EPA-560/6-78-003
ENVIRONMENTAL MONITORING
NEAR INDUSTRIAL SITES:
BETA-CHLOROETHERS
JUNE 1978
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
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EPA-560/6-78-003
June 1978
ENVIRONMENTAL MONITORING NEAR INDUSTRIAL SITES:
1 3-CHLOROETHERS
by
Paul L. Sherman
A. Melvin Kemmer
Leroy Metcalfe
Harlan D. Toy
Monsanto Research Corporation
Dayton, Ohio 45407
Contract 68-01-1980
Project Officer
John H. Smith
June 1978
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20640
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EPA REVIEW NOTICE
This report has been reviewed by the Office of Toxic Substances,
U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents
necessarily reflect the views and policy of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement of recommendation for use.
ii
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ABSTRACT
ampling, workup and analysis methods were developed for six $-
hloroethers in air, water, soil and sediment samples to evaluate
ossible environmental contamination by this class of compounds.
|The six ethers were chloroethyl ethyl ether, chloroethyl vinyl
sther, bis(2-chloroethyl) ether, bis(2-chloroisopropyl) ether,
(2-chloroethoxy) methane and bis (2-chloroethoxy) ethane.
tour types of samples were collected near eight industrial sites
iich were potential emitters of 3-chloroethers. The sites in-
3luded four plants where propylene oxide is produced via the
:hlorohydrin route. One plant produced propylene chlorohydrin;
one plant produced both ethylene chlorohydrin and propylene
phlorohydrin, and had produced various 3-chloroethers previously;
bne plant produced intermediates and surfactants for the textile
industry; and one plant produced polysulfide rubbers.
I
Air samples were collected by drawing air through Pyrex tubes
packed with Tenax-GC using personnel sampling pumps. Water
jsamples were collected either as grab samples or integrated 24-
jhour samples with a peristaltic pump. Soil and sediment samples
were transported in glass canning jars. Air sampling tubes were
iesorbed with methanol with a procedure developed at MRC. Water
samples were solvent extracted with methylene chloride. Soil and
sediment samples were Soxhlet extracted with methylene chloride.
The methylene chloride extracts from the water, soil and sediment
samples were each concentrated with a Kuderna-Danish evaporator
to a volume of 2-3 ml.
111
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Analysis of all of the extracts was performed by gas chromato-
graphy/mass spectrometry. The gas chromatographic column was
Tenax-GC. The mass spectrometer was operated in the selected ion
monitoring mode. Two characteristic ions of each compound were
monitored in this mode. Detection limits for the four types of
samples were: 7 x 10"7 g/m3 for air, 2 x 10"7 g/1 for water, and
4 x 10"9 g/g for soil/sediment.
Only three of the six g-chloroethers were detected in the environ-
mental samples collected. The three ethers were bis(2-chloro-
ethyl) ether, bis(2-chloroisopropyl) ether, and bis(2-chloro-
ethoxy) methane. At least one of these three 3-chloroethers was
found in at least one sample from four of the sites. The samples
from three sites in which a 3-chloroether was found were all
water samples. At the remaining site bis(2-chloroethoxy) methane
was found in at least one sample of air, water, soil and sediment.
«
At this same site bis(2-chloroethyl) ether was found in one water
and two sediment samples.
This final report was submitted in fulfillment of Research Re-
quest No. 2 of Contract No. 68-01-1980 by Monsanto Research
Corporation under the sponsorship of the U.S. Environmental
Protection Agency, Office of Toxic Substances.
