ENVIRONMENTAL MONITORING
NEAR INDUSTRIAL SITES:
BROMINATED CHEMICALS
PARTI
JUNE 1978
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
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ENVIRONMENTAL MONITORING NEAR INDUSTRIAL SITES: BROMINATED CHEMICALS
PART I
by
E. D. Pellizzari, R. A. Zweidinger and M. D. Erickson
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-01-1978
Project Officer
Dr. Vincent J. DeCarlo
Office of Toxic Substances
Washington, DC 20460
U. S. Environmental Protection Agency
Office of Toxic Substances
Washington, DC 20460
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The information presented in this document is subject to the following
qualifications:
(a) The mention of a specific company does not imply the intent to
regulate that company or its activities nor that, unless speci-
fically stated, the company is the source of a given compound;
(b) The identification of compounds were determined by mass spec-
trometric and retention index techniques and their identity
are subject to the limits of this methodology.
(c) The mention of compounds in this report does not imply that
they are necessarily carcinogenic or mutagenic;
(d) The possible mutagenic or carcinogenic activity attributed to
a compound is based upon cited literature,;
and (e) The experimental findings and conclusions presented in this
report should not be cited, reproduced, or included in other
publications without the expressed approval of the Project
Director of Officer.
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ABSTRACT
Sampling and analysis was designed to determine ambient concentrations
of ethylene dibromide and other brominated chemicals near production faci-
lities in El Dorado and Magnolia, AK. A characterization was made of the
environmental matrices - air, water, soil, sediment and biota - for the
presence and levels of ethylene dibromide, vinyl bromide and other related
chemicals surrounding the bromine industry.
111
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IV
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CONTENTS
Abstract iii
Figures ix
Tables xvii
Names, Abbreviations, and Structural Formulas of Brominated Compounds xxv
Acknowledgements xxviii
1.0 Summary and Conclusions 1
2.0 Introduction 7
3.0 Method Development and Validation 11
3.1 Inorganics in Ambient Air 11
3.1.1 Chloride/Bromide and Chlorine/Bromine Sampling and
Analysis in Ambient Air 11
3.1.1.1 Evaluation of the Impinger Train for the Collection
of Halides and Halogens 11
3.1.1.2 Analysis of Halides and Halogens 13
3.1.2 Determination of Inorganic Fluoride in Ambient Air . 25
3.1.3 Acid Mist Analysis in Ambient Air 26
3.2 Brominated Organics in Environmental Media 26
3.2.1 Air 26
3.2.1.1 Volatile Organics 26
3.2.1.2 Semi-Volatile Organics Associated with Particulates 33
3.2.2 Water and Sediment 37
3.2.2.1 Volatile Brominated Organics 37
3.2.2.2 Semi-Volatile Brominated Organics 40
3.2.3 Soil 42
3.2.3.1 Volatile Brominated Organics 42
3.2.3.2 Semi-Volatile Brominated Organics 42
3.2.4 Other Media 46
3.2.4.1 Hair 46
3.2.4.2 Milk 46
3.2.4.3 Placenta 47
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CONTENTS (cont'd)
3.3 References 47
4.0 Survey of Environmental Media for Chemicals Associated
with Bromine Industry 52
4.1 Technical Strategy 52
4.1.1 Sampling 53
4.1.2 Analytical Cross-Checking 57
4.1.3 Prioritization of Sample Analyses 58
4.2 Results and Discussion 58
4.2.1 Arkansas Chemical Incorporated 58
4.2.1.1 Sampling 58
4.2.1.2 Inorganics in Ambient Air 64
4.2.1.3 Bromine and Brorainated Organics in Brine 66
4.2.1.4 Organic Vapors in Ambient Air 66
4.2.1.5 Brominated Organics in Soil and Water 81
4.2.2 Great Lakes Chemical Corporation 84
4.2.2.1 Sampling 84
4.2.2.2 Survey of Chemicals on Glass Fiber and Cellulose
Filters 84
4.2.2.3 Inorganics in Ambient Air 106
4.2.2.4 Organic Vapors in Ambient Air 110
4.2.2.5 Brominated Organics in Water, Sediment and Soil . . 128
4.2.3 Michigan Chemical Corporation (Velsicol) 128
4.2.3.1 Sampling 128
4.2.3.2 Survey of Chemicals on Glass Fiber and Cellulose
Filters 128
4.2.3.3 Inorganics in Ambient Air 150
4.2.3.4 Bromine and Brominated Organics in Brine 151
4.2.3.5 Organic Vapors in Ambient Air 157
4.2.3.6 Brominated Organics in Soil and Water 173
4.2.4 Ethyl Corporation 174
4.2.4.1 Sampling 174
4.2.4.2 Inorganics in Ambient Air 174
4.2.4.3 Organic Vapors in Ambient Air 174
4.2.4.4 Brominated Organics in Soil, Water and Vegetation . 184
vi
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CONTENTS (cont'd)
4.2.5 Dow Chemical Co. and Vicinity 184
4.2.5.1 Sampling 186
4.2.5.2 Brominated Organics in Soil, Water and Vegetation . 186
5.0 Long-Term Monitoring for Volatile Brominated Organics. . . . 190
5.1 Sampling and Analysis 190
5.2 Results and Discussion 190
6.0 Characterization of Environmental Media Associated with Bro-
mine Industry 208
6.1 Technical Strategy 208
6.1.1 Sampling 208
6.1.2 Prioritization of Sample Analysis 208
6.1.3 Ozone Measurements in El Dorado, AK 210
6.2 Results and Discussion 210
6.2.1 Great Lakes Chemical Corporation and Vicinity .... 210
6.2.1.1 Sampling 210
6.2.1.2 Inorganics in Ambient Air 210
6.2.1.3 Brominated and Other Organics 210
6.2.2 Michigan Chemical Corporation (Velsicol) and Vicinity 223
6.2.2.1 Sampling 223
6.2.2.2 Inorganics in Ambient Air 238
6.2.2.3 Brominated and Other Organics 238
6.2.3 Ethyl Corporation and Vicinity 255
6.2.3.1 Sampling 255
6.2.3.2 Inorganics in Ambient Air 255
6.2.3.3 Brominated and Other Organics 255
6.2.4 Dow Chemical Company and Vicinity 262
6.2.4.1 Sampling 262
6.2.4.2 Inorganics in Ambient Air 262
6.2.4.3 Brominated and Other Organics 262
6.2.5 Samples from Human Population 277
6.2.5.1 Sampling 277
6.2.5.2 Brominated Organics 277
6.3 Quality Assurance 277
6.3.1 Analytical Protocol Validation 277
vii
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CONTENTS (cont'd)
6.3.2 Field Sampling Quality Assurance 280
6.3.2.1 Quality Control Samples 280
6.3.2.2 Sample Identification Protocol 280
6.3.2.3 Sample Containers 280
6.3.2.4 Sample Storage 288
6.3.3 Analytical Quality Assurance 288
6.3.3.1 Reagent and Glassware Control 288
6.3.3.2 Sample Logging 288
6.3.3.3 Instrumentation Control 288
6.3.3.4 Analysis of Quality Control Samples 288
6.3.3.5 Data Quality Assessment 291
6.3.3.6 Quality Assurance in Data Interpretation 291
6.4 Methyl Chloride and Methyl Bromide Analysis by GC/ECD and
Mass Fragmentography 291
6.4.1 Apparatus 291
6.4.2 Quality Control 291
6.4.3 Analysis of Samples 292
Vlll
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FIGURES
Page No.
3.1 Calibration curves for turbidimetric determination of
chloride and bromide 14
3.2 Anion exchange chromatography of Cl and Br AG-1 X8 16
3.3 Anion exchange chromatography on AG-1 XI - Arsenite impinger
solution containing chloride and bromide 18
3.4 Anion exchange chromatography on AG-1 X8 - Water blank. ... 19
3.5 Anion exchange chromatography of chloride and bromide ions on
AG-1 X19 (100/200 mesh) 4 x 70 mm column 23
3.6 Thin layer chromatogram of tris(2,3-dibromopropyl)-phosphate
on fluorescein impregnated silica ge; solvent:
methylene chloride 36
3.7 Retention volumes of some brominated compounds on HPLC. ... 48
3.8 High performance liquid chromatography of spiked milk extracts 49
3.9 Placenta extract - hplc chromatogram of (jStyragel column. . . 50
4.1 Schematic of duplicate (parallel) cartridge sampling and
designated sample analysis 54
4.2 Tandem midget impingers for collection and designated sample
analysis for halogenated substances 54
4.3 Hi-Vol filter and designated sample analysis 56
4.4 Schematic map of Arkansas Chemical Incorp., El Dorado -
sampling locations for PI - 9/20/76 60
4.5 Schematic map of Arkansas Chemical Incorp., El Dorado -
sampling locations for P2 - 9/21/76 61
4.6 Schematic map of Arkansas Chemical Incorp., El Dorado -
sampling locations for PI - 4/7/77 63
4.7 Total ion current profile of volatile organics in front brine
from Arkansas Chemical Incorp 67
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FIGURES (cont'd)
Page No.
4.8 Total ion current profile of volatile organics in tail brine
from Arkansas Chemical Incorp 68
4.9 Mass spectrum of l-chloro-2,3-dibromopropane in tail brine
sample (ACI) 69
4.10 Total ion current profile of volatile ambient air pollutants
from Arkansas Chemical Inc. site, El Dorado, Arkansas
(P1/C1/L1) 72
4.11 Ion chromatograms for ambient air samples from Arkansas
Chemical Inc. site, El Dorado, Arkansas (P1/C1/L1) ... 73
4.12 Total ion current profile of volatile ambient air pollu-
tants from Arkansas Chemical Inc. site, El Dorado,
Arkansas (P1/C1/L2) 74
4.13 Total ion current profile of volatile ambient air pollutants
from Arkansas Chemical Inc. site, El Dorado, Arkansas
(P1/C1/L3) 77
4.14 Total ion current profile of volatile ambient air pollutants
from Arkansas Chemical Inc. site, El Dorado, Arkansas
(P1/C1/L4) 80
4.15 Mass spectrum of Tetrabrom in soil sample P1/C1/L1 83
4.16 Schematic map of Great Lakes Chemical Corp., El Dorado -
sampling locations for PI - 9/22/76 88
4.17 Schematic map of Great Lakes Chemical Corp., El Dorado -
sampling locations for P2 - 9/22/76 89
4.18 Schematic map of Great Lakes Chemical Corp., El Dorado -
sampling locations for P3 - 9/24/76 90
4.19 Schematic map of Great Lakes Chemical Corporation, El Dorado -
sampling locations for PI - 4/7/77 92
4.20 Schematic map of Great Lakes Chemical Corporation, El Dorado -
sampling locations for P2 - 4/22/77 93
4.21 Great Lakes Chemical Corporation, El Dorado, Arkansas on
12/17/76 - 12/18/76 94
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FIGURES (cont'd)
Page No.
4.22 Electron microprobe spectrum of blank glass fiber filter. . . 94
4.23 Electron microprobe spectrum (a) and scanning electron
micrograph (b) of a region on an air sample collected
on glass fiber filter 96
4.24 Electron microprobe element map of region shown in Figure
4.23 97
4.25 Electron microprobe element map of region shown in Figure
4.23 98
4.26 Electron microprobe spectrum (a) and scanning electron
micrograph (b) of a region on an air sample collected
on a glass fiber filter 99
4.27 Electron microprobe element map of region shown in Figure
4.26 100
4.28 Electron microprobe element map of region shown in Figure
4.26 101
4.29 Electron microprobe element map of region shown in Figure
4.26 102
4.30 Mass spectrum of GFF-TLC extract obtained by direct probe . . 104
4.31 Mass spectrum of authentic Decabrom 105
4.32 Mass spectrum of (a) GFF-TLC extract and (b) authentic Deca-
brom obtained by GC/MS/COMP 107
4.33 Total ion current profile of ambient air sample from Great
Lakes Corp. site, El Dorado, Arkansas (P3/C1/L3) .... Ill
4.34 Ion chromatograms of ambient air sample from Great Lakes
Corp. site, El Dorado, Arkansas (P3/C1/L3) 112
4.35 Total ion current profile of volatile ambient air pollutants
from Great Lakes Corp. site, El Dorado, Arkansas
(P3/C1/L3 ELV) 114
4.36 Ion chromatograms of ambient air sample from Great Lakes
Corp. site, El Dorado, Arkansas (P3/C3/L3 ELV) 115
4.37 Total ion current profile of volatile ambient air pollutants
from Great Lakes Corp., El Dorado, Arkansas (P3/C3/L5 ELV) 116
XI
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FIGURES (cont'd)
Page No.
4.38 Ion chromatogram of ambient air sample from Great Lakes Corp.
site, El Dorado, Arkansas (P3/C3/L5 ELY) 117
4.39 Total ion current profile of volatile ambient air pollutants
taken on El Dorado, Arkansas city water tower 120
4.40 Ion chromatograms of ambient air sample from top of El Dorado
city water tower in Arkansas 121
4.41 Total ion current profile of volatile ambient air pollutants
taken on Parker's Chapel water tower near El Dorado,
Arkansas 124
4.42 Ion chromatograms of ambient air sample from top of Parker's
Chapel water tower near El Dorado, Arkansas 125
4.43 Gas chromatography/mass spectrometric analysis of volatiles
purged from water collected near Great Lakes Chemical
Corp., El Dorado, Arkansas (P1/C1/L2) - mass spectrum of
ethylene dibromide 130
4.44 Mass spectrum of soil extract (P1/C1/L1) exhibiting Tetrabrom. 131
4.45 Schematic map of Michigan Chemical Corp., El Dorado -
sampling locations for PI - 9/21/76 134
4.46 Schematic map of Michigan Chemical Corp. - sampling locations
for 4/7/77 136
4.47 Electron microprobe spectrum of a 24 hr Hi-Vol glass fiber
filter air sample taken at (a) Michigan Chemical Cor-
poration, El Dorado, Arkansas on 12/22/76 - 12/23/76.
3
Voluem sampled 2603.6 m air; (b) Great Lakes Chemical
Corporation, El Dorado, Arkansas on 12/17/76 -
12/18/76. Volume sampled 2,733.6 m3 air 138
4.48 Electron microprobe spectrum (a) and scanning electron micro-
graph (b) of a region on an air sample collected on a
cellulose filter 139
4.49 Electron microprobe element map of region shown in Figure
4.48 140
XII
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FIGURES (cont'd)
Page No.
4.50 Electron microprobe element map of region shown in Figure
4.48 141
4.51 Electron microprobe element map of region shown in Figure
4.48 142
4.52 Electron microprobe element map of region shown in Figure
4.48 143
4.53 (a) Scanning electron micrograph of a region on an air sam-
ple collected on a cellulose filter 144
4.54 Electron microprobe element map of region shown in Figure
4.53 145
/TO
4.55 Gas liquid chromatography/electron capture detection ( Ni)
of (a) an acetone extract of the Hi-Vol glass fiber
filter sample collected 12/22/76 - 12/23/76 at Michigan
Chemical Corp., El Dorado, AK; and, (b) a TRIS stan-
dard (0.8 ng) 147
4.56 Gas chromatography/mass spectrometry analysis with multiple
ion detection of (a) TRIS standard and, (b) extract of
Hi-Vol glass fiber filter sample collected at Michigan
Chemical Company 12/22/76 - 12/23/76 148
4.57 Total ion current profile of volatile organics in front
brine sample from Michigan Chemical Corp 153
4.58 Total ion current profile of volatile organics in tail
brine sample from Michigan Chemical Corp 154
4.59 Mass spectrum of bromodichloromethane in tail brine sample
(MCI) 155
4.60 Mass spectrum of dibromochloromethane in tail brine sample
(MCI) 156
4.61 Total ion current profile of volatile ambient air pollu-
tants from Michigan Chemical Corp. site, El Dorado,
Arkansas (P1/C1/L1) 159
4.62 Ion chromatograms for ambient air sample from Michigan
Chemical Corp. site, El Dorado, Arkansas (P1/C1/L1) . 160
Kill
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FIGURES (cont'd)
Page No.
4.63 Total ion current profile of volatile ambient air pollu-
tants from Michigan Chemical Corp. site, El Dorado,
Arkansas (P1/C1/L2) 163
4.64 Ion chromatograms for ambient air sample from Michigan
Chemical Corp. site, El Dorado, Arkansas (P1/C1/L2). . 164
4.65 Total ion current profile of volatile ambient air pollu-
tants from Michigan Chemical Corp. site, El Dorado,
Arkansas (P1/C1/L3) 167
4.66 Ion chromatograms for ambient air sample from Michigan
Chemical Corp. site, El Dorado, Arkansas (P1/C1/L3). . 168
4.67 Schematic map of Ethyl Corporation, Magnolia - sampling
locations for PI - 9/23/76 176
4.68 Map of area in vicinity of Ethyl Corporation, Magnolia,
Arkansas - sampling locations for water, soil, sediment,
and vegetation for PI - 5/17/77 178
4.69 Total ion current profile of volatile ambient air pollutants
from Ethyl Corp. site, Magnolia, Arkansas (P1/C1/L2) . 179
4.70 Ion chromatograms of ambient air sample from Ethyl Corp.
site, Magnolia, Arkansas (P1/C1/L2) 181
4.71 Total ion current profile of volatile ambient air pollutants
from Ethyl Corp. site, Magnolia, Arkansas (P1/C1/L3) . 182
4.72 Ion chromatograms of ambient air sample from Ethyl Corp.
site, Magnolia, Arkansas (P1/C1/L2) 183
4.73 Map of area in vicinity of Dow Chemical Company, Magnolia,
Arkansas - sampling locations for water, soil, sedi-
ment and vegetation for PI - 5/17/77 188
5.1 Map of El Dorado area - sampling locations for continuous
air monitoring 191
5.2 Map of Magnolia area - sampling locations for continuous
air monitoring 192
5.3 Map of area in vicinity of Dow Chemical Company, Magnolia,
Arkansas - sampling location for continuous air
monitoring 193
xiv
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FIGURES (cont'd)
Page No.
5.4 Map of area in the vicinity of Ethyl Corporation, Magnolia,
Arkansas - sampling location for continuous air moni-
toring 194
6.1 Schematic map of Great Lakes Chemical Company, El Dorado,
AK - air sampling locations for P2 (7/18/77) through
P5 (7/21/77) 215
6.2 Map of Great Lakes Chemical Co. Vicinity, El Dorado,
Arkansas - air sampling locations (7/17/77 - 7/24/77) 216
6.3 Map of Great Lakes Chemical Co. Vicinity, El Dorado,
Arkansas - air sampling locations (7/17/77 - 7/20/77) 217
6.4 Schematic map of Great Lakes Chemical Company, El Dorado,
Arkansas - soil sampling locations (7/21/77) 218
6.5 Vicinity map of Great Lakes Chemical Company, El Dorado,
Arkansas - water and sediment sampling locations
(7/17/77 - 7/24/77) 219
6.6 Schematic map of Velsicol, Inc., El Dorado, AK. Air
sampling locations PI (7/22/77) through P4 (7/25/77). 231
6.7 Vicinity map of Velsicol, Inc., El Dorado, Arkansas - water
and sediment sample locations (7/22/77 - 7/25/77) . . 233
6.8 Schematic map of Velsicol, Inc., El Dorado, Arkansas - water
and sediment sampling location (7/23/77) 234
6.9 Schematic map of Velsicol, Inc., El Dorado, Arkansas - soil
sampling locations (7/22/77 to 7/25/77) 236
6.10 Vicinity map of Velsicol, Inc., El Dorado, Arkansas - soil
sampling locations (7/22/77 to 7/25/77) 237
6.11 Schematic map of Velsicol, Inc., El Dorado, Arkansas -
vegetation and miscellaneous sampling locations
(7/22/77 - 7/23/77) 240
6.12 Map of the vicinity of Velsicol, Inc., El Dorado, Arkansas -
vegetation and miscellaneous sample locations (7/22/
77 - 7/22/77) 241
xv
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FIGURES (cont'd)
Page No.
6.13 Mass spectrum of GC peak eluting at 2.06 min from soil sam-
ple L1/C1/L3 251
6.14 Mass spectrum of GC peak eluting at 3.4 min from soil sam-
ple P1/C1/L3 252
6.15 Mass spectrum of GC peak eluting at 7.00 min from soil
sample P1/C1/L3 identified as decabrom-biphenyl ether . . 253
6.16 Mass spectrum of authentic firemaster 680 (direct probe) . . . 254
6.17 Schematic map of Ethyl Corporation, Magnolia, AK - air
sampling locations P1-P6 (7/26/77 through 7/30/77). ... 258
6.18 Schematic map of Dow Chemical Company, Magnolia, Arkansas -
air sampling locations for PI - 8/1/77 265
6.19 Schematic map of Dow Chemical Company, Magnolia, Arkansas -
air sampling locations for P2 - 8/2/77 266
6.20 Schematic map of Dow Chemical Company, Magnolia, Arkansas -
air sampling locations for P3 - 8/3/77 267
6.21 Water sampling locations in the vicinity of Dow Chemical
Co., Magnolia, Arkansas (7/29/77 - 8/3/77) 269
6.22 Sampling locations for soil samples collected in the vici-
nity of Dow Chemical Co. (7/30/77 - 8/2/77) 271
6.23 Field sampling protocol for condensed matrices 286
6.24 Field sampling protocol for ambient air 287
6.25 GC/ECD of methyl chloride and methyl bromide 293
6.26 GC/ECD of blank control sample 294
6.27 GC/ECD of methyl chloride and methyl bromide 295
xv i
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TABLES
Page No
1.1 Halogenated and Other Chemicals Identified in the
Environment 3
1.2 Maximum Concentrations of Brominated Chemicals Observed
in Selected Environmental Samples 5
1.3 Maximum Concentrations of Brominated Chemicals Observed in
Environmental Samples Taken in the Vicinity of Industry 6
3.1 Evaluation of Halide Impinger Train Performance 12
3.2 Columns Evaluated for Resolution of Chloride and Bromide . 13
3.3 Recoveries of Chloride and Bromide from Impinger Solutions 17
3.4 Solutions Applied to Ion Exchange Columns 20
3.5 Recoveries of Chloride and Bromide from Ion-Exchange
Chromatography on AG-1 X10 (100-200 Mesh) 1 x 15 cm
Columns 21
3.6 Recoveries of Chloride and Bromide from Ion-Exchange Chroma-
tography on AG-1 X10 (100-200 Mesh) 4 x 70 mm Columns. 24
3.7 Estimated Breakthrough Volumes for Several Halogenated Com-
pounds 27
3.8 Relative Molar Response Values for Several Halogenated
Compounds Based Upon Selected Ions 30
3.9 Estimated Limits of Detection for Several Halogenated
Hydrocarbons 31
3.10 Limits of Detection of Brominated Organics in Air 35
3.11 Thin-Layer Parameters for Semi-Volatile Brominated Organics
on Silica Gel 37
3.12 Conditions for Analysis of Tenax Cartridges From VOA Purge -
Recovery Studies 38
3.13 Recovery Studies - VOA Method 39
xvii
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TABLES (cont'd)
Page No.
3.14 Recoveries of Brominated Compounds from Water Using XAD-2
Resin 40
3.15 Extraction Efficiency of Several Organic Solvents for EDB
and TRIS 41
3.16 Recoveries from Sequential Solvent Extraction of Water ... 43
3.17 Losses of Ethylene Dibromide During Solvent Extraction ... 43
3.18 Limits of Detection of Brominated Organics in Water 44
3.19 Recoveries of Semi-Volatile Halogenated Organics from Soil
by Solvent Extraction 45
3.20 Amounts of Brominated Organics Added to Milk 47
4.1 Analytical Techniques Employed for Studying Pollutants in
Ambient Air Surrounding Bromine Industry in Arkansas . . 52
4.2 Sampling Protocol for Arkansas Chemical Incorp., Highway
15, El Dorado, Arkansas 59
4.3 Sampling Protocol for Arkansas Chemical Incorp., El Dorado . 62
4.4 Concentrations of Halogens and Halides in Ambient Air
Surrounding Arkansas Chemical Incorp 64
4.5 Acid Mist in Ambient Air Surrounding Arkansas Chemical
Incorp. as H SO, 65
4.6 Concentration of Bromine in Brine Samples 65
4.7 Halogenated and Other Organics Identified and Quantitated
in Brine Samples from Arkansas Chemical Incorp 70
4.8 Volatile Organics Identified in Ambient Air from Arkansas
Chemical Incorp. Site in El Dorado, Arkansas (P1/C1/L3). 75
4.9 Volatile Organics Identified in Ambient Air from Arkansas.
Chemical Incorp. Site in El Dorado, Arkansas (P1/C1/L4). 78
4.10 Halogenated Compounds Identified by GC/MS/COMP in Ambient
Air at Arkansas Chemical Incorp., El Dorado, Arkansas. . 71
4.11 Halogenated Hydrocarbons Identified and Quantitated in
Ambient Air Surrounding Arkansas Chemical Incorp., El
Dorado, AK 82
xviii
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TABLES (cont'd)
Page No.
4.12 Concentrations of Ethylene in Ambient Air 81
4.13 Analysis of a Soil Sample Collected Near Arkansas Chemicals,
Incorporated, El Dorado, AK 84
4.14 Sampling Protocol for Great Lakes Chemical Corporation,
Highway 15, El Dorado, Arkansas 85
4.15 Sampling Protocol for Great Lakes Corporation, El Dorado,
Arkansas 91
4.16 Neutron Activation Analysis of Ambient Air Hi-Vol Samples. . 103
4.17 Analysis of Hi-Vol Filters for Decabrom 106
4.18 Concentrations of Halogens and Halides in Ambient Air
Surrounding Great Lakes Chemical Corp 108
4.19 Concentrations of Bromide and Bromine in Ambient Air
Surrounding Great Lakes Chemical Corp 109
4.20 Concentrations of Fluoride/Fluorine in Ambient Air
Surrounding Great Lakes Chemical Corp 110
4.21 Acid Mist in Ambient Air Surrounding Great Lakes Chemical
Corp. as H SO, 110
4.22 Volatile Organics Identified in Ambient Air Taken on El
Dorado, Arkansas City Water Tower 118
4.23 Volatile Organics Identified in Ambient Air Taken on
Parker's Chapel Water Tower Near El Dorado, Arkansas . . 122
4.24 Halogenated Hydrocarbons Identified by GC/MS/COMP in
Ambient Air at Great Lakes Corp., El Dorado, Arkansas. . 126
4.25 Halogenated Hydrocarbons Identified and Quantitated in
Ambient Air Surrounding Great Lakes Corp., El Dorado, AK 127
4.26 Ethylene Levels in Ambient Air 128
4.27 Results of Analysis of Soil, Sediment and Water Samples for
Brominated Organics--Survey Sampling Near Great Lakes
Chemical Corporation, El Dorado, AK 129
4.28 Sampling Protocol for Michigan Chemical Corporation,
Highway 167, El Dorado, Arkansas 132
4.29 Sampling Protocol for Michigan Chemical Corporation, El
Dorado, Arkansas 135
xix
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TABLES (cont'd)
Page No.
4.30 Neutron Activation Analysis of Ambient Air Hi-Vol Samples. . 146
4.31 Peak Areas and Ratios of Selected Ions Obtained from
Analysis of TRIS by Gas Chromatography-Mass Spectrometry
in Multiple Ion Detection Mode 149
4.32 Concentrations of Halogens and Halides in Ambient Air Sur-
rounding Michigan Chemical Corp. (Velsicol) 150
4.33 Concentrations of Fluoride/Fluorine in Ambient Air
Surrounding Michigan Chemical Corp. (Velsicol) 151
4.34 Acid Mist in Ambient Air Surrounding Michigan Chemical
Corp. as H0SO, 152
24
4.35 Concentration of Bromine in Brine Samples 152
4.36 Halogenated and Other Organics Identified and Quantitated
in Brine Samples from Michigan Chemical Corp 157
4.37 Volatile Organics Identified in Ambient Air from Michigan
Chemical Corporation Site, El Dorado, Arkansas (P1/C1/L1) 158
4.38 Volatile Organics Identified in Ambient Air from Michigan
Chemical Corporation Site, El Dorado, Arkansas (P1/C1/L2) 162
4.39 Volatile Organics Identified in Ambient Air from Michigan
Chemical Corporation Site, El Dorado, Arkansas (P1/C1/L3) 165
4.40 Volatile Organics Identified in Ambient Air from Michigan
Chemical Corporation Site, El Dorado, Arkansas (P1/C1/L4) 169
4.41 Halogenated Hydrocarbons Identified by GC-MS-COMP in
Ambient Air at Michigan Chemical, El Dorado, Arkansas . 171
4.42 Halogenated Hydrocarbons Identified and Quantitated in
Ambient Air Surrounding Michigan Chemical Corp., El Dorado,
AK 172
4.43 Ethylene Levels in Ambient Air 173
4.44 Analysis of a Soil Sample from the Vicinity of Michigan
Chemical Corporation 174
4.45 Sampling Protocol fr Ethyl Corporation, Highway 79,
Magnolia, Arkansas 175
xx
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TABLES (cont'd)
Page No.
4.46 Sampling Protocol for Ethyl Corporation, Magnolia, Arkansas. 177
4.47 Concentrations of Halogens and Halides in Ambient Air
Surrounding Ethyl Corp 180
4.48 Halogenated Hydrocarbons Identified by GC/MS/COMP in
Ambient Air at Ethyl Corp., Magnolia, Arkansas 184
4.49 Halogenated Hydrocarbons Identified and Quantitated in
Ambient Air Surrounding Ethyl Corp., Magnolia, AK . . . 185
4.50 Ethylene Levels in Ambient Air 186
4.51 Sampling Protocol for Dow Chemical Co. Magnolia, AK . . . . 187
4.52 VOA Analysis of Environmental from the Vicinity of Dow
Chemical Co., Magnolia, AK 189
5.1 Sampling Protocol for Continuous Air Monitoring in the
El Dorado, Arkansas Vicinity - Location 1: Parker's
Chapel Water Tower 195
5.2 Sampling Protocol for Continuous Air Monitoring in the
El Dorado, Arkansas Vicinity - Location 2: El Dorado
Water Tower 199
5.3 Protocol for Continuous Air Monitoring, Magnolia, Arkansas. 203
5.4 Protocol for Continuous Air Monitoring Near Dow Chemical
Company, Magnolia, Arkansas 204
5.5 Protocol for Continuous Air Monitoring Near Ethyl Corpora-
tion, Magnolia, Arkansas 206
6.1 Inventory of Samples Collected in Southern Arkansas (7/15/77
to 8/5/77) 209
6.2 Sampling Protocol for Ambient Air Surrounding Great Lakes
Chemical Corp., El Dorado, AK 211
6.3 Soil Sampling Protocols Surrounding and on Great Lakes
Chemical Corp., El Dorado, Arkansas 213
6.4 Water and Sediment Sampling Protocol Surrounding and on
Great Lakes Chemical Corp. and the El Dorado, Arkansas
Area 214
xxi
-------
TABLES (cont'd)
Page No,
6.5 Halides and Halogens Quantitated in Ambient Air Surrounding
Great Lakes Chemical Corp., El Dorado, AK 220
6.6 Ambient Air Levels of Volatile Brominated Organics Sur-
rounding Great Lakes Corp., El Dorado, AK 221
6.7 Concentrations of Ethylene in Ambient Air Surrounding
Great Lakes Chemical Corp 224
6.8 Concentrations of Ethylene in Ambient Air Surrounding Great
Lakes Chemical Inc. - Marysville Plant 225
6.9 Results of the Analysis of Hi-Vol Filters for Semi-Volatile
Brominated Organics - Great Lakes Chemical Corp., El
Dorado, Arkansas 226
6.10 Results of Analysis of Sediment Samples for Semi-Volatile
Brominated Organics Great Lakes Chemical Company, El
Dorado, Arkansas 227
6.11 Results of Analysis of Soil Samples for Semi-Volatile
Brominated Organics Great Lakes Chemical Company, El
Dorado, Arkansas 228
6.12 Ambient Air Sampling Protocol Surrounding Velsicol Chemical
Corp., El Dorado, AK 229
6.13 Water and Sediment Sampling Protocol Surrounding and on
Velsicol Incoporation, El Dorado, Arkansas 232
6.14 Soil Sampling Protocols Surrounding and on Velsicol, Inc.,
El Dorado, Arkansas 235
6.15 Vegetation and Miscellaneous Sampling Protocols Surrounding
and on Velsicol, Inc., El Dorado, Arkansas 239
6.16 Halides and Halogens Quantitated in Ambient Air Surrounding
Velsicol, Inc., El Dorado, AK 242
6.17 Ambient Air Levels of Volatile Brominated Organics Sur-
rounding Velsicol Chemical Corp., El Dorado, AK 243
6.18 Concentrations of Ethylene in Ambient Air Surrounding
Velsicol Chemical Inc 244
xx ii
-------
TABLES (cont'd)
Page No.
6.19 Brominated Organics Found on Glass Fiber Filters from
Hi-Vol Samplers 245
6.20 TRIS Recovery Study 246
6.21 Results of Analysis of Sediment and Water Samples for Semi-
Volatile Brominated Organics - Velsicol, Inc., El Dorado,
Arkansas 247
6.22 Qualitative Analysis of Volatile Halogenated Organics in
Soil Samples Collected Near Velsicol Chemical
Corporation, El Dorado, AK 248
6.23 Results of Analysis of Soil Samples for Semi-Volatile
Brominated Organics - Velsicol, Inc., El Dorado,
Arkansas 249
6.24 Brominated Compounds Identified from Gas Chromatograpy -
Mass Spectrometry Analysis of Soil Sample P1/C1/L3 from
Velsicol, Inc., El Dorado, Arkansas 250
6.25 Ambient Air Sampling Protocol Surrounding Ethyl Corp.,
Magnolia, AK 256
6.26 Halides and Halogens Quantitated in Ambient Air Surrounding
Ethyl Corporation, Magnolia, AK 259
6.27 Ambient Air Levels for Several Volatile Brominated
Organics Surrounding Ethyl Corp., Magnolia, AK 260
6.28 Concentrations of Ethylene in Ambient Air Surrounding
Ethyl Corporation, Magnolia, AK 261
6.29 Ambient Air Sampling Protocol for Dow Chemical Co.,
Magnolia, AK 263
6.30 Water and Sediment Sampling Protocols for Dow Chemical
Company, Magnolia, Arkansas 268
6.31 Soil Sampling Protocols for Dow Chemical Company, Magnolia,
Arkansas 270
6.32 Halides and Halogens Quantitated in Ambient Air Surrounding
Dow Chemical Company Magnolia, AK 272
6.33 Estimated Levels of Volatile Brominated Organics in
Ambient Air Surrounding Dow Chemical Co., Magnolia, AK. 273
xxiii
-------
TABLES (cont'd)
Page No.
6.34 Concentrations of Ethylene in Ambient Air Surrounding Dow
Chemical Corp., Magnolia, AK 274
6.35 Qualitative Analysis of Water and Sediment Samples Collected
Near Dow Chemical Company, Magnolia, AK 275
6.36 Qualitative Analysis of Soil Samples Collected Near Dow
Chemical Company, Magnolia, AK 276
6.37 Sampling Protocol for Samples of the Human Population .... 278
6.38 Analysis of Human Hair Collected in El Dorado, Arkansas for
Semi-Volatile Brominated Organics 279
6.39 Inventory of Controls and Blanks for Quality Assurance
for Arkansas Field Sampling - July and August, 1977 . . . 281
6.40 Reproducibility of Replicate Measurements for Halogenated
Hydrocarbons on Tenax GC Sampling Cartridges 290
XXIV
-------
NAMES, ABBREVIATIONS, AND STRUCTURAL FORMULAS OF
BROMINATED COMPOUNDS
Methyl Bromide (MB)
Vinyl Bromide (VB)
Bromoform (BF)
Bromoethane (BE)
1,2-Dibromoethane (EDB)
l-Chloro-2-bromoethane (CBE)
Allyl Bromide (AB)
l-Chloro-3-bromopropane (CBP)
l-Chloro-2,3-dibromopropane (DBCP)
CH3Br
CH2=CH-Br
CHBr3
CH3CH2-Br
Br-CH2CH2-Br
ClCH2CH2-Br
CH2=CH-CH -Br
Cl-CH2CHBrCH2-Br
Bromobenzene (BB)
Decabromobiphenyl ether (Decabrom)
syn.-decabromobiphenyl oxide
Br
Br
2,2'-Bis(dibromo-4-hydroxyphenyl)propane
(Tetrabrom)
trivial name - Tetrabromobisphenol A
XXV
-------
1,2-Bis(2,4,6-tribromophenoxy)ethane
®
trade name - Firemaster 680
Br
Iris-(2,3-dibromopropyl)phosphate (TRIS)
trade name - Firemaster LVT23P
,®
0-CH2CHBrCH2Br
0=P-OCH2CHBrCH2Br
0-CH2CHBrCH2Br
XXVI
-------
ACKNOWLEDGEMENTS
Many devoted individuals were responsible for the success of this
program. The authors wish to thank Mr.'s L. Michael, S. Cooper, R. Keefe,
A. Billings, B. Garber and R. Cepko who participated in the field sampling
and laboratory support for this program. We also wish to thank Ms. D.
Smith, Mr. L. Kelner and Drs. J. Bursey and D. Rosenthal for their assistance
in mass spectrometry. A special thanks to Ms. N. Castillo for her invaluable
help in the interpretation of mass spectra and the identification of halogena-
ted compounds. The ozone measurements were provided through the assistance
of Mr. Mark Saeger and Cliff Decker of the Environmental Measurements
Department.
Most importantly, we wish to thank EPA personnel who assisted in the
many facets of this program, both from EPA Region VI, specifically Drs.
Frank Hall, Oscar Ramierez, Paul Fahrenthold and Tim Matzke and Dr. Vincent
DeCarlo of the Office of Toxic Substances.
Most assuredly the success of this program stemmed from the invaluable
help provided by Mr. Gerald Southall and John Mitchell of the State of
Arkansas Department of Pollution and Ecology who were responsible for
gaining access to the areas of interest for study and for their public
relations in El Dorado and Magnolia, AK. A special thanks is in order to
them.
We also wish to thank the various companies that were visited in El
Dorado and Magnolia and express our deep appreciation in their assistance
during our visit on their plant sites. A special thanks to Mr. Dick Karkan-
nien and the personnel at Arkansas Chemical Inc. for assisting in the
acquisition of power for the ozone measurements conducted on plant property.
xxv ii
-------
1.0 SUMMARY AND CONCLUSIONS
Development and/or validation of methods for the collection and analysis
of brominated chemicals (inorganic and organic) in environmental samples -
air, water, soil, sediment, and biota - was conducted and these techniques
were applied to the characterization of the environment surrounding the
bromine industry in El Dorado and Magnolia, AK. The final analytical
protocols which were adopted in this research program are given in Appendix A.
Evaluation of a miniature impinger train for the collection of halides
and halogens indicated that if molecular chlorine and bromide ion were
present in air the displacement of bromide from the first impinger would
occur. Thus, false high values of molecular bromine would be observed.
Determination of chloride and bromide was conducted by turbidimetric measure-
3
ments; the detection limit was approximately 10 |Jg/m . Differentiation of
chloride and bromide ions was accomplished by ion-exchange techniques or,
in some cases, the bromide was detected by a fluorescence quench method
using fluorescein. Inorganic fluoride was directly determined using a
3
fluoride ion-specific electrode and the detection limit was ^-2 [Jg/m .
Collection of volatile brominated organics in ambient air utilized
®
Tenax GC and carbon sorbents. In some cases aluminum vacuum cannisters
were used as alternatives to the sorbent methods for obtaining methyl
chloride, methyl bromide, vinyl chloride and vinyl bromide. Airborne
particulates were trapped on glass fiber and cellulose filters. Methods
for recoverying of brominated organics from air particulates, water, soil,
sediment and biota were developed and/or validated. Techniques such as
inert gas purging or solvent extraction were used to isolate the brominated
materials from the condensed phases.
The principal method for the identification of brominated organics was
gas chromatography/mass spectrometry/computer (gc/ms/comp). Quantitation
-------
was performed by gc/ms/comp and gc/ec. Alternate detection methods such as
neutron activation, spectrophotometry, and scanning electron microscopy/X-
ray dispersion were used for exploration and confirmation of the presence
of brominated substances.
A total of 26 brominated organic compounds was identified in environmen-
tal samples collected from a geographical area associated with the bromine
industry (Table 1.1). Many of the chemicals were detected in environmental
matrices off plant property indicating that their transport into the neigh-
boring environment was occurring. Quantification of most of the chemicals
in various environmental media (Table 1.1) was also conducted.
Examples of selected results exhibitng highest concentrations observed
in environmental samples are given in Tables 1.2 and 1.3. These preliminary
results indicate a spatial spreading of brominated compounds into the
environment.
Additional research would be required to establish the extent of
environmental contamination and man's exposure and body burden.
-------
Table 1.1. HALOGENATED AND OTHER CHEMICALS IDENTIFIED IN THE ENVIRONMENT
Substance
Matrix
chlorodibroraopropane
l-chloro-2,3-dibromopropane
1,2-dibromoethane
difluorodibromomethane
methyl bromide
bromobenzene
bromoethane
bromoform
l-chloro-2-bromoethane
l-chloro-3-bromopropane
1,3-dichloropropane
vinyl bromide
bromodichloromethane
allyl bromide
1 or 2-bromopropane
bromopropene
chlorobromopropene
1,l-dibromo-2-chloropropane
dibromopropane
dibromoethene
chlorobutene
air
air, water, soil, sediment, front and tail brine
air, water, soil, sediment
air
air
air, soil, sediment
air
air, sediment, front and tail brine
air, water, sediment
air
air
air
air, tail and front brine
air
air
air, water
air
air
air
water
water
(continued)
-------
Table 1.1 (cont'd)
Substance
Matrix
bromodichloropropane
1,2-dichloroethane
trichloroethylene
Decabrom ^
Tetrabromobisphenol A
Tris
Firemaster 680^^
dibromochloromethane
styrene
benzene
toluene
dimethyIdisulfide
thiacyclopentane
dithiol propane isomer
ethylbenzene
rt-undecane
n-dodecane
water
water, soil, sediment
water
air particulate, soil, sediment, human hair
air particulate, soil, sediment, human hair
air particulate, soil
air particulate, soil
front and tail brine
air
front and tail brine
front and tail brine
front and tail brine
front and tail (?) brine
front and tail brine
front brine
front and tail brine
front and tail brine
-------
Table 1.2. MAXIMUM CONCENTRATIONS OF BROMINATED CHEMICALS OBSERVED
IN SELECTED ENVIRONMENTAL SAMPLES
Company /Community
Great Lakes Chemical Corp.
Velsicol Inc.
Ethyl Corp.
Dow Chemical
Parkers Chapel
El Dorado, AK
Chemical
Cl2/Br2
Cl~/Br~
EDB
Decabrom
Decabrom
Cl~/Br~
Cl2/Br2
EDB
Firemaster 680
Tris
Decabrom
EDB
DBCP
Cl /Br2
EDB
DBCP
EDB
l-Chloro-2-
bromo ethane
Medium
Air
Air
Air
Air
Soil
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Air
Quantity
183,000 ng/m3
876,000 ng/m3
271,283 ng/m3
94,118 ng/m3
»225,000 tag/Kg
91,000 ng/m3
158,000 ng/m3
2,425 ng/m3
183 ng/m3
3
60 ng/m
72 ng/m3
20,250 ng/m3
1,688 ng/m3
3
64,000 ng/m
62,484 ng/m3
3
6,653 ng/m
1,260 ng/m3
4,200 ng/m3
-------
Table 1.3. MAXIMUM CONCENTRATIONS OF BROMINATED CHEMICALS OBSERVED IN
ENVIRONMENTAL SAMPLES TAKEN IN THE VICINITY OF INDUSTRY
Vicinity of —
Great Lakes Chemical Corp.
