EVALUATION OF THE 3ASIC
GC/MS COMPUTER ANALYSIS
TECHNIQUE FOR POLLUTANT ANALYSIS
by
J. E. Bunch, N. P. Castillo, D. Smith, J. T. Bursay and
E. D. Pellizzari
Research Triangle Institute
Post Office Box 12134
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2993
Project Officer
Kenneth Krcst
Organic Pollutant Analysis Branch
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 2771:
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AMD DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGE.NCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 2771.
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EVALUATION OF THE BASIC
GC/MS COMPUTER ANALYSIS
TECHNIQUE FOR POLLUTANT ANALYSIS
by
J. E. Bunch, N. P. Castillo, D. Smith, J. T. Bursey and
E. 0. Pellizzari
Research Triangle Institute
Post Office 3ox 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-02-2998
Project Officer
Kenneth Krost
Organic Pollutant Analysis Branch
Atmospheric Chemistry and Physics Division
Environmental Sciences Research Laboratory
Research Triangle Park, North Carolina 27711
ENVIRONMENTAL SCIENCES RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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DISCLAIMER
This report has been reviewed by the Environmental Sciences Research
Laboratory, U. S. Environmental Protection Agency, and approved for publi-
cation. Approval does not signify that the contents necessarily reflect
the views and policies, of the U. S. Environmental Protection Agency, nor
does mention of trade names or conmercial products constitute endorsement
or recommendation for use.
n
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ABSTRACT
The basic gas chromatographic/mass spectrometric/computer technique for
the analysis of vapor-phase organic compounds collected on a solid sorbent
was evaluated. Emphasis was placed on the assessment of performance and
improvement in techniques in the following areas: (1) wide bore wall
coated columns for organic vapor-phase analysis; (2) gas chromatography/nega-
tive chemical ionization mass spectrometry/computer analysis of halogenated
hydrocarbons in ambient air; (3) the concentration of vapor-phase organics
from the atmosphere on solid sorbents (in situ reactions); and (4) qualitative
and quantitative analysis of vapor-phase organics utilizing the improved
technology.
ill
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iv
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CONTENTS
Abstract iii
Figures vi
Tables ix
Acknowledgments xx
1. Introduction 1
2. Conclusions 3
3. Recommendations 5
4. Program Objectives 7
5. Preparation of Wide Bore VCOT Columns for Organic Vapor-Phase
Analysis 3
6. Gas Chromatography/Negative Chemical lonization Mass Spectro-
metry/Computer Analysis of Ambient Air Samples 38
7. In Situ Reaction Studies on Sorbents Used for Collection of
Vapor-Phase Qrganics A5
8. Qualitative and Quantitative Analysis of Vapor-Phase Ornanics
in Ambient Air "... 93
References 133
Appendices
A. Volatile Organics Identified in Ambient Air 130
Part I Baton Rouge and Plaquemine, LA and Vicinity .... Ml
Part II Lake Charles, LA 151
Part III Beaumont, TX 157
Part IV Houston, TX 178
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FIGURES
Page
1 GC/MS/COMP profile of performance mixture for capillary column
evaluation 20
2 Extracted ion current profile of m/z_ 186 for perf"Iuorobenzene
and perfluorotoluene in performance mixture 21
3 Extracted ion current profile of
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FIGURES CONT'D.
Page
15 Extracted ion current profile of a/z 57 for nonanone used in
calculating percent peak asymmetry factor 36
16 Extracted ion current profile of m/z 43 for octane and decane
used in calculating separation number 37
17 Electron impact GC/MS/COMP profile of vapor-phase organics in
ambient air of Deer Park, TX 41
18 Negative chemical ionizatioa GC/MS/COMP profile of upwind
ambient air sample for Deer Park, TX 42
19 Negative chemical ionization GC/MS/COMP profile of downwind
ambient air sample in Deer Park, TX 43
20 Schematic of instrumentation and devices for examining in situ
formation of oxygenated compounds on solid sorbents . . 48
21 Experimental sampling cartridge configurations for in situ
reaction studies 51
22 Schematic of instrumental devices used for in situ reaction
studies of ambient air 54
23 In situ reactions during ambient air sampling: d,Q-cyclohexene 87
24 In situ reactions during ambient air sampling: d.-styrene . 88
25 Schematic of vaporization unit for loading organics dissolved
in methanol onto Tenax GC cartridges 100
26 Location of plants in the East Baton Rouge Parish 110
27 Sampling locations in Baton Rouge, LA area Ill
28 Sampling locations in Plaquemine, LA area 112
29 Sampling locations in Lake Charles, LA 113
30 Sampling locations near Lamar University in Beaumont, TX . . 114
31 Sampling locations along Southern Railway in Beaumont, TX. . 115
32 Sampling locations along West Port Arthur Road in Beaumont, TX 116
33 Sampling locations in Port Heches, TX 117
34 Sampling locations in Groves, TX 118
vii
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FIGURES CONT'D.
Page
35 Sampling locations in Jacinto Port area near Houston, TX. . . . 119
36 Sampling locations in Deer Park and Pasadena, IX areas 120
Vlll
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TABLES
Page
1 Evaluation of a Coomerical Glass Capillary 19
2 Performance of Glass Capillary Prepared by Barium Carbonate Pro-
cedure 32
3 Operating Parameters for Negative Chemical lonization GLC/MS/
COMP System 40
4 Operating Parameters for GC Electron Impact MS/COMP System. ... 47
5 Experimental Design for Field In Situ Reaction Studies in
Baton Rouge, LA 50
6 Experimental Design for Field In Situ Reaction Studies Conducted
in Lake Charles, LA 52
7 Experimental Design for Field I_n Situ Reaction Studies Conducted
in Houston, TX 53
8 Experimental Design for In Situ Reaction Studies 55
9 Ozone Concentration in Baton Rouge, LA 57
10 Summary of the Detection of Halogenated Compounds and Nitrosamine
in Ambient Air Spiked with Molecular Halogens and Dimethyl-
amine-D, ia Baton Rouge, LA 53
11 Estimation of Levels of Halogenated Hydrocarbons I_n Situ Reac-
tion Studies: Ambient Air With and Without Chlorine Added . 59
12 Estimation of Levels of Halogenated Hydrocarbons In Situ Reac-
tion Studies: Ambient Air With and Without Bromine Added. . 60
13 Estimation of Levels for Selected Organics In Situ Reaction
Studies: Ambient Air With and Without Dimethylamine-D,
Added b. . . 61
14 Estimation of Levels of Selected Organics Li Situ Reaction
Studies: Ambient Air With and Without Chlorine Added. ... 62
15 Estimation of Levels of Selected Organics In Situ Reaction
Studies: Ambient Air With and Without Dimethylamine-D, Added 63
o
ix
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TABLES COMT'D.
Page
16 Estimation of Levels of Selected Organics In Situ Reaction
Studies: Ambient Air With and Without Chlorine Added. ... 64
17 Estimation of Levels of Selected Organics In Situ Reaction
Studies: Ambient Air With and Without Bromine Added .... 6.5
18 Estimation of Levels of Selected Organics In Situ Reaction
Studies: Ambient Air With and Without Dimethylamine-D,
Added 66
19 Estimation of Levels of Halogenated Compounds Effect of Ozone on
In Situ Reactions: Ambient Air With and Without Chlorine
Added 67
20 Estimation of Levels of Halogenated Compounds Effect of Ozone on
In Situ Reactions: Ambient Air With and Without Bromine
Added 68
21 Quantification of In Situ Reactions in Ambient Air of Lake
Charles, LA 70
22 Quantification of In Situ Reactions in Ambient Air of Lake
Charles, LA 72
23 Quantification of In Situ Reactions in Ambient Air of Lake
Charles, LA 73
24 Quantification of In Situ Reactions in Ambient Air of Lake
Charles, LA 75
25 Quantification of In Situ Reactions in Ambient Air in Lake
Charles, LA 77
26 Quantification of In Situ Reactions in Ambient Air in Lake
Charles, LA 79
27 Experimental Design for Sampling with Tenax Cartridges Loaded
With Cyclohexene-D,- 81
28 Experimental Design for Sampling with Tenax Cartridges Loaded
with Styrene-Dg 82
29 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Houston, TX (Pl/Ll-A/T^ 83
30 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Houston, TX (P1/L1-A/T3) 84
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TABLES CONT'D.
31 Vapor-Phase Halogensted and Other Selected Organics in Ambient
Air From Houston, TX (PS/Ll-A/T^ 85
32 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Houston, TX (PVLl-A/T-j) 86
33 In Situ Reaction Yields from D,--Cyclohexene and Molecular
Chlorine 89
34 In Situ Reaction Yields from Dg-Styrene and Molecular Chlorine. . 90
35 Summary of D. -Cyclohexene Study With and Without Molecular '
Halogen Added to Houston, TX Ambient Air 91
36 Summary of Dg-Styrene Study With and Without Molecular Halogen
Added to Houston, TX Ambient Air 92
37 Sampling and Experimental Protocol for In Situ Reaction Studies . 93
33 Quantification of In Situ Reactions Involving D, .-Cyclohexene and
Molecular Chlorine 94
39 Quantification of In Situ Reactions Involving Dg-Styrene and
Molecular Chlorine 95
40 Quantification of In Situ Reactions Involving D1Q-Cyclohexene
and Molecular Bromine 96
41 Quantification of In Situ Reactions Involving Dg-Styrene and
Molecular Bromine 97
42 Sampling Protocol for Baton Rouge, LA and Vicinity 102
43 Sampling Protocol for Vapor-Phase Organics in Lake Charles, LA. . 105
44 Sampling Protocol for Vapor-Phase Organics in Beaumont, TX and
Vicinity 107
45 Ambient Air Sampling Protocol for Houston, TX and Vicinity. . . . 109
46 Major Industrial Plants 121
47 Relative Ion Abundances for Perfluorotoluene Obtained on a Varian
Mat CH-7 GC/MS/COMP System 122
48 Relative Ion Abundances for Perfluorokerosene Obtained on a
Varian MAT CH-7 GC/MS/COMP System 123
xi
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TABLES CONT'D.
49 Suggested Mass and Intensity Tolerances Acceptable for Cali-
bration of Magnetic Instruments for Calibration 125
50 Relative Ion Abundances for Perfluorotoluene Obtained on a
LXB-2091 GC/MS/COMP System 126
51 Precision of Loading Napthalene Onto Tenax GC Cartridges and
Analysis by HRGC/Z IMS /COUP 127
52 Precision of Loading Selected Vapor-Phase Organics Onto Tenax
GC Cartridges and Analysis by HRGC/EIMS/COUP 128
53 Coefficient of Variation for RMRs as a Function of Relative
Retention Order for Selected Vapor-Phase Organics 129
54 Precision of Relative Molar Response Ratio as a Function of
Mass of Compound 131
55 Estimated Levels of Several Vapor Phase Organics'in Lake Charles,
LA Air 134
56 Estimated Levels of Organic Vapor-Phase Pollutants in Ambient
Air of Beaumont, TX and Vicinity 135
57 Estimation of Levels of Vapor-Phase Organics in Ambient Air in
Houston, Deer Park and Pasadena, TX and Vicinity 136
Al "Purgeable" Organics Identified in a Water Sample From Baton
Rouge, LA Area (P4/L1) 141
A2 Vapor-Phase Organics in Ambient Air From Baton Rouge, LA Area
(P4/L3) 142
A3 Vapor-Phase Organics in Ambient Air From Baton Rouge, LA Area
(P4/L4) 144
A4 Vapor-Phase Organics in Ambient Air From Baton Rouge, LA Area
(P5/L2) 145
A3 Vapor-Phase Organics in Ambient Air From Baton Rouge, LA Area
(P5/I3) 147
A6 Vapor-Phase Organics in Ambient Air From Baton Rouge, LA Area
(P6/L3) 149
A7 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (PI/LI - B/T2> 152
xii
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TABLES CONT'D.
Page
AS Vapor-Phase Halogenated and Other Selected Orgaaics in Ambient
Air From Lake Charles, LA (Pl/H - A/T^ 153
A9 Vapor-Phase Halogenated and Other Selected Orgaaics in Ambient
Air From Lake Charles, LA (P3/L1 - A/T2) ISA
A10 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air from Lake Charles, LA (P3/L1 - B2/T2) 155
All Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (P3/L1 - B2/?2) 156
A12 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (P4/L1 - B1/T2) 157
A13 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, La (P4/L1 - B/T2) 158
A14 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (P4/L1 - A2/T3) 159
A15 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (P5/L1 - B2/T2) 160
A16 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (P5/L1 - A/T^ 161
A17 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Lake Charles, LA (P5/L1 - B1/T2) 162
A1S Vapor-Phase Organics in Ambient Air From Lake Charles, LA
(P7/L3) 163
A19 Vapor-Phase Orgaaics in Ambient Air From Lake Charles, LA
(P8/L1) 165
A20 Vapor-Phase Halogenated and Other Selected Organics in Ambient
Air From Beaumont, TX (P2/L2) 163
A21 Vapor-Phase Organics in Ambient Air from Beaumont, TX (P4/L3). . 170
A22 Vapor-Phase Organics Identified in Ambient Air From Beaumont, TX
Vicinity (P3/L3) 172
A23 Vapor-Phase Organics Identified in Ambient Air From Beamont, TX
Vicinity (P5/L1) 174
xiii
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TABLES CONT'D.
A24 Vapor-Phase Organics Identified in Ambient Air From Beaumoat, TX
Vicinity (P6/L2) 176
A25 Vapor-Phase Organics Identified in Ambient Air From Houston, TX
(P9/L2) 179
A26 Vapor-Phase Organics Identified in Ambient Air From Houston, IX
CPU/13) 181
A27 Vapor-Phase Organics Identified in Ambient Air From Houston, TX
CP13/L4) 183
81 Vapor-Phase Halogenated Chemicals - EPA Region VI 187
xix
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ACKNOWLEDGEMENTS
The valuable assistance of Dr. K. Tomer is gratefully appreciated for
the analysis of samples by high resolution gas-liquid chromatograpby, electron
impact and negative chemical ionization/mass spectrooetry/ computer. Mr. D.
Utterback is acknowledged for his valuable support during the field collection
of ambient air samples.
The authors extend their gratitude to the personnel at the EPA Regional
Offices and industrial sites for their cooperation. The constant encourage-
ment and constructive criticisms of Mr. K. Xrost of NESC, STP, NC are apprecia-
ted.
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SECTION 1
I3TTRODUCTION
The need to know what chemicals nay escape into the environment and at
what level they may be harmful leads one to rather quickly ascertain that
until compounds are identified with certainty and accurately measured, then
effective controls of these chemicals is essentially impossible (1). Our
society has increasingly become aware of the presence of trace amounts and
sometimes far more than just trace amounts of hazardous organics which have
entered the environment inadvertently or otherwise. There is scarcely any
edition of a newspaper or a new magazine that does not contain a report of
some new environmental mishap. The classic example is, of course, the Old
Love Canal incident. Awareness has steadily increased that the ecological
balance is an extremely fragile thing which can very readily be disturbed by
the introduction of man-made products in a wide variety of areas. The
conmerical production and use of synthetic organic chemicals certainly
constitutes a possible major source of insult to the ecological balance.
Synthetic organic chemical production in the United States alone has
increased over the last 30 years at an annual rate of 11%. Types of direct
chemical introduction are exemplified by the widespread use of pesticides,
fungicides, herbicides, and insecticides, to name just a few of the organic
chemicals used extensively in today's society (2).
This fact of environmental contamination coupled with Federal regulation
to protect the environment from toxic chemicals has certainly placed a great
burden on the analytical chemist (3). In analysis of vapor- phase organics
in the atmosphere, the analyst is called upon to both identify and measure
organic substances. A tremendous range of atmospheric conditions, i.e.
rural to urban, and pollution sources, mobile to industrial (anthropoge-
nic/non-anthropogenic) is encountered. Indeed, as a result there has been
a heavy burden placed upon the separation sciences and instrumental develop-
ment for the analysis of vapor-phase organics.
During the past several years research has been conducted on the develop-
ment of a method for the collection and analysis of vapor-phase organics
including carcinogenic and mutagenic substances. The developed techniques
were to achieve ppt detection limits. During the development of these
techniques, a number of facets have required attention for successful comple-
tion of this concept (4). A concise presentation of the overall components
envisioned to encompass the analysis of organic vapors in ambient air using
high resolution gas chromatography/mass spectrometry/cooputer has been
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discussed (4). This research program begins to evaluate the various compo-
nents which have been assembled as a complete analytical system for organic
analysis.
The objectives of this program are to improve on techniques and/or
devices within this concept, and to provide the best technology available
for complete characterization and quantification of vapor-phase organics in
the atmosphere. This report discusses several of these areas: (1) improve-
ments in the preparation of high resolution columns for the analysis of
non-polar, semi-polar and polar organic vapor-phase constituents; (2) the
increased sensitivity and specificity offered by gas chromatography negative
chemical ionization mass spectrometry; (3) potential in situ reactions which
may occur on sorbents during the collection of vapor-phase organics; and (4)
the application of the improved technology to the qualitative and quantitative
analysis of vapor-phase organics in ambient air from several geographical
areas within the Continental U.S.
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SECTION 2
CONCLUSIONS
Studies were conducted on the preparation and evaluation of wide-bore
wall-coated open tubular (VCOT) columns for organic vapor-phase analysis.
The previous problems associated with the use of capillary columns such as
adsorption were substantially reduced with WCOTs prepared by the silanized
and barium carbonate treatment methods described in this report. Columns of
choice which provided a large linear dynamic range for qualitative and
quantitative analysis of vapor-phase organics were 1.0 M stationary film
thick wide-bore WCOT. Columns were 0.5 mm i.d. x 75 m in length coated with
SE-30 stationary phase. In conjunction with the use of capillaries for
analysis of vapor phase organics, a series of performance criteria were
developed which insure their chromatographic quality. The criteria were:
(a) percent peak asymmetry factor (PAF) to measure the extent of overloading
[capacity] and adsorption of the column; (b) effective Height Equivalent to
a Theoretical plate (HETP); (c) separation number [SN]; (d) resolution; and
(e) acidity and basicity. The performance mixture consists of ethylbenzene,
£-xylene, octane, decane, 1-octanol, nonanone, acetophenone, 2,6-dimethylphe-
nol and 2,6-dimethylaniline. The performance mixture was used daily to
assess the capillary column's performance and develop historical data on its
performance as well as to insure that the capillary continues to meet speci-
fied performance criteria for vapor-phase organic analysis.
Gas chromatography negative ion chemical ionization/mass spectrometry/
computer (NICI) analysis of organic vapor phase compounds was demonstrated
to be a useful method. The utility of this technique was exemplified with
the determination of halogen-containing compounds in complex atmospheric
samples. The technique is useful for rapid screening of samples for the
presence of chlorinated, brominated and iodine-containing compounds.
Studies were conducted on ui situ reactions which potentially occur as
the result of the presence of criteria pollutants (ozone, NO, N02, NO ),
molecular halogens and olefins simultaneously occurring in the atmospheres
samples. Although ozonization and halogenation of olefinic compounds were
detected when atmospheres containing reactive inorganic gases and molecular
halogens were collected on sorbent cartridges, the problems associated with
these reactions were considerably reduced below the detection limit when the
particulate filter was impregnated with sodium thiosulfate. Ozonization of
olefinic compounds was detected as well as chlorination and bromination of
olefins. However, difficulties exist in discerning between reactions associa-
ted with the collection device and those which are a result of a very rapid
atmospheric reaction. The primary in situ reaction products that were
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detected when molecular chlorine was added to ambient air were chlorinated
cyclohexanes derived from eadogeneous cyclohexene. Also bromofomt was a
principal reaction product when bromine was added to the ambient air. The
use of deuterated compounds in studying ui situ reactions facilitates the
differentiation between endogenous, halogenated hydrocarbons and those which
are formed as a result of an in situ reaction when GC/MS is employed. The
use of deuterated compounds is recommended when sampling reactive atmospheres
containing molecular halogens. In all of the in situ reaction studies,
ozone appeared to play a role in facilitating these reactions while in its
absence they were considerably reduced.
Quantification of selected organic compounds in ambient air requires
that the gas chromatographic/mass spectrometric/computer system be standardi-
zed in order to obtain reproducible and accurate data. Research was conducted
to achieve reproducible and quantitative data from a mass spectrometer by
incorporating a number of criteria that were delineated to serve as guidelines
to achieve this objective. Perfluorotoluene was used as a standard compound
to represent the m/z range of interest in the analysis and to insure that
the calibration of the mass spectrometer was within specified tolerances
(mass intensities) for an optimum standard spectrum. A relationship between
the percent standard deviation (coefficient of variation) of the relative
molar response ratios as a function of the relative retention order for
selected organics was found and the highest degree of quantitative precision
was obtained for the elution of internal standards near the compounds of
interest. The constancy of relative molar response ratios over the dynamic
mass (quantity) range of analysis was studied and found to be linear for the
WCOT capillaries which were developed and evaluated under this program.
Several levels of compound identification have been delineated which
defines the degree of certainty of the identify of an organic compound. The
five levels of identification were: (1) computer identification [lowest
level of certainty]; (2) manual interpretation; (3) manual interpretation
plus retention times/boiling point of compound; (4) manual interpretation
plus retention times of authentic compound; and (5) level (4) plus independent
confirmation techniques.
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SECTION 3
RECOMMENDATIONS
During the course of this research program, a number of areas have come
to light which require further attention. Four major phases of research
should be expanded and pursued:
(1) Further evaluation of capillary columns should be conducted for
the analysis of hazardous [amtagenie, carcinogenic, toxic] subs-
tances collected from the ambient air. These evaluations should
include the examination of the flexible fused silica columns
coated with non-polar, semi-polar and polar phases. Also, narrow
bore vs. wide-bore capillaries and thin film vs. thick films
should be examined according to the performance criteria specified
in this report. Research should be conducted on the selection of
an adequate polar phase for the analysis of polar vapor-phase
organics in ambient air.
(2) Research effort should be devoted to examining the optimum operating
parameters for negative and positive chemical ionization of vapor
phase organics. Research into a variety of reagent gases available
for use in chemical ionization should be conducted to ascertain
the possibility of developing operating parameters which are
selective for chemical classes as well as enhanced sensitivity.
Because negative ion chemical ionization is a relatively new tool,
this area of research appears to be virgin and requires considerable
study to fully utilize the selectivity and high sensitivity of
this method.
(3) Additional studies are recommended on potential in situ reactions
associated with the Tenax GC collection device. Particular emphasis
should be placed on the potential artifacts which may occur under
field sampling conditions and, if any problems exist, to delineate
procedures which might deplete or scavenge the reactive gases
prior to the collection of the organic vapor-phase fraction.
and (4) The use of deuterated internal standards should be developed for
the quantitative collection and analysis of vapor-phase organics.
Techniques for the sparging of ambient air with deuterated com-
pounds during the sampling period should be developed in order to
provide a means for the assessment of the collection efficiency
and recovery of vapor-phase organics as well as to uncover any
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potential in situ reactions which might have occurred during am-
bient air sampling.
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SECTION 4
PROGRAM OBJECTIVES
The overall broad term objective was to evaluate methodology encompassing
the use of a solid sorbent collection device for the collection of vapor-phase
organics in combination with gas chromatography/mass spectronetry/computer
for their analysis. The specific aims of this program were to evaluate thas
methodology while applying it to 10 different sites within the Continental
U.S. The limitations and the overall analysis capability were documented
with research improvements to be implemented to correct any uncovered defici-
encies. This program was divided into four general objectives:
(1) To collect and analyze samples from one site for a minimum of 4-5
days to obtain qualitative and/or quantitative data concerning
selected vapor-phase organics occurring in ambient air. These
data were to be reduced and presented in reports to the Project
Officer and any improvements in the analytical methodology necessary
to achieve the desired results were to be documented prior to the
next site visit. Additional sites were to be visited in sequence
with essentially the same format: namely, effecting what improve-
ments were necessary to maximize analysis capability. During
field evaluation of techniques qualitative and quantitative analysis
of ambient air samples for selected constituents was also to be
performed.
(2) To summarize the overall analysis capability highlighting and
recommending innovations or revisions in the methodology made as
a result of the test studies conducted while applying the capability
at the sites visited.
(3) To provide a listing of suspected toxic pollutants which were
identified in ambient air samples. Particular emphasis was to be
placed upon known or suspected carcinogens and profiling these
pollutants endemic to each site as they were studied.
and (4) To transfer the latest technological improvements developed under
this research program to the on-going EPA in-house research ef-
fort. To furnish any necessary hardware and/or technology and to
demonstrate the operation of the methodology for the EPA's in-house
function.
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As part of this objective, full documentation was to be provided for the new
technical developments or modifications made as a result of the evaluation
of the basic GC/MS/computer analysis system.
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SECTION 5
PREPARATION OF WIDE BORE WCOT COLUMNS FOR ORGANIC VAPOR-PHASE ANALYSIS
GENERAL OBJECTIVES
One of the objectives of this program has been to improve on the glass
capillary technology which is used in the basic GC/MS method for analysis of
vapor-phase organics in ambient air. Problems associated with the columns
previously employed such as SE-30 or OV-101 coated SCOT columns have been
the extraordinary adsorption of polar organic components which are collected
and thermally desorbed from the Tenax GC sampling cartridge. In general the
SCOT columns were adequate for the analysis of non-polar and semi-polar
materials, e.g., alkanes, aliyl aromatics, halogenated hydrocarbons and
oxygenated compounds such as aldehydes and ketones. However, with the more
polar substances these columns exhibited a high degree of adsorption during
chromatography of low levels (ppt) of organics. This problem is unacceptable
for two reasons. First, it precludes the chromatography of acidic compounds
such as phenols and bases. Secondly, when adsorption of organics on the
capillary column becomes significant, then the use of relative molar response
factors becomes invalid. This is due to the noa-linearity of response when
chromatographing low quantities of organics. For accurate usage of relative
molar response factors, linearity of response over the dynamic range of
interest and the extrapolation of the response curves through an intercept
of zero is necessary.
In addition to the problem of adsorption on SCOT capillaries, the
reproducible preparation of the SCOT capillary with silanized fumed silicon
dioxide as the support has been difficult. The quality of commercially
available material has varied from batch to batch. The quality control
steps employed in our laboratory for the preparation of SCOT capillaries
requires testing the silanized fumed silicon dioxide with a solution of
methyl red to ascertain whether it is neutral. This simple test has revealed
batch to batch variations.
For these reasons, an investigation into the preparation of wide bore
WCOT columns for the analysis of organic vapor-phase compounds was instituted.
Furthermore, while retaining capacity, the resolution of these columns is
superior to the SCOT. This section discusses the characteristics of WCOT
columns, their preparation, performance, and their application to the analysis
of vapor-phase organics in the ambient air (Section 8).
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INTRODUCTION TO WCOTS
There are several arguments for preparing capillaries in a research
laboratory. Among these arguments are that they offer an opportunity for
investigators to acquire a better understanding of this basic tool. It also
allows for more useful applications of the technique to a variety of problems
which otherwise would be limited to what is commercially available. Finally
one of the major advantages is that the full usage of this technique is
possible since the researcher may tailor-make the capillary to fit a specific
analytical problem.
A discussion of glass capillary technology is presented which has been
synthesized from a number of literature sources with the major contributions
from K. Grob's laboratory (7).
Characteristics of Glass/Quartz
Among the merits of glass/quartz vs. metal as a support or container
for the stationary phase are that it is: (1) transparent; (2) readily
available; and (3) offers a variety of approaches for the modification of
the surface for tailor-making columns. However, it is not without its
problems since quartz is ill-defined and can be considered as a "quasi-liquid"
material, i.e., there is always some internal diffusion of metal ions. It
has been demonstrated that the leaching of heavy metal ions from the surface
of glass (soft and pyrex) is only a temporary solution since after a period
of time and particularly at elevated temperatures, the heavy metal ions
migrate from the internal matrix to the surface (5). However, it is still
necessary to remove metal ions from the surface since they can be involved
in catalytic decomposition of organics during chromatography. Thus, all
glass materials must be pretreated by a method which leaches the calcium,
magnesium, iron, boron and lead that occur with different types of glasses.
A variety of glass types are available. In fact, this is one of the
major disadvantages with the use of glass as a container. In general pyrex
glass can be considered to be acidic, brittle and more compact in structure
than soft glass which is generally basic, has a more open structure and is
relatively stable mechanically. Because of the open structure of the soft
glass, the tendency for metal ions to migrate in the matrix is greater than
with pyrex. Fused silica has the lowest quantity of metal ions (6).
Requirement of Column Preparation
There are three general requirements in the preparation of wall coated
open tubular columns: (1) achieving wettability; (2) good deactivation; and
(3) high thermal stability. During the preparation of coated glass capillary
columns, it is important that the film of stationary phase is homogeneous
throughout the open tubular column since this gives the highest separation
efficiency. When drops or pools of stationary phase fora a reduced efficiency
is observed. The glass surface must be entirely deactivated, i.e., there
are no active sites which can participate in catalysis or adsorption.
Deactivation includes removal of metal ions and chemically shielding polar
groups (e.£., silanol). When a homogeneous film and good deactivation are
10
-------
achieved, then the column will exhibit excellent thermal stability and high
efficiencies.
There are two principal forms of wetting (7). The first involves inter-
molecular forces between the stationary phase and the glass vail. This
constitutes "chemical" wettability. It nay be achieved through hydro-
gen bonding, n-n interactions or Van der Waals forces. The use of the 0
charge transfer such as observed with nitrile bonding has often failed to
provide chemical wettability. A second type of wettability is "topographic"
or "geometric". Essentially this constitutes the roughening of the surface
to produce a lower contact angle between the stationary phase and the glass
surface. The topographic wetting produces a "quasi-film"; a reduced effi-
ciency is observed. In practice a combination of the two forms to achieve
wetting may be necessary; however, this is dictated by the interaction
between the phase and the glass capillary wall. For example, with an
apolar phase a smooth inactive surface is sufficient. With a moderately
polar stationary phase, a roughened surface that has been inactivated is
generally the best compromise. Finally, with polar stationary phases, a
rough and active surface allows for the best wetting or most homogeneous
film.
There are two generally accepted procedures for the deactivation of the
glass surface. The first involves the production of a "surface bonded
layer" of polar compounds with a glass wall. This is achieved by using com-
pounds such as Carbowaxes, triethanolamines, etc. The advantages of this
approach is that the deactivation is an easy step to execute and deactiva-
tion can be selective for specific compound types. The disadvantage occurs
in its thermal stability where the upper limit is "-2500C with the Carbowax
20M method. The second procedure for deactivation involves silylation. The
greatest advantage of this approach is in its thermal stability which can be
>350°C. The problem associated with silylation is that the surface of the
silica needs to be properly prepared which is difficult and can result in
reduced efficiency because of poor film stability even when using apolar
phases. The principal utility of silylation is obviously to eliminate the oxide
phase on the glass surface. To be successful, it is necessary to maximize
the density of the silanol groups and minimize dehydration which occurs
inevitably during the drawing of glass capillaries because of the high
temperatures required to soften the glass. Also it is necessary to remove
excess water prior to instituting the reaction. In general, the best results
are obtained with hexamethyldisilazane which has been reported by Grob
(7).
