Tr1chl oroben zene
3,5-D1chlorotoluene
2, 6-Dichl orotol uene
2,4-Dichlorotoluene
2,5-Dichlorotoluene
1, 2, 4-TM chl orobenzene
a ,4-01 chl orotol uene
2, 3-Dichl orotol uene
3, 4-Di chl orotol uene
1, 4-01 bromoben zene
1 ,3-D1bromobenzene
1, 2, 3-Tri chl orobenzene
Benzotri chloride
l,2-D1bromobenzene
Hexachl orobu tad 1 ene
2, 4, 5-Tri chl orotol uene
1,2, 3, 5-Tetrachl orobenzene
1,2, 4, 5-Tetrachl oroben zene
a,2,4-Trichlorotoluene
a,2,6-Tr1ch1orotoluene
Hexachlorocyclopentadlene
a,3,4-Trichlorotoluene
1,2,3.4-Tetrachlorobenzene
1,3,5-Trlbromobenzene
2-Chl orobl phenyl
Pentachl orobenzene
2 ,4-D1chl orobenzotrichl oride
2,3,4,5,6-Pentachlorotoluene
Hexachl orobenzene
Tribromobenzene
1,2,4,5-Tetrabromobenzene
gamma-BHC
delta-BHC
4, 4 '-01 chl orobl phenyl
OV-10lb
0.08
0.08
0.09
0.10
0.15
0.16
0.16
0.16
0.16
0.18
0.19
0.19
0.20
0.20
0.20
0.22
0.23
0.23
0.24
0.34
0.40
0.40
0.42
0.42
0.43
0.50
0.50
0.61
0.90
1.00
1.31
2.07
2.40
2.54
2.55
2.76
2.92
3.47
Mixedc
0.08
0.08
0.10
0.12
0.16
0.13
0.14
0.13
0.13
0.21
0.26
0.16
0.16
0.21
0.21
0.25
0.25
0.25
0.22
0.37
0.41
0.42
0.48
0.50
e
0.63
0.54
0.60
e
1.00
1.33
2.04
2.27
2.37
2.37
e .
4.42
e
Sensitivity
60
no
65
0.3
15
30
20
25
30
24
1.2
25
30
5
25
9
0.8
2
0.5
35
7
7
1
1.6
1.5
1.3
7
1.5
400
1.5
3
1
4
6.5
5
5
6
300
•Data taken from Reference 60.
bOV-l01 column parameters are given 1n Table 20.
cM1xed OV-101 + OV-210 column; operating parameters are given
1n Table 20.
dFor 50 percent full-scale deflection of the recorder pen
(electrometer sensitivity 1s 1x10-9 A for full-scale
deflection).
Information 1s not available.
A-66
-------
TABLE 30. RETENTION TIMES RELATIVE TO PENTACHLOROBENZENE (RR) FOR
VARIOUS COLUMNS AT 130°C AND 150°Ca
Compound
1 ,3,5-Trichlorobenzene
1 ,2 ,3-Tri chl orobenzene
1,2, 4-Tr i chl or oben zene
1,2, 3, 5-Tetrac hi orobenzene
1 , 2,3, 4-Tetrachl orobenzene
1,2,4,5-Tetrachlorobenzene
Hexachlorobutadiene
Pentachl orobenzene
Hexachl orobenzene
al pha-BHC
gamma -BHC
OV-225
Hi xed
0.14
0.24
0.19
0.40
0.52
0.40
0.20
1.00
2.42
3.38
5.08
RR at
OV-101
0.15
0.22
0.18
0.40
0.50
0.40
0.24
1.00
2.40
2.05
2.76
130°C
OV-105
0.18
0.29
0.22
0.44
0.57
0.42
0.25
1.00
2.32
2.74
3.73
OV-210
Mi xed
0.16
0.25
0.21
0.41
0.54
0.42
0.22
1.00
2.27
2.57
3.50
RR at 150°C
OV-225
Mixed
0.18
0.27
0.23
0.43
0.56
0.44
0.24.
1.00
2.27
3.05
4.42
aData taken from Reference 64.
A-67
-------
1. 1,3-Dichlorobenzene (4 ng)
2. Hexachloroethane (0.02 ng)
3. 1,4-Dichlorobenzene (8 ng)
4. 1,2-Dichlorobenzene (4 ng)
5. Hexachlorobutadiene (0.02 ng)
6. 1,2,4-Trichlorobenzene (0.8 ng)
7. 2-Chloronaphthalene (8 ng)
8. Hexachlorobenzene (0.02 ng)
8
1 2
| | I I I I I I I I I I I " I I ''
0 24 6 8 10 12 14 16
TIME (min)
Figure 8. GC/ECD chromatogram of chlorinated hylrocarbons analyzed on a 2 m
x 2 mm ID glass column packed with 1 percent SP-1000 on
Supelcoport (100/120 mesh) (Reference 65).
A-68
-------
TABLE 31. RELATIVE SENSITIVITIES (HCB = 10.0) AND CHARACTERISTIC IONS
OF CHLOROBENZENES AND HEXACHLOROBUTADIENE
Compound
Relative sensitivity3
ECDb
MSDC
Characteristic
ion at m/z
1,3-Dichlorobenzene
1,4-Dichlorobenzene
1,2-Oichlorobenzene
1, 3, 5-Trichl orobenzene
1,2,4-Trichlorobenzene
1 ,2,3-Trichl orobenzene
1,2,3, 5-Tetrachl orobenzene
1,2, 4, 5-Tetrachl orobenzene
1 ,2,3 ,4-Tetrachl orobenzene
Pentachl orobenzene
Hexachl orobenzene
Hexachlorobutadiene
0.26
0.19
0.27
2.02
1.65
2.49
4.40
2.34
3.88
6.22
10.0
12.1
5.55
5.17
4.97
5.06
4.79
5.05
d
d
4.64
8.52
10.0
4.46
146
146
146
180
180
180
216
216
216
250
284
225
Relative sensitivity for hexachlorobenzene was arbitrarily set at 10.0.
Data taken from Reference 25.
bRelative sensitivity of each compound on the electron-capture detector
was determined with a Carbowax 20M capillary column.
cRelative sensitivity of each compound on the mass-selective detector
was determined with an OV-1 capillary column using the SIM technique.
^information is not available.
A-69
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was reported by Drlscoll et al. (67). This detector has been tested with
chlorinated benzenes and was found to be sensitive 1n the 6- to 26-ng range
(Table 32). While the Coulson detector has a detection limit of a few ng,
the electrochemical detector seems to be nearly 1,000 times more sensitive.
3.5.3 Confirmation of Compound Identity
Several techniques are available for the confirmation of compounds
detected with the gas chromatograpMc detectors. These Include the
multi-column confirmation technique, the chemical der1vat1zat1on followed by
extract reanalysls, and confirmation by gas chromatography/mass spectrometry.
The multi-column technique has been and still 1s a widely practiced
procedure, although there have been reports that misinterpretation of
compound Identity occurred when the retention times were the only criteria
used for Identification. Two or three columns are routinely used to confirm
compounds when GC 1s used for analysis.
Chemical der1vat1zat1on techniques have been used Intensively for
confirmation 1n pesticide residue work but will be addressed only briefly
here since these techniques are beyond the scope of this project.
Table 33 Identifies some of the chemical der1vat1zat1on techniques reported
for BHC (3).
Confirmation of compound Identity by mass spectrometry has been
reported (25); this technique can only be applied to those samples 1n which
the compound concentration 1s above approximately 5 ug/L for water and
50 ng/g for soil samples. Alternatively, use of gas chromatography/mass
spectrometry 1n the selected 1on monitoring mode was found to give
sensitivities comparable to those achieved with the electron capture
detector.
In selecting the most appropriate method(s) for routine work,
consideration should be given to those procedures that allow unambiguous
confirmation of compound Identity and that circumvent Interference(s) 1n the
quantitative analysis. Furthermore, the method should use routine
Instrumentation, should be easy to standardize, and should not Include
fractlonatlon (the fractlonatlon of an extract 1s not desirable since 1t
Increases the number of analyses).
A-70
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TABLE 32. COMPARISON OF DETECTION LIMITS FOR CHLOROBENZENES
Detection 1imitsa
HNU
electrochemical Coulson
Compound detector (pg) detector (ng)
Chlorobenzene 26 23
1,2-Dichlorobenzene 15 2
1,2,4-Trichlorobenzene 12 2
1,2,3,4-Tetrachlorobenzene 6 1
Pentachlorobenzene 10 2
aData taken from Reference 67.
A-71
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TABLE 33. CHEMICAL CONFIRMATION OF BHC ISOMERS3
Compound s
Reagents
Reaction conditions
Known
interference
BHC isomers
(all)
BHC isomers
(alpha, beta, gamma)
BHC isomers
(alpha, gamma, delta)
2 percent KOH in
ethanol
0.1 g NaOMe in
MeOH (2 mL)
1 mL concentrated
H2S04 (2 mL)
100°C, 15 min,
GC column: 200°C
50°C, 15 min,
GC column: 200°C
Room temperature
BHC isomers mutually
interfere
BHC isomers mutually
interfere
aData taken from Reference 3.
t\>
-------
REFERENCES
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J. Wiley & Sons, 1979.
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A-73
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15. Test Methods for Evaluating Solid Waste, Third Ed., November 1986, U.S.
Environmental Protection Agency, Washington, DC, Volume I, Section B,
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Environmental Protection Agency, Washington, DC, Volume I, Section B,
Method 8010.
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Environmental Protection Agency, Washington, DC, Volume I, Section B,
Method 8020.
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Environmental Protection Agency, Washington, DC, Volume I, Section B,
Method 8080.
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Environmental Protection Agency, Washington, DC, Volume I, Section B,
Method 8250.
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Environmental Protection Agency, Washington, DC, Volume I, Section B,
Method 8270.
21. German Chemists Association, "Preservation of Water Samples," Water
Research 15:233-241, 1981.
22. Well, L., and K. E. Quentin, "The Analysis of Pesticides in Water.
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23. Millar, J. D., R. E. Thomas, and H. J. Schattenberg, "Determination of
Organochlorine Pesticides and Polychlorlnated Biphenyls in Water by Gas
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24. Pionke, H. B., G. Chesters, and D. E. Armstrong, "Extraction of
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1968.