Velsicol Inc.
El Dorado, AK
Chemical
Decabrom
Bisphenol A
Bisphenol A
Decabrom
Pentabromophenol
Bisphenol A
Decabrom
Tetrabrom
Firemaster 680
Tris
Tetrabrom
Firemaster 680
Tris
Bisphenol A
Decabrom
Medium
Sediment
Sediment
Soil
Soil
Soil
Sediment
Sediment
Soil
Soil
Soil
Sediment
Sediment
Sediment
Human hair
Human hair
Quantity
19,000 yg/Kg
22,000 yg/Kg
150,000 yg/Kg
25,000 yg/Kg
200 yg/Kg
330,000 yg/Kg
VL, 000, 000 yg/Kg
118 yg/Kg
253 yg/Kg
840 yg/Kg
30 yg/Kg
466 yg/Kg
2,000 yg/Kg
>13 yg/Kg
5 yg/Kg
-------
2.0 INTRODUCTION
Ethylene dibromide is a colorless non-flammable liquid of high density
and chloroform-like odor. It is a particularly good solvent for non-polar
materials such as gums, waxes and many other organic chemicals, but
its major use is as an additive in leaded gasoline. It is miscible with
benzene, carbon tetrachloride, ether, alcohols and other non-polar solvents.
Its low vapor pressure and slight water solubility suggest that it would
tend to be persistent in water and soil in cases where it is released into
the environment. The brominated hydrocarbons are less volatile than their
chlorine analogs. Ethylene dibromide melts at about 10°C. Ethylene
dibromide is commercially produced by reaction of ethylene and bromine.
The compound is generally regarded to be inert at normal temperatures
and pressures with slight decomposition resulting from exposure to light.
At elevated temperatures, it can be hydrolyzed to ethylene glycol and
bromoethanol. When heated to 340-370°C, it decomposes into vinyl bromide
and hydrobromic acid. It is considered a useful synthetic intermediate
since the terminal halogen atoms are reactive.
Studies indicate that ethylene dibromide is resistant to atmospheric
oxidation by peroxides and ozone and a half-life of 100 days or more has
(2)
been reported. It is generally regarded to be less reactive in the
atmosphere than the corresponding alkanes or olefins. Ethylene dibromide
has a half-life of ~5-10 days in water; its hydrolysis is favored by acid
(2)
conditions.
Ethylene dibromide is a major industrial chemical by virtue of its
use in leaded motor fuel which accounts for 85% of its demand. Domestic
production of the chemical by direct combination of ethylene and bromine
(r>\
totaled 331 million pounds in 1973. As a fuel additive O0.025% wt/vol)
ethylene dibromide serves to scavenge lead oxide residues from combustion
(3)
chambers of gasoline engines. Lead oxide residues result from the use
-------
of fuels containing tetra-alkyl lead compounds as anti-knock agents. The
ethylene dibromide undergoes combustion with fuel. As a consequence of
combustion, the bromine content of the chemical is released to the atmos-
phere as lead bromide through the engine exhaust. As the use of leaded
fuel is abandoned, the use of ethylene dibromide in this capacity will
probably also be reduced.
Another important use of ethylene dibromide has been as a fumigant
(4)
for disinfecting fruits, vegetables, food grains and in warehouses. It
is also commonly used in conjunction with methyl bromide as a nematicide
in tobacco fields where it is injected into the shank of tobacco plant
stalks. It also has commonly been used in citrus groves in Florida.
Ethylene dibromide may be used by itself or even frequently in combination
with fumigants such as carbon disulfide, ethylene dichloride and carbon
tetrachloride. '
Ethylene dibromide is also a useful synthetic intermediate for the
synthesis of dyes, Pharmaceuticals and other organics, but these applica-
tions account for ~5% of its current demand.
Similarly to ethylene dibromide, fumazone and methyl bromide are com-
monly used to control soil nematodes. Fumazone is a mixed halogenated
hydrocarbon, i-e., dibromochloropropane.
Another extremely important area of usage of brominated organics is
as fire retardants. Examples of these which are important to this program
are TRIS, Decabrom and Firemaster 680. In contrast to ethylene dibromide,
methyl bromide or fumazone, these are high molecular weight materials with
extremely low vapor pressures and high thermal, biological and chemical
stability. For these reasons these chemicals, if present, exhibit a long-
term persistence in the environment and would be associated with the con-
densed phase matrices. Also, gradual accumulation might be anticipated
with continued emissions.
The broad overview of this program has been to examine the potential
prevalence of chemicals emanating from the bromine industry in the El
Dorado and Magnolia, AK areas. The program was concerned with the acquisi-
tion of information about the types of chemicals associated with this
industry which were in the environment for subsequent studies on their
-------
environmental impact. Although the focus has been on the monitoring of
ethylene dibromide (1,2-dibromoethane) and vinyl bromide, other chemicals
which might occur were also of prime interest.
The specific aims of this study were to examine environmental matrices
surrounding the bromine industry in El Dorado and Magnolia, AK and to
identify as much as possible all brominated chemicals resulting from
industrial activities. Prior to this study a limited analysis had been
conducted in this area for ethylene dibromide. However, other chemicals
were not sought. For this reason, whether other brominated chemicals were
being released to the environment reamined unknown. It was the objective
of this study to acquire a maximum amount of information concerning the
potential pollution related to the bromine industry. As part of the
broad-based concept, the program was divided into a survey phase under
which a limited amount of monitoring was conducted for airborne materials
and the chemicals present in the environment were identified. A more in-
depth study of these chemicals was to follow by examining all environmental
matrices. In the survey study it was the principal objective to establish
the types of chemicals associated with the bromine industry which might be
released to the environment, while, in the second phase, the purpose was
to determine their occurrence and quantities both immediate and distant
from the plant sites. Furthermore, the specific aims eventually included
determining the potential prevalence and occurrence of brominated chemicals
in environmental matrices which might eventually expose local populations.
However, it was beyond the scope of this program to establish a direct
environmental impact by the identified brominated substances on the local
vegetation and human population.
References
1. Fieser, L. F., and M. Fieser, Organic Chemistry, 3rd Edition, Heath,
Boston, MA (1956), p. 145.
2. National Science Foundation Panel on Manufactured Organic Chemicals
in the Environment, SRI Data, 1975.
3. Standford Research Institute, Chemical Economics Handbook, Menlo
Park CA, 1975.
-------
4. Girish, G. K., R. K. Goyal, and K. Krishnamurthy, Bull. Grain Tech.,
10, 120 (1973).
5. Going, J. and S. Long, "Sampling and Analysis for Toxic Substances
Task II - Ethylene Dibromide", EPA 560/6-75-001, September, 1975, p.
30.
6. Malone, B., J. Assoc. Offic. Agr. Chem., 52, 800 (1969).
7. Malone, B. , J. Assoc. Offic. Agr. Chem., 53, 742 (1970).
10
-------
3.0 METHOD DEVELOPMENT AND VALIDATION
3.1 INORGANICS IN AMBIENT AIR
3.1.1 Chloride/Bromide and Chlorine/Bromine Sampling and Analysis
in Ambient Air
The method for collection and analysis of halides and halogens in
ambient air was initially specified in the Task request as the Texas Air
Control Board Method for chloride and chlorine. The performance of this
procedure and several supplementary analytical methods was evaluated in this
laboratory for utility in the proposed study.
3.1.1.1 Evaluation of the Impinger Train for the Collection of
Halides and Halogens
The impinger train specified by the Texas Air Control Board Method
is comprised of a midget impinger containing deionized water (20 ml) followed
by an impinger containing 0.005M NaAsO~ in 0.1M NaOH (20 ml). The performance
of this collection system had only been evaluated for chloride and chlorine
and its performance with respect to bromide/bromine was unknown. Artifacts
due to the presence of chlorine or other oxidants may affect the distribution
of the various halide species through the impinger train. Thus it was
necessary to examine these potential problems and to validate the method
prior to its implementation in this program.
The following species were tested for their distribution in the impinger
train: HC1, HBr, Br_ and Cl?. Hydrochloric acid and HBr were introduced as
aqueous solutions into an empty impinger at the beginning of the train.
Volatilization occurred during the course of the experiment. The halogens
were introduced by permeation tubes (Metronics Assoc., Inc., Palo Alto, CA).
The permeation rates were determined gravimetrically for each tube at the
temperature used for the experiments. The results are shown in Table 3.1.
The last experiment in the table included the spiking of the deionized water
impinger with HBr before initiating the experiment. The effluent from the
11
-------
Table 3.1. EVALUATION OF HALIDE IMPINGER TRAIN PERFORMANCE
N>
Midget Impingers (20 ml each)
Halide
species
HC1
HC1
HC1
HBr
HBr
HBr
C10
2
Cl
2
Br,
Br
L
Br
L
Br.
2
HBr/
ci2
Flow
rate
U/min)
1.9
1.9
1.68
1.65
1.63
1.98
0.5
1.62
1.02
0.6
1.82
1.44
1.78
Vol.
(*)
65.6
119
267
59.4
116
283
31.1
283
28.3
28.3
300
302
283
AIa>b Alia.b
(% recovery) (% recovery)
688 + 48 <12
3640 + 56 <12
725+4 < 6
1176 + 120 12
2392 + 136 12
<1788 178
1700 164C
94 + 5
(84)
44 + 7
(14)
27 + 7
(54)
33 + 6
(43)
61 + 6
(23)
27 + 6
(8)
24 + 2d«e
(6) .
348 + llf
(108)
Bic BIIC
(% recovery) (% recovery)
32
(29)
274 + 10 <5
(87) (<2)
18 + 0
(40)
35 + 0
(46)
182 +0 <5
(69) (<2)
29+7 11+1
(85) (3)
Overall
recovery
108
89
113
101
97
89
92
96
Analysis by turbidity except where stated otherwise
Impingers contained deionized water
Chloride determined by ion exchange chromatography
Determined by fluorescein fluorescence quench
e
Bromide determined by ion exchange chromatography
Impinger AI was initially doped with 400 iig HBr
-------
chlorine permeation tube was sampled and the deionized water analyzed by ion
exchange chromatography (see Section 3.1.1.2).
3.1.1.2 Analysis of Halides and Halogens
The turbidimetric method of detection of halides in the impinger
solutions is one of the more sensitive methods readily available. However,
it does not differentiate between chloride and bromide. When this method is
used alone, the results must be reported as total halide and in terms of
the halide used for calibration (usually chloride). The response is halide-
dependent as can be seen from the calibration curves shown in Figure 3.1.
By using chloride for calibration purposes, the results will be underestimated
by not more than 20% if the sample is pure bromide.
Separation of Chloride and Bromide.--In order to determine the specific
halides present in a sample the development of an ion exchange chromatogra-
(2)
phic separation similar to that described by DeGeiso et al. was underta-
ken. Following this chromatography, halide detection was made turbidimetri-
cally.
(2)
The chromatography described by DeGeiso was miniaturized and the
performance evaluated as a function of column length and resin type for five
1 cm diameter columns as indicated in Table 3.2.
Table 3.2. COLUMNS EVALUATED FOR RESOLUTION OF CHLORIDE AND BROMIDE
Column
1
2
3
4
5
Resin Type
Bio-Rad AG-1 X8
Bio-Rad AG-1 X8
Bio-Rad AG-1 X8
Bio-Rad AG-1 X8
Bio-Rad AG-1 X10
Mesh Size
100-200
100-200
100-200
100-200
200-400
Column Length
4.6 cm
6.4 cm
10.2 cm
13.5 cm
8.9 cm
The resins were converted from the chloride form to the nitrate form using
_o
0.5M NaNOQ. After equilibration, 5 ml of a 1.0 x 10 M NaCl solution was
then placed on each column and allowed to drain, and the sides of the
columns washed with 2 x 1.0 ml portions of deionized water. The column
13
-------
2 4 6 8 10 12 14 16 18 20 22 24
Concentration of Halide (jjg/ml)
Figure 3.1. Calibration Curves for Turbidimetric Determination of Chloride and Bromide
-------
was eluted with 0.5M NaNCL at ~1 ml/min and 2 ml fractions were collected
until all the chloride was removed. Chloride concentrations were measured
with a Beckmann Expandomatic 55-2 pH meter using a Beckmann chloride ion
selective electrode.
The void volume of column 1 was small enough to allow breakthrough of
the chloride before any of the 0.5M NaNCL eluant was passed through the
column. For columns 2-5, a longer length provided a greater retention of
the chloride on the column, but with only a very minor increase in peak
broadness (10 ml peak width for column 2 vs. 12 ml peak width for column
4). Work proceeded with columns 2 and 3, which required less time and
eluant per analysis.
The procedure above was repeated for columns 2 and 3 using 5 ml of a
1 x 10 M NaBr solution in 0.5M NaNO and washing with 2 x 1.0 ml 0.5M
NaNO,.. Each column was eluted with 0.5M NaNO,. to the point where all the
chloride had been removed as determined in the previous experiment. Then
2.0M NaNO,, was passed through the column at the same 1 ml/min rate until
all the bromide had been removed. Two ml fractions were collected. The
bromide concentrations were measured in the same manner.
It was apparent that the use of the initial eluant, 0.5M NaNO.,, as
the medium for application of the sample resulted in premature elution of
bromide and extreme band broadening. Since adding NaNO,, to the sample
o
represents one additional step this approach was deleted from further
studies.
Next to be evaluated was deionized water as the sample medium on
column 3. The procedure was identical to that described above, except
-2
that the 5 ml aliquot first placed on the column was both 1 x 10 M NaCl
-2
and 1.0 x 10 M NaBr. The column sides were washed with 2 x 1.0 ml of
deionized water, not 0.5M NaNO-.
The bromide ion on this 10.2 cm long column began to elute just prior
to changing NaNO_ concentrations (see Figure 3.2). Baseline resolution
was not quite attained. For this reason it was decided to lengthen the
column to 15 cm.
Two impinger solutions, deionized water and 0.1M NaOH-0.005M NaAsCL ,
-2 -2
were evaluated where both contained 10 M NaCl and 10 M NaBr. Two newly
15
-------
IU
2
IU
m
to
2
LU
Q.
-------
prepared AG-1 X10 columns 15 cm in length were used. Halide concentrations
of each fraction were measured turbidimetrically. The Texas Air Control
Board Method was used with the reagent volumes reduced by 1/4 to accommodate
2 ml samples. Examples of the chromatograms obtained are shown in Figures
3.2 and 3.3 and water baseline is shown in Figure 3.4. The greatest
difference in the elution pattern using the two different impinger solutions
was the amount of chloride recovered from each column (see Table 3.3).
Table 3.3. RECOVERIES OF CHLORIDE AND BROMIDE FROM IMPINGER SOLUTIONS
Impinger Solution % Recovery Cl % Recovery Br
Deionized water ^50
0.005M NaAsO -0.1H NaOH M.80
A contributing factor to the amount of chloride recovered using the
arsenite solution may have been the use of a prepared O.LM NaOH solution
with an unspecified chloride content (contamination). Subsequently all
solutions were prepared using NaOH electrolytic pellets with a maximum
chloride contaminant of .003% which corresponds to 0.12 |Jg/ml in the
impinger solution.
A thorough assessment of the halide recoveries using ten 1-cm diameter
columns of Bio-Rad AG-1 X10 (100-200 mesh) equilibrated with 0.5M NaNO£
was made. Each column was 15 cm in length. Because of problems with poor
recovery encountered in previous work, all of these columns were pre-
-2 -2
equilibrated with 15 ml of solution of 10 M chloride and 10 M bromide in
H?0. The 5 ml of halide solution was drained to the top of the column,
washed with 1 ml of deionized water twice, eluted with 26 ml of 0.5M
NaNO», then 15 ml of 2.0M NaNO,,, as if an analysis were to be performed.
.3 «3
Each column was then re-equilibrated with 0.5M NaNO,. by passing 100 ml of
the eluant through the column.
Five ml of the following solutions were placed on each column as
indicated in Table 3.4.
17
-------
I2r
10,
o>
LU 8
Q
U.
O 6
O
1 4
LU
i crsenrte i
16
0.5m Soi
24 32 40
VOLUME OF ELUATE , ML.
48
64
:N°3
. 2.0m NaNO,
Figure 3-3- Anion exchange chromatography on AG-1 XI - Arsenite
impinger solution containing chloride and bromide.
Column: 1 cm i.d. x 15 cm
Concentration: ICT^M
18
-------
10-
o>
J 8
g
_l
u.
O 6j-
g
I
0-
16 E4 33 40 48
VOLUME OF ELUATE , ML.
• 0.3m NoNO,
•*!*•
2.0m NoNO,
64
Figure 3.4. Anion exchange chromatography on AG-1 X8 - Water Blank.
Column: 1 cm l.d. x 15 cm
19
-------
For each column, the procedure was to place the 5 ml of halide solution
on the column and allow it to drain at 1 ml/min to the top of the column.
The sides were then washed with 1 ml of deionized water twice. Twelve ml
of 0.5M NaNCL were put through the column and discarded. Another 12 ml of
Table 3.4. SOLUTIONS APPLIED TO ION EXCHANGE COLUMNS
Sample No.
1 & 8
2 & 9
3 & 10
4 & 11
5 & 12
6 & 13
7 & 14
Chloride (M)
io-2
—
io"4
-
_2
10 Z
io-4
-
Bromide (M)
_
-2
10
-
-4
10
— U
10
io-2
-
0.5M NaNO,. were put through the column, and this was saved for analysis, as
it contained the chloride fraction. Then, two more ml of this same eluant
was run through and this was again discarded. The eluant was changed to
2.0M NaNO,,, and 15 ml was passed through the column and saved. This
fraction contained the bromide. The column was then re-equilibrated with
0.5M NaN00 and was ready for further use.
(1)
Analysis was done as previously described using the turbidimetric
method.
After work was completed with the halides in deionized water, the
same array of solutions was prepared using halides made up in 0.1M NaOH
and 0.005M NaAsO^, the halogen impinger solution. The procedure described
above was followed exactly. The results are reported in Table 3.5.
The recoveries at low concentration were low and the lowest concentra-
tion tested did not approach the required level for environmental samples.
20
-------
Table 3.5. RECOVERIES OF CHLORIDE AND BROMIDE FROM ION-EXCHANGE CHROMATOGRAPHY ON
AG-1 X10 (100-200 MESH) 1 x 15 cm COLUMNS
Sample Chloride
No. Added (,Jg)a Found (ug)
I'1 1773 940
2a - -0.05
3a 17.7 4.3
4a - 0.03
5a 1773 1060
6a 17.7 4.7
7a _ 0.45
8b 1773 1139
9b - 1.1
10b 17.7 19.5
llb - 12.1
12b 1773 950
13b 17.7 16.2
14b - 0.54
Bromide
Recovery (%)
53
-
24
-
60
26
-
64
-
109
-
54
92
-
Added (MB)«
-
3950
-
39.5
39.5
3950
-
-
3950
-
39.5
39.5
3950
-
round (pg)
0.05
4050
-0.04
42.7
21.3
3750
0.10
0.10
3675
0.3
11.2
18.0
3675
0.16
Recovery (%)
-
102
-
108
54
95
_
_
93
-
29
45
93
-
Sample was applied In 5 ml of deionlzed water
bSample was applied In 5 ml of 0.1M NaOH/0.005M NaAsO. (impinger solution)
-------
In an effort to improve the recoveries indicated above, new ion
exchange chromatographic conditions were investigated. The rationale of
the new approach was to increase specific interactions with respect to
nonspecific interactions: the first system explored was DEAE Sephadex
(Pharmacia, Uppsala, Sweden). The backbone of this ion exchange resin is
subject to many fewer nonspecific interactions than the polystyrene-
divinylbenzene backbone of the Dowex resins. The benefit of this type of
backbone was not realized due to two problems: (1) the DEAE (diethyl-
aminoethyl) functional group is weakly basic and as such does not show
sufficient discrimination between chloride and bromide, and (2) the resin
undergoes extreme volume changes (factors of 2 to 3) with relatively small
changes in ionic strength. Another approach to increasing specific to
nonspecific adsorption was to continue the use of the polystyrene-divinyl-
benzene type (AG-1 X10, 100/200 mesh), but to decrease the amount and use
less severe conditions for developing the chromatogram. The column diameter
was reduced from 1.0 cm to 0.4 cm and the length from 15 cm to 7 cm. The
resin in prepared columns was converted to the nitrate form and equilibrated
with deionized water. The sample was applied in 4 ml of deionized water
and washed on with 0.5 ml water. The elution was begun with 0.1M NaNCL
and changed to 0.5M NaNO after the chloride had eluted (see Figure 3.5).
Using the profile in Figure 3.5 a standard elution scheme was adopted: 4
ml 0.1M NaNO for chloride and 2 ml 0.5M NaNO for bromide. An evaluation
of recoveries over a range of concentrations was instituted. The results
are shown in Table 3.6. All of these samples were applied in deionized
water. Certain difficulties are encountered in 0.1M NaOH/0.005M NaAsO_
impinger solution. The presence of such a high anion concentration even
through it is the weakly adsorbing hydroxide ion diminishes the binding of
the halides during sample application and causes premature elution of the
chloride and bromide peaks.
Bromide by Fluorescein Fluorescence Quench.--The method of Axelrod,
(3)
Bonelli and Lodge was evaluated for the analysis of impinger solutions
containing bromide. The method employs hydrogen peroxide for the oxidation
of bromide in an acidic medium (glacial acetic acid) to give elemental
bromine. The bromine substitutes on the phenolic rings of the fluorescent
22
-------
ICO
90
£
V.
a>
UJ
O
80-
7C
60
50
20-
20
10-
•0.1 MNoNOi
cr
-0.5MNONO-:
81"
345
ELUT10N VOLUME (ml)
Figure 3.5. Anion exchange chromatography of chloride and bromide
ions on AG-1 X10 (100/200 mesh) 4 x 70 mm column.
23
-------
Table 3.6. RECOVERIES OF CHLORIDE AND BROMIDE FROM ION-EXCHANGE CHROMATOGRAPHY ON
AG-1 X10 (100-200 MESH) 4 x 70 mm COLUMNS
M
•P-
Sample
No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Chloride
added (vig)u
500
400
400
0
0
40
40
40
4
4
4
0
0
0
found (jig) Recovery (%)
570 + 60 114 + 12
336b 84b
397 99.2
1.2
16.8
-
34 . 4b 861'
33.6 84
-
1.6b 40b
4.0 100
1.1 + 0.1
<0.8h
<0.8
Uromlde
added Uig)a found (|jg) Recovery (Z)
0 17.8+3
0 - -
0 30.1
400 401 +2 100 + 0.5
400
40 40.8 + 1.2 102 + 2
0
40 31.0 77.6
4 4.0 + 0.2 100 + 5
0 - -
4 6.2 155
0 1.5+0.2
0
0 - -
Sample was applied in 4.0 ml delonlzed water
Collected fractions stored 48 hrs before analysis
-------
dye, fluorescein, to yield a nonfluorescent eosin-type product. The
decrease in fluorescence is measured. This procedure works well on stan-
(3)
dards in deionized water. The above authors have evaluated potential
interferences and found 5% or less interference due to 100 fold excess of
2-2-3- - + + 2+ 2+ 3+ 2+ 2+
S03 , SO^ , PO^ , N03 , K , NH4 , Mg , Ca , Fe , Cu , Pb , HCOOH,
CH3COCH3, HCOOH and CH.CH^H. Chloride does not interfere at 105 molar
excess over bromide. Greater than 5% error was found when I , N0_ ,
2+
Fe were present in 100 fold excess on a molar basis. Brominated organics
may interfere.
Suitable conditions for the analysis of bromide in the 0.1M NaOH/
0.005M NaAsO^ impinger solution were not found. Neutralization with
nitric acid and addition of 30% hydrogen peroxide before the addition of
the fluorescein reagent gave no response to bromide. Some response (^-70%)
was observed when the bromide in impinger solution was added to the peroxide
and followed immediately by the fluorescein reagent. This response is not
quantitative and results would not be reliable. A cation exchange resin
AG-50W-X8 was used in an attempt to neutralize the sample, but bromide
recoveries from this resin were low at the 1 ppm level tested.
The final analytical protocol which was adopted for this study is
given in Appendix A.
3.1.2 Determination of Inorganic Fluoride in Ambient Air
The sampling and analytical method for inorganic fluoride was specified
in the research request as that adopted by the Texas State Department of
Health, Air Pollution Control Board. *'
The fluoride ion selective electrode (Orion Model 96-09 combination
fluoride electrode) was evaluated over the range 1.27 to 19 ppm and found
to give a linear response. Initially the samples were evaluated directly
without distillation. If significant fluoride concentrations were found,
then verification would have been made using the steam distillation proce-
dure.
The final analytical protocol for collection and analysis of fluoride
in ambient air which was adopted for this study is given in Appendix A.
25
-------
3.1.3 Acid Mist Analysis in Ambient Air
(4)
The "acid mist" procedure was verified by confirming the sensitivity
of the titration to
-------
Table 3.7. ESTIMATED BREAKTHROUGH VOLUMES FOR SEVERAL HALOGENATED COMPOUNDS
ON TENAX GC
ho
Ambient Temperatures
Compound
*
Allyl bromide
Bromobenzene
ft
Bromodichlorome thane
Bromoform
ft
1-Bromopropane
l-Chloro-2-bromoethane
ft
l-Chloro-3-bromopropane
ft
l-Chloro-2 , 3-dibromopropane
ft
l,l-Dibromo-2-chloropropane
ft
Dibromochlorome thane
1 , 2-Dibromoethane
1 , 2-Dibromopropane
Methyl chloride
Methyl bromide
Vinyl chloride
Vinyl bromide
BP (°C)
70
155
89-90
149
70
107
141
-
-
135
131
141
-24
3.59
13
16
50°F
37
2,144
138
507
128
920
1,122
1,460
1,593
263
348
1,142
0.8
3
2
8
(continued)
60°F
27
1,521
102
386
94
676
856
1,114
1,216
200
255
871
0.6
2
1.5
6
70°F
20
1,079
75
294
70
500
656
850
928
153
188
665
0.5
2
1.25
4
80°F
(27°C)
15
764
54
224
51
367
500
649
-
117
138
508
0.4
1
1.0
3
90°F
(32°C)
11
542
40
171
38
270
382
496
510
89
101
387
0.3
1
0.8
2
100°F
(38°C)
8
384
29
130
28
198
291
378
413
68
74
296
0.25
0.9
0.6
1.8
-------
Table 3.7 (cont'd)
ro
oo
Compound
Epichlorohydrin
(l-chloro-2, 3-epoxypropane)
Epibromohydrin
(l-bromo-2 , 3-epoxypropane)
Trimethylene chlorobromide
Bromine
Chlorine
Iodine
Water
BP (°C)
116
134-6
142-5
58.7
-
184.3
100
50°F
200
678
1,130
0.032
0.030
0.032
0.060
60°F
144
479
927
0.028
0.025
0.028
0.050
Ambient
70°F
104
337
656
0.024
0.020
0.024
0.040
Temperatures
80°F
(27°C)
74
237
465
0.020
0.015
0.020
0.030
90°F
(32°C)
54
168
329
0.016
0.012
0.016
0.010
100°F
(38°C)
39
118
233
0.012
0.010
0.012
0.002
Values estimated on mathematical extrapolation from slop of linear regression in a homologous
series and boiling point of compound.
-------
Also, the breakthrough volumes for bromine, chlorine, iodine and
water are given. These inorganic gases have extremely low breakthrough
volumes. This is an important feature, for if they accumulate on the
sorbent, then potential in situ reactions could occur between the inorganic
gases, olefinic and aromatic compounds.
Determination of Relative Molar Response Factors for Quantification.--
The relative molar response (RMR) values were determined for several
halogenated compounds using unique ions for each compound. The methods
employed for determining the RMR values have previously been described.
These results are given in Table 3.8. In many cases, the RMR value for a
second ion was determined in the event it would be necessary to establish
the identity of the halogenated hydrocarbon by the theoretical ion cluster
intensity ratio. The RMR for the second ion was calculated using authentic
compounds. Thus each compound can be quantitated in the event that the
first ion is not sufficiently specific for that substance.
These data (Table 3.8) also indicate that as the degree of halogenation
increases, so does the RMR value, and thus a decrease in sensitivity for
the compound is experienced by the mass spectrometer.
The limits of detection (LOD) for several halogenated hydrocarbons
utilizing the technique of glass capillary gc/ms/comp are given in Table
3.9. The LOD's are estimated values using an average sampling volume of
150 £ at an ambient temperature of 27°C. The limit of detection is based
upon either the breakthrough volume or volume of air sampled, whichever is
less, and the measured RMR value. As shown in Table 3.9, the limits of
detection for the halogenated hydrocarbons of interest range, from 0.2-2.0
3
ng/m (sub-ppt). Table 3.9 thus provided a guideline as to the anticipated
sensitivity of the overall analytical technique and was the basis for
establishing the non-detectable levels. For the purpose of quantification,
generally 10-20 times the amounts listed in this table were required.
The analytical protocol for collection and analysis of volatile
brominated organics which was adopted for this research program is given
in Appendix A.
29
-------
Table 3.8. RELATIVE MOLAR RESPONSE VALUES FOR SEVERAL HALOGENATED COMPOUNDS BASED UPON
SELECTED IONS
1st Ion
2nd Ion
OJ
o
Compound
Allyl bromide
Bromobenzene
Bromodichloromethane
Bromoform
1- or 2-Bromopropane
l-Chloro-2-bromoe thane
l-Chloro-3-bromopropane
l-Chloro-2 , 3-dibromopropane
1 , l-Dibromo-2-chloropropane
Dibromochlorome thane
1 , 2-Dibromoethane
1,2- or 1, 3-Dibromopropane
Methyl chloride
Methyl bromide
Vinyl bromide
M.W.
120
156
162
250
122
142
156
234
234
206
186
200
50
94
106
R.
1.
2.
1.
2.
1.
1.
2.
3.
3.
-
2.
2.
0.
0.
0.
R.T
167
771
389
361
085
657
278
472
416
000
250
628
888
667
m/e (I)
120
156
129
173
124
144
158
157
157
129
109
123
50
94
108
(25)
(8)
(12)
(100)
(20)
(15)
(60)
(100)
(100)
(100)
(95)
(99)
( )
( )
(75)
RMR
3
2
1
2
3
1
4
9
9
6
3
3
1
1
2
.25
.18
.54
.75
.25
.12
.48
.46
.46
.53
.34
.37
.7
.9
.2
m/e (I)
122
158
85
252
122
63
160
159
159
208
188
202
52
81
110
(25)
( )
(60)
(10)
(20)
(100)
(120)
(25)
(25)
(10)
(2)
(65)
( )
( )
(10)
RMR
3.
-
6.
0.
3.
7.
1.
2.
2.
0.
0.
2.
0.
-
0.
25
16
30
25
39
12
37
37
70
50
21
66
30
-------
Table 3.9. ESTIMATED LIMITS OF DETECTION FOR SEVERAL HALOGENATED
HYDROCARBONS
Compound
Allyl bromide
Bromobenzene
Bromodichlorome thane
Bromof onn
1-Bromopropane
l-Chloro-2-bromoethane
l-Chloro-3-bromopropane
l-Chloro-2 , 3-dibroinopropane
1 , l-Dibromo-2-chloropropane
Dibromochloromethane
1 , 2-Dibromoethane
1 , 2-Dibromopropane
Fragment ion
(1st)
120
156
129
173
124
144
158
157
157
129
109
123
LOD3
ng/m3
1.6
0.6
2.0
0.8
0.9
0.2
0.5
0.4
0.4
0.5
0.7
0.5
Assuming an average sampling volume of 150 i and 27°C which was
experienced during the Phase I survey study.
31
-------
Analysis of Ethylene in the Presence of Other Gases.—During the
preliminary phases of this study an analytical protocol was developed for
the gas chromatographic analysis of ethylene in ambient air. To effect
separation of ethylene from other atmospheric hydrocarbons (e.g., ethane),
the air samples were chromatographed at -78°C on an OV-101 glass SCOT
capillary. Maintenance of a -78°C oven temperature was accomplished by
placing small blocks of dry ice in and above the oven. This successfully
lowered the oven temperature, but also resulted in the accumulation of
considerable water vapor condensate in the oven and surrounding electronic
components. Consequently, repeated instrument failure resulted.
Efforts to minimize condensation in the instrument centered on intro-
duction of a dry, cold gas stream and maintenance of adequate ventilation
in the oven. Initially this was accomplished by blowing a stream of
nitrogen gas through a liquid nitrogen-cooled cold trap and ultimately
into the gas chromatograph. This design proved troublesome as the gas
line tended to freeze in the cold trap, causing the flow to be erratic.
This system was modified by introducing nitrogen gas into an aspirator
fixed to a metal liquid nitrogen dewar, thereby spraying a gentle, fine
mist of liquid nitrogen into the oven. This technique was employed for
maintaining a cryogenic oven temperature during the ethylene analyses.
Difficulty was encountered in eliminating leaks from the column connections
since sealed connections at 20°C tended to leak at temperatures below -60°C.
Consequently, the oven was operated at -60°C with the temperature controlled
by the nitrogen flow and monitored with a calibrated iron-constantan
thermocouple connected with reversed polarity.
The ambient air samples, contained in stainless steel, septum-capped
bottles, were introduced into a 1.7 mm i.d. x 842 mm length stainless
steel gas sampling loop with a gas syringe. A minimum of 10 ml of sample
was passed through the loop to insure that no contamination from previous
samples would occur. The sample was injected onto a 60 m glass SCOT 1%
OV-101 capillary column by changing the position of a six-way valve to
direct the carrier gas (V3 ml/min) through the sampling loop. The valve
and oven injection port temperatures were 170 and 0°C, respectively.
Injection was sustained until the ethylene had eluted from the capillary
32
-------
column (approximately 2 rain). Detection was achieved with a flame ioniza-
tion detector operated at 150°C. Standard ethylene-nitrogen mixtures,
contained in Tedlar bags, were injected every third sample for quantitation.
The final analytical protocol for collection and analysis of ethylene
which was adopted for this study is given in Appendix A.
3.2.1.2 Semi-volatile Organics Associated with Particulates
Collection of Tris-(2,3-dibromopropyl)phosphate (TRIS) on Glass
Fiber and Cellulose Filters -- The sampling method used for the
collection of TRIS is given in Appendix A. The procedure was developed
under a separate Task Order of this contract. Two types of filter
material, glass fiber and cellulose, were field-tested during preliminary
sampling in Arkansas and the glass fiber was found to be definitely superior.
Two Hi-Vol samplers in parallel were used - one fitted with cellulose
filters and the other with glass fiber filters. This parallel sampling
demonstrated several reasons for the choice of glass fiber.
Gas-Liquid Chromatography-Electron Capture (GLC/ECD) and Gas-Liquid
Chromatography-Mass Spectrometry-Computer (GLC/MS/COMP) Analysis
for TRIS -- The analytical methods used are given in Appendix A. The
method was developed under a separate Task Order of this contract.
The approach is based upon the use of a short glass column (0.2 cm i.d. x
42 cm) packed with a nonpolar phase. The same type columns were used for
both GLC/ECD and GLC/MS/COMP analyses. Three liquid phases have been
used, SE-30, OV-101 and OV-17 with benzyltriphenylphosphonium chloride as
a surfactant. Detection limits upon GLC/MS/COMP were very poor; hence,
multiple ion detection was used almost exclusively. In this method the
mass filter is stepped through discrete ion masses repetitively instead of
scanning the entire mass range. The selected ions are detected for propor-
tionately more of the total time thereby improving signal-to-noise for
those ions. Confirmation of identity when required was accomplished
either by monitoring several selected ions and comparing ion intensities
with standards of TRIS or by direct probe MS.
Other Semi-volatile Organics Associated with Particulates -- The
sampling and solvent extraction procedures developed for TRIS were used to
screen for the presence of other brominated compounds. Several compounds
33
-------
were identified in the particulate samples by the use of direct probe mass
spectrometry. Quantitation, however, requires the combination of GLC/MS/
COMP analysis. In order to improve the sensitivity of the Finnigan 3300
for these high molecular weight compounds, multiple ion detection was
used. Table 3.10 lists these compounds, the ions used and the instrumental
limit of detection. Other factors such as collection efficiency and
recovery also affect these values. First of all, the flow rate through
the cellulose filter was 60% of that through the glass fiber filters and,
secondly, visual inspection of the filters revealed considerable break-
through of the particulate through the cellulose. The unexposed side of
the cellulose filter was colored and a glass fiber filter which was used
to support the cellulose was darkened. Mechanical strength was also a
problem. The breakthrough problem was further evidenced by consistently
lower values for TRIS and other brominated compounds in the cellulose
filters (see 4.2.3.2). On this basis glass fiber filters were used in all
subsequent sampling.
Other Analytical Methods -- Thin layer chromatography (TLC) may be
used for many of the compounds which are of interest here for either a
qualitative or quantitative analysis. These techniques have been used
here primarily as screening methods to supplement other analytical methods.
For some brominated compounds such as TRIS, the detection system reported
( 81
by Weichsel is useful. This method is based upon the reaction of
fluorescein with elemental bromine released through peroxide oxidation.
An evaluation in our laboratory of this TLC detection system has indicated
that semi-quantitative results may be obtained using the technique of
fluorescence quench thin-layer scanning. The basis for this detection
method is the conversion of fluorescein impregnated in the thin-layer to
the brominated analog, eosin. The resulting loss of fluorescence is then
fo\
detected by scanning the thin-layer in the reflectance mode. An example
of a chromatogram obtained in this manner is shown in Figure 3.6. This
detection system is highly specific for brominated compounds. However,
the limit of detection is of the order of 0.5 (Jg/spot. Some improvement
in sensitivity may be obtained by optimizing the chromatographic conditions.
Basic elements of the reaction are acidic medium (glacial acetic acid) , an
34
-------
Table 3.10. LIMITS OF DETECTION OF BROMINATED ORGANICS IN AIR
Compound
TRIS°
Tetrabrom
Pentabromophenol
Firemaster 680
Or
Decabrom
Ions
(m/e)
417*, 419*, 337
* *
529 , 531
488*, 490*
357*, 688, 690
800*, 802, 804
Limit of Detection '
(ng/m3)
614
10
25
10, 90f
20-100h
Octachloronaphthalene was used as an external standard (m/e 404).
These limits of detection are computed based upon the extract analyzed
representing 2 ml/m^ air sampled according to the procedure in Appen-
dix A.
Q
Tris-(2,3-dibromopropyl)phosphate.
2,2-Bis(dibromo-4-hydroxyphenyl)propane.
P
1,2-Bis(2,4,6-tribromophenoxy)ethane.
This value is based on mass 688 which was required due to interferences
with mass 357.
Or
Confirmed from full scan mass spectrum.
Substantial day-to-day variation of sensitivity to Decabrom.
35
-------
70
60
50
40
30
20
10
Excitation; 380 nm
Emission; 520nm
Slits 2x3 mm
Silica Gel treated with
Fluorescein developed in
methylene chloride.
TLC SCAN IN FLOURESCENCE QUENCH MODE
a S.T^g TRIS
bO.44^ TRIS
Figure 3.6. Thin layer chromatogram of tr±s_(2, 3-dibromopropyl)-phos-
phate on fluorescein impregnated silica gel', solvent:
methylene chloride. Scan in fluorescence quench mode.
a. 3.7 yg TRIS, b. 0.44 ug TRIS.
36
-------
oxidant [either H»0_ or chloramine-T (N-chloro-p_-toluene-sulfonamide)-
sodium] and fluorescein. Thin-layer parameters for several semi-volatile
brominated organics used throughout the program are given in Table 3.11.
Table 3.11. THIN-LAYER PARAMETERS FOR SEMI-VOLATILE BROMINATED ORGANICS
ON SILICA GEL
Compound
Decabrom
2,4, 6-Tribromophenol
Pentabromophenol
Tetrabrom
4-Bromopheno 1
Firemaster 680
Solvent
Hexane/Toluene
(95:05)
Toluene
Toluene
Toluene
Toluene
Hexane/Toluene
(60/40)
Rf
0.7
0.65
0.5
0.4
0.2
0.6
3.2.2 Water and Sediment
3.2.2.1 Volatile Brominated Organics
An adaptation and validation of the Volatile Organic Analysis (VOA)
method was employed for the more volatile brominated compounds.
Recovery studies were performed to determine the efficiency of the
purge procedure in removing various volatile organic species at approxima-
tely the 1 |Jg level from water and sediment. The final analytical protocols
adopted are presented in Appendix A. Samples were spiked by the addition
of 5 |Jl °f a standard mixture containing ^200 ng each of six halogenated
compounds in methanol. The loaded cartridges were analyzed by GC/FID on a
silanized OV-101 SCOT column (0.36 mm i.d. x 100 m length) using helium
carrier at 2 ml/min. The sample was injected by thermal desorption with
purging of the compounds loaded on the Tenax GC cartridge into a liquid
nitrogen-cooled nickel-capillary trap. The condensed vapors are then
introduced onto the high resolution gas chromatographic column by raising
the temperature of the nickel capillary trap. The analytical conditions
are summarized in Table 3.12. The results are given in Table 3.13.
37
-------
Table 3.12. CONDITIONS FOR ANALYSIS OF TENAX CARTRIDGES
FROM VOA PURGE — RECOVERY STUDIES
GC Conditions -
Column: OV-101 (2.5%) SCOT column
(0.36 mm i.d.)
Column Temperature: Programmed from 30° to
220°C at 4°/min
Detector: FID
Carrier gas: Helium
Flow rate: 2 ml/min
Thermal Desorption Conditions -
Desorption temperature: 270°C
Purge gas: helium
Flow rate: 30 ml/min
Purge time: 5 min
Ni capillary temperatures: -77°C during purge
150°C during injection
38
-------
Table 3.13. RECOVERY STUDIES - VGA METHOD
Amount Spiked
Compound (yg)
1-chloro-l-butene
1 , 2-dichloroethane
l-bromo-2-chloroethane
1 , 2-dibromoethane
bromobenzene
m-chloro toluene
1-chloro-l-butene
1 , 2-dichloroethane
l-bromo-2-chloroethane
1 , 2-dibromoethane
bromobenzene
ni-f.hlorotol.ueno
l-chloro-l-butf:iie
1 , 2-dichloroethane
l-bromo-2-chloroethane
1 , 2-dibromoethane
bromobenzene
m-chloro toluene
0.926
0.853
1.137
2.253
1.663
1.400
0.880
0.810
1.080
2.140
1.580
1 .330
0.880
0.810
1.080
2.140
1.580
1.330
Medium
dist. H20
dist. ino
dist. ICO
dist. H20
dist. H20
dist. H20
stream H^O
stream H?0
stream H«0
stream H^O
stream H~0
sir earn lL-,0
soil
soil
soil
soil
soil
soil
Amount Recovered
(Mg)
(1) (2) (3)
0.710
0.739
0.922
1.839
1.435
1.355
0.651
0.593
1.041
1.969
1.657
1.337
0.266
0.436
0.679
1.471
0.968
0.881
0.743
0.654
0.913
1.655
1.927
1.358
0.628
0.556
1.022
1 . 850
1.326
0.999
0.238
0.481
0.625
1.600
1.254
0.830
Data
Not
Available-
Intrumental
Error
0.554
0.255
1.099
2.643
1.810
1.074
0.392
0.611
0.978
1.922
1.417
1.134
Average
Recovery
78.5
81.6
80.7
77.5
10.1 . 8
96.9
69.4
57.8
96.6
100.7
101.1
8.5.5
33.9
62.9
70.4
77.8
76.8
71.3
Standard
Deviation
0.0233
0.0601
0.00636
0.130
0.347
0.00212
0.0507
0.185
0.0401
0.428
0.247
0.178
0.0820
0.0909
0.190
0.232
0.227
0.163
-------
3.2.2.2 Semi-Volatile Brominated Organics
Sample Preparation.—Two approaches to the recoveries of semi-vola-
tile organics from water were evaluated: one, the extraction of trace
organics with a macroreticular resin (XAD-2) and elution with an organic
solvent (diethyl ether), and the other direct solvent partitioning. Using
(9)
the procedure described by Junk et al. , recoveries of EDB and TRIS
were determined using GC/ECD by comparison of peak areas with standard
solutions chromatographed at the same time. The extraction method was as
follows: methanol-extracted XAD-2 was placed in a column 6 mm i.d. to a
height of 10 cm. The column was rinsed free of methanol with distilled
water (3 x 20 ml). An aliquot (200 ml) of sample, spiked water or blank
was filtered through the resin bed. The adsorbed organics were eluted
with diethyl ether (25 ml) added in two portions, 15 ml and 10 ml, allowing
each to equilibrate for 10 min. The ether extract was then dried over
sodium sulfate and analyzed by GC/ECD. The recoveries are shown in Table
3.14. Extraction of the filtered water with diethyl ether recovered ~ 40%
of the added EDB indicating poor extraction efficiency by the resin.