One of the principal approaches developed by Grob for roughening the
surface of a glass wall is the "barium carbonate method". This approach is
for roughening only and not deactivating the glass column. The primary
purpose of a roughened surface is to increase the thermal stability of the
stationary film. The extent of the roughening is controlled by the starting
concentration of barium hydroxide which is converted to barium carbonate
crystals via C02 gas. For polar phases, a saturated solution is employed
while a 1:5 and 1:30 dilution is used for moderately polar and apolar sta-
tionary phases, respectively. According to Grob (7) the orientation of
the barium carbonate crystals is important for the production of a highly
11
-------
efficient column. For example glass surfaces which have not been leached to
remove ions yield barium carbonate needles standing in an erect position
while a leached glass surface produces needles lying down. The barium
carbonate roughened surface of a glass open tubular column can be considered
as slightly basic; however,when using a highly diluted barium hydroxide
solution with an extensively leached surface, it will be slightly acidic.
Other methods of roughening such as the etching of soft glasses produces
sodium chloride crystals; however, these are less stable to the presence of
water in the samples while not being any more active than barium carbonate
crystals. The production of sodium chloride crystals is less reproducible
than production of barium carbonate (7).
Coating Methods
There are three fundamental methods for coating a stationary phase on
the surface of a glass capillary column. These are static, static/forced
evaporation, and dynamic. The static method simply involves filling of
glass capillary column with the stationary phase dissolved in an appropriate
solvent at a concentration whereupon after evaporating the solvent, the
stationary film is formed at an exactly predictable thickness. Upon filling
the capillary, one end is sealed and then a vacuum is applied to the open
end.
The forced evaporation method has been described by several investigators
(7). The column after filling is sealed at one end and the open end is
screwed through a heated zone which vaporizes the phase/solvent mixture.
The stationary phase is "sprayed" and adheres to the surface of the glass.
The dynamic method requires pushing a plug of stationary phase/solvent
mixture through the capillary using a mercury plug behind the coating solution.
The film thickness produced depends upon the viscosity of the solution and
the velocity used. The deposited film is subject to evaporation-condensation
of the solvent as it passes through the capillary. The technique generally
cannot be used with gum-type phases. The use of the mercury plug facilitates
the dynamic coating method; however, some solvents such as acetone are not
suitable (7).
Column Evaluation
During the evaluation of glass capillary columns, documentation of
performance is required for: (1) adsorption [by the use of polar test
compounds]; (2) acidity/basicity [by the use of acid and base in the test
mixture); (3) separation efficiency [by the use of a pair of homologs which
do not adsorb]; and (4) film thickness [which is related to capacity and is
established by the elution temperature for a reference standard component].
Adsorption characteristics can be expressed in two ways. The first may
be exhibited by a process which produces tailing or broad chromatographic
peaks with an incorrect area for the compound relative to the amount that
was chromatographed. In the second case, adsorption may be expressed by a
perfectly symmetrical chromatographic peak; however, the area is reduced
12
-------
with respect to that which theoretically should have been obtained for the
amount chromatographed. Thus, reduced sensitivity is observed. In the
first case, the adsorption may occur via a mechanism which is reversible
whereas in the second it is not.
Adsorption expressed as chrotnatograptvic peak tailing may be traced to
active sites in the column which may be due to hydrogen bonding, n-n inter-
action, or complexation with metal impurities. A test mixture which con-
tains 1-octanol, a-nonanone, and naphthalene facilitates the differentiation
of these types of adsorption. Adsorption undergoing the second mechanism
generally can be attributed to acidity or basicity of the column. To detect
these properties, 2,6-dimethylaniline and 2,6-dinethylphenol are often used.
However, these compounds only reveal relatively strong acid/base characteris-
tics of the capillary. To demonstrate weakly acidic and basic characteristics
in a chromatographic column, 2-ethylhexanoic acid and dicyclohexylamine may
be used (7).
MATERIALS AND METHODS
Drawing Capillaries
Glass capillaries were drawn from 1.22 m lengths of pyrex glass (8 mm
o.d. x 4 mm i.d.) to yield an internal diameter of either 0.36 ami or 0.47 mm
using a Hupe and Busch (Hewlett-Packard Corp., Avondale, PA) or Shimadzu
(Seisakusho LTD, Koyoto, Japan) drawing machines. The pyrex glass tube was
washed with 50 ml each of IN HC1, water and dried with acetone prior to
drawing.
Pretreataent of Capillaries
Acid Leaching—
To produce-a pure silica surface by eliminating any oxide layer and to
produce a maximum density of silanol groups, acid leaching was performed on
the capillary. The capillary column was filled with 20% HC1 by introducing
the HC1 solution into 10% of the total capillary length. An inert gas (N2)
was used to force the HC1 solution through the capillary and the process was
continued until 2% of the solution remained in the capillary. The filled
end of the capillary was flame sealed and the open end connected to a
vacuum source. A vacuum was created in the capillary for "-5 min and the end
was flame sealed prior to disconnecting the vacuum. The capillary was then
heated at 180°C for ^18 h. Upon cooling, the capillary was opened at both
ends and the remaining HC1 solution was slowly displaced by introducing
distilled water which filled ^25% of the capillary volume. Immediately
following the water plug, an equal volume of methanol was introduced.
Capillaries designated for the BaC03 method were heated for 5 h at
260-280°C under a low flow of nitrogen gas (e.g., 0.2 ata/50 m length). For
capillaries to be silanized, the glass column was heated to 250°C with both
open ends connected to a vacuum source (water aspirator) outside the oven.
The column was heated for 13 h (for US pyrex glass).
13
-------
Barium Carbonate Roughened Surface--
Solutions of Ba(OH)2 (Bl-saturated, B2-l:5 of saturation, and B3-l:30
of saturation each containing 4, 2 and 1 ppm of Marlazin L10, respectively)
were prepared.
Into ^5 coils of the previously HC1 leached and dehydrated capillaries,
0.5% HC1 was drawn. The appropriate Ba(OH)2 reagent (31-B3) was drawn into
10 coils of the capillary with an air plug interposed between the HC1 and
Ba(OH)2 solutions. An air plug was then also introduced at the rear end of
the Ba(OH)2 solution (inlet end of the capillary) O20 cm long for Bl and B2
and 50 cm for B3). While protecting the column from temperature gradients,
C02 gas was flushed into the capillary to move the solutions at a rate of
1.5 - 2 cm/sec (25-30 sec/40 cm coil). Care was instituted to prevent the
interruption of the carbon dioxide flow. The exit end of the capillary was
connected to a "buffer" column of a similar internal diameter and ^5-10 m
in length. As soon as the rear meniscus of a Ba(OH}2 solution entered into
the buffer column, the C02 gas supply was replaced by an inert gas such as
nitrogen at a pressure of 0.2 atm. After M.O nin, or when the C02 was
flushed from the column, acetone was introduced into ^25% of the column
length at a rate of 2-3 cm/sec (15-20 sec/40 on coil) and passed through to
dry it. Vacuum was applied to one end for 5 oin and the column was then
dried in an oven at 280°C for 30 min at 0.3-0.5 atm of N2.
For glass capillaries treated with the Bl solution, the capillary was
directly coated with polar stationary phases. For the B2 treated columns,
further preparation was necessary. The glass capillary was quickly rinsed
with a 1% solution of Carbowax 1000 in CH2C12 at a rate of 20 sec/coil.
Both ends of the capillary were connected to a vacuum source via a tee and
the vacuum applied for 5 min. Both ends of the column were then flame
sealed prior to disconnecting the vacuum source. The capillary was heated
to 280°C for 18 h. Upon cooling, the ends were cut and fire polished and
rinsed with methylene chloride. The glass capillary column containing BaC03
from B2 treatment was then ready for coating with moderately polar phases
such as OV-17 and nitrile phases.
For capillaries prepared with the 83 Ba(OH)2 solution, the columns were
quickly rinsed with 0.1% solution of Triton 300 in C^Cla- A vacuum was
applied to one end for 5 min. With the application of a 0.2 ata pressure of
inert carrier gas (N2), the capillary was then heated to 250°C for 30 min.
Upon cooling, the capillary was then rinsed with CH2C12 and dried under N2
flow. This column was then ready for coating with apolar phases.
Reactivation by Silanization—
To produce essentially a totally non-adsorptive and non-catalytic
surface with extreme heat stability in capillaries, a silanization technique
was employed. Hexamethyldisilazane (Applied Science, State College, PA) was
drawn into a dehydrated capillary until ^10% of the capillary length was
filled with the reagent. Using a head pressure of N2 gas, the reagent was
pushed through the capillary at a rate of ^2 cm/sec. No buffer column was
employed. When the reagent had passed through the capillary, the gas supply
was immediately disconnected and a vacuum was applied to both ends via a
tee. A vacuum was applied for "*5 oin for a 20 m length (10 min for 50 m
14
-------
and 15 oin for 75 m). Both ends of the capillary were flame sealed prior to
disconnecting the vacuum. The capillary was then heated to 400°C for 12 h.
The degree of silanization is checked by breaking one of the ends of
the capillary under toluene. When a few coils were filled with toluene from
the vacuum, the column was switched to methanol and then to ether. When the
front end of the toluene plug ceased to move, the length of the empty tubing
was noted. As a general rule, 5-10% of the total length which remains empty
indicates mild silanization while 20-50% of an empty column indicates heavy
silanization. The second end of the capillary was opened and the liquids
were forced through the capillary by applying S2 gas to the end which contai-
ned ether. Various intensity of silanization produces powdery plugs which
can impair movement. The problem can be overcome by gently warming the
plugged area with a small flame. The capillary was then ready for coating
with apolar phases.
Coatiag Techniques
'Static—
The coating solution was prepared according to the desired film thickness
(FT). This is given by the following relationship:
FT (pM) = 0.25 D (mm) x C.
where 0 = the internal diameter,
C = the concentration of phase in parts-per-thousand (W/V)
For apolar and polar stationary phases, n-pentane and oethylene chloride
were the solvents used, respectively. In all cases the solutions were
freshly prepared except for gum phases which were allowed to sit for "*4 hrs
after mixing with the solvent.
One end of the capillary column was inserted through a silicone rubber
fitting into the coating solution. The bottle containing the coating solution
was connected to a source of N2 gas at M).5 ato, and the capillary was
filled with coating solution and flushed with an additional 25% (of column
length) with coating solution. The gas pressure then was reduced to 0.1 atai
and the exit end of the column was inserted into water glass. This procedure
insures that small air bubbles are flushed from the column end. The inlet
end of the capillary was then removed from the bottle containing the coating
solution. A low pressure was applied to the inlet end to push the meniscus
of the water glass to a few cm from the end. The pressure was then disconnec-
ted. The water glass bottle was tilted in such a way that the column end
was located in the water glass and not contaminated with coating solution.
A low vacuum was immediately applied to the inlet end to move the meniscus
1-2 cm. The exit end was removed from the water glass and immediately the
excess water glass was wiped from the capillary end. The water glass and
interface to the coating solution were checked for gas bubbles. In the
event that there were any, the procedure was repeated by cutting the water
glass plug and applying low pressure to the inlet end. This method of
sealing was conducted in order to avoid the introduction of air bubbles
15
-------
between the water glass and the coating solution. The column was then
allowed to sit for 6-3 h or overnight prior to evaporation of the solvent.
The capillary column was inserted into a water bath at room temperature
with both ends ~6 on out of the bath. The open end of the capillary was
then attached to a vacuum source (water aspirator) and a low vacuum was
initially applied and then a higher vacuum when the solvent meniscus had
moved to the interior of the capillary. For capillaries >50 o in length the
water bath was slowly heated to 40°C over a 1 h period.
Once the solvent had evaporated the closed end was opened. The vacuum
was continued for a few minutes and then disconnected. The capillary was
then prepared for installation.
Static/Forced Evaporation—
The coating of glass capillaries using a forced evaporation technique
has been previously reported (3).
Dynamic—
Into an empty glass capillary column, a plug of coating solution was
drawn (10-15 coils). Immediately following the coating solution, a 10 cm
plug of mercury was also drawn. Then the column was subjected to a gas
pressure head at the end containing the mercury plug and the mercury plug
was pushed through the column at a rate "»1 min/turn. A buffer column was
attached to the other end of the capillary in order to maintain a uniform
velocity of the coating solution. During the dynamic coating process, the
capillary was also protected from temperature gradients.
Preparation of Capillary Ends for Installation
Straightening of capillary ends which had been coated with stationary
phase was accomplished by using oxygen or air flowing through the column
during the straightening process. Prior to straightening, capillaries
containing film thicknesses of 0.8-1.0 microns were washed free of phase by
introducing solvent into 1-1 1/2 coils of the column using a 100 pL syringe.
This step was also performed under a positive pressure. Straightening was
accomplished by slowly rotating the capillary into a small microflame (1/2-1"
in length), allowing gravity to pull the softened glass. The column ends
were flamed to avoid problems with insertion through ferrules or septa.
Hexane was used to remove silicone oils and gums from columns which had
been straightened while CHjClj was used for Carbowaxes and other polar
phases. Injection and withdrawal was repeated three times. The capillary
ends were then deactivated by introducing a solution of 0.1% Carbowax 1000
in CH2C12-
RESULTS AND DISCUSSION
Performance Criteria
The glass capillary columns were evaluated according to the following
criteria:
16
-------
(1) percent peak asymmetry factor (PAF)
I PAF = | x 100
where B = the area of the back half of a chromatographic peak
F - area of the front half of the chromatograpbic peak both
measured 10% above baseline
(2) effective Height Equivalent to a Theoretical Plate (HETPgff)
off = 1
611 5.54 (X/Yr
where X = the corrected retention distance for sweep time of the com-
pound,
Y = chromatographic peak width at 1/2 peak height,
L = column length (mm)
(3) separation number (SN)
SN = „ D ,. -1
where D = the distance between two peaks,
W.,W = widths at 1/2 height
(4) resolution (R)
2 A W
R =
where AW = average base width,
W = peak width at base.
(5) Acidity and Basicity
. . _ weak base (peak area or height)
y - acet0pneilone (peak area or height)
_ _ weak acid (peak area or height)
asici y - acet0pnenone (peafe area or height)
These criteria were used to assess the preparation of a number of glass
capillary columns to delineate a systematic method for discerning the utility
of glass capillary columns for ambient air pollution analysis. Performance
criteria are necessary in order to provide quality control and quality
assurance on the analysis of ambient air samples utilizing GC/MS/COMP with
glass capillary columns. An important aspect of analysis with glass capillary
columns is the continual assessment of the performance of a new column as it
ages in order to discern when the column is no longer useful for this type
of analysis. The criteriona of percent peak asymmetry factor has been
incorporated as a quality control step in the selection and usage of
17
-------
capillary columns for ambient air pollution qualitative and quantitative
analysis. The compounds which have been selected for assessing the performance
of the columns are: 1-octanol, 5-aonanone and acetophenone. The use of
these compounds provides information as to the degree of adsorption and the
type of adsorption mechanisms during the interactions between solute molecules
and the glass capillary wall. 1-Octanol serves as a means of determining
the extent of deactivation of the glass surface and principally singles out
adsorption due to hydrogen bonding. The hydrogen bonding which may occur
results from incomplete deactivation of the silanol groups on a glass
surface. Furthermore, the use of 5-nonanone assesses the extent of adsorp-
tion occurring from a n-n adsorption mechanism. Finally, adsorption of
acetophenone incorporates the characteristics of 5-nonanone plus the aroma-
tic n ring system of acetophenone which assist in the determination of the
extent of the adsorption due to the presence of metal impurities on the
glass surface.
The acidity and basicity of the capillary column are assessed by the
adsorption of weak bases and acids, respectively. This performance test in-
volves the chromatography of 2,6-dimethylaniline and 2,6-dimethylphenol and
their respective peak areas (or heights) are ratioed to the peak area for
acetophenone. Thus if the percent asymmetry factor is low for acetophenone
(<250%)', then the acidity and basicity of the column can be assessed using
this relationship. In particular the capillary columns prepared by the barium
carbonate procedure exhibit a slight basicity and thus the irreversible adsorp-
tion of 2,6-dimethylphenol is observed.
Finally the resolution and separation number of a column is determined in
order to insure that the complex ambient air pollution mixture can be adequately
resolved for the qualitative and quantitative analysis to be performed. For this
purpose, the resolution between ethylbenzene and £-xylene and the separation
number for octane and decane are determined.
Case Examples of Performance Evaluation of Glass Capillary Columns
Table 1 presents the results for the evaluation of a commercial glass
capillary column. The resolution, separation number, percent asymmetry factor
and acidity and basicity of the column are given. In general the column
exhibits very low adsorption characteristics and is acceptable for the
analysis of semi-polar compounds. The column exhibits slight acidity. The
resolution as measured for ethylbenzene and £-xylene is *l while the separa-
tion number is 50. Figure 1 presents the chromatogram obtained utilizing
the operating parameters for the GC/MS/COMP system given in Section 8. The
performance mixture contained perfluorobenzene, perfluorotoluene, ethyl-
benzene, £-xylene, octane, decane, 1-octanol, 5-nonanone, acetophenone, 2,6-
dimethylaniline and 2,6-dimethylphenol which were loaded onto Tenax GC
sampling cartridges and then thermally desorbed using the standard condi-
tions described in Section 8. The commercial capillary was an SE-30 wall
coated open tubular with the dimensions of 0.5 mm i.d. x 27 m in length.
The film thickness was 0.41 microns. Figures 2-11 present the single ion
plots for the components in the performance mixture.
18
-------
Table 1. EVALUATION OF A COMMERCIAL GLASS CAPILLARY3
Parameter
Resolution
Separation Ho.
% Peak Asymmetry Factor
Acidity
Basicity
Test Compound
Ethy Ibenzene : £-Xylene
Octane :Decane
1-Octanol
Noaaaone
Acetophenone
2,6-Dimethylaniline:Acetophenone
2 , 6-Dimethylpnenol : Acetophenoae
Value
1.0
50
200%
120%
150%
0.7
0.9
aS£-30 WCOT, 0.5 ami i.d. x 27 n, 0.41 p film thickness.
19
-------
21 ••
ro
o
ia.w-
-
•1C.
m
•I
3
ot a
§3
is
ft 0
8,3
O *M
3 M
rH 01
•4-4 (X
\-t
a.1
\
S
id
M
CJ
o
01
2
^*£ 192
- — • 1 1
IM 20*
4. it 8:29
6
BKI2I
01
S 8
01 01
N 'U
d I
o) r;|
rf)
T* ^
fj
M
ai at
2
.O
28
i-t
tf
I
pi
L. 331 »2 fl
3
01
0> O -H
o a . i
O 01 .1
a> n .c d
gaj (X cd
d tH . i
d o >> ^
01 d A .u
J= 1 W 4J
a. "-. 41
1r>i cs"
^ 5»7 53
0
d
3
0
0
r 5*
JlLuL
MM 4M 5M Mt SCAN
12: M 16:4* 2»:5» 25:69 1IIIE
Figure 1. GC/MS/COMP profile of performance mixture for capillary column evaluation
(SE-30 WCOT, 0.5 mm i.d. x 27 m, 0.41 \t film thickness; 30-250°C & 4°C/mln)
-------
186
0)
t:
s
g
O
3
14
0)
6«5«.
0)
g
o
M
0)
(X
IM
Figure 2.
I
2M
8:2*
12:3*
I
1*»
16:
SCAN
TIME
Extracted ion current profile of m/_z 186 for perfluorobenzeiie and perfluoro-
loluene in performance mixture (see Fig. 1 for operating conditions).
-------
• I
-a
236
296.071
ro
1—
3M
—I—
•low
Hi:-HI
6:2*
STAN
1IIIE
Figure 3.
lixtracted ion current profile of m/z 236 for perfluorotoluene In performance
mixture (aee Fig. 1 for operating condttlonu).
-------
1*9.*
I •.5M
SCAN
Tlllt
Extracted Ion current profile of m/z 41, 43, 57 and 114 for n-octane and n-decane
in performance mixture (see Fig. 1 for operating conditions).
-------
IM.tt
IM.*
57 _
I«M.«
1
g 6I68'
•
3 2 ,
o -S
Ai °' . 4i:£!?
1 . 1 Iv
„ I
• TI - | t i : | . ,
-
A i.
6168.
* «!so«
A A^^
6168.
i57.«!7
•i | 'i1 j- • !• it • | • i
6168.
142.442
* «.so»
* A
I 1 > 1 • 1 • 1 • 1
M'n ><• 'XlA^k itl.VM *vJ 'AM
jtW JWi VW DiTJ ot»o o^nn
. N «:.'(» 12:3* 16:4* ?«:5« 2Si«M TIKfc
Figure 5. Extracted ion current profile of m/z 41, 43, 57, and 142 of n-octane and n-decane
in performance mixture (see Fig. 1 for operating conditions).
-------
1641.0-
H
SI.015
J.32
IM.
r-j
196
IM.
553
1256*.
T
1256*.
1*6
Mc.cn
«.5M
IM
8:2«
12: It
16:4*
5M
2S:(
SCAN
Tlllt
Figure ft. Extracted ion current profile of ra/z 51, 81 and 106 for ethylbenzene and £-xylene
in performance mixture (see Fig. I for operating conditions).
-------
IM.t-
•1
IM.
UK.
IM.*
IM
131
4:1*
Figure 7.
8:2*
g
n
g
•s
0)
0)
1
3WI
12. («
1
J$L
JSL
•>««
i
64NI
l2fM.
M5.ni
1266*.
IM.932
t o.soa
SCAN
HUE
Extracted Ion current profile of m/js 91, 105 and 107 for ethylbenzene and p-xylene
In performance mixture (see Fig. 1 for operating conditions).
-------
Mil.
41
55 .
1
4488.
41.012
* §.«•
44B8.
5S.»I6
* •:•
4488.
56
tic.
IM
4:1*
•~1—
.'»!«
8:2*
i
T~
12:3*
JL
jlLi
16:4*
5W
6tW
»;«•
56.017
• St»»
56128.
SCAN
1IIIE
Figure 8. Extracted ion current profile of m/jz 41, 55 and 56 for 1-octanol in performance
mixture (see Fig. 1 for operating parameters).
-------
188.8
57 .
188.
58
It*
£ «
918.
1
li
188
4.18
Figure 9.
288
8:2«
Ill A ji
388
12:38
488
16:18
S88
28:f>0
688
25:68
• 168.
57.817
8.508
6168.
58.817
8.588
6168.
85.825
* 8.588
56128.
SCAN
TIDE
Extracted ion current profile of m/jz 57, 58, and 85 for 5-nonanone in performance
mixture (see Fig. 1 for operating parameters).
-------
W7
*-•
•a
vO
CN|
IK7.032
121 .
121.«36
k «.5M
33M.
tsJ
122 .
•1C.
11
ll
Li
IM
1;lt
2M
6:2H
3M
13:31
16:
5M
2«:5«
I22.«37
56128.
—I—
6tt»
25:««
SCAN
TIME
Figure 10. Extracted Ion current profile of m/z 107, 121 and 122 of 2,6-dimethylphenol
in performance mixture (aee Fig. 1 for operating parameters).
-------
IM.
121 .
IM.
o 122 .
IIC.
ii
i
8:2«
TT-
3M
I2i3«
s
I
TJ
16:4*
25:M
4448.
l«6.
* «.5M
4448.
121.«36
* t.SM
4448.
122.«17
* «.5««
56128.
SCAN
TIME
Figure 11. Extracted Ion current profile of m/z 106, 121, and 122 for 2,6-dlmethylaniline
In performance mixture (see Fig. 1 for operating parameters).
-------
Table 2 presents the performance obtained for a glass capillary column
prepared by the barium carbonate procedure. In this case the column was 75
m in length and contained a 1 micron film thickness of SE-30. The capillary
ml mm was evaluated immediately after its preparation and continually for a
period of six months and the performance was calculated for this entire
period of time and the standard deviation included. A column length of 75 m
has been found to be required to obtain sufficient resolution and separation
of the complex mixtures obtained from ambient air. It is suggested that the
resolution and separation number of the column be at least 1.3 and 70,
respectively. It is the experience of this laboratory that this is the
minimum requirement to obtain adequate information on the qualitative and
quantitative aspects of ambient air mixtures.
For the analysis of semi-polar compounds, the percent peak asymmetry
factor should be at a minimum within the ranges specified in Table 2. For
more polar compounds, the performance of the column must be far superior.
Figures 12-16 provide the extracted ion current profiles for the various
ions of the component in the performance mixtures used in calculating the
performance criteria.
Similar evaluation was conducted for the Grob silanized type glass
capillaries. The results were superior with respect to the percent asymmetry
factor for these compounds and the capillaries exhibited better non-basicity
characteristics. However, it is not known what the lifespan of the Grob
silanized column will be under continual usage for the analysis of ambient
air pollutants utilizing Tenax GC cartridges followed by thermal desorption.
The barium carbonate columns deactivated using Carbowax 20M and coated with
SE-30 have proven to be versatile and rugged for this application. Several
columns have been prepared and have exhibited lifespans of 6-9 months.
For the purpose of maintaining quality control during the analysis of
ambient air samples using the cartridge technique, it is recommended that
these performance criteria be adopted and that the performance mixture be
loaded onto the Tenax cartridge utilizing the flash evaporation technique
described in Section 8 with the performance mixture analyzed on a daily
basis. In this manner historical documentation of the performance of the
entire system including thermal desorption, chromatography and transfer to
the ion source can be developed and recorded. The incorporation of perfluoro-
toluene in the performance mixture serves the purpose of checking the mass
intensity calibration of the instrument under scanning capillary chromato-
graphy. The use of perfluorotoluene for calibration of mass and intensity
is dicussed in Section 8.
31
-------
Table 2. PERFORMANCE OF GLASS CAPILLARY PREPARED BY BARIUM CARBONATE PROCEDURE
Parameter
Test Compound(s)
Value + S.D. (C.V.)
Resolution
Separation No.
% Peak Asymmetry Factor
Acidity
Basicity
Ethylbenzene:£-Xylene
Octane:Decaue
1-Octanol
Nonanone
Acetophenone
2,6-Dimethylaniline:Acetophenone
2,6-Dimethylphenol:Acetophenone
1.30 + 11 (8)
73+6 (8)
239 + 141 (59)
130 + 32 (25)
260 + 34 (13)
1.00 + 0.07 (9)
0.82 + 0.03 (5)
SE-30 WCOT/BaCOa, 0.48 nun i.d. x 75 m, I ji film thickness. Capillary had been in use for analysis of
ambient air pollutants by GC/MS/COMP for six months when final evaluation was performed.
-------
SD
O
I
V
u
aj
C
U
C.
Q
m/z 105
CV!
IT C i-
U [-» Z
« e.
in
tu o c
— r.
a c *•.
— a. o
u. wi —
I
e
Scan No.
Figure 12. Extracted ion current profile of m/j: 105 for acetophenone
in calculating percent peak asymmetry factor.
33
-------
s
s
C\J
c
c:
Scan No.
Figure 13. Extracted ion current profile of W_z 91 for £-xylene
and ethylbenzene used in calculating resolution.
-------
s
s
I
it in — —
Scan No.
Figure 14. Extracted ion current profile of m/_z 70 and 84 for
1-octanol used for calculating percent peak asymmetry
factor.
35
-------
n e K
gKS
UJ fe
-------
s.
ll
J
u
o
T
Figure 16. Extracted ion current profile of m/z^ A3 for octane and decane used in calculating
separation number.
-------
SECTION 6
CAS CHROMATOGRAPHY/NEGATIVE CHEMICAL IONIZATION MASS SPECTROMETRY/
COMPUTER ANALYSIS OF AMBIENT AIR SAMPLES
INTRODUCTION
The prevalence of halogenated hydrocarbons in the environment is well
documented. In ambient air alone, over 250 halocarbons have been identified
by glass capillary GC/MS/computer. In a single air sample, often 10-50
halogenated hydrocarbons may be present along with the large number of other
organic vapor-phase compounds. Because of their wide spread occurrence and
the need for improvements in the selectivity of analysis for halogenated
compounds in ambient air, the technique of negative chemical ionization mass
spectrometry was investigated as a potential method for their analysis. The
collection device (Tenax GC) employed in the collection of organic vapor
phase compounds from ambient air is highly efficient since in a sample over
200 organic compounds are routinely detected. With the advent of an additio-
nal sorbent to collect the more volatile vapor-phase organics for which
Tenax GC is not suitable, an extremely complex mixture of compounds will be
presented to the GC/MS/computer system. In order to improve upon the selec-
tivity of analysis negative chemical ionization mass spectrometry was investi-
gated as a potential technique for halogenated compounds. Ultimately,
examination of negative chemical ionization (NCI) for measuring other chemical
classes through the judicious selection of reagent gases is a subject of
future investigations.
Electron capture in itself is a relatively old detection mode and has
been well studied. The series of potential non-dissociative and dissociative
reactions which can occur between a thermal energy electron and an organic
molecule possessing an appreciable electron capturing affinity has been
reviewed (9). These reactions are extremely important not only to the
understanding and utilization of the electron capture detector as a detector
for gas chromatography, but also in NCI mass spectrometry. Whether the
mechanism of electron capture is one of a dissociative or non-dissociative
nature depends upon the ability of the molecules to distribute the electron
charge via a resonance mechanism in the parent molecule or via resonance in
a product ion. In general, molecules which undergo dissociative electron
capture exhibit higher sensitivity than those which are non-dissociative.
Furthermore, as one increases the temperature the sensitivity also increases
for those molecules which undergo a dissociative mechanism. Conversely the
temperature sensitive relationship is inversely proportional for non-dissocia-
tive type mechanisms. In this section the new technique of NCI is briefly
examined as a potential tool for the selective detection of halogenated
38
-------
hydrocarbons. Furthermore its potential as a tool for rapidly screening for
the presence of halogenated hydrocarbons in ambient air samples is presented.
MATERIALS AND METHODS
Sampling
The collection of vapor phase organics from ambient air is described
under Section 8. Replicate samples which served as backup samples for those
subjected to conventional electron impact capillary GC/MS/computer analysis
were submitted to NCI analysis.
Instrumental Methods
An LKB Model 2091 GC/MS system was used in these studies. The mass
spectrometer was equipped with a POP/11-04 32K central processor computer
system. The data system contained a dual 24 million byte disk system,
nine-track Pertec IBM-compatible magnetic tape drive, a Versatec 800A
printer/plotter, an operator console and a Tektronix 4012 display. The
GC/MS system was equipped with a Pye-Unicam 104 gas chromatograph and a dual
ionization source for electron impact (El) and chemical ionization. A
single stage Becker-Ryhage separator interfaced the GC to the mass spectrome-
ter. Scan speeds (either parabolic or exponential) of 1-2 sec/mass decade
were used.