25. Lee, H-B, R. L. Hong-You, and A. S. Y. Chau, "Analytical Reference
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26. Oliver, B. G., and K. D. Bothen, "Extraction and Cleanup Procedures for
Measuring Chlorobenzenes 1n Sediments and Fish by Capillary Gas
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27. Oliver, B. G., and K. D. Bothen, "Determination of Chlorobenzenes 1n
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28. Elchelberger, J. W.t E. H. Kerns, P. Olynyk, and W. L. Budde,
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55:1471-1479, 1983.
29. Baumann Ofstad, E., G. Lunde, and H. Drangsholt, "Chlorinated Organic
Compounds in the Fatty Surface Film on Water," Intern. J. Environ. Anal.
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30. Mohnke, M., K-H Rohde, L. Brugmann, and P. Franz, "Trace Analysis of
Some Chlorinated Hydrocarbons 1n Waters by Gas-Liquid Chromatography,"
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31. Jungclaus, G. A., V. Lopez-Avila, and R. A. H1tes, "Organic Compounds in
an Industrial Wastewater: A Case Study of Their Environmental Impact."
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32. Melcher, R. G., T. L. Peters, and H. W. Emmel, "Sampling and Sample
Preparation of Environmental Material," 1n: Topics 1n Current Chemistry
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33. Michael, L. C., M. A. Moseley, J. W. Hines, and E. D. PelUzzari,
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600/4-85/073, October 1985.
34. Warner, S. J., M. C. Landes, and L. E. Slivon, "Development of a Solvent
Extraction Method for Determining Semivolatile Organic Compounds in
Solid Wastes," Second Symposium ASTM STP-805, 203-213, 1983.
35. Jan, J., and S. Malnersic, "Chlorinated Benzene Residues in Fish in
Slovenia (Yugoslavia)," Bull. Environ. Contam. Toxlcol. 24:824-827,
1980.
36. Mes, J., "Chlorinated Hydrocarbon Residues in Primate Tissues and
Fluids." Trace Analysis 3:71-112, 1984.
37. Mills, P. A., B. A. Bong, L. R. Kamps, and J. A. Burke, "Elution Solvent
System for Florlsil Column Cleanup in Organochlorine Pesticide Residue
Analyses," J. Assoc. Off. Anal. Chem. 55:39-43, 1972.
38. Law, L. M., and D. F. Goerlltz, "Mlcrocolumn Chromatographic Cleanup for
the Analysis of Pesticides 1n Water," J. Assoc. Off. Anal. Chem.
53:1276-1287, 1970.
39. McMahon, B., and J. A. Burke, "Analytical Behavior Data for Chemicals
Determined Using AOAC Multiresidue Methodology for Pesticide Residues in
Foods," J. Assoc. Off. Anal. Chem. 61:640-652, 1978.
40. Mes, J., "Experiences in Human M1lk Analysis of Halogenated Hydrocarbon
Residues," Intern. J. Environ. Anal. Chem. 9:283-299, 1981.
A-75
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41. Albro, P. W., and C. E. Parker, "General Approach to the Fractionatlon
and Class Determination of Complex Mixtures of Chlorinated Aromatic
Compounds," J. Chrom. 197:155-169, 1980.
42. LeBel, 6. L., and D. T. Williams, "Determination of Halogenated
Contaminants 1n Human Adipose Tissue," J. Assoc. Off. Anal. Chem.
69:451-458, 1986.
43. Alford-Stevens, A., "Identification and Measurement Procedures for PCBs,
Chlorinated Pesticides and Selected CLP Target Compounus." Protocol for
SAS 2914-HQ, May 17, 1987.
44. Goerlitz, D. F., and L. M. Law, "Note on Removal of Sulfur Interferences
from Sediment Extract for Pesticides Analysis," Bull. Environ. Contam.
Toxicol. 6:9, 1971.
45. Blummer, M., "Removal of Elemental Sulfur from Hydrocarbon Fractions,"
Anal. Chem. 29:1039, 1957.
46. Ahnoff, M., and B. Josefsson, "Cleanup Procedures for PCB Analysis on
River Water Extracts," Bull. Environ. Contam. Toxicol. 13:159, 1975.
47. Jensen, S., L. Renberg, and L. Reutergardth, "Residue Analysis of
Sediment and Sewage Sludge for Organochlorlnes 1n the Presence of
Elemental Sulfur," Anal. Chem. 49:316-318, 1977.
48. Mattson, P. E., and S. Nygren, "Gas Chromatographlc Determination of
Polychlorinated Blphenyls and Some Chlorinated Pesticides in Sewage
Sludge Using a Capillary Column," J. Chrom. 124:265, 1976.
49. Lopez-Avila, V., S. Schoen, J. Mi lanes, and W. F. Beckert,
"Single-Laboratory Evaluation of EPA Method 8080 for the Determination
of Chlorinated Pesticides and PCBs 1n Hazardous Wastes," J. Assoc. Off.
Anal. Chem. 71:375-387, 1988.
50. Burke, J. A., P. A. Mills, and D. C. Bostwlck, "Experiments with
Evaporation of Solutions of Chlorinated Pesticides," J. Assoc. Off.
Anal. Chem. 49:999-1003, 1966.
51. EMckson, M. D., M. T. Glguere, and D. A. Whitaker, "Comparison of
Common Solvent Evaporation Techniques 1n Organic Analysis," Anal. Lett.
14:841-857, 1981.
52. Crow, F. W., A. Bjorseth, K. T. Knapp, and R. Bennett, "Determination
of Polyhalogenated Hydrocarbons by Gas Capillary Gas Chromatography-
Negative Ion Chemical lonization Mass Spectrometry," Anal. Chem.
53:619-625, 1981.
53. Haken, J. K., and I. 0. 0. Korhonen, "Retention Increments of Isometric
Chlorobenzenes," J. Chrom. 265:323-327, 1983.
A-76
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54. Pacholec, F., and C. F. Poole, "Evaluation of Calibration Marker Scheme
for Open Tubular Column Gas Chromatography with On-Column Injection and
Electron-Capture Detection," J. Chrom. 302:289-301, 1984.
55. Cortes, H. J., B. E. Richter, C. D. Pfeiffer, and D. E. Jensen,
"Determination of Trace Chlorinated Benzenes in Fuel Oil by On-line
Multidimensional Chromatography Using Packed-Capillary Liquid
Chromatography and Capillary Gas Chromatography," J. Chrom. 349:55-61,
1985.
56. Mehran, M. F., W. J. Cooper, R. Lautamo, R. R. Freeman, and W. Jennings,
"A New Bonded Stationary Phase for the Gas Chromatographic Separation
of Volatile Priority Pollutants and Chlorinated Pesticides", J. High
Resol. Chrom. & Chrom. Communic. 8:715-717, 1985.
57. Lautamo, R., (J & W Scientific), personal communication, 1987.
58. Bartram, R. J., (Supelco, Inc.), personal communication, 1987.
59. Langhorst, M. L., and T. J. Nestrick, "Determination of Chlorobenzenes
in Air and Biological Samples by Gas Chromatography with Photoionlzation
Detection," Anal. Chem. 51:2018-2025, 1979.
60. Yurawecz, M. P., and J. B. Puma, "Gas Chromatographic Determination of
Electron Capture Sensitive Volatile Industrial Chemical Residues in
Foods Using AOAC Multlresidue Extraction and Cleanup Procedures," J.
Assoc. Off. Anal. Chem. 69:80-86, 1986.
61. Lamparskl, L. L., M. L. Langhorst, T. J. Nestrick, and S. Cutie,
"Gas-Liquid Chromatographic Determinaton of Chlorinated Benzenes and
Phenols in Selected Biological Matrices," J. Assoc. Off. Anal. Chem.
63:27-32, 1980.
62. J & W Scientific High-Resolution Chromatography Products Catalog,
1987/1988.
63. Supelco Chromatography Supplies Catalog, 1988.
64. Daft, J. L., "Gas Chromatographic Determination of Chemical Residues in
Food Using a Rugged High Resolution Mixed-Bed Column," Anal. Chem.
56:2687-2692, 1984.
65. The Supelco Reporter, "Improved Analyses of Chlorinated Hydrocarbons by
EPA Method 612," Vol. Ill, No. 4, October 1984.
66. Miller, D. A., and E. P. Grlmsrud, "Correlation of Electron Capture
Response Enhancements Caused by Oxygen with Chemical Structure for
Chlorinated Hydrocarbons," Anal. Chem. 51:851-859, 1979.
67. Drlscoll, J. N., D. W. Conron, and P. Ferloli, "Comparison of a New
Electrochemical Detector for Gas Chromatographic Analysis with the
Electrolytic Conductivity Detector," J. Chrom. 302:269-276, 1984.
A-77
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A-78
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APPENDIX B
METHOD 8120 — CHLORINATED HYDROCARBONS (REVISED)
B-l
-------
B-2
-------
METHOD 8120
CHLORINATED HYDROCARBONS
1.0 SCOPE AND APPLICATION
1.1 This method provides procedures for the determination of certain
chlorinated hydrocarbons in liquid and solid sample matrices. Table 1
indicates compounds that may be determined by this method and lists CAS
Registry numbers and method detection limits (MDL) for each compound in a
water matrix. The MDLs for the compounds of a specific sample may differ from
those listed in Table 1 because they are dependent upon the nature of
interferences in the sample matrix. Table 2 lists the practical quantitation
limits (PQL) for other matrices.
1.2 When this method is used to analyze for any or all of the compounds
listed in Table 1, compound identification should be supported by at least one
additional qualitative technique. This method describes analytical conditions
for a second gas chromatographic column that can be used to confirm the
measurements made with the primary column. Retention time information
obtained on two gas chromatographic columns is given in Table 3.
Alternatively, gas chromatography/mass spectrometry could be used for compound
confirmation.
1.3 This method 1s restricted to use by or under the supervision of
analysts experienced 1n the use of a gas chromatograph and in the
interpretation of gas chromatograms.