Table 3.14. RECOVERIES OF BROMINATED COMPOUNDS FROM WATER
USING XAD-2 RESIN
Compound
EDB
TRIS
Concentration yg/£
1.45
13.4
134
2.09
19.3
193
% Recoveries
12
12
8
115
44
57
Three solvents have been screened for their extraction efficiency for
EDB and TRIS. The results are given in Table 3.15. Of those tested the
best solvent for EDB is hexane. Toluene is best for TRIS. A sequential
extraction procedure was evaluated in which 20 ml of sample water (or
spiked water) was partitioned first with 20 ml of hexane and then with 20
40
-------
Table 3.15. EXTRACTION EFFICIENCY OF SEVERAL ORGANIC SOLVENTS FOR EDB AND TRIS'
Diethyl ether
Hexane
Toluene
Volume
(ml)
40b
20
20
20
20
20
No. of
Extractions
1
2
1
2
1
2
EDB
Amount added
(ug)
2.00
2.00
2.00
TRIS
% Recovery
86
<2.5
80
<5
87
<5
Amount added
(ug)
20.0
20.0
20.0
% Recovery
46
<7.5
49
<15
111
<15
200 ml of distilled water was spiked with the indicated amounts of EDB and TRIS.
Diethyl ether was partially soluble and 40 ml was required to recover 20 ml of extract.
-------
ml of toluene. The recoveries for each stage of this sequence are shown
in Table 3.16 for TRIS and EDB. There is a problem, however, with merely
combining the fractions when analyzing a volatile compound such as EDB.
Toluene severely "tails" during GC analysis which affects the response of
the EC detector to EDB. For this reason a parallel extraction scheme was
selected for the analytical protocol (Appendix A). To verify the need to
use a volatile solvent such as hexane for the analysis of volatile consti-
tuents, EDB losses upon evaporation of three solvents were compared (Table
3.17). In actual practice, only a five-fold concentration of the sample
is required to detect EDB at the ppb level by GC/ECD when hexane was used.
Sediment samples were treated in the same manner as soils described
in Section 3.2.3.2 except that the sample size was 10 g.
GLC/ECD and GLC/MS/COMP Analysis -- GLC/ECD methods for the semi-
volatile brominated organics were developed for the purpose of method
validation and sample screening. Two types of packed columns were used.
A short 42 cm non-polar column (Section 3.2.1.2) for TRIS and a semi-polar
column [170 cm x 0.2 cm i.d., Carbowax 20M on Chromosorb G AW/DMCS, (100/120
mesh)] for more volatile compounds such as EDB. A 42 cm x 0.2 cm i.d.
column coated with 2% OV-101 on Supelcoport was used for all the GLC/MS/COMP
analyses. The analytical procedure for the mass spectral analysis was the
same as that described in Section 3.2.1.2. The limits of detection varied
as indicated in Table 3.18.
3.2.3 Soil
3.2.3.1 Volatile Brominated Organics
The same general procedure was used for soil (and sediment) as for
water except the sample size is 20 g in 450 ml of distilled water added to
suspend the solids. The additional requirement for mechanical stirring to
maintain the suspension was met by using a 500 ml round bottom flask and a
magnetic stirrer (see Appendix A). Recovery studies were performed for
soil in the same manner as for water. The results are shown in Table
3.13.
3.2.3.2 Semi-volatile Brominated Organics
Sample Preparation -- The recovery of a wide variety of compounds
from a matrix such as soil poses a difficult problem. If the solvent is
42
-------
Table 3.16. RECOVERIES FROM SEQUENTIAL SOLVENT EXTRACTION
OF WATERa
% Recovery
Distilled Water Stream Water
Hexane
TRISd 72
EDBe 91
Toluene0 Total Hexane Toluene0 Total
15 87 91 24 115
<10 91 82 <10 82
o
200 ml of sample extracted with 20 ml of each solvent.
First extraction of the series.
Q
Second extraction.
TRIS was added to give 100 ppb in water.
Q
EDB was added to give 10 ppb in water.
Table 3.17. LOSSES OF ETHYLENE DIBROMIDE DURING SOLVENT EXTRACTION3
Solvent
diethyl ether
hexane
toluene
Concentration Factor
122
93
15
% Loss
14
50
33
100 ml of the test solvent containing 11.6 yg of EDB.
Concentrated in Kuderna-Danish (K-D) apparatus and micro K-D on steam
bath. Snyder columns were used throughout.
Q
Concentrated in flat bottom flask using Snyder column and a hot plate
for heat.
43
-------
Table 3.18. LIMITS OF DETECTION OF BROMINATED ORGANICS IN WATER
Method
GLC/ECD
Compound (yg/£)
EDB 1
TRIS 0.2
Tetrabrom
Pentabromophenol
Firemaster 680
Decabrom
GLC/MS
(ug/£)
a
500-1000
50
100
50°, 800d
10
Other
(yg/A)
-
20b
-
-
-
2.5
*a
Not determined.
Thin-layer chromatography.
/-i
Based upon m/e 257, a non-specific ion.
Based upon m/e 688, the parent ion.
44
-------
not selective for the compound of interest the background may be seriously
elevated and extensive clean-up procedures required. With this in mind,
two soil extraction procedures were evaluated. One employed a water/aceto-
nitrile/ ethyl ether partition and the other water/acetone/toluene. A soil
sample (50 g) was wetted with 50 ml of water and extracted with 50 ml of
acetonitrile/ ethyl ether (1:1) followed by two 50 ml ethyl ether extractions,
Recoveries from the first solvent combination were very low (<10%) for
decabromobiphenyl ether (Decabrom) and EDB, two of the three compounds
selected as "marker" compounds for this evaluation. The latter solvent
combination proved more satisfactory. In this procedure, 50 g of soil was
extracted with 50 ml of diethyl ether; 10% of this extract was reserved for
volatiles (EDB) analysis with the remainder combined with subsequent frac-
tions. Ether extraction was followed by the addition of water (5 ml),
acetone (40 ml) and toluene (80 ml) and mixing. The organic layer was
removed and filtered. The acetone and toluene extraction was repeated two
more times and the volume reduced before GC/ECD analysis. Table 3.19 gives
the recoveries for selected compounds.
Table 3.19. RECOVERIES OF SEMI-VOLATILE HALOGENATED ORGANICS
FROM SOIL BY SOLVENT EXTRACTION3
Compound
1, 2-Dibromoethane
Tris-(2,3-dibromo-
propyl) phosphate
Decabromobiphenyl
ether
Concentration yg/£
1000
100
1000
100
1000
100
% Recoveries
52
7.9b
81
77
85
84
of extraction described in the text.
An evaporation step was employed which may be responsible for the loss of
EDB. This step has since been found to be unnecessary for GC/ECD analysis.
GLC/ECD and GLC/MS/COMP Analysis of Soil Extracts -- The GLC/ECD
methods described in Section 3.2.2.2 were applicable to screening of soil
samples for TRIS. Where very high levels were present, TLC methods for
45
-------
Decabrom were used. In general, however, GLC/MS/COMP was used in the MID
mode for the analysis of soil sample extracts. The same conditions were
used as those described in Section 3.2.1.2. Limits of detection were
higher than for water by a factor of 2 to 3.
3.2.4 Other Media
3.2.4.1 Hair
Samples were extracted in a Soxhlet apparatus with toluene for 16 hrs
and the volume reduced to 5-10 ml using a Snyder column. Aliquots (0.5 ml)
were evaporated to dryness and weighed to determine total solids (oil).
Octachloronaphthalene was added to each sample as an internal standard.
These aliquots were redissolved and purified using high performance liquid
o
chromatography on a pStyragel (500A) column with toluene as a solvent.
Prior to sample analysis the elution volumes of several marker compounds
were established (Decabrom and Firemaster 680) and these elution volumes
were used to select the fraction collected. Two chromatographs of 50 to
100 |jl of extract (^4-8 mg of hair oil) were performed on each sample. The
fractions from each sample were combined and the volume reduced for submis-
sion to GC/MS/COMP analysis. The same GLC/MS analysis conditions were used
as for the soil and sediment samples.
3.2.4.2 Milk
Several attempts at direct solvent extraction were unsuccessful due to
emulsion formation. However, the following procedure was successful. A
well-mixed weighed sample (10 g) was mixed with clean glass wool and the
proteins precipitated by the addition of 100 ml of acetone. Separation of
the precipitate was sometimes facilitated by centrifugation. The acetone
was decanted and filtered as were two additional 25 ml acetone fractions.
The volume of the acetone was reduced to "^20 ml using a Snyder column. The
precipitate was washed two times with 10 ml of toluene. The toluene
fractions were combined with the acetone. Two phases formed due to the
water in the acetone and the aqueous phase was removed. The organic phase
was dried over sodium sulfate and the volume reduced to 5-10 ml. This
procedure was followed using blank raw cows' milk and milk which was
spiked in the amounts given in Table 3.20.
46
-------
Table 3.20. AMOUNTS OF BROMINATED ORGANICS ADDED TO MILK
Sample
Compound
2 , 4, 6H-Tribromophenol
Tetrabrom
TRIS
Decabrom
MB
0
0
0
0
Ml (yg/g)
1.2
1.0
2.4
1.0
M10 (yg/g)
12
10
24
10
Figure 3.7 shows the elution volumes of several brominated compounds
relative to sample MB (Figure 3.7-F). Figure 3.8 shows the chromatogram
for M10 with both uv (300 nm) and refractive index (RI) detection. The
chromatogram of the Ml extract showed some of the appropriate peaks on the
UV detector but the RI detector is too insensitive to detect TRIS at this
level (1.1 |Jg). The other brominated compounds such as Decabrom and
tribromophenol, were clearly present in the expected amounts.
3.2.4.3 Placenta
The placenta samples were extracted by the same procedure as used for
the milk samples with the addition of homogenization with a Virtis Blender
after the addition of acetone. HPLC clean-up was attempted on the placenta
extracts; however, the lipids in this case appeared to be relatively low
molecular weight compared to milk (see Figure 3.9).
3.3 References
1. "Determination of Chlorine and/or Chlorides - Turbidimetric Method",
Adopted January 31, 1975, Texas Air Control Board.
2. Degeiso, R. C., W. Rieman and S. Linderbaum, Anal. Chem., 26, 1840
(1954).
3. Axelrod, H. D., J. E. Bonelli and J. P. Lodge, Jr., Environ. Sci.
Tech., 5, 420 (1971).
4. Stern, A. C., Air Pollution, Vol. II, 2nd Edition, 1968, p. 77.
5. Pellizzari, E. D., "Analysis of Organic Air Pollutants by Gas Chro-
matography and Mass Spectrometry. Publication No. EPA-600/2-77-100.
Contract No. 68-02-2262, June 1977, 104 pp.
47
-------
A
6 8 10
TIME (min)
12
14
16
Column: pStragel (28 cm); Solvent: Toluene
Flow rate: 1 ml/min; UV: 300 mm
Figure 3.7.
Retention volumes of some brominated compounds on HPLC.
A - TRIS (466 pg), RI detector, x8; B - l-chloro-2,3-
dibromopropane (118 ug), RI detector, x8; C - tetrabrom
(40 yg), uv detector, 0.4 AUFS; D - decabrom (40 Ug),
uv detector, 0.4 AUFS; E - hexabromodiphenyl (2 yg),
uv detector, 0.1 AUFS; F - blank milk extract.
-------
8 10 12
TIME (min)
14
16
13
20
Column: yStyragel (28 cm); Solvent: toluene;
Flow rate: 1 ml/min; UV: 300 nm - 0.1 AUFS;
RI: 8X
Figure 3.8.
High performance liquid chromatography of spiked milk extracts:
A - extract M10 (200 \il injected or 4% of extract); RI detec-
tor; B - Extract Ml (100 yl injected or 4% of extract), UV
detector; C - Extract M10 (200 yl injected or 4% of extract),
UV detector.
49
-------
J I I L
O 24 6 8 10 12 14 16
TIME ( M 1 N )
Figure 3.9- Placenta extract - hplc chromatogram of yStyragel
column.
50
-------
6. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal.
Lett., 9, 45 (1976).
7. Pellizzari, E. D. , "Sampling and Analysis for Selected Toxic Sub-
stances", EPA Contract No. 68-01-1978, Task Order No. III.
8. Weichsel, H., Mikrochim. Ichnoanal. Acta, 1965, 325.
9. Junk, G., J. J. Richard, M. D. Grieser, D. Witiak, J. L. Witial, M. D.
Arguella, R. Vick, H. J. Svec, J. S. Fritz and G. V. Calder, J.
Chromatog., 99, 745 (1974).
51
-------
4.0 SURVEY OF ENVIRONMENTAL MEDIA FOR CHEMICALS ASSOCIATED WITH BROMINE
INDUSTRY
4.1 TECHNICAL STRATEGY
The strategy which was adopted for the Survey Phase attempted simulta-
neously to evaluate the analytical techniques employed for characterizing
the ambient air and to acquire a maximum amount of information about the
chemicals surrounding the bromine industry.
The analytical methods utilized in this study are given in Table 4.1.
Scanning electron microscope (SEM) equipped with energy dispersing X-ray
(EDX) capabilities (Section A, Appendix A) was used for element mapping of
particles collected on glass and cellulose fiber filters. Primary applica-
tion of SEM and EDX was for detecting the presence and relative amounts of
Cl, Br, S, and counterions (Na, K, Ca, etc.).
Table 4.1. ANALYTICAL TECHNIQUES EMPLOYED FOR STUDYING POLLUTANTS IN
AMBIENT AIR SURROUNDING BROMINE INDUSTRY IN ARKANSAS
Technique
Information Type
Scanning Electron Microscope
and Energy Dispersive X-ray
Analysis
Neutron Activation Analysis
Spectrophotometric Techniques
Gas Chromatography Flame
lonization Detection
Gas Chromatography Electron
Capture Detection
High Resolution Gas Chromatography/
Mass Spectrometry/Computer
Cl, Br, counterions,
particle topography
Total Cl, Br
Cl~ + Br~, Cl~, Br~
Ethylene
Methyl chloride, Methyl
bromide
Structural characterization
and quantification of
volatile organics
52
-------
Neutron activation analysis (Section B, Appendix A) was employed for
determining the total Cl and Br content in various collected sample matrices.
Depending on the information type desired semi-quantitative and quantitative
data were obtained where possible.
Turbidity measurements (Section G, H, Appendix A) were made for total
halide (and halogen) and when feasible individual species were quantitated
after applying ion-exchange methods. In some cases neutron activation,
SEM, and EDX were used in concert with spectrophotometric methods (Sections
I, J, and Appendix A).
A variety of gas chromatographic methods was employed with specific
detectors for organic analysis. Flame ionization was employed for ethylene
analysis (Section C, Appendix A). Methyl chloride and methyl bromide were
detected by electron capture (Section D, Appendix A).
For obtaining a broad overview of the types of organics and the levels
present in ambient air, high resolution gas chromatography/mass spectrometry/
computer techniques were used (Section E, F, Appendix A).
4.1.1 Sampling
In order to cross-check the analytical techniques, sampling efforts
were designed to acquire sufficient quantities of samples (replicates) for
multi-analyses. Figure 4.1 depicts a schematic of the cartridge sampling
train used for fractionating non-volatile, semi-volatile and volatile
components from ambient air. A glass fiber filter preceded the Tenax GC
cartridge. The filter was used for removing non-volatile or particulate
material from the air. The volatiles were trapped on Tenax GC. In tandem
with the Tenax GC cartridge we used an SKC carbon as a back-up material for
stopping the very volatile organics (e.g., vinyl chloride, vinyl bromide,
methyl chloride and methyl bromide).
Molecular chlorine, bromine and the halides, chloride and bromide,
were collected in midget impingers (Figure 4.2) in a tandem arrangement
(Sections G, H, Appendix A). Sufficient impinger volumes were used in the
collection scheme for subsequent multi-analyses. Fluoride was collected in
a separate, single midget impinger concomitantly and in parallel with the
Cl/Br devices (Section I, Appendix A).
Acid mist was collected on cellulose filters and in duplicate (Section
J, Appendix A).
53
-------
AIR IN
AIR IN
SCANNING
ELECTRON J
MICROSCOPE L
ANALYSIS
HIGH RESOLUTION
GLC/MS/COMP
ANALYSIS
HIGH RESOLUTION
GLC/MS/COMP
ANALYSIS
i
FILTER -
TENAX _
CARTRIDGE
CARBON
CARTRIDGE
NEUTRON ACTIVATION
ANALYSIS
.NEUTRON ACTIVATION
ANALYSIS
NEUTRON ACTIVATION
ANALYSIS
OUT
OUT
Figure 4.1. Schematic of duplicate (parallel) cartridge sampling
and designated sample analysis
TURBIDITY ANALYSIS -T
NEUTRON ACTIVATION-I"
AIR IN
TURBIDITY ANALYSIS
NEUTRON ACTIVATION
Figure 4.2. Tandem midget impingers for collection and designated sample
analysis for halogenated substances
54
-------
Hi-Vol glass and cellulose fiber filters (Figure 4.3) were used for
collecting particulates for SEM and EDX analysis. As part of the sampling
protocols in each of these cases, "Hi" and "low" volume cartridge sampling
was performed with the intent of collecting adequate quantities of material
for characterization by high resolution GLC/MS/COMP. A Nutech Model 221-A
sampler (Nutech Corp., Durham, NC) was utilized for "Hi" volume sampling
and a DuPont personal sampler (Section F, Appendix A) for "low" volume
sampling. The DuPont sampler was also evaluated for potential long-term
sampling (24-36 hr) and sampling in highly remote and distant locations
from the plant sites.
The DuPont samplers were located off the property of the Great Lakes
Corp. and Arkansas Chemical, Inc. area. They were placed on the water
tower in Parker's Chapel and on a water tower in downtown El Dorado, Arkansas
The purpose of this sampling was to determine whether it was possible to
detect and quantify halogenated organic volatiles during an overnight
period. We intended to demonstrate whether halogenated organic vapors were
transported from the plant sites to populated areas resulting in potential
exposure. The Parker's Chapel water tower is located between Great Lakes
Corp. and Arkansas Chemical, Inc. on Arkansas Highway 15. It is approxima-
tely one mile from Great Lakes (line of sight) and about 1.5 miles from
Arkansas Chemical, Inc.
Inorganics were collected during separate sampling periods at the same
locations as for organics.
During all sampling periods, meteorological data were recorded continu-
ously at one sampling location with a Meteorological Research, Inc. instru-
ment (temperature, wind direction and speed). Every 30-60 min, wind speed
and direction, temperature, barometric pressure and humidity were recorded
using hand-held instrumentation. These parameters were estimated with a
Dwyer Wind Meter (Dwyer Inst. Inc., Michigan City, IN), a pocket altimeter
(Gischard, West Germany), and a sling psychrometer (Taylor Inst. Co.,
Rochester, NY). Direction bearings and distances were measured with a
lensatic compass and a Rangematic Distance Finder (Ranging Inc., Rochester,
NY), respectively.
55
-------
SCANNING
ELECTRON
SURVEY
>
NEUTRON
ACTIVATION
ANALYSIS
ORGANIC ANALYSIS
Figure 4.3. Hi-Vol filter and designated sample analysis
56
-------
Other subjective observations were also made.
4.1.2 Analytical Cross-Checking
In order to evaluate the analytical methodology and to obtain a broad
spectrum of information concerning potential pollutants, several instrumental
techniques were used in a cross-check fashion. The glass fiber filters
(Figure 4.3) from the cartridge sampling train were examined by SEM, EDX
(when feasible) and NA techniques. Using this approach it would be possible
to determine the relative amounts of Cl, Br, and S occurring in the non-
volatile fraction (particulate) and to a certain degree whether these
elements are predominantly organic or inorganic by counterion studies using
SEM-EDX. The use of SEM-EDX and NA also serves as a rapid preliminary
screening technique to determine whether analysis for organics, inorganics
or both is justified by other more definitive (but time-consuming) methods.
The volatile organic compounds trapped on the Tenax cartridge were
designated for analysis by high resolution GC/MS/COMP techniques and by
neutron activation (Figure 4.1). High resolution GC/MS/COMP analysis of
the Tenax cartridge allowed the identification and quantification of organic
volatiles which were emitted by the bromine extraction or synthetic organic
units at the plant facility. In some cases duplicate analysis of the Tenax
cartridges by high resolution GC/MS/ COMP was conducted in order to determine
the reproducibility of analysis. In other cases, a second cartridge was
not subjected to high resolution GC/MS/COMP analysis, but instead submitted
for neutron activation. In this manner, it was possible to determine
whether chlorinated and brominated compounds escaped detection by the high
resolution GC/MS/COMP analysis since it was possible by the more general
technique of neutron activation to obtain total equivalents of Cl and Br.
Carbon cartridges (Figure 4.1) were analyzed similarly to the Tenax cart-
ridges, by high resolution GC/MS/COMP and by neutron activation analysis.
Although high resolution GLC/MS/COMP was used for unequivocal identifi-
cation of vinyl chloride, vinyl bromide, methyl chloride and methyl bromide
from Tenax GC cartridges, these halogenated compounds were also quantified
by independent methods, i..e. , GC with electron capture (Section D, Appendix
A) and mass fragmentography (Section E, Appendix A).
57
-------
In addition to the sampling of low volumes (^75-1502) of air with the
cartridge train, Hi-Vol sampling was employed (Figure 4.3). Glass and
cellulose filters were subjected to SEM-EDX and NA analysis.
The first impinger solution contained primarily halides (Figure 4.2)
and was examined by NA and turbidity methods. In some cases, ion-exchange
separation of Cl and Br was performed to determine individual halide
concentrations in air. The second impinger trapped molecular chlorine and
bromine; it was treated in the identical manner to the first.
4.1.3 Prioritization of Sample Analyses
Many samples were taken for organic and inorganic analyses. Since the
major objectives of this study were to obtain a broad overview of the major
pollutants occurring from the bromine industry and to evaluate analytical
techniques for collection and analysis, samples were prioritized and "best
samples" were examined. These were selected on the basis of the best
sampling conditions as reflected by the meteorological parameters during
the sampling period. Also, consideration was given to significant potential
emissions during the most active periods of the plant facility operations.
Lower priority was given to those cases where the plant operations were
believed to be unfavorable for collection of adequate amounts of chemicals
for study. Furthermore, when meteorological conditions were unstable or
when emissions from the plant sites were not continuously carried to the
sampling locations, the samples were given a low analysis priority.
The prioritization scheme for the Survey Phase was necessary to obtain
a maximum amount of information with the expenditure of only a moderate
level of effort.
4.2 RESULTS AND DISCUSSION
4.2.1 Arkansas Chemical Incorporated
4.2.1.1 Sampling
The sampling protocol and sample descriptions for Arkansas Chemical
Inc. are given in Table 4.2. The corresponding Figures 4.4 and 4.5 designate
the sampling locations for September 20 and 21, 1976. Soil and water
samples were also collected on April 4, 1977. These protocols are given in
Table 4.3 and Figure 4.6.
58
-------
Table 4.2. SAMPLING PROTOCOL FOR ARKANSAS CHEMICAL INCORP.,
HIGHWAY 15, EL DORADO, ARKANSAS
Meteorological Conditions
Period Cycle Location
9/20/76 Cl LI
PI L2
L3
L4
C2 LI
L2
L3
L4
C3 LI
L2
L3
L4
LI
L2
L5
LI
L5
L6
9/21/76 Cl LI
P2 L2
L3
Sampling
Time
1330-1523
1330-1525
1330-1530
1325-1524
1545-1614
1545-1614
1545-1615
1545-1615
1637-1800
1637-1757
1640-1758
1636-1758
1720
1742
1748
1723
1727
1727-1742
1805-1835
1808-1826
1808-1835
Sampling
Volume (H)
103
102
137
14S
44
54
43
81
272
154
137
90
1
1
1
0.28
0.28
0.28
184
235
243
Type of
Sample T (°C) % RH
HHCa 25-26 95
Hlica 25-26 95
HUG* 25-26 95
HllCa 25 95
F, CBN, CBD
F, CBN, CBD
F, CBN, CBD
F, CBN, CBD
AM
AM
AM
AM
TED
TED
TED
VAC
VAC
VAC
HHCa 27 44
HHCa
HHCa
Wind Dlr./
Speed (kmph) Other
270°/6 Full Cloud Cover, rain
210° Id Full Cloud Cover, rain
270V6 Full Cloud Cover, rain
270°/6 Full Cloud Cover, rain
Odor of H2S, Br2
Clear
Nutech Model 220 sampler 3-6 ft elevation.
Locations shown in Figures 4 and 5.
Key to Sample Type:
HHC - Halogenated Hydrocarbon
F - Fluorine and Fluoride
CBN - Bromine and Chlorine
CBD - Bromide and Chloride
AM - Acid Mist
TED - Tedlar Bag
VAC - Aluminum Vacuum Can
-------
ARKANSAS CHEMICAL-EL DORADO
Figure 4.4.
APPROX. SCALE 1 cm = 110 m
Schematic map of Arkansas Chemical Incorp.,
El Dorado - sampling locations for PI -
9/20/76.
A - Br2 facility
60
-------
ARKANSAS CHEMICAL-EL DORADO
APPROX. SCALE 1 cm = 110
Figure 4.5.
Schematic map of Arkansas Chemical Incorp.,
El Dorado - sampling locations for P2 -
9/21/76.
A - Br facility.
61
-------
Table 4.3. SAMPLING PROTOCOL FOR ARKANSAS CHEMICAL INCORP.,
EL DORADO
Sample
Period Cycle Location Size
1 Cl LI 2
4/7/77 2
L2 2
2
L3 2
2
1
cores
cores
cores
cores
cores
cores
a
Type of Sample
SHHC-V
SHHC-SV
SHHC-V
SHHC-SV
SHHC-V
SHHC-SV
WHHC-V/SVS'
Stream 30 cm wide, 10 cm deep in drainage ditch.
Water was collected from standing puddles.
Key to sample type:
SHHC - soil for halogenated hydrocarbons
WHHC - water for halogenated hydrocarbons
VHHC - vegetation for halogenated hydrocarbons
SEHHC - sediment for halogenated hydrocarbons
SCHHC - scum on water for halogenated hydrocarbons
MHHC - milk for halogenated hydrocarbons
V - for volatile organic analysis
SV - for semi-volatile organic analysis
62
-------
Figure 4.6.
Schematic map of Arkansas Chemical Incorp.,
El Dorado - sampling locations for PI -
4/7/77.
63
-------
4.2.1.2 Inorganics in Ambient Air
Chloride/Bromide and Chlorine/Bromine.--The results obtained by turbidi-
metric determination of total halide are given in Table 4.4. The site,
period and cycle designation are given in the sampling protocols and the
location on the schematic maps (Fig. 4.4).
Table 4.4. CONCENTRATIONS OF HALOGENS AND HALIDE5
SURROUNDING ARKANSAS CHEMICAL INC.3'
IN AMBIENT AIR
Species
Cl2/Br2C
Br2d
c
Cl /Br
d
Br
Locations
LI L2 L3 L4
<109 <92 <100 <61
238 - 28
<75 <61 69 49 + 53
<19 - <12
Samples are from P1/C2.
Values are in yg/m .
°By turbidity.
By neutron activation analysis.
Arkansas Chemical Inc. showed only one detectable concentration of
halide by turbidity at L4 (downwind of a group of ponds, see Fig. 4.4).
Neutron activation analysis of that location indicated no bromide. A high
bromide level was found at L2 which is inconsistent with the total halide
determination. Cellulose filters used in the sampling cycle immediately
following the impinger sampling cycle showed no detectable bromine.
Fluoride/Fluorine.--No fluoride or fluorine was detected in any of the
samples in ambient air surrounding Arkansas Chemical Inc. The limits of
detection are based upon the background levels observed in control solutions
and are indicated by "less than" values. A detection limit of 0.02 ppm in
the impinger solution was achieved for the volume of air sampled.
Acid Mist.--No titratable acid was detected in any samples (Table
4.5). Table 4.5 summarizes the upper limit of acid mist concentration in
these samples. Again, they are represented as "less than values".
64
-------
Table 4.5. ACID MIST IN AMBIENT AIR SURROUNDING
ARKANSAS CHEMICAL INCORP. AS H.SO.a
2 4
Locations
Period Cycle LI L2 L3 L4
PI C3 -b <30 - <52
values in yg/m .
Not determined.
Table 4.6. CONCENTRATION OF BROMINE IN BRINE SAMPLES
Site Sample Type yg Br/ml
Arkansas Chemical Incorp. Front brine 6588.2
Tail brine 418.2
65
-------
4.2.1.3 Bromine and Brominated Organics in Brine
Neutron Activation Analysis.--Table 4.6 lists the concentrations of
bromine (molecular plus halides) in front and tail brine samples. A 93%
reduction of the bromine concentration was observed between front and tail
brines. Significant quantities of bromine were detected in the tail brine
samples; however, the technique of neutron activation does not distinguish
whether the bromine is present as molecular bromine, bromide ion or bromina-
ted organics. Furthermore, the number of bromine atoms per molecule
cannot be delineated. The importance of these results is primarily attribu-
ted to the presence of substantial quantities of "bromine" even after
bromine extraction.
GC/MS/COMP Analysis for Volatile Organics.--The front brine from
Arkansas Chemical Inc. was purged (Appendix A) to recover volatile brominated
organics for subsequent identification by GC/MS/COMP and estimation of
concentrations. The front brine sample from Arkansas Chemical Inc. (Fig.
4.7) contained benzene, dimethyldisulfide, toluene, thiacyclopentane,
dithiopropane isomer, ethylbenzene, cyclooctatetraene, undecane and n-
dodecane. The tail brine sample (Fig. 4.8) contained benzene, dimethyldisul-
fide, toluene and l-chloro-2,3-dibromopropane (Fig. 4.9).
In Table 4.7 the concentrations of halogenated and other organics in
brine samples from Arkansas Chemical Inc. are provided. In general the
concentration of halogenated hydrocarbons did not appreciably increase
after recovery of bromine from brine.
The above results represent the analysis of only a single sample in
each case. For this reason the concentration of volatile organics in these
samples may not be representative of the change in composition between
front and tail brine. The results do, however, give an indication of the
types of compounds which are present as volatile organics. It would be
interesting in future studies to also include the examination of semi-
volatile brominated organics in brine samples.
4.2.1.4 Organic Vapors in Ambient Air
Qualitative Analysis by High Resolution GC/MS/COMP.--Analysis was
conducted according to the protocols given in Appendix A.
66
-------
30000-1
C
0)
M
M
0
o
td
4J
H
EOOOO-
1 0000-
0-"
5000
-|- I [-
5050
5100
5150
5300 5250
Mass Spectrum No.
I i" I I"' i '"I" I " i "''"'I
5MOO 5
Figure 4.7. Total ion current profile of volatile organics in front brine from Arkansas Chemical
Incorp. Peak No. A = hexafluorobenzene (eS), 5 = chloroform, 6 = perfluorotoluene
(eS), 7 = benzene, 8 = dimethyldisulfide, 9 = toluene, 10 = thiacyclopentane, 12 =
dithiopropane, 1A = ethylbenzene, 19 = cyclooctatetraene, 21 = jn-undecane, 22 =
CnoH0/- isomer, and 2A = n-dodecane.
—
-------
30000-1
C
OJ
3
U
C
O
E 0 0 0 0 -
1 0 P 0 0 -
0--
HE 00
I ......... I""
H550
VI
4600 4650 4? 00
Mass Spectrum No.
m^^
M75Q 4800 MS50
-•
M900 H'JSO
Figure A.8. Total ion current profile of volatile organics in tail brine from Arkansas Chemical
Incorp. Peak No. 2 = hexafluorobenzene (eS), 3 = perfluorotoluene (eS), 4 = benzene,
5 = dimethyldisulfide, 6 = toluene, and 15 = l-chloro-2,3-dibromopropane.
-------
I 00-g
9U-:
4J
>
•H
4-1
a
o--
, J,Li| , Illlj iflllliljjiljllillllllllllil.ijlilijiiy lIlilN^iJIIli^.l^ii,,.^,,,^,. llj.^^p.^,!,,,^^,,,,.^^,!..,.^^,,^,.^^,,-,,, p,.,...,-,.,*,!,,., ,.,,,1i,,™T, ,-,..(,.-, :. ,.,.-, ,,..Y ,- ,. i
E 0 100 1 E 0 E 0 0 e'!.. U 3 0 0 "J S 0
m/e
Figure 4.9. Mass spectrum of l-chloro-2,3-dibromopropane in tail brine
sample (ACI). Peak No. 15 in Figure 4.8.
-------
Table 4.7. HALOGENATED AND OTHER ORGANICS IDENTIFIED AND
QUANTITATED IN BRINE SAMPLES FROM
ARKANSAS CHEMICAL INCORP.a
Sample Type
Front Brine Tail Brine
Dibromochloromethane 540 N.D.
l-Chloro-2,3-dibromopropane 40 56
Hexafluorobenzene (eS)
Perf luorotoluene (eS)
Ethylene dibromide
Benzene
Toluene
Dime thy Idisulf ide
Thiacyclopentane
Dithiopropane isomer
Ethylbenzene
n-Undecane
n-Dodecane
Cyclooctatetraene (tent.)
600
10,000
1,600
800
1,600
1,200
3,200
1,600
800
-
T(?)
2,285
3,200
1,714
T
1,400
N.D.
1,600
850
N.D.
o
Concentrations are in ppt.
eS = external standard, 200 ng.
70
-------
Figures 4.10 and 4.11 depict the total ion current profile and ion
chromatograras for the volatile ambient air pollutants which were collected
on the Tenax GC cartridges at Location No. 1 on the bank of the spent brine
ponds at ACI. Figure 4.11 clearly depicts the presence of 1,2-dibromoethane
and l-chloro-2,3-dibromopropane. No bromoform was detected in this sample.
The profile for the volatile organics at Location No. 2 on this site is
given in Figure 4.12. This sample was found to contain a trace of allyl
bromide and 1,2-dibromoethane.
1,2-Dibromoethane was also identified at Location No. 3 (Table 4.8,
Figure 4.13). No other halogenated compounds which were unique were found
in this sample. An ambient air sample taken at Location No. 4 (Table 4.9,
Figure 4.14) contained a new compound which was tentatively identified as
difluorodibromomethane. 1,2-Dibromoethane was also present.
The use of ion chromatograms or mass fragmentography (Fig. 4.11) is
highly advantageous once the identity of the compound has been established
in samples. The selection of the unique ion in a mass spectrum of a compound
and the display of the intensity of that ion vs. the mass spectrum number
(retention time) allows further deconvolution of the complex ambient air
profile. This technique has been utilized throughout the study for display-
ing the relative intensities of the halogenated organics that were identified
in the samples. The mass spectrum number of the halogenated compound is
also related to the retention time in the chromatographic run. From this
information it is possible to locate the peak which corresponds to the
compound of interest by its retention time and the intensity of this ion is
directly proportional to the concentration of the compound in the sample.
Table 4.10 summarizes the halogenated compounds which were identified
by GC/MS/COMP in ambient air at Arkansas Chemical Inc. in El Dorado, Arkansas.
Table 4.10. HALOGENATED COMPOUNDS IDENTIFIED BY GC/MS/COMP IN
AMBIENT AIR AT ARKANSAS CHEMICAL INCORP., EL DORADO, ARKANSAS
Compound
Compound
Chlorodibromopropane
l-Chloro-2,3-dibromopropane
1,2-Dibromoethane
Difluorodibromomethane (tent.)
Methyl Bromide
71
-------
30000-1
eoooo
0)
>
•H
4-J
CO
,H 10000-
OJ
Pi
fcBOO
6850
Figure 4.10.
6900 6950 7000 7050 7100 7150 7BOO
Mass Spectrum No.
Total ion current profile of volatile ambient air pollutants from Arkansas
Chemical Inc. site, El Dorado, Arkansas (P1/C1/L1).
-------
3
u
>
•H
U
nj
QJ
Pi
PT (.1)
BP
i
-J\_
Its UO OgSO 0300 03SO OHOO 0450 OSOO OS50
Mass Spectrum No.
Figure 4.11. Ion chromatograms for ambient air sample from Arkansas Chemical Inc.
site, El Dorado, Arkansas (P1/C1/L1). BF = bromoform, CDBP = 1-
chloro-2,3-dibromopropane, EDB = ethylene dibromide.
-------
Mass Spectrum No.
Figure 4.12. Total ion current profile of volatile ambient air pollutants from
Arkansas Chemical Inc. site, El Dorado, Arkansas (P1/C1/L2).
-------
Table 4.8. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR FROM ARKANSAS
CHEMICAL INC. SITE IN EL DORADO, ARKANSAS (Pl/Cl/L3)a
Chromato-
grsphic
Peak No.
1
1A
2
2A
2B
3
3A
3B
3C
3D
3E
4
4A
5
6
6A
6B
6C
7
7A
7B
7C
8
9
9A
9B
9C
9D
9E
10
10A
11
11A
11B
12
12A
12B
13
13A
13B
Elutior.
Temperature Compound
45
46
47
48
50
51
53
55
56
57
57
58
59
60
63
64
65
67
68
68
69
70
73
75
79
79
80
84
85
87
90
93
94
96
96
97
100
101
103
104
dichlorodifluoromethane
acetaldehyde
trichlorofluoromethane
acetone
dichlorome thane
freon 113 (BKG)
isopropanol
butenal isomer
2-methylpentane
3-nethylpentane
butanal (tent.)
hexafluorobenzene (el)
n-hexane
chloroform
perfluorotoluene (ej)
methylcyclopentane
1,1, 1-trichloroethane
benzene
carbon tetrachloride
cyclohexane
C7H16 ls°mer
methylbutanal isomer
n-pentanal
n-heptane
C7H14 isonier
CgH.g isomer
methylcyclohexane
4-nethyl-2-pentanone
methylpentanal isomer
toluene
C8H18 i8OT>er
£,-hexanal •*• 1,2-dibromo-
ethane
C8H16 i*01ner
siLace compound (BKG)
£-oct»ne
tetrachloroethylene
C.H^ isomer
hexamethylcyclotrlsil-
oxane (BKG)
ethylcyclohexane
C9H20 i*OIIler
Chromato-
graphic
Peak No.
14
15
16
16A
17
18
ISA
18B '
19
19A
20
21
21A
22
23
24
25
25A
25B
26
26A
27
28
29
30
31
32
32A
33
34
35
35A
36
37
38
39
40
41
42
43
44
(continued)
75
Elution
Temperature Compound
CO
106
108
109
110
111
112
112
113
113
115
116
118
119
120
121
122
123
123
124
125
126
127
128
129
130
132
133
134
135
136
137
138
138
139
140
141
142
144
145
147
149
ethylbenzene
£-xylene
CgH2o isomer
C^gH.,2 isomer
styrene
2,2, 4- trioethy Iheptane
m-xylene
£-heptanal
C.,.H.2 isomer
C9H18 iSOffler
n-nonane
C10H20 isomer
C10H22 is°mer
dime thy 1-ethylbenzene
isomer
Cj-H,- isomer
C10H20 isomer
C.-Hj,, isomer
C10H16 1SOner
C.-E-. isomer
benzaldehyde
£-propylbenzene
£-e thy 1 toluene
C._H-2 Isomer
C11H24 iaoaer
C11H24 iBomer
C11E24 i80mer
C,-alkyl benzene isomer
C10H20 i301ner
4-methyldecane
£-decane
''11^22 ^somer
C10H16 I90ner
C11H24 lsolner
C,-alkyl benzene isomer
C11H24 lsomer
C10H16 isomer
C^^H,, isomer
C11H24 l80mer
acetophenone
C11H24 lsoner
C,-alkyl benzene isomer
-------
Table 4.8 (cont'd)
Chroma to-
graphic
Peak No.
44A
45
45A
46
46A
46B
46C
47
47A
Elucion
Temp .
150
152
153
154
157
157
159
160
163
Compound
C-. ..H- . isomer
12 24
n-nonanal
C,,H_- isomer
11 22
n-undecane
C -alkyl benzene isomer
C, -H., , isomer
1_ Zb
C ,H isomer
3-phenylpropenal
C.-alkyl benzene isomer
Lnroma to-
graphic
Peak No.
48
48A
49
49A
50
50A
SOB
50C
^luC ion
Tenip .
164
165
169
170
171
174
184
188
Compound
C...H-,. isomer
iz /b
C ^H.,, isomer
Ij 28
n-decanal
C H , isomer
n-dodecane
C ,H,_ isomer
C13H2g isomer
C_ _H00 isomer
1 J /o
See Table 4.2 for sampling protocol,
76
-------
30000-1
C
0)
i-i
M
D eoooo-
U
c
o
n)
.u
O
0)
•H
01
Pi
IOuUO-
(i
81
(I
8150
8200
8250
8300
• 3SO
Mass Spectrum No.
8400 • 8450
85(10
Figure 4.13. Total ion current profile of volatile ambient air pollutants from Arkansas
Chemical Inc. site, El Dorado, Arkansas (P1/C1/L3).
-------
Table 4.9. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR FROM ARKANSAS
CHEMICAL INC. SITE IN EL DORADO, ARKANSAS (Pl/Cl/L4)a
Chromato-
graphic
Peak So.
2
2A
2B
3
3A
4
4A
5
5A
5B
5C
6
7
8
9
9A
10
10A
10B
11
11A
11B
12
12A
12B
12C
13
14
14A
14B
14C
15
ISA
16
16A
17
17A
17B
17C
17D
18
Eiution
Temperature Compound
CO
41
46
47
48
49
50
51
52
53
54
55
56
58
59
60
61
64
65
67
68
69
70
71
71
72
73
74
76
80
84
85
87
92
93
93
95
96
96
102
103
106
co2
acetaldehyde
difluorodib romome thane
(tent.)
crichlorofluoromethane
iscpentane
acetone
dichloromethane
freon 113 (BKG)
isopropanol
ter-butanol
butenal
2-methylpentane
3-methylpentane
hexaf luorobenzene (el)
n-hexane
chloroform
methylcyclopentane
perf luorotoluene (es)
1,1, 1-trichloroe thane
benzene
cyclohexane
C,H, , isomer
/ 10
methylbutanal isomer
C,H, , isomer
/ J.Q
hexamethyldisiloxane (BKG)
n-pentanal
n_-heptane
methylcyclohexane
4-methyl-2-pentanone
methylpentanal isomer
toluene
C.H,, iaomer
o lo
1, 2-dibromoe thane
ri-hexanal
n— octane
tetrachloroethylene
C8H16 I80mer
C8H16 ttomer
C9H20 1*omer
ethylbenzene
Chroma to*
graphic
Peak No.