The operational parameters for NCI GC/MS analysis are given in Table 3.
The recovery of vapor-phase organics collected on Tenax GC cartridges was
achieved using standard operating parameters. The chromatographic column
was a 75 m glass SE-30 coated wide bore barium carbonate WCOT (Section 5).
RESULTS AND DISCUSSION
Negative chemical ionization mass spectrometry has great potential in
the analysis of vapor phase organics collected from ambient air. A case
example exhibiting its utility is exemplified for an ambient air sample
using El and NCI. The Tenax GC sampling cartridge was utilized to collect
vapor-phase organics for the subsequent analysis by negative chemical ioniza-
tion. Figure 17 depicts a GC/MS/COMP profile obtained by thermal desorptioa
of the Tenax GC cartridge using electron impact. Well over 100 compounds
were observed. However, when a corresponding duplicate sample was analyzed
utilizing the same technique except for operating the mass spectrometer in
the NCI mode, the results shown in Figure 18 were obtained. These results
represent a sample taken upwind from an industrial area in Deer Park, TX
(see Section 8). Representated are the reconstructed ion intensities for
35C1, 37C1, 79Br and 8lBr. By noting the chromatographic peaks at specific
retention times, the number and combination of chlorine and bromine atoms in
a molecule are clearly evident. Figure 19 depicts a profile for an ambient
air sample taken downwind from the same industrial area in Deer Park, TX.
In addition to the compounds which were detected in the upwind samples,
several new compounds are also detected in the downwind sample.
39
-------
Table 3. OPERATING PARAMETERS FOR NEGATIVE CHEMICAL IONIZATION
GLC/MS/COMP SYSTEM
Parameter
Setting
Inlet-manifold
desorptioa chamber
valve
capillary trap - minimum
maximum
thermal desorption time
He purge rate
GLC
75 m glass SE-30 wide bore (0.47 mm) WCOT,
1 pM film thickness
carrier (He) flow
separator/transfer line
MS
scan range
ion source temperature
electron energy
trap/box current
reagent gas
reagent gas pressure
accelerating voltage
scan interval
270°C
270°C
-1958C
+250°C
8 min
15 mL/min
4 nin/40°C; 40-240CC,
4°C/niji
1.5 mL/min
250°C
m/z 20 -> 500
250°C
50 eV
250 MA
CH4
4 x 10 5 T
3500 V
2.0 sec
40
-------
Mass Spectrum No.
Figure 17. Electron impact GC/MS/COMP profile of vapor-phase organlca in ambient air of Deer Park, TX.
-------
•
••
s.
•
L
IL
» —
/ 3?
T* ~vr "Tr ~i
r. ^ ^ ^ ^ ^ ^
MASS SPECTMIH NO.
Figure 18. Negative chemical ionlzation CC/MS/COUP profile of upwind ambient air sample for
Deer Park, TX.
-------
CJ
r——t—^—
i.
-v5 .?
i I ! S S I I I !
MASS SPECTRUM NO.
Figure 19. Negative chemical lonlzation CC/HS/COMP profile of downwind ambient air sample In
Ueer Park, TX.
-------
The power of this technique is exemplified in the specificity and
sensitivity which is not afforded in El mode. As can be seen from these
data, the intensity of each of the peaks which corresponds to halogenated
hydrocarbons is much greater than in the electron impact mode. The technique
is on an average of 2-3 orders of magnitude more sensitive than electron
impact. Furthermore, NCI/MS provides considerable specificity which is
mandatory for the analysis of vapor-phase organics in ambient air if elaborate
purification methods are to be circumvented. Extensive purification of an
ambient air sample is precluded by the high volatility of the compounds and
severe losses would occur in the transfer step(s).
The utility of this method is apparent for the analyst who is interested
in halogenated hydrocarbons in the environment. This tool is extremely
beneficial for the preliminary quick screening of samples collected in a
geographical area for which little information exists on the qualitative or
quantitative composition of the atmosphere. By judiciously selecting samples
collected surrounding a geographical area it is possible to quickly ascertain
the significant halogenated compounds present by using NCI. This technique
circumvents labor intensive steps which otherwise would be necessary using
El when searching for halogenated hydrocarbons in complex organic vapor-phase
mixtures. A quick inspection such as exemplified by Figures 18 and 19
allows the analyst to quickly ascertain the number and magnitude of the
halogenated hydrocarbons potentially present in the ambient air samples.
The alternate conventional method of El analysis requires the examination of
all data generated for identification and/or detection of halogenated com-
pounds. The level of effort necessary with this approach can be as much as
5-10 times greater than by simply analyzing a replicate sample by NCI and
reconstructing the m/z isotopic profiles for chlorine, bromine, iodine and
fluorine.
This technique was also applied to studies on in situ reactions occurring
between molecular halogens and organic vapors collected on Tenax GC XAD-4
and charcoal sorbents (see Section 7).
In summary, the technique of capillary GC/NCIMS/COMP analysis of vapor-
phase organics offers a considerably faster method for detecting and for
potentially quantifying electron capturing substances present in ambient air
samples. This serves as an improvement in the basic GC/MS/COMP analysis of
vapor-phase organics in air and its full potential use for this type of
analysis still awaits full exploitation.
44
-------
SECTION 7
IN SITU REACTION STUDIES ON SORBENTS USED FOR COLLECTION OF
VAPOR-PHASE ORGANICS
INTRODUCTION
In previous reports, the detection, identification, and quantitation of
halogenated hydrocarbons in the ambient air have been described. Ambient
air was sampled using a Tenax GC cartridge technique and sample analysis
employed high resolution (glass capillary) gas chromatography/oass spectrome-
try/computer (HRGC/MS/COMP) methods. Since the beginning of the development
of this technique over 7 years ago, many halogenated hydrocarbons have been
identified and quantified in ambient air from several geographical regions
throughout the Continental U.S.
In view of the potency in the broad spectrum of the carcinogenic activity
(in experimental animals) for the halogenated hydrocarbons identified, the
detection of these compounds in the atmosphere has generated considerable
interest in their origin. Previous studies were initiated to determine
emission of halogenated hydrocarbons from stationary and fugitive sources as
well as their potential formation through photochemical reactions.
In order to determine whether halogenated hydrocarbons may be present
in the atmosphere from industrial sources or as products of atmospheric
chemical reactions, it is first necessary to know the extent to which these
compounds may form at trace levels as an "artifact" of the technique employed
or the sample collection process.
The primary concern has been with the use of the Tenax GC sampling
cartridge which has been extensively employed for collecting organic vapor
from ambient air for characterization and quantification purposes. Since
the Tenax GC cartridge may concentrate reactive compounds, including ozone,
NO and, for example, molecular chlorine or bromine, in situ formation of
artifact compounds may occur even though inorganic gases do not appreciably
accumulate on the sorbent. Thus the purpose of this study was to further
supplement previously reported observations, i-e., the in situ formation of
nitrosoamines and to determine whether other additional in situ reactions
could occur on the Tenax GC sampling cartridge under field sampling conditions.
Because urban air often contains substantial concentrations of ozone
and NO , a limited number of laboratory experiments and to a greater extent
field experiments were performed to determine whether air containing these
gases might be more effective than air containing only olefins plus molecular
45
-------
halogens. Experiments were designed to delineate the transformation of
olefins (whether adsorbed cm sorbents or occurring in air) via homogeneous
or heterogeneous reactions which might take place on the walls of the sample
inlet tube or the sorbent bed itself. In addition to the halogenation of
olefins (endogenous or exogenous in air) the possibility of reactions between
ozone and these olefins producing polar products to be considered as artifacts
of the collection process was investigated.
EXPERIMENTAL
Apparatus For Laboratory Studies
The apparatus used to determine whether air containing ozone, olefins
and water might convert olefins to oxygenated products on Tenax GC (35/60
mesh, Applied Science Lab., State College, PA) is depicted in Figure 20.
Ozone was generated by an ultraviolet lamp equipped with a sliding cover for
obtaining different concentrations. The concentration of ozone was measured
using a Bendix Ozone Analyzer. The intake for this instrument was at the
same point as the intake for the Tenax GC glass cartridge sampler (6.0 cm
bed length x 1.5 cm i.d.) through which air was drawn by a Nutech Model 221A
(Nutech, Durham, KC) sampler. The sampling cartridge and the analyzer inlet
tube were centered in the air flow pattern from the reaction tube. Various
levels of relative humidity in the air stream were produced by changing the
temperature of the humidifier bath.
Perdeuterated toluene and styrene were introduced to a Tenax GC sampling
cartridge as a discrete band at one end of the sorbent bed. An air stream
containing ozone (200 ppb) was sampled. Control cartridges consisted of a
blank (no deuterated compound) and deuterated compounds loaded onto Tenax GC
cartridges which were analyzed without exposure to ozone.
Preparation of Sorbent Cartridges
Prior to its use, Tenax GC was purified by Soxhlet extraction for 13 h
with methanol and n-pentane, respectively. After drying in a N2 atmosphere,
Tenax GC was heated to 150°C for 2 h in a vacuum oven (12" of water), sized
into a 35/60 range and packed into glass tubes (6.0 cnt bed length x 1.5 cm
i.d.). All sample cartridges were preconditioned by heating to 275°C for 20
min under a helium purge of 20-30 mL/min. While cooling in precleaned
Kimax culture tubes, the containers were sealed to prevent contamination of
the cartridge.
Sample Analyses
HRGC/EI/MS--
A Varian MAT CH-7 GC/MS with a 620 L computer system equipped with an
inlet manifold was used for analyzing Tenax GC cartridges where structural
confirmation was required. The software programs available with this system
provide reconstructed gas chromatograms and extracted ion current profiles
for correlation between mass spectrum number and retention time. Operating
parameters for the HRGC/MS/COMP system are given in Table 4. A single stage
46
-------
Table 4. OPERATING PARAMETERS FOR GC ELECTRON IMPACT MS/COMP SYSTEM
Parameter
Setting
Inlet-manifold
thermal desorption chamber
valve
cryo-focusing capillary trap - minimum
maximum
desorption time
GC
75 • SE-30 BaC03 WCOT (0.47 mm i.d.)
He carrier flow
separator/transfer line
MS
scan range
scan, automatic-cyclic
filament current
multiplier
ion source vacuum
270°C
270°C
-195°C
+250°C
8 min
30-240°C, 4°C/siin
1.5 ml/min
245 °C
m/z 20-500
1 sec/decade
300 |JA
4.5
ca. 4 x 10 6 T
47
-------
scnuitfH
IN AIM
AIH
tumv
HflONMEMBRANf
MlItH
00
otoM
UOMIIOH
^CONNECTOR
GIASSAIACriOHIUlf
Cm 11 ilJml
ITHVLfNt
IN
Figure 20. Schematic of I usLrumenLa Lion and devices for examining jn situ formation of
uxygenated cnuipcMinds on solid sorbents.
-------
glass jet separator interfaced the SE-30 wide bore BaC03 WCOT capillary
(Section S) to the mass spectrometer.
HRGC/NCI MS/COMP—
Samples generated from laboratory and field in situ reaction studies
were analyzed by HRGC/NCIMS/COUP using the operating parameters previously
described (Section 6).
Field Sampling Experiments
Baton Rouge and Plaquemine, LA—
Field artifact studies were conducted in Baton Rouge, LA and vicinity.
Table 5 presents the experimental design. A schematic of the configurations
under examination in the artifact study is given in Figure 21. In this
study we examined the potential bromination, chlorination and nitrosation of
endogenous atmospheric organics by employing a tandem arrangement (configura-
tion A, Fig. 21). Ambient air (~120 L) was pulled through the glass fiber
filters and glass tubes followed by a cartridge containing the adsorbent,
Tenax GC. The glass tube designated as T2 contained a permeation tube of
either bromine (^4 x 10" 7 g/min), chlorine (^1 x 10~6 g/min) or dimethylamine-
dg (7 x 10"7 g/min). Thus, molecular halogen or dimethylamine-dg which
permeated at constant rates provided a constant sparging of the atmosphere
just prior to the adsorbent. The corresponding parallel arrangement served
as a control (T}). By examining independently the cartridges labeled AD
and ADg, it was possible to differentiate endogenous compounds from those
which were formed as an HI situ reaction.
Lake Charles, LA—
A more in-depth study was performed on in situ reactions under field
sampling conditions and this experimental design is given in Table 6. In
contrast to the studies which were conducted in Baton Rouge, this study
incorporated a second configuration (configuration B, Fig. 21) as well as
the comparison of treated (NajSaOs) and untreated glass fiber filters, and
teflon filters for the occurrence of in situ reactions.
Houston, TX--
Table 7 presents the experimental design for the field in situ reaction
studies conducted in Houston, TX. This study was repeated to provide a
greater diversity of industrial atmospheres while determining the effect of
molecular halogen on the endogenous hydrocarbon background present in the
atmosphere. Also, cyclohexene-d10 and styrene-dg ("-1 pg each) were added to
Tenax cartridges prior to samples as a discrete band at one end of the
sampling bed.
Raleigh, NC--
Figure 22 presents the experimental configuration for sparging atmosphere
near a major interstate with balogenated compounds and deuterated substances
with the collection of the potential products by using Tenax GC sampling
cartridges. Table 8 gives the experimental design for this field study.
49
-------
Table 5. EXPERIMENTAL DESIGN FOR FIELD IN SITU REACTION
STUDIES IN BATON ROUGE, LA*
Filter Glass tube
Sample Code
P1/L5A-1
P1/L5A-2
P1/L5B
P2/L5A
P2/L5B
P2/L5C
P3/L5A
P3/L5B
P3/L5C
F'
GFF-UC
GFF-U
GFF-U
GFF-U
GFF-U
GFF-U
GFF-U
GFF-U
GFF-U
F2 T T2
GFF-U - + Br.
GFF-U - + C12
GFF-U - * DMA-d6
GFF-U - + Br2
GFF-U - + C12
GFF-U - + DMA-d6
GFF-U - + Br2
GFF-U - + C12
GFF-U - + DMA-d,
Adsorbent
Adl
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Ad2
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
Tenax
See Table 42 and Figures 27 and 28 for sampling protocol and
locations, respectively.
Experimental configuration given in Figure 21.
CGFF-U = glass fiber filter, untreated.
50
-------
AMBIENT AIR
AMBIENT AIR
T2 (GlawTubel
Ad,
Ad2 (AdiorbonO
PUMP
CONFIGURATION A
Ad,
T2 IGlauTubi)
F2 (Filur)
Ad2
PUMP
CONFIGURATION B
FJgure 21. Experimental sampling cartridge configurations for In situ reaction studies,
-------
Table 6. EXPERIMENTAL DESIGN FOR FIELD JN SITU REACTfON STUDIES
Ol
CONDUCTED IN LAKE CHARLES, LAa
lltttir c.taau T«be Adaurbenl
Sample
(.oJi
PI/LI
PJ/LI
P4/LI
PVLI
f6/l.l
ra/u
P9/LI
PIO/L1
K»l>crlneiilal . „ _
Configuration 1 2
A
B
A
Bl
B2
Al
A2
B
Bl
B2
A
B
A
A
B
aSee Table 43
Experimental
CGFF-U
of Na
= glass
2S2°3'
«p-oc
-
TP-U
GPP-U
TP-U
TP-U
CPP-T
GPP-T
TP-U
TP-T
TP-T
GPF-U
CPP-T
TP-T
TP-T
CFP-U
-
-
crp-0
TP-U
TP-U
-
r.pp-T
TP-B
TP-T
-
CPP-TJ
fiPP-T
TP-T
TP-T
", '« Tl T2 T,
CFF-U niP-U -«ri - -IBr
OIP-U - *Br2
TF-U - - *Br^
+tl2
*Brz
tci2
crr-i - +»r
4Br2
*«2
«Br2
TP-T - -»Br2
WI2
*ci2
*ri2
tri2
All, AD,
Tennji Tcnait
-
TenaH
Tciias Tens*
Ten AX Telia*
TenuM Tcnax
Tcfiax
TttiiBiK TCIIAH
Ten.. Ten«
TCIIH TCHBI
Teuaa
Ten» Ten«a
Tenax Tenai
Tenam Tcnac
Tens* TcnaE
*°j *"*
Tcnax Teil»«
Teiiax
Tciian
-
-
_
TcnM
-
._ .
-
Tenax
-
-
-
-
for sampling protocol.
configurations were given In Fig. 21.
fiber filter, untreated, and CFF-T Indicates filter
Likewise, TF-U, TF-T are untreated and treated Teflon
treated with
filters.
10% solution
-------
V/l
Table 7. EXPERIMENTAL DESIGN FOR FIELD JN _SITU REACTION STUDIES CONDUCTED IN
HOUSTON, TXa
Saaiila Code
Pl/Ll
PI/1.1
fl/Ll
P4/L1
Pl/Ll
F6/L1
Pl/Ll
r»/Li
P9/L2
rn/Li
P1J/L*
taper laental
Conf laumt Ion
A
A
A
A
A
A
A
A
A
A
A
r
crr-u
crr-u
cir-u
crr-T
GPP-T
CFP-T
crr-T
CPP-U
GPP-U
crr-u
crr-u
rilier i;iaan
r2 r3 r, T, T,
CPP-T CPP-U UPP-T *Clj «Clj
crr-r r.pp-u CPP-T «Br2 «Br2
GPP-T crr-T crr-u «Br. -tar.
crr-u crp-u CPP-U «Br2 +Br2
crp-u GPP-U crp-u >ci2
crp-u - - tci2
CPP-U - - +CI, -
CPP-U -
CPP-U - - -
CPP-U ....
CPP-U -
lube
TJ T» *",
•*Br2 *Brj Teuaa
•>ri2 - Tenaa
+CI2 - T.,..«
•fCl. - TeiiaH
Tana*
Tenaa
- - Tena*
Tcnam
Tenax
Tenaa
- - Tenaji
AJaurbenl
AO,
Tenaa
Tana*
TeiiMa
Teiiaa
Tcnaa
Tenaa
Tenaa
Tanaa
Tenaa
Tenaa
Tenaa
*"] *°*
Tanaa Teiiaa
Tana* Tanaa
Tanaa Tenaa
Tanaa Tanaa
TenaB TaoaM
-
-
-
-
-
-
See Table 45 for sampling protocol.
i>
See Fig. 21 fur definition of configurat
ion.
-------
I/I
MASS
FLOW
CON I ROLLERS
AMBIENT
MR
Figure 22. Schematic of instrumental devices used for in ai tu reaction studies of ambient air.
-------
Table 8. EXPERIMENTAL DESIGN FOR IN SITU REACTION STUDIES
U-GFF U-GFF T-GFF T-GFT _ .
Experiment No. — — — -= Halogen
Tl I2 X3 £4
1 .
2 di
-------
RESULTS AND DISCUSSION
Laboratory Studies
Analysis of Tenax cartridges that had been preloaded with d1(j-cyclohexene
and dg-styrene and been exposed to ozone under laboratory conditions indicated
the production of polar products. The polar products contained carbonyl
moieties. Also a hydroxyl carbonyl compound was identified as a product
from djo-cyclohexene. In parallel experiments when the particulate filter
preceding the Tenax GC cartridge was impregnated with sodium thiosulfate,
the production of polar products was inhibited.
Field Studies
Baton Rouge, LA—
Three different atmospheric conditions were selected for field iri situ
reaction studies in Baton Rouge. The first was conducted during a period of
time representing the highest level of ozone, the second during a high level
of NO and auto exhaust, and finally the third during low levels of ozone
(nigh£). Ozone and NO levels were also measured during this phase of the
study. The results ofthe ozone levels are presented in Table 9.
In each of the samples collected, the halogenated hydrocarbons were
characterized and these results are summarized in Table 10. T2-Samples
(designation in the code) in all cases represent the adsorbent cartridge
which was in line with a permeation tube containing either molecular halogen
or dimethylamine-dg. It is readily apparent that a number of chlorinated
and brominated compounds were detected at trace levels which were not present
in the corresponding controls. Also indicated in the table are the results
for the in situ nitrosation reaction study (DMA-dg). Trace levels of dg-di-
methylnitrosamine were tentatively detected.
The levels of halogenated hydrocarbons in the ambient air samples were
estimated and these results are given in Tables 11-20. Table 11 presents
the results obtained for ambient air and was compared with air sparged with
chlorine. The compounds unaffected by the presence of chlorine are given in
the upper portion of the table, whereas increased levels appeared for other
compounds. Table 12 presents the similar experimental design; however, a
permeation tube containing molecular bromine was used in the T2 glass chamber
instead of molecular chlorine. In this case methyl bromide, ethylene dibro-
mide, bromoform and dibromocyclohexane were quantified.
Table 13 gives the results for dimethylamine-dg spiked in the ambient
air. A trace quantity of dimethylnitrosamine-dg was detected.
The sparging of ambient air with molecular chlorine was repeated during
a second sampling period which represented a period of high auto exhaust
levels. Again chlorinated cyclohexanes were formed. In addition, a chloro-
phenol isomer was detected (Table 14).
Tables 19 and 20 list the estimated levels of halogenated compounds for
ambient air with and without molecular chlorine and bromine added. In this
56
-------
Table 9. OZONE CONCENTRATIONS IN BATON ROUGE, LA*
Hour
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
5th
0.001
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.001
0.010
0.026
0.029
0.022
0.022
0.024
0.017
0.000
0.000
0.000
0.000
0.000
0.000
0.000
December, 1978
6th
0.000
0.00
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.002
0.014
*
*
0.047
0.041
0.043
0.033
0.019
0.017
0.019
0.018
0.010
0.004
0.001
7th
0.000
0.000
0.000
0.000
0.000
0.000
0.000
O.OOG
0.000
0.002
0.004
0.010
0.005
0.008
0.005
0.003
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Data supplied by the Louisiana Air Control Commission from their
L.S.U. Station.
*
Performed calibration.
57
-------
Table 10. SUMMARY OF THE: DETECTION OF IIALOCENATED COMPOUNDS AND N1TROSAMINE IN
AMBIENT AIR SPIKED UJTII MOLECULAR HALOGENS AND DIMETIIYLAMLNE-I>6 IN BATON ROUGE, LA
Pl/LiA-l/T, Pl/LSA-l/1
(-» (tBi,)
Methyl chlucU* 4 4
Itrtliylciit chlnrlda 4 4
Chlurofuraj + 4
Carbon tetrachlotlda - 4
1.2-Dlchloroathane 4 4
1.1,1-Trlcfalarocilunc + 4
Trlchloraitlijleae 4 4
Tetrachloroetlijrlcua 4 4
1.2-DUhloiopropane
CMorocytlahcMaiM lamer
GlchlorocycloliajiaiK lauoer
« "
TrlchlurocirclolMjuna lauaer
"
«l II
*• M
Mcthfl brtnlde _ +
Klliylciu dlbroajlda . (
""""''"• - »
~ *
Chlurob«al«ii« 4 ^
a-B-p-Ulclilurobenicued) 4 +
€liluraph«nal launel
Dl«thylnllro>aa>lua-d
rz Pl/I.SA-2/Tj Pl/ISA-2/T2
(-) (H.I,)
* 4
+ +
+ 4
4 4
+ 4
4 4
4 4
4 4
-
4
4
4
4
4
4
-
-
-
4
~ —
4 4
4 4
-
Sanple o
PI/LH-I/T2
(+WW-db»
_
4
4
4
4
4
4
4
4
-
-
-
-
-
-
-
_
-
-
-
»
4
.
>dc
P2/I.SA-I/T,
(-•Br,)
_
4
4-
4
4
4
4
4
-
-
-
-
-
-
-
-
4
4
4
4
4
t
_
F2/LSB/T2
(itl^J
*
4
4
4
4
4
4
4
-
4
4
4
4
4
4
-
_
4
_
4
4
4
P2/LSC/T, Fl/LSA/T]
(UMA'dfe) (4Brj)
»
4 4
4 4
4
^ 4
4 4
4 4
4 4
-
-
-
-
-
-
-
-
4
4
„ _
4 4
^ _
_ ^
PI/I.IB/TI
<«O1^>
_
4
4
4
4
4
4
4
.
4
4
_
4
4
4
4
.
4
_
4
4
.
Pl/LJC/Ti
.
4
-
4
4
4
4
4
.
-
-
_
-
-
-
_
_
_
+
(lent.)
-------
Table 11. ESTIMATION OF LEVELS OF HALOGENATED HYDROCARBONS
IN SITU REACTION STUDIES: AMBIENT AIR WITH AND WITHOUT
CHLORINE ADDED
Chemical
Ethylene dibromide
1,1, 1-Triculoroe thane
Carbon tetrachloride
Tr i chl a roethy lene
Tetrachloroethylane
Benzene
Chloroform
Chlorobenzene
Dichlorobenzenes (2)
Dichlorohexanes (2)
Trichlorohexanes (3)
Chlorocyclohexane
-ci2a
GIT-U
1,825C
164
563
55
389
989
725
21
32
ND
ND
ND
+Cl2b
GIT-U
1,547
171
443
79
278
1,135
1,099
153
194
1,834
3,355
651
aPl/L5A-2/T1.
bPl/L5A-2/T2.
tallies are in ng, ND = not detected.
59
-------
Table 12. ESTIMATION OF LEVELS OF HALOGENATEL HYDROCARBONS
Dl SITU REACTION STUDIES: AMBIENT AIR WITH AND WITHOUT
BROMINE ADDED
Chemical
Chloroform
Ethylene dicfaloride
1 , 1 , 1-Trichloroethane
Carbon tetrachloride
Tetrachloroethylene
Chlorobenzene
Benzene
Methyl bromide
Ethylene dibromide
Bromofonn
Dibromocyclohexane
-Br2'
GFF-U
606C
1,794
173
ND
371
18
669
ND
ND
ND
ND
+Br2b
GFF-U
642
1,427
246
ND
304
13
916
61
28
3,510
1,332
bPl/L5A-l/T2.
values are in ng, ND = act detected.
60
-------
Table 13. ESTIMATION OF LEVELS FOR SELECTED ORCANICS
ttl SITU REACTION STUDIES: AMBIENT AIR WITH AND WITHOUT
DIMETHYLAMINE-D, ADDED
o
Chemical
Chloroform
1,2-Dichloroethaae
1 , 1 , 1 -Tri chl o roethane
Benzene
Carbon tetrachloride
1 ,2-Dichloropropane
Trichloroethylene
Dimethylnitrosaoine-dg
Chlorobeozene
Dichlorobenzene isomer
-DMA-d6a
GFF-U
515C
1,557
224
961
273
24
107
-
22
18
+D«A-d6b
GFF-U
338
945
112
659
195
19
112
5
18
17
*P1/L5B/T] .
bPl/L5B/T2.
Values in ng/cartridge, - = not detected.
61
-------
Table 14. ESTIMATION OF LEVELS OF SELECTED ORGANICS
JJ SITU REACTION STUDIES: AMBIENT AIS WITH AW) WITHOUT
CHLORINE ADDED
Chemical
Chloroform
Ethylene dichloride
1,1, 1-Trichloroetb.ane
Benzene
Carbon tetrachloride
Trichloroethylene
Tetracbloroethylene
Ethylene dibromide
Chlorobenzene
Bromoform
Chlorocyclohexane
Chlorophenol isoner
o-£-Di Chlorobenzene
o-Di chlo r obenzene
Di Chlorocyclohexane isoaer
Dichlorocyclohexane isoner
Trichlorocyclohexane isomer
Trichlorocyclohexane isomer
Trichlorocyclohexane isomer
•C12*
GFT-U
45C
7
624
1,127
47
60
59
17
1
-
19
-
10
5
15
7
-
-
-
GFF-U
109
70
40
1,161
38
55
39
126
150
74
172
24
28
45
921
220
245
386
789
aP2/L5B/Ti .
C- = not detected, values in ng/cartridge.
62
-------
Table 15. ESTIMATION OF LEVELS OF SELECTED ORGANICS
IN SITU REACTION STUDIES: AMBIENT AIR WITH AND WITHOUT
DIMETHYLAMINE-D, ADDED
o
Chemical
Chloroform
Ethylene dichloride
1 , 1 , 1-Trichloroethane
Benzene
Trichloroethylene
Tetrachloroethylene
Dime thy Ini trosamine-d,
o
Chlorobenzene
-DMA-ds3
GIT-U
64C
84
145
1,191
112
62
-
15
+D«A-d6b
GFF-U
37
76
105
930
57
56
10
5
aP2/L5C/T,.
bP2/L5C/T2.
CValues in ng/cartridge, - = not detected.
63
-------
Table 16. ESTIMATION OF LEVELS OF SELECTED ORGANICS
.IN SITU REACTION STUDIES: AMBIENT AIR WITH AND WITHOUT
CHLORINE ADDED
Chemical
GFF-U GFF-U
Chloroform
1 , 2-Dichloroe thane
1 i 1 , 1-Trichloroethane
Benzene
Carbon tetrachloride
Trichloroethylene
Chlorocyclohexene isomer
Tetrachloroethylene
Chlorobenzene
Chlorocyclohexane isomer
Dichlorobeazene isomer
Dichlorobenzene isomer
Dichlorocyclohexane isomer
Dichlorocyclohexane isomer
Trichlorocyclohexane isomer
Trichlorocyclohexane isomer
Trichlorocyclohexane isomer
aP3/L5B/Ti.
bP3/L5B/T2.
NDC
ND
ND
ND
ND
ND
ND
65
4
-
14
3
-
-
-
-
-
284
86
145
1,538
137
183
18
169
115
242
33
46
1,587
71
395
454
655
ND - not determined, - s not detected, values in ng/cartridge.
64
-------
Table 17. ESTIMATION OF LEVELS OF SELECTED ORGANICS
IX SITU REACTIQX STUDIES: AMBIENT AIR WITH AND WITHOUT
ADDED
Chemical
Chloroform
1 , 2-Dicaloroethane
1,1, 1-Trichloroetbane
Benzeae
Carbon tetracfaloride
Trichloroethylene
Tetracbloroethylene
Chlorobenzene
Bromoform
-Br,'
GFF-U
64C
75
204
1.3S4
130
9
73
4
•
*Br2b
GFF-U
95
76
197
144
117
129
147
18
T
bP3/I5A/T2.
• - act detected, values in ng/cartridge.
65
-------
Table 18. ESTIMATION OF LEVELS OF SELECTED ORGANICS
IH SITU REACTION STUDIES: AHBIENT AIR WITH AJJD WITHOUT
DIMETHYLAMINE-D-. ADDED
o
Chemical
I ,2-Dichloroethane
1,1, 1-Trichloroethane
Benzene
Carbon tetrachloride
Trichloroe thy lane
Tetrachloroethylene
Dime thy lnitrosamine-d,
0
Dichlorobeozene isomer
Dicalorobenzene isoner
-DMA-d63
GFF-U
NDC
ND
ND
ND
ND
ND
•
ND
ND
+DMA-dsb
GFF-U
52
99
348
91
49
45
10
12
5
9P3/L5C/Ti.
bP3/L5C/T2.