2.0 SUMMARY OF METHOD
2.1 A measured volume or weight of sample (100 ml to 1 L for liquids, 10
to 35 g for sol Ids) 1s extracted by using one of the appropriate sample
extraction techniques specified 1n Methods 3510, 3520, 3540, and 3550. Liquid
samples are extracted at neutral pH with methylene chloride by using either a
separatory funnel (Method 3510) or a continuous liquid-liquid extractor
(Method 3520). Solid samples are extracted with hexane/acetone (1:1) by using
a Soxhlet extractor (Method 3540) or with methylene chloride/acetone (1:1) by
using a sonicator (Method 3550). After cleanup, the extract is analyzed by
gas chromatography with electron capture detection (GC/ECD).
2.2 The sensitivity of Method 8120 usually depends on the level of
Interferences rather than on Instrumental limitations. If Interferences
prevent detection of the analytes, Method 8120 may also be performed on
samples that have undergone cleanup. This method provides a Florisil column
fractionatlon, an elemental sulfur removal procedure, and a gel permeation
chromatography cleanup procedure to aid 1n the elimination of Interferences.
3.0 INTERFERENCES
3.1 Refer to Method 3500, 3600, and 8000.
8120 - 1 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
-------
3.2 Solvents, reagents, glassware, and other hardware used in sample
processing may introduce artifacts which may result in elevated baselines
causing misinterpretation of gas chromatograms. These materials must
therefore be demonstrated to be free from interferents under the conditions of
the analysis by analyzing method blanks. Specific selection of reagents and
purification of solvents by distillation in all-glass systems may be required.
Pesticide-grade or distilled-in-glass solvents are suitable for trace analysis
without further purification. Each new batch of solvent should be checked for
possible Interferents as follows: concentrate to 1 ml the amount of solvent
equivalent to the total volume to be used in the analysis. Inject 1 to 2 yl_
of the concentrate into a gas chromatograph equipped with an electron capture
detector set at the lowest attenuation. If extraneous peaks are detected that
are greater than 10 pg on-column, the solvent must be purified either by
redistillation or by passing it through a column of highly activated alumina
(acidic or basic alumina, activated at 300°C to 400°C) or Florisil.
3.3 Interferents coextracted from the samples will vary considerably
from waste to waste. While general cleanup techniques are provided as part of
this method, specific samples may require additional cleanup steps to achieve
desired sensitivities.
3.4 Glassware must be scrupulously clean. Clean all glassware as soon
as possible after use by rinsing with the last solvent used followed by
thorough washing of the glassware in hot, detergent-containing water. Rinse
with tap water, distilled water, acetone, and finally pesticide-quality
hexane. Heavily contaminated glassware may require treatment in a muffle
furnace at 400°C for 2 to 4 hours. Some high-boiling materials, such as PCBs,
may not be eliminated by this treatment. Volumetric glassware should not be
heated in a muffle furnace. Glassware should be sealed and stored in a clean
environment immediately after drying and cooling to prevent any accumulation
of dust or other contaminants. Store the glassware by inverting or after
capping with aluminum foil.
3.5 Phthalate esters, if present in a sample, will interfere only with
the BHC Isomers because they elute 1n Fraction 2 of the Florisil procedure
described in Method 3620. In the case of the Florisil cartridge procedure,
the phthalate esters elute in the same fraction as the chlorinated
hydrocarbons. However, they interfere only with the BHC isomers because the
retention times of the phthalate esters are longer than those of the
chlorinated hydrocarbons. The presence of phthalate esters can usually be
minimized by avoiding contact with any plastic materials.
3.6 The presence of elemental sulfur will result in large peaks and
often mask the region of compounds eluting after 1,2,4,5-tetrachlorobenzene
(Compound No. 18 1n the gas chromatogram shown in Figure 1). The
tetrabutylammonium (TBA)-sulflte procedure (Method 3660) works well for the
removal of elemental sulfur.
3.7 Waxes and Uplds can be removed by gel permeation chromatography
(Method 3640). Extracts containing high amounts of liplds are viscous and may
even solidify at room temperature.
8120 - 2 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
-------
4.0 APPARATUS AND MATERIALS
4.1 Glassware: See Methods 3510, 3520, 3540, 3550, 3620, 3640, and 3660
for specifications.
4.2 Kuderna-Danlsh (K-D) apparatus, standard taper 19/22 ground glass
joints (Kontes K-570025-0500 or equivalent):
4.2.1 Concentrator tube, 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to minimize evaporation of
solvent after removal of the concentrator tube from the concentration
apparatus.
4.2.2 Evaporation flask, 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs.
4.2.3 Snyder column, three-ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Springs, 1/2-inch (Kontes K-662750 or equivalent).
4.2.5 Boiling chips, approximately 10/40 mesh. Heat to 400°C for 30
min or Soxhlet-extract with methylene chloride prior to use.
4.3 Gel permeation chromatograph (GPC):
4.3.1 Automated system:
4.3.1.1 Gel permeation chromatograph; Analytical Biochemical
Labs, Inc.; GPC Autoprep 1002, or equivalent, including:
4.3.1.2 25-mm ID by 600- to 700-mm heavy-wall glass column
packed with 70 g Bio-Beads SX-3, 200/400 mesh, Bio-Rad Laboratories,
or equivalent.
4.3.1.3 Syringe, 10 mL with Luer Lock fitting
4.3.1.4 Syringe filter holder and filters, stainless steel and
TFE, Gelman 4310, or equivalent.
4.3.2 Manual system assembly from parts:
4.3.2.1 24-mm ID by 600- to 700-mm heavy-wall glass column
packed with 70 g Bio-Beads SX-3, 200/400 mesh, Bio-Rad Laboratories,
or equivalent.
4.3.2.2 Pump, Altex Scientific, Model No. 1001A,
semipreparative, solvent-metering system or equivalent. Pump
capacity: 28 mL/m1n.
8120 - 3 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
-------
4.3.2.3 Detector, Altex Scientific, Model No. 153 or
equivalent, with 254-nm UV source and 8-pL semi preparative flowcell
(2 mm pathlengths).
4.3.2.4 Microprocessor/controller, Altex Scientific, Model No.
420 or equivalent, Microprocessor System Controller, with extended
memory.
4.3.2.5 Injector, Altex Scientific, Catalog No. 201-56, sample
injection valve, Teflon, with 10-mL sample loop, or equivalent.
4.3.2.6 Recorder
4.3.2.7 Effluent switching valve, Teflon slider valve, 3-way
with 0.060-inch ports.
4.3.2.8 Supplemental pressure gauge with connecting tee, U.S.
gauge, 0 to 200 psi, stainless steel installed as a "downstream"
monitoring device between column and detector. Flowrate is
typically 5 mL/min of methylene chloride.
4.4 Vacuum system for eluting disposable solid-phase cartridges.
4.4.1 Vacuum manifold consisting of individually adjustable, easily
accessible flow control valves for up to 24 cartridges, sample rack,
chemically resistant cover and seals, heavy-duty glass basin, removable
stainless steel solvent guides, built-in vacuum gauge and valve.
4.4.2 Vacuum trap made of 500-mL side arm flask fitted with a one-
hole stopper and glass tubing.
4.4.3 6-mL, 1-g solid-phase cartridges, LC-Florisil or equivalent,
prepackaged, ready to use.
4.5 Gas chromatograph: An analytical system complete with gas
chromatograph suitable for on-column injection, and all required accessories
Including syringes, analytical columns, gases, electron capture detector, and
recorder/integrator or data system.
4.5.1 Column 1: 30 m x 0.53 mm ID fused-sillca capillary column
chemically bonded with trlfluoropropyl methyl siloxane (DB-210 or
equivalent).
4.5.2 Column 2: 30 m x 0.53 mm ID fused-sllica capillary column
chemically bonded with polyethylene glycol (DB-VJAX or equivalent).
4.6 Chromatograph 1c column for FlorisH: 200-mm x 11-mm ID glass
column.
8120 - 4 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
-------
5.0 REAGENTS
5.1 Reagent water: Water 1n which an Interferent is not observed at the
MDL of the parameters of interest.
5.2 Preservatives:
5.2.1 Sodium hydroxide (ACS certified), ION in distilled water.
5.2.2 Sulfuric acid (ACS certified), mix equal volumes of
concentrated sulfuric acid and distilled water.
5.3 Acetone, hexane, isooctane, diethyl ether, methylene chloride,
petroleum ether: pesticide quality or equivalent.
5.4 Sodium sulfate (ACS certified) granular, anhydrous. Purify by
heating at 400°C for 4 hours in a shallow tray.
5.5 Florisil pesticide grade (60/100 mesh): Before use, activate for at
least 16 hours at 130°C. Alternatively, store Florisil in an oven at 130°C.
Cool Florisil before use.
5.6 Tetrabutylammonium-sulfite reagent: A solution of 3.39 g (0.01 mol)
tetrabutylammonium hydrogen sulfate in 100 ml of water 1s extracted with three
20-mL portions of hexane (to remove Impurities); this solution 1s split into
1-mL portions to which 250 mg anhydrous sodium sulfite (ACS grade) are added.
5.7 Corn oil: 200 mg/mL in methylene chloride.
5.8 Stock standard solutions (1.0 yg/pL): Can be prepared from pure
standard materials or can be purchased as certified solutions.
5.8.1 Prepare stock standard solutions by accurately weighing about
0.0100 g of pure compound. Dissolve the compound in Isooctane and dilute
to volume 1n a 10-ml volumetric flask. If compound purity 1s 96 percent
or greater, the weight can be used without correction to calculate the
concentration of the stock standard.
5.8.2 Transfer the stock standard solutions Into sealed screw-cap
bottles or ground-glass-stoppered reagent bottles. Store at 4°C and
protect from light.
5.9 Calibration standards should be prepared at a minimum of five
concentrations by dilution of the stock standards with Isooctane. The
suggested levels are listed 1n Table 4. However, the concentration levels
should correspond to the expected range of concentrations found in real
samples and should define the working range of the GC. Calibration solutions
must be replaced after six months, or sooner if ongoing QC (Section 8)
Indicates a problem.
8120 - 5 Revision 2
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**** DRAFT September 30, 1988 ****
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5.10 Internal standards: 2,5-dibromotoluene, 1,3,5-tribromobenzene, and
a.o'-dibromo-m-xylene. The analyst can use any of the three compounds provided
that they are resolved from matrix interferences.