IV
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CONTENTS
Abstract
Figures
Tables
1
2
2.1
2.1.1
2.1.2
2.1.3
2.1.3.1
2.1.3.2
2.1.4
2.1.4.1
2.1.5
2.2
2.2.1
2.3
2.3.1
2.3.1.1
2.3.1.2
Summary 1
Introduction and Literature Review 7
Description of Industrial Processes 10
Involving 3-Chloroethers
3-Chloroether Consumption and Uses 10
3-Chloroether Production 14
$-Chloroethers Formed as By-Products 14
/
Bis(2-Chloroethyl) Ether— 14
Bis(2-Chloroisopropyl) Ether— 17
3-Chloroether Users 21
Bis(2-Chloroethoxy) Methane 21
Chemical Production Plant Sites 21
with the Potential for Release of
3-Chloroethers
Detection of Haloethers in the Envi- 27
ronment
Hydrolytic Stability of 3-Chloroethers 27
Methods for the Isolation Concentra- 30
tion and Analysis of 3-Chloroethers
Air 30
Direct Analysis— 31
Sorbents— 31
v
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2.3.1.3 Derivatives— 31
2.3.2 Water 33
3 Sampling Site Selection 36
4 Sampling Methods 40
4.1 Air 40
4.2 Water 42
4.3 Soil 45
4.4 Sediment 46
5 Sample Workup Methods 47
5.1 Air 47
5.2 Water 47
5.3 Soil 49
5.4 Sediment 49
6 Analytical Methods 50
6.1 Six $-Chloroethers 50'
6.2 Bis(l-Chloromethyl-2-Chloroethyl) 62
Ether
6.2.1 Attempted Synthesis of bis(1-Chloro- 63
methyl, 2-Chloroethyl) Ether
6.2.1.1 Experiment 1— 67
6.2.1.2 Experiment 2— 67
6.2.1.3 Experiment 3— 67
6.2.1.4 Experiment 4— 67
6.2.1.5 Experiment 5— 68
6.2.2 Simulated Epichlorohydrin Synthesis 68
6.3 Other Compounds • 69
6.4 Characterization of Air and Water 70
Samples
vi
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7 Recovery Studies 72
7.1 Laboratory Recovery Studies 72
7.1.1 Air 72
7.1.2 Water 77
7.1.3 Soil 77
7.2 Field Recovery Studies 79
7.2.1 Air 79
7.2.2 Water * 81
\
7.2.3 Soil 84
7.3 Assessment of Error 84
7.3.1 Sample Collection 84
7.3.2 Sample Workup and Analysis 85
7.3.2.1 Air— 85
7.3.2.2 Water— 85
7.3.2.3 Soil and Sediment 87
7.3.3 Total Error 87
8 Sampling and Analysis for 3-Chloro- 89
ethers at Olin Corporation, Bran-
denburg , Kentucky
8.1 Presampling Survey 89
8.1.1 Description of the Plant Site 89
8.1.2 Surrounding Area 90
8.2 Sampling and Analysis Results 90
8.2.1 Air Samples 93
8.2.2 Water Samples 93
8.2.3 Soil Samples 99
vii
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9 Sampling and Analysis for g-Chloro- 105
ethers at Dow Chemical USA,
Freeport, Texas
9.1 Presampling Survey 105
9.1.1 Description of the Plant Site 105
9.1.2 Surrounding Area 110
9.2 Sampling and Analysis Results 110
9.2.1 Air Samples 110
9.2.2 Water Samples 116
9.2.3 Soil Samples 121
10 Sampling and Analysis for 3-Chloro- 123
ethers at Jefferson Chemical Co.,
Inc., Port Neches, Texas
10.1 Presampling Survey 123
10.1.1 Description of the Plant Site 123
10.1.2 Surrounding Area 126
10.2 Sampling and Analysis Results 128
10.2.1 Air Samples 128
10.2.2 Water Samples 132
10.2.3 Soil Samples 142
10.2.4 Sediment Sampling 142
11 Sampling and Analysis for p-Chloro- 146
ethers at Dow Chemical USA,
Plaquemine, Louisiana
11.1 Presampling Survey 146
11.1.1 Description of the Plant Site 146
11.1.2 Surrounding Area 148
11.2 Sampling and Analysis Results 151
11.2.1 Air Samples 151
Vlll
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11.2.2 Water Samples 155
11.2.3 Soil and Sediment Samples 162
12 Sampling and Analysis for 3-Chloro- 165
ethers at Thiokol Corporation,
Moss Point, Mississippi
12.1 Presampling Survey 165
12.1.1 Description of the Plant Site 165
12.1.2 Surround Area 166
12.2 Sampling and Analysis Results 169
12.2.1 Air Samples 169
12.2.2 Water Samples 175
12.2.3 Soil and Sediment Samples 183
13 Sampling and Analysis for 0-Chloro- 186
ethers at Union Carbide Corporation,
Institute, West Virginia
13.1 Presampling Survey 186
13.1.1 Description of the Plant Site 186
13.1.2 Surrounding Area 187
13.2 Sampling and Analysis Result 191
13.2.1 Air Samples 191
13.2.2 Water Samples 197
13.2.3 Soil and Sediment Samples 204
14 Sampling and Analysis for g-Chloro- 207
ethers Milliken Chemical, Inman,
South Carolina
14.1 Presampling Survey 207
14.1.1 Description of the Plant Site 207
14.1.2 Surrounding Area " 208
14.2 Sampling and Analysis Results 211
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14.2.1 Air Samples 211
14.2.2 Water Samples 215
14.2.3 Soil and Sediment Samples 224
15 Sampling and Analysis for 0-Chloro- 226
ethers at Eastman Kodak Company,
Rochester, New York
15.1 Presampling Survey 226
15.1.1 Description of the Plant Site 226
15.1.2 Surrounding Area 227
15.2 Sampling and Analysis Results 227
15.2.1 Air Samples 231
15.2.2 Water Samples 231
15.2.3 Soil and Sediment Samples 241
16 References 243
x
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FIGURES
Number Page
1 Diagram of a typical chlorohydrin 20
propylene oxide plant (Fyvie [36],
1964).