Values in ng/cartndge, - = not detected, ND = not determined.
66
-------
Table 19. ESTIMATION OF LEVELS OF HALOGENATED COMPOUNDS
EFFECT OF OZONE ON _IN SITU REACTIONS: AMBIENT AIR
WITH AND WITHOUT CHLORINE ADDED
Chemical
Chlorobenzene
Dichlorobenzenes (2)
Dichlorohexanes (2)
Trichlorohexanes (3)
Chlorocyclohexane
•a/
03 = 27 ppb
21e
32
ND
ND
ND
+Cl2b
03 = 27
153
194
1,834
3,355
651
+C12C
03 = 20
150
73
1,141
1,420
172
«,«
03 * 0
115
79
1,656
1,504
242
3Pl/L5A-2/Ti .
bPl/L5A-2/T2 .
P3/L5B/T2 .
Values in ng/ cartridge.
67
-------
Table 20. ESTIMATION OF LEVELS OF HALOGENATED COMPOUNDS
EFFECT OF OZONE ON ]£ SITU REACTIONS: AMBIENT AIR
WITH AND WITHOUT BROMINE ADDED
Chemical
Methyl bromide
Ethylene dibromide
Bromofonn
Dib romo cy cl obexane
-Br2'
03 = 27 ppb
ND
ND
ND
ND
+Br2b
03 = 27
61*
28
3,510
1,332
+Br2C
03 = 20
38
28
1,404
882
+Br2d
03 = 0
ND
ND
T
ND
Pl/L5A-l/T2
P2/L5B/T2 .
6 Values are in ag/ cartridge,
68
-------
case Che three sampling periods are compared to contrast the Levels of
halogenated compounds that were formed under varying levels of ozone. When
bromine was added to ambient air, it appears that ozoote facilitated the
bromination .of organics, since at an ozone concentration of zero, the bromina-
Ced organics disappeared to only a trace quantity.
Lake Charles, LA--
Table 21 presents the quantification of 22 selected organics. In
Tables 22-27, sampling configurations A and B (Fig. 21) were compared for
cases in which the ambient air was either spiked with molecular chlorine or
bromine. These results indicate that considerably less chlorination of
endogenous material occurred in contrast to the results obtained in Baton
Rouge, LA.
Houston, TX--
In this experiment, the Tenax sampling cartridges were loaded with a
discrete zone of dio-cyclohexene (Table 28} or dg-styrene (Table 29). The
spiked cartridges were then taken to the field for use in sampling (configura-
tion B, Fig. 21). Tables 29-32 present the vapor-phase halogenated and
other selected orgaaics which were identified in the ambient air from Houston.
Quantitative analysis of these cartridges yielded the results shown in
Figures 23 and 24 (also Tables 33 and 34).
Tables 35 and 36 summarize the results for the d^Q-cyelohexene and
dg-styrene studies for the various configurational arrangements in sampling
and the use of untreated and treated glass fiber filters with sodium thio-
sulfate.
Raleigh, NC--
Table 37 presents the sampling protocol for in situ reactions utilizing
deuterated compounds sparged into the air sampling stream.
Tables 38-41 list the levels of deuterated compounds formed from
djQ-cyclohexene or d8-styrene and molecular chlorine or bromine, respec-
tively.
-------
Table 21. QUANTIFICATION OF Ut SITU REACTIONS IN AMBIENT AIR OF LAKE CHARLES, LA8
Chemical
Benzene
Vinyl idene chloride
Chloroform
Carbon tetrachlorlde
1, 2-Dlchloroethane
1,1, 1-Trlchloroethane
Trlchloroethylene
Tetrachloroetliylene
Dlclilorobenzene isomer
Dlchlorobenzene laoroer
1, 2-Dlchloroethylene Isomer
1,2-Dlcliloroethylene Isomer
1,1, 2-Trichloroethane
1,1,1,2-Tetrachloroelhane
Chlorobensene
1,1,2, 2-Tetrachloroe thane
1, 3, 5-Trlchlorobenzene
Pentachlo roethane
Peutachlorobromnethane
PI/LI-A/TI
(+C12>
277
131
90
43
117
106
76
56
8
ND
ND
ND
ND
ND
ND
130
ND
ND
ND
P1/L1-A/T2
(-)
208
ND
129
48
117
ND
55
56
8
T
ND
ND
ND
ND
ND
NU
ND
ND
ND
Sample code
P1/L1-A/T3
(+Br2)
208
ND
56
34
82
83
63
57
6
ND
ND
ND
ND
ND
ND
HI
ND
NO
Nil
PI/LI-A/TU
(-)
225
ND
115
42
98
ND
62
70
6
T
ND
ND
ND
ND
ND
ND
ND
NU
ND
PI/LI-B/TM
<+Br2)
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(continued)
-------
Table 21 (cont'd.)
Sample code
Chemical
Pentaclilorobutadlene
llexachlorobutadlene
Bromoform
Dlbromocyclohexane Isomer
Cliloromethylbutene Isomer
P1/L1-A/T,
(+C12)
NO
ND
ND
ND
T
P1/L1-A/T2
(-C12)
ND
ND
ND
ND
ND
Pl/Ll-A/Tj
(+Br2)
ND
ND
582
338
ND
P1/L1-A/T,,
<-Br2)
ND
ND
ND
ND
ND
Pl/Ll-B/Ti,
<+Br2)
ND
ND
ND
538
ND
See Table 6 for experimental design.
-------
Table 22. QUANTIFICATION OF IN SITU REACTIONS IN AMBIENT AIR OF LAKE CHARLES. LA*
Supple Coda
Ch»lc«l
Bin»iM
Vlnjlldm* chloride
Chlarolam
C«cbaa l«t»cb.lerld>
l.2-Dlchlaro«MiaiM
I.I. l*Ttlchloco«lh*M
Ir lcKlaco«th| l«a«
T«c racbloio* Itiyl tat
Dlchlatob*ai«M l»om»r
Dlcblon>b«at«n« tmommt
1.2-Dlchli>ni*lhrl*n« limr
1.2-DUtiioratlhrtciM ICOMI
1.1.1-TrlcbloroclhM*
1,1,1.2-Tclrachloroclhan*
Chlarobcam*
1 . 1 . 2. 2-T»t(«chlara«lb>a*
l.l.VTilchlorabmuM
r«Dl«cblora«lli«i.
H.»chloiobut.dl«i€
BiiMDfam
Olbio*ocycloh««i« l«Mur
ChUroMthilbut.D. UoMr
PWLl-A/T,
HO
T
161
M
11
ua
61
39
1
ND
HO
m>
NO
ND
41
ND
NO
NO
NO
HD
MO
II)
PJ/tl-»/Tj
447
T
If
36
16
61
1)
ie
6
T
HD
HB
11
NO
23
68
HD
HD
HD
221
IS
HO
Pl/LI-Bt/Ti
SOI
106
lie
46
II
60
41
14
11
T
ND
HD
4t
HD
11
ND
ND
NO
NO
ND
NO
HD
NO
"'"eft"
21 >
HB
101
46
»
10
20
24
6
HO
HD
NO
HD
HO
I
HO
HD
HD
NU
NO
HO
HO
JM
ri/LI-B2/T|
3*0
T
161
If
11
12B
6*
If
1
ND
NO
NO
HD
HO
NO
41
NO
ND
ND
ND
ND
ND
m
n/LI-Bl/T]
1*1
111
16
14
16
2«
T
22
1
HU
HD
HO
MO
MO
ND
2lf
MD
MO
NO
ND
14
40
HD
See Table 6 for experimental design.
-------
Table 23. QUANTIFICATION OF IN SITU REACTIONS IN AMBIIiNT AIR UP LAKE CHARLES, LA*1
Sample Code
Chemical
Benzene
Vinyl idene chloride
Chloroform
Carbon tecrachlorlde
1.2- Dlchlor oe t hane
1,1,1-Trlchlo roe thane
Trlchloroethylene
Tetrachloroethylene
Dlchlorobenzene laotner
Dlchlorobenzene lnomer
Dlchlorobenzene iaoraer
1 , 2-Dlchloroethylene Isoner
1,2-Dichloroethylene Isomer
1,1,2-Trlchloroe thane
1 , 1 , 1 , 2-Te t rachlo methane
Chlorobenzene
1,1,2.2-Tetracliloroethane
1 ,J,5-Triclilorobenzcne
Pen tach loroeltiane
P4/L1-A1/T|
<-)
64
ND
62
27
104
IS
121
50
9
ND
ND
ND
ND
ND
ND
50
ND
NO
ND
P4/L1-A1/T2
(+C12)
289
4.220
68
36
67
29
74
42
12
T
ND
ND
ND
ND
ND
6
88
ND
ND
P4/Ll-A2/Ti
(-)
237
3,446
51
31
62
37
55
26
T
ND
ND
ND
ND
ND
ND
ND
116
ND
NO
P4/L1-A2/T3
<+Br2)
280
1.880
600
T
19
75
20
55
T
ND
ND
ND
ND
ND
ND
ND
16
ND
ND
P4/L1-B/T2
(+Br2)
286
3, 808
84
39
89
83
67
52
ND
ND
ND
ND
ND
ND
ND
4
17
ND
ND
(continued)
-------
Table 23 (cont'd.)
Sample code
Chemical
Pentaclilorobromoe thane
tentachlorobutadlene
Hexaclilorohutad lene
Bromofona
Dlbromocyclohexane Isumer
ChJorometliyl butane Isomer
P4/L1-A1/T,
<-)
ND
NO
ND
ND
ND
ND
P4/L1-A1/T2
(+C12)
ND
ND
ND
ND
ND
145
P4/L1-A2/T!
(-)
ND
ND
ND
T
ND
ND
F4/L1-A2/T3
(+Br2)
ND
ND
ND
3L4
32
72
P4/L1-B/T2
(+Br2>
ND
NU
ND
ND
166
ND
See Table 6 Cor experimental design.
-------
Table 24. QUANTIFICATION OF IN SITU REACTIONS IN AMBIENT AIR IN LAKE CHARLES, I.A&
in
Chemical
Benzene
Vlnylidene chloride
Chloroform
Carbon tetrachloride
1, 2-Dichloroethane
1,1. 1-Trlchloroe thane
Trlchloroelhylene
Tetrachloroethylene
Dlchlorobenzene Isoroer
Dlchlorobenzene iaomer
1,2-Dlchloroetliylene Isomer
1,2-Dlchloroethylene isomer
1,1, 2-Tr Ichloroethane
1, 1.1,2-Tetrachloroethciiie
Chlorobenzene
1,1,2, 2-Tetracliloroetliaiie
1,3. 5-Tr Ichlorobenzene
t'enlacliLoruetliiine
PS/LI-BI/T!
(-)
147
201
293
49
596
83
76
464
5
NO
B7
ND
75
ND
Nl)
ND
Nl)
Nl)
P5/L1-B1/T2
(+C12)
156
ND
642
51
490
136
102
447
9
T
ND
ND
36
Nl)
ND
Nl)
Nl)
Nl)
Sample code
P5/LJ-B2/T2
<+Br2)
ND
329
391
62
160
128
121
514
5
ND
Nl)
ND
ND
Nl)
Nl)
Nl)
Nl)
Nl)
P5/Ll-A/T!b
(-)
113
ND
354
44
490
106
78
388
T
T
ND
ND
50
ND
ND
ND
ND
ND
P5/L1-A/T3
<+Br2)
199
226
698
48
756
128
119
379
4
T
ND
ND
35
ND
ND
ND
ND
ND
(continued)
-------
Table 24 (cont'd.)
Sample code
Chemical
Pentachlorobutadlene
tlexachlorobucadlene
Br onto form
Dlbromocyclohexane isoroer
Chloromethylbutene isomer
P5/L1-B1/TI
<-)
NU
T
ND
ND
ND
P5/L1-B1/T2
(+C12)
ND
69
ND
ND
ND
P5/L1-B2/T2
<+Br2)
ND
T
122
ND
216
P5/Ll-A/Tib
<-)
ND
ND
ND
ND
ND
P5/L1-A/T3
<+»r2)
ND
T
196
104
ND
aSee Table 6 for experimental design.
(control).
-------
Table 25. QUANTIFICATION OF _IN SITU REACTIONS IN AMBIENT AIR IN LAKE CHARLES. LA*
Chemical
Benzene
Vlnylldene chloride
Chloroform
Carbon tetrachloride
1 . 2-Dichloroethane
1,1,1-Trlchlo roe thane
Trlchloroethylene
Tecrachloroethylene
Dichlorobenzene iaoner
Dichlorobenzene Isomer
1,2-Dlchloroethylene Isomer
1,2-Dlchloroethylene isomer
1. 1, 2-Trlchloroechane
1, 1, 1, 2-Tetrachloroethane
Chlorobenzene
1,1,2, 2-Tet rachloroethaite
1 , 3, 5-Tr Ichlorobenzcne
Venlacliloroei Itane
P6/L1-B/TJ
(->
6,369
ND
214
32
1,639
76
82
70
7
T
ND
ND
ND
ND
4
NIJ
ND
ND
Sample
P6/L1-B/T2
(+C12>
457
ND
96
41
1.416
76
72
83
5
T
ND
ND
ND
ND
4
ND
ND
ND
code
PB/LI-A/TI
(-)
376
ND
175
256
426
56
80
55
5
ND
ND
ND
ND
ND
4
ND
ND
NO
P8/L1-A/T2
(+C12)
436
139
670
4,393
426
106
88
65
29
28
ND
ND
ND
ND
9
ND
T
ND
(continued)
-------
Table 25 (cont'd.)
-J
oo
Sample code
Chemical
Pentachlorobromoetliane
Pentachlorobutadiene
llexachlorobutadlene
Bromoform
Dlbronocyclohexane laomer
Chloromethylbutene laomer
F6/U-B/T,
<->
Nit
ND
ND
ND
ND
ND
P6/L1-B/T2
(+C12)
ND
ND
ND
ND
ND
ND
PS/LI-A/TI
<-)
ND
ND
ND
ND
ND
ND
P8/L1-A/T2
(+C12)
ND
ND
ND
ND
ND
ND
aSee Table 6 for experimental design.
-------
Table 26. QUANTIFICATION OF IN SITU REACTIONS IN AMBIENT AIR IN LAKE CHARLES, LA
Chemical
Benzene
Vlnylidene chloride
Chloroforn
Carbon tecrachlorlde
1, 2-Dlciiloroethane
1,1, 1-Tr Ichloroethane
Trlchloroethylene
Tetrachloroethylene
Dlchlorobenzene laomer
Dlchlorobenzene isomer
1,2-Dlchloroethylene laomer
1, 2-Dlcliloroetliylene iaoiner
1,1,2-Trlchloroethane
1,1,1, 2- Tetrachloroe thane
Clilorobenzene
1,1,2, 2-Tetrachloroethane
1, 3,5-Trichlorobenzeue
Pen tachloroe thane
P9/Ll-A/Ti
(-)
387
ND
152
188
255
69
47
66
6
T
ND
ND
ND
ND
ND
ND
Nl>
ND
Sample
P9/L1-A/T2
(+C12)
439
ND
349
144
255
67
76
59
T
T
ND
ND
ND
ND
11
ND
ND
ND
code
PIO/LI-B/TI
<->
324
ND
366
65
64
79
86
67
T
ND
ND
ND
ND
ND
14
ND
ND
ND
P10/L1-B/T2
<+Cl2)
384
ND
636
62
69
121
90
35
4
T
ND
ND
ND
ND
19
ND
ND
ND
(continued)
-------
Table 26 (cont'd.)
00
o
Sample code
Chemical
Pett tachlorobromoe thane
Pentachlorobutadlene
iiexachlorobutadlene
Bromoform
Dlbrootocyclohexane Isomer
Chloromethylbutene laoroer
P9/Ll-A/Ti
ND
ND
ND
ND
ND
ND
P9/L1-A/T2
ND
ND
ND
ND
ND
ND
PIO/LI-B/TI
ND
ND
ND
ND
ND
69
F10/L1-B/T2
ND
ND
ND
ND
ND
ND
a
'See Table 6 for experimental design.
-------
Table 27. EXPERIMENTAL DESIGN FOR SAMPLING WITH TENAX CARTRIDGES
LOADED WITH CYCLOHEXEKE-D^
Sample cede
PI/LI
P2/I.I
P3/L1
Cartridge no.
TL
T2
13
T4
Tl
T2
T3
T4
Tl
T2
T3
T4
Cyclotiexene-d §o
-
1 Mg
1 Mg
1 MB
-
1 Mg
I Mg
1 Mg
-
1 Mg
1 Mg
1 Mg
Na2S203b
-
-
1%
10%
-
-
1%
10%
-
-
1%
10%
Halogen (pg)C
- (o)
- (0)
- (0)
- (0)
+ (11.3)
+ (11.3)
+ (H.3)
+ (11.3)
+ (H.4)
+ (11.4)
* (11-4)
* (11.4)
03d (ppb)
35
35
35
35
37
37
37
37
2B
28
28
28
Cyclohexene-d|o (nominal level) was loaded onto Tenax GC cartridge prior to sampling.
Glass fiber filter was impregnated with aqueous solution of Na2S203.
C12 permeation rate was 1.24 x 10 6 g/min and added to ambient air to give final concentration of
39 ppb, thus 11.3 pg passed through each cartridge. Br2 permeation rate was 7.65 x 10 7 g/rain and
added to ambient air to give final concentration of 17.5 ppb, thus 11.4 pg passed through each
cartridge.
03 was measured in ambient air sampled.
-------
oo
K>
Table 28. EXPERIMENTAL DESIGN FOR SAMPLING WITH TENAJC CARTRIDGES
LOADED WITH STYRENE-Da
o
Sample code Cartridge no.
PI /LI Tl
T2
T3
T4
P2/L1 Tl
T2
T3
T4
P3/L1 Tl
T2
T3
T4
u
Styrene-dg
1
1
1
-
1
1
1
-
1
1
1
MB
Mg
Mg
ii
Mg
Mg
Mg
Mg
Mg
Mg
Na2S2O3
1%
10%
-
-
1%
10%
-
-
1%
10%
ft
Halogen dig)
Cl
Cl
Cl
Cl
Br
Br
Br
Br
-
2
2
2
2
2
2
2
2
(0)
(0)
(0)
(0)
-------
Table 29. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS
IN AMBIENT AIR FROM HOUSTON, TX
Uticlcn
Top.
F«ak to. (*C1
ChroMie-
iraohlc
Fuk So.
CC5
1
2
3
4
4
6
7
8
9
10
11
12
13
li
li
16
17
*•
«9
J*
63
6*
«a
69
71
72
73
76
92
95
chloroMthaw (tracts) (taat.)
{Macaa}
chlarlda
tana Ut)
ehiorofara
l,l,l-trlehlow«ih«n«
carbon cmaeJilarld*
colutn*
18
1*
20
21
11
23
2*
Z3
26
27
28
29
3D
31
M
101
10*
108
113
U8
122
1*0
1*8
162
14*
177
•aa (tracas)
ta trachloriMtlirlaii*
C7»12 Si CiB10°
wkaowB dautartw caaipouad
broaDfen
-l (tut.)
dlchlarebaaiaaa laeaar (traca)
dlchlora-d.Q-cyclabauaa
dlehloro-d-.-cyclahaxana
Itemtr (taat.)
duatarlta coapouad uaknown
haucUerabutadlaaa
See Tables 45 and 7 for protocol and experimental design.
83
-------
Table 30- VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS
IN AMBIENT AIR FROM HOUSTON, TX (P1/L1-A/T3)
Cbromto- tlutlon
irtphlc I tap.
P«»k to. {'C'y
Elutloa
friphte
ruk .IP.
1
2
3
*
i
7
8
9
10
11
12
13
14
U
54
(2
63
M
«T
M
70
71
71
7?
7*
78
91
Mtftylm* chloride
ehlorafen Ctr*et»)
P»flaeroioliiaM (if]
1,1, l-nle!aoro«th*n«
d»~
ejrboo »tr«ehl«rtd«
talun*
U
16
17
U
19
20
U
12
23
2*
23
26
95
100
107
112
123
1.18
141
Ul
1M
174
irowfors
ilehlorobcBieti iwmir (tract)
dldU9rab«u*B* iiamat (tr«e«i
(ITICM)
(cat.)
See Tables 45 and 7 for sampling and experimental design.
34
-------
Table 31• VAPOR-PHASE HALOGENATED AND OTHER SELECTED GRGANICS
IN AMBIENT AIR FROM HOUSTON, TX (P3/L1-A/T )*
llatiaa
tap.
C'C)
Chrawto- Uutloa
triphlc THp.
r««k «B. (*o
1
2
3
*
5
6
7
t
9
10
11
44
41
J*
39
S3
S3
71
TS
»
(tracu)
ehlorldi
(•t)
(•ff)
1.1,
12
13
14
IS
16
17
U
19
20
21
*!
106
112
lli
122
137
141
168
174
173
eUatotaanM
kreaefon
dieUarobaxa* IMMT (tr«ct)
ilbroBDtaBiBti Itrmft (tricf)
41b«OMO-du-«yclaliM(M IMMT
ilbraaeeTciobcxjat
See Tables 45 and 7 for sampling and experimental protocols.
85
-------
Table 32- VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM HOUSTON, TX (P4/Ll-A/T3)a
OiroBito- Elution
iriphle Top.
PMfc Sa. I'C)
traphlc Top.
FMfc 10. CO
1
2
3
k
i
6
7
a
10
11
12
54
63
63
66
67
66
71
77
100
chloride
dvlotafoTB
1.1.1-crlcUoroachM*
cirbov citrachland* (trien)
tTlchloTMthrlm (truci)
talunc
14
U
16
17
18
19
20
21
22
107
110
116
12*
1J9
147
149
li*
US
180
chlnmbcBin*
dlchlorcfccuMn* 1
dlehlara-d
tr (trace)
it
Uoaar
a5ae Tables 45 and 7 for sampling and experimental prococols.
36
-------
00
ICNIOHO «,re»ClOMf««iOl
CMMMf
ftHf.U*HI)M
FIIUH
«,,CVIOHEXENE
C(0,(0 ISOMER
1.4 »M 14 IX)
a
j
AMIIENT
AIM
C(0|(0»OMEHSIII
1I.MH.4X)
OICHI OHO *„ CVCI OHEK*« ISOMERS 111
II.I «M I MM
I.I *M ll.tXI
Figure 23. In situ reactions during ambient air sampling: dln-cyclohexene.
-------
TfNAX
CAIIIHIIIGE
rilTER
CHlOfllNE
rillMEAIIOM
IUIE
,
I I u-ii'Hiiinifin I
AMMCNT
• HI
4,STVRENE
4rSTVREME
00
00
XTTMCNE nil III OH III (
M-MISX)
Figure 24. It\
reactions during ambient air sampling: dft-styrene.
-------
Table 33. IS SITU REACTION YIELDS FROM Din-CYCLOHEXENE AMD
MOLECULAR CHLORINE l
Compound
Dichloro'd^.-cyclohexane isomer
Dicliloro-d.. -cyclohexane isomer
2-Chloro-d.g-cyclohexanol
+Cl2a
GHMJ
17.2 (24)
1.1 (1.6)
9.2 (13)
+C12
GFF-T
0
0
0.5 (0.7)
3GFF-U s untreated glass fiber filter; GFF-T = glass fiber filter
treated with 1% solution sodium thiosulfate; values are in oM with
percent yield in parentheses.
89
-------
Table 34. IN SITU REACTION YIELDS FROM D_-STYR£NE AND
MOLECULAR CHLORINE
Compound
d_-Chlorostyrene isomer
d_-Chlorostyrene isomer
dg-Styrene dichloride
-ci2a
GFF-U
0
0
0
+C12
GFF^U
0.25 (0.5)
2.04 (4.3)
1.14 (2.4)
+C12
CEf^T
0
0
0
a-, * = without and with Clg added to ambient air; GFF-U = untreated
glass fiber filter; GFF-T = glass fiber filter impregnated with
1% solution sodium thiosulfate; values are in nM and percent
yield given in parentheses.
90
-------
Table 35. SUMMARY OF d,0-CYCLOIIEXENE STUDY WITH AND WITHOUT MOLECULAR HALOGEN
ADDED TO HOUSTON, TX AMBIENT ALK
Cuapound
Chlorolora
Carbon (.trichloride
Chlorob.nian.
Dlchlorob.ni.fi. lamer
Otchlurob.nien. looarr
Methyl clilorafora
Ti IchUroethy l«n«
T.trachlero.ttiyl.n*
d|0-Cycl.h.««
4 -Cyclob.Badl.ae
d0-B.ni.a.
VlO0 *"*"
Ct0100 ,.o~.
C.D..O leaMr
No halogen* *C12
PI/LI/TI
ND
NU
ND
NU
NU
ND
ND
ND
-
-
-
-
-
-
PI/LI/TI PI/LI/TI P1/I.I/T4 PJ/LI/Tl
ND
ND
HU
ND
ND
ND
HO
HD
1,211
*
11
6
110
12
HD
ND
ND
HD
HD
ND
HD
HD
1,080
11
10
11
4
14
ND
ND
ND
KD
ND
ND
NO
ND
1,441
16
IB
6
ia
a
2
T
14
-
-
T
T
T
-
-
-
-
-
-
P2/L1/T? P2/L1/T1 P2/I.I/T4 Pl/LI/TI
11 T
10 T T
21 12 10
11 T
14 -
16 T T
14 T T
16 16 T
1.I99 2,142 2,04«
100 29 10
11B 12 12
IB 1 -
36 IB
120
NO
ND
ND
ND
HO
NO
HO
HD
-
-
~
-
-
-
+Br,
PJ/LI /T2
HD
HD
HD
HD
HO
HO
NO
HO
1.414
2O
21
6
»
11
Pl/LI/TI
ND
HD
HD
HD
HD
HD
HD
HD
1.149
21
n
•
21
12
Blank
PI/L1/T4
HO
ND
HD
HD
NO
HD
ND
BD
1.194
27
30
•
11
12
Dlchloro-4, -cyclohcuM
l*ra*r«
DlchloroC7cloricx«n«
I uommt
,,080
2J
2-Aroaa-d.
plb»K>-410-Lyi|0hc
imomtf*
DlbrMOdPcloho.il.
l.I-Ulbroucthin.
142
119
T
J1J
II?
426
32
S6B
211
194
91
368
22B
91
32
-------
Table 36. SUMMARY OF da-STYRENE STUDY WITH AND WITHOUT MOLECULAR HALOGEN
ADDED TO HOUSTON, TX AMBIENT AIK
vO
10
Compound
1,2-DlcMoroathanc
1.1. l-TrUtiloroathsiM
Carbon l««r»chlor Ide
Ttlchloiaalhjlcn*
TaCrachloracth/laiM
Chloiobaicma
Dldiloiobaiieaa laoajcr
Dlctilorubb«n»n«
Dlbraocycloheuna
Braofen
No halogen +Clj
PI/LI/TI P1/U/T2
r
1 4
I T
T
T
11 1J
T T
-
I»
96
-
•• "
-
-
" *~
.
-
-
P1/L1/T3 PI/Ll/T*
T
1 ft
T T
t T
T T
27 12
T
-
119 I.16S
«9 64
-
~ ™
-
-
~ ~
-
-
-
P1/L1/TI PZ/Ll/TZ P2/LI/T1 P1/LI/T4
.
10 T T 9
HIT «
I T T 14
1 « 10 11
T 16 14 10
T T T T
IT T
1.412 1.291 1.392
11) 111 209
T T
"
_
_ _ • —
.
-
-
- - - -
*Bl,
ri/ti/Ti ri/um
-
» T
9 T
T T
11 10
7 T
T T
T
1.100
If)
-
-
~ ™
-
218 216
691 266
ri/Ll/T)
-
T
9
T
T
I
T
-
1.400
111
-
-
™
-
124
' 19
• lank
Pl/Ll/r4
-
-
•
T
7
-
-
-
1.490 1.140
96 96
-
-
"
-
244
14
-------
Table 37. SAMPLING AND EXPERIMENTAL PROTOCOL FOR IN SITU REACTION STUDIES
U)
Tl T! TJ
POl -
roz d,0-c d|(J-c
FOJ d8-S dj-S
" " ilO~C *\Q~C
tl - d -C d -C
10 10
" - "io-c dio-c
P4 - da-S «(-C
PI - dg-S dB-C
Pt - dfl-s *B-c
-
-
-
d|0-C - 16
d.o-C *Cl. 17
d|(|-C +«r. 10
de-C - 24
d(-C -IClj 24
dB-C -IBrt 10
HO
-
-
-
O
0
0
0
0
O
Sample VoluM
(0
0
a
0
98
«*
100
98
99
9.
•wurka
Ofl* TCMP.
-
-
-
1/10/19 9l*P
8/10/79 9Z*P
tl 30/79 89*f
9/6/79 90*P
9/6/T9 90' P
»/•/!* 10*P
TIM
l))OI-lttO>
lAilZ-17 i!2
17il4-16>14
14iOV-19iOO
lit 10-161 10
It 120-17 1 20
Site was at Tryon Hills, Raleigh, NC.
U-GFF « untreated glass fiber filter, d,n-C = cyclohexene-d,rt and d_-S « atyrene-da.
J.II J.U O O
CT-GFF • glass fiber filter with 1% sodium ttilosulfate.
.»
» glass fiber filter treated with 10Z sodium thlosulfate.
-------
Table 38. QUANTIFICATION OF IN SITU REACTIONS INVOLVING D -CYCLOHEXENE
AND MOLECULAR CHLORINE3
vo
Sample Code
Compound
d,-Benzene
o
d0-CycL
-------
Table 39. QUANTIFICATION OF IN SITU REACTIONS INVOLVING Djj-STYRENE AND MOLECULAR CHLORINE*
Compound
dg-Styrene
d ,-Ben zaldehy d e
dj-Chlorostyrene Isomer
dj-Chlorostyrene Isomer
d0-Styrene dichloride
D
P4/LI-A/T3
4.180
475
36
298
209
P4/L1-A/T4
3,526
237
ND
ND
ND
P6/L1-A/T1
4.080
307
ND
ND
ND
P6/L1-A/T2
3,395
445
ND
ND
ND
*See Table 37 for experimental protocol, values In ng/cartrldge.
\o
L/l
-------
Table 40. QUANTIFICATION OF IS SITU REACTIONS INVOLVING
DIQ-CYCLOHEXENE AND MOLECULAR BROMINE*
Compound
d, -Benzene
0
dg-Cyclohexadiene
d.Q-Cyclohexene
C7DU or C6D1Q0 isomer
C,D.. - isomer
7 12
C,D, . isomer
7 10
Dibromo-d.g-cyclohexane isomer
Dibromocyclohexane isomer
P1/L1-A/T3
40
48
1,076
13
19
44
6,258
1,033
P1/L1-A/T4
17
97
1,126
11
14
21
1,442
ND
9See Table 37 for experimental protocol, values in ng/cartridge.