5.10.1 Prepare an internal standard spiking solution which contains
50 ug/mL of any of the compounds listed above. Addition of 10 yL of this
solution to 1 ml of sample extract is recommended. The spiking level of
the internal standard should be kept constant for all samples and
calibration standards. Store the internal standard spiking solutions at
4°C in Teflon-sealed containers. Standard solution should be replaced
when ongoing QC (Section 8) indicates a problem.
5.11 Surrogate standard spiking solution:
5.11.1 The performance of the method should be monitored using
surrogate compounds. Three surrogate compounds are recommended:
a,2,6-tr1chlorotoluene, 1,4-dichloronaphthalene, and 2,3,4,5,6-
pentachlorotoluene. Surrogate standards are added to all samples, method
blanks, matrix spikes, and calibration standards.
5.11.2 Prepare a surrogate standard spiking solution which contains
1 ug/mL of a,2,6-trichlorotoluene and 2,3,4,5,6-pentachlorotoluene and
10 ng/mL of 1,4-dichloronaphthalene. Addition of 1 ml of this solution
to 1 L of water sample or 10 g of solid sample is equivalent to 1 ug/L or
100 ng/g of a,2,6-trichlorotoluene and 2,3,4,5,6-pentachlorotoluene and
10 yg/L or 1,000 ng/g of 1,4-dichloronaphthalene. The spiking level of
the surrogate standards may be adjusted accordingly if the final volume
of extract is reduced below 10 ml. Store the spiking solutions at 4°C in
Teflon-sealed containers. The solutions must be replaced after 6 months
or sooner if onging QC (Section 8) indicates problems.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See introductory material to this chapter, Organic Analytes,
Section 4.1.
6.2 The stability of the chlorinated hydrocarbons in soil has not been
systematically investigated. Storage of soil samples at room temperature
should be avoided since degradation of some chlorinated hydrocarbons has been
reported to occur. Deep-freezing at -10°C or -20°C appears to be the most
suitable method for storage of solid matrices since it has the widest range of
application, causes the least changes in the samples, and makes the addition
of preservatives unnecessary.
6.3 All aqueous samples must be extracted within 3 days of sample
collection; all soil and sediment samples must be extracted within 30 days of
sample collection. Extracts must be stored at <4°C and must be analyzed
within 30 days of extraction.
8120 - 6 Revision 2
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7.0 PROCEDURES
7.1 Extraction:
7.1.1 Refer to Chapter Two for guidance on choosing the appropriate
extraction procedure. In general, water samples are extracted at a
neutral pH with methylene chloride by using a separatory funnel (Method
3510) or a continuous liquid-liquid extractor (Method 3520). Solid
samples are extracted with hexane/acetone (1:1) by using a Soxhlet
extractor (Method 3540) or with methylene chloride/acetone (1:1) by using
a sonicator (Method 3550).
7.1.2 Spiked samples are used to verify the applicability of the
chosen extraction technique to each new sample type. Each sample must be
spiked with the compounds of Interest to determine the percent recovery
and the limit of detection for that sample. Spiking of water samples
should be performed by adding appropriate amounts of the Method 8120
compounds, dissolved in methanol or acetone, to the water samples
immediately prior to extraction. After addition of the spike, mix the
samples manually for 1 to 2 minutes. Typical spiking levels for water
samples are 0.1 to 20 yg/L for samples in which the Method 8120 compounds
were not detected and 2 to 5 times the background level in those cases
where compounds are present. Spiking of solid samples should be performed
by adding appropriate amounts of Method 8120 compounds, dissolved in
methanol or acetone, to a soil slurry in water. The solid sample should
be wet prior to the addition of the spike (typical moisture levels are 35
to 40 percent) and should be mixed thoroughly with a blender. Transfer
the whole portion that was spiked with the test compounds to the
extraction thimble for Soxhlet extraction (Method 3540) or proceed with
the sonlcation in the case of Method 3550.
7.2 Solvent exchange: Prior to Flor1s1l cleanup or gas chromatographic
analysis, the extraction solvent must be exchanged to hexane. Sample extracts
that will be subjected to gel permeation chromatography do not need solvent
exchange. The exchange 1s performed during the K-D procedures listed 1n all
of the extraction methods. The exchange 1s performed as follows:
7.2.1 Following K-D concentration of the methylene chloride
extracts to 1 ml using the macro-Snyder column, allow the apparatus to
cool and drain for at least 10 minutes.
7.2.2 Increase the temperature of the hot water bath to about 90°C.
Momentarily remove the Snyder column, add 50 ml of hexane, a new glass
bead, and attach the macro-Snyder column. Place the K-D apparatus on the
water bath so that the concentrator tube 1s partially immersed in the hot
water. Adjust the vertical position of the apparatus and the water
temperature, as required, to complete concentration in 5 to 10 minutes.
At the proper rate of distillation, the balls of the column will actively
chatter, but the chambers will not flood. When the apparent volume of
liquid reaches 1 ml, remove the K-D apparatus and allow 1t to drain and
cool for at least 10 minutes.
8120 - 7 Revision 2
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**** DRAFT September 30, 1988 ****
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7.2.3 Remove the Snyder column and rinse the flask and its lower
joint into the concentrator tube with 1 to 2 ml of hexane. A 5-mL
syringe is recommended for this operation. Adjust the extract volume to
10 ml. Stopper the concentrator tube and store at 4°C if further
processing will be performed immediately. If the extract will be stored
longer than two days, it should be transferred to a Teflon-lined screw-
cap vial. Proceed with cleanup or gas chromatographic analysis.
7.3 Cleanup/Fractionation:
7.3.1 Cleanup procedures may not be necessary for a relatively
clean matrix. If removal of interferences such as chlorinated phenols,
phthalate esters, etc., is required, proceed with the procedure outlined
in Method 3620. Collect Fraction 1 by eluting with 200 ml petroleum
ether and Fraction 2 by eluting with 200 ml of diethyl ether/petroleum
ether (1:1). Note that, under these conditions, benzal chloride and
benzotrichloride are not recovered from the Florisil column. The elution
patterns and compound recoveries are given in Table 5.
7.3.2 As an alternative to Method 3620, the following Florisil
cartridge procedure can be used for extract cleanup. With this method,
benzal chloride and benzotrichloride are also recovered quantitatively.
7.3.2.1 Every lot of Florisil cartridges must be checked prior
to use as follows. Install 1-g cartridges in the vacuum manifold.
Wash each cartridge with 4 ml pesticide-grade hexane and discard the
eluate. Add to each cartridge 2 ml of a composite standard
containing the test compounds at 0.05 to 10 ug/mL and elute each
cartridge with 5 ml hexane/acetone (9:1 v/v). Adjust the final
volumes to 10 mL and analyze the eluates by GC/ECO. The lot of
Florisil cartridges is acceptable if all 22 target compound
recoveries are between 80 and 120 percent and if no other
interferences are detected.
7.3.2.2 Prior to cleanup of sample extracts, the cartridges
must be washed with hexane. This is accomplished by placing 10, 12,
or 24 cartridges in the vacuum manifold (the number depends on the
type of vacuum manifold; for example, Vac Elut SPS24 from
Analytlchem International can accommodate 24 cartridges) and passing
at least 4 ml pesticide-grade hexane through each cartridge. While
washing the cartridges, adjust the vacuum applied to each cartridge
so that the flows through the cartridges are approximately equal.
Do not allow the cartridges to go dry after they have been washed.
7.3.2.3 After the cartridges have been washed, release the
vacuum and replace the collecting vials with 5-mL volumetric
flasks. Care must be taken to ensure that the solvent line from
each cartridge 1s placed Inside the correct volumetric flask.
7.3.2.4 After the volumetric flasks have been set in the
vacuum manifold, the vacuum 1s restored and the sample extracts are
8120 - 8 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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added to the appropriate cartridges. Use a syringe or a volumetric
plpet for transferring the extracts.
7.3.2.5 Elute each cartridge with 5 ml hexane/acetone (9:1
v/v) and collect the eluate in the 5-mL volumetric flask held inside
the vacuum manifold. Adjust to the 5-mL mark if not all solvent is
recovered. Transfer the eluates to clean sample vials for further
concentration using nitrogen blow-down evaporation with a gentle
stream of pure nitrogen. The elution patterns and compound
recoveries are given in Table 6.
7.3.3 Removal of waxes and lipids by gel permeation chromatography
(optional):
7.3.3.1 Packing the column: Place 70 g of Bio-Beads SX-3 in a
400-mL beaker, cover the beads with methylene chloride, and allow
them to swell overnight (before packing the column). Transfer the
swelled beads to the column and pump methylene chloride through the
column from bottom to top at 5.0 mL/min. After approximately
1 hour, adjust the pressure to 7 to 10 psi and pump solvent for an
additional 4 hours to remove all air from the column. Adjust the
column pressure periodically, as required, to maintain 7 to 10 psi.
7.3.3.2 Calibration of the column: Load 5 mL of the corn-oil
solution into sample loop No. 1 and 5 mL of the chlorinated
hydrocarbons standard into sample loop No. 2. Inject the corn oil
and collect 10-mL fractions (I.e., change fractions at 2-m1nute
intervals) for 36 minutes. Inject the chlorinated hydrocarbons
standard and collect 15-mL fractions for 60 minutes. Determine the
corn-oil elution pattern by evaporating each fraction to dryness and
determining the residue gravimetrically. Analyze the chlorinated
hydrocarbons by gas chromatography and plot the concentration of
each component 1n each fraction versus the total eluant volume (or
time) from the Injection points. Choose a "dump time" which allows
>85 percent removal of the corn oil and >85 percent recovery of the
chlorinated hydrocarbons. Choose the "collect time" that will
extend at least 10 minutes past the elution of chlorinated
hydrocarbons. Wash the column for at least 15 minutes between
samples. Typical parameters selected are a dump time of 30 minutes
(180 mL), and a wash time of 15 minutes (75 mL). The column can
also be calibrated by the use of a 254-nm UV detector 1n place of
gravimetric and GC analysis of the fractions. Measure the peak
areas at various elution times to determine appropriate fractions.