18A
19
20
20A
21
22
22A
23
23A
23B
24
24A
25
25A
26
27
28
29
29A
30
32
33
34
35
36
37
38
39
40
41
41A
413
42
43
44
45
46
46A
47
Eiution
Temperature Compound
CO
106
107
108
100
111
112
112
113
113
114
115
117
118
119
119
120
121
122
122
123
126
128
129
131
132
134
134
135
136
138
138
139
140
141
142
144
145
147
148
C.H,- isomer
p_-xylene
C9H20 lsoner
C9K20 is°mer
styrene
C10H20 is°mer
m-xylene
m-heptanal
C,0H,T isomer
CqH.. - isomer
n-nonane
CqH^ „ isomer
tetramethylhexane isomer
C,-alkyl benzene isooer
trimethylheptane isomer
dime thy 1-e thy Ihexane
isomer
C H isomer
trimethy Iheptane isomer
C10H16 is°mer
benzaldehyde
C10H20 isotner
m-e thy 1 toluene
C11H24 lsomer
C,,H_, isomer
C10H16 isomer
C10H22 ls°mer
C11H24 lsomer
n-decane + dichloro-
benzene isomer
C11H24 isomer
C10H16 Is0mer
C, -alkyl benzene' isomer
C11H24 isoner
C10H16 il0mer
C11H24 isomer
C11H24 isaa"
C11H24 lsom"
acetophenone
C..H., isomer
12 26
C10H12 i801ner
CgH, 0 iaomer
(continued)
78
-------
Table 4.9 (cont'd)
Chromato-
graphic
Peak No.
47A
48
48A
49
49A
49B
Elucion
Temp .
149
150
151
152
155
158
Compound
C10H12 + C11H20 isomer
n-nonanal
C11H22 isomer
n-undecane
C,-alkyl benzene isomer
3-phenylpropenal
Chromato-
graphic
Peak No.
49C
49D
49E
50
51
51A
Elusion
Tenp .
161
165
167
168
169
177
Compound
dlmethylphenol
dimethylphenol
n-decanal
c1-iH24 isolr'er
n-dodecane
C7 -,'ri-, . isomer
isomer
isomer
See Table 4.2 for sampling protocol.
79
-------
Co
O
88SO
9050
Mass Spectrum No.
9800
9 2 E (i
Figure 4.14.
Total ion current profile of volatile ambient air pollutants from Arkansas
Chemical Inc. site, El Dorado, Arkansas (P1/C1/L4) .
-------
Quantification of Halogenated Hydrocarbons.--The identified halogenated
hydrocarbons were quantified (Section F, Appendix A). Table 4.11 presents
the levels of halogenated hydrocarbon in samples taken near the spent brine
pond on the Arkansas Chemical Inc. site. The highest level observed was
3
133 ng/m (1,2-dibromoethane). This sample was taken at L4 and it actually
represented an upwind sample from the brine pond and the bromine extraction
facility. For this reason it was believed that the brominated compound had
been transported from another facility since the analysis of spent brine
indicated only a trace of EDB.
Estimation of Methyl Chloride, Methyl Bromide, Vinyl Chloride and
Vinyl Bromide.--Methyl chloride was detected by GC/EC in one sample (P1/C3/L1)
3 3
at a level of 200 |Jg/m . The detection limit was about 200 pg/m for
3
methyl chloride and 120 (Jg/m f°r methyl bromide. No other halogenated
species (of these four) were detected at ACI.
Ethylene.--The levels of ethylene found at ACI are given in Table
4.12. These values were typical background levels observed in most samples
taken in this area.
Table 4.12. CONCENTRATIONS OF ETHYLENE IN AMBIENT AIR3
Site Period/Cycle/Location ppra
ACI P1/C3/L1 0.76 + 0.16
P1/C3/L2 0.85 + 0.15
P1/C3/L5 0.76 + 0.16
£S
See Table 4.2 for sampling protocol and Fig. 4.4 for locations.
4.2.1.5 Brominated Organics in Soil and Water
All of the soil and water samples were screened by the VOA method
(Appendix A) for the presence of EDB and other volatile brominated compounds,
and none were found. One of the soil samples [P1/C1/L1 (April 4, 1977)]
was selected for analysis for semi-volatile brominated organics. The
results are given in Table 4.13.
The spectrum of Tetrabrom obtained from the soil sample P1/C1/L1 is
shown in Figure 4.15.
81
-------
Table 4.11. HALOGENATED HYDROCARBONS IDENTIFIED AND QUANTITATED IN AMBIENT AIR SURROUNDING
ARKANSAS CHEMICAL INCORP., EL DORADO, AK
o
Period/Cycle/Location
P1/C1/L1
L2
L3
L4
QJ
T)
•H
g
0
(^
M
rH
i-H
70
T
29.7
-
e
o
M-l
O
O
(-1
PQ
Tb
c
-
-
0)
c
td
Q
M
(X
0
e
o
(-1
1
CM
O
rH
-
-
5.5
6.7
i
o
o
i-i
•H
P
1
CO
n
INI
1
O
M 01
0 C
i— 1 tfl
O O
1 >-<
1.87
-
-
-
01
T)
•H
g
O
£
•H
•X)
QJ
C
01
i-H
rd
4-1
W
CM
rH
3.10 + 0.8
5.30
81
133
01
C
cfl
,c
4-1
0)
O
B
o
M
r^
•H
O
V-<
O
3
r— \
•H
P
-
-
-
T
CO
Refer to Table 4.2 for sampling protocol, values are in ng/m .
T = trace detected.
- = not detected.
-------
00
OJ
100 -i
Ml
1 il::||i|! SlP * ,4_,,
" >n inn
flFI ni.i'C IS
• inn j'.,o
ft* 11-iUOi. -B./I'.V.IJ, -1 I
Figure 4.15. Mass spectrum of Tetrabrom in soil sample P1/C1/L1.
-------
Table 4.13. ANALYSIS OF A SOIL SAMPLE COLLECTED NEAR ARKANSAS
CHEMICALS, INCORPORATED, EL DORADO, AK
Period/Cycle/Location
P1/C1/L1
EDB
(yg/k)
ND
Decabrom
(g/k)
260a'b
Tetrabrom
(yg/kg)
4,100a'C
SQuantitated by GC/MS/COMP with multiple ion detection (MID).
Confirmed by GC/MS/COMP-MID using ion intensity ratios; m/e 800:960 was
3.0 for standards and 2.7 for the sample.
CConfirmed by GC/MS/COMP in full scan mode.
4.2.2 Great Lakes Chemical Corporation
4.2.2.1 Sampling
The sampling protocol and sample descriptions for Great Lakes Chemical
Corporation are given in Table 4.14. The corresponding Figures 4.16-4.18
designate the sampling locations for September 22-24, 1976. The sampling
protocols for April 7, 22, and 29 and May 17, 1977 are given in Table 4.15
and their locations in Figures 4.19 and 4.20.
4.2.2.2 Survey of Chemicals on Glass Fiber and Cellulose Filters
Scanning Electron Microscopy (SEM) and Electron Microprobe (EM) Analy-
sis .—Samples were collected at Great Lakes Chemical Corp. by the State of
Arkansas Air Pollution Control Division using Hi-Vol samplers. Glass fiber
filters (GFF) and cellulose filters (CF) were sampled in parallel. Each
site was sampled for three 24 hour periods. One period from each site has
been analyzed by SEM and EM. Both types of filter material were examined.
Sufficient sample was concentrated on the surface of the GFF to permit
direct analysis without the usual carbon-coating to prevent charge buildup
on the sample.
Initially, an examination for the presence of bromine and its subsequent
mapping was performed. In Figure 4.21 the EM spectrum shown is expanded
for the greatest sensitivity in the bromine region. Traces were detectable
in both samples when compared to the background in Figure 4.22. However,
these traces are insufficient to produce an elemental map.
84
-------
Table 4.14. SAMPLING PROTOCOL FOR GREAT LAKES CHEMICAL CORPORATION,
HIGHWAY 15, EL DORADO, ARKANSAS
00
Meteorological Conditions
Period Cycle Location
9/22/76 Cl LI
PI L2
L3
LA
C2 L5 (ELV)
1.2 (ELV)
L2
1.3
LA
C3 LI
L2
L3
LA
CA LI
L2
L3
LA
1.5
L6
L7
Sampling
Time
1026-123A
1026-123A
1026-123A
1026-1233
1010-1702
9A5-1702
9A5-1702
1026-1700
1026-1602
1238-1337
1236-1336
1236-1336
1233-1336
13AO-1A50
1337-1A51
1337-1A51
13AO-1A53
1130
1138
11A3
Sampling
Volume (I)
109
122
140
100
-
-
-
-
-
A6.7
5A.6
A8.1
77.8
123
137
103
125
1
1
1
Type of
Sample T (°C) % RH
HMCa 24-26 51-A6
HHCa
IMC* 26
IHlCa 2A 51
HHCC 26
mice
micb
HIICb 26
Hlicb 28-30
F, CBN, C11D 27
F, CBN, CBD
F, CBN, CBD 28
F, CBN, CBD
AM
AM
AM
AM 28
TED
TED
TED
Wind Dir./
Speed (kn.ph) Other
130/3-230/3-6 Clear
variable/light Clear, slight odor
of Br2
Clear, odor of
bromobenzene Brine
Pit-heavy odor
calm Clear, odor of Br2
calm
230/3-6
Clear, blight odor
of Br2
shifted to
South
230/3-6 No drift
Clear
(continued)
-------
Table 4.14 (cont'd)
00
Period Cycle Location
9/22/76 L6
PI L8
9/22/76 Cl LI
P2 L2
L3
L4
9/22,23/76 C2 Packers Chapel
Water Tower
C3 LI
L2
L3
C4 L5
9/24/76 Cl LI
P3 L2
L3 (ELV)
L4
C2 L3 (EI.V)
L5 (ELV)
Sampling
Time
1130
1143
1553-1802
1548-1608
1600-1831
1549-1823
1730-1030
1813-1913
1827-1932
1803-1916
1930
1200-1420
1200-1420
1200-1420
1200-1420
1740-948
1745-945
Sampling
Volume (I)
0.28
0.28
116
96
160
191
-
36.8
73.6
59.4
-
229
178
205
216
_
-
Meteorological Conditions
Type of Wind Dir./
Sample x (°C) % RH Speed (kmhli) Other
VAC
VAC
WIC" 22 65 South/3 Clear
HHCa
HUC" 33-30 38 clear Clear, odor of
brine steam
HHCa 270"/5-5KTS Clear, light Br2
odor
HHCC
F, CBN, CBU
F, CBN, CBD
F, CBN, CBD 30 240° /5-8
VAC
HHCa 29 38 North/8
HHCa
HUCe Clear, odor phenol,
slight Br2
HHCf Upset at 1304-1309
HHCd 30° / 3- 10
,,,lCd 180V3-11
(continued)
-------
Table 4.14 (cont'd)
oo
Meteorological Conditions
Period Cycle Location
9/24/76 C3 L4
F3 L6 (ELV)
C4 L7
L2
L3
L4
C5 L7
L2
L3
L4
C6 L7
1.2
L3
L4
Sampling
Time
1018-1818
1145-1824
1428-1536
1430-1536
1430-1536
1430-1536
1540-1652
1540-1652
1542-1652
1540-1652
1657-1806
1657-1758
1659-1706
1657-1803
Sampl ing
Volume (H)
-
62
59
85
74
119
147
110
143
51
54
64
68
Type of
Sample T (°C) % RH
HIICd
HHCC
F, CBN. CBD 28-29 38-42
F, CBN, CBD
F, CBN, CBD
F, CBN, CBD
AM
AM
AM
AM
F, CBN, CBU
F, CBN, CBD
F, CBN, CBD
F, CBN, CBD
Wind Dir./
Speed (kai|)h) Other
30°/3-10
ENE-NNE/8-13 Clear, visible Br2
plume SE, Black
smoke ME, odor of
Clear, strong odor
of Br2 and phenol
Clear, slight odor
of Br2
Odor of phenol
Nutech Model 220 sampler 3-6 ft elevation
UuPont sampler 3-6 ft elevation
c|)uPont sampler 15-18 ft elevation
Overnight sampling
Sampling done on top of 3 story tower
Sampling done on top of Tank
Locations shown in Figures 7, 8, and 9.
Key to Sample Type: HliC
F
CBN
CBD
AM
TED
VAC
Halogenated Hydrocarbon
Fluorine and Fluoride
Bromine and Bromide
Chlorine and Chloride
Acid Hist
Tedlar bag
Aluminum Vacuum Can
-------
GREAT LAKES CHEMICAL CO E. D.
Figure 4.16.
Schematic map of Great Lakes Chemical
Corp., El Dorado - sampling locations
for PI - 9/22/76
A - EDB facility
B - Br2 facility
C - H S stripper
D - Tetrabrom facility
88
-------
GREAT LAKES CHEMICAL CO E.D.
APPROX. SCALE 1 cm = 110 m
Figure 4.17.
Schematic map of Great Lakes Chemical Corp., El
Dorado - sampling locations for P2 - 9/22/76.
A - EDB facility
B
C
D
Br facility
H S facility
Tetrabrom facility
89
-------
GREAT LAKES CHEMICAL CO E. D.
-^^A\ HOLDING
y \\ POND
APPROX. SCALE 1 cm = 110 m
Figure 4.18. Schematic map of Great Lakes Chemical Corp.,
El Dorado - sampling locations for P3 - 9/24/76,
A - EDB facility
B
C
D
Br~ facility
H S stripper
Tetrabrom facility
90
-------
Table 4.15.
SAMPLING PROTOCOL FOR GREAT LAKES CORPORATION,
EL DORADO, ARKANSAS
Period
PI
4/7/77
P2
4/22/77
P3
4/29/77
P4
5/17/77
Cycle Location
Cl LI
L2
L3
L4
Cl LI
L2
L3
L4
Parkers
Chapel
Cl Parkers
Chapel
Sample
Size
a
2 core
2 core
i a
2 core
2 core
1 I
2 core
2 core
—
1 0
Type of Sample
SHHC-V
SHHC-SV
WHHC-V/SV
VHHC-VC,
h
VHHC-SV
SHHC-V
SHHC-SV
WHHC-V/SV
SHHC-V
SHHC-SV
VHHC-V
VHHC-SV
SEHHC-V/SV
SCHHC-V/SV
SEHHC-V/SV
SCHHC-V/SV
MHHC-V/SV
VHHC-V/ SVe
Core ^5 cm diameter, 13 cm depth.
m wide, ^1 cm deep in dry weather (no rain for 1 week).
Needles stripped from 40 cm of pine bough sampled at ^5 m above ground
from trees showing damage.
Stream ^30 cm wide, ^5 cm deep in dry weather (no rain for 1 week).
Apples.
Key to sample type:
SHHC - soil for halogenated hydrocarbons
WHHC - water for halogenated hydrocarbons
VHHC - vegetation for halogenated hydrocarbons
SEHHC - sediment for halogenated hydrocarbons
SCHHC - scum on water for halogenated hydrocarbons
MHHC - milk for halogenated hydrocarbons
V - for volatile organic analysis
SV - for semi-volatile organic analysis
91
-------
/ TANK \
( O \
Figure 4.19.
Schematic map of Great Lakes Chemical Corporation, El Dorado
sampling locations for PI - 4/7/77.
92
-------
Figure 4.20.
Schematic map of Great Lakes Chemical Corporation, El Dorado
sampling locations for P2 - 4/22/77.
93
-------
40 KEU 564034 INT
""' 20 EU AB
n •> ti 4 e 6
Figure 4.21.
Great Lakes Chemical Corporation,
El Dorado, Arkansas on 12/17/76 -
12/18/76. Volume sampled 2,733.6
3 air.
m
OX10-0S 16 64 KEU
US* IK A+B
K Z-35 BR
548408 I NT
:- 20 EU AB
Figure 4.22.
Electron microprobe spectrum of
blank glass fiber filter.
94
-------
An inspection of the total spectrum of the GFF from Great Lakes Chemical
Corp. (Fig. 4.23a) reveals several other elements which were significantly
above background (that is, chlorine, aluminum, and iron). The amount of
sulfur is especially high compared to chlorine. Electron microprobe maps
of chlorine, sulfur, aluminum, and silicon are shown in Figures 4.23-4.25
along with the SEM maps of the region (Fig. 4.23). There is some degree of
coincidence of aluminum and silicon indicating an aluminum silicate particu-
late is probably present.
In general, this analysis surveys the types of particulate which were
present. Since elements of low atomic number are not observed, carbon and
its compounds escape observation. Indirect evidence may be obtained for
halogenated organics by eliminating possible counterions. Such was the
case of a particulate found on a GFF used during halogenated hydrocarbon
sampling (P1/C1/L4). The spectrum, SEM and maps for chlorine, sodium,
potassium, calcium and magnesium are shown in Figures 4.26-4.29. There
were relatively low amounts of counterions as compared to the chlorine.
Calcium is at background. Magnesium shows the greatest intensity, but even
so it is weak compared to chlorine.
Neutron Activation Analysis.--A segment of each filter was submitted
to neutron activation analysis. The segment was 2 x 2 cm cut from the
medium fold with the distal edge of the segment 3 cm from the filter edge.
The results of the neutron activation analysis are shown in Table 4.16.
3
The highest concentration of bromine (20.2 |Jg/m )• was detected in a sample
taken on December 17, 1976. Also, this represented the period for the
3
highest chlorine value (1.7 (Jg/m ) observed during the three day sampling
period.
Brominated Organics.--The filters above were extracted as described in
Appendix A and analyzed by thin layer chromatography-scanning densitometry
for Decabrom. The results are listed on Table 4.17. A second extraction
of the GFF from 12/18/76 was rechromatographed and the band corresponding
to Decabrom scraped from the plate and eluted. This fraction was submitted
to direct probe MS analysis. The spectrum is shown in Figure 4.30. A
spectrum of authentic Decabrom is shown in Figure 4.31. Large amounts of a
yellow material remained near the origin on the GLC plate. This material
95
-------
1280
Figure 4.23.
Electron microprobe spectrum (a) and scanning electron
micrograph (b) of a region on an air sample collected
on glass fiber filter. Sample Volume: 2,733.6 m^;
Location: Great Lakes Chemical Corporation, El
Dorado, Arkansas. Collected 12/17/76 - 12/18/76.
96
-------
1280 x
1280 x
Figure 4.24.
Electron microprobe element map of region shown in
Figure 4.23.
(a) Chlorine map; (b) Sulfur map.
97
-------
1280 x
1280 x
Figure 4.25.
Electron microprobe element map of region shown in
Figure 4.23.
(a) Aluminum map; (b) Silicon map.
98
-------
0,08 KEU
22 TI
5225918 INT
HS- 28 EU A
*x*s
Figure 4.26.
Electron microprobe spectrum (a) and scanning
electron micrograph (b) of a region on an air
sample collected on a glass fiber filter.
Sample Volume: 0.1 m3 air. Location: Great
Lakes Chemical Corp., El Dorado, Arkansas.
Collected 9/22/76
99
-------
b
520 x
Figure 4.27..
Electron microprobe element map of region shown
in Figure 4.26.
(a) Chlorine map; (b) Sodium map.
100
-------
a
520 x
b
520 x
Figure 4.28.
Electron microprobe element map of region shown
in Figure 4.26.
(a) Potassium map; (b) Calcium map.
101
-------
520 x
Figure 4.29.
Electron microprobe element map of region shown
in Figure 4.26.
Magnesium map.
102
-------
Table A.16. NEUTRON ACTIVATION ANALYSIS OF AMBIENT AIR HI-VOL SAMPLES
o
U)
Site
GRLa
GRL
CRL
Date
12/13/76-
12/14/76
12/16/76-
12/17/76
12/17/76-
12/18/76
Medium
GFFb
CFC
GFF
CF
GFF
CF
Br (lig/m3)
0.089
0.230
0.574
0.24
20.2
2.44
Cl (yg/nf
N.D.
0.043
0.345
0.086
1.70
0.40
All were 24 hr samples.
GFF = glass fiber filter.
CCF = cellulose filter.
-------
o
J>
100-
90-
80-
~!
'70-
-
H
60-
UJ
a: 30-
UJ
a; 20
10-
100
90
_ 80
-"70
2 60
a: 30
»
UJ
10-
160 1IJO
Illl Mill, I
l|llll| I l|llll[llll |.lll III ^III Illljll.. .jlllll. | l.l|l.ll|. • l.|.llljllll|.l . I
520 510 560 5iJO 600 620
M/e
, ..., ..
1 i ')' i '.J-1 I Q.1 i
0 660 680
720
'Tii'i'i'iii'i'i '~r ' I ' I ' r " i ' i ' I ' I i " '' i ' i '
800 820 810 860 880 900 920 9'l0 960 980 1000
M/e
3 HVFG EinRK GRL TLC DECflBROM
Figure 4.30. Mass spectrum of GFF-TLC Extract Obtained by Direct Probe.
-------
o
IOO-,
90-
80-
»-«
V70-
*— t
in 60-
ijj
^SO-
t-l
UMO-
rc 30-
— i
UJ
<* 20-
10-
ll !l
.Illl 1 ...il^ll.luiLI liUllu
.dill,!., .ili. ulilhL.^uj.^
-
~
-
.
-
1 ..li|inn .|i.iYip.,. | 1 | | 1 1 l"|""l"| 1 1 I"]""1' 1 ' 1 ' 1 ' 1 ' 1 ' l~r~l
ido 180 500 520 S<0 5(5fl 5^0 600 620
M/e
190-
qij-
On
OU -
• ^
•v." 70-
t —
en 60-
tlj
t;-,o-
i- ^
uj iio-
i i
U~ -10-
1
tu
"- 20-
10-
j
1
1
.1 'Hi. .1.1.1. .ill ill
T i 'I'l'i'J'l1]1! 1
f.lo 6CO 6BO 71)0 12
1
il .IE. ..., J.!
I
I ,
§1
it .in, Ji!i,L tiJJJ.t i,. i J Li
i( i~l f~t r 1 ' 1 ' j I \ i ' | * I i | i | i i i j i i r-j i i i 'i1 "t T^T i r1! ' 'r1 ' |"I'J '' '('" i i — i — TT i i
0 710 760 7HO 800 B20 n'lo B60 8BO 900 120 910 9 0 980 1000
M/e
DCCnBROMOBIPIIENYL ETHER
Figure 4.31. Mass spectrum of authentic Decabrom.
-------
was eluted and subjected to GC/MS/COMP. The GC/MS spectrum is shown in
Figure 4.32 along with the spectrum of authentic Tetrabrom.
Table 4.17. ANALYSIS OF HI-VOL FILTERS FOR DECABROM
Date
12/13, 14/76
12/16, 17/76
12/17, 18/76
Filter Type
GFFa
CFb
GFF
CF
GFF
CF
3
Decabrom (ng/m )
<13.3
<16.5
94.3
22.9
118
113
aGFF = glass fiber filter
CF = cellulose filter
4.2.2.3 Inorganics in Ambient Air
Chloride/Bromide and Chlorine/Bromine.--The results obtained by turbidi-
metric determination of total halide and halogen are given in Table 4.18.
The site, period and cycle designation were given in the sampling protocols
(Table 4.13) and the location on the schematic maps (Fig. 4.16-4.18).
Sampling was performed on two days yielding a total of three sets of
impinger samples. During Period 1, halides were detected at L4 (Fig. 4.16)
adjacent to the holding pond. During Period 2 halides were found at L2
(Fig. 4.17) downwind of the bromine extraction and ethylene dibromide
facilities. At 1304 to 1309 hours an upset occurred. At 1430 hours Cycle
4 for halides and halogens was initiated (Fig. 4.18). Both halides and
halogens were found in some of these samples. Neutron activation analysis
indicated low, but detectable, amounts of bromide in L3 and L4 (Table
4.19); however, the NAA bromine value for L2 is inconsistent with both the
orientation with respect to the meteorological conditions and of course the
halide and total halogen value. Cycle 6 which was taken four hours after
the upset showed the highest halide values at L3 and L4 (Fig. 4.18), but no
detectable halogens. Neutron activation analysis depicted no detectable
bromine or bromide at L3 which gave the highest total halide values. There
106
-------
o
(a)
',4ti
sj'i
-'-•••+ J.J-
I
:4l
"H- ••"M!'j'i-
wMJiJJ
i>— -^-A-o^jk.,.^ , , ,.4., ,-, , ill.. ,iL
latiCPOm'D SifflUMf KO
? CPLTIC. issf 10. \">n*a* -n.-t.i .•
(b)
Figure 4.32. Mass spectrum of (a) GFF-TLC extract and (b) authentic
Decabrom obtained by GC/MS/COMP.
-------
Table 4.18. CONCENTRATIONS OF HALOGENS AND HALIDES IN AMBIENT AIR SURROUNDING
'GREAT IARES CHEMICAL coRi>.a>b
Period
PI
P2
P3
P3
Cycle LI L2
C3 -C -
C3 <130 <65
C4 <79
C6
Cl2/Br2 Cl /Br
L3 L4 L7 LI L2 L3 L4 L7
<103 <62 - - - <65 53+8
<81 - - <90 140 + 0 <56
60 + 12 <67 183 +17 - - 186+4 137 +37 61 + 86
<77 <71 <94 - - 876 + 11 324 + 20 <61
Ma.., . ,3
o Values in yg/m .
co b
Determined by turbidity.
£>
Not analyzed.
-------
Table 4.19. CONCENTRATIONS OF BROMIDE AND BROMINE IN AMBIENT AIR
SURROUNDING GREAT LAKES CHEMICAL CORP.3'
Period
PI
P2
P3
P4
Cycle LI
C3
C3
C4
C6
Br2
L2 L3
<42
-
484 <24
<32
Br
L4 L7 LI L2 L3 L4 L7
- - <21 -
_______
<27 <16 - <17 28 26 <47
- - <" - -
values ±n yg/m .
By Neutron Activation Analysis.
Q
Not analyzed.
is some question about this value since ion exchange chromatographs showed
at least 80% of the halide at L3 was bromide. In addition, glass filters
and cellulose filters used in sampling cycles before and after the P3, C4
impinger sampling cycle showed high halogen concentrations at L3. There is
apparently a change in the prevalent species between Cycle 4 and 6 from
halogens to halide. More detailed studies should be required to verify
this change and determine its etiology.
Fluoride/Fluorine.--No fluoride or fluorine could be detected in any
samples taken of ambient air surrounding Great Lakes Chemical Corp. (Table
4.20). The limits of detection were 0.012 ppm in the impinger solution
based on the volume of air sampled and the sensitivity of the turbidimetric
method.
109
-------
Table 4.20. CONCENTRATIONS OF FLUORIDE/FLUORINE IN AMBIENT AIR
SURROUNDING GREAT LAKES CHEMICAL CORP.3'
Locations
Period
PI
P2
P3
P3
Cycle
C3
C3
C4
C6
LI L2 L3
<4.2
<5.4 <2.7 <3.4
<3.4 <2.4
<2.8
L4
<2.6
-
<2.7
<2.6
L7
-
-
<3.2
<3.9
3
Determined by ion specific electrode method.
Values in pg/m .
b
Acid Mist.--No titratable acid was found in any samples. Table 4.21
summarizes the upper limit of ambient air concentration of acid mist.
Table 4.21. ACID MIST IN AMBIENT AIR SURROUNDING
GREAT LAKES CHEMICAL CORP. AS H0SO.a
2. 4
Location
Period Cycle L3
PI C4 <45
P2 C5 <43
_
values in yg/m .
4.2.2.4 Organic Vapors in Ambient Air
Qualitative Analysis by High Resolution GC/MS/COMP.--Figures 4.33 and
4.34 depict the total ion current and ion chromatograms of organic volatiles
which were collected at L3 on the Great Lakes Corp. site (Fig. 4.18 for
sampling location). Several halogenated compounds were identified. They
were bromopropane, 1,2-chlorobromoethane, 1,2-dibromoethane, l-chloro-3-
bromopropane, bromoform and bromobenzene. The sampling location was on top
of a three-story facility which was not in operation and is normally used
110
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1 ' . ll
1 ' L' d,,J
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Mass Spectrum No.
Figure 4. 33-
Total ion current profile of ambient air sample from Great Lakes Corp. site,
El Dorado, Arkansas (P3/C1/L3) .
-------
3000-1
C
QJ
V-i
t-l
D
c
o
0)
•H
4-1
n)
i-H
OJ
Pi
3300
3350 3HOO 3HSO
1 T: t-
Mass Spectrum No.
Figure A.3A. Ion rJiromatograms of ambient air sample from Great Lakes Corp. site, El Dorado,
Arkansas (P3/C1/L3). BP = bromopropane, CBK = l-chloro-2-bromoethane, ED15 =
ethylene dibromide, CRT = 3-cbJoro-3-bromopropane, BF = bromoform, BB = bromobenzene.
-------
for the production of sodium bromide. Another sampling period was between
1740 to 945 hours (overnight) using a DuPont personal sampler. At L3
(ELV), EDB was clearly identified (Peak No. 34, Fig. 4.35 and 4.36). The
results corresponding to L5 (ELV) are depicted in Figures 4.37-4.38.
On the night of September 24, 1976, two DuPont personal samplers were
deployed on two water towers, one located in El Dorado and the second in
Parker's Chapel on Highway 15. Samplers were set to sample at ^110 ml/min/
cartridge during the 13 hour sampling period. The sampling period began at
approximately 0500 hrs.
Table 4.22 lists the volatile organics which were identified in ambient
air taken on the El Dorado city water tower. No halogenated compounds were
identified in this sample. Most compounds appeared to be from auto exhaust.
Figure 4.39 depicts the total ion current profile for this sample. Figure
4.40 represents the ion chromatogram for this ambient air sample. No
brominated compounds were detected.
Table 4.23 lists the volatile organics in the ambient air at the
Parker's Chapel water tower. Although we were unable to identify in the
sample any brominated compounds from full mass spectral interpretation, we
were able to detect them by mass fragmentography. Figure 4.41 depicts the
total ion current profile for this sample and Figure 4.42 depicts the ion
chromatograms. Allyl bromide, bromopropane and 1,2-dibromoethane were
clearly detected.
Table 4.24 summarizes the halogenated hydrocarbons which were identified
by GLC/MS/COMP in ambient air surrounding and in the vicinity of Great
Lakes Chemical Corp.
Quantification of Halogenated Hydrocarbons.--Table 4.25 presents the
concentrations of halogenated hydrocarbons surrrounding the Great Lakes
Corp. site. Also presented in this table are the concentration of allyl
bromide, 1- or 2-bromopropane and 1,2-dibromoethane which had been detected
in the ambient air samples taken on Parker's Chapel water tower. The
highest concentration observed were for 1,2-dibromoethane which reached a
3
level of 1,837 ng/m in a sample taken at Location 3 which was on the
sodium bromide production facility.
113
-------
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i«
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6S 67 1 J
Ml 123 ! 1 ol " 9J /
i/jUl'v^5|i)l'''0J1'jj',l'7 f| /'.l'\ V \ s
mrm|>i.T)n"l'"'|"rll""r''l""|'"Tl""|""r '"I"1 i" '(' ' i "V "i1" (' -'1 '"1 '"( '••'('"••""I'"'1"''!""1'" | ''
1 8 S 0 l"'ffiti 1 9 S U t' U u n ii li S i)
Figure A.35.
Mass Spectrum No.
Total ion current profile of volatile ambient air pollutants from Great Lakes
Corp. site, El Dorado, Arkansas (P3/C3/L3 ELV).
-------
Hill
3000-1
8000-
1 000-
_J
PFB PFT (eS)
AB-T
..|...,....(...,....|....,...rT
1650
«-^iv-A,.
*>
r-^\,.,..,.,
» 11 u ^^
.r^'Il^fi^ts^-^-.,-'^-" -••*-•"•'»"' •"-----^
V^JL
""I"T-'|'T'"| |...|r.-r~r^pT^;> IjtoTApfT
1700
1750
1600 leso t4oo
Mass Spectrum No.
I960
Jrfl^j'.^.^.H.I,..!.^,,.! | f [..
£' 0 S fi
Figure 4.36. Ion chromatograms of ambient air sample from Great Lakes Corp. site, El, Dorado,
Arkansas (P3/C3/L3 ELV). AB = allyl bromide, EDR = 1,2-dibromoethane.
-------
30000-,
4J
c
M
l-i
a
u
aoooo-
o
H
4J
(0
Pi
10000-
0-
1100
IN.'
1 ISO
r I i""'~r rr-rn" i r-
1200 1850
w^to
1300
1350 1400
87 'O
-,/A"
Figure 4.37,
Mass Spectrum No.
Total ion current profile of volatile ambient air pollutants from Great Lakes
Corp., El Dorado, Arkansas (P3/C3/L5 ELV).
-------
3000-1
1 150
iaoo
1 6 E 0
Mass Spectrum No.
Figure 4.38.
Ion chromatograms of ambient air sample from Great Lakes Corp. site, El Dorado,
Arkansas (P3/C3/L5 ELV). MB = methyl bromide, AB = allyl bromide, CBE = 1-chloro-
2-bromoethane, EDB = ethylene dibromide, BB = bromobenzene.
-------
Table 4.22.
VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR TAKEN ON
EL DORADO, ARKANSAS CITY WATER TOWERS
Chromato-
graphic
Peak No.
1
1A
2
3
4
5
6
6A
6B
7
7A
8
8A
9
9A
9B
10
10A
10B
IOC
10D
IDE
10F
10G
10H
101
10J
11
12
12A
13
13A
13B
14
15
ISA
15B
16
17
Elution
Temperature
44
44
46
47
47
48
50
51
52
54
54
55
56
57
57
58
61
64
65
66
66
67
68
68
69
71
72.
73
78
80
81
84
84
85
87
89
90
91
94
Compound
dichlorodif luoromethane
n— butane
acetaldehyde
isopentane
trichlorof luoromethane
acetone + C-H-i- isomer
dichloromethane + freon
113 (BKG)
ji-pentane
isopropanol
2-methylpentane
butenal isomer
3-methylpentane
ji-butanal
ii-hexane
chloroform
methylcyclopentane -f
perfluorotoluene (el)
C,H, , isomer
7 14
C.H,, isomer
/ 16
benzene
carbon tetrachloride
cyclohexane
2-methylhexane
2 , 3-dimethy Ipentane
3— methylhexane
n-pentanal
C-H, . isomer
7 14
n-heptane
aethylcyclohexane
C8H16 lsomer
C-H., „ isomer
C7H14 lsolner
C.H, . isomer
8 18
toluene
C-H,., isomer
0 lo
C8H18 I80mer
4-methyl-2-pentanone
ii-hexanal + 3-methylpen-
tanal
n-octane
(cont]
Chromato-
graphic
Peak No.
17A
18
19
20
21
22
23
23A
23B
24
25
25A
26
26A
27
28
28A
28B
28C
29
29A
3D
30A
31
31A
31B
32
33
34
35
35A
35B
36
37
38
39
40
41
42
43
44
tnued)
118
Elution
Temperature
95
95
98
101
103
105
107
108
109
110
111
111
112
114
TIC
X J. J
119
119
122
122
123
124
125
127
128
129
130
131
133
134
135
136
137
138
140
142
143
144
146
148
149
151
Compound
tetrachloroethylene
CpH, , isomer
0 ID
C-H, isomer
o 16
ethylcyclohexane
CgH^ isomer
ethylbenzene
£-xylene
C9H20 isomer
Vl8 iS°mer
C9H20 isomer
styrene + C-H,- isomer
2,3-dizethylpentanal
n_-heptanal
CQa „ isomer
isopropylbenzene
C9H18 + C1CH22 isomer
C10H20 is°ner
C10H12 1SOmer
C,,H-. isomer
11 24
CnH, „ isomer
9 18
benzaldehyde
Cj_H_2 + C,-alkyl benzene
isomers
C10H22 + C10H20 isomers
C11H24 1SOmer
C10H22 ls°mer
octanone isomer
ii-octanal
C10H20 is°mer
n— decane
C10H20 1SOmer
C10H20 i80mer
C11H24 I90mer
C. -H-, isomer
11 24
C11H24 ia°m"
^10H20 isomer
acetophenone
C11H24 i80mer
C11H24 i80mer
2-uonanone
n-nonanal
-------
Table 4.22 (cont'd)
Chromato-
graphic
Peak No.
44A
45
46
46A
47
48
Elucion
Temp.
(°C)
152
153
155
160
162
167
Compound
C H isomer
n-undecane
C.-alkvl benzene isomer
phenylpropenal isomer
dimethylphenol isomer
2-decanone
Chroma co-
graphic
Peak No.
49
50
50A
SOB
51
Elucion
Temp .
CO
169
171
172
173
173
Compound
n-decanal
n-dodecane
C., ^H_0 isomer
13 28
C, 0H_, , isomer
C10H16 isolner
aAmbient air sampled with DuPont personal sampler (ca. 110 ml/min) on
9/24-9/25/76 from 2000-900 hr.
119
-------
30000-
AJ
C
OJ
M
M
3
CJ
C
o a oo oo-
M
rH
0)
0
H
01
.H 10000-
4-1
tfl
0)
BJ
0_
93 0
1
HF'
0 9350
^
9400
9150
' ' ' *5l 5»/*«»
.^—y^ AA^-»_, . ' •-—.
KTl.mmrt.t|Kn]
-------
4-1
Curren
c
o
(-1
QJ
elativ
'• A
ifto(j
}
i
J
1 ' ' ' ' ' * '
9300 9350
w
A 1 Jx
II ' 'I
ill 1
\
^^*^^\X~** (•• A • * A
9400 945U 9500 9550 9bOO 9650 9700
lei
1 tO
Mass Spectrum No.
Figure 4.40. Ion chromatograms of ambient air sample from top of El Dorado city
water tower in Arkansas.
-------
Table 4.23. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR TAKEN ON
PARKER'S CHAPEL WATER TOWER NEAR EL DORADO, ARKANSAS3
Chromato-
graphic
Peak No .
1
2
2A
3
4
5
5A
5B
6
6A
6B
7
8
8A
9
10
10A
11
11A
12
12A
12B
12C
13
13A
14
14A
15
15A
16
16A
17
18
19
20
20A
21
21A
Elution
Temperature
45
47
47
48
49
49
50
50
51
52
54
55
57
57
58
59
59
62
63
64
65
66
66
67
67
68
69
69
70
71
72
72
73
73
75
77
79
80
Compound
butane + dichlorodif luoro-
methane
acetaldehyde
isopentane
trichlor of luorome thane
propanal + C.H g isomer
n-pentane
acetone
CJ.H..- isomer
dichlorome thane + fluoro-
trichlorome thane
isopropanol
C,H. . isomer
D 12
2-methylpentane
3-methy Ipentane
C,H isomer
o LL
hexafluorobenzene (eS)
n-hexane
chloroform
perfluorotoluene (e£)
methylcyclopentane
1,1, 1-trichloroethane
butanal isomer
C_H, , isomer
7 14
C,Hln isomer
D 1U
benzene
carbon tetrachloride
cyclohexane
C_H. , isomer
/ 14
2-methylhexane
2 , 3-dime thy Ipentane
3-methylhexane
methyl isopropyl ketone
dimethyl eye lopentane
isomer 4- pentanal
methylhexane isomer +
trichloroethylene
C_H, , isomer
7 14
ti-heptane
C.H. , isomer
/ 14
methylcyclohexane
C H isomer
o ID
/
Chrociato-
graphic
Peak No.
22
23
23A
24
24A
25
25A
26
26A
27
27A
28
29
29A
30
30A
31
31A
3 IB
31C
32
32A
33
34
35
36
36A
36B
36C
37
37A
37B
38
38A
39
40
Elution
Temperature
81
83
83
85
85
86
87
88
88
89
90
91
92
92
93
94
95
96
96
98
99
100
101
102
102
103
104
105
106
107
107
108
109
110
110
111
Compound
2,4-dimethylhexane
1,2, 3- trime thy Icy c lo-
pentane
C...H,, isomer
H ID
trimethy Ipentane isomer
C-H.. , isomer
o ID
toluene
2 , 3-dimethylhexane
2-methylheptane
4-methylheptane
3-methylheptane
l,trans-2-dimethylcyclc—
hexane
1, c is- 2-dime thy 1 cyclo-
hexane
C9H2Q isomer
hexanal
C-H,. isomer
o ±o
C~H., isomer
n-octane
tetrachloroethylene
C,H, , isomer
S ID
C0H,, isomer
o ID
C9H2Q isomer
s i lane c ompound ( BKG )
2,4-dimethylheptane
2-tnethyloctane or 2, 6-
dimethylheptane
ethylcyclohexane
C_H_n isoner
CgH, g isomer
trime thy Icy clohexane
isomer
C9H20 is°mer
ethylbenzene
trime thy Icy ciohexane
isomer
4-methyloctane
p_-xylene
C9H20 isoiner
m-xylene
3-methyloctane
122
-------
Table 4.23 (cont'd)
Chromato-
graphic
Peak No.
40A
40B
41
41A
42
42A
43
44
44A
45
45A
46
47
47A
48
49
49A
50
50A
51
51A
52
52A
53
54
55
56
56A
57
57A
57B
58
58A
59
59A
59B
60
60A
Elution
Temperature
112
112
113
114
115
116
117
118
119
120
120
121
122
123
123
124
125
125
126
127
127
128
129
129
130
131
133
133
134
135
136
137
138
138
139
139
140
140
Compound
styrene + CqH1ft isomer
dimethylpencanal (tent.)
isomer
o-xylene
n-heptanal
methyl ethylcyclohexane
isomer
C.H g isomer
n-nonane
C_H..,, isomer
C10H20 isoffier
isopropylbenzene
dimethyloctane isomer
tetramethylhexane isomer
C10H22 isomer
C10H20 is°raer
propylcyclohexane
Clf.H«.? isomer
C10H20 isomer
n-propylbenzene + benz-
aldehyde + C H isomer
C10H20 isomer
£-ethyltoluene
C1AH_0 isomer
m-ethyl toluene
C, n&jj isomer
C. ..H~ , isomer
11 24
C..H0, isomer
11 24
3-methylnonane
dimethyloctane isomer
C1 ^ H~, isomer
o- ethyl toluene
C H isomer
C1 1 H,,. isomer
n-decane
C,-alkyl benzene isomer
C, ., H- . isomer
11 24
C H isomer
1,2, 3-trimethylbenzene
C-TH,.. + C,-alkvl benzene
11 24 4
isomers
C _H^ , isomer
Chromato-
graphic
Peak So.
61
62
63
63A
64
64A
64B
64C
65
66
67
68
69
70
70A
71
71A
72
72A
73
73A
73B
73C
7 3D
73E
73F
Elution
Temperature
ro
141
142
143
144
145
145
146
146
147
148
149
149
150
151
151
152
153
153
154
155
157
163
165
170
173 .
191
Compound
C-. ,H_ . isomer
11 24
Cn «H isomer
iz zo
butylcyclohexane
C- oH^, isomer
C,-alkyl benzene isomer
C.. ?H,j,. isomer
n-butylbenzene + propyl-
toluene isomer
C.. 1 H7_ isomer
C12H26 isomer
C, ,H- , isomer
11 24
C,»H_. isomer
12 26
C,.H0, isomer
12 26
C^ . H,,_ isomer
C11H24 isomer
C12H24 isomer
C, ,H_- isomer
11 22
C11H24 isomer
nonanal
C11H22 isolner
n-undecane
C12H2' isomer
C, 0H_, isomer
IZ Zo
C, ^H_0 isomer
13 28
CT-H-, isomer
iz Zb
n-dodecane (tent.)
C15H32 isomer
Ambient air sampled with DuPont personal sampler (ca. 110 ml/min) on 9/24-9/25/76
from 2130-930 hr.
123
-------
3
O
o
H
0
0100
I I I ' ' ' I ' I • I I I ' I ' ' ' I ' I I I " I I I" I I I • I ' I " ' I" ' '"'' I"'1 I ' I I I I l-i-yi-T
0250 0300 03(0 0100 0160 OSOO
Mass Spectrum No.
Figure 4.41. Total ion current profile of volatile ambient air pollutants taken on
Parker's Chapel water tower near El Dorado, Arkansas.
-------
Ki
Ln
C
0)
C
O
•H
4.J
(J3btJ
Mass Spectrum No.