96
-------
Table 41. QUANTIFICATION OF IN SITU REACTIONS INVOLVING
Dg-Sm£NE AND MOLECULAR BROMINE3
Compound P3/L1-A/T1 P3/L1-A/T2
dg-Styrene 756 646
d6-8enzaldehyde 264 47
aSee Table 37 for experimental protocol, values io ng/m •
97
-------
SECTION 8
QUALITATIVE AND QUANTITATIVE ANALYSIS OF VAPOR-PHASE ORGANICS IN AMBIENT AIR
INTRODUCTION
During the evaluation of the basic GC/MS/computer system for the
analysis of vapor-phase organics in ambient air, the improved methods were
applied to the analysis of several industrial atmospheres for the presence
of nutagenie and carcinogenic vapors. This section presents the results on
the qualitative analysis of vapor-pbase organics in air for several geogra-
phical areas.
In using a GC/MS/COMP system for the purpose of quantification of
selected organic compounds in ambient air, it is important that instrument
parameters be standardized in order to obtain reproducible and accurate
data. In order to achieve reproducible and accurate quantitative data from
a mass spectrometer, a number of criteria have been delineated which serve
as guidelines to achieve this objective. These are:
(1) the selection of a standard compound which represents the m/z
range of interest in the analyses;
(2) the calibration of the mass spectrometer to an "optimum" standard
spectrum to adjust relative ion (m/z) abundances within specified
tolerances;
(3) the minimum number of data points per chromatographic peak required
to achieve acceptable precision during acquisition of full scan
data;
(4) the documentation of stability of the mass spectrometer during the
analysis period;
(5) the relationship between the percent standard deviation (coeffi-
cient of variation) for the relative molar response ratios as a
function of the relative retention order for selected vapor-phase
orgaaics and the internal standard(s) selected for quantification;
and (6) the constancy of relative molar response ratios over the dynamic
mass (quantity) range of analysis (from the limit of detection of
the mass spectrometer to the overloading of the capillary column).
These factors are also discussed here.
98
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EXPERIMENTAL METHODS
Quantitative Factors
Instrument Standardization—
The standard which has been selected for determining instrument stabi-
lity as related by resolution and relative ion abundance is perfluorotoluene.
Perfluorotoluene exhibits ions throughout the mass range of interest for
vapor-phase organics with intensities of between 10 and 100% relative abun-
dance. Furthermore, this compound has been routinely included as an internal
standard for the quantification of vapor-phase organics in ambient air. In
order to select an optimum standard spectrum, six mass spectra from samples
which were analyzed on a Varian MAT CH-7 GC/MS/CQMP in each of the years
1977, 1978 and 1979 were randomly chosen and an average relative intensity
of each ion (5/2) in the spectrum, standard deviation, and coefficient of
variation were calculated. Likewise the same concurrent information was
tabulated for perfluorokerosene, a calibration standard commonly employed
with magnetic sector instruments. Furthermore, six samples for the years
1978 and 1979 were selected which had been analyzed on an LKE 2091 GC/MS/COMP
system. From all of these data, the average percent intensity, standard
deviation and range were determined.
Precision of Loading Tenax GC Cartridges—
To measure responses as a function of concentration, the compounds of
interest must be first be reproducibly loaded and desorbed from the Tenax
cartridge. The loading apparatus shown in Figure 25 was used. Helium was
purified by passing it through a cryogenic trap followed by two carbon
traps. The sample was loaded from a methanol solution by injection through
the septum of the heated loading tube. Vaporized components were swept onto
the Tenax GC cartridge by the helium flow. By judiciously selecting a total
purge volume of ~1.2 L, the majority of the methanol was passed through tbe
Tenax GC cartridge and since the compounds of interest have larger break-
through volumes they were retained on the Tenax cartridge. Thus, it was
possible to load relatively non-volatile compounds, specifically those which
are not amenable to preparation as permeation tubes.
To test this system, an initial set of cartridges was loaded with
zylene and naphthalene using a loading tube temperature of 170°C, the Tenax
cartridge temperature at 30°C, and 300 ml of helium purge volume (30 oL/min).
Under these conditions, naphthalene, which was considered as representative
of low vapor pressure compounds in the vapor-phase fraction, was found not
to be reproducibly loaded. On the other hand, xylene was reproducibly
loaded. To insure complete loading of naphthalene, the Loading tube tempera-
ture was increased to 275-280°C. The Tenax GC tube temperature was 33-35°C
and a helium flow of BO mL/min for 15 min was used. Four replicate cartridges
were loaded with 270 ng each of naphthalene, desorbed, and analyzed by GC on
a 55 m SE-30 wide bore WCOT capillary at 120°C for 4 min and then programmed
to 220eC at 4*C/min.
99
-------
TENAX GC CARTRIDGE CARBON TRAPS
I SEPTUM 3 WAY STOPCOCK / I
/ / 1 -• HaFLOWpOmLAnin)/ [
-*• wm—n A n=ntf—flOTI—
^, TO FLOW
o METER
0 * * LOADING TUBE WRAPPED
WITH ALUMINUM FOIL
TEFLON UNIONS AND HEAT.NG TAPE
Figure 25. Schematic of vaporization unit for loading organics dissolved In methano1 onto Tenax
CC cartridges.
-------
RMRs vs. Relative Retention Order to Standards-
Twelve compounds - dichlarooiethaae, 1,1-dichloroethane, perfluorobenzene,
chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, carbon tetrachloride,
trichloroethylene, bromodichloromethane, tetrachloroethylene, chloroform,
and dichlorobeazene - were loaded as a replicate set of six on Tenax GC
cartridges. Cartridges were then analyzed by thermal desorption GC/MS/CQMP
using an 1KB 2091 system and standard conditions. A second set of six was
analyzed on a Variau MAT CH-7 GC/MS/CQMP system.
Data sets were statistically analyzed to obtain coefficients of varia-
tion.
RMR vs Vapor-Phase Component Quantity—
The objective of this set of experiments was to deterime whether: (1)
the relative molar response ratio was constant and independent of mass
quantity over the range of interest when chromatographing the vapor-phase
organics on the SE-30 wide bore capillary columns; and (2) whether a mass
quantity dependence might occur due to changes in sample pressure in the ion
source.
Tenax GC cartridges were loaded with diethyl ether, nitromethane, 1,2-
dichloroethane, n-butanol, chlorobenzene, anisole, and naphthalene at three
mass quantities 7^800, *80, Mi ng/cartridge) over the dynamic capacity range
of the wide bore SE-30 coated capillaries and including near the limits of
detection of the mass spectrometer. A replicate set of six cartridges for
each mass level was analyzed by GC/MS/COMP and the data were statistically
treated.
Qualitative and Quantitative Analysis of Ambient Air Samples
The technique for collection of vapor-phase organics has been previously
described. Improvements described in this report were incorporated into the
sampling and analysis protocol. These improved methods were used for the
analysis of vapor-phase organics in Baton Rouge and Lake Charles, LA, Houston
and Beaumont, TX.
The GC/MS/COMP analysis parameters used were identical to those described
in Section 7 (Table 4).
Tables 42-45 and Figures 26-36 present the sampling protocols for Baton
Rouge, Lake Charles, Beaumont and Houston and their respective sampling
locations. Table 46 provides the listing of the major industrial firms in
Baton Rouge, LA and vicinity depicted in Figures 26 and 27.
RESULTS AND DISCUSSION
Quantitative Factors
Instrument Standardization—
Previously recorded data accumulated on a Vanan CH-7 for perfluoroto-
luene (PIT) and perfluorofcerosene (PTK) for the years 1977, 1978 and 1979
are given in Tables 47 and 48, respectively. Included are statistics for
101
-------
Table 42. SAMPLING PROTOCOL FOR BATON ROUGE, LA AND VICINITY
o
to
Slt< Sibling Period/Location*
B*IM Brage, L* Pl/tJA-l.Z
110 and College Dr.
" PI/158
PI/tJA
M/LJB
P2/UC
" Pl/LJ*
P3/LSB
PJ/I.SC
Sampling Tl» ValuM Supled
(•lal U>
110 104
120 9J
114 116
11* 101
111 *0
110 lit
1ZO 101
110 »»
••Wflt*
1I/S/1B
si'r
ISO/It.
IZ/I/IB
WP
IBD/U.
11/J/H
H*f
VM/ll.
1I/J/78
JJ'P
VAM/lt.
11/S/I*
Ji-r
VM/lt.
tl/J/M
*T*r
VM/O
1I/1/T6
tl'P
VM/O
n/sm
4I*P
VM/O
1141-1)4}
SOI *M
1110-1)30
»OX «H
I1U-1MO
«ox nt
1 601-1400
401 W
D1B-1BOO
*OS BH
1114-1014
m M
lB»-10t»
T2S Mi
1BIO-101D
I2X Ml
(continued)
-------
Table 42 (cont'd.)
Slt<
lod/Lac*t Ion*
TIM
(•In)
(0
Baton louse . LA
Hv. 61 *nd Thau* Rd.
Bilaa •oug*. tA
Htt. 61} Ml. 1. 4. bull'*
reach
T4/L1
r4/L2
M/LJ
Mi
talon Roug*. LA
Chaclan Id. and fhln Si.
Btton Bang*. LA
Off Rout* ISO
B*tva •out*. LA
Off Uoodlmti U.
PS/ LI
PS/L7
Pi/Li
P5/L1
120
120
120
171
12O
110
1*4
191
1*1
232
1*6
I2/6/7B
74*r
10>7-UH
tit RH
12/D/IB
7i'r
90/U.
17/6/7B
90/U.
12/6/78
7i-r
VAR/lt.
U 14- 1314
621 RH
mo-i»o
«1X RH
1210-1410
62> RH
17/7/78 0*11-1102
BO*P 791 RH
160/10 kt«
111 J Hi OV4O-II40
eo-r 191 MI
1*0/10 U*
12/»/7S
•o*r
ieu/to k
09)2-11)2
ill RH
12/7/78 1416-16)1
Bl'r 771 RH
IBO/ll kt*
(continued)
-------
Table 42 (cont'd.)
S«vlln| lime
Sit. Bufllng rcrlod/Locatlon
-------
Table 43. SAMPLING PROTOCOL FOR VAPOR-PHASE ORGAN1CS IN LAKE CHARLES, LA
o
Ln
Site Sampling Period/Location
Lake Charles, LA
Off Highway 90 Vest
& 1-10
ii
Lake Charles, LA
Off 1-210
Lake Charles, LA
Off Highway 90 Vest
& 1-10
ii
it
ii
it
Lake Charles, LA
Off 1-210
PI/LI
P2/L1
P2/L2
P3/LI
P4/L1
P5/L1
P6/L1
P7/L1
P7/L3
Sampling Time Volume
(min) (£) Remarks
75 135.8 2/14/79
69 °F
120 143.0 2/14/79
72°F
120 166.1 2/14/79
72°F
60 113.4 2/14/79
69°F
60 101.1 2/15/79
65 °F
60 110.6 2/15/79
65°F
60 112.0 2/16/79
56 °F
120 126.0 2/16/79
53°F
120 148.4 2/16/79
52°F
0835-0950
19°/10 kts
1230-1430
1BOV20 kts
1230-1430
180°/10-12 kts
1639-1739
180°/15 kta
0904-1004
17°/12 kts
1653-1753
1?°/12 kts
1419-1519
4S°/5-10 kts
1443-1643
45°/5-10 kts
1445-1645
Var/Lt.
(continued)
-------
Table 43 (cout'd.)
Site Sampling Period/ Location
Lake Charles, LA P8/L1
Off Highway 90
& 1-10
P9/L1
" P10/LI
Sampling Time Volume
(mi a) (£) Remarks
60 101. 0 2/19/79
3A°F
60 103.0 2/19/79
36°F
60 104.0 2/19/79
36°F
0907-1007
270°/5-8 kts
1013-1113
270°/5 kts
1123-1223
270°/5 kts
o
a-
-------
Table 44. SAMPLING PROTOCOL FOR VAPOR-PHASE ORGANICS IN BEAUMONT, TX AND VIC1NITH
Sampling Time Volume
Site Sampling Period/Location (rain) (£)
Port Heches. TX
Spur 136 Farm Rd.
Beaumont, TX
Vest Port Arthur Rd.
it
»
Groves, TX
Farm Road 366
it
ii
Port Neches, TX
Spur 136 Farm Rd.
ii
Pl/Ll
P2/11
P2/L2
P2/L3
P3/L1
P3/L2
P3/L3
P4/L]
P4/L2
2898
120
120
120
120
120
120
120
120
162.3
99.7
101.9
68.6
103.5
113.6
96.7
111.6
106.6
Remarks
3/27-28/79
73°F
3/27/79
77'F
3/27/79
77°F
3/27/79
77°F
3/28/79
75°F
3/28/79
7S*F
3/28/79
75°F
3/30/79
72°F
3/30/79
72°F
0955-1013
180°/10-15 kts
1240-1440
180V 10-15 kts
1240-1440
180°/10-15 kts
1240-1440
180°/10-15 kts
1210-1410
290°/15-20 kts
1210-1410
290°/15-20 kts
1210-1410
290°/15-20 kts
1135-1335
2900/ 10-20 kts
1135-1335
290°/10-20 kts
(continued)
-------
Table 44 (cont'd.)
o
00
Sampling Time Volume
Site Sampling Period/Location (mln) (I) Remarks
Port Heches. TX P4/L3
Spur 136 Farm Rd.
Beaumont. TX P5/L1
Spur 380
11 P5/L2
P5/L3
FM 347 P6/L1
P6/L2
" P6/L3
120 114.7 3/30/79
72"F
102 4/3/79
63°F
98 4/3/79
121 4/3/79
60 86.9 4/5/79
62°F
60 78.6 4/5/79
62°F
60 80.3 4/5/79
62°F
1135-1335
290°/10-20 kta
1125-1325
270V10-15 kts
1125-1325
270°/10-15 kta
1125-1325
270V10-15 kts
0945-1045
90°/5-10 kts
0945-1045
90-/5-10 kts
0945-1045
90°/5-10 kts
-------
Table 45. AMBIENT AIR SAMPLING PROTOCOL FOR HOUSTON, TX AND VICINITY
Site Sampling Period/Location
Houston, TX
16530 Pennlaula Blvd.
Pasadena, TX
Off Highway 225E
Pasadena, TX
Off Richey St.
Deer Park, TX
Off Highway 225K
PI/LI
P2/L1
P3/L1
P4/L1
PS/Li
P6/L1
P7/L1
P9/L1
P9/L2
P11/L3
P13/L4
Sampling Time
(min)
90
90
90
90
90
90
90
90
90
90
90
Volume
U)
91
105
89
76
93
102
101
102
119
94
95
Remarks
6/7/79
86-F
6/7/79
86°F
6/8/79
86" F
6/8/79
82'F
6/8/79
84° F
6/8/79
84" F
6/8/79
87-F
6/11/79
75"F
6/11/79
75°F
6/12/79
85°F
6/13/79
85°F
1355-1525
210*7^15 kta
1545-1715
210°/^10 kts
940-1110
180" /5-10 kts
1115-1245
200*75-10 kts
1300-1430
180° 75-10 kts
1433-1603
210*75-10 kts
1606-1736
210°/10 kts
1030-1200
45*710-15 kta
1000-1130
45*710 kts
1430-1600
45*75-10 kts
1500-1630
45'/Lt
-------
\
KOTUNCVILL£
Figure 26. Location of plants in the East Baton Rouge Parish.
110
-------
Figure 27. Sampling locations in Bacon Rouge, LA area.
Ill
-------
Figure 28. Sampling locations in Plaquemine, LA area.
112
-------
Figure 29. Sampling locations in Lake Charles, LA.
113
-------
Figure 30. Sampling locations near Lamar University in
Beaumont, TX.
114
-------
L3
Figure 31. Sanpling locations along Southern Railway in Beaumont, TX.
115
-------
VELSICOL
Figure 32. Sampling locations along West Port Arthur Road in Beaumont, TX.
116
-------
a F GOODRICH
CHEMICAL
NECHES
BUTANE PRODUCT
Figure 33. Sampling locations in Port Neches, TX.
117
-------
1 i I—ill I \ ~r
L3
I I I I I f
SAS
I
r
Figure 3A. Sampling locations in Groves, TH.
118
-------
~."
Figure 35- Sampling locations in Jacinto Port area near Houston, TX.
119
-------
IIMI1I II . I » I I .
MPAMIMt Nl HI I HI IMU
UtIM ItUK >l SIHI» 1
K)
O
I '
Figure 36. Sampling locations in Deer Park and Pasadena, W areas.
-------
Table 46. MAJOR INDUSTRIAL PLANTS
Plant A
Plant B
Plant C
Plane D
Plant £
Plant F
Plant G
Plant H
Plant I
Plant J
Plant K
Plant L
Rollins Environmental Services
Allied Chemical Corporation, Plastics Plant
Uniroyal Inc.
American Hoechst Co.
Stauffer Chemical Co.
Kaiser Aluminum & Chemical Corp.
Copolymer Rubber & Chemical Co.
Allied Chemical North Works, Industrial Chem.
Ethyl Corporation
Uniroyal Inc., Gulf States Road Plant
Exxon USA, refinery
Allied Chemical South Works, Speciality Chem.
121
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Table 47. RELATIVE ION ABUNDANCES FOR PERFLUOROTOLUENE OBTAINED ON A VARIAN HAT CH-7
GC/HS/COMP SYSTEM8
m/z
69
74
79
93
98
117
£ 1Aa
167
186
217
218
236
237
1977
%I J S.D. (C.V.)
36 + 17 (48)
4 + 2.1 (55)
9 + 4.1 (44)
18 + 7.3 (39)
14 +_ 5.3 (38)
48 + 15 (31)
11 + 2.4 (22)
17 + 1.9 (11)
62 + 2.8 (4)
100 + 0 (0)
8 + 0.4 (5)
67 + 7.2 (11)
6 + 0.8 (15)
1978
%I + S.D. (C.V.)
38 + 7.0 (18)
6 + 2.7 (45)
14 + 7.1 (51)
20 + 6.2 (31)
11 + 0.9 (9)
47 + 9.3 (20)
10 + 3.1 (31)
18 + 4.7 (26)
59 + 12 (20)
100 + 0 (0)
8 ± I. I (14)
63 + 17 (27)
6 + 1.5 (25)
1979
%I + S.D. (C.V.)
34 + 2.7 (8)
6 + 1.7 (29)
11 + 2.2 (20)
15 + 1.6 (11)
14 + 3.1 (22)
45 + 9.7 (22)
10 + 1.5 (15)
17 + 1.9 (11)
66 + 6.3 (10)
100 + 0 (0)
10 + 3.0 (30)
68 + 6.1 (9)
7 + 1.2 (17)
•77 + '78 + '79
%I + S.D. (C.V.)
36+2 (5)
5 + 1.1 (23)
11 + 2.5 (23)
18 + 2.5 (14)
13 + 1.7 (13)
47 + 1.5 (3)
10 + 0.6 (6)
17 + 0.6 (4)
62 + 3.5 (6)
100 + 0 (0)
9 + 1.1 (13)
66 + 2.6 (4)
6 + 0.6 (10)
Data obtained during capillary chromatography.
-------
N)
CiJ
Table 48. KKI.AT1VE ION ABUNDANCES FOR PERFLUOROKEKOStNE OBTAINED ON A
VAKIAN MAT CII-7 GC/MS/COMP SYSTtM
m/z
51
100
1193
131
169
181
219
231
1977
%l + S.D.
38
21
100
88
60
65
26
32
+ 8.0
+ 3.2
(C.V.)
(21)
(16)
1 0 (0)
+ 6.7
+ 4.5
+ 5.0
+ 3.3
+ 4.6
(8)
(8)
(8)
(13)
(15)
1978
%I + S.D.
44
21
100
85
56
58
22
25
+ 4.9
+ 1.4
1979
(C.V.)
(11)
(7)
± 0 (0)
+ 2.5
+ 1.7
+ 6.3
+ 1.0
+ 1.9
(3)
(3)
(11)
(4)
(7)
%1 + S.D.
36
24
100
95
59
62
25
29
+ 4.1
+ 2.1
(C.V.)
(H)
(9)
+ 0 (0)
+ i.2
+ 4.0
+ 4.8
+ 1.3
+ 2.6
(I)
(7)
(8)
(5)
(9)
'77 +
•78 + '79
%l + S.D. (C.V.)
39 +
22 +
100 +
89 +
58 +
62 +
24 +
29 +
4.1 (11)
1-7 (8)
0 (0)
5.1 (6)
2.1 (4)
3.5 (6)
2.1 (9)
3.5 (12)
Intensities were normalized to m/z 119 since m/z 69 was saturated in all cases.
-------
the relative ion abundances for sets of data collected during each year and
then a composite data set. Variations are observed in the relative intensity
of each ion (n/z) from sample to sample; however, the coefficients of varia-
tion are relatively constant when comparing data sets. No attempts had been
made to "control" mass resolution and relative ion intensities for PF8 when
calibrating this instrument. Thus, the coefficients of variation might be
expected to be larger than for a more closely "controlled" calibration. The
software system on this system only tests mass resolution fits.
An "optimum" m/z vs. relative intensity listing for PFK and PFT is
given in Table 49." In order to achieve a ±7% C.V. the suggested range was
proposed. Use of tight relative ion intensities over the mass (m/z) range
should allow the use of RMR data determined either during analysis of a
sample set or from previously recorded data with a minimal variation in the
RMRs.
Table 50 presents similar data obtained on an LXB-2091 for the years
1978 and 1979. In this case the software program requires mass and intensity
fits to be obtained. It is very evident that the coefficients of variation
are considerably better than from the CH-7 system. Concomitantly, RMR data
for vapor-phase compounds have been rather constant over an extended period
of time for which information exists (."• 1 year).
Precision of Loading Tenax GC Cartridges—
Results given in Table 51 indicate that naphthalene can be reproducibly
loaded by the vaporization method (Fig. 25). Since the Tenax GC cartridge
temperature doesn't exceed 35"C, more volatile compounds should be success-
fully loaded without loss. To verify this a solution of the following
composition was prepared and loaded: 1,2-dichloroethane - 400 ng, nitrome-
thane - 400 ng, toluene - 250 ng, diethyl ether - 1000 ng and naphthalene -
290 ng. Desorption and analysis by GC/MS/COMP gave the results in Table 52.
Blank No. 1 was obtained by loading only a 10 pL volume of methanol. Blanlc
No. 2 was placed in series with the cartridge tube and represents the break-
through concentration. These data indicate that the more volatile compounds
can also be loaded at the higher temperature.
An initial problem encountered with the more volatile components was
that the methanol peak from the solvent was partially obscuring these compo-
nents . In addition the amount of methanol that was retained on the Tenax GC
cartridge was too large and interfered with the operation of the ion source
in the GC/MS. It was then decided to increase the volume of helium to
1.2 L, a setting well below the breakthrough volume of the majority of
compounds of interest.
RMR vs. Relative Retention Order to Standards--
Perhaps the most interesting observations were made when arranging the
components in the elution order vs. the internal standard giving the lowest
deviation limits under various operating conditions. Table 53 lists the
coefficients of variation for RMRs as a function of relative retention order
for selected vapor-phase organics. These data represent the analysis of six
Tenax GC sampling cartridges which were loaded with the corresponding
124
-------
Table 49. SUGGESTED MASS AND INTENSITY TOLERANCES ACCEPTABLE FOR
CALIBRATION OF MAGNETIC INSTRUMENTS FOR QUANTITATIOS
Perfluorotoluene*
JJ/_Z
69
79
93
117
167
186
217
236
21 (C.V.)
33 (5)
11 (10)
16 (8)
43 (8)
15 (7)
59 (5)
100 (0)
66 (4)
Perfluorokerosene
m/z
51
100
119
131
169
181
219
231
ZI (C.V.)
39 (10)
22 (8)
100 (0)
89 (5)
58 (4)
62 (6)
24 (5)
29 (8)
aTo be achieved in the chromatagraphy node.
125
-------
Table 50. RELATIVE ION ABUNDANCES FOR PERFLUOROJOLUENE
OBTAINED ON AN LX3-2091 GC/MS/COHP SYSTEM
JB/J
69
74
79
93
98
108
117
148
167
186
217
218
236
237
1978
%I + S.D. (C.V.)
30+3 (10)
4+0.6 (13)
10+1.0 (10)
16 + 1.2 (8)
12 + 1.4 (11)
4+0.38 (9)
37 + 2.4 (6.8)
8 + 0.50 (6)
13 + 0.64 (5)
56+1.4 (3)
100 + 0 (0)
8 + 0.42 (6)
68 + 3.3 (5)
6+0.46 (3)
1979
%I + S.D. (C.V.)
30 + 1.2 (4.0)
5 + 0.23 (4.0)
11 + 1.0 (14)
17 + 1.2 (7)
13 + 1.8 (14)
4 + 0.26 (6.5)
40 + 2.5 (6)
9 + 0.92 (10)
15 + 0.78 (5)
57 + 2.8 (5)
100 + 0 (0)
8 + 0.66 (8)
67 + 1.6 (2)
6 + 0.33 (5)
1978 + 1979
%I + S.D. (C.V.)
30 + 2.3 (7.6)
5 + 0.82 (17)
11 + 1.4 (13)
16 + 1.3 (8)
13 + 1.6 (12)
4 + 0.37 (9)
39 + 3.0 (8)
9 + 0.73 (9)
14 + 0.96 (7)
56 + 2.2 (4)
100 + 0 (0)
8 + 0.58 (7)
67+2.7 (4)
6 + 0.39 (7)
Data obtained in the chromatography mode.
126
-------
Table 51. PKECIS1ON OF LOADING NAPHTHALENE ONTO TENAX GC CARTRIDGES
AND ANALYSIS BY IIRGC/EIMS/COMP
Run no.
1
2
3
4
Naphthalene
-------
Table 52. PRECISION OF LOADING SELECTED VAPOR-PHASE ORGAN1CS ONTO TENAX GC CARTRIDGES
AND ANALYSIS BY HRGC/E1MS/COMP
Peak Height
Run No. Naphthalene
1 19.3
2 19.6
3 19. A
1 ,2-Dichloroethane
2.1
2.7
1.6
Nitromethane
7.3
6.0
7.1
Toluene
23
24
22
Mean + S.D. (C.V.J
Blank 1
Blank 2
19.4 + 0.15 (0.7)
0.7
0.1
2.1 + 0.55 (26)
6.8 + 0.7 (10) 23+1 (4)
2.4
2.1
-------
Table 53. COEFFICIENT OF VARIATION FOR RMRs AS A FUNCTION OF
RELATIVE RETENTION ORDER FOR SELECTED VAPOR-PHASE ORGANICS
Compound
Dichloromethane
1 , 1-Dichloroethane
Perfluorobenzene (if)
Chloroform
1 , 2-Dichloroethane
1,1, 1-Trichloroe thane
Carbon tetrachloride
Trichloroethylene
Bromodichlorooe thane
Tetrachloroethylene
Chlorobenzene
Dichlo robenzene
Relative retention
0.75
0.89
1.00
l.OA
1.17
1.19
1.28
1.44
1.44
2.03
2.20
3.06
Set no.
5
5
—
8
3
8
7
12
13
3
13
12
C.V.
lb Set no. 2C
22
11
—
12
8
12
10
12
18
22
~
—
aSee Table 4 for instrument conditions.
bData obtained using an LKB-2091 GC/MS/COMP.
CData obtained using a Varian MAT CH-7 GC/MS/COMP.
129
-------
compounds and then analyzed under normal operating conditions by GC/MS/COHP
with an LKB-2091 system. The first set of data indicate that the coefficient
of variation increased as the relative retention time to that of the internal
standard perfluorobenzene also increased. For example, compare the coeffi-
cient of variation for chloroform (8%) to that of dichlorobenzene (12%).
The experiment was repeated using a Varian MAT CH-7. The scan cycle times
were 1.7 and 3.7 sec on the 1KB 2091 and Varian CH-7 systems, respectively.
The increase in the coefficient of variation between the two systems is
evident since the number of data points generated per chromatographic peak
on the LKB 2091 was greater than the Varian CH-7 since the average resident
time of a chromatographic peak is M>-8 sec on wide bore capillaries. It
appeared that a minimum of 5 data points (scans) was necessary to adequately
describe the chromatographic peak using the reconstructed total ion current
obtained from full scan data. These data suggest that a second standard is
required which elutes in the chromatographic range near chlorobenzene/naphtha-
lene to obtain the highest precision.
The observations described here have been thoroughly studied and also
reported elsewhere (10).
RMR vs. Vapor-Phase Component Quantity—
Experiments were conducted in order to determine whether or not relative
molar response values of vapor-phase organics analyzed by GC/MS/COMP were
independent of mass over the dynamic range of interest. Since the RMR value
is ultimately based upon a response/molecule, it should be mass quantity
independent. An observed dependence of RMR values on mass may occur, £•£•»
due to adsorptive losses on the chromatographic column which would then
inherently negate the validity of the assumption. The use of relative molar
response ratios is based upon a one point calibration curve with a required
linearity over the entire range of interest and an intercept through zero.
A dependence on mass due to, for example, changes in sample pressure in the
ion source would, however, also negate the assumption of a constant RMR.
This question therefore is a major one which must be answered positively if
the concept of RMR is to be used as a means of obtaining quantitative informa-
tion with a GC/MS/COMP system.
The compounds selected for the study of the effect of concentrations on
the relative molar response ratio are shown in Table 54. Diethyl ether,
anisole, chlorobenzene, 1,2-dichloroethane, nitromethane, naphthalene, p_-
xylene and toluene were chosen because they represent vapor-phase organics
which are typical of the classes that have been detected in the ambient air.
These compounds were loaded at three concentration levels over two orders of
magnitude and six replicates were run at each loading level. The analyses
were run on an LKB 2091 using a 75 m SE-30 wide bore WCOT capillary (Table
4). Relative molar response ratios relative to perfluorobenzene were deter-
mined by peak heights. These results are shown in Table 54. These data
show remarkable consistency over a concentration of two orders of magnitude.
The coefficients of variation are comparable with those found in other
experiments and the errors involved include those encountered in loading,
desorption and analysis. It should be pointed out that the lowest concentra-
tion of the three is quite close to the detection limit of the mass spectro-
meter for all compounds under these operating conditions.
130
-------
Table 54. PRECISION OF RELATIVE MOLAR RESPONSE RATIO
AS A FUNCTION OF MASS OF COMPOUND
Compound jn/.z
Di ethyl ether 59
Nitronethane 61
1,2-Dichloroethane 62
a-Butanol 56
Chlorobenzene 112
Anisole 108
Naphthalene 123
Quantity
(ag)
842
84.2
8.4
800
80
8
800
80
8
800
80
8
800
80
8
800
80
8
750
75
7.5
RMR + S.D. (C.V.)