The SX-3 Bio-Beads column may be used for several months even if
discoloration occurs. System calibration usually remains constant
over this period of time if the column flowrate remains constant.
7.3.3.3 Prefllter the extracts or load all extracts via the
filter holder to retain partlculates that might cause flow
stoppage. Load one 5.0-mL aliquot of the extract onto the GPC
column. Use sufficient clean solvent after the extract loading to
transfer the entire aliquot Into the loop. Between extracts, purge
8120 - 9 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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the sample loading tubing thoroughly with clean solvent. Process
the extracts by using the dump, collect, and wash parameters
determined from the calibration and collect the cleaned extracts in
250-mL amber bottles. Concentrate the extracts as described in
Section 7.2.
7.3.4 Elemental Sulfur Removal (optional) — Add 1 mL 2-propanol
and 1 ml TBA-sulfite reagent to the hexane extract (2 ml) and shake for
at least 1 minute. Add approximately 100 mg sodium sulfite crystals. If
the sodium sulfite disappears, more sodium sulfite is added in 100-mg
portions until a solid residue remains after repeated shaking. Water (5
mL) is added, and the test tube is shaken for another minute; this
process is followed by centrifugation. Finally, the hexane layer is
transferred to another vial for gas chromatographic analysis. Additional
details of this procedure can be found in Reference 1.
7.4 Gas chromatography conditions (recommended):
7.4.1 Column 1: 30 m x 0.53 mm ID DB-210 fused-silica capillary
column, 1-um film thickness; carrier gas is helium at 10 mL/min; makeup
gas is nitrogen at 40 mL/min; temperature program from 65°C to 175°C
(hold 20 minutes) at 4°C/min; injector temperature 220°C; detector
temperature 250°C.
7.4.2 Column 2: 30 m x 0.53 mm ID DB-WAX fused-silica capillary
column; 1-ym film thickness; carrier gas is helium at 10 mL/min; makeup
gas is nitrogen at 40 mL/min.; temperature program from 60°C to 170°C
(hold 30 minutes) at 4°C/min; Injector temperature 200°C; detector
temperature 230°C.
7.4.3 Tables 1 and 3 give the MDLs and the retention times for 22
chlorinated hydrocarbons. Examples of the separations achieved with the
DB-210 and DB-WAX fused-siHca capillary columns are shown in Figures 1
and 2, respectively.
7.5 Calibration:
7.5.1 Refer to Method 8000 for proper calibration techniques. Use
Table 4 for guidance.
7.5.2 The procedure for Internal or external calibration may be
used. Refer to Method 8000 for a description of each of these
procedures.
7.6 Gas chromatographic analysis:
7.6.1 Refer to Method 8000. If the Internal standard calibration
technique 1s used, add 10 uL of internal standard to the sample prior to
Injection.
8120 - 10 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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7.6.2 Follow step 7.6 1n Method 8000 for instructions on analysis
sequence, appropriate dilutions, daily retention time windows, and
identification criteria.
7.6.3 Record the sample volume injected and the resulting peak
areas.
7.6.4 Using either internal or external calibration procedures
(Method 8000), determine the identity and quantity of each component peak
in the sample chromatogram which corresponds to the compounds used for
calibration purposes.
7.6.5 If the response of a peak exceeds the working range of the
system, dilute the extract and reanalyze.
7.6.6 Identify compounds in the sample by comparing the retention
times of the peaks in the sample chromatogram with those of the peaks in
standard chromatograms obtained on the two columns specified in
Section 7.4. The retention time window used to make identifications
should be based upon measurements of actual retention time variations
over the course of 10 consecutive injections. Three times the standard
deviation of a retention time window can be used to calculate a suggested
window size.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
Quality control to validate sample extraction 1s covered in Method 3500 and in
the individual extraction method protocols. If extract cleanup is required,
follow the QC presented in Method 3600 and in the specific cleanup method
protocols.
8.2 Mandatory quality control to evaluate the GC system operation is
found in Method 8000, Section 8.6.
8.2.1 Analyze a quality control check standard to demonstrate that
the operation of the gas chromatograph 1s in control. The frequency of
the check standard analysis 1s equivalent to 10 percent of the samples
analyzed. If the recovery of any compound found in the check standard 1s
less than 80 percent of the certified value, the laboratory performance
1s judged to be out of control, and the problem must be corrected. A new
set of calibration standards must be prepared and analyzed.
8.3 Calculate surrogate standard recoveries for all samples, blanks, and
spikes. Determine 1f the recovery 1s within limits (limits established by
performing QC procedures outlined 1n Method 8000, step 8.10).
8.3.1 If the recoveries are not within limits, the following are
required:
8120 - 11 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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• Check to be sure that there are no errors in calculations,
surrogate solutions, and internal standards. Also check
instrument performance.
• Recalculate the data or reanalyze the extract if any of the
above checks reveals a problem.
• Reextract and reanalyze the sample if none of the above is a
problem or designate the data as "estimated concentration."
8.4 An internal standard peak area check must be performed on all
samples. The internal standard must be evaluated for acceptance by
determining whether the measured area for the internal standard deviates by
more than 50 percent from the average area for the internal standard in the
calibration standards. When the internal standard peak area is outside that
limit, all samples that fall outside the QC criteria must be reanalyzed.
8.5 GC/MS confirmation: Any compound confirmed by two columns may also
be confirmed by GC/MS if the concentration is sufficient for detection by
GC/MS as determined by the laboratory-generated detection limits.
8.5.1 The GC/MS would normally require a minimum concentration of 1
ng/uL in the final extract for each compound.
8.5.2 The sample extract and the associated blank should be
analyzed by GC/MS as per Section 7.0 of Method 8270.
8.5.3 A reference standard of the compound must also be analyzed by
GC/MS. The concentration of the reference standard must be at a level
that would demonstrate the ability to confirm the compounds identified by
GC/ECD.
8.6 Include a mid-level calibration standard after each group of 20
samples in the analysis sequence. The response factors for the mid-level
calibration must be within >30 percent of the average values for the
multilevel calibration.
8.7 Demonstrate through the analyses of standards that the Florisil
fractionation scheme is reproducible. When using the fractionation scheme
given in Method 3620, batch-to-batch variations in the composition of the
Florisil material may cause a change in the distribution patterns of the
chlorinated hydrocarbons.
8.7.1 Whenever compounds are found in more than one fraction, add
up the amounts of the various fractions. It is up to the analyst to
decide whether the cut-off point should be 5 percent or less of the
concentration 1n the fraction where the compound is expected to elute.
9.0 METHOD PERFORMANCE
9.1 The MDL is defined as the minimum concentration of the test compound
that can be measured and reported with 99 percent confidence that the value is
8120 - 12 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
-------
above zero. The MOLs listed 1n Table 1 were obtained by using reagent water.
Details on how to determine MDLs are given In Reference 2. The MDLs actually
achieved In a given analysis will vary since they depend on Instrument
sensitivity and matrix effects.
9.2 This method has been tested 1n a single laboratory by using reagent
water and sandy loam samples and extracts which were spiked with the test
compounds at one concentration. Single-operator precision and method accuracy
were found to be related to the concentration of compound and the type of
matrix. For exemplification, results of the single-laboratory method
evaluation are given 1n Tables 7 and 8.
9.3 The accuracy and precision obtained will be determined by the sample
matrix, sample preparation technique, optional cleanup techniques, and
calibration procedures used.
10.0 REFERENCES
1.0 Jensen, S., L. Renberg, and L. Reutergardh, "Residue Analysis of Sediment
and Sewage Sludge for Organochlorines in the Presence of Elemental Sulfur,"
Anal. Chem. 49: 316-318, 1977.
2.0 Glazer, J. A., G. D., Foerst, G. D., McKee, S. A., Quave, and W. L.
Budde, "Trace Analyses for Wastewaters," Environ. Sc1. and Technol. 15:1426-
1431, 1981.
8120 - 13 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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Table 1.
CHLORINATED HYDROCARBONS THAT CAN BE DETERMINED BY
METHOD 8120 AND THEIR METHOD DETECTION LIMITS
Compound name
BenzalchloHde
BenzotrichloHde
Benzyl chloride
2-Chloronaphthalene
l,2-D1chlorobenzene
l,3-D1chlorobenzene
l,4-D1chlorobenzene
Hexachlorobenzene
Hexach 1 orobutad 1 ene
alpha-Hexachlorocyclohexane (alpha-BHC)
beta-Hexachlorocyclohexane (beta-BHC)
gamma-Hexachlorocyclohexane (gamma-BHC)
delta-Hexachlorocyclohexane (delta-BHC)
Hexach 1 orocyc 1 opentad 1 ene
Hexachloroethane
Pentach 1 orobenzene
1,2,3, 4-Tetrach 1 orobenzene
1,2,4, 5-Tetrach 1 orobenzene
1,2,3, 5-Tetrachl orobenzene
1,2, 4-Tr 1 ch 1 orobenzene
1,2,3-Trlchlorobenzene
1,3, 5-TH chl orobenzene
CAS no.
98-87-3
98-07-7
100-44-7
91-58-7
95-50-1
541-73-1
106-46-1
118-74-1
87-68-3
319-84-6
319-85-7
58-89-9
319-86-8
77-47-4
67-72-1
608-93-5
634-66-2
95-94-2
634-90-2
120-82-1
87-61-6
108-70-3
MDLa
(ng/L)
2-5b
6.0
180
1,300
270
250
890
5.6
1.4
11
31
23
20
240
1.6
38
11
9.5
8.1
130
39
12
aMDL 1s the method detection limit for reagent water. MDL
was determined from the analysis of eight replicate allquots
processed through the entire analytical method (extraction,
Flor1s1l cartridge cleanup, and 6C/EC analysis).
MDL = t(n_ifo.99)xSD where t(n-l,0.99) 1s the student's
t value appropriate for a 99 percent confidence Interval and
a standard deviation with n-1 degrees of freedom, and SD 1s
.the standard deviation of the eight replicate measurements.
bEst1raated from the Instrument detection limit.
8120 - 14 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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Table 2.