Figure 4.42. Ion chromatograms of ambient air sample from top of Parker's Chapel
water tower near El Dorado, Arkansas. AB = allyl bromide, BP =
bromopropane, and EDB = 1,2-dibromoethane.
-------
Table 4.24. HALOGENATED HYDROCARBONS IDENTIFIED BY GC/MS/COMP IN
AMBIENT AIR AT GREAT LAKES CORP., EL DORADO, ARKANSAS
Compound
Compound
Bromobenzene
Bromoethane
Bromofluoromethane (tent.)
Bromoform
l-Chloro-2-bromoethane
1-Chloro-3-bromopropane
1,2-Dibromoethane
1,3-Dichloropropane
Methyl Bromide
Methyl Chloride
Pentachloroethane (tent.)
Vinyl Bromide
126
-------
Table 4
HALOGENATED HYDROCARBONS IDENTIFIED AND QUANTITATED IN AMBIENT AIR SURROUNDING GREAT LAKES
CORP., EL DORADO, AK
N3
--J
Period/Cycle/Location
P3/C1/L1
L2
L3
L4
P3/C3/L4
L6 (ELV)
P3/C3/L3 (ELV)
L5 (ELV)
E.D., AK water tower
P.C., AK water tower
_b
8.4
-
-
T
8
-
2.5
-
24.8
_
20.7
60
-
-
-
-
25
-
"
1.9
9.6
15
-
T(?)
26.4
-
-
-
"
—
15.1
11.96
-
-
-
-
-
-
"
13.4
10.8
16.8
15.4
55
16
4
11.8
-
25.2
_
2.8
6.6
-
-
13
-
0.3
-
~~
_
-
23.7
-
-
-
T
T
-
—
_
-
-
T°
-
-
-
-
-
"""•
7.4
1,107
1,837
-
-
430
89
500
-
7.2
_
-
-
-
?
-
-
?
-
"~
_
-
-
-
-
-
-
7
-
—
['Refer to Table 4.13 for sampling protocol, values are in ng/m .
- = not detected
c
T = trace detected
-------
Estimation of Methyl Chloride, Methyl Bromide, Vinyl Chloride and
Vinyl Bromide.--None of these substances occurred at levels which were
quantifiable by GC/ECD or mass fragmentography. The LOD for methyl chloride
3
and methyl bromide was 200 and 120 |Jg/m , respectively, by GC/ECD. For
mass fragmentography the LOD was about 20 ppb.
Ethylene.--The levels of ethylene detected represented typical back-
ground levels as observed for all samples (Table 4.26).
Table 4.26. ETHYLENE LEVELS IN AMBIENT AIR
Site Period/Cycle/Location PPm
GRL
P1/C4/L5
P1/C4/L6
P1/C4/L7
1.20 + 0.10
0.90 + 0.10
0.90 + 0
4.2.2.5 Brominated Organics in Water, Sediment and Soil
The samples were screened by the VOA method for the presence of EDB
and other volatile brominated organics and selected samples were analyzed
for semi-volatile brominated organics. The results are summarized in Table
4.27. Confirming spectra for EDB and Tetrabrom are shown in Figures 4.43
and 4.44, respectively.
4.2.3 Michigan Chemical Corporation (Velsicol)
4.2.3.1 Sampling
The sampling protocol and sample descriptions for Michigan Chemical
Corp. are given in Table 4.28. The corresponding figure 4.45 designates
the sampling locations for September 21, 1976. Table 4.29 and Figure 4.46
present the protocol for April 7, 1977.
4.2.3.2 Survey of Chemicals on Glass Fiber and Cellulose Filters
Scanning Electron Microscopy (SEM) and Electron Microprobe (EM) Analy-
sis .--Samples consisting of three sampling periods, each 24 hours in length
were collected at the Michigan Chemical Corp. plant site. Glass fiber
filters (GFF) and cellulose filters (CF) were used in parallel sampling.
Both types of filter material were examined. Sufficient sample was concen-
trated on the surface of the GFF to permit direct analysis without the
usual carbon coating to prevent charge buildup on the sample.
128
-------
Table 4.27. RESULTS OF ANALYSIS OF SOIL, SEDIMENT AND WATER SAMPLES FOR BROMINATED ORGANICS—
SURVEY SAMPLING NEAR GREAT LAKES CHEMICAL CORPORATION, EL DORADO, AK
Ethylene Decabromo-
Period /Cycle/Location dibromide biphenyl ether
iype (wg/kg) (yg/kg)
P1/C1/L1 S/HHC ND 16,000a'b
(4/7/77) c d
W/HHC 22 ' ND
L2 S/HHC *C
W/HHC 620C'd NDC
L3 S/HHC *°
P2/C1/L1 SD/IIHC ND 19,OOQa'b'C
(4/22/77)
L2 W/HHC *
L3 SD/HHC ND
W/HHC ND
L4 W/HHC ND
Quantitated by gas chromatograpliy-mass spectrometry with
multiple ion detection (GC-MS-MID) .
Identity confirmed by direct probe-mass spectrometry.
o
Confirmed by gas chromatography-mass spectrometry in the
full scan mode.
Quantitation by gas chromatography-electron capture detec-
tion.
£
Scum on water.
letrabromo- .
, , . n , Polybrominated
bisphenol A ...
, ,, x biphenyls
(yg/kg) F '
»225,OOOa'b'C * (tent.)b
NDC
ND°
22,OOOa'b'C NDb'°
Key:
* = Identified but not quanti
tated
ND = not detected
S = soil
W = water
SD = sediment
HI 1C = for halogenated hydro-
carbon analysis
-------
Lo
O
1 Mi;.
90-
BM •
?(!-
to-;
5 O"
4 0 -
3 (.1
..,,!,|'!'"i'VTM..
SPEC It
LI1
i o 1:1
1:1 o
BTE.P
Figure 4.43. Gas chromatography/mass spectrometric analysis of volatiles purged from water
collected near Great Lakes Chemical Corp., El Dorado, Arkansas (P1/C1/L2) -
mass spectrum of ethylene dibromide.
-------
POCK II?
y'fi
iiU|
.:fin
j^^il^iuiM^
i... nvioi • i
i!i
i. ,>',
Figure 4.44. Mass spectrum of soil extract (P1/C1/L1) exhibiting Tetrabrom.
-------
Table 4.28. SAMPLING PROTOCOL FOR MICHIGAN CHEMICAL CORPORATION, HIGHWAY 167, EL DORADO, ARKANSAS
Period Cycle Location
9/21/76 Cl LI
L2
L3
LA
C2 L2
L3
LA
L4 (ELV)
L5 (ELV)
C3 LI
M L2
£ L3
LA
C4 LI
L2
L3
L4
1.3
L4
L5
LI
L2
L3
LA
Sampling
Time
11AO-1415
1140-1411
11AO-1415
1140-1415
1140-1614
1140-1614
1124-1625
1120-1625
1105-1742
1419-1513
1415-1513
1415-1513
1415-1513
1516-1614
1513-1614
1516-1614
1516-1614
1335
1330
1340
1335
1330
1330
1343
Sampling
Volume (ft)
130
123
171
175
_
_
-
-
-
48
30
59
58
93
107
93
91
0.28
0.28
0.28
1
1
1
1
Meteorological Conditions
Type of Wind Dlr./
Sample T (°C) % RU Speed (luuph) Other
HIICa
HHCa 27-30 56 350°/8-010'/8 Clear, slightly
cloudyd
HHCa 31 Clear, odor of
H2S + Bra
MIC* d
HHCb 29 358/8 Clear4
HHCb 31 d
HIICb d
HI1CC
HHCc
F, CBN, CBD Br2 plume visible
F, CBN, CBD
F, CBN, CBD Clear, odor of Br2
F, CBN, CBD
AM
AM
AM 31 Clear, odor of Br2
AM
VAC
VAC
VAC
TED
TED
TED
TED
(continued)
-------
Table 4.28 (cont'd)
Meteorological Conditions
Period
9/21/76
Cycle Location
C4 LI
L2
L5
L6
Sampling
Time
1510
1548
1548
1600
Sampling
Volume (I)
0.28
0.28
1
1
Type of
Sample T (°C) 2 RH
VAC
VAC
TED
TED
Wind Dlr./
Speed (kroph) Other
North Uest/11
u>
U)
Nutech Model 220 sampler 3-6 ft elevation
Dui'imt sampler 3-6 ft elevation
OuFont sampler li-18 ft elevation
dBr. emission visible at 1408
Locations ahoun In figure 37.
Key to Sample Type:
HIIC - Halogenated Hydrocarbon
F - Fluoride and Fluorine
CBN - Bromine and Chlorine
CUD - Bromide and Chloride
AM - Acid Mist
TED - Tedlar bag
VAC - Aluminum Vacuum Can
-------
MICHIGAN CHEMICAL CORP E.D.
APPROX. SCALE 1 cm = 110
m
Figure 4.45.
Schematic map of Michigan Chemical Corp.,
El Dorado - sampling locations for Pl-
9/21/76.
A = Br facilities
B = EDB facilities
134
-------
Table 4.29. SAMPLING PROTOCOL FOR MICHIGAN CHEMICAL CORPORATION,
EL DORADO, ARKANSAS
Sample
Period Cycle Location Size
PI Cl LI 2 cores3
4/7/77 2 cores
1 5
— c
L2 2 cores
2 cores
i a
c
Type of Sample
SHHC-V
SHHC-SV
WHHC-V/SV
VHHC-V
VHHC-SV
SHHC-V
SHHC-SV
WHHC-V/SV
VHHC-V
VHHC-SV
Core ^ 5 cm diameter, 13 cm.
Water was collected from standing puddles.
'Needles stripped from 40 cm of pine bough sampled ^5 m above ground
from trees showing damage.
Key to sample type:
SHHC - soil for halogenated hydrocarbons
WHHC - water for halogenated hydrocarbons
VHHC - vegetation for halogenated hydrocarbons
SEHHC - sediment for halogenated hydrocarbons
SCHHC - scum on water for halogenated hydrocarbons
MHHC - milk for halogenated hydrocarbons
V - for volatile organic analysis
SV - for semi-volatile organic analysis
135
-------
Figure 4.46.
Schematic map of Michigan Chemical Corp,
sampling locations for 4/7/77.
136
-------
Initially a search for the presence of bromine and its potential for
mapping was made. In Figure 4.47, the EM spectrum from this site was
expanded for greatest sensitivity in the bromine region. Traces were
detectable when compared to the background in Figure 4.47. These traces
were not sufficient, however, to produce an elemental map.
Electron microprobe maps for chlorine, sulfur, aluminum, and silicon
are shown in Figures 4.49-4.52 along with the SEM map of the region (Fig.
4.48) for the cellulose filter from Michigan Chemical Corp. The spectrum
(Fig. 4.48) depicted a higher chlorine peak than sulfur peak, the reverse
of what was observed for Great Lakes Chemical Corp. In addition, aluminum,
silicon and calcium are above background levels. This region was micrograp-
hed (Fig. 4.53) and mapped for chlorine, sodium, sulfur, calcium, silicon
and aluminum. There was a significant substantial coincidence for sodium
and chlorine, calcium and sulfur, but very little for silicon and aluminum
(Fig. 4.54). Another region of the sample was carbon coated, and in this
region there was almost no chlorine, but substantial amounts of calcium and
sulfur appeared together. Many silicon particles appeared, but the majority
are unassociated with aluminum.
Neutron Activation Analysis.--Samples of airborne particulates which
had been collected by the State of Arkansas Air Pollution Control Division
using a Hi-Vol sampler were examined by neutron activation for the presence
of halogens, halides, etc. A segment of each filter was submitted to
neutron activation analysis. The segment was 2 x 3 cm, cut from the median
fold with the distal edge of the segment 3 cm from the filter edge. The
results of the neutron activation analysis are shown in Table 4.30. On the
third day of sampling the highest concentration of bromine and chlorine
were observed for both types of filters used. The analysis of these samples
for the presence of brominated organics is discussed under Section 4.2.3.5.
Gas-Liquid Chromatography/Electron Capture.--The Hi-Vol filters which
were used in sampling at the Michigan Chemical Corp. site were analyzed for
trig-(2,3-dibromopropyl)phosphate. Two by five cm segments from the central
portion of the filters were cut out. Filter segments were placed in silani-
zed 3 dram vials and extracted with 5 ml of acetone for two hours on a
reciprocal shaker at approximately 120 cycles/min. These extracts were
137
-------
0X10^03
US« IK
40 KEU
LK 2-35 BR
374460 INT
20 EM AB
t 0 1
a*-
Figure 4.47.
Electron microprobe spectrum of a 24 hr Hi-Vol glass
fiber filter air sample taken at (a) Michigan Chemical
Corporation, El Dorado, Arkansas on 12/22/76 - 12/23/76,
Volume sampled 2603.6 m^ air; (b) Great Lakes Chemical
Corporation, El Dorado, Arkansas on 12/17/76 - 12/18/76,
Volume sampled 2,733.6 m3 air.
138
-------
1200 x
Figure 4.48.
1200 x
Electron microprobe spectrum (a) and scanning electron
micrograph (b) of a region on an air sample collected on
a cellulose filter. Sample Volume: 1463.9 m3 air.
Location - Michigan Chemical Corp., El Dorado, Arkansas.
Collected 12/22/76 - 12/23/76.
139
-------
1200 x
1200 x
Figure 4.49. Electron microprobe element map of region shown in Figure
4.48.
(a) Chlorine map; (b) Sodium map.
140
-------
1200 x
1200 x
Figure 4.50. Electron microprobe element map of region shown in
Figure 4.48.
(a) Sulfur map; (b) Calcium map.
141
-------
300 x
300 x
Figure 4.51. Electron microprobe element map of region shown in
Figure 4.48.
(a) Calcium map; (b) Sulfur map.
142
-------
1200 x
1200 x
Figure £.52. Electron microprobe element map of region shown in
Figure 4.48.
(a) Silicon map; (b) Aluminum map.
143
-------
300 x
300 x
Figure 4.53.
(a) Scanning electron micrograph of a region on an air
sample collected on a cellulose filter. Sample Volume:
1463.9 m^. Location - Michigan Chemical Corp., El Dorado,
Arkansas. Collected 12/22/76 - 12/23/76; (b) Electron
microprobe chlorine map of the region shown in a.
144
-------
300 x
300 x
Figure 4.54.
Electron microprobe element map of region shown in
Figure 4.53.
(a) Aluminum map; (b) Silicon map.
145
-------
Table 4.30. NEUTRON ACTIVATION ANALYSIS OF AMBIENT AIR HI-VOL SAMPLES
Site
MIC3
MIC
MIC
Date
12/19/76-
12/20/76
12/21/76-
12/22/76
12/22/76-
12/23/76
Medium
GFFb
CFC
GFF
CF
GFF
CF
Br (yg/m3)
2.05
0.18
0.16
0.16
6.23
19.6
Cl (pg/m3)
0.91
0.062
0.37
0.31
28.25
8.25
a
All were 24 hr samples.
GFF = glass fiber filter.
CCF = cellulose filter.
analyzed by GLC/ECD. The resulting chromatogram for one such sample is
shown in Figure 4.55, along with the standard. The chromatograms were
surprisingly free of interferences using the described conditions. An
evaluation of the completeness of extraction was performed for both glass
fiber filter samples and cellulose filters. A second extraction with a
fresh 5 ml portion of acetone was performed. The recoveries of 20 and 10%
in the second extract for glass fiber and cellulose filters, respectively,
are consistent with solvent holdup of each filter. Extraction efficiency
was greater than 90% for a single extraction.
The results of the GLC/ECD analysis were negative for TRIS in samples
collected from 12/18/76-12/22/76; however, 70 + 0.12 ng/m3 and 50 + 0.11
3
ng/ m of TRIS were found on glass fiber filter and cellulose filter,
respectively, collected from 12/22/76-12/23/76. These must be regarded as
minimum values since collection efficiencies and recoveries have not been
vigorously established for Hi-Vol filters. The determinations reported
above were replicates performed on two days on a different segment of the
filters.
GLC/MS/COMP.--Confirmation of the presence of TRIS was achieved by
GLC/MS using multiple ion detection. The chromatograms of an extract and a
TRIS standard are shown in Figure 4.56 and the peak areas of the selected
ions are given in Table 4.31.
146
-------
Pulse » 100fi sec
Attenuation = 64 x 10'' ' afs
Column
,-11
42 x 0.2 cm
3% SE - 30 on
100/120 mesh
Chromosorb W (HP}
30 cc/min
Time (min)
Figure 4.55.
Gas liquid chromatography/electron capture detection ( Ni)
of (a) an acetone extract of the Hi-Vol glass fiber filter
sample collected 12/22/76 - 12/23/76 at Michigan Chemical
Corp., El Dorado, AK; and, (b) a TRIS standard (0.8 ng).
147
-------
80.0-
60. Q-
4C . 0-
- - 4 1 5 X I
.' ; 61 7X1 " '-337X1 \
'-••-'•.-21 9 X 1
FILE F! tiC. IS
TP 1 ?.- 1 r 1G -TIL, 3:'SE~rJ, 22D < C .
o.e-
~ C> ['
GO . U
6E.O-
4Q.C-.V
' ..417X2
.'619X3 .
-•. 219X1
. .
•••••"•••••••••.•-'•337X2
Figure 4.56.
F!uE El HO. 11
IHVFG-M IC-E: :TR . 2. -BCZO , 220 (-, -9.2.41 ;v. -JIICL . FEE i r
Gas chromatography/mass spectrometry analysis with
multiple ion detection of (a) TRIS standard and, (b)
extract of Hi-Vol glass fiber filter sample collected
at Michigan Chemical Company 12/22/76 - 12/23/76.
148
-------
Table /.. 31. PEAK AREAS AND RATIOS OF SELECTED IONS OBTAINED FROM ANALYSIS OF TRIS BY
GAS CHROMATOGRAPHY-MASS SPECTROMETRY IN MULTIPLE ION DETECTION MODE
Ratio of m/e Values
„ . i a
Sample m/e
TRIS standard 217
219
335
337
415
417
617
619
-£•• Extract of Hi Vol 217
sample collected 219
at Michigan Chemi- 335
cal Co. , 12/22/76- 337
12/23/76 (C.F.F.) 415
417
617
619
RT
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
(min)b
.69
.68
.69
.63
.68
.68
.71
.61
.56°
.61
.46
.44
.48
.48
.43
.46
Peak Area
1150
1063
1J4
219
37
103
08
09
2059
1888
413
837
144
389
36
36
.78
.84
.98
.62
.60
.72
.72
.46
.92
.80
.10
.44
.92
.50
.60
.74
Background Observed
05
04
0.1
01
00
Ot
00
00
26
31
LO
09
07
1)6
03
03
.18
.54 '
.34
.14 '
.90 ,
.00
.88 ,
.84 }
.44 ,
.54 '
.30 ,
.58
.38
.06 '
.46 ,
.44 '
1
0
0
.08
.52
.36
0.91
1
0
0
1
.09
.49
.36
.00
Pi e
1
0
0
1
1
0
0
1
dieted
.01
.51
.34
.02
.01
.51
.34
.02
Ratioed
217/219
335/337
415/417
617/619
217/219
335/337
415/417
617/619
b)
c)
These m/e values were selected as most characteristic of TRIS.
Retention time on gc column (3% SE-30 on Supelcoport 100/120 mesh; 42 x 0.2 cm col; Tool = 220; flow rate
30 ml/min.
Slight variation in retention time represents day to day variation as the retention time for an extract run on
the same day was 4.76 + 0.08 min.
-------
4.2.3.3 Inorganics in Ambient Air
Chloride/Bromide and Chlorine/Bromine.--The results obtained by turbi-
diraetric determination of total halide are given in Table 4.32. The site,
period and cycle designation were given in the sampling protocol (Table
4.28) and the locations on the schematic maps (Fig. 4.45).
Table 4.32. CONCENTRATIONS OF HALOGENS AND HALIDES IN AMBIENT AIR
SURROUNDING MICHIGAN CHEMICAL CORP. (VELSICOL)3'
Species
Cl0/Br_C
2 2
Br d
c
Cl /Br
d
Br
Locations
LI L2
300 + 99 293 + 280
<42 <68
<69 300 + 110
<21 <34
L3 L4
<80 <82
<17 <35
<56 <57
35 50
*a
Samples are from P1/C3.
Values are in yg/m .
°By turbidity.
By neutron activation analysis.
At Michigan Chemical Corp., detectable quantities of halogens were
found at LI (downwind from the holding pond) and L2 (Fig. 4.45). Detectable
quantities of halide were found at L2 only. Comparable data for bromine
obtained by neutron activation analysis (Table 4.32) indicate the predomi-
nant element is probably chlorine and/or chloride. Neutron activation
analysis performed on cellulose filters (acid mist) used in sampling imme-
diately following the impinger sampling showed significant amounts of
bromine collected at L3 and L4.
Fluoride/Fluorine.--No fluoride or fluorine could be detected in any
samples (Table 4.33). The limits of detection were approximately 0.012 ppm
in the impinger solution based on the volume of air sampled and the sensiti-
vity of the turbidimetric technique.
150
-------
Table 4.33. CONCENTRATIONS OF FLUORIDE/FLUORINE IN AMBIENT AIR
SURROUNDING MICHIGAN CHEMICAL CORP. (VELSICOL)3'
Locations
Period Cycle LI
PI C3 <4.2
L2 L3 L4
<6.7 <3.2 <3.1
aT 3
Determined by ion specific electrode.
Acid Mist.--No titratable acid was found in any sample. Table 4.34
summarizes the upper limit of ambient air concentration of acid mist.
4.2.3.4 Bromine and Brominated Organics in Brine
Neutron Activation Analysis.--Table 4.35 lists the concentration of
bromine (molecular plus halide) in brine samples. A reduction of 90% of
the bromine concentration was observed between the front and tail brine.
Significant quantities of bromine were still detected in the tail brine
samples. However, the technique of neutron activation did not distinguish
whether the bromine is present as molecular bromine, bromide ion or bromina-
ted organics. Furthermore, the number of bromines per organic molecule
could not be delineated by this technique. The importance of these results
is primarily attributed to the presence of substantial quantities of "bromine"
even after bromine extraction.
GLC/MS/COMP Analysis for Volatile Organics.--Volatile halogenated or-
ganics were recovered from water using previously described methods (Appen-
dix A). Figures 4.57 and 4.58 depict the total ion current chromatograms
for the volatile organics which were observed in front and tail brine
samples. The unequivocal identification of benzene and toluene was establi-
shed in Michigan Chemical Corp. front brine sample (Fig. 4.57). In the
tail brine sample (Fig. 4.58) from the same site we identified bromodichloro-
methane (Fig. 4.59), toluene, dibromochloromethane (Fig. 4.60) and bromoform.
The halogenated and other organics which were identified and quantitated
in brine samples from Michigan Chemical Corp. are shown in Table 4.36. The
151
-------
Table 4.34. ACID MIST IN AMBIENT AIR SURROUNDING
MICHIGAN CHEMICAL CORP. AS H0SO.a
z 4
Locations
Period Cycle LI L2 L3 L4
PI C4 <50 <44 <50
values as yg/m .
Table 4.35. CONCENTRATION OF BROMINE IN BRINE SAMPLES
Site Sample Type yg Br/ml
Michigan Chemical Corp. Front brine 6421.5
Tail brine 645.8
152
-------
Ul
OJ
3 0 0 0 0 -
c
Q)
M
3
U
a
o
n)
4-1
o
H
E 0 0 0 0 -
1 0 0 0 0 -
0--
/—
35 00
-
" |""i"T"i""|""'"
3550
3600
r^r-n
3700
3650 3700 37EO
Mass Spectrum No.
3SOO
lr""T'r"
385 V
3900
Figure 4.57- Total ion current profile of volatile organics in front brine sample from Michigan
Chemical Corp. Peak No. 4 = hexaf luorobenzene (eS) , 5 = perfluorotoluene (eS) •;
7 = benzene and 9 = toluene.
-------
3 (i 0 0 G -i
C
Q)
!-i
t-i
CJ SOOOO-
C
o
o
H
i o n D [i -
Ln
»[i 0 0
4050
TT"i""r"r|"T"1""1""1""1 ...... '"I ......... '""'""I ......... I" ....... l""1""1" ....... l""'""l ......... '""'""'' ........ |m'""1 ......... 1""'""1 ......... 1 ......... 1 ......... '"" ..... I""'""1 ......... i""'""1 ...... '"! ........ 'fT"
4100 M150 4800 4250 4300 4350
4400
Mass Spectrum No.
4450
Figure 4.58.
Total ion current profile of volatile organics in tail brine sample from Michigan
Chemical Corp. Peak No. 2 = hexafluorobenzene (eS), 3 = perfluorotoluene (e$),
5 = benzene, 6 = bromodichloromethane, 8 = toluene, 9 = dibromochloromethane,
and 10 = bromoform.
-------
Ul
1 00-;
9 0 -;
r.o-1
W :
•^ ?o-^
0) :
C S
|.._j ;
EO-;
(U :
•H 4 0 _ j
•i-J ;
"oJ 3 0 -j
jjo-i
;
1 CI -1
0 --
. \f JJ!l»Jll
i.^-ji
50
N j.
100 150 V. 0 0 £ ? 0 3 0 0 3
m/e
Figure 4.59. Mass spectrum of bromodlchloromethane in tail brine sample
(MCI). Peak No. 6 in Figure 4.58
-------
Ln
ON
100-j
90-1
•H =
s ro^
c fctl i
M :
Q) tO -I
•H 1
5 ""I
01 -,t| J
EO-j
•
1 0-[
1
. f 1 7 1
i.,, ar,_,
iii
i i i i | i | i , i i | i | i i i | i | i | i | i | i | i r ' i i f • i i i '
100
- I ti
1 E 0
i? 0 0
m/e
Figure 4.60- Mass spectrum of dibromochloromethane in tail brine sample
(MCI). Peak No. 9 in Figure 4.58.
-------
Table 4.36. HALOGENATED AND OTHER ORGANICS IDENTIFIED AND QUANTITATED IN
BRINE SAMPLES FROM MICHIGAN CHEMICAL CORP.3
Compound
Methyl Chloride
Bromof orm
Bromodichloromethane
Dibr otno chlorome thane
Hexaf luorobenzene (eS)
Perf luorotoluene (eS)
Toluene
Benzene
Front brine
5.3
8.0
6.7
1.3
1,120
240
Sample Type
Tail Brine
N.D.
752
52
800
3,200
120
Concentrations are in ppt.
el = external standard, 200 ng.
concentrations of bromoform, bromodichloromethane and dibromochlororaethane
were observed to increase significantly after the brine passed through the
bromine extraction process.
4.2.3.5 Organic Vapors in Ambient Air
Qualitative Analysis by High Resolution GLC/MS/COMP.--Table 4.37 lists
the volatile organics which were identified in ambient air taken from the
Michigan Chemical Corp. site. This sample represents the sampling location
upwind from the bromine extraction and organic synthesis facilities. The
compounds listed in this table are representative of the many components
that are generally found in ambient air with the primary contribution from
fossil fuel and its combustion. Several halogenated compounds, for example,
dichlorodifluoromethane, trichlorofluoromethane, dichloromethane, chloroform,
1,1,1-trichloroethane, carbon tetrachloride and methyl chloride are commonly
found as background compounds in ambient air samples taken throughout the
Continental United States. Figures 4.61 and 4.62 depict the total ion
157
-------
Table 4.37. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
MICHIGAN CHEMICAL CORPORATION SITE, EL DORADO, ARKANSAS
(Pl/Cl/Ll)a
Chromato-
graphic
Peak. No.
1
2
2A
IS
3
3A
4
5
5A
5B
5C
6
6A
7
7A
7B
3
3A
SB
9
9A
10
10A
11
11A
11B
11C
11D
HE
12
12A
13
13A
14
15
16
16A
17
18
Elution
Temperature
CO
40
41
42
43
44
46
46
47
47
43
48
49
53
54
54
55
55
56
56
57
57
59
61
62
64
65
66
66
67
67
63
69
70
72
77
78
83
85
Compound
CO,
dichlorodifluoromethane
chlorome thane
1-butene
acetaldehyde
is op en t an e
trichlorof luorome thane
propanal + n-pencane >
fur an
C-H0 isomer + acetone
3 3
dimethyl ether + diethyl
ether (tent.)
dichlorome thane
freon 113 (BKG)
2-methylpropanal
2-methylpentane
crotonaldehyde
vinyl acetate (tent.)
3-methylpentane
n-butanal
methyl vinyl ketone
methyl ethyl ketone +•
methylfuran isomer
n-hexane
chloroform
C,S, - isomer
6 12
methylcyclopentane
1, 1, 1-trichloroethane
3-methylbutanal
benzene
carbon tetrachloride
cyclohexane
2-methylhexane
2, 3-dimethylpentane
3-me thylhexane
C-H, , isomer
n-pentanal
^-heptane
methylcyclohexane
C.H., isomer
O Lo
toluene
c3Hia I30mer
Chromato-
graphic
Peak tfo.
19
19A
20
20A
21
2U
22
22A
23
24
25
26
26A
26B
27
27A
28
29
29A
30
30A
31
32
32A
33
33A
34
34A
35
35A
36
37
37A
38
39
40
41
42
43
47
Elution
Temperature
CO
87
88
89
90
92
97
98
99
100
103
105
106
107
108
110
111
113
120
120
121
123
125
127
129
129
130
132
135
133
141
142
144
147
149
151
162
164
166
168
139
Compound
CaHia isomer
o io
C-H,, isomer
a 10
o_-hexanal
C.Hj, Isomer
n-oc cane
C.H,_ isomer
C-H,,.. isomer
C_H,, isomer
CgH,0 isomer
ethylbenzene
£-xylene
CgHj.. isomer
C,a,0 isomer
styrene
n-heptanal
CgH^g isomer
n-nonane
C10H22 l30mer
C10H16 i30n;er
benzaldehyde
C.j-al'«cyl benzene isomer
C10H22 lsomer
C10H22 i30mer
C^-alkyl benzene isomer
n-octanal
C, ,-H-.. isomer
10 20
n-decane
1,2,3-trlmethylbenzene
C11H24 isomer
C.-alkTl benzene
4
acetophenone
C11H24 i30iner
unknown
Cj.H,- isomer + n_-nonanal
n-undecane
diethyl phthalate
decanone isomer
C12H24 l30mer
n_-dodecane
n_-tridecane
See Table 4.28 for sampling protocol.
158
-------
30000-
4-1
c
0)
J^J O JOOOO-
* c :
0
M
rH
tfl
4-1
O
H
•H
4-J
CD
rH
-------
3000-
c
0)
t-1
h
3 eooo-
o
d
o
•H
4-J
0)
cri
1000-
t o«
BF
BDCM
BH
UI)CM
EUB
ISA
£00
300
3SO
HSO
SSU
Mass Spectrum No.
Figure 4.62.
Ion chromatograms for ambient air sample from Michigan Chemical Corp.' site,
El Dorado, Arkansas (P1/C1/L1). BF = bromoform, BP = bromopropane, EDB =
ethylene dibromide, BDCM = bromodichloromethane.
-------
current profile and ion chromatogram generated by the GLC/MS/COMP system of
the volatile ambient air pollutants which were identified in Table 4.37.
The relative total ion current axis is fully attenuated to allow the compari-
son of overall intensity of the pollution profiles.
In Figure 4.62 ion chromatograms are depicted for the ambient air
sample taken from the upwind location at Michigan Chemical Corp. The ions
chosen - m/£ 85, m/e 109, m/e 124, m/e 129 and m/e 173 - correspond to
bromodichloromethane (BDCM), ethylene dibromide (EDB), bromopropane (BP),
bromodichloromethane (BDCM) and bromoform (BF), respectively.
Table 4.38 lists the volatile organics identified in ambient air
sample taken at L2 on the Michigan Chemical Corp. site. The sampling
location in this case was on the bank of the pond and downwind from the
spent brine pond, but upwind from the bromine extraction and organic synthe-
sis facilities. During the entire sampling period, the wind direction was
toward the main plant facility. Dibromochloromethane and bromoform were
identified. Figure 4.63 depicts the total ion current profile of the
volatile ambient air pollutants listed in Table 4.38. Figure 4.64 shows
the ion chromatograms for m/e^ 186, m/e 173, m/e 129 and m/e 124. In this
figure the peaks which correspond to DBCM and BF are marked.
Table 4.39 lists the volatile organics which were identified at L3 on
the Michigan Chemical Corp. site. In this sample, bromomethane, a chloro-
bromopropene isomer, 1,2-dibromoethane, and 1,l-dibromo-2-bromochloropro-
pane were identified. Figure 4.65 represents the profile of the volatile
ambient air pollutants which were listed in Table 4.39. The relatively
large peaks (46 and 47) which appeared in this chromatogram could not be
identified, however, based upon the mass spectra of these two chromatographic
peaks, it was concluded that they did not contain halogen. A series of ion
chromatograms for Figure 4.65 is shown in Figure 4.66. The ions at m/e
186, m/e 109, m/e 157, m/e 85 and m/e 124 represent the external standards,
perfluorobenzene and perfluorotoluene, and 1,2-dibromoethane, dibromochloro-
propane, bromodichloromethane and bromopropane, respectively. The identities
of the components of a sample taken at L4 are given in Table 4.40. The
relationship of this location to the brine ponds, bromine extraction, and
organic synthesis facilities is shown in Figure 4.45. In this sample we
161
-------
Table 4.38. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
MICHIGAN CHEMICAL CORPORATION SITE, EL DORADO, ARKANSAS
(Pl/Cl/L2)a
Chroraato-
graphic
Peak Mo.
1
1A
IB
1C
ID
IE
2
2A
23
2C
3
3A
4
4A
5
5A
5B
5C
6
5A
7
7A
8
8A
3B
9
9A
10
10A
10B
IOC
11
11A
11B
12
13
14
15
16
17
17A
13
19
Elution
Temp . Compound
39
40
41
41
42
44
45
46
46
47
47
48
48
51
52
53
54
54
55
56
56
57
59
60
61
63
64
65
66
67
63
69
70
71
71
76
• 78
33
35
30
87
89
91
CO,
dichlorodifluoromethane
chloromethane
1-butene
£-butane
acetaldehyde
trichlorofluorome thane
C.H.Q isomer
C.Hg isomer
isopentane
acetone +• dinethyl ether
+ diethyl ether (tent.)
dichlorome thane (tent.)
freon 113 (BKG)
n_-pentane
2-nethylpentane
2-methylpropenal
3-methylpentane
n-butanal
hexafluorobenzene (el)
n-hexane
chloroform
methyl ethyl ketone
perfluorotoluene (ei)
methycyclopentane
1,1, 1- trichloroethane
benzene
carbon tetrachloride
2-methylhexane
2,3-dimethylpentane
3-methylhexane
C-H, , isomer
3-methylbutanal •*• C-H. ,
Isomer
bromodichlorome thane
n_-pentanal
n-heptane
methylcyclohexane
4-methyl-2-pentanone
toluene
C8H18 i30mer
dibromochloronie thane
C-H, , isomer
o 10
n-hexanal 4- C0H,, isomer
-~ o 10
n-octane
Chromato-
graphic
Peak Ho.
19A
19B
20
20A
21
21A
21B
22
22A
23
23A
23B
24
24A
24B
25
25A
26
27
23
29
29A
30
30A
31
31A
31B
32
33
34
34A
34B
35
35A
36
37
37A
38
38A
39
40
40B
40C
Elution
Temp.
(°C)
92
93
102
103
104
105
106
107
108
109
110
111
112
116
118
120
121
121
123
125
127
129
130
131
132
134
135
137
142
144
145
147
149
150
151
154
155
156
160
177
179
185
188
Compound
tetrachloroethylene
C-Hj, isomer
ethylbenzene
C9H20 I30ner
£-xylene
bromoforn
C.H-Q isomer
C9H2Q isomer
styrene
o_-xylene
C9H18 ls°ner
hep canal
n.-nonane
C10H22 l30mer
C10H2Q isomer
C1QR22 isomer
CQH, - isoaer
7 ia
benzaldehyde
p_-e thy 1 toluene
C10H2, isomer
C10H22 * V311
isomera
methylheptanal
n_-octanal
C10H20 + C3-a"
isomers
n-decane
C11H24 lsomer
cyL benzene
tsoraer
cyl benzene
C,-alkyl benzene isomer
C11H24 i30ner
acecophenone
cresol isomer
C11H24 isoIDer
C11H22 l30mer
n_-nonanal
C..H2- isomer
n-undecane
C12H26 iaomer
cioa:6 lsomer
dimechylphenol
^12^26 l3omer
C..H,, isomer
C.,H,0 iaomer
1J &o
C.,H,g isomer
C14H30 l30mer
iaoner
See Table 4.27 for sampling protocol.
162
-------
30(100-1
Mass Spectrum No.
Figure 4.63. Total ion current profile of volatile ambient air pollutants from Michigan
Chemical Corp. site, El Dorado, Arkansas (P1/C1/L2).
-------
6000-
c
(U
)-l
3
u
01
•H
•U
cfl
1000-
»"i""i""i""ri"T i
0
fc£0
.
1)11 CM i
!lF
1
?UO 750 bull (fbu 9GU
...... (....,...,..
*Cu
.,,..:...r,.T. , .,...,. ...,.., ,i i
1 UU 0 I O'.i li
Mass Spectrum No.
Figure 4.64. Ion chromatograms for ambient air sample from Michigan Chemical Corp. site,
El Dorado, Arkansas (P1/C1/L2). BF = bromoform, DBCM = dibromochloromethane.
-------
Table 4.39. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
MICHIGAN CHEMICAL CORPORATION SITE, EL DORADO, ARKANSAS
(Pl/Cl/L3)a
Chromato-
graphic
Peak No.
1
LA
IB
2
2A
3
4
4A
5
5A
5B
6
6A
6B
7
7A
3
9
10
11
11A
12
14
14A
14B
15
15A
16
16A
17
17A
18
ISA
13B
19
20
21
22
22A
22B
23
23A
Elucion
Temp . Compound
CO
39
41
43
43
44
46
47
47
48
48
49
50
52
53
54
55
56
57
58
59
61
62
66
66
67
68
69
70
70
71
73
74
75
75
81
86
88
89
91
91
92
92
co2
dichlorodifluoromechane
1-bucene + n-butane
acecaldehyde
bromomechane
trichlorofluoromechane
C5H10 i30ner
propanal + propeoal +
fur an
acetone
C.H- isomer
J 9
dichlorome thane
freon 113 (BKG)
ti-pentane
2-butenal
2-methylpencane
2-aethylpropenai
n-butanal + 3-methyl-
pentane
hexafluorobenzene (el)
n-hexane
chloroform
methyl echyl ketone
pert luorotoluene (el)
benzene
carbon tetrachloride
cyclohexane
2-aechylhexane
2,3— dimechylpencane
3-methylhexane
C,H0 isomer
o 8
3-methylbutanal
ii-pencanal
^-heptane
C7H14 isoner
C-H^, isomer
C,H, -0 isomer
0 Li.
toluene
CgH.g isomer + chlorobromo—
propene isomer (tenc.)
CjH, , isomer
o io
2-methylpentanal
C.H,, isomer
or-hexanal
dlbromoethane
Chroma to-
graphic
Peak Mo.
23B
23C
24
25
25A
25B
25C
26
27
27A
23
2SA
29
30
30A
31
31A
31B
31C
31D
32
32A
33
33A
34
35
36
37
37A
37B
38
38A
383
39
39A
40
40A
40B
40C
41
41A
41B
41C
410
(continued)
165
Elucion
Temp.
CO
93
93
94
95
98
99
99
104
106
107
108
109
110
111
112
114
116
118
119
120
121
122
123
124
125
126
127
128
129
130
131
131
132
133
135
136
136
137
137
138
139
140
141
141
Compound
CgH..,, Isomer
C.H., isomer
^-octane
tetrachloroethylene
C9H20 l30mer
C-H.g isomer
C.H2Q isomer
echylbenzene
2-xylene
CqH2Q isomer
C.H,. Isomer
2-heptanone
styrene
o_-xylene +• n-heptanal
C9H18 l30mer
n_-nonane
CgH.g isomer
isopropylbenzece
C.-H,- isomer
C10H22 l30mer
propylcyclohexane
C10H16 I301ner
benzaldehyde + C1QH22
isomer
n-propylbenzene
£-ethyltoluene
^10^22 ^30mer
C11H24 isoraer
C10H22 isomer
C.QH22 isomer
C..,H-., Isomer
10 20
oc canal
c-e thy 1 toluene
C...H_-. isomer
n_-decane
C10320 lsomer
1,2, 3-crime thylbanzene
C.-alkyl benzene isomer
C-.H2. isoner
C10S20 t30mer
C..H,, Isomer
C10H20 I30mer
C11H24 l3OT>er
C,-alkyl benzene iscmer
CUH24 lsomer
-------
Table 4.39 (cont'd)
Chroma co-
graphic
Peak No.
41E
42
43
44
El union
Temp.
(°C)
142
143
145
149
Compound
C ,-alkyl benzene isomer
C'ri,,, + l,l-dibromo-2-
11 24
chloropropane
C , H9/ isomer
C H0 isomer
Chrorr.aco-
grdphic
Peak No.
45
^5A
46
47
t-lution
(°C')
151 n-undecane
152 C, ^H-^. isomer
LL ^b
212 unknown
217 unknown
See Table 4.28 for sampling protocol.
166
-------
c
01
(-1
3
o
o
H
-------
Ch
00
c
OJ
J-l
3
O
c
O
•H
4-1
Vt'R PFT (cii
V.
r
u
1
n
H 1) S 0 4100 H 1 S
Mass Spectrum No.
Figure 4.66. Ion chromatograms for ambient air sample from Michigan Chemical Corp,
site, El Dorado, Arkansas (P1/C1/L3). BDCM = bromodichloromethane,
EDB = ethylene dibromide, DBCP = 1,l-dibromo-2-chloropropane.
-------
Table 4.40. VOLATILE ORGANICS IDENTIFIED IN AMBIENT AIR FROM
MICHIGAN CHEMICAL CORPORATION SITE, EL DORADO, ARKANSAS
(Pl/Cl/L4)a
Chromato-
graphic
Peak No.
1
3
4
4A
5
5A
6
6A
7
7A
3
3A
9
9A
10
10A
11
11A
11B
11C
11D
12
12A
13
13A
14
14A
14B
15
ISA
16
17
18
20
21
22
23
24
24A
25
26
26A
26B
27
Elution
Temp . Compound
CC)
39
41
42
43
44
45
46
46
47
47
49
51
53
54
55
55
56
57
58
59
59
60
61
62
62
64
65
65
66
67
67
69
72
77
79
84
85
87
88
39
9Q
90
92
93
co2
dichlorodifluorome thane
1-butene
bromoethane (tenc.)
acetaldehyde
isopentane
trichloro£luorome thane
propenal +• propanal + furan
n-pentane + CCH- isomer
~~ JO
acetone
dichloromethane +• freon 113 (BKG)
2-methylpropenal
2-me thy Ipentane
2-methylpropenal
3-methy Ipentane
n-butanal
hexafluorobeazene (el)
n-hexane
chloroform
methyl ethyl Ice cone
bromopropane isomer (tent.)
perf luorotoluene (el)
methylcyclopentane
1,1,1-trichloroe thane
allyl bromle
benzene
carbon tetrachlorlde
cyclohexane
2-methylhexane
2, 3-d ime thy Ipentane
3-methylhexane
p/-pentanal
ri-heptane
aethylcyclohexane
4-methyl-2-pentanone
toluene
chlorobromopropene isomer
(tent.) +• CgH18 isomer
3-me thy Ihep cane
C,H.,, isomer
o 10
2-methylpentanal * diiso-
butylene
jB-hex*nal
dibromoethane isomer
CgH,, isomer
ri-octane
Chroma to-
graphic
Peak No.