0.36 ± 0.036 (10)
0.36 ± 0.188 (52)
0.353 —
Mean 0.36 ± 0.012 (3)
0.14 ± 0.044 (31)
0.13 ± 0.016 (12)
0.17a —
0.15 ± 0.021 (14)
0.65 ± 0.046 (7)
0.71 ± 0.036 (5)
0.79 ± 0.130 (16)
0.73 ± 0.21 (28)
0.33 ± 0.073 (22)
0.32 ±a0.068 (21)
• M
0.32 ± 0.070 (21)
1.39 ± 0.07 (5)
1.19 ± 0.13 (11)
2.03 ± 0.35 (17)
1.65 ± 0.47 (28)
0.96 ± 0.055 (6)
0.85 ± 0.049 (6)
0.92 ± 0.115 (12)
0.91 ± 0.094 (10)
1.51 ± 0.19 (12)
1.51 ± 0.47 (31)
1.94 ± 0.59 (30)
1.65 ± 0.51 (30)
Near or below limit of detection.
May result from a poor loading of one sampling cartridge.
131
-------
Use of Deuterated Compounds During Ambient Air Sampling
It is recommended that, during ambient air sampling, deuterated coo-
pounds be incorporated into the sampling regime. There is a high probabi-
lity that deuterated organics will not be found in ambient air and thus they
will not interfere with the subsequent analysis. The mass spectrometer
provides an ability to differentiate between deuterated compounds which are
considered exogenous as compared to the endogenous vapor-phase organics in
ambient air.
The incorporation of deuterated compounds can be performed in two ways:
(1) a series of deuterated compounds [£-g-, d$-dimethylamine, d$-benzene,
ds-broooethane, d10-cyclohexene and dg-styrene may be loaded as a discrete
zone directly onto the Tenax GC sampling cartridge using the vaporization
system depicted in Figure 21 or from permeation tubes; and (2) by the use of
permeation tubes during field sampling whereby the ambient air stream is
spiked with known quantities.
The use of deuterated compounds in the sampling regime provides an
ability to check on potential artifacts which may occur as a result of the
reactivity of the atmosphere being sampled. The suggested deuterated
compound would allow for determination whether nitrosation, ozonization or
halogenation might have occurred during the concentration of organics onto
the sampling cartridges, since the mass spectrometer provides the opportunity
to identify any deuterated by-products. Furthermore the incorporation of
the suggested deuterated compounds provides a check on the breakthrough
volumes which have been calculated for a series of compounds of interest in
order to quantify them. Any variations in the breakthrough volume of a
compound as a direct result of the specific air sampled would be reflected
by these compounds since they span a large range of breakthrough volumes
that are experienced for vapor-phase compounds. The premature disappearance
of these compounds would indicate that the quantity of air sampled is beyond
the dynamic range of the collection device (i.*e., capacity which exists as a
function independent of frontal displacement chromatography). A standard
technique used by most laboratories employs backup sampling cartridges to
determine whether premature breakthrough of organic constituents has occurred.
Although this technique has been employed in the quantification of vapor-phase
organics by GC/MS/COMP, the use of deuterated compounds as suggested above
is preferred. The use of a backup cartridge alters the pressure differential
across a sampling device and thus complicates the determination of premature
breakthrough since vacuum stripping of adsorbed materials also becomes a
factor leading to premature breakthrough.
Statistical Analysis of Permeation Rates
In previous reports, research has been described in the development of
a permeation system and the use of permeation tubes for the purpose of cali-
brating the GC/MS/COMP system for quantification of vapor-phase organics in
ambient air samples. Procedures have employed the weekly to biweekly gravi-
metric determinations of the weight losses of permeation tubes to calculate
the permeation rate for each organic compound. A statistical approach has
been developed in this laboratory which utilizes a linear regression analysis
132
-------
of the six most recent gravimetric determinations for each permeation tube.
The permeation rate calculated on this basis thus has associated with it an
error band (standard deviation). Permeation rates which exhibit percent
standard deviations of >10% or a significant non-zero slope are rejected for
purposes of calibrating the GC/MS/COMP systems.
Qualitative and Quantitative Analyses
The vapor-phase organics which were identified in ambient air from
Baton Rouge, Plaquemine and Lake Charles, LA, Beaumont, Groves, Port Neches,
Houston, Deer Park and Pasadena, TX are given in Appendix A.
Many of the halogenated hydrocarbons which have been previously identi-
fied during sampling trips executed between the period of 1973 to 1977 were
again identified in these samples. The site-specific and ubiquitous halogena-
ted hydrocarbons were again detected in these atmospheres. Tables 55-57
present the estimated levels of several of these vapor-phase organics.
Several levels of compound identification have been employed in the
course of analysis of vapor-phase organics in ambient air samples. These
criteria have developed throughout several years of experience in the identi-
fication of organic compounds and have been used in our laboratories to
establish the degree of certainty of the identity of an organic compound.
These levels of identification are as follows:
Level I Computer Interpretation. The raw data generated from the
analysis of samples are subjected to computerized deconvolution/
library search and compound identification made using this
approach has the lowest level of confidence. In general
Level I is reserved for only those cases where compound
verification is the primary intent of the qualitative analysis.
Level II Manual Interpretation. The plotted mass spectra are manually
interpreted by a skilled interpreter and compared to those
spectra compiled in a data compendium. In general a minimum
of five masses and intensities (±5% S.D.) should match be-
tween the unknown and library spectrum. This level does not
utilize any further information such as retention time since
many compounds the authentic compound may not be available
for establishing retention times.
Level III Manual Interpretation Plus Retention Time/Boiling Point of
Compound. In addition to the effort as described under Level
II, the retention time of the compound is compared to the
retention time which has been derived from previous chromato-
graphic analysis. Also the boiling point of the identified
component is compared to the boiling points of other compounds
in the near vicinity of the one in question when a capillary
coated with a non-polar phase has been used.
133
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Table 55- ESTIMATED LEVELS OF SEVERAL VAPOR PHASE ORGANICS IN
LAKE CHARLES, LA AIR3
Chemical
Benzene
Vinylidene chloride
Chloroform
Carbon tetrachloride
1, 2-Dichloro ethane
1, 1, 1-Trichloroethane
Trichloroechylene
Tetrachloroethylene
Dichlorobenzene isomer
Dichlorobenzene is oner
1,2-Dichloroethylene
1,2-Dichloroethylene
1,1,2-Trichloroe thane
1,1,1,2-Tetrachloroethane
Chlorobenzene
1, 1,2, 2- Tetrachloro ethane
1, 3, 5- Trichloro benzene
Pentachloroethane
Pentachlorobromoethane
Pentachlorobutadiene
Hexachlorobutadiene
Bromoform
Bromocyclohexane isomer
Chloromethylbutene isomer
aSee Table 43 for sampling
Upwind sample, all values
P2/L1-T1
223
51
118
46
66
98
45
50
6
T
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
protocol.
in ng/m .
Sample
P2/L2-Tlb
223
ND
107
44
47
69
29
40
6
2
ND
ND
ND
ND
T
ND
ND
ND
ND
ND
ND
ND
ND
ND
Code
P7/Ll-T1b
217
ND
96
46
1,309
67
61
69
5
T
ND
ND
53
ND
8
64
ND
ND
ND
ND
ND
ND
ND
ND
P7/L3-T1
867
6,226
862
107
11,516
1,739
9,557
3,504
13
12
8,233
8,240
3,632
741
40
4,946
8
273
347
713
1,312
ND
ND
ND
134
-------
Table 56. ESTIMATED LEVELS OF ORGANIC VAPOR-PHASE POLLUTANTS IN AMBIENT AIR OF
BEAUMONT, TX AND VICINITY3
Co-found rz/tl P1/L2 PI/LI PI/LI Pl/1.2 Pl/LJ ' P4/LI M/LZ P4/L1 PS/LI PS/LI PI/L3 Pft/tl Pb/LI P6/L1
Clhyl •cct.t* 111 158*91 100 8. ZOO T 681 + liZ 1.649 SB1 4,140 9.111 4,140 T HO 1.640 +J T
»«n«MMi 4. Z» J.II9»I.M4 1.9JS 14.619 111 I.4IB fr 104 1.181 1.061 ]),B4< B.14S 6. lit 3.000 4.411 Z. 478* 117 6,110
1.1-Dlchlaiopruptacr T ND H> MD Z.141 1,»W tOHDTHD TWD1MD HO T
T*tr«chloracthrlcn* 2JO 111 * n> 20> 8Z<) 204 790 084 449 9Z) 1.960 6ZO 496 114 JO) + • MO
CfalarabaiHni 90 119 i M 90 10 114 1.190 61 91 84 SO T T HO ND T
Carbon tttrachlorUe SSI 6&6 + IS 811 l.SOO 611 »*9 » 194 944 HI Bll 16.189 111 I.OOO I/Z 1.639 * 2)0 l,IJl
l.Z-Dlbrn»e:thaac> f T HD MD ND TTKBT I.6OO 1.J9O T HO MB T
a
See Table 44 for sampling protocol.
-------
Table 57. ESTIMATION OF LEVELS OF VAPOR-PHASE ORGANICS IN AMBIENT AIR IN
HOUSTON, DEER PARK AND PASADENA, TX AND VIC1NITY3
Period/Local Ion
Compound
PI/LI
P1/L1A
PJ/L1B
P4/LI
PS/LI
P6/L1
P9/L1 P9/L2 Plt/Ll Pll/L*
Co
1.2-DlchloroclhM*
1.1.1-Tr Ichloroctlila*
Carbon (•trichloride
Trlchloroatbf l«iu
BraBodlcblor
Dlbrmnchlora
Tatiachloroothylmi*
Chtarobmem
Dlchlorobaaun* iaoaar
Dlcblorobracan* Imtmer
BeMchlorobutadlma
26.100± 4.000 7.221+1.025 S.82i + 1.92J 4.2001600 13.4SO 11.0S04tOO
900
620 1 100 900 1 140
1.266 1 1,113 1,767 + 100
2.4331600 1.36710
ND
MD
23.404
HD
ND
IJ.862 1 3.167
T
67
76
318 «• 31
980 ± 140
1.566 » 33
1.183 * 183
MD
MD
1,140 + 100
861 + 0
650 ± 110
MO
HD
640 * 123
T
T
416
12.107 + 3.219 2.112 * 12}
477 » 241 2,7«6 + 3»
T t
T T
404 «• 134 237
7.JJO T
760 1.360 1 S20 1.360 560 720
933 9331131 600 6.6OO 1.467
167 567 T 3.131 3.813
ND MO MD MD NO
ND ND MD ND ND
1.330 1.420130 140 2.269 9S7
1.300 900 1 40 T 84 T
T T MO HD T
MD 80 MD T ND
T 220 HD T HO
700
ND
606
149
191
•D
MD
See Table 45 for sampling protocol.
-------
Level IV Manual Interpretation Plus Retention Time of Authentic Com-
pounds . Under this Level, the authentic compound has been
chromatographed on the same capillary column using identical
operating conditions and the mass spectrum of the authentic
compound is compared to that of the unknown.
Level V Level IV Plus Independent Confirmation Techniques. This Level
utilizes other physical methods of analysis such as GC/
fourier transfonn/IR, GC/high resolution mass spectrometry, or
NMR analysis. This Level constitutes the highest degree of
confidence in the identification of organic compounds.
The predominant qualitative analysis that has been performed during the
past several years has utilized Level III for qualitative analysis.
Appendix B gives the profile listings for the halogenated compounds
identified. Many of these have been suggested as potential atmospheric
carcinogens.
137
-------
REFERENCES
1. National Academy of Sciences. Report of the Committee for the Working
Conference on Principles of Protocols for Evaluating Chemicals in the
Environment, "Principles for Evaluating Chemicals in the Environment",
Washington, D.C., (1976), p. 299.
2. Commoner, Barry, "Identification and Analysis of Organic Pollutants in
Water", L. H. Keith, Ed., Ann Arbor Sciences Publishers, Inc., Ann
Arbor, MI, (1976), p. 51.
3. Budde, W. L., and J. W. Eichelberger, Anal. Chem., 51, 567A (1979).
4. Pellizzari E. D., "Analysis of Organic Air Pollutants by Gas Chromato-
graphy and Mass Spectroscopy", EPA 600/2-79-057, Final Report, March
1979, 243 p.
5. Lee, M. L., R. P. Wright, L. V. Phillips and D. M. Hercules, "Correla-
tion of Surface Chemistry of the Glass Capillary Column and Chromato-
graphy Performance: A Study of Various Column Treatments for Auger
Spectroscopy", Expochem, Houston, TX (1979).
6. Dandeneau, R. D., P. F. Bente, III, and D. Smith, "Application of Fused
Quartz GC Capillary Columns to Biomedical and Environmental Problems,
Int. Symp. Adv. in Chromatog., Lausanne, Switzerland, (1979).
7. Grob, K., private,communications.
3. Jennings, W., "Gas Chromatography with Glass Capillary Columns", Acacemic
Press, Inc., New York, NY (1978), p. 184,
9. Pellizzari, E., Chromatog. Rev., 98, 323 (1974).
10. Pellizzari, E., et al., Preliminary Draft Report, "Master Scheme for
the Analysis of Organic Compounds in Water - Part III: Experimental
Development and Results", EPA Contract No. 68-03-2704, January (1980).
138-'
-------
APPENDIX A
VOLATILE QRGANICS IDENTIFIED IN AMBIENT AIR
Part I Baton Rouge and Plaquemine, LA and Vicinity
Part II Lake Charles, LA and Vicinity
Part III Beaumont, Orange, Groves, and Neches, TX
Part IV Houston, Deer Park, and Pasadena, TX
139
-------
Part I - BATON ROUGE AND PLAQUEMINE, LA
140
-------
Table Al. "PURGEABLE" ORGANICS IDENTIFIED IN A WATER SAMPLE
FROM BATON ROUGE, LA AREA (P4/L1)3
£111*109
Ptrt So.
iriphie
?«kSo.
Compound
7
8
9
10
10A
10B
11
12
13
14
14A
IS
13A
16
17
IB
20
21
22
24
23
57
60
62
64
67
68
69
72
73
78
79
82
88
92
93
98
100
102
108
113
117
41
42
46 •e«t*ldihrd«
32 00,
54
35
56 dieblaroHtlun
Fr«ee 113
£-butJBBl
-------
Table A2. VAPOR-PHASE ORGANICS IN AMBIENT AIR FROM
BATON ROUGE, LA AREA (P4/L3)a
Qir
(i*phlc
Fuk No
Uutloa
reap.
f'C)
griphle
Puk Ho.
Uatioa
tap.
C*C)
1
3
JA
4
5
7A
3
9
9A
10A
11
11A
12
13
14
14A
13
ISA
1SB
16
17
17A
18
ISA
19
19A
20
20A
21
22
ZZA
23
23*
24
24A
23
23A
231
2*
26A
»
C4B.
furaa +
«c««ra«
aaUiylow cblarlda
ttlrylrain* Ct«nc.)
t-butanol
iMbatana
chlorocthylca*
(cent.)
49 o-feataaa
JO acataldafafd*
52 C,B
S7
53
59
60
64
66
67
67
70
71
71
72
73
74
74
74
76
77
78
2-aathylpncu*
t«t)
chloroform
aathyl atbyl kctona
athyl acatata
pcrfluorocBluto*
80
80
83
84
83
83
86
87
iS
90
91
91
93
92
96
W Mi
100
1.1, 1- crlchloro«th«n«
carbon t«cr*chlaride
C7>16
2. 3-dlaeehylpaotaa*
tt-b*pttn«
aeaclc «eld
268
26C
27
28
28A
29
2»A
29B
30
31
32
32A
32B
33
33A
34
35
36
37
36
38A
39
40
40A
41
42
43
43A
44
44A
44B
44C
44D
43
44
47
47A
47B
48
4BA
49
SO
31
su
101
102
103
104
107
108
110
111
113
116
117
120
122
123
123
128
130
132
133
134
134
133
137
143
144
143
146
147
147
144
146
149
130
130
131
131
132
133
133
134
cyanobutadleaa
4-fcntna altrtla
Celuaaa
l-CT*ao-l-b«it«tt«
tetr»chloro«thyl«o«
4-vlnyleTelolMUQB
(toot.)
•v tad/or p-«yl«n«
C9BZO *****
(cant.)
•tyrcu
Ciofla
propylcyclahuui *•
C10H20
C10B16
C10S2fl
ctalarotolinaa liomar
boaaldabyte
•- and/or g-achyltoli
SAa
CUH24
142
(continued)
-------
Table A2 (cont'd.)
Chzomaxo-
graphlc
Peak *>.
52
S3
53A
54
55
J5A
55B
55C
5«
57
58
58A
588
59
59A
59B
60
61
61A
61S
6:
63
64
64A
65
6SA
66
66A
67
68
68A
69
69A
69B
70
70A
70B
70C
71
71A
71B
72
73
Eluclon
Tenp.
CO
155
156
156
157
159
159
159
160
161
162
163
164
164
165
165
166
166
167
167
168
169
169
170
171
173
173
174
175
176
177
173
179
180
180
181
181
132
183
184
184
185
186
186
Compound
C10H20 1*WBf
1,2,4-CTlaachylbeozane
=10H20 1«~r
2-decane
benzyl chloride «•
C4-alkyl baniana Uomer
Cj-alkyl benzana laoaer
C.1BZ4 iaomer
C,,H24 leaner
C^H24 laomar
C11S24 i"om" *
1 . 2 . >er lae thy Ibeuene
C12H26 laomar
aicblozobeosene laomer Ccraca)
indan
bucylcyclohexaae *
C11B24 1""*r
C11H22 llc~r
C4-elkyl beazane laomer
=UH24 Uo"r
C^-alkyl beuene iaomar
CUH22 laoaer
C,,H,4 iaomar
acatopheoone
^Il"l4 laoaer
C12H,A iaomer
C&-*lkyl beozane laomer
C,.B24 laomer
uaaac. hydrocarbon
CUH22 llol"r
C11B20 **oaar
jv-undaeaBe
cii*:2 tso«r
ll^lfl iMLMr
C12H26 Uo"r
C&>alkyl tMniane laoaar
unaac. hydrocarbon
C12H26 t~~r
Clia20 1»°~r
C12a24 t— *
uaaac. hydrocarbon
C.-alkyl eyclohaxane laomar
C11S22 i«»"
C12a.t laomar
C,2a26 laomar
<2*26 i«»»
Chromato-
graphle
Peak No.
74
74A
73
73A
73B
73C
76
77
77A
77B
78
79
79A
79B
79C
79D
79E
79?
79C
79H
791
79K
80
80A
808
30C
800
80E
80F
aoc
80R
801
80J
aox
81
81A
81B
Eluclon
leap.
(*CJ
187
188
188
189
190
190
191
192
194
194
193
196
198
198
199
200
200
202
202
203
204
208
209
210
211
212
213
215
216
217
218
220
211
121
223
225
239
Compound
C12H26 iao-r
C12HJ4 leaner
Cl2H2ft laomer
C.-alkyl benzene iaomer
(tracaa)
crlchlorobeazane iaemer
(tracea)
1 "rH lAOBIT
aaphthilana
B^dodacane
C12H22 Uo"r
C12H24 1~B"r
C13H28 im"
uaaac. hydrocarbon
C13H26 *— '
CjjHjg iaoaar
CUH26 SMa"
C.-alkyl cyelohejun* iaomer
C13*2S 1*"*r
C14330 1*OB"
1* 11 4 tfUWH^V
Cir28 1*™"
C13a26 Uo"r
Cwaj(J laomar
C13H26 lgOBtr
0,-crldecaae
S-nechylnaphchalene
C14B30 lloa«r
•^methy Inaphthal ana
C15a32 *""**
C14H28 liml"
Cl*830 1§e**r
C15H32 i<01*r
unaac. hydrocarbon
CliH32 l*oa*T dracea)
blphenyl (craeea)
Cuai8 llomflr
B_-cetradacane
unaac. hydrocarbon
CUfl12 imn
See Table 42 for protocol.
143
-------
Table A3. VAPOR-PHASE ORGANICS IN AMBIENT AIR FROM
BATON ROUGE, LA AREA (P4/L4)
ChreBBCo-
traphie
Peak No.
1
2
2A
2B
3
1A
4A
5A
*
7
9
9A
10
U
12
13
14
13
16
16A
17
17A
18
ISA
19
20
21
21A
22
23
24
24A
25
26
27
28
2SA
29
30
32
J3
34
33
33A
Uucion
Top. Compound
CO
41
42
44
46
46
47
47
SO
52
S3
55
61
62
63
64
64
65
68
70
70
71
72
74
73
76
77
78
to
82
83
83
90
91
n
98
99
101
103
107
109
114
119
121
123
124
H2*°2
"2
Ittbuun
C4Hg Uooor
n-*ut«n«
•c*tald«hyd*
C4B8 Uo**r
Icopataaa
£-7*9 can*
•cetoM
dlehloroMthu*
2-MChylpanuiia
CSH10 l"~r
3-Mth7lP«kUB*.
CjH^ IMBir + butaoal (tat.)
heMfliMTObeazui
±-h«zu«
•chyl icitat*
pnfluorouluau (
MtbTlcyclapnunt
C7BU iaoacr
(•i)
if)
1.1,1-tricUoToichiai
C^ iMMr
banna
cirbon tttr«chlorld« («««•)
cyclobuua
2-wtbylhuuaa
3-vtbylltaaiiB
C^^ iMMr
CjS^ i«n.r
9-iwpcu*
HCbylcyclotwuiu
Vl6 Uo~r
CgHls lK«r
toluan*
Cjalg ljoa»
CgHlg imoacT
CgHjj l«m»
v-aeuaa
t«tr>chloro«chylcoi
*-vlnylcyclabKUDc
•tbylbcaccni
•- tad/or 2-*yl«n«
cga,0 IMMT
C10322 la°Mr
QUOMtD-
Peak So.
36
37
37A
38
38A
39
3»A
40
40A
41
42
42A
43
44
43
46
47
47A
47B
48
48A
49
50
51
)1A
52
JZA
S2B
S3
54
54A
33
33A
36
36A
57
38
39
60
62
Zlutlon
CC)'
123
126
127
129
131
132
134
133
136
139
140
141
142
144
147
148
149
130
131
132
132
133
136
137
138
160
162
163
166
175
177
181
182
183
184
18S
186
192
198
212
Cnpood
•tyro*
o-rylene
C.H., Uoatr
n_-non«n«
C10H20 im"
C10H22 itm" *
icepropylbeaxcne
C10"20 lla"r
C10822 Uo"P *
pnpylcyclohnaiic
onsat. bydrocarbon
£-pTBp?lbMX«»
bntuldchyde
tehyltoliMM l>oo>r
Cllfl24 Uoit"
C11H24 ltoa>r
Cj-alkyl brazen* licoar
D-d*eu*
C.'ftlkyl bcDXVBC Iwoir
C4-Ukyl bacot* iMMr
Clia24 1*00€r
l,2,>trlaethylb«at«o« +
CUH24 Uowr
C12H26 lio~r
CUH24 tto~r
C&-«lkyl bcaun* lienar
C4-*lkyl ImaiciM iwmer
CUH24 IM..T
C4-«Ikyl beaxcoc laooar
C..H., IMMF
a-und*cue
us. hydrocarbon
c12flj6 i«».i
=1^24 t*""r
tupbehAlana
>-dodac«o«
C12H24 i"*"
tat. hydrocarbon (teat.}
C13a28 110"r
watt, hydrocarbon
2-crldcean*
2-c«cr*d«cn>*
See Table 42 for protocol.
144
-------
Table A4. VAPOR-PHASE ORGANICS IN AMBIENT AIR FROM
BATON ROUGE, LA AREA (P5/L2)3
irapnlc
7uk Ho.
1
2
2A
1
3A
4
4A
5
5A
6
7
8A
9
10
IDA
11
11A
12
14
14A
15*.
16
17
18
19
19*
20
21
21A
22
23
23A
=4
:s
26
26A
26B
27
27*
28
29
29A
30
30A
Elution
reap.
41
42
43
46
47
48
49
50
51
52
S3
55
56
57
57
57
58
58
60
62
64
65
66
67
68
69
70
71
71
72
73
7ft
7S
76
77
78
79
ao
il
ai
32
83
84
84
COBBOUDd
«2*B2
a2
xenon (tracii)
propane
C.H. laoaar * vinyl calorld*
* 9
(tractaUtrac.)
n-butaae
C4B_ Uomer
•citaldehyd*
ethyl chloride (trace*)
CSB10 1
-------
Table A4 (cont'd.)
O>TOB«CO
jrtphlc
Puk So.
Uutloa
T«»p.
CO
CMpooad
Chrouco- Elutio
|T«phic Top.
y«jk So. CO
Compound
S9A
59B
SO
60A
61
4 LA
62
624
43
63A
64
63
63A
65B
66
67
68
69
70
71
71A
72
73
74
74A
73
73A
7«
76A
77
78
78A
78B
79
79A
80
81
82
82A
82B
83
83A
8*
34A
85
125
123
126
127
128
129
130
132
132
133
134
135
136
138
139
140
141
142
142
143
144
145
146
146
147
148
149
149
130
131
131
152
132
133
153
154
155
155
L56
137
138
Via
Vii
Via
laowi
C10H20
o- end/or £-«thyltolu*m
Ca.3M IsoBflr
1.3.5-erlMehy Ibanna
* C9910
1,2,4-trlMthylbauraa
C10H20 *****
»-dec«u
braxo* l*ootr
C11H24 lto""r
Ct-«lkyl bmseaa UOBBF
1,2.3-crlMchy Ibonxene
C11H24 1IOM:
C10a!2
86
87
87A
88
88A
89
90
90A
90S
91
92
93
93*
93B
94
94A
95
95A
95B
95C
96
96A
96B
97
98
99
100
100A
100B
100C
101
102
103
104
104A
1048
104C
105
103A
10JB
106
106A
106B
106C
1060
106E
106F
107
158
159
139
160
160
161
162
162
103
163
16*
166
168
168
169
169
170
171
171
172
173
173
174
17S
175
176
176
177
177
179
180
180
183
184
186
189
190
191
193
193
195
197
198
199
200
205
210
211
C11H24
t— «
aettoplmioM
C10H18 lloa"
bmzna In
llOOBt
ilkyl boumi itomui
D-undtcue
Wu
bcnxana isoaar
C1JB26
C12flJ6
C12B24
Cj-ilkyl b«nz«n« iienar
Cj-«lkyl b«az«M iiea*r
C11H22 tlo~r
C12H24 lio"«r
bcnimi iaoBtr
* C4 *lkyl baxaa* i.»oo«rs
Cj-ilkyl bnxn* IUMT
bnuma Isooar
^
uoMt. hydrocarbon
C13B24 1§OBtr
BBpfattulau
1, >h««chlorobuE«di«B«
C6-ilkyl eyelohexu* iwner
8,g tcooer
C13«26 UOB"
thyluphtlulnw
30
1428
See Table 42 for protocol.
146
-------
Table AS. VAPOR-PHASE ORGANICS IN AMBIENT AIR FROM
BATON ROUGE, LA AREA (P5/L3)3
£lutlm
T«*.
CO
CSiro
irap
Puk *>.
T*ap.
1
2A
2B
2C
3
4
JA
5S
5C
6
6A
7
9A
98
10
10A
11
12
13
14
IS
1JA
US
ISC
16
16A
17
18
19
19A
20
21
211
22
22A
23
24
24*
25
26
26*
27
42
43
46
46
48
50
51
51
51
52
S2
53
35
35
56
57
58
sa
59
60
61
62
U
63
S3
44
65
66
68
70
73
74
75
77
78
79
80
SO
32
35
87
88
90
91
92
propane
•ceuldahyd*
Uopantu*
CjHg UOMT
o-pmtBM
teeton*
Mthyl«s« eUorUt +
eyclopancn*
Khar
=6=12 1M"
£tt)
bauan*
eyelolMUM at C^R.^
Uanr
niehlataM hylww
Via
27A
28
28*
29
30
31
32
33
33A
34A
35
33*
36
37
17*
38
19A
39
39A
40
41
41A
42
43
45
46
46*
47
47*
48
49
50
51
J1A
SIB
52
53
S3*
54
54*
35
55*
56
92
94
95
U
97
99
100
102
103
105
105
106
108
109
110
110
112
112
113
114
115
117
118
111
121
122
123
125
126
127
129
130
1J1
132
131
133
133
114
136
126
U7
137
138
139
140
toluene
aai6
Caai6 lM-r
c«KaclilerMthyl»«
l.oo.r
C,H,Q
4-vlayl-l-cyclahwun
C9B18
^D
•thylbmzae
t^ and/at £-«yl«n«
•tyr«n«
C,flu
C10B22
C10820
C10H22
C10B20
bauldchyda
•tftyltallMM 1MMT
1,3.5-erlmthylbnxe
Clia24
147
(continued)
-------
Table AS (cont'd.)
Chrouto-
trapaic
Paak Me.
56A
57
58
58A
588
59
59A
60
UA
SI
6U
62
62A
63
64
Si
66
66A
67
67A
68
68A
69
70
71
72
73
74
74A
748
75
76
76A
77
77A
77»
77C
770
Hut ion
T*n».
CO
140
141
142
142
143
144
144
145
146
147
147
148
149
150
Ul
132
153
153
154
135
156
"156
157
US
158
159
160
161
161
162
162
164
164
165
166
166
167
168
CflVBpomd
So920 U«.r
C10B22 1*OBeT
CjSj-benxana laeawr * a-ackyl
benxana
CyjHjg + C^JQ iaca»rx
C11H24 i*8B*r
l-oachyl-4-lMpropylcyc.lo-
buana
CjBj-BOaxaoa taour
1,2. 4-erlaachy Ibancana
C10B20 Uoa"t
a-dacaoa
C10a20 Uo"r
crUaoburylena + C^-Ukyl bouone
laaaar
C4-alkyl bonxaae IBOBR
C4-alkyl baaiaaa + Ciiaj4
laoaarf
C4-.lkyl banana laoaai
CjjHjj Uoaer
C11H24 i— «
tndan
C^-alkyl erelOBaxtaa iaoaar
ladana (tracaa) -»• CJIBJJ laeaar
C..Bj& + C&-aIkyl baaxana iaeaari
C4-alkyl bauaaa laaaar
C4-alkyl banxana laooar
C11H74 Uc«r
CUB24 Ucaar
acatophaaeoa * C-.B.4 laooar
C11H24 iiom"
Cr«lkyl baaxaaa laeoar
=11=22 U°~r
C4B7 banxana laooar (tracaa)
C4-alkyl banxaoa iaaMr
^1*22 Uoaer
C4H7 banxana laoaar
n-adaeaiM
C11B22 Uo"r
C4-«lkyl banxaaa taeaar
C11H22 U"»"
Cl2S26 Uo"r
Chraaata-
graphle
Puk so.
78
78A
79
79A
80
81
81A
81B
82
S3
84
MA
84B
85
85A
86
86A
87
87A
871
88
89
89A
90
91
91*
92
93
93A
93B
94
94A
95
M
MA
96B
96C
Elutlon
Tanp.