PRACTICAL QUANTITATION LIMIT (PQL) FACTORS FOR VARIOUS MATRICES*
Matrix Factor6
Ground water 10
Low-level soil by sonication with GPC cleanup 670
High-level soil and sludges by sonication 10,000
Waste not mlscible with water 100,000
aSample PQLs are highly matrix-dependent. The PQLs
listed herein are provided for guidance and may not
.always be achievable.
bPQL = (Method detection limit (Table 1)] x [Factor
(Table 2)). For nonaqueous samples, the factor is on
a wet-weight basis.
8120 - 15 Revision 2
September 1988
**** DRAFT September 30, 1988 ****
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Table 3.
GAS CHROMATOGRAPHIC RETENTION TIMES FOR THE CHLORINATED HYDROCARBONS
Compound no.
Compound name
Retention time (min)
DB-WAX&
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachl orobenzene
Hexachlorobutadiene
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
Hexachl orocyclopentadiene
Hexachloroethane
Pentachl orobenzene
1,2, 3, 4-Tetrac hi orobenzene
1 , 2 ,4 ,5-Tetrachl orobenzene
1,2, 3, 5-Tetrachl orobenzene
1, 2, 4-Trichl orobenzene
1, 2, 3-Trichl orobenzene
1,3, 5 -Trichl orobenzene
6.86
7.85
4.59
13.45
4.44
3.66
3.80
19.23
5.77
22.21
25.54
24.07
26.16
8.86
3.35
14.86
11.90
10.18
10.18
6.K6
8.14
5.45
15.91
15.44
10.37
23.75
9.58
7.73
8.49
29.16
9.98
41.62
33.84
54.30
33.79
c
8.13
23.75
21.17
17.81
17.50
13.74
16.00
10.37
(continued )
aGC operating conditions: 30 m x 0.53 iron ID DB-210
fused-silica capillary column; 1-ym film thickness; carrier
gas is helium at 10 ml/min; makeup gas is nitrogen at
40 mL/min; temperature program from 65°C to 175°C (hold 20
minutes) at 4°C/min; injector temperature 220°C; detector
temperature 250°C.
bGC operating conditions: 30 m x 0.53 mm ID DB-WAX
fused-silica capillary column; l-^m film thickness; carrier
gas* is helium at 10 mL/min; makeup gas is nitrogen at
40 mL/min; temperature program from 60°C to 170°C (hold 30
minutes) at 4°C/min; injector temperature 200°C; detector
temperature 230°C.
cCompound decomposes on-column.
8120 - 16
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
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Table 3.
(CONCLUDED)
Retention time (min)
Compound no.
Compound name
nB-210a
Internal standards
2,5-Dibromotoluene
1,3,5-Tribromobenzene
a,a'-Dibromo-meta-xylene
Surrogates
9.55
11.68
18.43
a,2,6-Trich1orotoluene 12.96
1,4-Dichloronaphthalene 17.43
2,3,4,5,6-Pentachl orotol uene 18.96
18.55
22.60
35.9*
22.53
26.83
27.91
aGC operating conditions: 30 m x 0.53 mm ID DB-210
fused-silica capillary column; 1-um film thickness; carrier
gas is helium at 10 mL/min; makeup gas is nitrogen at
40 mL/min; temperature program from 65°C to 175°C (hold 20
minutes) at 4°C/min; injector temperature 220°C; detector
temperature 250°C.
bGC operating conditions: 30 m x 0.53 mm ID DB-WAX
fused-silica capillary column; 1-um film thickness; carrier
gas is helium at 10 mL/min; makeup gas is nitrogen at
40 mL/min; temperature program from 60°C to 170°C (hold 30
minutes) at 4°C/min; injector temperature 200°C; detector
temperature 230°C.
cCompound decomposes on-column.
8120 - 17
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
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Table 4.
SUGGESTED CONCENTRATIONS FOR THE CALIBRATION SOLUTIONS*
Compound
Concentration (ng/yL)
Benzal chloride
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichl orobenzene
Hexachlorobenzene
Hexachlorobutadiene
al pha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachl orocycl opentad iene
Hexachl oroethane
Pentachl orobenzene
1,2,3,4-Tetrachlorobenzene
1,2, 4, 5-Tetrachl orobenzene
1,2, 3, 5-Tetrachl orobenzene
1 ,2,4-Trichl orobenzene
1,2, 3-Tri chl orobenzene
1, 3, 5-Trichl orobenzene
0.1
0.1
0.1
2.0
1.0
1.0
1.0
0.01
0.01
0.1
0.1
0.1
0.1
0.01
0.01
0.01
0.1
0.1
0.1
0.1
0.1
0.1
0.'2
0.2
0.2
4.0
2.0
2.0
2.0
0.02
0.02
0.2
0.2
0.2
0.2
0.02
0.02
0.02
0.2
0.2
0.2
0.2
0.2
0.2
0.5
0.5
0.5
10
5.0
5.0
5.0
0.05
0.05
0.5
0.5
0.5
0.5
0.05
0.05
0.05
0.5
0.5
0.5
0.5
0.5
0.5
0.8
0.8
0.8
16
8.0
8.0
8.0
0.08
0.08
0.8
0.8
0.8
0.8
0.08
0.08
0.08
0.8
0.8
0.8
0.8
0.8
0.8
1.0
1.0
1.0
20
10
10
10
0.1
0.1
1.0
1.0
1.0
1.0
0.1
0.1
0.1
1.0
1.0
1.0
1.0
1.0
1.0
Surrogates
a,2,6-Trich1orotoluene
1,4-Dichloronaphthalene
2,3,4,5,6-Pentachl orotol uene
0.02
0.2
0.02
0.05
0.5
0.05
0.1
1.0
0.1
0.15
1.5
0.15
0.2
2.0
0.2
aOne or more internal standards should be spiked prior to GC/ECO
analysis into all calibration solutions. The spike level of
the internal standards should be kept constant for all calibration
solutions.
8120 - 18
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
Table 5.
ELUTION PATTERNS OF THE METHOD 8120 COMPOUNDS FROM THE FLORISIL COLUMN
BY ELUTION WITH PETROLEUM ETHER (FRACTION 1)
AND 1:1 PETROLEUM ETHER/DIETHYL ETHER (FRACTION 2)
Compound
Benzal chlor1ded
Benzotrlchloride
Benzyl chloride
2-Ch 1 oronaphthal ene
l,2-D1chlorobenzene
1,3-Dichlorobenzene
l,4-D1chlorobenzene
Hexachlorobenzene
Hexach 1 orobutad 1 ene
alpha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexach 1 orocyc 1 opentad i ene
Hexachloroethane
Pentachlorobenzene
1,2,3, 4-Tetrachl orobenzene
1,2,4, 5-Tetrach 1 orobenzene®
1,2,3, 5-Tetrach 1 orobenzene6
1,2,4-Trlchlorobenzene
1,2,3-Trlchlorobenzene
1,3,5-Trlchlorobenzene
Amount
(M9)
10
10
100
200
100
100
100
1.0
1.0
10
10
10
10
1.0
1.0
1.0
10
10
10
10
10
10
Recovery (percent)*
Fraction lb Fraction 2C
0 0
0 0
82 16
115
102
103
104
116
101
95
108
105
71
93
100
129
104
102
102
59
96
102
^Values given represent average values of duplicate experiments.
Fraction 1 was eluted with 200 mL petroleum ether.
GFract1on 2 was eluted with 200 mL petroleum ether/dlethyl
ether (1:1).
This compound coelutes with 1,2,4-trlchlorobenzene; separate
experiments were performed with benzal chloride to verify that this
compound 1s not recovered from the Flor1s1l cleanup 1n either
fraction.
6Th1s pair cannot be resolved on the OB-210 fused-s1!1ca capillary
columns.
8120 - 19
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
Table 6.
RECOVERY OF THE METHOD 8120 COMPOUNDS FROM THE FLORISIL CARTRIDGE BY
ELUTION WITH HEXANE/ACETONE (9:1 v/v)
Compounds
Benzal chlorideb
Benzotr1chlor1de
Benzyl chloride
2-Chloronaphthalene
l,2-D1chlorobenzene
l,3-D1chlorobenzene
1 , 4-D 1 ch 1 orobenzene
Hexachlorobenzene
Hexachlorobutadlene
alpha-BHC
beta-BHC
delta-BHC
gamma-BHC
Hexach 1 orocyc 1 opentad 1 ene
Hexachloroethane
Pentachlorobenzehe
1,2,3,4-Tetrachlorobenzene
1 , 2 , 4 , 5-Tetrach1orobenzenec
1,2,3, 5-Tetrach 1 orobenzene0
!,2,4-Tr1chlorobenzeneD
1,2,3-Trlchlorobenzene
1, 3, 5-Tr1chl orobenzene
Average
Amount recovery* .
(ng) (percent)
10
10
100
200
100
100
100
1.0
1.0
10
10
10
10
1.0
1.0
1.0
10
10
10
10
10
10
99
90
101
95
102
101
100
78
95
100
95
97
99
103
95
104
99
98
98
99
97
98
Precision
(percent RSD)
0.8
6.5
1.5
1.4
1.6
2.3
2.3
1.1
2.0
0.4
1.8
2.7
0.7
3.3
2.0
1.5
1.3
3.1
3.1
0.8
2.0
2.2
*
The number of determinations 1s 5.
These pairs cannot be resolved on the DB-210 fused-slUca
capillary column.
8120 - 20
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
Table 7.
ACCURACY AND PRECISION DATA FOR METHOD 3510 AND METHOD 8120
Compound
Spike
level
(ug/L)
Average
recovery3 »b
(percent)
Precision
(percent RSCP
Benzal chloride0
Benzotrichloride
Benzyl chloride
2-Chloronaphthalene
1,2-Dichl orobenzene
1,3-Dichlorobenzene
1,4-Dichl orobenzene
Hexachlorobenzene
Hexachlorobutadiene
al pha-BHC
beta-BHC
gamma-BHC
delta-BHC
Hexachlorocyclopentadiene
Hexachloroethane
Pentachl orobenzene
1,2,3,4-Tetrachlorobenzene
l,2,4,5-Tetrach1orobenzened
,2,3,5-Tetrachlorobenzened
,4-Trichl orobenzene0
1,2,3-Trichlorobenzene
1,3,5-Trichl orobenzene
1.