28
29
29A
29B
30
31
31A
32
33
34
35
36
36A
36B
37
37A
37B
38
39
40
41
42
42A
43
43A
44
45
46
47
47A
47B
47C
48
49
50
50A
51
52
53
54
53
56
57
58
(continued)
169
Elusion
Temp.
CC)
94
100
100
101
102
104
105
106
107
108
110
111
111
112
114
116
117
118
119
120
121
123
123
125
126
127
128
130
131
132
133
133
134
136
137
139
140
141
142
144
145
147
149
150
Compound
tetrachloroethylene
C-H2g isomer
ethylcyclohexane
dibromopropane isomer
l-chloro-3-bromopropane
ethylbenzene
C10H22 I30n"
£-xylene
C9H20 1SOmer
C9H2Q isomer
styrene + 2,4-dimethyl-
pencanal
o-xylene
£-heocaldehyde
CnH.. . Isomer
7 19
ii-nonane
Cq3i - isomer
isopropylbenzene
C-rtK.,- isomer
C10H22 i30m"
propylcyclohexane
C10H22 + C10H16 lsome"
benzaldehyde
n-propylbenzene
p_— ethyl toluene
''10^22 lsomer
C10H22 isomer
C,-alkyl benzene isomer
dlmethylhexanal or C-H.,0
o 10
isooer
(i-octanal
C^-allcyl benzene isomer
C.-allcyl benzene isomer
C..H.« isomer
iv-decane
C10H16 lsom'r
C,-allcyl benzne isomer
C11H24 i30mer
C11H24 l301ner
'"11^22 ^somer
C,-alkyl benzene isomer
C,-alkyl benzene isomer
1-chloro— 2 1 3— dibcomopropane
C llnrl h '
Cg-alkyl aldehyde isomer
n^-nonaoal
-------
Table 4.40 (cont'd)
ChromaLo-
graphic
Peak N'o.
58A
59
61
Elution IChroT,aco- Clue ion
Temo.
(°C>
152
153
163
CorT.pound
C-. , H^n isonier
1± 22
n-undecane
dimechylphenol isomer
Peak No. rC)
62 167 C1-H24 isori;er
62A 169 C -jK_,. isotner
See Table 4.28 for sampling protocol.
170
-------
identified bromomethane, bromopropane, allyl bromide, chlorobromopropene,
1,2-dibromoethane, a dibromopropane isomer, l-chloro-3-bromopropane and 1-
chloro-2,3-dibromopropane. In all of the samples which contained bromopropane,
we were unable to determine whether it was a 1- or 2-bromopropane (identical
mass spectra) since the authentic material was not available to us for
establishing the chromatographic retention time.
Table 4.41 summarizes the halogenated hydrocarbons which were identi-
fied by GLC/MS/COMP in ambient air surrounding the Michigan Chemical Corp.
plant site.
Table 4.41. HALOGENATED HYDROCARBONS IDENTIFIED BY GC-MS-COMP IN
AMBIENT AIR AT MICHIGAN CHEMICAL CORPORATION, EL DORADO, ARKANSAS
Compound Compound
Allyl Bromide l-Chloro-3-bromopropane
Bromobenzene l-Chloro-2,3-dibromopropane
Bromodichloromethane Dibromochloromethane
Bromoform 1,l-Dibromo-2-Chloropropane
1- or 2-Bromopropane 1,2-Dibromomethane
Bromopropene Dibromopropane
Chlorobromopropene Methyl Bromide
Methyl Chloride
Quantification of Halogenated Hydrocarbons.--Table 4.42 lists the halo-
genated hydrocarbons which were identified and quantitated in ambient air
surrounding the Michigan Chemical Corp. site. In this case, the concentra-
3
tions were generally in the ng/m range. The highest detected was chloro-
bromopropene at L5 where a personal sampler was placed at an elevation of 15
feet from ground level. This location was between two buildings which pro-
vided a wind corridor coming directly from the organic synthesis facilities.
The sampler was approximately 100 meters from that facility. At L4, another
171
-------
Table 4.42. HALOGENATED HYDROCARBONS IDENTIFIED AND QUANTITATED IN AMBIENT AIR
SURROUNDING MICHIGAN CHEMICAL CORP., EL DORADO, AK
Period /Cycle /Location
P1/C1/L1
L2
L3
L4
P1/C2/L2
L4
L4 (ELV)
L5 (ELV)
01
T3
•H
e
o
1H
f
rH
X
rH
rH
6
o
^
o
rH
.C
u
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m
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6.4
5.2
-
-
-
-
-
o
m
0
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26.4
-
-
T
-
-
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c
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47.2
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20.8
24.8
35
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cd
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-
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g
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•H
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ai
c
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-
-
T
-
dJ
TJ
•H
g
0
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,Q
rH
K*~>
4-1
CU
s
_
-
-
T
-
-
T
-
a ~3~
See Table 4.28 for sampling protocol, values are in ng/m .
- = not detected.
T = trace detected.
-------
DuPont personal sampler was approximately 10 feet from ground level, whereas
the remaining samplers were approximately 4 feet above ground.
Estimation of Methyl Chloride, Methyl Bromide, Vinyl Chloride and Vinyl
Bromide.--None of these chemicals were detected in ambient air by GC/ECD or
mass fragmentography. The LOD of methyl chloride and methyl bromide was 200
and 120 Mg/m3 by GC/ECD.
Ethylene.--The levels of ethylene determined at the Michigan Chemical
Corp. site are given in Table 4.43. The observed concentrations were generally
regarded as background quantities.
Table 4.43. ETHYLENE LEVELS IN AMBIENT AIR
Site Period/Cycle/Location ppm
MCI P1/C4/L1 0.85 + 0.15
P1/C4/L2 0.85 + 0.05
P1/C4/L3 0.80 + 0
P1/C4/L4 0.75 + 0.05
P1/C4/L5 0.85 + 0.05
P1/C4/L6 0.85 + 0.05
See Table 4.28 and Figure 4.45 for sampling protocol and locations.
4.2.3.6 Brominated Organics in Soil and Water
The soil and water samples were screened for EDB and other volatile
brominated organics by the VGA method. None were found in any of these
samples. The soil sample P1/C1/L1 was extracted and analyzed for semi-
volatile brominated organics by direct probe high resolution mass spec-
trometry and GC/MS/COMP. The results are given in Table 4.44.
173
-------
Table 4.44. ANALYSIS OF A SOIL SAMPLE FROM THE VICINITY
OF MICHIGAN CHEMICAL CORPORATION
Decabrom Tetrabrom
Period/Cycle/Location (ug/kg) (ug/kg)
P1/C1/L1 NDS l,100a
aQuantitation by GC/MS/COMP-MID.
4.2.4 Ethyl Corporation
4.2.4.1 Sampling
The sampling protocol and sample descriptions for Ethyl Corp. are given
in Table 4.45. The corresponding Figure 4.67 designates the sampling loca-
tions for September 23, 1976. Table 4.46 and Figure 4.68 present the
protocol and locations for May 17, 1977.
4.2.4.2 Inorganics in Ambient Air
Chloride/Bromide and Chlorine/Bromine.--The results obtained by the
turbidimetric determination of a total halide are given in Table 4.47. The
site, period and cycle designation were given in the sampling protocols
(Table 4.45) and the locations on schematic map (Fig. 4.67). No detectable
halogens and halides were observed in samples of ambient air surrounding
Ethyl Corp.
Fluoride/Fluorine.--No fluoride or fluorine could be detected in any
3
samples. The limit of detection was less than 2.7 (Jg/m based on the
volume of air sampled and the sensitivity of the ion selective electrode.
Acid Mist.--No titratable acid was found in any samples. The upper
3
limit of ambient air concentration of acid mist was 41 Mg/m when standardized
as H-SO,.
2 4
4.2.4.3 Organic Vapors in Ambient Air
Qualitative Analysis by High Resolution GC/MS/COMP.--Sampling locations
2 and 3 were 200-250 yards from the bromine extraction and organic synthesis
facilities. Location 1 represented an upwind sample near a large storage
tank area (see Fig. 4.67 for sampling locations). Figure 4.69 depicts the
total ion current profile of the volatile organic pollutants collected at L2
on the Ethyl Corp. site. The large peak (No. 19) was identified as toluene
174
-------
Table A.45. SAMPLING PROTOCOL FOR ETHYL CORPORATION, HIGHWAY 79, MAGNOLIA, ARKANSAS
Period Cycle
9/23/76 Cl
PI
C2
C3
C4
Location
LI
L2
1,3
\J<
1,1
1.2
L3
LI
L2
1.3
1,4
L5
L6
1.7
L5
Sampling
Time
1427-172*.
1427-1726
1422-1726
1355-1903
1729-1830
1729-1R30
1729-1830
1835-1944
1834-1944
1832-1944
1508
1502
1512
1517
1502
Samp 11 ng
Volume («.)
143
140
197
50.9
28.3
70.8
11
1 15
115
1
1
1
1
0.28
Meteorological Conditions
Type of Wind Dlr./
Sample T (°C) % R|| • Speed (kmnt.) Other
IIHCa 2/-30 40-70 180/4-rnlm Clear
IIIIC"
IIHC-1 "-13 Clenr, Blight Br2 +
1I2S odor
HllCb
F, CBN, CBO
r, CBN, CBD
F, CBN, CBD Clear
AM
AM
AM
TEI)
TED
TF.n
TF.D
VAC
"Ntiterh Model 220 nnmpler 3-6 ft elevation.
Key to Sample Type:
DuPont sampler 3-6 ft elevation.
Locations shown In Flfctire 10.
IIHC - Halogenated llydrocarhon
F - Fluorine and Fluoride
CBN'- Bromine and Chlorine
CBD - Bromide and Chloride
AM - Acid Mist
TF.D - Tedlar Bag
VAC - Aluminum Vacuum Can
-------
ETHYL CORP - MAGNOLIA
APPROX. SCALE 1 cm = 110 m
Figure 4.67.
Schematic map of Ethyl Corporation, Magnolia
sampling locations for PI - 9/23/76.
A - EDB and Br_ facilities
B = EDB facilities
176
-------
Table 4.46.
SAMPLING PROTOCOL FOR ETHYL CORPORATION,
MAGNOLIA, ARKANSAS
Period Cycle Location
PI Cl LI
5/17/77 LI
L2
L3
L4
L5
L5
L6
L6
L6
L7
L7
Sample Size
2
2
1
1
2
2
1
2
2
a
core
core
a
£
core
core
£
core
core
Type of Sample
SHHC-V
SHHC-SV
VHHC-V/SV^
VHHC-V/SV
WHHC-V/SV0
WHHC-V/SV1:
VHHC-V/SV
SHHC-V
SHHC-SV
WHHC-V/SVe
SHHC-V
SHHC-SV
Core Vj cm diameter, 13 cm depth.
Needles stripped from 40 cm of pine bough sampled at V5 m above ground from
trees showing damage.
wide, slow moving portion of stream.
Blackberries.
Well water.
Peaches.
Key to sample type: SHHC - soil for halogenated hydrocarbons
WHHC - water for halogenated hydrocarbons
VHHC - vegetation for halogenated hydrocarbons
V - for volatile organic analysis
SV - for semi-volatile organic analysis
177
-------
Figure 4.68. Map of area in vicinity of Ethyl Corporation, Magnolia,
Arkansas - sampling locations for water, soil, sediment,
and vegetation for PI - 5/17/77.
178
-------
c
01
t-l
3
to
4-)
O
QJ
>
•H
4-)
CO
OS
btSO 6700
r-,- v p-i-,--,-^',-"!
Mass Spectrum No.
Figure 4.69. Total ion current profile of volatile ambient air pollutants from
Ethyl Corp. site, Magnolia, Arkansas (P1/C1/L2).
-------
Table 4.47. CONCENTRATIONS OF HALOGENS AND HALIDES IN
AMBIENT AIR SURROUNDING ETHYL CORP.3'
Location
Species L3
Cl2/Br2C
Br/ 2
2
c
Cl /Br
d
Br
<70
<29
<44
<14
*a
Samples are from P1/C3.
bT7 . . ,3
Values are in yg/m .
CBy turbidity.
By neutron activation analysis.
and the large concentration probably occurred because a diesel powered tank
trailer passed by the sampling location. On the backside of this large peak
(Peak No. 20), 1,2-dibromoethane was detected. This is more clearly presented
in Figure 4.70 which presents the ion chromatograms for m/e 85, m/e 109, m/e
120 and m/£ 124. The peaks corresponding to allyl bromide and 1,2-dibromo-
ethane which were identified in this sample are also noted in this figure.
At L3 (see Fig. 4.67) several halogenated organics were detected. The
profile for this location is shown in Figure 4.71 and the ion chromatograms
are shown in Figure 4.72. In Figure 4.72 the presence of bromopropane,
chlorobromoethane, bromodichloromethane and 1,2-dibromoethane are clearly
evident. Table 4.48 summarizes the halogenated hydrocarbons identified by
GC/MS/COMP in ambient air samples from Ethyl Corp.
180
-------
CO
a
0)
3
O
a
o
ctf
rH
CU
Mass Spectrum No.
Figure 4.70. Ion chromatograms of ambient air sample from Ethyl Corp. site,
Magnolia, Arkansas (P1/C1/L2). AB = alkyl bromide, EDB =
ethylene dibromide.
-------
00
c
a)
V-* 3 If U U 0 -
a
u :
a
o -i
M
, ? li U (1 1* -
rH
rt
o
H :
n Jll'
10 !l
viJfe
i *• 5
.,
>i "• » »
11 k i * i i
^ JH'Msi^ ^akJJL/0^ '
, , , ,,. I , 1 , . , I , 1 , I , I , , ,..,.., | ,,.,,, | | i T , , , i-.-p.-r-,-, , , i^-p^-r-,-,.-,.^,.
7300 73S»
Mass Spectrum No.
.>*..
Figure 4.71. Total ion current profile of volatile ambient air pollutants
from Ethyl Corp. site, Magnolia, Arkansas (P1/C1/L3).
-------
00
7JO» ?3S«
7-»00 7-450
Mass Spectrum No.
Figure 4.72.
Ion chromatograms of ambient air sample from Ethyl Corp. site,
Magnolia, Arkansas (P1/C1/L2). BP = bromopropane, CBE = chloro-
bromoethane, BDCM = bromodichloromethane and EDB = 1,2-dibromo-
ethane.
-------
Table 4.48. HALOGENATED HYDROCARBONS IDENTIFIED BY GC/MS/COMP IN AMBIENT AIR
AT ETHYL CORP., MAGNOLIA, ARKANSAS
Compound Compound
l-chloro-2-bromoethane 1,2-dibromoethane
bromopropane vinyl bromide
bromodichloromethane allyl bromide
Quantification of Halogenated Hydrocarbons.--The levels of halogenated
hydrocarbons in the ambient air samples surrounding Ethyl Corp. are given
in Table 4.49. The highest concentration of any halogenated hydrocarbon of
all the samples which were collected at all the sites occurred in the
sample taken at L4. The sampling location was approximately 20 yards from
the 1,2-dibromoethane synthesis facility. The level of 1,2-dibromoethane
3
was 20,215 ng/m .
Estimation of Methyl Chloride, Methyl Bromide, Vinyl Chloride, and Vinyl
Bromide.--None of these chemicals were detected by GC/ECD or mass fragmento-
graphy.
Ethylene.--The ethylene levels observed are given in Table 4.50.
Typical background values were seen.
4.2.4.4 Brominated Organics in Soil, Water and Vegetation
All of the samples described in Table 4.46 were analyzed by the VGA
procedure for EDB and other halogenated organics. No EDB was detected in
any of the samples nor were any other volatile halogenated organics identi-
fied. A soil sample P1/C1/L1 was extracted for semi-volatile organics and
submitted to high resolution mass spectral analysis (direct probe) and no
halogenated organics were found.
4.2.5 Dow Chemical Co. and Vicinity
During the survey study ambient air monitoring for brominated organics
was not conducted at this plant site. However, condensed phase samples
were collected and some of these data are presented here.
184
-------
Table' 4.49. HALOCENATED HYDROCARBONS IDENTIFIED AND QUANTIFIED IN AMBIENT All
SURROUND]NO ETHYL CORP., MAGNOLIA, AK
Period/Cycle/Location'
oo
Ln
P1/C1/L1
1,2
L3
1M/C2/L4
9.4
15.8
3.4
6.8
16.2
26.6
1.2
Refer to Table 4.45 for sampling protocol, values are in ng/m~
b
- = not detected
T = trace detected
227
174
21.2
20,250
-------
Table 4.50. ETHYLENE LEVELS IN AMBIENT AIR
£\
Site Period/Cycle/Location ppm
EC P1/C4/L4 0.76 + 0.06
P1/C4/L5 0.60 + 0
P1/C4/L6 0.70 + 0.10
P1/C4/L7 0.73 + 0.13
o
See Table 4.45 and Figure 4.67 for protocol and locations.
4.2.5.1 Sampling
Samples of soil, water and vegetation were collected in the vicinity of
Dow Chemical Co., Magnolia, AK. The sampling protocol is given in Table 4.51
and Figure 4.73.
4.2.5.2 Brominated Qrganics in Soil, Water and Vegetation
Environmental samples were analyzed by the VOA procedure for the pre-
sence of EDB and other volatile halogenated organics. The results are given
in Table 4.52.
186
-------
Table 4.51.
SAMPLING PROTOCOL FOR DOW CHEMICAL CO.
MAGNOLIA, ARKANSAS
Period Cycle Location
PI Cl LI
5/17/77 LI
LI
L2
L3
L4
L4
L5
L5
L5
L6
L6
L7
Sample Size
2
2
1
1
2
2
1
2
2
1
a
cores
cores
£
I
cores
cores
H
cores
cores
£
Type of Sample
SHHC-V
SHHC-SV
VHHC-V/SV
WHHC-V/SV
WHHC-V/SV0
SHHC-V
SHHC-SV
WHHC-S/SV
VHHC-S/SV*:
VHHC-S/SV
SHHC-S
SHHC-SV
WHHC-S/SV
Core V5 cm diameter, 13 cm depth.
^2 m wide, VL5 cm deep in dry weather (no rain for 1 week).
"Farm ponds.
Lake.
3
"Leaves of pecan tree.
Potatoes.
Key to sample type:
SHHC - soil for halogenated hydrocarbons
WHHC - water for halogenated hydrocarbons
VHHC - vegetation for halogenated hydrocarbons
V - for volatile organic analysis
SV - for semi-volatile organic analysis
187
-------
Figure 4.73. Map of area in vicinity of Dow Chemical Company,
Magnolia, Arkansas - sampling locations for water,
soil, sediment and vegetation for PI - 5/17/77.
188
-------
Table 4.52. VGA ANALYSIS OF ENVIRONMENTAL SAMPLES FROM THE VICINITY OF
DOW CHEMICAL CO., MAGNOLIA, AK
Period/Cycle/Location Sample Type EDB
P1/C1/L1 Soil ND
L2 Water ND
L3 Water ND
L4 Soil Detected
L5 Vegetation (potatoes) ND
Vegetation (pecan leaves) ND
Water ND
L6 Soil ND
189
-------
5.0 LONG-TERM MONITORING FOR VOLATILE BROMINATED ORGANICS
Sites were selected in the El Dorado and Magnolia areas to continuously
monitor for volatile brominated organics in ambient air. The objective was
to determine whether significant levels of brominated organics in ambient
air were being transported from the bromine industry to populated areas.
Thus the specific aim was to assess potential exposure to volatile brominated
organics, specifically, 1,2-dibromoethane.
5.1 SAMPLING AND ANALYSIS
Two sites were selected in El Dorado - one on the water tower at
Parker's Chapel and the other on a water tower in El Dorado. Figure 5.1
shows the location of these sites with respect to Great Lakes Chemical
Corporation and Arkansas Chemical Inc. Three sites were selected in Magnolia
and their locations are shown in Figures 5.2-5.4 with respect to the city of
Magnolia, Dow Chemical Co. and Ethyl Corporation, respectively.
The sampling and analysis methodology employed in this study is given
in Appendix A, Section F.
5.2 RESULTS AND DISCUSSION
The sampling protocols for ambient air samples collected in El Dorado
are given in Tables 5.1 and 5.2. 1,2-Dibromoethane was detected on three
different days at the Parkers Chapel water tower (Table 5.1). On the first
3
day of sampling, a level of 700 ng/m was measured and the highest value was
found during the 26th sampling period at which time it achieved a level of
3
1,260 ng/m . As can be seen in Table 5.1, during these three days of sampling
the predominant wind direction was from the general area of the Great Lakes
Chemical Corp. Low concentrations of l-chloro-2-bromoethane, dibromopropane
and allyl bromide were found in samples taken on the El Dorado water tower
(Table 5.2). In general, these sampling periods represented times when the
wind direction was generally from the west to southwest direction.
Tables 5.3-5.5 present the sampling protocols for the air monitoring
conducted in Magnolia, AK near Dow Chemical Co. and near Ethyl Corporation,
190
-------
Figure 5.1. Map of El Dorado area - sampling locations
for continuous air monitoring.
191
-------
Figure 5.2. Map of Magnolia area - sampling locations for
continuous air monitoring.
192
-------
60
C
D.
1
tn
en
cfl
en
C
cfl
O
C
M
cfl
S
C
CO
D-
O
U
cfl 60
O C
•H -H
S M
5 o
x: ±J
u -H
3 o
o e
p
h
4-i -H
O Cfl
>, en
u 3
•H O
C 3
•H C
O -H
•H -U
> C
O
C O
cfl O
-------
Figure 5.4.
Map of area in the vicinity of Ethyl Corporation,
Magnolia, Arkansas - sampling location for
continuous air monitoring.
194
-------
Table 5.1. SAMPLING PROTOCOL FOR CONTINUOUS AIR MONITORING IN THE EL DORADO, ARKANSAS
VICINITY - LOCATION 1: PARKERS CHAPEL WATER TOWER
Meteorology
Volatile Brominated
Organics Volume Wind speed
Period ng/m^ Time/Date (m^) Temp. °C3 Wind Dir. (Knts) Precipitation Comments
PI 700b 1425,
1625,
P2 ND 1635,
1706,
P3 ND 1706,
1550,
P4 ND 1550,
1725,
P5 ND 1725,
1555,
P6 ND 1555,
1715,
P7 ND 1715,
1700,
P8 ND 1700,
1655,
P9 ND 1655,
1718,
3/5/77- 0.131 17/1° NE-NW 0-10
3/6/77
3/6/77- 0.147 20/-2 NW-SW calm 0-10
3/7/77
3/7/77- 0.136 23/1 calm NW, SW 0-15
3/8/77
3/8/77- 0.153 21/5 calm, SW.S.SE 0-15
3/9/77
3/9/77- 0.134 24/4 SE 5-10
3/10/77
3/10/77 0.152 23/12 SE,W 10-15 2.06 cm
3/12/77
3/11/77- 0.142 23/10 SE.SW.W 5-15 Rain, Wind and water damage to
3/12/77 to sampler. Various malodors
present.
3/12/77- 0.143 27/10 SW,W 5-10
3/13/77
3/13/77- 0.146 29/6 calm S.SW 0-15 Dust storm coming into area.
3/14/77
ND
1718, 3/14/77 0.138
30/17 SW,W
(continued)
0-10
-------
Table 5.1 (cont'd)
Meteorology
Volatile Brominated
Organics Volume
Period ng/m3 Time/Date (m3)
Pll 280b 1615,
1830,
P12 ND 1830,
1600,
P13 ND 1600,
1708,
P14 NU 1708,
1705,
P15 ND 1705,
1750,
P16 ND 1750,
1535,
P17 ND 1535,
1530,
P18 ND 1530,
0900,
P19 ND 0900,
1555,
P21 ND 1635,
1855,
P22 ND 1855,
1614,
3/15/77- 0.158
3/17/77
3/16/77- 0.129
3/17/77
3/17/77- 0.151
3/18/77
3/18/77 0.144
3/19/77
3/19/77- 0.148
3/20/77
3/20/77- 0.130
3/21/77
3/21/77- 0.144
3/22/77
3/22/77- 0.105
3/23/77
3/23/77- 0.186
3/24/22
3/25/77- 0.158
3/26/77
3/26/77- 0.128
3/27/77
Temp. °Ca Wind Dir.
30/12 N.NE
25/14 NE,E,SE,S
26/16 S.SW.NW
21/14 NE,E,SE
20/-1 calm NW,E
SE
26/9 calm SE,E,W
26/1 NW.NE
18/1 calm
23/8 S, Calm
25/16 SE
25/18 SE.S
(continued)
Wind Speed
(Knts) Precipitation Comments
5-15
5-10
5-15
0-10
0-10
0-15
0-10
Strong odor, not U.S.
0-5 0.56 cm
5-10
5-15 2.67 cm
-------
Table 5.1 (cont'd)
Volatile Brominated
Organics Volume
Period ng/m3 Time/Date (m3)
P23 ND
P24 ND
P25 ND
P26 l,260b
P27 ND
P28 ND
P29 ND
P 30 ND
P31 ND
1614,
1706,
1706,
1600,
1600,
1850,
1850,
1353,
1353,
1200,
1200,
1515,
1515,
1655,
1655,
1752,
1615,
3/27/77- 0.149
3/28/77
3/28/77- 0.144
3/29/77
3/29/77- 0.161
3/30/77
3/30/77- 0.114
3/31/77
3/31/77- 0.190
4/1/77
4/1/77 0.245
4/2/77
4/2/77- 0.205
4/3/77
4/3/77- 0.164
4/4/77- 0.146
4/5/77
Meteorology
Wind Speed
Temp. °Ca Wind Dir. (Knts) Precipitation Comments
27/13 S,SE -20 G 2.08 cm
S-SW
24/14 S.SW.SE 5-10
29/17 calm S,SW,W 5-10
23/17 NW.N.NE 5-10
23/11 NE,E 5-10 0.08 cm
24/15 SE.S.SW 5-10 0.79 cm
22/13 calm SW.S.NE 0-15 1.40 cm
18/15 E.NE, calm W 0-15 0.56 cm
(G 22)
18/6 W,NW 0-15
(G 23)
(continued)
-------
Table 5.1 (cont'd)
Meteorology
Volatile Bromlnated
Organics Volume Wind Speed
Period ng/m3 Time/Date (m3) Temp. °Ca Wind Dir. (Knts) Precipitation Comments
P32 ND 1615, 4/5/77- 0.156 18/4 calm NW.W.SW 0-10
1825, 4/6/77
P33 ND 1825, 4/6/77- MK135 29/9 calm W 0-14
£ aHigh/low
o> b
1,2-dibromoethane
-------
Table 5.2. SAMPLING PROTOCOL FOR CONTINUOUS AIR MONITORING IN THE EL DORADO, ARKANSAS
VICINITY - LOCATION 2: EL DORADO WATER TOWER
Meteorology
Volatile Brominated
Orpanics Volume
Period ng/m3 Time/Date (m3)
PI
P2
P3
P4
P5
P6
P7
P8
P9
P10
2,520b 1650,
1700,
4,200b 1700,
1840,
ND 1840,
1615,
ND 1516,
1802,
560C 1802,
1620,
ND 1620,
1746,
ND 1746,
1725,
ND 1725,
1725,
ND 1725,
1816,
ND 1816,
1645,
3/5/77- 0.145
3/6/77
3/6/77- 0.134
3/7/77
3/7/77- 0.129
3/8/77
3/8/77- 0.170
3/9/77
3/9/77- 0.120
3/10/77
3/10/77- 0.129
3/11/77
3/11/77- 0.142
3/12/77
3/12/77- 0.144
3/13/77
3/13/77- 0.149
3/14/77
3/14/77- 0.135
3/15/77
Temp. °C3 Wind Dir.
17/1 NE-NW
20/-2 NW-SW calm
23/1 calm NW.SW
21/5 calm SW,S,SE
24/4 SE
23/12 SE,W
23/10 SE.SW.W
27/10 SW,W
29/6 calm S,SW
30/17 "SW.W
Wind Speed
(Knts) Precipitation Comments
0-10
0-10
0-15
0-15
5-10
10-15 2.06 cm
5-15
5-10
0-15
0-10
(continued)
-------
Table 5.2 (cont'd)
Volatile Brominated
Organics
1'erlod ng/m3 Time/Date
Pll ND 1745,
1855,
P12 700b 1855,
1630,
ixj PI 3 ND 1630,
0 1745,
H14 Nl) 1745,
1730,
P15 ND 1730,
1810,
P16 ND 1810,
1600,
PI 7 ND 1600,
1455,
P18 ND 1455,
0925,
P19 ND 0925,
1625,
P21. ND 1600,
1925,
3/15/77-
3/16/77
3/16/77-
3/17/77
3/17/77-
3/18/77
3/19/77-
3/19/77
3/19/77-
3/29/77
3/20/77-
3/21/77
3/21/77-
3/22/77
3/22/77-
3/23/77
3/23/77-
3/24/77
3/25/77-
3/26/77
Volume
(m3)
0.157
0.129
0.152
0.142
0.148
0.157
0.183
0.116
0.203
0.164
Meteorology
Wind Speed
Temp. °Ca Wind Dir. (Knts) Precipitation Comments
30/12 N,NE 5-15
25/14 NE.E.SE.S 5-10
26/16 S.SW.NW 5-15
21/14 NE,E,SE 0-10
20/-1 calm NW.E, 0-10
SE
26/9 calm SE,S,W 0-15
26/1 NW,NE 0-10
18/1 calm
23/8 S calm 0-5 0.56 cm
25/16 SE 5-10 Raining
(continued)
-------
Table 5.2 (cont'd)
Meteorology
Volatile Brominated
Organics Volume
Period ng/m3 Time/Date (m3)
P22 ND
P23 280d
P24 ND
P25 ND
P26 ND
P27 ND
P28 ND
P29 ND
P30 ND
P31 280
1925,
1652,
1652,
1735,
1735,
1625,
1625,
1922,
3922,
1415,
1415,
1220,
1220,
1450,
1450,
1720,
1720,
1824,
1740,
3/26/77- 0.129
3/27/77
3/27/77- 0.148
3/28/77
3/28/77- 0.137
3/29/77
3/29/77- 0.162
3/30/77
3/30/77- 0.113
3/31/77
3/31/77- 0.132
4/1/77
4/1/77-
4/2/77
4/2/77- 0.136
4/3/77
4/3/77- 0.180
4/4/77- 0.152
4/5/77
Wind Speed
Temp. °Ca Wind Dir. (Knts) Precipitation Comments
25/18 SE,S
27/13 S,SE,W-SW
24/14 S.SW.SE
29/17 calm, S,SW,W
23/17 NW,N,NE
23/11 NE.E
24/15 SE.S.SW
22/13 calm, SW,S,NE
18/15 E,NE,calm,W
18/6 W.NW
5-15 2.67 cm Raining
5-20 (G) 2.08 cm
5-10
5-10
5-10
5-10 0.08 cm
5-10 0.79 cm Pump stopped during sampling
interval
0-15 1.40 cm
0-15 0.56 cm
(G 22)
0-15
(G 23)
(continued)
-------
Table 5.2 (cont'd)
Volatile Brominated
Organics
Period ng/m3
P32 T
P33 260
Meteorology
Volume Wind Speed
Time/Date (m3) Temp. °C3 Wind Dir. (Knts) Precipitation Comments
1740,4/5/77- — 18/4 calm,NW,W,SW 0-10 Pump stopped during sampling
interval
1856, 4/6/77- ^0.135 29/9 calm W 0-14
TT ' 1 / T
l-chloro-2-bromoethane
"dibromopropane
allyl bromide
-------
Table 5.3. PROTOCOL FOR CONTINUOUS AIR MONITORING, MAGNOLIA, ARKANSAS
Meteorology
Volatile Brominated
Organics Volume
Period ng/m3 Time/Date (m3)
PI ND 1740,
1900,
P2 ND 1900,
1150,
P3 ND 1150,
1605,
K> PA Tb 1605,
0 1705,
P5 ND 1705,
1700,
P6 ND 1700,
1750,
P7 ND 1750,
2025,
P8 TC 2025,
1130,
P9 Tb 1130,
1450,
P10 ND 1450,
1700,
PH ND 1700,
2220,
4/9/77- 0.148
4/11/77
4/11/77- 0.123
4/13/77
4/13/77- 0.157
4/15/77
A/15/77- 0.147
4/17/77
4/17/77- 0.144
4/19/77
4/19/77- 0.146
4/21/77
4/21/77- 0.152
4/23/77
2/23/77- 0.116
4/25/77
4/25/77- 0.137
4/28/77
4/28/77- 0.150
5/1/77
5/1/77- 0.488
5/8/77
Temp. °Ca Wind Dir.
29/10 calm S,SW,SE
29/11 calm S,SE
29/11 calm SE
29/14 calm SE
28/14 SE.S
28/18 calm SE
26/11 E,SE,SW,W
calm
26/9 N,NW calm
29/7 cairn, NW
S,SW
28/11
29/10
Wind Speed
(Knts) Precipitation Comments
0-10
0-10
(G 16)
0-10
(G 19)
0-15
5-10 4.98 cm
0-10 0.30 cm
0-10 1.37 cm
0-10 trace
0-15
0-8
0-10
High/low
dibromochloropropane
"allyl bromide
-------
Table 5.4. PROTOCOL FOR CONTINUOUS AIR MONITORING NEAR DOW CHEMICAL COMPANY, MAGNOLIA, ARKANSAS
P6
P7
I'H
Volatile Bromlnated
Organics Volume
od ng/m3 Time/Date (in3)
ND
ND
Tb
ND
ND
ND
ND
1315,
1825,
1825,
1120,
1120,
1935,
1935,
1540,
1540,
1620,
1620,
1925,
1925,
1905,
4/9/77- 0.012
4/11/77
4/11/77- 0.123
4/13/77
4/13/77- 0.078
4/15/77
4/15/77- 0.127
4/17/77
4/17/77- 0.146
4/19/77
4/19/77- <0..153a
4/2/77
4/2/77- 0.145
4/23/77
Meteorology
Wind Speed
Temp. °C Wind Dir. (Knts) Precipitation Comments
29/10 calm,S,SW,SE 0-10
29/11 calm.S.SW 0-10
(G 16)
29/11 calm, SE 0-10 Sharp odor in air 4/15/77
(G 19)
29/14 calm, SE 0-15 Flare at Dow emitting grey smoke
which was drifting northeast ol
sampler. Wind from southeast.
28/14 SE.S 5-10
28/18 calm, SE 0-10 4.98 cm
26/11 E,SF,,SW,W 0-10 0.30 cm Flume seen over plant site with
calm very weak wind blowing in direc-
ND
142,
tion of sampler.
1905, 4/23/77- 0.120
1100, 4/25/77
1130, 4/25/77- 0.209
2010, 4/28/77
26/9 N.NW.calm 0-10
29/7 calm,NU,S,SW 0-15
(continued)
1.37 cm
trace
-------
Table 5.4 (cont'd)
Ln
Volatile Brominated
Organics
Period ng/m3
P10 81, C 24d
Pll ND
P12 35,c 18d
Time/Date
2010, 4/28/77-
1740, 4/30/77
1740, 4/30/77-
1130, 5/2/77
1130, 5/2/77-
1200, 5/4/77
Volume
(m3)
0.167
0.097
0.146
Meteorology
Wind Speed
Terap. °Ca Wind Dir. (Knts) Precipitation Comments
29/13 calm.SW.SE 0-10 Odor in air, jind from plant
direction.
29/12 - 0-8 Faint odor from plant, winds
from plant direction.
29/11 - 0-10
aHigh/low
allyl bromide
Q
1,2-dibromoethane
dibromochloropropane
-------
Table 5.5. PROTOCOL FOR CONTINUOUS AIR MONITORING NEAR ETHYL CORPORATION,
MAGNOLIA, ARKANSAS
Volatile Brominated
Organics Volume
PIT tod ng/m-" Time/Date (m )
PI. ND 1130,
1130,
P2 ND 1800,
1050,
P3 ND 1050,
1900,
0 P4 ND 1900,
^ 1425,
P5 ND 1435,
1535,
P6 ND 1535,
1845,
P7 ND 1845,
1750,
P8 ND 1750,
1100,
P9 ND 1100,
1905,
P10 57b 1905,
1625,
4/9/77 <0.144a
4/11/77
4/11/77- 0.122
4/13/77
4/13/77- 0.202
4/15/77
4/15/77- 0.130
4/17/77
4/17/77 0.147
4/19/77
4/19/77- 0.134
4/21/77
4/21/77- 0.141
4/23/77
4/23/77- 0.123
4/23/77
4/25/77- <0.120a
4/28/77
4/28/77- 0.130
4/30/77
Temp. °Ca
29/10
29/11
29/11
29/14
28/14
28/18
26/11
26/9
29/7
29/13
Meteorology
Wind Speed
Wind Dir. (Knts) Precipitation Comments
calm, S.SW.SE 0-10
calm S,SE 0-10
(G 16)
calm SE 0-10
(G 19)
calm SE 0-15
SE,S 5-10
calm, SE 0-10 4.98 cm Odor of bromine.
E,SE,SW,W 0-10 0.3 cm
N.NW.calm 0-10 1.37 cm
calm, NW 0-15 trace
SW,S
calm.SW 0-10
High/low
1,2-dibromoethane
-------
respectively. In a few of the ambient air samples taken from these sites,
dibromochloropropane (DBCP), allyl bromide and 1,2-dibromoethane were detected.
Traces of DBCP and allyl bromide were detected at the air montoring station
on the Southern Arkansas University campus. 1,2-Dibromoethane and DBCP were
detected in ambient air samples taken at a sampling station located north of
Dow Chemical Co. (Table 5.4). During the periods in which the brominated
organics were detected, the wind direction was generally from the southeast,
and south to southwest directions (Table 5.4). During one sampling period,
a low concentration of 1,2-dibromoethane was detected in an ambient air
sample taken north of Ethyl Corporation (Table 5.5).
207
-------
6.0 CHARACTERIZATION OF ENVIRONMENTAL MEDIA ASSOCIATED WITH BROMINE INDUSTRY
6.1 TECHNICAL STRATEGY
6.1.1 Sampling
As pointed out in Section 4.1, the strategy of the Survey Study was to
evaluate the analytical techniques employed for characterizing ambient air
and to acquire a maximum amount of information about the chemicals surround-
ing the bromine industry. With this information in hand as well as the
information which was acquired during the long-term continuous monitoring
for volatile organic vapors and from condensed phase media for semi-volatile
and volatile brominated organics, we proceeded to design a sampling and
analysis regime to more extensively study the environmental media surrounding
the bromine industry. The concept included extensive sampling of air,
water, soil, sediment and biota on the plant sites as well as off-site.
Subsequent prioritization of the samples for analysis was necessary in
order to best characterize the potential contamination of environmental
media by the activities associated with the bromine industry in El Dorado
and Magnolia, AK. The sampling strategy included collection of samples
immediate and distant from the various industrial sites in order to possibly
demonstrate the transport of brominated organics. The sampling strategy
was designed not only to investigate transport of brominated organics but
also the potential impact on populated areas.
The sampling methods employed during this phase of the program were as
described in Appendix A which provides the analytical protocols.
6.1.2 Prioritization of Sample Analysis
Table 6.1 presents the inventory of samples which were collected in
Southern Arkansas between July 15 and August 5, 1977. As indicated in the
table, a total of 439 samples was collected. However, samples were selected
for analysis based upon several criteria which were used to provide a
guideline in prioritizing these samples for analysis. The samples of
ambient air were selected on the basis of the most favorable meteorological
203
-------
Table 6.1. INVENTORY OF SAMPLES COLLECTED IN SOUTHERN ARKANSAS (7/15/77 to 8/5/77)
a
Type of Sample
Tenax GC/Carbon
(air)c
imp Ingers
(halides, air)°
lli-Vol Kilters
(air)
Vacuum Can.
(alr)c
Soil
Water
Vegetation
Sediment
§ Milk
Miscel laneous
Great Lakes ,
El Dorado
21
16
4
IB
20
25
23
14
3
9
Ve Islcol
El Dorado
19
16
4
15
19
5
5
5
1
2
Ethyl Corp.
Magnolia
15
12
6
14
20
3
5
2
1
1
Dow Chemical
Minolta
13
16
6
6
20
11
4
4
0
0
Great Lakes
Marysville
1
4
2
4
0
0
0
0
0
0
Other
1
0
0
0
8
0
0
0
0
8
Arkansas Chemical
Co. - El Dorado
0
0
8
0
0
0
0
0
0
0
Total
70
64
30
57
87
44
37
25
5
_20_
439
Samples indicated for an industrial site include both on property and vicinity samples,
Formerly Michigan Chemical Co.
CEach sampling train counted as a sample even though two analyses were made.
-------
conditions with respect to the sampling locations and the proximity of the
industrial facility. Other environmental media such as soil, water, sediment
and biota were selected for analysis in the initial phases of the program
based upon samples taken in the immediate vicinity of the plant area but
off-site. When environmental samples collected off-site indicated the
presence of brominated compounds, then additional samples more distant from
the plant sites were selected for analysis.
6.1.3 Ozone Measurements in El Dorado, AK
During the period from July 22-August 12, hourly ozone concentrations
were tabulated. Appendix A, Section M describes the techniques used for
determining the ozone concentration. The results are given in Appendix D.
6.2 RESULTS AND DISCUSSION
6.2.1 Great Lakes Chemical Corporation and Vicinity
6.2.1.1 Sampling
The sampling protocols for ambient air, water, soil, etc. surrounding
Great Lakes Chemical Corporation in El Dorado, AK are given in Tables 6.2-
6.4. The sampling period, cycle, location, sampling time, volume and type
of sample as well as meteorological conditions are described; the correspond-
ing locations are shown on Figures 6.1-6.5.
6.2.1.2 Inorganics in Ambient Air
The halides and halogens which were quantitated in ambient air sur-
rounding Great Lakes Chemical Co. are given in Table 6.5. The turbidimetric
method was used for determining halide and halogen. The values given in
Table 6.5 are expressed as chloride and molecular chlorine. However, if
bromide or bromine was the predominant species, the values would be multi-
plied by 1.5. The highest concentration of halide was observed at location
3
2 at which time it reached a level of 274 (Jg/m . For this period L4 repre-
sents the upwind sample.
6.2.1.3 Brominated and Other Organics
Air.—Table 6.6 presents the ambient air levels of volatile brominated
organics which were detected during the five day period. The highest
3
concentration was 271,283 ng/m of 1,2-dibromoethane which occurred at
location 2 during the second sampling period. This represented a downwind
sampling station approximately 200 yds from the organic synthesis facility.
210
-------
Table 6.2. SAMPLING PROTOCOL FOR AMBIENT AIR SURROUNDING GREAT LAKES CHEMICAL CORP.,
Period
PI
7/17/77
P2
7/18/77
P3
7/19/77
PA
7/20/77)
Cycle Location
Cl LO
Cl LI
L2
L3
L4
L5
LI
L2
L3
L4
L5
Cl LI
L2
L3
L4
L5
LI
L2
L3
L4
L6
L7
L5
Cl LI
L2
L3
L4
L5
LI
L2
L3
L4
Sampling
Time
1955-1420
1139-1240
1155-1305
1242-1315
1543-1352
1514-1334
1438-1800
1444-1807
1244-1815
1359-1824
1530-1335
1256-1110
1310-1121
1321-1131
1400-1147
1347-1139
1250-1725
1310-1735
1317-1738
1355-1747
1855
1858
1345-1455
1118-1032
1127-1047
1137-1130
1152-1150
1147-1143
1018-1520
1024-1527
1031-1533
1058-1540
(7/18/77)
(7/19/77)
(7/19/77)
(7/19/77)
(7/19/77)
(7/19/77)
(7/19/77)
(7/20/77)
(7/20/77
(7/20/77)
(7/20/77)
(7/20/77)
(7/20/77)
(7/21/77)
(7/21/77)
(7/21/77)
(7/21/77)
(7/21/77)
Sampling
Volume (8.)