CO
169
170
170
171
172
173
174
174
175
175
176
176
177
177
179
180
181
182
183
183
184
US
189
191
194
196
197
199
201
204
»S
207
209
212
213
217
218
C^a-u,
C4-alkyl banxaoe lunar
CUa20 I8<*"r
C12B2, ljc*"r
C^2B?4 laoatr
C.-alkyl banxana Uoaer
onaat. hydrocarbon
C.-alkyl bantena ttoaar
C4B? banxana laoxar
C4-alkyl banxana laaoar
C.-alkyl bannna laonMr
C12826 *""•*
C.-alkyl baniBBa Ixoan
C12H26 t*°~r
Cj-alkyl banxana laoaiar
unaae. hydrocarbon
naphchalooa
C.-alkyl bouana iaeaar
t^dodacana
C12H24 t— r
C.-*lkyl baoxaaa lamar
C^qBjg laooar
C13926 l>om*T
C.-«lkyl Crelohaxaaa laooar
0
1-ahaaylhosaae
C14a30 U°-r
inuac. hydrocarbon
«-crldac*Ba
9-aathylnaphchalana
•-•achylnapnchalana
anaat. hydrocarbon
BBMC. hydrocarbon
C^-ilkyl bonxaoa lieaar
C15H32 lM™r
C14a30 laOB*r
C2-alkyl aaphthalaaa laooar
onaae. hydrocarbon
au. hydrocarboa
aSee Table 42 for protocol.
148
-------
Table A6. VAPOR-PHASE ORGAHICS IN AMBIEST AIR FROM
BATON ROUGE, LA AREA (P6/L3)
Chioaaco- Elation
graphic Tap.
Puk So. CO
Chreuto- Uotlon
graphic Top-
Puk no. (*C)
1
2A
3
3A
5
6
7'
TA
9
9A
10
11
12
13
i*
13
16
16A
17
18
18A
19
:o
20A
21A
22
23
24
25
ISA
26
27
23
29
30
31
32
13
34
MA
35
36
37
38
39
42
46
47
47A
52
33
54
S4A
55
55A
60
62
63
64
65
67
68
68A
70
71
TU
74
75
75A
76
7«A
78
80
81
83
83A
89
91
92
93
95
97
98
100
101
101A
105
107
109
111
112
"2
C^3g laoatr
laopentu*
Tinylid«n« cfelerld*
Mtbylvn* chloTiAft
dUoloTMChjlca* IMBT
3-MthylpatJae
chloroform
ttlryl tcicatt
P«flu0rocolu*a* (
trlealarectlrflcM
(tCBE')
itoaur (cat)
1.1,2-tTicUere*chaa
Vii
Vil
t»tr«ctiloto«cli7l«
39A
40
40A
41
41A
42
43
44
4SA
*JB
46
4«A
47
48
49
49A
50
51
32
SI
53A
S3B
34
35
56
5«A
37
58
38A
39
59B
39C
60
61
»1A
62
63
63A
64
64A
64B
65
65*
658
113
113
114
U7
117
U»
121
121
124
125
126
137
129
131
132
U4
135
137
138
139
140
140
141
141
142
143
144
145
147
147
148
149
149
UQ
Ul
152
Ul
134
155
156
157
157
158
159
159
160
•cbylcyclolujuac
Via 1IC~r
trlchleroprapine
•- «nd/er
SH20
1,1.2 , 2-coCTicUaroatluaa
eriehlaroprapiBC i«on*r (cant,)
C1Q3,, laancr *• liapropylb«nx«ia
C10H22
C10a22
a-propylbuxaa*
•- aadVar
pmuchlorecctuac
bauldihydt
Sftj
a-«tttylEalu
C11H24
1.WWT
1.2.
»-d«emae
C4-«lkyl benzRM
C10820 il™BT
C^a,^ iaom*r
C^-«lkyl b«nt«n«
1,2,3-crlM thylbeojane
ladaa
SAA
H, lioaers
CiA4
Ct-«lkyl
aectapl
Clia24
149
(continued)
-------
Table A6 (cont'd.)
Oiroaaco-
iraphie
roak Ho.
SiC
66
67
18
&8A
69
69*
70
70A
71
7 LA
718
72
Elutlon
Teop.
fC)
160
161
162
165
166
168
170
172
172
174
175
175
176
Coopouad
Cj-alkyl benzene laoaer
he&ichloroethane leoaar
C^-alkyl benzene laoaer
n-usdicane
C&- alkyl benzene laoaer
C.*alkyl banzam iacBBr
-Cj-alkyl benzene iaoaar
Cjj^Hjj laoaar
C_« alkyl banxana iaoaar
C12H,6 laoacr
C . ™ Alkyl bmzcnc iaioBsr
Cj-alkyl beaiene laoaar
CU"j» ia»"
ChrouCD-
trapnlc
?eak *>.
72A
72B
73
74
75
75A
75B
75C
76
76A
763
76C
Elutlon
leap.
CO
178
180
180
181
185
189
193
194
197
199
201
211
Coopaund
C.- alkyl beniene leaner
Cj-«lkyl benzene laooer
oaphchalene
n-dedaeana
1 , 3-hexaehlorobutadiane
vnaac. hydrocarbon
C14B30 Uo~r
C13H26 Uo«r
n-erldeeane
3-Mchylnaphchalene
o-mithylnaphclulene
•at. hydrocarbon
See Table 42 for protocol.
150
-------
Part II - LAKE CHARLES, LA
151
-------
Table A7. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (PI/LI - B/T2)a
OiroMto-
iriphlc
Puk So.
1
2
Uuclon
Top. CovpouBd
t*C)
S* b««i..
104 coluen*
Chro»«to-
griphle
Puk Mo.
3
Uuclon
Top.
(*C)
189
(^mp««.iint
dlbromocyelohaxaa* iiamn
Table 43 and 6 for protocol and experimental design.
152
-------
Table AS. VAPOR-PHASE HALCGENATZD AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (?1/L1 -
Chroaua-
inphic
?uk So.
1
2
3
*
5
6
Eludon
Tap.
CO
67
69
72
14
75
n
Capoad
haifluotetaein* («f)
chlarofon
pvxiluDTOtoliMB* (•!)
1 . 3-d Ichlonw thue
l,J,l-crieltlatB«tha*
baxan*
Chrooito-
traphte
Puk No.
6A
7
S
9
9A
Elutloa
Tap.
C*C)
79
S6
101
lli
128
Caaaund
urban ectraefalaiid*
trlchloTo
-------
Table A9. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (P3/L1 - A/T2>a
ChroMEO-
triphlc
P*>k So.
1
2
3
*
5
6
7
Uution
Top.
CO
43
sa
59
71
74
7«
77
COBpousd
oo2
Mthyleae chloride
iMufluorobmzu* (el)
chlorofom
perfluerotolaene (ef)
1.2-41chlomath*M
l,l,l-crlchloro«th*ne
OiraMto-
Itaphle
?uk No.
8
9
10
11
12
13
14
Elusion
leap.
CO
SO
81
as
103
113
126
193
CO^*
benzene
orboo tetrichloride
(t»c»)
trleUoroeehylene
-------
Table AlO. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS
AMBIENT AIR ?ROM LAKE CHARLES, LA (P3/L1 - B2/T2)a
IN
Chrouco-
(riphle
Ptak So.
1
2
3
*
5
6
7
8
Elueioa
Top. Compound
CO
43 COj
47 ehlamactwo* (tr«c«»)
38 ntJiylm* chloride (trwai}
67 huuttuorobusn* (•!)
69 chlonfan
73 p«rflnoTDC01iMM (••)
74 l.i-illchl«To«tlun«
73 1.1,1-cHehloraathu*
Puk No.
f
10
11
12
13
14
U
Elutloo
Tap.
CO
78
79
85
87
101
ill
131
Caapauad
b«,m
emrboo tttraehlaridt
(trices)
chloroMtliylbutmi Liamer
crlchloro* thyltna
teluoM
ce mcUorocthyla*
ilefclorab«ax«B« taeatr (tr*c«)
Tables 43 and 6 for sampling protocol and experimental design.
155
-------
Table All. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (P3/L1 -
Chromaco-
traDblc
?uk !to.
1
2
3
4
5
6
7
Uutloa
Tea?.
CO
43
56
47
69
»
74
73
0^-
°°2
•acnyleae chloride (tracae)
BaxafluoTobaazao* (at)
chlarafon
parfluarotaluaa* (••)
1.2-41chloroechane
1.1,1-czichlaroaehaae
Chroaato-
graphic
Peak So.
8
9
10
11
12
13
14
Elutloa
Top.
CO
78
79
86
100
111
124
191
Covaound
ban lane
carbon titracblorlda (cracaa)
trichloreetliylen* (trace*)
toluene
tetrachloroethrlene
broaefora (trace*)
dlbroaocycloeazana iaoojer
IA
See Tables 43 and 6 for sampling protocol and experimental design.
156
-------
Table A12. VAPOR-PHASE HALOCENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (PA/LI -
Chro««c»-
IMphlc
Ft»k No.
I
2
3
*
i
6
Eluclon
Top.
CO
47
J7
IS
W
70
73
Ground
ehleroacthiM (tne«)
vlB*lldm ehlorld*
•achylmt chiorid* (tr*e«»)
tmaflua»b«i>«M (tf)
chiarofan
^•rfluarotoliMiii (.
t*n
7S
76
80
88
111
131
Cnpooad
l,2-*dlchloTMthin»
l.l,l-tTlchlorMth*o«
e*rboa ttcrachlorldt
crichlorocthrlm*
t«tr«chloro«£hyl«a«
dlchlerabraiac Inner (crac«)
See Tables 43 and 6 for sampling protocol and experimental design.
157
-------
Table A13. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS
IN AMBIENT AIR FROM LAKE CHARLES, LA (P4/LL -
ChrnHto-
iraphlc
?«tk So.
1
Z
3
4
s
&
Elution
Temp.
C*«
a
:c
66
68
71
73
Cnapumri
"j
rtnylidBiB chloride
twufliBTObtactM <•!)
eUorofotB
f«ifluorotolu«n« (d)
1.2-dlcUotMthu*
Chrooato-
tr.phle
?t*k Ho.
7
1
»
10
U
Uuclon
Top.
(•H
74
78
84
110
190
Caapound
1.1, l-trleUaTO€th*n«
emttao t»trachloTid«
trlchloieathylnM
ei t rachlote« tfaylaa
dibraoocyelalMsn* Iwnar
See Tables 43 and 6 for sampling protocol and experimental design.
158
-------
Table A14. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (P4/L1 - A2/T3)a
ChroMto-
ircphie
Fuk So.
1
:
3
4
Elation
Tap.
CO
69
7J
76
SO
Compound
chlomforo
l,2-diciUaro«thn*
l.l.l-crleUerMCh«a«
urban tttrachlerld* (traen)
Chroaaco-
jrmphlc
?uk No.
S
«
7
a
Elutlon
Top.
CO
16
111
124
190
Ceapenad
trlchlarMtliylin*
MCTietdetMthylat
bnnfon
dlbTOM«7eJah«aM Uooar
See Tables 43 and 6 for sampling protocol and experimental design.
159
-------
Table A15. VAPOR-PHASE HALOGE3ATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (P5/L1 - B2/T2)
Chromita-
irtptiie
1
2
3
t
5
6
ElUtlM
Top. compound
CO
37 Mchylau cUorld*
67 inufliiarabcnHM (««)
69 ehloroforn
72 pcrf luorocoluiDV (•!)
74 1, Z^dlchLoTOtt&uff
7i l,l,l>crlehlBTaccbu*
Qxaatto-
?ufc No.
S
9
10
u
12
13
Uutlon
Tap.
36
»9
111
125
1J1
191
Capeuad
eilcum^l..
1.1, J-crlefaloTO* thuw
(•tTiehloro«thylina
broaofoiB
dlchlarob«iK» lioaar (cane.)
dlbraocTclohuuu Luacr
See Tables 43 and 6 for sampling protocol and experimental design.
160
-------
Table A16. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (P5/L1 -
Cbrmfco-
jraphic
Ptmk So.
1
2
3
4
i
&
Siatiaa
Top-
CO
38
67
49
73
7*
7}
Coapouad
4ichloroB*chu*
bwufluorobmiM (««)
chlorcfan
parfluorocoluai (••}
1 , 2-dlclilora
-------
Table A17. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM LAKE CHARLES, LA (P5/L1 - B1/T2)
ir.phic
1
2
3
4
S
6
Elucion
Top.
CO
S7
66
68
71
73
74
Coapound
Mthylm eUerld*
h*ufluonb«aa«M (••)
eblorofon
yerfluoTotaliMn* (•!)
1. 2-dlcJiioro«c&u*
1 , 1 ,l-trlehloro«th*n«
grip hie
P«*k So.
7
8
9
10
11
12
Elation
T«p.
CO
79
85
98
110
139
151
Cnpaund
urban citrtchlorld*
ulehlaro* t hy l«o«
1.1,2-crleUoTMClMne
t«ti tehlara* thy IBD«
2.3-dlchloro-l-pTapuol (tint.)
dleUerebnxa* luatr (tr«e«)
See Tables 43 and 6 for sampling protocol and experimental design.
162
-------
Table A18. VAPOR-PHASE ORGANICS IB AMBIENT AIR FROM
LAKE CHARLES, LA (P7/L3)3
Qrmto-
trtahle
lo.
Elutloa
Top.
f*C)
tnvhle
?wk Do.
CO
1
U
2
3
34
4
44
54
6
7
7A
8
»
10
104
11
11A
12
13
134
14
15
16
164
17
IS
19
194
:o
21
22A
223
23
24
244
25
26
27
274
27S
28
284
29
43
44
45
*7
47
48
48
50
53
53
35
36
56
57
58
60
62
63
65
66
66
67
68
68
69
70
72
72
73
73
78
78
79
10
12
83
84
85
87
88
89
92
93
94
(tncM)
2
vioyl eWorld*
•chyl ehlorld*
ad..
vlnyUdcn* eUoTlda
Mtbyln* chloride
Ftwrn 113
4lcohol (tat.)
dlchloxotthyln
C6H12
(tf)
••thy! «ttayl taton*
ehloTofon
1.1, l-crtchlarmcha*
eartoa cimehlorld*
(tnt.)
CAo" t
=7"!,
«eld
-------
Table A18 (cont'd.)
Chrouco-
iraphle
Vufc sa.
Blutlon
tap.
C'Cl
to- Elutiea
Ho.
I6A
56B
57
57*
575
58
J8A
59
59*
60
60*
60B
61
62
62*
63
63*
63B
64
65
66
66A
67
68*
68B
18C
69
49*
30
145
145
146
147
148
148
149
ISO
151
152
152
152
153
154
155
156
156
157
157
153
159
161
162
162
163
164
164
165
165
166
157
168
bauldthyite
»-«thyltolu«ii«
SiH.
1 ,2 , 4-t rla«tbr Ibcnciu
Cj-tlkyl bt
diehlorobnnai I«OMT
C4-«lkyl
iioaari
C^-ilkyl bnan* l*oa»
ilkyl
branae Uawr
C-4lkyl bmai
(ttot.)
Ct-*lkrl bnim
72
73
74
74*
74B
74C
73
ISA
76
76A
77
77A
77B
77C
78
79
79A
SO
81
81A
VI
32
84
S4A
848
84C
85
85*
86
86A
87
aa
169
171
173
173
174
175
175
17ft
177
177
179
180
181
182
183
184
186
197
13«
191
131
200
20!
203
JOS
212
214
215
216
228
240
C11H24
Uoaan
C11H20
Cj-ilkyl bum* itaemi
flfy.t !•«••*
C.-tUqrl cyclehex«m
C12H26
Cj tlkyl teoiao* UOMI
p«nt*ehlorobut»dl«n«
C12H24
uphehtlau
C12824
C14a30
C14HM «"
blphcnyl
l-ondecme
dlpftmyl «clur
C1SB32 i*n-r
1,1,4- uiatthy l?«nt»-l, 3-ilal
di-i«obutyr»t« CBKC}
See Table 43 for sampling protocol.
164
-------
Table A19. VAPOR-PHASE ORGANICS IN AMBIENT AIR FROM LAKE CHARLES, LA (P8/L1)'
tuphlc
P«k So.
1
1A
3
3A
31
4
6
7
7 A.
3
9
9A
10
10A
11
11A
12
13
13A
14
13
13A
13B
13C
15D
16
16A
16B
17
17A
18
ISA
19
20
20A
20B
21
21A
21B
22
22A
23
24
24A
25
26
EluUon
1*09.
CO
42
46
47
32
53
35
36
37
37
61
61
64
64
63
66
67
69
70
71
72
73
76
77
77
78
79
90
31
83
33
34
33
96
96
87
91
92
94
94
96
97
98
99
CBBnouad
CD2
mm (tracaa)
Irabu un
c4a8 lamar
acataldahyda
fbacaaa
laapaauaa
Bn.antiB.
CjH1() UOBM
•achylana chloride
acataaa
•ieohcl (cent. )
CTclepantane
2-«th7l!.«ntana
3-Mtbrlpaacaaa
C&H12 iaoaar
haxallaorobaauna (at)
aj-haaaa
chlarofora
•thyl acataca
parfluorouluaaa (afl)
•a t hyleyelopentana
l,2-diehloro«thana
1,1,1-crlctdaroathaDa
Vlo Itoaar
baaxaaa
carton eattmeUaclda
cjelehaaaaa
2-uthTlhaguaa
2 , 3-41oat bylpaat ana
3-«*tbylhauaa
C,al4 Ueaar
C^lt> laoawr
VlS ifaa"
crlchloroathrlaaa
paataul
a^heptaBa
C*B. t l«w*Mr
Cgal8 laonr
MGhTlcTclehaxaaa
CgHjj l*cn*r
CgHjg Itonr
Vl6 »"
CgBjj laenr
Vis llaier
caluaaa
Chroaato-
Paak Bo.
27
28
29
30
31
J1A
32
32A
33
33A
J*
35
35A
36
36A
37
37A
37B
38
38A
39
40
41
41A
41B
42
42A
43
43A
43B
44
45
45A
45B
46
46A
47
47A
47V
47C
48
49
49A
49B
Elutiaa
Ta>».
CO
101
102
104
105
106
107
ioa
109
110
110
112
114
115
115
116
117
118
120
121
122
123
124
126
127
12S
128
129
130
131
132
133
134
135
136
136
137
138
138
139
140
141
142
143
144
CoBpouad
C8H1(| lanar
C.fl laoaar
diaathrlcyclobaune
C a iMBat
CJ14 lunar
Vlft 1>oa«r
D.-oetaaa
Vl6 1«" r
catrachlaroathylaea
CgL, Uoaar
V:o 1«°-r
C H imaar
CgH,Q iaeaar
C.a[8 laoan
«thylcyelohax«ne +
<• a IMMT
C B Ucmar
Cjail° 1»oa*T (cane.)
athylbaaiaaa
c H i,ea,P
»- and/or £-<7laa«
V» Ii0-r
V20 Um»T
aenaaa
aj-sjrlaoa •*• V:o lion*r
C-H-g iaoaar
a-ooaaaa
C10S22 Uel"r
Vis uo-r
C10B22 lM«"r
taaoTaoylbaaxaa
Vl6 t>c~r
C10H22 1— "
^Ao llcatr
propylcTclobuune +•
C10H22 1*™*r
C. B- iaoflar
10^20
C..B.. laoaar
C10H20 Uo"r
ft^*ffn>pylpamaiia
y cod/or jh-vthrlwluana
C10BJ2 1"""
165
(continued)
-------
Table A19 (cont'd.)
Cbreoato-
triphle
Puk So.
30
51
J1A
52
53
53A
SA
54A
55
55A
56
56A
56B
S6C
37
57A
53
58A
59
59A
60
60A
61
61A
SIB
61C
62
62A
62S
Elutlen
Top.
CO
144
145
145
146
147
149
149
130
151
152
152
152
153
154
154
153
156
157
157
158
159
159
161
161
162
162
163
163
163
Compound
C11B24 t""r
b€B(ald«hyd«
C10"22 1§aMr
o^cthyltolun* * cjjH24 itamu
C11H24 t""«
CjoHj,, KOMT
1.2, 4-crlMtlirlbnsrac
Clfla2() l«OMr
a-dceu*
C10B20 1§OMr
C,,B,. inner
11 24
C^-ilkyl bttuan Uemer
dlchlorebaz«M IMUT
Cjjajt iioxr
1,2,3-crinthylbrazm*
CjjHjj Uenr
C12B26 U""
ladn
C12B26 u~"
C10B20 llem«r
C..B-, + C,-«lkyl
11 24 a '
b«az«M lioacri
C4-«lkrl baitn* IJIOMT
C^-tlkyl b«BXUM itaa*T
CUH24 lKmer
C..B., l»oa«r
C11H24 itn*r
CUB24 i*cm,r
C4-«lkyl boz«u Uoacr
SAs 1-~r
Oiromato-
fraphlc
P««k He.
63B
62C
62D
62E
627
63
63A
63B
64
6AA
65
65A
65B
«5C
65D
6SE
66
66A
66B
«6C
660
66E
67
67A
67B
68
68A
68B
69
Elution
Top.
CO
163
164
164
165
1««
166
167
167
168
L69
172
17S
176
17«
177
177
178
178
179
180
ISO
1S4
185
192
195
200
202
204
217
Cnpound
C10Hlg i.«.i
•CBCophanona
C,-«lkyl buizm*
C..B,. itmei
C4a7-6.n»Bn« KOI
C^-clkyl bax«n«
Iwoat
MT -
Uoaar
C4H.,-b«n*tn« iceair
C11H22 **""
£-und«ue
C^-alkyl bcnzta*
C4-klkyl bmxen*
Cj-clfcyl tanioi*
C.-clkyl bcazaai
C4B7-ba»ua Uoa
C12H24 *****
C-"€ikyl bmzvBfl
C12B26 tiowr
C!2H26 iumr
C.-tltyl bnzcaa
aiphtbaln*
n-dodieni
C12B24 1§™«r
C133J6 ltoa
-------
Part III - BEAUMONT, TX
167
-------
Table A20. VAPOR-PHASE HALOGENATED AND OTHER SELECTED ORGANICS IN
AMBIENT AIR FROM BEAUMONT, TX (P2/L2)
Cbrooata*
iraphic
Peak Ho.
1
1*
2A
3
IA
4
4A
4B
6
7A
a
9
10*
10B
11
12
12A
13
13A
13B
13C
14
15
16
ISA
17
ia
ISA
19
20
2
-------
Table A20 (cont'd.)
graphic
60
60A
61
62
63
^
64A
65
6SA
65B
66
66A
66B
67
67A
66
b£A
09
70
70A
71
71A
72
?2A
73
73A
73B
74
Uuclon
Top.
CO
162
162
163
16.
165
165
166
168
169
173
171
172
173
174
175
176
177
178
180
181
181
182
183
133
184
186
186
187
Compound
C11H24 l*°**r
C4-aIkyl b«xWT
C.-alkyl b«iMnc iioacr
C13H26 lio~r
uniac. h*droe«rbon
C6-«lkyl cycloheunc iieacr
Cl3Hj8 ttOMT
C13H,8 iMMr
C.4B.. iioatr
n.-crld*eu«
0* ^B thy 1 n Ap h c tiM i CBC
i S 15 LCOBCr
a-«athyln>phthal*nc
C14H28 Iseatr
C^-tlkyl cyclohtxaat laeoer
C14H30 lloatT
C15H32 l.«.r
C1*H30 l>Mtr
Cj.Hj, liooar
ilkyl butyra:t
Cj4H,g liomtr
£-t*trad*einc
15 30 *^*
C1SH32 i>OI"r
n-7«ntidtc»n«
See Table 44 for sampling protocol.
169
-------
Table A21. VAPOR-PHASE ORGANICS IN AMBIENT AIR FROM
BEAUMONT, TX (P4/L3)3
Chrooaco-
jrephic
?«ak So.
1
IX
2
2A
3
JA
38
4
5
6
JA
a
9
10
11
11A
12
12A
12B
13
14
IS
ISA
16
ISA
17
17A
17B
18
19
19A
193
19C
19D
20
20A
20B
21
22
22A
23
2JA
24
Slutlon
Teap.
CC)
43
44
47
48
49
SO
51
SI
S3
SS
56
57
58
iO
62
63
64
63
66
67
70
71
71
72
73
74
74
73
77
78
79
dO
82
83
83
84
85
86
88
90
91
92
93
CoBpouad
»2
xenon (traces)
propane
buceae lamer
butadiene
C4B10 t"»"
c4ag UO«T
C4HS laoojer
CjB10 laomr
iaopentaae
VlO 1""*r
n-oentane
acetone + VlO itm*T
methylena chloride +
VlO *•«"
CjBg learner
ieopxopenol
i-butenol
C.Bj Laoaer
CjBjj laoaer
2-Mthylpmtaae
C-S. * Ixooer
bu canal
hoxaUuorobeozene (el)
Vl2 lieB>r *
•ethyl ethyl ketone
chlorotaTB (traeu)
ethyl acetate
perfluorocolueae (tf)
* CS312 laooar
alcohol (laoaer)
1.1.1- erlcUoroethaae
VlO u"»r
carbon tetracblorlde (tzacei)
eycJoheune
2-ejatliylkeuae
3-Mthylheune
C^^ laocer
C^B^ Uoowr 4 pentaaal Cent.)
trlchloroechylene (tracea)
o-hepcane
OiroMto-
iraphie
?eak Ho.
24A
24B
25
26
27
28
29
30
30A
30B
30C
31
32
32A
33
34
34A
35
36
36A
17
37A
37B
39
40
40A
40B
41
414
42
42A
43
U
44A
44B
45
46
47
47A
48
49
49A
SO
SOI
51
31A
Uutioa
Temp.
CO
9*
94
95
96
97
98
100
101
103
104
105
105
107
108
108
110
in
112
114
115
115
116
117
119
121
122
123
125
125
127
127
129
130
132
133
134
137
138
138
139
141
142
143
144
145
147
Compound
C7B14 iaoaer
C fl iaooer
dllaobutylene
CjH,6 laoaer
eechylcyelohexane
CjH16 Uooer
Vl4 * Vl6 lmmtT*
CgB,, leaver
heua&l
Cg314 leonr
CaB16 laoner
toluene
CjHia laoaer - Ucaaol (cent.)
Cgfl^ iianr
CJ , laoaer
CJ . laoner
imaat. hydrocarbon
£-octane
CJ., laooer
tetrachloroechylene
Vl6 Uol"r
C B laoaer
4-vlnyl-l-eyclohexene
f B 4
V?o ltaamt
ethylbenxene
C9818 l«"-r
^^ tOOt OT ^••XylflDA
V:o 1<01-r
icyrene
£-tylene
Vl8 tie™r
Ei-nonaae
Vl8 Ue~r
laoproeylbenxene
Vl6 i"~r
C10H22 1*™"
beaaeldehyde
a-fronylheaxene
•» and/or g-ethyltoluene
C10H22 110Mr
(continued)
170
-------
Table A21 (cont'd.)
Chroaaio-
jraphic
Peak to.
52
53
54
55
56
56A
57
58
59
S9A
598
59C
60
60A
MB
61
62
6IA
61B
62C
63
64
64A
6!
«5A
6«
66A
67
Eluclon
Tap.
167
148
149
150
151
152
152
153
154
155
135
156
156
137
157
157
158
159
159
160
160
161
162
162
163
163
165
165
O^nd
C10HU l«.r
C^Hjj laour
o-«thyl toluene
CUa24 *—•*
C1(JHM 1— r
C10H20 laC-r
l,2.*-crt«etBYlben*«n«
Cioa:o 1"""
o-decan
Cj^Hj^ laoaer Cent.}
C4-«Ik7l bauene laowx
crlleobucylena
1 . 2 . 3-cr iMtlty Ibcnieo*
C4-tlltyl b«u«ag tMa*r
Clia24 l(Onz
Clia24 ttOMr
CjgHjg IMMt
ladu (tracBt)
C4-Ukyi erelobcua* Uour
C^Hjj IWMt
CuUj4 llOMT
Ct-«lkyl b«Mo« IJOMT
C4-«lkrl bvuwM l«om«r
C12H22 IUOM
-------
Table A22. VAPOR-PHASE ORGAN1CS IDENTIFIED IN AMBIENT AIR FROM
BEAUMONT, TX VICINITY (P3/L3)
ITtpUC
P««k Bo.
ElUtlOD
Top.
CO
1
3
3A
3B
4
4A
48
4C
6
7
SA
SB
10
11
12
13
14
IS
15A
16
17
17A
IB
19
19A
20
IDA
21
22
22*
13
24
25
ISA
26
26A
27
28
28A
29
30
31
32
42
47
49
49
50
51
ss
37
60
63
67
67
69
72
73
76
77
78
80
83
84
85
36
87
88
89
89
90
91
93
95
98
99
100
101
102
102
103
104
105
107
109
110
*ctt«U«y4* (tot.)
CtHg 1MMT
iMflBtUI
i chloride
Uepropual (tat.)
•tthjrl «thyl katoM
chlonlon
parfluorotaliMM (••)
•Mhrlcyclapatau
1,1,1-trlcU.arattbnu
carboB Mtneblerida (t»e«»)
cyclohoui
•leatol (tat.)
1,2-dlcUoraprovi
(rlcUoreathyl
Via
COllUB*
Vl8
Vl6
32*
33
33A
34
34A
33A
J5B
33C
3«
MA
37
37A
38
3BA
388
39
J9A
39B
40
40*
41
41A
412
42
42A
429
43
43*
43B
43C
43B
45
45A
45B
46
47
48
49
49A
50
50A
51
112
114
114
115
120
121
121
121
111
124
125
126
127
129
129
130
131
131
132
133
134
136
137
138
139
140
141
142
143
144
145
145
146
14T
148
148
149
150
131
153
156
154
156
157
Vl6
C9H20
Vl8
•thyl!
f «nd/ot
po«nyUc«tyl«w (trie**)
•tyrm
Vl8
ut. bydrourbon
*-prepyll>«
C10a22 *
C10H22
plMaol * banolcril*
C10B22
banfuran
dlehlareb«ai«ai
CWH20
172
(continued)
-------
Table A22 (cont'd.)
Chroma co-
iraphie
?iak So.