1,2,
Surrogates
a,2,6-Trichlorotoluene
1,4-Dichloronaphthalene
2,3,4,5,6-Pentachlorotoluene
10
1.0
100
200
100
100
100
1.0
1.0
10
10
10
10
10
1.0
1.0
10
10
10
10
10
10
1.0
ln
1.0
95
97
90
91
92
87
89
92
95
96
103
96
103
97
96
89
96
93
Q3
05
95
93
85
78
80
3.0
2.1
6.2
6.*
8.7
7J
3.6
2.6
3.6
2.8
2.7
5.1
4.0
6.5
3.4
4.6
4.6
3.0
4.4
6.2
6.5
6.1
5.9
aThe number of determinations was 5.
bpinal volume of extract was 10 ml. Florisil cleanup was not
performed on any of the samples.
c»dThese pairs cannot be resolved on the OB-210 fused-silica
capillary column.
8120 . 21
**** PPAFT September 30, 1988 ****
Revision 2
September
-------
Table 8.
ACCURACY AND PRECISION DATA FOR METHOD 3550 AND METHOP 8120
Compound
Spike
level
(ng/g)
Average
recovery3,13
( percent)
Precision
(percent RSD)
Benzal chloridec 3,300
Benzotrichloride 3,300
Benzyl chloride 33,000
2-Chloronaphthalene 66,000
1,2-Dichlorobenzene 33,000
1,3-Dichlorobenzene 33,000
1,4-Dichlorobenzene 33,000
Hexachlorobenzene 330
Hexachlorobutadiene 330
alpha-RHC 3,300
beta-BHC 3,300
gamma-BHC 3,300
delta-BHC 3,300
Hexachlorocyclopentadiene 330
Hexachloroethane 330
Pentachlorobenzene 330
1,2,3,4-Tetrachlorobenzene 3,300
l,2,4,5-Tetrachlorobenzened
l,2,3,5-Tetrachlorobenzened
1,2,4-TrichlorobenzeneC
1,2,3-Trichl orobenzene
1,3,5-Trichlorobenzene 3,300
Surrogates
ct,2,6-Trichlorotoluene 330
1,4-Dichloronaphthalene 3,300
2,3,4,5,6-Pentachlorotoluene 330
3,
3,
3,
3,
300
300
300
300
89
90
121
100
84
81
89
81
83
100
«2
99
97
44
83
81
88
80
80
89
79
75
86
88
98
7.7
?.o
5.9
6.4
7.1
12.6
11.0
3.2
4.7
2.9
?.A
4.1
1.5
25.9
4.6
3.5
2.9
4.3
5.3
2.7
4.5
11.7
aThe number of determinations was 5.
bFinal volume of extract was 10 mL. Florisil cleanup was not
performed on any of the samples.
c»dThese pairs cannot be resolved on the DB-210 fused-silica
capillary column.
****
8120 - 22
DRAFT September 30, 1988
****
Revision 2
September 1988
-------
1S.
_
[
S
1
•vll
I
1 . Hi
1
i a
9
2
-
M«
O i
•i
21 1
1
1 1
0 S
1
18
4
9
i
r
t
i
11
9
19
1 I
*A
J 1
I
Z 11
13
..
LA lw
i i i
10 16 20 25 3
TIME (mln)
Figure 1. GC/EC chromatogram of Method 8120 composite standard analyzed on a
30 m x 0.53 mm ID OB-210 fused-slllca capillary column. GC
operating conditions are given In Section 7.4.
8120 - 23
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
17
4
16
11
13
JL
12
10 15 20 25 30 35
TIME (min)
40
45
50 55
Figure 2. GC/EC chromatogram of Method 8120 composite standard analyzed on
a 30 m x 0.53 mm ID OB-WAX fused-silica capillary column. GC
operating conditions are given in Section 7.4.
8120 - 24
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
Method 8120 - Chlorinated Hydrocarbons (Flowchart)
• 7.1.1
Choose appropriate
extraction procedure
7.1.2
Add appropriate spiking
compounds to sample prior
to extraction procedure
7.2
Exchange extraction solvent
to nexane during K-D
procedures
75.1
Following concentration of
methytene chloride, allow
K-D apparatus to drain and
cool
Proceed with 7.3.4
7.3.3
Proceed with 7.3.3.1,
7.3.3.2, 7.3.3.3
7.3.4
Elemental
sulfur removal
required?
7.3
Ctoos* appropriate cleanup
technique, if necessary;
Florisl cleanup is
recommended. Refer to
Method 3620 or to Section
7.3.2.
7.2.2
Increase temperature of hot
water bath; add nexane:
attach Snyder column;
place apparatus on water
bath; concentrate; remove
from water bath; cool
7.2.3
Remove column; rinse flask
and joints with nexane;
adjust extract volume
No
processing
performed
within 2
days
7.2.3
Transfer extract to Teflon-
sealed screw-cap vials;
refrigerate
8120 - 25
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
METHOD 8120 — CHLORINATED HYDROCARBONS (FLOWCHART)
(continued)
7.2.3
Stopper concentrator
tube and refrigerate
7.4.1
Set Column 1 conditions
7.4.2
Set Column 2 conditions
7.4.4
Refer to Table 3 for retention
times and Table 1 for MDLs;
refer to Figures 1 and 2 for
examples of chromatograms
7.5.1
Refer to Method 8000 for
calibration techniques; select
lowest point on calibration
curve
7.5.2
Choose and perform internal
or external calibration (refer
to Method 8000)
7.6.1
Add internal standard if
necessary
7.6.2
Establish daily retention
time windows, analysis
sequence, dilutions, and
identification criteria
8120 - 26
**** DRAFT September 30* 1988 ****
Revision 2
September 1988
-------
METHOD 8120
— CHLORINATED
(concluded)
HYDROCARBONS (FLOWCHART)
7.6.3
Record sample volume
injected and resulting peak
sizes
7.6.4
Determine identity and
quantity of each component
peak that corresponds to
compound used for
calibration
.6.5
Does peak
exceed
working range
of system?
7.6.5
Dilute extract; reanalyze
7.6.6
Compare standard and
sample retention times;
identify compound*
8120 - 27
**** DRAFT September 30, 1988 ****
Revision 2
September 1988
-------
APPENDIX C
PREPARATION OF SPIKED SOIL SAMPLES
Preparation of reference materials is an area that needs attention, and
some effort has been devoted in this study to the development of such
materials. We prepared a wet reference material in which a slurry of sandy
loam soil in water (approximately 60 to 70 percent moisture) was spiked with a
concentrated stock solution of the target compounds in isooctane and mixed
thoroughly in a blender. Blending resulted in a smooth slurry. Subsampling
was done immediately to avoid setting. The material was split Into 35-g
portions, and individual portions were extracted and analyzed. In addition,
we evaluated overnight tumbling and overnight equilibration of the wet soil
with the spike to establish which preparation technique is most efficient.
Tables 1, 2, and 3 summarize the results of the even-numbered aliquots from
those experiments that were analyzed immediately. The results indicate that
the blending technique gave better reproduc1b1lH1es and higher recoveries
than the other two techniques. Additional effort 1s needed to develop a
technique for the preparation of reference materials.
Soil/sediment reference materials can be prepared using actual samples that
contain the compounds of Interest at known levels. This is very important
since spiking the test compounds Into a soil/sediment matrix could result 1n
misleading Information and generate false results. The following approach is
recommended.
1. Identify possible sources based on the target compounds (e.g., Great
Lakes sediments have been reported to contain chlorinated benzenes).
2. Collect a sufficient amount of sample and prepare reference materials
(freeze-dry sediment, grind, sieve, homogenize).
3. Perform a gross characterization of the material (density, size,
mlneralogical composition, pH, TOC, TOX, etc.).
4. Subject the material to various extraction procedures (e.g., Soxhlet
extraction, sonlcatlon, rotary shaker) and several solvents (such as
hexane/acetone (1:1) and toluene/methanol (1:1)). Compare the
extraction procedures by determining the total extractable material
for each extraction/solvent combination.
C-l
-------
TABLE 1. HOMOGENEITY OF SPIKED SOIL SAMPLES OBTAINED BY BLENDING
o
I
r\»
Concentration (ng/pL extract)
Compound
Hexachloroethane
1,3-Dichlorobenzene
1 ,4-01chlorobenzene
1,2-Dichl orobenzene
Benzyl chloride
1 , 3,5-Tr ichl orobenzene
Hexachl orobutad lene
Benzal chloride15
1 ,2,4-Trichlorobenzeneb
Benzotrlchlorlde
1.2,3-TMchl orobenzene
Hexachl orocycl opent ad 1 ene
1 ,2,4,5-Tetrachlorobenzenec
1 ,2 , 3. 5-Tetrac hi orobenzene0
1 ,2 ,3 ,4-Tetrachl orobenzene
2-Chloronaphthalene
Pentachl orobenzene
Hexachl orobenzene
al pha-BHC
gamma -BHC
beta-BHC
delta-BHC
Surrogates recovery (percent)
a ,2 ,6-Tr Ichl orotol uene
1 . 4-D1 chl orona phthal ene
2 ,3.4,5,6-Pentachlorotol uene
-2a
O.OR
4.40
8.60
6.20
5.80
0.51
0.07
1.24
0.44
0.63
0.03
0.60
0.80
18.9
0.07
0.05
0.93
0.83
0.73
0.75
70
79
74
-6*
0.06
2.86
3.58
4.11
3.95
0.35
0.05
0.88
0.22
0.49
0.03
0.44
0.64
17.04
0.06
0.05
0.94
0.76
0.66
0.72
80
100
79
-8a
0.06
2.79
2.77
3.89
3.68
0.35
0.05
0.86
0.15
0.46
0.02
0.44
0.64
14.89
0.05
0.04
0.84
0.75
0.65
0.69
66
70
67
-10a
0.07
3.66
5.96
5.68
5.03
0.52
0.07
1.06
0.11
0.66
n.05
0.69
0.87
19.77
0.08
0.08
1.04
0.94
0.89
0.90
75
91
78
-12a
0.05
2.07
3.50
2.82
2.57
0.30
0.04
0.69
0.04
0.44
0.03
0.45
0.65
14.40
0.06
0.05
0.88
0.80
0.72
0.72
55
64
56
-14a
0.04
2.04
6.02
2.64
2.61
0.29
0.04
0.61
0.04
0.42
0.04
0.43
0.64
16.76
0.06
0.05
0.89
0.84
0.76
P. 79
51
69
55
-16a
0.05
2.04
6.62
2.58
2.49
0.30
0.04
0.64
0.05
0.45
0.04
0.47
0.70
18.82
0.07
0.07
0.95
0.87
0.80
0.81
64
73
69
-18a
0.05
9.21
4.04
3.44
2.58
0.38
C.06
0.80
0.11
0.52
0.01
0.56
0.75
20.00
0.07
0.07
0.97
0.89
O.P2
0.81
51
62
57
Average
0.06
3.63
5.14
3.92
3.59
0.37
0.05
0.85
0.14
P.51
0.03
0.51
0.71
17.57
0.06
0.06
0.93
0.83
0.75
0.77
64
76
67
Percent
RSO
22.1
66.?