100
202
204
199
129
208
246
238
356
265
1,949,000
192
180
188
123
185
204
247
266
254
0.5
0.5
2,051,000
188
<189
193
129
194
220
216
247
279
Meteorological Conditions
Type of Wind Direction
Sample T(°C) %RH Speed (kmph) Other
HHCab
HHCab,
HHCab
HHC K
HHCh
HHC 20-35 E.SE, calm, N
CBD.CBN0
CBD.CBN0
CBD.CBN0
CBD.CBN0
Hi-Vol
HHCab
imcab
Hlic'r Strong odor of H,S
HHCab i
HHC 20-32 90 N, NE, calm
CBD,CBNC NE to W/3-7
CBD.CBN0
CBD.CBN0 N, calm Strong odor of H S
CBD.CBN0
VAC
VAC
Hi-Vol
HHC3^ 20-27 60-90 S.with periods of calm Upset 1730
Illic" 3-6 Pump stopped during
interval
HHC™ Upset 1730
HHCab Raining 1150
imcab
CBD.CBN0 gusty unstable
CBD.CBN0 pattern
CBD.CBN0
CBD.CBN0
(continued)
-------
Table 6.2 (cont'd)
N>
h-1
N3
Period
P4
7/20/77
Cycle Location
Cl (Continued)
LI
L2
L3
L4
1.5
L8
Sampling
Time
1520
1530
1533
1540
1512
1730
Sampling
Volume (fc)
0.5
0.5
0.5
0.5
0.5
0.5
Meteorological Conditions
Type of Wind Direction
Sample T(°C) %RH Speed (kmph) Other
VAC
VAC
VAC
VAC
VAC
VAC Middle of Methylchlorlde
L9
L5
1732
0.5
VAC
1500-1520 (7/21/77) 1,928,000 Hl-Vol
storage tanks
Upwind of Methylchlorlde
storage tanks
P5
7/21/77
Cl LI
L2
L3
L4
L5
LI
1.2
L3
L4
LI
L2
L3
L4
LI
L2
L3
L4
L5
L5
1042-0845 (7/22/77)
1115-0900 (7/22/77)
1138-0910 (7/22/77)
1210-0950 (7/22/77)
1150-0925 (7/22/77)
1010-1455
1016-1500
1025-1504
1031-1507
1230
1230
1230
1212
0845 (7/22/77)
0900 (7/22/77)
0910 (7/22/77)
0950 (7/22/77)
0925 (7/22/77)
1525-0931 (7/22/77)
179
176
174
117
175
205
216
249
221
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
1,475,000
'HHCa° 20-30 60-90 S.NW-NE, calm/1-8
^'^ah
11HC™
^ «h
HHCdb
CBD,CBNC S.SW/5-6
CBD.CBN0 Bromine upset at N1045
CBD.CBN0
CBD.CBN0 Near cooling water tower
VAC
VAC
VAC
VAC
VAC
VAC
VAC
VAC
VAC
Hi-Vol
DuPont sampler 3-6 ft elevation.
Overnight sampling.
CNutech Model 220 sampler 3-6 ft elevation.
Locations shown in Figures 6.1 and 6.2
Key to Sample Type:
HHC - Halogenated Hydrocarbon
CBN - Bromine and Chlorine
CBD - Bromide and Chloride
VAC - Aluminum Vacuum Can
-------
Table 6.3. SOIL SAMPLING PROTOCOLS SURROUNDING AND ON GREAT LAKES CHEMICAL CORP.,
EL DORADO, ARKANSAS
Period Cycle
PI Cl
7/17/77
P4 Cl
7/20/77
P5 Cl
7/21/77
P7 Cl
7/23/77
P8 Cl
7/24/77
Location
Lla
L2a
L3a
L4a
L5a
L6a
L7a
L8b
L9b
U0b
Lllb
L12b
L133
L14a
L153
L16a
L17a
L18a
L19a
Sample
Type
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
. S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
S/HHC
Sample Comments
Size
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
cores Taken '^6 M from the road in school yard
cores Parkers Chapel School
cores Samples from dry ditch beside railroad
cores
cores
cores West of methyl bromide storage in a swampy area
cores
cores
cores Northeast ^-30 M from laboratory building
cores On road to south dump
cores ^20 M west of holding pond on south edge of property
cores
cores
cores
cores
corea
cores
cores
cores
See Figure 6.3 for map of sample locations.
[3
See Figure 6.4 for map of sample locations.
S = soil samples
HHC = for halogenated hydrocarbon analysis.
-------
Table 6.4. WATER AND SEDIMENT SAMPLING PROTOCOL SURROUNDING AND ON GREAT LAKES
CHEMICAL CORPORATION AND THE EL DORADO, ARKANSAS AREA
K>
Period Cycle
PI Cl
7/17/77
P3 Cl
7/19/77
P4 Cl
7/20/77
P5 Cl
7/21/77
P7 Cl
7/23/77
P8 Cl
7/24/77
P13 Cl
7/29/77
Locution
Ll
L2
L3
L4
L5
L6
L7
L8
1.9
L10
Lll
L12
L13
L14
L15
L16
L17
LIB
L19
L10
Lll
Sample
Type
SD/HHC
SD/I11IC
W/IIHC
W/IIHC
W/HHC
W/HHC
SD/HHC
SD/HHC
W/HHC
W/HHC
W/IIHC
SD/HHC
W/IIHC
SD/HHC
W/HHC
SD/HHC
W/UHC
SD/HHC
W/IIIIC
SD/HHC
W/HHC
SD/HHC
SD/HHC
W/IIHC
W/IIIIC
SD/HHC
W/HIIC
SD/HHC
W/IIIIC
W/HIIC
SD/IIIIC
W/HIIC
W/IIHC
W/IIIIC
Sample
Size («.)
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
4
4
2
2
2
2
2
2
2
2
Comments
in swampy area
Roof run off during rain
Hard bottom ^ 21 M east (downstream)
of culvert under road - directly draining from Great Lakes
Puddle east side of Lion oil tank
Pond ^ 60 M in diameter with oil slick
Clear running water
Creek
Out fall of Great Lakes a
Upstream of out fail
Hard clay (grey)
Water backed up in reclaimatlon area
Clay/sand bottom, probably new since the entire area was recently graded
Pond 200 M north of Parker's Chapel water tower
Creek
Stream
Well water (9 M deep)
Pond
Well water
Out fall of Great Lakes
Upstream of out fall
aldentified by Jarrell Southall, Arkansas State Pollution Control and Ecology.
Locations are shown in Figure 6.5.
W = Water sample
SD = Sediment sample
HHC = for halogenated hydrocarbon analysis
-------
GREAT LAKES CHEMICAL CO E. D.
Figure 6.1- Schematic map of Great Lakes Chemical Company,
El Dorado, AK - Air sampling locations for
P2 (7/18/77) through P5 (7/21/77).
215
-------
Figure 6.2. Map of Great Lakes Chemical Co. Vicinity,
El Dorado, Arkansas - air sampling locations
(7/17/77 - 7/24/77).
216
-------
Figure 6.3. Map of Great Lakes Chemical Co. Vicinity,
El Dorado, Arkansas - soil sampling locations
(7/17/77 - 7/20/77).
217
-------
GREAT LAKES CHEMICAL CO E. D.
Figure 6.4.
Schematic map of Great Lakes Chemical Company,
El Dorado, Arkansas —_Soil Sampling Locations. (7/21/77)
218
-------
^^ < ^~*^*=*-
i X ^ s^'dStifi
, , \ -7" r" "'^ vi
:~ •-- \ ^,^i
'
•;. A ^
j , !, :• ^_V^
Figure 6.5.
Vicinity map of Great Lakes Chemical Company, El Dorado,
Arkansas - Water and sediment sampling locations (7/17/77
7/24/77).
219
-------
Table 6.5. HALIDES AND HALOGENS QUANTITATED IN AMBIENT AIR SURROUNDING
GREAT LAKES CHEMICAL CORP., EL DORADO, AK
Period/Cycle/Location3 Halide as Cl~b Halogen as Cl
1 t
ug/mj
o
P2/C1/ LI
L2
L4
P3/C1/ LI
L2
L3
P5/C1/ LI
L3
244
274
< 9
151
26
13
54
113
± 120
± 184
± 34
± 13
± 8
± 16
± 53
58
217
34
49
63
71
88
56
± 9
± 16
± 8
± 2
± 2
± 21
± 15
± 9
a
Refer to Table for sampling protocol
Values are expressed as Cl or Cl , however if Br or Br_ is the predominate species, the values should be
multiplied by 1.5.
-------
Table 6.6. AMBIENT AIR LEVELS OF VOLATILE BROMINATED ORGANICS SURROUNDING
GREAT LAKES CORP., EL DORADO, AK3
Period /Cycle /Location
01
c
0)
N
c
oi
,0
o
B
o
to
w
1 01
CNI (3
1 tO
o ji
to 4->
O 0)
rH O
rC 6
C-> O
1 h
rH PQ
1
O
s
0
to
Ji
•H 01
O fi
1 n)
CM ^
*• 4-J
rH 0)
1
O
to
0
rH
.c
o en
O 0)
B C
O nJ
rJ (X
& O
•H VJ
P ft
B
to
O
<+->
O
B
0
to
PQ
0)
1 C
CO o>
i ft
0 O
w to
o a
rH 0
fi B
o o
i to
rH M
1
O
)-i
O
rH
,c
O
•H 0)
T3 C
O «
B X
O 4J
to 01
PQ B
01
-a
•H
B
o
M
,£>
rH
>•.
rH
rH
<
tn
01
C
nj
tx
o
M
a
0
B
0
M
PQ
CO
0)
C
tO
ft
o
to
ft
O
B
0
to
rO
•H
Q
1
0
B
o
to
,Q
•H
TJ 0)
0 C
to to
0 rC
rH 4J
,C 0)
CJ B
0)
C
cfl
rC
4-1
0)
B
O
B
0
to
&
•H
P
P1/C1/L1
P2/C1/L1
L2
L3
L4
L5
P3/C1/L1
L2
L3
L4
L5
P4/C1/L1
L2
L3
L4
L5
5.3 ND
1.7
ND
ND
ND
ND
ND N
N
ND
ND
470
3,842
188
1,131
ND
29
4,276
20
51
ND
280
1,041
22
980
ND
73
70
34
2.8
ND
T
ND
ND
ND
T
ND
T
ND
22
95
271,283
2,408
20
T
2.8
8,092
39,060
3,352
32,872
ND
118
896
190
35,056
ND
1.4
1.4
ND
T
T
T
T
T
2.8
T
ND
ND
ND
5.6
T
25
20
ND
22
T
T
T
T
98
ND
T
104
ND
37
ND
ND
T
ND
ND
T
ND
ND
ND
ND
ND
T
ND
ND
ND
T
T
ND
ND
ND
T
T
ND
ND
T
ND
T
T
ND
T
ND
ND
T
ND
ND
T
ND
ND
ND
ND
ND
ND
T
T
ND
T
T
ND
T
ND
T
ND
ND
T
ND
ND
ND
ND
ND
ND
ND
ND
T
ND
ND
ND
ND
ND
ND
ND
ND
T
T
ND
T
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
(continued)
-------
Table 6.6 (cont'd)
Period /Cycle/Location
0)
c
0)
N
cl
CD
rO
O
B
O
h
pq
1 0)
CM C
1 to
o ,£
rJ 4-1
O
^
i-H
>>
rH
i-H
-------
Bromobenzene, l-chloro-2-bromoethane, dibromochloropropanes and bromoform
were also measured. Trace levels of several other brominated organics were
detected. However, in contrast to the survey sampling phase, chlorodibromo-
methane and dibromomethane were not detected.
Tables 6.7 and 6.8 present the concentration of ethylene in ambient
air surrounding the Great Lakes Chemical Corp. plants in El Dorado and
Marysville. The background levels of ethylene were approximately 1 ppm
and, in some cases, reached 6-7 ppm at locations 3 and 4 at the El Dorado
plant site. Elevated concentrations of ethylene were not detected at the
Marysville plant.
Analysis of the particulate material collected on Hi-Vol glass fiber
filters revealed the presence of traces of tetrabromobisphenol A (Table
6.9). The highest level was observed during the fourth sampling period
3
when it reached 1.8 (Jg/m . Also at this time Decabrom was detected at a
3
level of 25 Mg/m • This sampling period generally favored a downwind
position from the Tetrabrom facility.
Sediment.--Samples of sediment which were selected for analysis did
not contain detectable levels of pentabromophenol. However, relatively
large quantities of Tetrabrom and Decabrom were found (Table 6.10). In
fact, these samples represented the most contaminated of those examined. A
level of 1 g/kg of Decabrom was found in sediment taken from near an "outfall
pipe" which presumably came from Great Lakes Chemical Corp.
Soil.--Pentabromophenol was quantified in a soil sample taken ~1 mile
off property of Great Lakes Chem. Significant quantities of Tetrabrom and
Decabrom were found in other soil samples, one of which (L4) contained 150
mg/kg and 25 mg/kg of these chemicals, respectively (Table 6.11).
6.2.2 Michigan Chemical Corporation (Velsicol) and Vicinity
6.2.2.1 Sampling
The ambient air sampling protocol for Velsicol Chemical Corporation in
El Dorado, AK is given in Table 6.12. A schematic map of Velsicol showing
the air sampling locations is given in Figure 6.6. Table 6.13 presents the
sampling protocols for water and sediment surrounding and on Velsicol, Inc.
Figures 6.7 and 6.8 present the water and sediment sampling locations.
Table 6.14 presents the soil sampling protocol and Figures 6.9 and 6.10, the
223
-------
Table 6.7. CONCENTRATIONS OF ETHYLENE IN AMBIENT AIR SURROUNDING
GREAT LAKES CHEMICAL CORP.
Period/ Cycle/Location
P4/C1/L1
P4/C1/L2
P4/C1/L3
P4/C1/L4
P4/C1/L5
P4/C1/L9
Lab-la
Lab-2a
Field- 1°
Field- 2^
h
Field-3
Lab-la'<:
Lab-2a
Field-1 '°
Field- 2^ '^
b d
Field- 3°'°
b d
Field-4D>
ppm Ethylene
4.4
1.0
7.2
6.3
4.8
2.6
0.1
2.2
0.3
0.9
0.4
3.8
10.1
1.7
4.9
6.5
10.0
aStored @ 4°C in the lab.
Transported to the sampling area and returned to the lab.
Q
Spiked with 0.9 ppm ethylene.
Spiked with 9.7 ppm ethylene.
224
-------
Table 6.8. CONCENTRATIONS OF ETKYLENE IN AMBIENT AIR SURROUNDING
GREAT LAKES CHEMICAL, INC. - MARYSVILLE PLANT
Period /Cycle /Location
P1/C1/L2
P1/C1/L3
P1/C1/L4
P1/C1/L5
Lab-la
Lab-2a
Field- I?
Field- 2^
Field-3
Lab-la'°
Lab-2a>
Field- l£'C
Field- 2^'^
Field-3?**
Field-4b'd
ppm Ethylene
1.4
1.1
2.1
1.7
0.1
2.2
0.3
0.9
0.4
3.8
10.1
1.7
4.9
6.5
10.0
HStored at 4°C in the lab.
Transported to the sampling area and returned to the lab.
Q
Spiked with 0.9 ppm ethylene.
Spiked with 9.7 ppm ethylene.
225
-------
Table 6.9. RESULTS OF THE ANALYSIS OF HI-VOL FILTERS FOR SEMI -VOLATILE
BROMINATED ORGANICS - GREAT LAKES CHEMICAL CORPORATION,
EL DORADO, ARKANSAS
Tetrabromobisphenol A Decabromobiphenyl ether
Period/Cycle/Location (yg/m^)
P2/C1/L5 0.08° 8.0C
P3/C1/L5 1.2° 1.0°
P4/C1/L5 1.8C'd 25C'e
P5/C1/L5 NDC 2.0°
*q
See Table 6.2 and Figure 6.2 for locations of samples.
ho b
& 2,2 '-Bis (dibromo-4-hydroxyphenyl) propane.
Q
Quantitation by gas chromatography-mass spectrometry with multiple ion detection.
Confirmed by ion intensity ratio of 1.7 for the sample vs . 1.5 for the standard for 529/531.
g
Confirmed by ion intensity ratio for the sample of 2.8 compared to 2.7 for the sample for ion pair
800/804.
-------
Table 6.10. RESULTS OF ANALYSIS OF SEDIMENT SAMPLES FOR SEMI-VOLATILE BROMINATED ORGANICS
GREAT LAKES CHEMICAL CORPORATION, EL DORADO, ARKANSAS
Q
Period/ Cycle /Location
P4/C1/L5
P4/C1/L8
P5/C1/L10
P5/C1/L13
P6/C1/L14
Pentabromophenol
(Mg/Kg)
NDC'd
NDd
-
NDd
NDd
Tetrabromobisphenol A
(Hg/Kg)
630d
24,000d
-
330,000d
300d
Decabromobiphenyl ether
(yg/Kg)
NDC'd
14,000d
i,ooo,oooe
6,300d
NDd
See Table 6.4 and Figure 6.4 for locations of samples.
2,2'-Bis(dibromo-4-hydroxyphenyl)propane.
"Not detected - approximately 100 Mg/Kg is required to detect these compounds.
Quantitation by gas chromatography - mass spectrometry using multiple ion detection.
^
"Quantitation by thin layer chromatography.
-------
Table 6.11. RESULTS OF ANALYSIS OF SOIL SAMPLES FOR SEMI-VOLATILE BROMINATED ORGANICS
GREAT LAKES CORPORATION, EL DORADO, ARKANSAS
CO
Period/ Cycle /Location
P1/C1/L1
P4/C1/L4
P4/C1/L7
P8/C1/L38
P8/C1/L20
Pentabromophenol
(Mg/Kg)
ND°
ND
ND
200
ND
Tetrabromobisphenol A
(yg/Kg)
NDC
150,000e
8,000
2,000
ND
Decabromobiphenyl ether
(yg/Kg)
ND°
25,000d
1,400
120
ND
See Table 6.3 and Figure 6.1 for location of samples.
2, 2 ?-Bis(dibromo-4-hydroxypheny])propane.
"Not detected - approximately 50 yg/kg is required for detection of these compounds.
Quantitation by gas chromatography/mass spectrometry using multiple ion detection.
^
"Identity confirmed by full scan gc/ms analysis.
-------
Table 6.12. AMBIENT AIR SAMPLING PROTOCOL SURROUNDING. VELSICOL CHEMICAL CORP.,
EL DORADO, AK
Period
PI
7/22/77
P2
7/23/77
Sampling
Cycle Location Time
Cl LI
L2
L3
L4
L5
LI
L2
L3
L4
LI
L2
L6
L7
L8
L4
Cl LI
L2
1.3
L4
L5
LI
L2
L3
L4
LI
L2
L3
L4
L5
L4
1130-0925 (9/23/77)
1140-0945 (9/23/77)
1205-1000 (9/23/77)
1105-1015 (9/23/77)
1220-1040 (9/23/77)
1010-1455
1016-1500
1025-1504
1031-1507
1547
1550
1540
1554
1600
1115-1025 (9/23/77)
0935-0925 (9/24/77)
1400-0945 (9/24/77)
1010-1000 (9/24/77)
1020-1010 (9/24/77)
1040-1025 (9/24/77)
0930-1350
0945-1355
1000-1405
1015-1405
0930
0950
1005
1018
1040
1030-1010 (9/24/77)
Sampling
Volume W
179
<162
191
81
116
205
216
249
221
0.5
0.5
0.5
0.5
0.5
1,573,000
138
150
150
26
114
214
187
247
197
0.5
0.5
0.5
0.5
0.5
1,587,000
Meteorological Conditions
Type of Wind Direction
Sample T(°C) ZRH Speed (kmph) Other
HHCab
HUCab 18-38 52-88 NW-5-8 (4 hrs.) Pump stopped
HHCab S/0-3 (18 hrs.)
HHCab
HIICab
CBD,CBNC
CBD.CBN0 Variable Bromine upset -H045
CBD,CBNC SE,W,NW,/7
CBD,CBNC
VAC
VAC
VAC
VAC
VAC
Hi-Vol
HHCab 21-40 50-92 N,NW, variable/0-8 (13 hrs.)
HHCab S/2-8 (12 hrs.)
HHCab
HHCab
HIICab
CBD,CBNC Variable/3-5
CBD,CBNC
CBD,CBNC
CBD,CBNC
VAC
VAC
VAC
VAC
VAC
Hl-Vol
(continued)
-------
Table 6.12 (cont'd)
r-o
UJ
o
Sampling
Period Cycle Location Time
P3 Cl LI
7/24/77 L2
L3
L4
L5
LI
L2
L3
1.4
L4
1>4 Cl LI
7/25/77 1.2
L3
L4
LI
L2
L3
L4
LI
L2
1.3
L4
L5
L4
0940-1002
0950-1017
1005-1033
1055-1045
1055-1040
0925-1400
0945-1402
1005-1405
1018-1410
1015-1040
1010-1019
1026-0830
1040-0840
1055-0850
1005-1432
1025-1436
1045-1440
' 1052-1445
1005
1023
1035
1055
1100
1050-0850
(9/25/77)
(9/25/77)
(9/25/77)
(9/25/77)
(9/25/77)
(7/26/77)
(7/26/77)
(7/26/77)
(7/26/77)
(7/26/77)
Sampling
Volume (H)
121
176
149
97
26
224
189
208
199
1,617,000
218
<200
170
119
218
181
206
188
0.5
0.5
0.5
0.5
0.5
1,438,000
Meteorological Conditions
Type of Wind Direction
Sample T(°C) XRH Speed (kmph) Other
HHCab
HilC, 21-38 45-92 S/3-11 (15 hrs.)
HllCab NE.N/4-5 (5 hrs.)
H11C, Varlable/5 (5 hra.)
HllCab
CBD,CBNC S, variable/4-7
CBD,CBNC
CBD,CBNC
CBD,CBN°
Hl-Vol
HHCab 20-37 56-90 S.SE/2-12 (M6 hrs.)
HL1C NE/4-10 (^-5 hrs.) Pump stopped
HtIC,
micab
CBD,CBNC S.SE/10-12
CBU.CBN0
CBD,CBN°
CBD,CBNC
VAC
VAC
VAC
VAC
VAC
Hi-Vol
L)uPont sampler 3-6 ft elevation.
Overnight sampling.
Q
Nutech Model 220 sampler 3-6 ft elevation.
Locations shown in Figure 6.6.
Key to Sample Type:
HHC - Halogenated Hydrocarbon
CBN - Bromine and Chlorine
CBD - Bromide and Chloride
VAC - Aluminum Vacuum Can
-------
i
Figure 6.6. Schematic map of Velsicol, Inc., El Dorado, AK. Air sampling locations PI
(7/22/77) through P4 (7/25/77).
-------
Table 6.13. WATER AND SEDIMENT SAMPLING PROTOCOL SURROUNDING AND ON VELSICOL, INCORPORATED,
EL DORADO, ARKANSAS
Period
PI
7/22/77
P2
7/23/77
7/25/77
Cycle Location
Cl LI
L2
L3
Cl L4
Cl L5
Sample
Type
W/HHC3
SD/HHCa
W/HHCS
W/HHCa
W/HHCb
SD/HHC
W/HHCa
SD/HHC3
Sample
Size (£)
2
2
2
2
2
2
2
2
Comments
^1/2 km north of plant in
corridor
Sessile water
Walker Creek
^400 m west of Firemaster
Creek dried up except for
power lane
680 facility
a puddle
See Figure 6.7 for map of sample locations.
See Figure 6.8 for map of sample locations.
W = water
SD = sediment
HHC = for halogenated hydrocarbon analysis
-------
Figure 6.7. Vicinity map of Velsicol, Inc., El Dorado,
Arkansas - Water and sediment sample locations
(7/22/77 - 7/25/77).
233
-------
K)
OJ
L
$
Ju°[
IK
f
\
. , ,
L_
d
'L
V. ml.
Ik
_J
c:
T
^3
1
p
^3
n
=^
Scw<
1
^ >
qe
J ©
J
/
\
6.8. Seliematic map of Velsicol, Inc., lil Dorado, Arkansas - Water and sediment
sampl.iii(> location (7/23/77).
-------
Table 6.14. SOIL SAMPLING PROTOCOLS SURROUNDING AND ON VELSICOL, INC.,
EL DORADO, ARKANSAS
Period Cycle
PI Cl
7/22/77
P2 Cl
7/23/77
P4 Cl
7/25/77
Location
LI
L2
L3
L4
L5
I (\
LO
L7
L8
L9
L10
Lll
LI 2
L13
L14
L15
L16
L17 .
L18
L19
Sample
Type
S/HHCB
S/liHCa
S/l!HCa
s/nuca
S/HHC8
q /nvira
a/ llrllj
S/HliC8
S/HHC3
S/HHcf'
S/I1HC
S/HHC
S/I1HC
S/HHC
S/HHC!"
S/HHC
S/HUC
S/HHC3
S/HHCd
S/HHCr
Sample
Size
2
2
2
2
2
•i
^
2
2
2
2
2
2
2
2
2
2
2
2
2
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
cores
Comments
Near r.r. tracks (fill dirt).
Between r.r. tracks and sewage treatment facility in a dry stream bed.
Near r.r. tracks.
In power line right of way - woods on either side.
West of plant beyond a fill area - woods on west side of location.
Near service road.
From clearing next to car wash at entrance.
'^-500 M from bromine extraction In power line corridor.
^20 M north of road in a grassy area.
^2 KM WSW of Velsicol on trail through woods.
Between dirt road and r.r. tracks near power substation.
'^1/2 KM east of plant at a power substation.
M/2 KM north of plant.
^2 KM due south of plant.
From ditch with water probably run off next to Flremaster 680 warehouse.
From the hill above the ditch (L17).
^1 KM due east of plant on power line right of way.
aSee Figure 6.9 for map of sample locations.
See Figure 6.10 for map of sample locations.
S = soil sample
HHC = for halogenated hydrocarbon analysis
-------
Figure 6.9.
Schematic map of Velsicol, Inc., El Dorado,
Arkansas - Soil sampling locations (7/22/77
to 7/25/77).
216
-------
Figure 6.10. Vicinity map of Velsicol, Inc., El Dorado,
Arkansas - Soil sampling locations (7/22/77
to 7/25/77).
237
-------
corresponding sampling locations. Table 6.15 gives the sampling protocols
for the biota which were taken surrounding and on Velsicol, Inc. while
Figures 6.11 and 6.12 depict the locations of sampling.
6.2.2.2 Inorganics in Ambient Air
Table 6.16 gives the concentrations of halides and halogens in ambient
air surrounding Velsicol. The samples were selected for analysis on the
basis of meteorological conditions. The detection limit for halide was
3
approximately <10 [Jg/m . The highest halide level detected occurred during
3
the fourth sampling period at L3 when a level of 91 Hg/m was reached. The
3
concentration of halogen, on the other hand, was observed to be 219 [Jg/m
at the third location during the third sampling period. Inspection of
these data indicate a concomitant increase and decrease in the levels of
halides and halogen during the various sampling periods.
6.2.2.3 Brominated and Other Organics
Air.--The ambient air levels of volatile brominated organics surrounding
Velsicol, Inc. are given in Table 6.17. Many brominated organics which
were detected during the Survey Phase (see Section 4.2.3.5) were not detected
during this phase. Ethylene dibromide, dibromochloropropane (DBCP) and
chlorodibromomethane were detected at relatively low concentrations through-
out each of the four sampling periods.
Table 6.18 gives the concentrations of ethylene in ambient air.
Recalling that the background concentration is M).6 - 1.0 ppm, the highest
level of ethylene was found at L7 at which time it reached 6.8 ppm.
The glass fiber filters were analyzed according to the procedures in
Appendix A for semi-volatile brominated organics. The results are presented
in Table 6.19. With the particulate samples collected by Hi-Vol samplers
the interpretation of a positive finding is complicated by the possibility
that the compounds found may not be current emissions. They may be adsorbed
onto soil particles which continue to be resuspended in the air. The
primary counterindication of the above is the presence of varying combina-
tions of material from day to day especially TRIS and Firemaster 680 with
very similar meteorology.
A control filter was spiked with TRIS, Tetrabrom and Decabrom using a
2
matrix of 10 cm (2 cm x 5 cm) alternating spiked areas with blank areas. A
238
-------
Table 6.15. VEGETATION AND MISCELLANEOUS SAMPLING PROTOCOLS SURROUNDING AND ON
VELSICOL, INC., EL DORADO, ARKANSAS
Period Cycle
PI Cl
7/22/77
P2 Cl
7/23/77
Location
LI
L2
L3
L4A
L4B
L5
Sample Type
V/HHCa
V/HHCJ*
V/HHC:*
V/HHC"
V/HHC
M/HHCb
Sample Size (£) Comments
Fern type leaves
Corn
Tomato
Cabbage
0.5 Cow's milk
%
See Figure 6.11 for map of sample locations.
See Figure 6.12 for map of sample locations.
V = vegetation
M = miscellaneous samples
HHC = for halogenated hydrocarbon analysis
-------
Figure 6.11.
Schematic map of Velsicol, Inc., El
Dorado, Arkansas - Vegetation and
miscellaneous sampling locations
(7/22/77 - 7/23/77).
240
-------
Figure 6.12. Map of the vicinity of Velsicol, Inc., El
Dorado, Arkansas - Vegetation and miscellaneous
sample locations (7/22/77 - 7/23/77).
241
-------
Table 6.16. HALIDES AND HALOGENS QUANTITATED IN AMBIENT AIR SURROUNDING
VELSICOL, INC., EL DORADO, AK.
Period /Cycle /Location
P1/C1/L1
L3
L4
P2/C1/L1
L3
L4
P3/C1/L1
L3
L4
P4/C1/L1
L3
L4
Halide as Cl b
3
yg/m
83 ± 18
27 ± 6
51 ± 1
<21
35 i 7
<18
<15
63 ± 8
<10
< 8
91 ± 8
<18
Halogen as Cli
yg/m
41 ±
75 ±
75 ±
< 8
81 ±
<20
<17
219 ±
<20
41 ±
158 ±
74 ±
10
45C
30
38C
9
16
44C
21
'Refer to Table 6.12 Cor sampling protocol.
hValue.4 are expressed as Cl~ or Cl . However, if Br~ or
should be multiplied by 1.5.
is the predominant species, the values
"An amber color developed when AgNO was added in the procedure.
-------
Table 6.17. AMBIENT AIR LEVELS OF V01JVITLE BROMINATED ORCANICS SURROUNDING
VELSICOL CHEMICAL CORP., EL DORADO, AK
Period /Cycle /Location
P1/C1/L1
L2
L3
L4
L5
P2/C1/L1
L2
L3
L4
L5
P3/C1/L1
L2
L3
L4
L5
P4/C1/L1
L2
L3'
L4
OJ
c
n)
rC
4-1
OJ
O
B
o
^4
fd
•H
P
1
04
rH
493
227 + 45
501
45
448
T
868
T
280
120
T
T
2,425
ND
342
67
ND
193
171
i
o
j-<
o
rH
^
O
O QJ
e c
O n)
M (X
& O
•H 1-1
P fX
93
174
7.8
34
14
12
187
37
32
T
ND
T
T
T
T
ND
ND
T
T
B
H
o
M-l
o
B
o
H
PQ
ND
T
T
ND
ND
ND
T
ND
T
ND
T
ND
T
ND
ND
ND
ND
ND
ND
o
B
o
M
.O
1
C*"l
1
0
M QJ
0 R
rH n)
rC ex
U 0
•H (X
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
I
o
r-|
0
rH
_r{
O
•H QJ
T3 C
o m
fc rG
O 4J
)-l QJ
W B
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
QJ
TD
•H
B
O
A
rH
J>^
rH
rH
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
W
OJ
c
(X
0
M
CX
0
B
O
M
PQ
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
w
QJ
C
(0
tx
O
n
{X
O
B
0
,£>
•H
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
•
i
0
B
o
,0
•H
tj QJ
O C
t-l CO
O £.
rH 4-J
.C QJ
ND
QJ
C
r^
4-1
QJ
B
O
B
O
M
,0
•H
P
ND
8.4 + 2.8 ND
ND
T
31
ND
T
ND
T
22
T
23
ND
8L
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
values are in ng/
m
-------
Table 6.18. CONCENTRATIONS OF ETHYLENE IN AMBIENT AIR SURROUNDING
VELSICOL CHEMICAL INC.
Period/Cycle/Location ppm Ethylene
P1/C1/L1
P1/C1/L2
P1/C1/L6
P1/C1/L7
P1/C1/L8
Lab-13
Lab-2a
Field- if
Field- 2T
Field-3
Lab-l3'*:
Lab-2a'£
Field- if 'C
Field- 2? 'j
r\ H
Field- 3^'^
Field-4 '
0.6
3.8
2.3
6.8
5.3
0.1
2.2
0.3
0.9
0.4
3.8
10.1
1.7
4.9
6.5
10.0
o
Stored at 4°C in the laboratory.
Transported to the sampling area and returned to the lab.
£
Spiked with 0.9 ppm ethylene.
Spiked with 9.7 ppm ethylene.
244
-------
Table 6.19. BROMINATED ORGANICS FOUND ON GLASS FIBER FILTERS FROM HI-VOL SAMPLERS
NJ
-p-
Ul
Period/Cycle/Location
P1/C1/L4
P2/C1/L4
P3/C1/L4
P4/C1/L4
aGLC/MS/COMP analysis
b
ion intensity ratio
Tetrabromobis-
phenol A
28a,b
ND3
ND3
NDa
in the multiple ion
of m/e 529/531 was 1
Firemaster 680
ng/m^
39a,c
NDa
1?2a,c
183a>C
Tris (2 , 3-dibromo- Decabromobiphenyl
propyl)phosphate ether
60d ND
44d NDa
51d NDa
NDd 723>C
detection mode.
.42 vs. 1.48 for standard tetrabromobisphenol A.
c
One ion monitored, no confirmation.
3
Analysis by GLC/ECD. Results are uncorrected for recovery which was 87% at an equivalent to 27 ng/nT
and 91% at an equivalent to 287 ng/m of TRIS.
-------
24 hr Hi-Vol air sample of 2000 m3 was collected at RTI, RTF. Recoveries
of 2 areas analyzed for TRIS are given in Table 6.20.
Table 6.20. TRIS RECOVERY STUDY
Amount
of TRIS added
(Hg)
11.1
1.04
Amount of TRIS found3
(yg)
10.2
0.90
% Recovered
91
87
aAnalysis by GLC/ECD.
This filter was transported to the field and returned before analysis.
Water and Sediment.--Water samples P1/C1/L1 and P4/C1/L5 (see Table
6.13 and Figures 6.6 and 6.8) were analyzed by the VOA method for qualitative
information. No brominated compounds were identified by this method.
Water and sediment samples from Velsicol were analyzed for semi-vola-
tile brominated organics according to the protocol in Appendix A. The
results are shown in Table 6.21. The TRIS found in the water sample P1/C1/
L3 is indicative of water transport since the creek sampled is part of the
Velsicol watershed. The origin of Firemaster 680 and TRIS at P4/C1/L5 is
less obvious. This location is 1.5 km from the facility and airborne
contamination may contribute. The watershed for this stream extends to
within 0.6 km of the facility. At the time the sample was collected drought
had reduced the stream to a pool approximately 2 x 5 m. The combination of
airborne dispersion and collection and dispersion of runoff water may have
resulted in the TRIS and Firemaster 680 levels observed.
Soil.--Qualitative analysis of soil samples near Velsicol Chemical
Corp. was performed on two samples. The findings are presented in Table
6.22.
Analysis of soil samples was by GLC/MS/COMP according to the protocol
in Appendix A. The results are given in Table 6.23. Soil sample P1/C1/L3
was further analyzed in the full scan mode. The results of the spectral
interpretation are given in Table 6.24, Spectra of three peaks are included
as Figures 6.13, 6.14, 6.15, and 6.16 along with the spectra of standards
246
-------
Table 6.21.
RESULTS OF ANALYSIS OF SEDIMENT AND WATER SAMPLES FOR SEMI-VOLATILE
BROMINATED ORGANICS - VELSICOL, INC., EL DORADO, ARKANSAS
a
Period /Cycle/Location
P1/C1/L1
P1/C1/L3
P4/C1/L5
Sample
Type
SD/HHC
W/HHC
SD/HHC
W/HHC
SD/HHC
W/HHC
Tetrabromo-,
bisphenol A
Mg/kg
30d
NDf
ND
Firemaster
680C
Pg/kg
"6"e
NDf
ioh
Tris(2,3-dibromo-
propyl) phosphate
Ug/kg
NDf
26008
ND8
NDf
108
NDf'8
2g
See Table 6.13 and Figures 6.7 and 6.8.
2,2'-Bis(dibromo-4-hydroxyphenyl)propane.
"1,2-bis(2,4,6-tribromophenoxy)ethane.
j
Quantitation by gas chromatography-mass spectrometry with multiple ion detection. The ions
529 and 531 were monitored giving an intensity ratio of 1.57 for the sample compared to 1.5 + 0.1
for standards under the same conditions.
a
"Quantitation by gas chromatography-mass spectrometry with multiple ion detection. The ion 357
and retention time were used for identification. This ion is not very specific; however, it is the
most prominent in the mass spectrum of Firemaster 680.
g
Not detected by gas chromatography-mass spectrometry with multiple ion detection.
Quantitation by gas chromatography-electron capture detection.
Quantitation by gas chromatography-mass spectrometry with multiple ion detection using three ions,
m/e 690 and 688 which are very specific for Firemaster 680 although less sensitive than m/e 357.
-------
Table 6.22. QUALITATIVE ANALYSIS OF VOLATILE HALOGENATED ORGANICS
IN SOIL SAMPLES COLLECTED NEAR VELSICOL CHEMICAL CORPORATION,
EL DORADO, AK
Period/Cycle/Location
Halogenated Compounds Identified
P1/C1/L2
P1/C1/L3
bromobenzene
l-chloro-2,3-dibromopropane'
1,2-dichloroethane
None detected
Tentative identification
248
-------
Table 6.23.
RESULTS OF ANALYSIS OF SOIL SAMPLES FOR SEMI-VOLATILE BROMINATED ORGANICS -
VELSICOL, INC., EL DORADO, ARKANSAS
a
Period/Cycle/Location
P1/C1/L2
P1/C1/L3
P1/C1/L5
P1/C1/L7
P1/C1/L9
P1/C1/L10
Tetrabromo-,
blsphenol A
Mg/Kg
ND
13°h
90h
ND
60f
ND
118f
Firemaater
680C
Wg/Kg
5900d
64006
400?
330h
ND
<6
166d
253d
Trls(2,3-dibrom0-
propyl) phosphate
Pg/Kg
NDk>1
100 - 5008
1300i»J
NDk
300
NDk>1
NDk>1
mkti
P1/C1/L13
P2/C1/L14
ND
ND
68"
iood
840 *J
NDk>1
. Soo Table 1 and llrurcM 2 nut] 3 fur location of camples,
2,2-Bin (d lbroiuo-6--lrlhri>rm>phened. m/c 'i!9. '"17 nnd 337. The st anJ.irilri
Ion Intensities ratios of 0.8 1 0.2; l.Oj 1.9 i 0.2, rospect ively ,
p.tred tn the sample Intensity r.itloa of II.',; 1.0; 3.8. 'Ihln la not very |;ood agreement and Indicates further n.iniplf pur I f leal ion
ii'<|nlrid lor a rlp,'ir
-------
Table 6.24. MOMINATED COMPOUNDS IDENTIFIED FROM GAS CHROMATOGRAPHY - MASS SPECTROMETRY ANALYSIS OF
SOIL SAMPLE Pl/Cl/L3a FROM VELSICOL, INC., EL DORADO, ARKANSAS
Retention
Time (min) Compound
0.19 C10H,Br00 (tent.)
12 O L
0.33 [m/e 360, 362; Br = 3]
0.39 C^oBr, (tent.) and CJ^.O.P BrQ (tent.)
624 9 14 4 J
2.06 cH° Br[2»2
C H O.P Br [Tris(2,3-dibromopropyl)phosphate]
3.33 C, . H00,,Br , [ 1 , 2-bis (2 ,4 , 6-tribromophenoxy) ethane ]
14 o 2. O
6.06 C10H,Br,.0 (tent.)° and C.-HJBr,. (tent.)C
12 5 5 12 5 j
o 6.59 [m/e 690 + 1, 576 + 1 and 439 + 1 containing halogens]
6.86 [m/e 626 + 1, 609 + 1, 594 + 1, 576 + 1, 429 + 1 and
339 + 1 containing halogens]
7.06 C _Br 0 [decabromobiphenyl ether]
aSee Table 6.14 and Figures 6.8 and 6.9 for sample location.
Gas chromatography conditions: 2% OV-101 on Gas Chrom Q; column, 45 cm x 0.2 cm i.d.; 20 cc/min helium;
initial temperature 220°C, programmed at 12°/min to 300°C.
The identification represents the empirical formula for the highest mass observed in the mass spectrum;
however, the higher brominated homologs in this series also give these ions. The retention time is
similar Lo that of the octa- or nona- brominated biphenyl or biphenyl ether.
-------
160-
90-
80-
70-
60-
50-
-40-
30-
20-
10
oo -
200
2 B
;.FECTFUir 31
EiHLl.&K'OUIIti
300 3-50
.06'IIIMUTES
TF.I' "
.,„„„, ftf — ^-p^Y^-TT-pr.
(a)
»lin 1? J.Od MIHUTlS
(b)
(c)
Figure 6.13.
Mass spectrum of GC peak eluting at 2.06 min from soil sample L1/C1/L3.
(a) Sample spectrum (GLC); (b) TRIS spectrum (Direct probe); (c) Tetra-
brom spectrum (Direct probe).
-------
Itl
,
350
I—X'lB-->
.150
f.uu
slo
sda
10-
10-
°" '1 1 1""" ,'i-r-r-n-l •T-f-r-r- , .
nl) ?*.o
fkr',i'SPt'l TK'UH" SI 3.'3'il IIIIIUTES'
SUBTf'hCTf li '
T '"'I ....... I "'• '|
BUO
-T~r-T-.|-r-rr1~n-,-r-,-p-.|-n-rr.T..T.T"T..p.-,
A] 'njo y,n
l'-b-S :l IK -a. 21'Q I \2 i II. -S. 2i:V.":i ILL ,
Figure 6.14. Mass spectrum of GC peak eluting at 3.4 min from soil sample P1/C1/L3.
-------
M
Ul
CO
IUO-
iit)
E:0-
i'H-
i.iJ-
•4i-l-
V
II I
p.T.^.H,,!i! .'lltnpl^vj
bBQ
!uu-|
^n-
CO
'0
bU
50
lu-
(ill,
fjlll
rrJ^-l~
;V
" I OS ?.n
.FYii.iiili Ulfmiii II I'
111
i|
0. At 9UU
C-y.?i'Oi | j i .-M.-8.2I V.~.|ir
Figure 6.15. Mass spectrum of GC peak eluting at 7.00 min from soil sample
P1/C1/L3 identified as decabrom-biphenyl ether.
-------
400 4'JO *QO
r-o
Ui
IQd-
90-
BQ-
70-
60-
40-
30-
20-
1U
00-
S'Jll ' ' ' ' 600 ' ' ' ' do ' '
V\-y> SF'EinkMII .17 5.?3 II1IIUTES
ChCKGPOIJIIb
'|
TOO
FIREm3TEF:e30,»IP.PRUBE.-8. 1.7KV. 10-03-7?
Figure 6.16. Mass spectrum of authentic Firemaster 680 (direct probe)
-------
of the brominated compounds identified. This is the first occasion where
TRIS could be confirmed by full scan rather than ion intensity ratios.