2 . Sites where g-chloroethers have been 29
found.
3 e-Chloroethers sampling sites. 39
i
4 Air sampler arrangement. » 41
5 Pyrex sampling tube packed with 43
Tenax-GC.
6 Water sampler arrangement 44
7 Solvent desorption apparatus. 48
8 Total ion chromatogram of g-chloro- 53
ethers.
9 Mass spectra of 2-chloroethyl vinyl 55
ether and 2-chloroethyl ethyl ether
(CEVE and CEEE).
10 Mass spectrum of bis(2-chloroethyl) 56
ether.
11 Mass spectrum of bis(2-chloroisopropyl) 57
ether (BCIPE).
12 Mass spectrum of bis(2-chloroethoxy) 58
methane (BCEXM).
13 Mass spectrum of bis(2-chloroethoxy) 59
ethane (BCEXE).
14 STM chromatograms for 3-chloroethers 60
(1.5-7.5 min).
14 SIM chromatograms for 3-chloroethers 61
(7.5-13.5 min).
xi
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Number Page
15 Potential chloroethers from epich- 62
lorohydrin manufacture.
16 Mass spectrum of earlier eluting com- 64
pound in epichlorohyrdrin synthesis
mixture.
17 Mass spectrum of later eluting compound 65
in epichlorohydrin synthesis mixture
[bis(l-chloromethyl-2-chloroethyl)
ether?].
18 Possible interpretation of mass fragments 66
BCMCEE (Figure 7).
19 Thermal desorption apparatus. 71
22 Field Recovery Studies - Air 82
23 Field Recovery Studies - Water 83
20 Approximate plant boundaries at Olin 91
Corporation, Brandenburg, Ky.
21 Composite panoramic photograph of Olin 92
Corporation, Brandenburg, Kentucky.
22 Diagram of array air samplers at Olin 94
Corporation, Brandenburg, Ky.
23 Air sampling sites-array at Olin Cor- 95
poration, Brandenburg, Ky.
24 Air sampling sites - perimeter at Olin 96
Corporation, Brandenburg, Ky.
25 Water sampling sites at Olin Corpora- 100
tion, Brandenburg, Ky.
26 Photographs of water sampling locations 102
at Olin Corporation, Brandenburg, Ky.
27 Soil sampling sites at Olin Corpora- 104
tion, Brandenburg, Ky.
28 Topographical map of Freeport area 106
showing location of Dow Chemical,
Plant A and Plant B.
XII
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Number
29 Topographical map showing dimension 108
for Dow Chemical, Plant A.
30 Composite Panoramic Photograph of Dow 109
Chemical Plant A, Freeport, Texas.
31, Location of air sampling sites at Dow 111
Chemical, Freeport, Texas, June
20-21, 1977.
32 Total ion reconstructed chromatogram 115
of Freeport Sample A-8.
33 Water sampling sites at Dow Chemical, 117
Freeport, Texas.
34 Photographs of two water sampling 119
locations at Dow Chemical, Freeport,
Texas.
35 Total ion reconstructed chromatogram 120
of water sample, W-l, Dow Chemical
USA, Freeport, Texas.
36 Soil samples locations at Dow Chemical, 122
Freeport, Texas.
37 Jefferson Chemical location in Port 124
Neches Groves, Texas.
38 Dimension of area around Jefferson 125
Chemical.
39 Composite Panoramic Photograph of 127
Jefferson Chemical at Port Neches,
Texas.
40 Air sampling sites at Jefferson 129
Chemical,. Port Neches, Texas.
41 Total ion reconstructed chromatogram 133
of Port Neches air sample A-9.
42 Water sampling sites at Jefferson 135
Chemical, Port Neches, Texas.