38.6
35.0
35.4
24.5
24.2
25.5
92.6
17.6
40.2
18.8
12.3
12.2
14.2
23.0
6.6
7.8
10.8
8.8
17.1
17.5
14. P
aThe numbers given represent the various 35-g portions that were serially labeled in the order in which
they were removed from blender; -4 was lost during sample preparation.
pairs cannot be resolved on the DB-P10 fused-silica capillary column.
-------
TABLE 2. HOMOGENEITY OF SPIKED SOIL SAMPLES OBTAINED BY TUMBLING
Concentration (ng/pL extract)
Compound
Hexachl oroethane
1,3-Dichlorobenzene
1 ,4-Di chl orobenzene
1,2 -01 chl orobenzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachl orobutad iene
Benzal chloride1'
1, 2, 4-Trichl orobenzene5
Benzotrichloride
1 ,2,3-Trichlorobenzene
Hexachl orocyclopentadlene
l,2.4,5-Tetrachlorobenzenec
1.2,3,5-Tetrachlorobenzenec
, 1,2.3,4-Tetrachlorobenzene
u> 2-Chloronaphthalene
Pent ac hi orobenzene
Hexachl or ob enzene
alpha-BHC
gamna-3HC
beta-BHC
delta-BHC
Surrogates recovery (percent)
u,2,6-Tr ichlorotol uene
1 ,4-Oi chl oronaphthalene
2,3,4 , 5, 6-Pentachl orotol uene
-2*
0.004
O.OS
2.0
0.19
1.07
0.04
0.004
0.15
0.02
0.09
0.03
0.09
0.22
13.69
0.02
0.03
0.74
0.62
0.73
0.69
75
99
80
-4a
0.004
0.79
4.70
0.13
1.13
0.03
0.003
0.09
0.01
0.06
0.03
0.06
0.11
12.46
0.01
0.01
0.58
0.48
0.66
0.64
74
89
81
-6a
0.003
(1.59
2.41
0.10
0.68
0.02
0.002
0.08
n.oi
0.05
0.02
0.04
0.09
10.97
0.01
o.ni
0.50
0.40
0.63
0.62
78
78
117
-8a
0.003
0.68
2.38
0.22
0.71
0.03
0.002
0.09
0.01
0.06
0.03
0.05
0.11
10.10
n.oi
0.01
0.54
0.46
0.68
0.67
82
114
91
-10a
0.003
0.49
1.91
0.17
0.73
0.03
0.003
0.08
0.01
0.05
0.03
0.04
0.08
10.95
0.01
0.01
0.44
0.36
0.61
0.60
n
73
83
-12a
0.003
0.53
1.98
0.15
0.75
0.03
0.003
0.08
o.ni
0.06
0.03
0.04
0.10
d
0.02
0.02
0.49
0.42
0.66
0.71
74
95
85
-14»
0.004
0.51
3.02
0.27
1.12
0.05
0.003
0.11
0.01
0.07
0.04
0.05
0.12
14.24
0.01
0.01
0.55
0.47
0.78
0.73
102
98
113
-16*
0.005
0.88
3.23
0.28
1.06
0.04
0.004
n.n
0.01
0.08
0.03
0.07
0.13
d
0.02
0.01
0.56
0.48
0.71
0.69
86
100
91
-18a
n.nne
0.82
2.43
0.24
1.39
0.09
0.006
0.30
0.02
0.07
0.04
0.14
0.28
15.80
0.03
0.02
0.77
0.65
0.80
0.76
85
111
90
Average
0.004
0.64
2.67
0.19
0.%
0.04
0.003
0.12
0.012
0.066
0.03
0.06
0.14
12.60
P. 016
0.014
0.57
0.48
0.70
0.68
82
95
92
Percent
RSD
26.7
23.9
33.2
32.9
26.0
51. S
37.1
59.0
36.7
20.2
19.4
51.3
47.9
16.4
45.4
51.9
19.5
1<».9
9.3
7.7
11.5
14.3
14.7
*The numbers given represent the various 35-g portions that were serially labeled In the order In which they were removed
.fro* blender. 01 chl orobenzene Isomers were not Included In the spiking solution because they were present in the sample.
".•'-These pairs cannot be resolved on the DB-210 fused-siHca capillary column.
"Not able to quantltate due to Improper peak Integration.
-------
TABLE 3. HOMOGENEITY OF SPIKED SOIL SAMPLES OBTAINED BY OVERNIGHT
EQUILIBRATION WITH OCCASIONAL STIRRING
Concentration (ng/pL extract)
Compound
Hexachloroethane
l,3-D1chlorobenzene
1 ,4-D1chl orobenzene
1 ,2-DI chl orobenzene
Benzyl chloride
1 ,3,5-Trichlorobenzene
Hexachl or obutad lene
Benzal chloride^
l^^-Trlcnlorobenzeneb
Benzotrichlorlde
1,2,3-Trichlorobenzene
Hexachl orocycl opentad lene
1.2,4,5-Tetrachlorobenzenec
1,2, 3, 5-Tetrachl orobenzene0
1,2,3,4-Tetrachlorobenzene
2-Chl oronaphthal ene
Pentachl orobenzene
Hexachl orobenzene
alpha-BHC
gamma-BHC
beta-BHC
delta-BHC
Surrogates recovery (percent)
a ,2 ,6-Tr1chlorotol uene
1 ,4-Dichloronaphthalene
2,3.4,5,6-Pentachlorotoluene
-2a
0.004
0.94
2.29
0.12
0.39
0.07
0.005
0.31
0.20
0.13
0.01
0.29
0.30
10.70
0.04
0.05
0.89
0.76
0.66
0.71
64
79
68
-4a
0.005
1.55
5.84
0.79
0.09
0.06
0.005
0.29
0.15
0.13
0.01
0.29
0.31
10.99
0.04
0.05
0.94
0.80
0.73
0.77
88
82
84
-6a
0.005
1.59
6.87
0.77
0.13
0.08
0.006
0.23
0.08
0.08
0.005
0.18
0.19
10.24
0.03
0.04
0.80
0.68
0.66
0.70
91
86
89
-sa
0.006
2.54
7.67
0.48
0.18
0.09
0.007
0.30
0.13
0.12
0.006
0.24
0.28
14.30
0.04
0.05
0.99
0.85
0.83
0.87
95
103
90
-10a
0.005
2.87
7.23
0.44
0.19
0.13
0.007
0.32
0.13
0.14
P.01
0.26
0.27
16.01
0.03
0.05
0.9?
0.79
0.76
0.77
91
122
88
-12a
0.003
1.57
5.20
0.57
0.17
0.04
0.003
0.15
0.06
0.06
0.003
0.14
0.15
13.49
0.0?
0.03
0.71
0.60
0.65
0.67
93
83
90
-14a
0.004
0.82
2.71
0.19
0.43
0.05
0.005
0.27
0.14
0.11
0.004
0.22
0.29
15.49
0.04
0.05
1.04
0.91
0.88
0.88
92
117
86
-18a
0.003
1.74
5.22
0.57
0.10
0.04
0.002
0.14
0.03
0.06
0.003
0.14
0.16
11.61
0.03
0.03
0.75
0.64
0.80
0.74
93
115
91
Average
0.004
1.70
5.38
0.49
0.21
0.07
0.005
0.25
0.12
n.io
0.006
0.2?
0.24
12.85
0.034
0.044
0.88
0.75
0.75
0.76
88
98
86
Percent
RSD
26.5
41.4
37.1
49.4
61.5
43.2
35.5
28.5
45.6
32.5
52.7
?7.ft
27.5
17.6
21.9
20.0
13.3
14.2
11.5
10.1
11.4
18.2
8.8
"The maters given represent the various 35-g portions that were serially labeled In the order In which they were
removed fron blender. Dlchlorobenzenes were not Included 1n the spiking solution because they were present 1n
.the sample; -16 was lost during sanple preparation.
D(CThese pairs cannot be resolved on the DB-210 fused-s1l1ca capillary column.
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5. Set up a study to investigate the effect of long-term storage on the
level of the compounds of interest in the freeze-dried sediment
(2 years, 24 time events, triplicate analyses).
6. Establish the homogeneity of the reference material (take 6 aliquots,
30 g each, 2 from the top, 2 from the middle, and 2 from the bottom;
analyze each in triplicate). Two-way analysis of variance (ANOVA)
should be performed to test the homogeneity of the material. Should
the analysis of variance show the material to be not yet homogenous,
then blending and homogeneity shall be continued.
7. Analyze the material by at least two methods (e.g., GC/ECD with two-
column confirmation and gas chromatography/mass spectrometry).
Compare results. Establish which extraction procedure gives the
highest concentration for the compounds of interest and the lowest
background.
8. Have an independent laboratory verify results using the same methods
that were used in certifying the material.
The following are some of the difficulties that may be encountered when
using actual samples for the preparation of the reference materials.
• Identifying sites for collection of material may be difficult.
• The target compound concentration will not be known unless analyses
are carried out by at least two different methods and two
laboratories (preferable).
• Target compound concentration may not be suitable for quality
control studies.
• Matrix interferences could severely affect the determination of the
target compound.
C-5
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