Soil sample P1/C1/L2 and P1/C1/L3 represent contamination by facility
activities such as loading and processing the materials found. The samples
at locations 5, 7 and 9, although within the facility, are not in areas
obviously involved in processing or handling brominated compounds. Locations
10 and 14 are even more remote from the process area and there is no obvious
activity which should lead to contamination except for airborne dispersion.
(The watershed drains the opposite direction.)
6.2.3 Ethyl Corporation and Vicinity
6.2.3.1 Sampling
Table 6.25 presents the sampling protocol for ambient air surrounding
Ethyl Corporation in Magnolia, AK. The corresponding air sampling locations
for these periods are given in Figure 6.17.
6.2.3.2 Inorganics in Ambient Air
Table 6.26 presents the halides and halogens which were quantified in
ambient air surrouding Ethyl Corporation. Relative to other bromine indus-
trial units, the concentrations of halide and halogen which were detected
at Ethyl Corporation were much lower and nearer the detection limit of the
analytical methods.
6.2.3.3 Brominated and Other Organics
Air.--The ambient air levels for several volatile brominated organics
surrounding Ethyl Corporation are given in Table 6.27. Only three brominated
organics, ethylene dibromide, a bromopropane and l-chloro-3-bromopropane
were detected. The highest concentrations observed were for 1,2-dibromo-
3
ethane which was generally at levels of 1-5 (Jg/m • No other brominated
organics were detected in ambient air (Table 6.27).
Table 6.28 gives the concentrations of ethylene in ambient air that
were detected at Ethyl Corporation. Except for Location 1 (9.8 ppm), the
concentrations of ethylene were near background levels.
Soil.--No brominated organics were detected.
255
-------
Table 6.25. AMBIENT AIR SAMPLING PROTOCOL SURROUNDING ETHYL CORP.,
MAGNOLIA, AK
|NJ
Ln
Period Cycle
Fl Cl
(7/26/77)
P2 Cl
(7/27/77)
P3 Cl
(7/28/77)
Sampling
Location Time
LI
L2
L3
LI
L2
L3
LA
LI
L2
L3
LA
LI
L2
L3
LA
L5
LI
L2
LI
L2
L3
LA
LI
L2
L3
LA
LI
L2
L3
LA
L6
LI
L2
1620-0935
1655-1000
1708-1018
09A5-08A5
1005-0900
1020-1000
1055-1012
0945-1AOO
1005- 1A05
1020-1A10
10A5-1A15
09AO
1000
1022
10AO
1300
0940-0850
1002-0900
0850-08A5
0915-0915
1002-1005
1035-0955
08A5-12A5
0930-12A5
0955-1420
1010-1A55
08A5
0900
0955
1010
1050
0855-0855
12A7-0905
(7/27/77
(7/27/77)
(7/27/77)
(7/28/77)
(7/28/77)
(7/28/77)
(7/28/77)
(7/28/77)
(7/28/77)
(7/29/77)
(7/29/77)
(7/29/77)
(7/29/77)
(7/29/77)
(7/29/77)
Sampling
Volume W
99
126
79
120
18A
113
•x, AO
181
311
200
175
0.5
0.5
0.5
0.5
0.5
1,475,000
2,187,000
70
177
118
•^210
167
178
225
171
0.5
0.5
0.5
0.5
0.5
1.A67.000
1,792,000
Type of Meteorological Conditions
Sample T(°C) %RH Wind Direction
Speed (kmph) Other
HHCak 17-33 50-90 N.NE/6-10
HHCa°
HHCab
HHC3^ 19-32 65-90 E/5-6 (2 1/2 hrs)
HHCa° N/7-20 (2 hra.)
HHCa^ E to N Bhlftlng/A-6 (5 hrs)
HHC N, NW/1-3 (12 1/2 hrs) pump not fully functional
CBD,CBNC
CBD,CBNC 19-3A 65-92 E/5-6 (2 1/2 lire)
CBD.CBN0 N/7-20 (2 hrs)
CBD.CBN0
VAC
VAC
VAC
VAC
VAC
Hl-Vol
Hi-Vol
IIHCa[> 22-32 68-92 SE to W/A-5 (A hra)
tlHc'T E to W/8-10 (7 hrs)
HHCa^ N, calm (7 hrs) with inter-
HHC mittant NE/5 (1 hr) and battery dead at end
SE/8 (1 hr) of period
SE/5 (2 hrs)
CBU.CBN0
CBD.CBN0
CBD.CBN0
CBD.CBN0
VAC
VAC
VAC
VAC near tank car marked
VAC allyl chloride
Hl-Vol
Hi-Vol
(continued)
-------
Table 6.25 (cont'd)
K>
Ln
Period Cycle
P4 Cl
(7/29/77)
Sampling
Location Time
LI
L2
L3
L4
LI
L2
L3
L4
LI
L2
L3
L4
LI
L2
0900-1125
0925-1130
1015-1150
1000-1150
0900-1315
0930-1350
0830-1245
0950-1405
1340
1350
1415
1405
0900-1245
0910-1205
(7/30/77)
(7/30/77)
(7/30/77)
(7/30/77)
(7/30/77)
(7/30/77)
Sampling
Volume (£)
126
192
118
<418
170
187
171
177
0.5
0.5
0.5
0.5
1,673,000
2,331,000
Type of Meteorological Conditions
Sample T(°C) ZRH Wind Direction
Speed (krnph) Other
mca* 19-32 60-92 SW to W/9-12 (9 hrs)
HllCa£ mostly calm (11 hrs) with
KHCa. occasional gust (S and
HHC" SE at 3-5) pump stopped
S/4-15 (5 hrs)
CBD.CBN0 SW to W/9-12 upset at 0915, orange
CBD.CBN0 clouds moving toward
CBD,CBNC location 1
CBD.CBN0
VAC
VAC
VAC
VAC
Hl-Vol
Hi-Vol
DuPont sampler 3-6 ft elevation
Overnight sampling
GNutech Model 220 sampler 3-6 ft elevation
A field adapted Walker Minnow aeration pump.
Locations shown in Figure 6.17.
Key to Sample Type:
HHC - Halogenated Hydrocarbon
CBN - Bromine and Chlorine
CBD - Bromide and Chloride
VAC - Aluminum Vacuum Can
-------
Ln
OO
Figure 6.17.
Schematic map of Ethyl Corporation, Magnolia, AK - Air sampling
locations P1-P6 (7/26/77 through 7/30/77).
-------
Table 6.26. HALIDES AND HALOGENS QUANTITAXED IN AMBIENT AIR SURROUNDING
ETHYL CORPORATION, MACNOLFA, AR3
Period/Cycle/Location Halide as Cl Halogen as Cl
3 3
yg/m yg/m
P2/C1/L1 <1A <22
L2 18+12 19 ± 6
L3 <17 <20
LA 39 ± 20 <22
P3/C1/L1 36 ± 12 96 ± 36
M L2 A5 ±23 3A ± 23
£ LA <12 A6 ± 23
PA/C1/L1 57 ± 23 A5 ± 11
L2 <20 AO ± 20
LA Al ±51 A5 ± 22
r\
Refer to Table 6.25 for sampling protocol.
Values are expressed as Cl or Cl 5 however, if Br or Br_ is the predominant species, the
values should be multiplied by 1.5.
-------
Table- 6.27. AMBIENT AIR LEVELS
i FOR SEVERAL VOLATILE BROMINATED ORGANICS SURROUNDING
ETHYL CORP., MAGNOLIA, AK
Period /Cycle /Location
c
cO
.r!
4-J
-------
Table 6.28. CONCENTRATIONS OF ETHYLENE IN AMBIENT AIR SURROUNDING
ETHYL CORPORATION, MAGNOLIA, AK
Period/Cycle/Location
P3/C1/L1
P3/C1/L2
P3/C1/L3
P3/C1/L4
P3/C1/L6
Lab-la
Lab-2a
Field- 1?
h
Field- 2°
Field-3
Lab-la'C
Lab-2a
Field-!?'0
Field- 2^'°
Field-3?'*
h H
Field-4D'a
ppm Ethylene
9.8
2.9
3.5
3.4
2.1
0.1
2.2
0.3
0.9
0.4
3.8
10.1
1.7
4.9
6.5
10.0
Stored at 4°C in the laboratory.
Transported to the sampling area and returned to the lab.
Spiked with 0.9 ppm ethylene.
Spiked with 9.7 ppm ethylene.
261
-------
6.2.4 Dow Chemical Company and Vicinity
6.2.4.1 Sampling
Table 6.29 gives the ambient air sampling protocol for Dow Chemical
Company. Figures 6.18-6.20 depict the air sampling locations described in
Table 6.29. Table 6.30 presents the sampling protocols for water and
sediment for this area. Figure 6.21 depicts the sampling locations for
water and sediment on and in the vicinity of Dow Chemical Co. in Magnolia.
Table 6.31 lists the sampling protocols for soil and the locations are
given in Figure 6.22.
6.2.4.2 Inorganics in Ambient Air
The concentrations of halides and halogens determined in ambient air
surrounding Dow Chemical Co. is given in Table 6.32. No halide was detected
3
in any of these samples with a detection limit of ^5 pg/m . Relatively low
concentrations of halogen were detected in samples at locations 3 and 4
during cycles 1 and 2.
6.2.4.3 Brominated and Other Organics
Air.--Table 6.33 presents the concentrations of volatile brominated
organics which were estimated in ambient air surrounding Dow Chemical Co.
The most prevalent brominated species was 1,2-dibromoethane and the highest
3
concentration observed was 62,848 ng/m during the second sampling period
at location No. 4. Included are the concentrations of styrene which were
detected in the air samples taken at Dow Chemical Co. The most prevalent
occurrence of styrene was observed at L2 during the third sampling period
3
at which time it reached a level of 19,656 ng/m .
Table 6.34 presents the concentrations of ethylene in ambient air
surrounding Dow. As indicated in this table, the levels of ethylene were
generally near background concentrations.
Water and Sediment.--Water and sediment samples were analyzed by the
VGA procedure given in Appendix A. The results are presented in Table
6.35. Among the sediment and water samples, P3/C1/L7 contained an extensive
number of halogenated organics. These samples were taken in an area subject
to overflow runoff from the settling ponds nearby.
Soil.--Soil samples were analyzed by the VGA procedure in Appendix A
for the identification of halogenated organics. The results are given in
Table 6.36.
262
-------
Table 6.29. AMBIENT AIR SAMPLING PROTOCOL FOR DOW CHEMICAL CO., MAGNOLIA, AK
tsi
C^
LO
Period Cycle Location
8/1/77 Cl LI
PI L2
L3
1.1
L3
L4
LI
L4
8/2/77 Cl LI
P2
1.2
L3
L4
1.5
LI
L3
L4
L5
L3
L5
LI
L2
L3
L4
L5
Sampling
Time
1055-0950
1130-1030
1208-1100
1045-1510
1200-1535
1150-1530
'1045-1000
1210-1155
1000-1005
1040-1025
1150-1105
1110-1045
•12)0-0945
1015-1440
1155-1450
1115-1455
0955-1355
1100-1040
1005-0950
1020
1030
1230
1200
1400
(8/2/77)
(8/2/77)
(8/2/77)
(8/2/77)
(8/2/77)
(8/3/77)
(8/3/77)
(8/3/77)
(8/3/77)
(8/3/77)
(8/3/77)
(8/3/77)
Sampling
Volume (4)
169
89
169
198
168
161
1,520,000
1,996,000
130
77
729
75
670
223
183
169
183
1,950,000
1,472,000
-
-
-
-
Type of Meteorological Conditions
Sample T(°C) ZRH Wind Direction
Speed (kmph) Other
IIIIC3!' 17-32 70-90 N.NE.NW./2-7
HHCab
HIICab
CBN,CBD°
CBN,CBD°
CBN,CBD£ 30-32 70 n.nw/5-7
Hi-Vol£
Hl-Vol
HHCab 14-33 55-92 NE.NW/2-9
IIIIC
HIICCb
line
imc
CIIN,CI)DC 27-33 60-80 NE/9
CUN,C1)DC
CBN.CBD0
CBN.CBD'"
Ill-Vol^
Hl-Vol
VAC
VAC
VAC
VAC
VAC
DuPoiit sampler 3-6 ft elevation
Overnight sampling
Nulech Model 220 sampler 3-6 ft elevation
Locations shown In Figures 6.18—6.20
Key to Sample Type:
IIIIC - Nalogenated Hydrocarbon
CBN - Bromine and chlorine
CBD - Bromide and Chloride
VAC - Aluminum Vacuum Can
(continued)
-------
Table 6.29 (cont'd)
I'erlod Cycle
8/V77 Cl
P3
C2
Dul'ont sampler 3-6 ft
Overnight sampling
kl ..*-,. ~l. »J.. .1 ., 1 O Tf\ — .. 1
Location
1,1
L2
1.3
L4
1.5
1.1
L3
L4
1.5
L6
1.3
L5
1.1
L3
1.4
L5
elevation
1 1 £ c *.
Sampling
Time
1015-0830
1035-0840
1120-0846
1100-0900
1000-0820
1005-1615
1045-1630
1100-1645
0950-1600
1600
1050-0850
1000-0825
1625-0830
1640-0850
1650-0900
1615-0820
_ 1 ». j
(8/4/77)
(8/4/77)
(8/4/77)
(8/4/77)
(8/4/77)
•
•
(8/4/77)
(8/4/77)
(8/4/77)
(8/4/77)
(8/4/77)
(8/4/77)
Sampling
Volume (H)
180
59
640
178
652
302
280
275
287
_
1,793.000
1,313,000
506
424
518
392
Type of
Sample T("C)
HHC^ 16-35
IIIIC,ab
micb,c
iincf
imcbc
C11N,CBDC 32-34
CBN.CBD0
CBN,CBDC
CBN.CBD0
VAC
111-VoC
Hl-Vol
CBN,CBDbC 16-34
CBN.CB1)
CBN,CUU°C
CBN.CBD
— r™ — ~
Meteorological Conditions
2RU Wind Direction
Speed (ktnph) Other
45-92 E Var, NW/2-9
48 E Var/5-8
Upset of Br.. during at least
the last 1/2 hr. Odor of Br.
2
45-92 E/3-5.(4 hrs.) Upset of Br, Just before
NW/<2 (12 hrs.) Sampling
Odor noticeable, possibly
IIBc
Key to Sample Type: IIHC - Halogenated Hydrocarbon
CBN - Bromine and chlorine
Location shown in Figures 6.18-6.20
CRD - Bromide and Chloride
VAC - Aluminum Vacuum Can
-------
Figure 6.18. Schematic map of Dow Chemical Company, Magnolia,
Arkansas - Air sampling locations for PI -
8/1/77
265
-------
Figure 6.19. Schematic map of Dow Chemical Company, Magnolia,
Arkansas - Air sampling locations for P2 -
8/2/77.
266
-------
Figure 6.20. Schematic map of Dow Chemical Company, Magnolia,
Arkansas - Air sampling locations for P3 -
8/3/77
267
-------
Table 6.30. WATER AND SEDIMENT SAMPLING PROTOCOLS FOR DOW CHEMICAL COMPANY,
MAGNOLIA, ARKANSAS
oo
Period Cycle
PI Cl
7/30/77
P2 Cl
8/1/77
P3 Cl
8/2/77
P4 Cl
8/3/77
Location
LI
L2
L3
L4
L5
L6
L7
L8
L9
L10
Lll
Sample
Type
W/HHC
W/HHC
SD/HHC
W/HHC
W/HHC
SD/HHC
W/HHC
W/HHC
W/HHC
SD/HHC
W/HHC
W/HHC
W/HHC
SD/HHC
W/HHC
Sample
Size
21
21
2£
2£
2£
2£
2£
2£
2£
2£
2£
2£
2£
2£
2£
Comments
water from small pond - runoff after rain
pond water
pond sediment (drainage from pond)
drainage from pond
stream water
stream sediment
runoff (after rain) from Dow settling ponds
stream water
standing water
stream water
small stream
pond beside road
pond beside road
very slow stream
Locations are shown in Figure 6.21.
W = water samples
SD = sediment samples
HHC = for halogenated hydrocarbon analysis
-------
•H
i—I
O
G
60
O
CJ
cfl
O
-H
0)
4=
u
I
p
O
•H
to --.
C ro
O —
•H CO
4-1
tfl I
O
O r^
t—I r~-
00 C^
C CN
•H --.
-H r~
{Xs-'
Cfl M
M Cd
cn
VJ C
o
•H
269
-------
Table 6.31.
SOIL SAMPLING PROTOCOLS FOR DOW CHEMICAL COMPANY,
MAGNOLIA, ARKANSAS3
Period Cycle
PI Cl
7/30/77
P3 Cl
8/2/77
Location
LI
L2
L3
L4
L5
L6
Sample Size
2
2
2
2
2
2
cores
cores
cores
cores
cores
cores
Comments
Box Springs Road
Near air sampler
Near air sampler
At NE corner of drive
Rt. 344 at Rt. 132
into plant
Locations of sampling are shown in Figure 6.22.
-------
Figure 6.22. Sampling locations for soil samples
collected in the vicinity of Dow Chemical
Co. (7/30/77 - 8/2/77).
271
-------
Table 6.32. HAL1DES AND HALOGENS QUANTITATED IN AMBIENT AIR SURROUNDING
DOW CHEMICAL COMPANY MAGNOLIA, AK
K>
Q
Period /Cycle /Location
a
b
P3/C1/L2
L3
L4
P3/C2/L2
L3
L4
Refer to Table 6.29 for sampling protocol.
_
Halide as Cl b
yg/m3
< 5
< 5
< 6
< 5
< 6
< 4
_
Halogen as Cl-
yg/m
< 12
64 ± 5
< 6
< 10
14 ± 7
18 ± 9
Values are expressed as Cl or Cl ; however, if Br or Br? is the predominant species, the values should be
multiplied by 1.5.
-------
Table 6.33.
ESTIMATED LEVELS OF VOLATILE BROMINATED ORGANICS IN AMBIENT AIR SURROUNDING
DOW CHEMICAL CO., MAGNOLIA, AR3
Period/Cycle/Location
01
c3
01
N
M
0)
43
O
O
M
«
1
O
B
o
j-j
43
I
CM
1
O
(-1
O 0»
rH C
0 43
1 4J
rH 0)
OJ
PJ
cd
r*{
4-1
0)
O
B
o
M
43
•H
P
1
r-T
01
C3
cd
CX
o
ex
o
o
rH
_(-;
a
o
B
o
43
•H
P
B
0
M-l
O
S
o
M
M
1
O
0
o
43
I
1
O
M 01
0 C
rH CO
43 CX
0 0
I M
CM cx
01
cd
o
M
CX
o
B
o
J-l
43
•H
P
|
o
M
Q
rH
fi
o
O 01
B C3
o cd
(-1 43
43 4-J
•H 0)
P B
0)
C3
0)
J-i
4J
CO
—J
(-0
P1/C1/L1
L2
L3
P2/C1/L1
L2
L3
L4
L5
P3/C1/L1
L2
L3
L4
L5
ND
ND
ND
ND
ND
ND
ND
ND
ND
66
23
140
35
ND
ND
445
ND
ND
163
1,089
32
ND
ND
304
251
403
62
462
40,415
1,509
ND
30,156
62,484
14,028
179
1,744
30,172
921
59,438
25
75
1,996
99
ND
624
6,653
300
36
100
795
188
2,002
ND
ND
8
ND
ND
ND
ND
ND
ND
380
ND
ND
50
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
T
ND
T
T
T
T
ND
ND
T
T
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
907
694
12,158
1,103
10,016
15,978
1,758
960
19,656
5,089
130
14,272
a 3
Concentrations are in ng/m .
-------
Table 6.34. CONCENTRATIONS OF ETHYLENE IN AMBIENT AIR SURROUNDING
DOW CHEMICAL CO.
Period /Cycle/Location
P2/C1/L1
P2/C1/L2
P2/C1/L3
P2/C1/L4
P2/C1/L5
Lab-la
Lab-2a
Field- 1?
Field- 2^
Field-3
Lab la'C
Lab-23'^
Field- LT'C
Field- 2 '^
Field- 3^'^
Field-4 '
ppm Ethylene
1.6
2.4
1.8
2.2
1.9
0.1
2.2
0.3
0.9
0.4
3.8
10.1
1.7
4.9
6.5
10.0
Stored at 4°C in the laboratory.
Transported to the sampling area and returned to the lab.
Q
Spiked with 0.9 ppm ethylene.
Spiked with 9.7 ppm ethylene.
274
-------
Table 6.35. QUALITATIVE ANALYSIS OF WATKR AND SEDIMENT SAMPLES COLLECTED NEAR
DOW CHEMICAL COMPANY, MAGNOLIA, AK
Period/Cycle/Location
Sample Medium
Halogenated Compounds
Identified3
P1/C1/L2
L4
P2/C1/L5
P3/C1/L7
P4/C1/L11
water
water
water
water
sediment
water
ND
ND
tetrachloroethylene
bromopropene
1,2-dichloroethane
dibromoethene
trichloroethene
chlorobromoethane
1,2-dibromoethane
chlorobutene
bromodichloropropane
l-chloro-2,3-dibromopropane
bromobenzene
bromoform
1,2-dibromoethane
1-chloro-2-bromoethane
l-chloro-2,3-dibromopropane
1,2-dichloroethanec
£
1,2-dichloroethane
''Analysis by VOA method with GC/MS/COMP detection.
None detected.
"Tentative identification.
-------
Table 6.36. QUALITATIVE ANALYSIS OF SOIL SAMPLES COLLECTED NEAR
DOW CHEMICAL COMPANY, MAGNOLIA, AK
Period/Cycle/Location Halogenated Compounds Identified
P1/C1/L1^ NDb
L2 1,2-dichloroethane
P3/C1/L3 chloroform
L4 ND
L5 1,2-dichloroethane
L6 ND
Analysis by VGA method with GC/MS/COMP detection.
b>-
None detected.
Q
Tentative identification.
276
-------
6.2.5 Samples from Human Population
6.2.5.1 Sampling
Samples of human hair were obtained from El Dorado and Magnolia barber
shops (Table 6.37). In order to obtain enough material for analysis,
composite samples were made.
In conjunction with a local pediatrician (Dr. James Sykes), human
placenta and cord were obtained from six deliveries in El Dorado, AK during
the period of July 22 to August 5, 1977.
6.2.5.2 Brominated Organics
Composites of human hair from each of the barber shops were analyzed
as three separate samples (Table 6.38). Two of the three composites had
detectable quantities of Decarbrom. Since the three composites surveyed a
total of ^40 individuals, these findings mean that a minimum of 5% (2 out
of 40) of the population had detectable levels of Decabrom. Tetrabrom was
confirmed in one sample but interferences prevented confirmation in either
of the other two composites.
Eight of the placenta samples were extracted and four were submitted
to GC/MS/COMP analysis. The level of background was so high that mg/kg
concentrations would have had to be present for detection. No brominated
compounds could be identified in these samples. Further purification would
no doubt improve the sensitivity of the analysis.
6.3 QUALITY ASSURANCE
The validity of the data generated under this task depended directly
upon the quality of the analytical procedures. As such, a strict quality
assurance program was established as discussed below. The heart of the
quality assurance program was the division of the task into subtasks which
focused upon the medium or analysis to be performed. Each subtask had a
leader who was responsible for its execution including method validation,
sampling, sample analysis, quality control, and data interpretation. The
definite delineation of responsibilities reduced the chances of error
through poor communication.
6.3.1 Analytical Protocol Validation
Depending on the exact nature of the analytical scheme, each step of a
protocol was validated through the use of blanks and spiked samples. The
277
-------
Table 6.37. SAMPLING PROTOCOL FOR SAMPLES OF THE HUMAN POPULATION
OO
Period
PI
7/23/77
P2
7/27/77
P3
7/30/77-
8/4/77
Cycle Location
Cl LI
L2
L3
Cl LI
Cl LI
L2
L3
L4
L5
L6
L7
L8
Site
El Dorado
HI Dorado
El Dorado
Magnolia
Union County
Hospital
El Dorado
Sample Type
Hair
HaLr
Hair
Hair
Placenta/
Cord
Comments
approximately 16 indiv
approximately 20 inclLv
7 individuals
unknown number of
individuals
i duals
i duals
tissue from normal deliveries
at the hospital during
period shown
the
-------
Table 6.38. ANALYSIS OF HUMAN HAIR COLLECTED IN EL DORADO, ARKANSAS FOR
SEMI-VOLATILE BROMINATED ORGANICS*
Tetrabromobisphenol A Decabromobiphenyl ether
Period/Cycle/Location (yg/Kg) (yg/Kg)
P7/C1/L14 2.0d 5e
P7/C1/L15 >13f 0.3g
P7/C1/L16 >0.7f NDh
Quantitation by gas chromatography/mass spectrometry using multiple ion detection.
See Table 6.37 for protocol.
2,2*-Bis(dibromo-4-hydroxyphenyl)propane.
The two ions, 528 and 530, were observed at the correct gc retention time with the correct intensity
ratio, 1.6 vs. 1.5 for the standard.
Confirmed by full scan gas chromatography/mass spectrometry.
The two ions, 528 and 530, were observed at the correct gc retention time; however, the ion intensity
ratios were 2.3 and 0.94 for P7/C1/L15 and P7/C1/L16, respectively, compared to 1.5 for the standard.
These samples would require further purification in order to determine whether tetrabromobisphenol A
is or is not present.
Cf
Unconfirmed.
Not detected - approximately 0.1 Mg/g is required to detect this compound.
-------
validations were conducted using sufficient replication to provide statis-
tically reliable recovery data.
The specific details of the validation experiments and their results
are discussed in Section 3.0.
6.3.2 Field Sampling Quality Assurance
6.3.2.1 Quality Control Samples
Blank and spiked samples were created to assure that compounds identi-
fied in field samples are not artifacts and to assure that compounds collec-
ted in the field are retained in the sample through storage and analysis.
For most of the sample matrices, duplicate blank and spiked samples were
taken to the field to approximate the conditions to which the samples were
subjected. In addition, duplicate blank and control samples remained in
the laboratory to monitor storage efficiency and to provide a crosscheck on
the field blank and control samples. Blanks and control samples for each
medium are summarized in Table 6.39.
6.3.2.2 Sample Identification Protocol
During sample collection, a sample data sheet (Figures 6.23 and 6.24)
was maintained for each sample. The sampling locations for each sampling
period were recorded on a detailed area map. The coded form contained
information such as date and time of sampling, locations, sampling parameters
and meteorological information. The alpha-numeric sample code was also
fixed directly to the sample container at that time.
Following each day's sample collection, the protocol sheets and sample
labels were independently reviewed by two field personnel to assure that
all information was logged in, that the codes were self-consistent and that
there was no duplication. Upon returning to the laboratory, the samples
were again checked for proper labeling.
6.3.2.3 Sample Containers
Sample containers were selected for inertness and ability to maintain
sample integrity. Screw caps were lined with foil or teflon and plastic
@
bags were made of Tedlar . No polyethylene or other standard commercial
plastic was allowed to come in contact with the samples. Prior to field
sampling, each container was scrupulously cleaned as discussed in Section
3.3.3.1.
280
-------
, Table 6.39. TNVKNTORY OF CONTROLS AND JU.ANKS FOR QUALITY ASSURANCE
H)K ARKANSAS I'M I'M.]) SAMI'l.INC - JULY AND AUGUST, 1977
ho
oo
Sample Manks . Controls
Type Laboratory Field Laboratory
Charcoal
cartridges 2 72
Tenax 2 32
cartridges
>
>
i
2
Vacuum 2 33
canals ters
2 32
Tmplnger 4 4 8
solutions
4 48
"
Field Compound
8 methyl chloride
methyl bromide
vinyl chloride
vinyl bromide
4 perf luorobenzene $
perf luorotoluene $
ethylene dibromide
bromobenzene
1, 2-dlbromopropane
l-brorao-2-chlo roe thane
dibromomethane
2 perf luorobenzene it'
perf iuorotoluene X
dibromomethane
1 , 2-dlbromopropane
1-br omo- 2- ch lor oe thane
4 methyl chloride
methyl bromide
4 ethylene
ethane
8 chloride, bromide
in deionized water
8 chloride, bromide
Con cen t rat ions
309 ng
100 ng
254 ng
250 ng
201 ng
85 ng
350 ng
250 ng
304 ng
308 ng
150 ng
250 ng
105 ng
J55 ng
314 ng
320 ng
6, 60 and 300 ppb
35, 350 and 1750 ppb
0.884 and 9.72 ppm
0.880 and 9.69 ppm
0.5 and 1.0 ppm each ion
0.5 and 1.0 ppm each ion
In alkaline arsenlte
solution
(continued)
-------
Table 6.39 (cont'd)
Sample
Type L
Glass fiber
filters
Blanks
aborutory Field
2
3
Controls
Laboratory Field Compound
Concentrations
2 tetrabromobisphenol A
decabromoblphenyl
. ether
49,
49,
198,
198,
260,
260,
520
520
rig /cm
ng/cm
2
2
Water
DO
ro
tria-(2,3 dlbromopropyl)
phosphate
1-chloro-l-butene
1,2-dichloroethane
l-bromo-2-chloroethane
1,2-dibromoethane
broinobenzene
m-chlorotoluene
tris(2,3-dibromopropyl)
phosphate
pentabroiuophenol
2,4,6-tribromophenol
tetrabromobisphenol A
decabromobiphenyl ether
tetrabromophthalic
anhydride
2,3-dibromopropanol
bromobenzene
1,2-dlbromo-3-chloro-
propane
hexabromocyclododecane
bromoform
1,2,-dibromoethane
2,2' ,4,4',6,6'-hexabromo
biphenyl
1 and
1 and
1 and
1 and
1 and
1 and
21
5
5
5
5
5
5
101, 202, 540, 1080 ng/cm2
Ug/100 ml
Mg/100 ml
Ug/100 ml
pg/100 ml
Ug/100 ml
JJg/100 ml
and 210 ppb
9.6 and 95 ppb
10.7 and 107 ppb
9.8 and 100 ppb
9.6,96 and 105 ppb
10 and 100 ppb
20 and 200 ppb
10.8 and 108 ppb
11.2 and 112 ppb
10 and 100 ppb
12.2 and 122 ppb
14.5 and 145 ppb
9.6 and 96 ppb
(continued)
-------
Table 6.39 (cont'd)
Blanks
Controls
Sample
Type Laboratory Field Laboratory Field
Compound
Concentrations
Vegetation
Milk
1-chloro-l-butene
1,2-dichloroethane
l-bromo-2-chloroethane
1,2-dibromoethane
bromobenzene
m-chlorotoluene
trls(2,3-dibromopropyl)
phosphate
pentabromophenol
2,4,6-tribromophenol
tetrabromobisphenol A
decabromoblphenyl ether
1-chloro-l-butene a
1,2-dichloroethane a
l-bromo-2-chloroethane a
1,2-dibromoethane a
bromobenzene a
m-chlorotoluene a
tris(2,3-dibromopropyl)
phosphate
pentabromophenol
2,A,6-tribomophenol "
tetrabromobisphenol A^,
decabromobiphenyl ether
10 and 50 pg/2 g Vegetation
21 and 210 ppb
9.6 and 96 ppb
10.7 and 107 ppb
10.0 and 100 ppb
10.5 and 105 ppb
5 lig/100 ml
5 lig/100 ml
lig/100 ml
)ig/100 ml
IJg/lOO ml
yg/100 ml
/i2 and ft.2 [Jg/200 jnl
1.9 and 19 JJg/200 ml
2.1 and 21 ng/200 ml
2.0 and 20 |Jg/200 ml
2.1 and 21 ]lg/200 ml
(continued)
-------
Table 6.39 (cont'd)
Blanks
Controls
Sample _____
Type Laboratory Field Laboratory Field
Soil
ho
00
-C-
Sediment
Compound
1-chloro-l-butene
1,2-dichloroethane
1-b r oiiio-2-chlo roe thane
1,2-dJ bromoethane
bromobenzene
m-chlorotoluene
tris(2,3-dibromopropyl)
phosphate
pentabromophenol
2,4,6-tribromophenol
tetrabromobisphenol A
decabromobiphenyl ether
1-chloro-l-butene
1, 2-dicbloroetliane
l-bromo-2-chloroethane
1,2-dibromoethane
bromobenzene
m-chloroto Luene
tris(2,3-dibromopropyl)
phosphate
pentabromopbenol
2,4,6-trJbromopbenol
tetrabromohisphenol A
decabromobiphenyl ether
Concentrations
10 and 50 pg/20 g soil.
21 and 210 ppb
9.6 and 96 ppb
10.7 and 107 ppb
10.0 and 100 ppb
10.5 and 105 ppb
10 and 50 Mg/20 g soil
21 and 210 ppb
9.6 and -96 ppb
10.7 and 107 ppb
10.0 and 100 ppb
10.5 and 105 ppb
(continued)
-------
Table 6.39 (cont'd)
a Laboratory and field blanks serve for volatile and semi-volatile analysis,
Two of these contols contained only the first five compounds at the
higher concentration.
c Two of these controls contained the first six compounds and two
contained the last five compounds.
$
hJ External standard
CO
-------
Abbr. Code:
Date:
FIELD SAMPLING PROTOCOL SHEET - B
Medium:
Project No.
Municipality
Address
Site
Location
Samnle Code
Operator
Code Key: W - Water
S - Soil
SD - Sediment
G - Grab
Period
Medium/Rationale
V - Vegetation
A - Animal
M - Miscellaneous
C - Comoosited
State
Sample size
Sampling rate
Time leap. Wet. Dry Time Temp. Wet. Dry
Re. Humid % Wind Dir./Speed / Rel. Humid 7. Wind Dir./Speed /_
Cloud
Remarks
End: Time
Start: Time
Odor
_, Date
, Date
Cloud _
Remarks
Odor
Remarks/Map:
Figure 6.23. Field sampling protocol for condensed matrices,
286
-------
I ( _ ) • ( _ ) ( _ •) ( _ )
_ _
Project i.'o. Operator Seq. Sa=pler/?.atisnala State
_ _____ _ ( J
( )
Sa=?le Code
D—er.sicr.s
No. (c=) Sorbent Eat2/Ar.aly cicsl ?r=cscur
_ _ f y.) _
f H)
CC A=?s _ Sa=?li=S Rasa (L?X) _ Vacuua ("HS)
Xa:ior.ala: Quai. Aral (7) _ Er.d: Ti=s _ ft3
3
q-.-ar.r. Ar-si. (I) _ Calibration (C) _ Start: Ti=s
:c?s
Z:c?sri=er.tai: Lab
-------
6.3.2.4 Sample Storage
At the end of each day's sample collection, the samples were sorted,
the labels checked, caps and seals were checked for leaks and the containers
boxed. The soil, Tenax cartridges, carbon cartridges, milk, vegetation,
and tissue samples were transferred to frozen storage. Water and sediment
samples, which could not be frozen, were refrigerated. Upon return to the
laboratory the samples were again frozen or cooled until analysis.
6.3.3 Analytical Quality Assurance
Samples were extracted, worked up and analyzed according to the detailed
procedures outlined in Appendix A. Throughout the entire procedure, the
analysts endeavored to maintain sample integrity and assure accurate analy-
tical results. The salient features of the analytical quality assurance
are outlined below.
6.3.3.1 Reagent and Glassware Control
Reagent and glassware control was required in order to minimize containi-
ng
nation. Sample containers, glassware, etc. were cleaned with Isoclean ,
rinsed with deionized-distilled water and heat treated at 450-500°C to
insure the removal of all traces of organic compounds. Solvents were
redistilled in glass in our laboratories prior to their use.
6.3.3.2 Sample Logging
In addition to the field sampling protocol sheets prepared during
sample collection, records of analysis progress were maintained. Immediately
on return from the field, a log book was established for each sample matrix
and each sample logged in. The progress of each sample through the analy-
tical protocol was followed in the sample logbook.
Each instrument operator maintained a detailed log book indicating
when the sample was run, the conditions under which it was run, the data
which were printed out and the mode of data storage.
6.3.3.3 Instrumentation Control
The performance of each instrument used for sample analysis was evalu-
ated daily by running a standard.
6.3.3.4 Analysis of Quality Control Samples
Quality control samples were interspersed with field samples in the
queue for analysis. This protocol was designed to detect contaminants or
variations in extraction efficiency with time.
288
-------
Volatile Brominated Organics.--In addition to the analysis of control
samples in Table 6.39, the reproducibility of analysis for volatile bromina-
ted organics collected on Tenax GC using GC/MS/COMP (mass fragmentography)
was examined on several sets of samples. The results are given in Table
6.40. The first sample of a replicate set was analyzed approximately two
and one-half weeks after collection in October of 1976. The second sample
from the replicate set was analyzed four months later. The second sample
had been kept at -20° during the entire period prior to its analysis. It
is evident (Table 6.40) that the reproducibility of analysis ranges from a
few percent to +25%. From these results it was concluded that percent
reproducibility for analysis of halogenated hydrocarbons by the technique
of high resolution gc/ms/comp was more than adequate for the purpose of
this study.
Ethylene.—Validation of sample integrity was achieved through the
preparation of eleven vacuum cannisters as blanks or controls. These
"quality control" samples, either transported to and from the field with
the samples or refrigerated in the laboratory, were prepared to insure (1)
that no undetected contamination occurred as a result of transport or
storage and (2) that any losses due to leakage from the container or adsorp-
tion to the interior of the container be detected. The results of the
analysis of these samples were presented in Section 6.0.
The average ethylene concentration found in the blank samples is 0.8
ppm (range 0.1-2.2 ppm). This relatively high blank value is reflected in
the results of the control samples, particularly of those spiked at the 0.9
ppm level. Consequently, 0.8 ppm represents the approximate limit of
detection for ethylene by this technique. Recovery from control samples
containing 9.7 ppm ethylene was significantly closer to that expected. The
average recovery at this concentration was 91%.
Decabrom and Tetrabrom.—Soil from the Research Triangle Park was
spiked with 100 |Jg/kg each of Decabrom and Tetrabrom. Analysis by GC/MS/COMP
found 110 and 162 (Jg/kg, respectively. These levels are very near the
limit of detection.
Other controls per Table 6.39 were analyzed interdispersed with field
samples.
289
-------
Table 6.40. REPRODUCIBILITY OF REPLICATE MEASUREMENTS FOR HALOGENATED HYDROCARBONS
ON TENAX GC SAMPLING CARTRIDGES3
Site
Creat Lakes
Corp.
Ethyl Corp.
Arkansas Chem.
Inc.
Michigan Chem.
Inc.
Period /Cycle /Location
P3/C1/L2
P3/C1/1.3
P1/C1/L2
P1/C1/L3
P1/C2/L4
•o
•H
14
"Tl
r-i
8.4 + 5.6
-
-
29.7 + 1
32.9 + 1.5
CU
£
N
c
-------
6.3.3.5 Data Quality Assessment
The data generated by each analysis were thoroughly examined by the
instrument operator to assure quality. In the case of mass spectral data,
the data were screened by the instrument supervisor before release. This
screen assured data quality and also that the sample had been run according
to the request of the analyst.
6.3.3.6 Quality Assurance in Data Interpretation
Both qualitative interpretations and quantitation were spot checked by
a second person.
6.4 METHYL CHLORIDE AND METHYL BROMIDE ANALYSIS BY GC/ECD AND MASS
FRAGMENTOGRAPHY
6.4.1 Apparatus
Aluminum sample containers were evacuated with a vacuum pump for 15
minutes, flushed with helium, then evacuated again for 15 minutes. They
were then checked with a vacuum gauge, and were deemed satisfactory if they
showed a vacuum >29".
A stainless steel column (6 ft x 1/8" i.d.) packed with Durapak n-
octane/Porasil C (100/120 mesh) was used for the analysis. A 1 ml aliquot
of each sample was transferred from the container to the column with a 1 ml
®
Pressure-lok gas syringe (Precision Instrument Corp.). The lower limit of
measurement for MeCl and MeBr was 35 ppm and 5 ppm, respectively.
6.4.2 Quality Control
Standards were prepared using the permeation line system. A flow rate
was set across the permeation tubes of MeCl and MeBr to create a certain
concentration of MeCl and MeBr in N_. An evacuated aluminum cannister was
then attached to a permeation line and allowed to equilibrate with the
system, after which the cannister was sealed. Blanks were prepared by
filling an evacuated cannister with helium at 1 atm.
The following blanks and controls were prepared:
291
-------
Type Number
Blank Lab 2
Field 3
6 ppm MeBr + 35 ppb MeCl Lab 1
Field 1
60 ppm MeBr + 350 ppb MeCl Lab 1
Field 2
300 ppb MeBr + 1750 ppb MeCl Lab 1
Field 1
6.4.3 Analysis of Samples
Standards (Fig. 6.25) to be run each day were prepared on the permeation
line, with 1 ml of a standard being drawn directly from the line with a gas
syringe. All lab blanks (Fig. 6.26), field blanks, lab controls, and field
controls were analyzed. All samples from Dow Chemical were also analyzed.
Blanks contained several large peaks eluting in the general area of
MeCl and MeBr, but none that interfered directly with the analysis of the
two compounds. None of the controls, however, contained any detectable
levels of MeCl and MeBr, indicating that these compounds were not stable in
the aluminum cannisters for the period of time stored. Blanks and controls
had been stored for 8 to 9 weeks.
Samples from Dow showed no detectable levels of MeBr and MeCl. These
samples had been stored for 5 1/2 weeks.
A new control, 900 ppb MeCl and 180 ppb MeBr (Fig. 6.27), was prepared
in a cannister exactly as before and analyzed immediately. The appropriate
levels of MeCl and MeBr were found. Analysis of this new control five days
layer showed approximately a 15% loss of MeCl and MeBr.
No methyl chloride or methyl bromide was detected by mass fragmentography
from the analysis of carbon cartridges (Appendix A). Vinyl chloride and
vinyl bromide were also not detected.
292
-------
LLJ
co
2
O
Q.
CO
LU
DC
LU
CC
Q.
<
u
z
O
CC
60 ppb MeBr
TIME (MIN)
Figure 6.25. GC/ECD of methyl chloride and methyl bromide.
293
-------
LU
CO
z
o
85
LU
cc
LU
CC
a.
o -
o
cc
o
LU
_1
LJJ
TIME (MIN)
Figure 6.26. GC/ECD of blank control sample.
294
-------
01
V)
O
Q.
CO
LLJ
DC
LU
oc
Q.
O
z
O
cc
t-
o
LU
180 ppb MeBr
900 ppb MeCI
TIME (MIN)
Figure 6.27. GC/ECD of methyl chloride and methyl bromide.
295
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA-560/6-78-002
4. TITLE AND SUBTITLE
Environmental Monitoring Near Industrial Sites:
Brominated Chemicals
7. AUTHOR(S)
E. D. Pellizzari, R. A. Zweidinger and M. D. Erict
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Toxic Substances
U. S. Environmental Protection Agency
Washington, DC 20460
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
June 1978
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
:son
Task II Final Report
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-1978
13. TYPE OF REPORT AND PERIOD COVERED
Final- 7/1Q/77 - 12/16/77
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
Sampling and analysis was designed to determine ambient concentrations of
ethylene dibromide and other brominated chemicals near production facilities in
El Dorado and Magnolia, AK. A characterization was made of the environmental
matrices - air, water, soil, sediment and biota - for the presence and levels
of ethylene dibromide, vinyl bromide and other related chemicals surrounding
the bromine industry.
17. KEY WORDS AND DOCUMENT
a. DESCRIPTORS b.lDENTI
18. DISTRIBUTION STATEMENT 19.SECU
RELEASE TO PUBLIC 20. SECU
UNCL
ANALYSIS
FIERS/OPEN ENDED TERMS C. COSATI Field/Group
RITY CLASS (This Report! 21. NO. OF PAGES
ASSIFTF.n Part I - 325
RITY CLASS (Thispage) 22. PRICE
OSSIFIED
EPA Form 2220-1 (Rev. 4-77)
PREVIOUS EDITION IS OBSOLETE
296
-------
- C INSTRUCTIONS
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