N"
43 Photograph of Jefferson Chemical, Port 137
Neches, Texas. Water outfall and
downstream sampling location.
xiii
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Number Page
44 Total ion reconstructed chromatogram 138
of Port Neches downstream water
sample #1.
45 Mass spectra of unknowns in downstream 140
#1 water sample, Port Neches, Texas.
46 Total ion reconstructed chromatogram 141
of Port Neches, downstream water
sample - Tenax GC.
47 Unknown (RT=18.9 min) (see Figure 46). 143
48 Soil sampling sites at Jefferson 144
Chemical, Port Neches, Texas.
49 Sediment sampling sites at Jefferson 145
Chemical, Port Neches, Texas.
50 Dow Chemical location in Plaquemine, 147
Louisiana.
51 Dimension of area around Dow Chemical 149
USA, Plaquemine, Louisiana.
52 Composite panoramic photograph of Dow 150
Chemical USA, Plaquemine, Louisiana.
53 Air Sampler location at Dow Chemical 152
USA, Plaquemine, Louisiana.
54 , Total ion reconstructed chromatogram 156
of air sample A-8, thermally desorbed,
Dow Chemical USA, Plaquemine, La.
55 Water sampler location at Dow Chemical 158
USA, Plaquemine, Louisiana.
56 Photographs of drainage ditch and water 160
sampling locations, Dow Chemical USA,
Plaquemine, Louisiana.
57 Total ion reconstructed chromatogram 161
for downstream #2 water sample (W-2),
Dow Chemical USA, Plaquemine, La.
58 Mass spectra of unknown compounds in 163
downstream #2 water sample, Plaquemine,
Louisiana.
xiv
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flumber Page
59 Soil and sediment sampling locations 164
Dow Chemical USA, Plaquemine, La.
60 Topographical map of the Moss Point, 167
Mississippi area showing the location
of the Thiokol Corporation plant and
dimensions of the area around the
plant.
61 Composite panoramic photograph of 168
Thiokol Corporation, Moss Point, Miss.
62 Location of air samplers at Thiokol 170
Corporation, Moss Point, Mississippi.
63 Total ion reconstructed chromatogram 174
of air sample A-9, Thiokol Corpora-
tion, Moss Point, Mississippi.
64 Location of water samplers at Thiokol 177
Corporation, Moss Point, Mississippi.
65 Photographs of water sampling locations 178
at Thiokol Corporation, Moss Point,
Mississippi.
66 SIM chromatogram of Thiokol Corporation 179
outfall sample #1 (W-3), Moss Point,
Mississippi showing BCEXM ions.
67 Total ion reconstructed chromatogram of 181
Thiokol Corporation outfall sample #1,
Moss Point, Mississippi.
68 Mass spectra from Thiokol Corporation 182
outfall sample #1 (W-3), Moss Point,
Mississippi (see Figure 67).
69- Location of soil samples at Thiokol 184
Corporation, Moss Point, Mississippi.
70 Location of sediment samples at Thiokol 185
Corporation, Moss Point, Mississippi.
71 Location of Union Carbide Corporation 188
plant on topographical map of Insti-
tute, W. Va. area.
xv
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Number Page
72 Dimensions of the Union Carbide complex 189
and location of upstream water samples
at Institute, West Virginia.
73 Composite panoramic photograph of Union 190
Carbide Corporation, Institute, W.Va.
74 Air sampling locations at Union Carbide, 192
Institute, West Virginia.
75 Total ion reconstructed chromatogram of 196
air sample A-3, thermally desorbed,
Union Carbide, West Virginia.
76 Downstream and outfall water sampling 198
locations at Union Carbide, Institute,
West Virginia
77 Photographs of water sampling locations 200
and outfall at Union Carbide, Insti-
tute, West Virginia.
78 Total ion reconstructed chromatogram of 202
water sample W-7, Union Carbide,
Institute, West Virginia.
79 Total ion reconstructed chromatogram 203
and single ion chromatograms for m/e
ions 73 and 147 for water sample W-7,
Union Carbide, Institute, West Virginia.
80 Mass spectra of two unknowns in water 205
sample W-7 extract (see Figure F-8
for chromatogram).
81 Soil and sediment sampling locations 206
at Union Carbide, Institute, W. Va.
82 Location and dimensions of the Milliken 209
Chemical Division plant, Inman, S.C.
on the topographical map of the area.
83 Panoramic photograph of Milliken Chem- 210
ical Division, Inman, S.C. and a
photograph of the main entrance of
the plant.