52
52*
S3
53A
54
54A
SAB
55
56
56*
S6B
57
SB
58*
UlltlOD
Top. CoBpouod
LS8 C11874 **°«"r
15? dlehlorebcnxm* Uoaar
160 CUHJ4 i«o»ar
160 C^, 1—r
161 Si3:* UoBtr
162 C.*alfcyl baame iMBar
162 C4-aikyl b«BMnt Iwsmar
163 aeatophaoen*
165 C11H'<* 1>aa>r
168 GU^ 1«"M'
169 CjjHjj iaomar
171 £-undacina
175 Cua26 isowr
179 cnH:t i>
-------
Table A23. VAPOR-PHASE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
BEAUMONT, TX VICINITY (?5Ol)
1
U
2*
ZB
3
U
4
6
6*
6B
7
9
»*
ffi
«C
9E
10
10A
10B
U
UB
12
12B
14
14*
ii
13*
16
16*
17
18
18*
18B
19
20
ZOA
11
22
23
24
42
43
47
48
49
S4
J*
19
U
U
U
70
71
JI
72
74
76
77
78
79
79
82
83
84
U
Si
VI
88
90
91
92
93
95
98
99
100
100
102
103
104
103
107
109
«2
MM«ldurd*
Uopacnt
Mtbylmc chloride
erclapaun*
C«f)
v-hauai
(*f)
beam*
urban t«tt«eMotld«
2,J-dla«thrlp*aca»
•leebal (tat.)
crlehlorMtbylm*
o-top tin*
•Ikyl «eid
Via '—
LOlU
Via
25
ISA
2SB
26
17
27B
27C
29
Z9»
293
30
30A
KB
31
31*
32
32*
33
33*
3*
34*
IS
33*
SSI
35C
3*
364
37
37*
38
38*
MB
38C
380
Iflt
39
40
40*
41
42
43
U
44*
110
112
113
11*
113
119
in
122
122
123
125
126
UJ
127
128
128
129
130
1)1
132
132
133
134
US
135
156
137
138
139
140
141
141
142
142
143
144
14)
143
147
148
149
130
151
132
133
134
1.2-dlbmDitha*
»-oet«n«
•thylb«ni«n«
•r
»- ud/or
•tjrrn* (cracn)
(trieu)
bauldihydt
C4-«lkyl
B
24
1.2.4-trtMthrlbuii
Cioa:o
v-itcaa
174
(continued)
-------
Table A23 (cont'd.)
iraphic
Ftak So.
46
46A
46B
47
48
49
49A
SO
5QA
51
51*
511
52
52A
S3
54
54A
348
Elution
Top. rimy 1
fa
iss cua,4 uo«,r
ice ft g *
435 ^1 22 HOwBjT
136 dlchlorobenxme iaonar
136 Cj^ IJOMT
137 1,2.3-eriMCbylboun* +
CUB24 i*omz
139 C^ I— T
160 C^ l««r
^ £A CO 1 ^IMIIMV
161 C11H22 ^*">*f
161 C12B26 tsour
162 Cj-alkyl bonzeiu itoaar
162 C11H22 li°"r
163 C^-alkjrl baza* laoaar
164 C4-«lkyl b«oitn« UOMT
163 ut. hydrocarbon
166 ut. hydrocarbon
167 Ct-«lfcyl b«u*M IWMT
168 aeieeplwaeiM
Chroma to-
Ptak Ho.
53
55A
55B
56
56A
5«B
37
57A
SB
59A
39B
39C
39D
60
61
42
63
Uutlon
")"
169
170
171
171
173
174
17S
17!
171
180
181
182
1B7
188
192
202
214
Compound
C(-ilkyl bcnznn* +
C11H24 Uo«»
^Hjj iMBir
C.-alfcyl bmume laoacr
D-undacanc
C&-*lkyl bouni ijoaar
C,2H-t itaaur
C12326 U«-r
C4-tlkyl b«ointa I«OMT
Cj-alkyl benzene *
auat. hydrocarbon
Cj-«lkyl benxaai IMBBT
C12826 1«a"r
C12*24 lio"r
oaphcfaalrae
a-4edecaae
onaat. hydrocarbon
C..I,- Uoaar
14 30
tlkyl buryraca
See Table 44 for sampling protocol.
175
-------
Table A24. VAPOR-PHASE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
BEAUMONT, TX VICINITY (P6/L2)*
Chrooato- Eluclon
traphlc Taajp.
?«ak !fc>. CO
Slutlon
griphic
7«tk Ho.
CO
1
IA
1
3A
4A
48
4C
4D
6
8
SB
9
10
1QA
11
12
13
13*
13B
14
14*
15
15*
1SB
16
16*
17
17A
171
17C
18
19
19*
19B
19C
19D
20
21
22
22B
23
24
25
43
44
47
49
49
51
52
32
54
56
39
63
66
69
70
71
72
73
74
76
77
80
B2
S3
S4
as
36
87
39
90
91
92
97
98
99
100
101
104
106
100
109
111
113
US
117
"2
xanoo (HI
propana
Vs
laobutaju
fr-butaaa
laoputaM
•Baton*
•aehylaaa ehlorldo
laoBropanol (taut)
2-^athylpantane
3-oacbyloancane
C&HU laaaar (uac)
hnafluoraboaian* (af)
ealorofom
•atbyl aebyl katena
•thyl acatato
parfluoTotoloana (at) *
1.1.1
bania
carbon tatrachlorlda
2-Mthyltesn*
2, 3-dloachylpacKB
crichlotoctlqrlaw
Vis
U*
26
27
27A
28
28A
29
30
30A
30B
31
31A
32
33
33A
34
34A
35
35A
35B
35C
35D
36
36A
36B
37
38
39
40
40A
41
414
42
42A
42S
43
44
45
45A
46
46A
47
47A
47B
48
119
121
126
126
127
129
130
132
132
133
134
136
137
138
138
139
140
141
141
143
144
145
146
146
147
149
150
152
152
153
154
134
155
US
157
158
160
160
161
163
165
166
168
171
179
ewFM
C10H22
C10H22
tmaaturacad hydrocarbon
C10H20
•tbylcoluana laoaar
banuldahyda
CU824 «—«
oceawcbrleyelatacraaUouaa
Iwawr
phanol
C11H24
CUH22
ilehloTobi
(trace)
or Mturacad hrdrocarbon
uaaaturatad hydrocarbon
Mturaead hydrocarbon
Si"a *—r
Mturacad hydrocarbon
aeoeapbaaono
a-«ada
C1232*
(continued)
176
-------
Table A24 (cont'd.)
Chroaito- Uuilo
triable Top.
PMk !«o. (*CL
Chroaato- Elutlon
triphlc Top.
PMk Ho. CO
Compound
49
49A
49B
49C
490
50
50A
51
52
180
180
182
184
186
187
189
191
194
txlcikloTafacaxaa UCMT
53
54
5S
56
56A
57
58
5BA
202
207
214
217
224
226
228
229
ill ID* conpoiaul
•Ikyl boryru*
•llin*
C15a30
See Table 44 for sampling protocol.
177
-------
Part IV - HOUSTON, TX
173
-------
Table A25. VAPOR-PHASE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
HOUSTON, TX (P9/L2)3
Qirmto-
Mo.
UutiOD
Top.
CO
Chrooito- Zlutloa
graphic tap.
P««k Ho. CO
1
1A
3B
4
S
6
7
8
8A
9
9*
10
10*
11
11*
11B
12
12*
129
13
14
14*
148
15
16
16*
168
17
17*
178
18
18*
19
19*
20*
21
21A
22
23
23*
24
24*
23
26
26*
52
55
56
56
58
60
61
62
62
64
66
68
69
70
71
71
72
72
73
74
75
75
76
78
80
80
81
82
84
85
86
87
37
88
91
93
93
94
96
97
98
98
101
104
106
Ucp«nt«n«
••thyIra* chloride
qrclapatadlae or C
but*n*l IMMT
eyelopaatJB*
2-mthylpant«u
BBCtiyl vinyl k*tou
n-but«a«l
••thyl athyl ttton*
(eS)
alcohol (cat.)
chloroforn (tr«cM)
porfluoracolima (at)
Mtbyleyclopatu*
1,2-dl chlar Mthau
Cj&KjO l*BBtr (teat.)
dlchlarapropcM Uoacr (taat.)
urban cacriehlorldi
2 . 3-d la* t h7lp«ne + butyl
-------
Table A25 (cont'd.)
Coronate- Slutlcn
graphic Taap.
Paak So. (*C)
iriphic
r«*k So.
Elutlaa
Top.
CO
48B
48C
480
49
49*
49B
50
50*
51
51A
51B
52
52A
52B
53
S3A
538
54
54A
53
55A
55B
56
56A
57
58
5BA
58B
58C
59
60
SOA
SOB
61
614
62
6ZA
63
63A
63B
159
160
160
161
162
162
163
164
165
166
167
168
169
170
170
171
171
172
173
173
174
175
175
176
176
177
179
ISO
180
180
181
182
183
183
185
185
IBS
187
187
188
propyIcyclebaxana
banxaJdahyda +
pr-propylbani
jr and/or £7*thy1col
1,3.5-ir laachy1 bantana
Bj-butyl aathacrylaca
o-«chyltoluene
Via1
phenol
£-acuaal
vnaaturatad hydrocarbon
dlcalorobansaM iaoaar (traea)
1,2,3-crlaathylbansaoa
* C4-«lkyl
C^-alkyl eyelahao* icenn
acatophanona + CjjHj4 !•
C4-alkyl bancaaa laooar
63C
630
63!
63T
64
64A
648
65
65A
65B
66
67
67A
68
68A
69
69A
69B
70
70A
70B
70C
700
70E
TOG
70H
71
71A
72
72A
73
73A
73S
73C
7 30
73B
74
74A
189
189
191
191
191
192
193
194
193
195
197
199
200
200
202
203
204
20S
209
209
209
210
213
214
215
216
216
217
219
220
221
222
224
227
238
239
240
240
240
C12B26
C4-«lkyl
C-Ukyl IMUOI* l*an*r
aacuracad hydrocarbon (cant.)
C12H24 1*~*r
C4-«lkyl
Cj-alkyl cyclohexaaa laoaar
C12H24
C.-tlfcyl bcnziao Uomr
Cj-«lkyl haHu Uoaar
saturated hydrocarbon
aj-daeaaal
Cj-«lkTl bauano iaoaar
a^dodaeana
unaaciiracad hydrocarbon
C13H26 1—'
MCiRKed hydrocaTbon
alcohol (cant.)
C13H26 **""
tt-trtdacana
nachylaaphchalana laoMr
See Table 45 for sampling protocol.
ISO
-------
Table A26. VAPOR-PHASE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
HOUSTON. TX (P11/L3)3
Chroa
(Mph
?uk
i
2A
29
ZC
3
JA
4
s
JA
6
6A
»B
6C
7
7A
78
8
8A
9
9A
10
IDA
11
1U
UB
i:
12A
12B
1IC
13
14
16A
148
15
16
16A
16B
17
17A
17B
18
ISA
188
19
19*
•c»- Elucioa
ie tap.
*>. (•«
SO
54
55
57
S8
S3
59
61
62
S3
66
68
69
69
70
70
n
72
73
74
75
78
80
80
82
85
86
86
87
90
93
94
9S
96
99
101
102
105
106
106
108
110
112
114
116
Coapouad
CO,
prooana (teat.)
c4a8 i«-r
C4B8 laour
VlO *•— r
icoaaacaaa
•eacoaa
£-p«nuaa
C3aiO tB— T
•attiylaoa ehlotlda
C^SjQ l«aaar (cant.)
CjH^ lioaar (cent.)
CTclopaune
2-*acbylpmtana
bu canal
aachyl visyl kacooa (cane.)
aaehyl tcny! katooa +
3-aathylpaaCBaa
C^a. , Ueoar
haufluerobaaiana (••)
o-haUB.
chlarafen
C^j laoMr
perfluorocoluoM (if)
aachrlc7elopaataaa
l,l.l-crlehloro«tlJ4n«
baueaa
C^^ iaoaar
carbon tatr*ehlorlda
eyclohazaaa
2-«atl>TlliasaBa
3-Mthrlhaxna
pncanal
C7Blk lieur
trlchlon«thrlaa«
»-hapc«M
C7a14 laeaar
=8*18 i— '
aat hylCTclo henna
CjfljjO laoawr
C^j Ueaar
C8H18 lioB«r
Csai6 laonar
CBH16 l*~"
coluaae
C^j iiOMr
Chroaaco-
iripblc
?«ak Do.
20
20A
21
22
22A
22B
22C
23
23A
13B
23C
230
23E
23T
24
24A
23
25A
26
26*
27
27A
27B
27C
28
:BA
28B
29
30
30A
30B
30C
30D
31
31A
31B
31C
31D
32
32A
32B
33
33A
34
34A
ttucloa
Taap.
CO
117
118
119
120
121
123
123
126
132
133
134
135
133
136
140
141
142
143
144
145
145
147
147
148
148
149
150
130
133
133
133
137
157
138
138
160
1C1
162
163
163
164
16S
165
167
168
.*-.
C8H18 1~-r
C.B,,0 laoaar
CgH^ lunar
C.B.. lionar
C8Blfl ixnar
£-aetaaa
tactacUoToichTlraa
C9a2g Icnar
C.a,0 iMatr
chlorobonicat (tracaa)
(CbylcrclohMau
C J I.OMT
C.H.- iMnar
•ttaylbcnzma
C.B., iwaar
f ud/or £-«yl«n«
C.B,. icemr
C9H20 Uc"r
C^,^ iwaai
C9B20 t'°«'T
•CTTBDa
Cga.. iaoMT
C9a20 Uo~r
C • laoaar
C10a22 1>0"t
a-aaaaac
C10H20 1>0~t
tioprnpTlbcuenc
(^gB. Ueur
CjjBj, laoaar
*ufu igo"r (t">e-)
propylC7clohacan«
Cl(]B2z l«nar
LO^lfr '
C10"20 lnamr
Saxao
Cj0B22 l««.r
f ind/or £-Tltaliuae
b«nioniirll« (crieai)
181
(continued)
-------
Table A26 (cont'd.)
Chrauto-
iraphle
?aak So.
34B
J4C
J4D
33
35A
36
36A
37
38
3BA
MB
38C
39
39A
39B
39C
40
40A
41
41A
41B
42
42A
42B
42C
43
43A
43B
43C
43D
Elueloa
Tat*.
CO
169
169
170
170
171
172
173
173
175
176
177
178
179
181
182
183
183
184
185
186
188
189
191
191
192
193
195
197
199
201
Compound
1.3.5-crlaathylbmzoM
C10B22 lloatr
SAo i§— •*
CjjBjj Uoaar
fr-athyltoluana + phenol
SAi *•«"
S(T16 tl—tt
C11H24 t*°**r
1 . 2. 4-criaatbylbanzene
^Ao la~"
^Hjj iaoaar
dlehlorobantana 1i
-------
Table A27. VAPOR-PHASE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
HOUSTON, TX (P13/L4)a
KB-
iriphlc
Puk Mo.
irtphle
?uk Ho.
Xlutiea
tap.
CO
1
2A
3
3A
4
3
3A
3B
JC
6A
7
8
9
10
10A
11
11A
12
12A
13
14
144
148
14C
14D
13
16
17
18
ISA
19
20
20A
208
U
21A
22
23
23A
24
24A
23
23A
238
"
47
47
49
U
31
32
32
32
33
34
36
36
38
39
39
60
61
62
62
63
64
64
65
66
67
69
70
72
73
74
73
7«
76
77
78
78
79
79
U
12
U
86
16
(tract* )
(t«t.
farm (inc.)
Vio l*"il
a-paatne
VlO l«~r
•tchyloM chloride
Vl4 »—*
CjH10 IMMF (teat.)
2-wtlqrlpnuM
Via
Vio
CS812
.1.1. 1'trtcUoTMthHa
urban t«tr»eUerld« (tr«c«»)
3-MthTllMUD*
C7"l4
23C
26
27
27A
2>
29
29A
30
31
32
33
33A
338
34
34A
34B
31
33A
36
37
37A
38
39
39A
40
41
42
43
44
44A
43
43A
46
47
47A
47ft
48
49
30
31
SLA
32
33
17
87
89
91
92
94
94
93
96
97
98
99
99
101
101
102
103
10)
103
107
107
107
108
108
109
110
111
112
U3
114
113
116
117
117
119
120
120
121
123
124
123
126
127
Vl6
tot
Via
Vl2(
Vl8
Vl6
V20
Vl6
(t«nt.)
totraehlero* chylue
Vl6
Vl6
V20
chloral
Via
via
(t«nc.)
•cbylbnsme
Via1""'
f ad/or £>*yl*u
Via
C10a22
Via
Vl6
Vl8
iaopropyll
C10H22
h&O
183
(continued)
-------
Table A27 (cont'd.)
drooato- Ilutlon
trmphlc Teop.
Peak So. (*C>
CeapouBd
ChroMCO- Eiutlon
graphic Top.
Peak Ho. f*C)
53A
54
54A
548
54C
S3
S5A
56
S6A
57
57*
37>
58
3BA
59
59A
598
60
60A
61
61A
612
62
62A
62B
62C
63
63A
63B
64
65
65A
66
<6A
66B
66C
67
67A
68
68A
688
6BC
68D
68E
69
69A
128
128
129
129
129
130
131
131
132
132
133
133
133
134
134
134
135
135
136
137
137
138
140
140
141
142
142
143
143
144
145
146
146
147
147
147
148
148
149
142
150
150
150
151
151
152
C10H22
bauldBhyda
=10H20
f md/or 2-«th7lcoliMn«
1,3,5-ulaMhylbaMM
C10H20
phool
C10"22
Icooer
1.2.4-
a-dacana
C4-«lkrl benzine
C11B22
1,2, 3-irlBethylbeniene
CUH24
=11H24
Clia24
CU824
C^-alkyl cycle
=11*24
Clia22
•eiuplMnoD*
C-alkyl bain*
C11824
C11H22
bau«u UaMr
C1JB24
70
70A
70S
71
71A
71B
72
72A
72B
72C
73
73A
73B
74
74A
73
75A
75B
76
76A
77
77A
77B
78
78A
7 SB
79
79A
79B
79C
80
81
81A
8U
81C
810
81E
817
82
82A
83
83A
838
153
153
153
154
154
154
155
133
157
157
157
158
159
160
160
163
163
164
165
167
167
168
169
170
171
172
173
173
173
173
174
177
177
178
178
180
181
182
184
186
187
189
190
C4-.lkrl
C4B,
Clia22
Uamr
Uo-r
C12fl24
benz«
C12H24
Cj-tlfcyl bcniena
Cj-ilkyl beaiene +
eiA»
bauma
Vn
C.-elkyl benxene
beaseae Uemr
0
CcracM)
tieM^«i«»yi»_l| |
C121I24
C12a22
C12a24
C13H26
C12H24
Cs-«lkyl bee;
C13B26
C13H28
b«n««n« tooaar
un* l«oaer
fanmld*
(tat.)
Mthylnaphth«l«
C13H26
184
(continued)
-------
Table A27 (cont'd.)
Ctiromato-
iriphlc
?»k "to.
a*
8AA
MB
Si
3JB
UuEioa
Trap. Canpound
t*C)
190 .-trid.^.
193 Ci4»jo l»»«T
197 Cj^, imr
198 alkyl butyrat*
205 C, H iMBBr
Cbraaaea-
pipblc
?«lk HO.
UC
S5D
85E
86
A?A
Slucion
CO
123
US
214
a?
37Q
Coop
-------
APPENDIX B
VAPOR-PHASE HALOGENATED CHEMICALS MEASURED IN AMBIENT AIR
136
-------
Table Hi. VAPOR-PHASE HA1.0GENATED CHEMICALS - EPA REGION VI
oo
EPA
Region CoBpound CASS 1 Site
VI Vinyl chloride 75-01-4 Baton Bongs. I.A
l«ka Iharlea. LA
ethyl chloride 75-00-3 Baton Rouge. LA
Lake Charlea. LA
Vinyl Ident chloride 75-35-4 FlaqueaJne. LA
Lake Charles. LA
He thy lent chloride 75-09-2 Baton Rouge, LA
Baton Rouge. LA
Baton Rouge. LA
Baton Rouge, LA
Plaqunlne. LA
Lake Cliarlea. LA
Lake Charlea. LA
Beaumont. TX
Baton Rouge. LA
Uroveo. TI
Beaumont. TX
Beaiiaont, TX
Panadena. TX
Paaadena. TX
Deer Park, TX
Chloroform 67-66-3 Baton Rouge. LA
Flaquenlne. LA
Baton Rouge. LA
Lake Cliarlea. LA
Lake Charlea. LA
Beaunont . TX
Baton Rouge. LA
Crovea. TX
Beaumont , TX
Beaumont, TX
Paaadeiia. TX
Pasadena, TX
Address
Route I*U
Oil 1-210
Route 190
Off 1-210
Route 988
Off 1-210
Hw. 61
Hw. 61
Route 190
Route 190
Route 988
Off 1-210
Hw. 90 a 1-10
H. Pott Arthur Rd.
llu. 61
Para Rd. 366
Spur 380
rH 347
In.. 225
Off Rickey St.
IIU. 225E
H». 61
Route 988
llu. 9O & 1-10
Off 1-210
Hw. 90 ft 1-10
W. Port Arthur Rd.
Hw. 61
Far* Rd. 366
Sour 380
KM-J47
Hu. 22SE
Off Rickey St.
Saaul Ing
Tine
0940-1140
I44&-I64S
0940-1140
144S-I64S
1502-1632
1445-1645
1I30-11SO
1210-1410
0940-1140
0952-11*2
1502-1632
1445-1645
0901-1007
1240-1440
1150-1350
1210-1410
im-im
094S-104S
1000-1130
14 JO- 1600
1500-1630
1150-1350
1502-1632
083S-09M)
1445-1645
0907-1007
1240-1440
1150-1350
1210-1410
1125-1325
0945-1045
1000-1130
1430-1600
Calender Cane.
Day - Tear
-------
Table Bl (cont'd.)
co
oo
EPA
Region Compound CASS 1 Site
Carbon tetrechlorlde 56-21-5 Baton Rouge. LA
Baton Rouge. LA
Baton Rouge. LA
Plaqucnlne. LA
Lake Cliarlea, LA
Lake Charlea, LA
Lake Charlee. LA
Beaumont. TX
Baton Rouge. LA
Grovee. TX
BcauBont. TX
Beaumont. TX
Paaedena. TX
Paaadena. TX
Deer Park, TX
1,2-Dlchloroethane 107-06-2 Baton Rouge. LA
Plaquemlne. LA
Lake Char lea. LA
Lake Chart ee, LA
Lake Charle*, LA
Beauaunt. TX
Paaadena. TX
Deer Park, TX
1.1.1-Trlchloroethane 71-55-6 Baton Rouge, LA
Baton Rouge, LA
Baton Rouge, LA
Baton Rouge. LA
Lake Charlea. LA
Uke Charlea. LA
Lake Charlea. LA
Beaumont. TX
Baton Rouge. LA
Grovea. TX
Addreee
Hw. 61
Hw. 61
Route 190
Route 988
Hw. 90 4 1-10
Off 1-210
Hw. 90 4 1-10
II. Port Arthur Rd.
Hw. 61
Para Rd. 166
Spur 160
PM 341
Hw. 225E
Off Rickey St.
Hw. 22 SE
Hw. 61
Route 988
Hw. 90 4 1-10
Off 1-210
HH. 90 4 1-10
Spur 380
Hw. 225E
HW. 225E
Hw. 61
Hw. 61
Route 190
Route 190
Route 988
HH. 90 6 1-10
Off 1-210
Hw. 90 4 1-10
W. Port Arthur Rd.
Hw. 61
Perm Rd. 366
Sampling
TIM
1150-1330
1210-1410
0940-1140
1502-1612
0835-0950
1445-1645
O907-1007
1240-1440
1150-1350
1210-1410
1123-1123
0945-1045
1000-1110
1430-1600
1500-1610
1150-1350
1302-1632
0815-0950
1445-1645
0907-1007
1125-132}
1000-1130
1500-1630
1130-1350
1210-1410
0940-1140
0952-1152
1302-1632
0907-1007
1443-1645
0907-1007
1240-1440
1150-1350
1210-1410
Calendar
Day - Tear
341-78
341-78
342-78
342-78
43-79
48-79
50-79
87-79
141-78
88-79
97-79
98-79
163-79
164-79
165-79
341-78
342-78
45-79
48-79
50-79
94-79
163-79
165-79
141-78
341-78
342-78
342-78
342-78
10-79
48-79
30-79
• 7-79
341-78
•8-79
Cone.
107
749
6.600
1.467
11.316
7.730
700
1.739
(continued)
-------
Table BL (cont'd.)
co
BPA
•eg loo Cmpound CASS 1 Site
l.l.l-Trlchlorostbsne 71-11-6 Beausunt. IX
(cant 'a.) Beaumont, TX
Faaadeua, TX
Paaadena, TX
Deei Park. TX
1.1.2-Trlchlorecthaiie 79-OO-i Baton Rouge, 1.A
Plau.uealiie, LA
Lake Uiarles, LA
Trtchloroethrlen* 79-01-6 Baton Rouge, LA
Baton Rouge, VA
Baton Rouge, LA
PlaqueBlne. LA
Like Charles. LA
Lskc duties, LA
Uke Charles. LA
Beauoont, TX
Baton Range, LA
Crave a, TX
BeauBOnt. TX
Beaumont, TX
Paaadena, TX
Paaadena, TX
rstrachloroethrleiM 127-18-* Baton Rouge, LA
Baton Rouge, LA
Bftion lunge, LA
Batuii Koug«, LA
flmjueulne. LA
l^ke Charles, LA
Lake diaries, IA
l^ike Clwrlea, LA
•eauMnt, TX
Baton Rouge, TK
Groves, TX
Addreas
Spur 360
m M7
llw. Z»B
Off Slckef St.
Hw. 22it
Rout* 190
Route »88
Off 1-210
Hw. 61
Route 190
Route 190
Route SflS
HH. 90 4 1-10
Off 1-210
Hw. 90 * 1-10
W. Part Arthur Rd.
Hw. 61
RM M. Je6
Spur 180
PH 147
iiw. me
Off Rickey St.
Jtw. •!
UK. 61
lauls 190
Ruule 190
Route 980
llw. 90 » 1-10
Off 1-210
Hu. 9O k 1-10
H. Port Arthur Rd.
Hw. 61
FM Rd. 366
Sampling
Time
MZS-I12S
0»4i-IO«S
IOIM-I110
It 30-1 600
1 500- 1610
09*0-1140
1*02-1631
I*4i-l64»
1ISO-11SO
0940-11*0
04)2-1152
I»02-I612
0907-1001
I44i-l643
0907-1007
USO-1440
11 SO- 13 JO
1210-141Q
112S-I12S
094S-I04S
1000-1110
la 10- 1600
UiU-lliO
1110-1410
0940-1140
0912-I1H
1)01-1612
0901-100?
144S-164S
0907-LOU7
1240-1440
1 ISO- 1 ISO
1210-1410
Calender
Day - Year
9*-79
98-79
163-79
164-79
16»-79
142-78
142-78
48-79
141-71
14J-78
142-7D
142-78
JO-79
40-79
iO-79
87-79
141-78
89-19
94-79
96-79
163-79
164-79
141-78
141-7U
142-76
J4Z-78
142-78
SO- 79
48-79
SO-79
87-79
141-78
88-79
Dine.
-------
Table Bl (cont'd.)
BFA
Region Compound
TatraeMoroethylena
(cont'd.)
1.1, 1.2-Tet rachloroethaae
l,1.2,2-Tetrechlor«ethane
Pntechloco* thane
Heiachloroethane
1 , 2-Dlchloropropana
Dlchloropropene laoBar(e)
Trlchloropropene laOBer(a)
Peatachlorabutadlene
1, l-Hea«chlorobucedlena
Qilorobeaiena
CASS 1 Site
127-18-4 BcaiiBont. TI
BeaiiBont. TX
Faaad«na. TX
Faaadcna. TX
Deer Pack, TX
Baton Rouge. LA
Leke Oierlea. LA
Plaqucalne, LA
Lake Charlea. LA
FlaqueBlne. LA
Lake Charlea. LA
Grove* , TX
FlaqutBlne. LA
Paeedena, TX
Faaadcna. TX
FlaqucBlna. TX
Lake Charlea. LA
87-68-3 Baton Rouge. LA
PlaqucBlne. LA
Lake Charlea. LA
108-90-7 take Charlea. LA
BeeuBont. TX.
Crave*. TX
Faaadena. TX
Faaadcna. TX
Deer Park. TX
Addraaa
Sour ]BQ
FN 347
DM. 221R
Off Rickey St.
ttu. 22SB
Route 190
Off 1-210
Route 988
Off 1-210
Route 988
Off 1-210
Fan Bd. 366
Route 988
HM. 225B
HM. 22IB
Route 988
Off 1-210
Route 190
Route 988
Off 1-210
Off 1-210
V. Port Arthur Rd.
FH Hd. 366
Hu. 221E
Off Rickey St.
HM. me
TlB*
1121-1321
0941-1041
1UOO-1130
1430-1600
1100-1630
0940-1140
1441-1641
1S02-1632
1441-1643
1102-1632
140-1641
1
1210-1410
1102-1632
1000-1130
1000-1130
1 102-1032
1441-1641
0940-1140
1102-1632
1441-164!
1441-1641
1240-1440
1210-1410
1000-1130
1430-1600
1JOO-1630
Calendar
Day - Veer
94-79
96-79
163-79
164-79
161-79
342-78
48-79
342-78
48-79
342-78
48-79
88-79
142-78
161-79
161-79
342-78
48-79
342-78
342-78
48-79
48-79
•7-79
88-79
163-79
164-79
161-79
Cane.
2.269
917
606
741
4.947
273
1.419
713
1.312
40
1.190
84
149
(continued)
-------
Table Bl (cont'd.)
\o
Era
legion Compound
Dlchlorobenccne lnuaer(i)
Trlclilorobenaene laoaer(a)
Chlorololuene laowrla)
Benayl chloride (tent.)
1,1-Dlbroaoethena
•eataetilorobroBoatliane (lent.)
CASS f Site
S4I-73-1 Baton Rouge, LA
or L*\Lf Charles. LA
95-50-1 Late Charles, LA
teaimuiit. TI
Ba 1 un Rouge i LA
Cro vea , TX
B«aununtt TX
Beaunont, TX
faaaJeiia. TX
VaaadenaB TX
120O2-4B-1 Baton Rouge, LA
Baton Rouge, LA
T
Baton Rouge i LA
106-93-4 BeauBoat. TX
Lak* Chaclea. LA
Addreaa
II- . 61
H». 90 i 1-10
on i-zio
M. Pore Arthur Rd.
HH. 61
nt 366
Spur 380
m 341
iiu. ziie
Off Rickey Si.
Hw. 61
Hw. 61
Hw. 61
Spur 380
Off 1-110
Saapl Ing
Tlae
1150-1)50
Otl)5-U«50
1445- 16V5
1240-1440
1150-1350
1110-1410
1125-1325
O94S-I04S
1000-1130
1430-1600
1150-1350
1150-1)50
!
1150-1350
1115-1325
1445-1645
Calender Cone.
Day - Year (ng/B1)"
341-18
45-»9
48-79 J5
ai-i>
341-18
88-19
94-IV
96-19
163-19 T
164-79
341-18 8
341-78
341-78
94-79
48-79 34?
------- |