84 Air sampling locations at Milliken Chem- 212
ical Division, Inman, South Carolina.
xvi
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Dumber Pa9e
85 Total ion reconstructed chromatogram 216
of thermally desorbed air sample,
A-l, Milliken Chemical, Inman, S.C.
86 N Water sampling locations at Milliken 217
Chemical, Inman, S.C.
87 SIM chromatograms of water sample, W-2, 220
Milliken Chemical, Inman, S.C.
88 SIM chromatogram of water sample, W-3, 221
Milliken Chemical, Inman, S.C.
89 Total ion reconstructed chromatogram 222
of water sample, W-2, Milliken Chem-
ical, Inman, South Carolina,
90 Mass spectra of two unknown compounds, 223
(see Figure 89).
91 Soil and sediment samples locations 225
around Milliken Chemical, Inman, S.C.
92 Topographical map showing Kodak Park 228
Division, Eastman Kodak, Rochester,
New York.
93 Photographs of Kings Landing Waste 229
Treatment Facility and portions of
Kodak Park Division of Eastman Kodak,
Rochester, New York.
94 Dimensions of the Kodak Park Division 230
of Eastman Kodak, Rochester, New York.
95 Air sampling locations at Eastman Kodak, 232
Rochester, New York.
96 Water sampling locations at Eastman 236
Kodak, Rochester, New York
97 Photographs of the Genesee River Gorge 238
and downstream #2, W-l, water sam-
pling location at Rochester, New York.
98 Total ion reconstructed chromatogram 239
of downstream #1, W-2, water sample
at Eastman Kodak, Rochester, N.Y.
xvi i
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Number Page
99 Mass spectra of unknown compounds 240
found in downstream #1, W-2, water
sample (see Figure 98).
100 Soil and sediment sampling locations 242
at Eastman Kodak, Rochester, N.Y.
xvi 11
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TABLES
Table Page
1 Samples in Which 3-Chloroethers 3
were found
2 Organic Chemical Compounds Found in 5
Environmental Samples Collected in
the 3-Chloroether Study
3 Organic Chemical Compounds Found in En- 6
vironmental Samples Collected in the
3-Chloroether Study
4 Properties of 3-Chloroethers Studied 8
5 Products and Uses of 3-Chloroethers 11
6 Manufacturing Process or Synthesis 15
Methods for Production of 3-Chloro-
ethers
7 Chemical Production Plant Sites with 22
Potential for Release of 3-Chloro-
ethers (45)
8 3-Chloroethers Detected in Water 28
9 Analysis of Haloethers in Air with 32
Sorbent Gas Chromatography/Mass
Spectrometry
10 Derivative Formation for Analysis 34
for BCME in Air
11 Analysis of Haloethers in Water 35
12 List of Preferred Sampling Sites 37
by Categories
xix
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List of Tables (continued)
Table page
13 Plant Sites for 3-Chloroethers Sampling 38
and Analysis
14 3-Chloroethers Analyzed for by GC/MS/ 51
SIM
15 Gas Chromatograph/Mass Spectrometer 52
Conditions for 3-Chloroether Analysis
16 Compounds Related to 3-Chloroethers 69
17 Recovery of 3-Chloroethers from Tenax- 74
GC. 100 yl of ^2.5 x lO^g/cm3 of
each 3-Chloroether Added
18 Recovery of 3-Chloroethers from Tenax- 75
GC - Effects of Conditioning
19 Recovery of 3-Chloroethers from Tenax- 76
GC - Effects of Air Pulled Through
Tubes for 6 Hours
20 Recovery of 3-Chloroethers from Water 78
21 Recovery of 3-Chloroethers from Soil 80
22. Field Recovery Studies - Air 82
23 Field Recovery Studies - Water 83
24 Assessment of Error in 3-Chloroether 86
Air Sample Workup and Analysis
25 Assessment of Error in 3-Chloroether 86
Water Sample Workup and Analysis
26- Assessment .of Error in 3-Chloroether 88
Soil and Sediment Workup
27 Reproducibility of GC/MS Analysis for 88
3-Chloroethers. Replicate Injections
of a Standard 3-Chloroether Mix on
July 26, 1977
28. Total Estimated Error 88
xx
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List of Tables (continued)
Table Page
29 Air Sampling at Olin Corporation 97
Brandenburg, Ky. on 31 March - 1 April
1977
30 Weather Conditions During Sampling at 98
Olin Corporation, Brandenburg, Ky-
31 March 1977
31 Water Sampling at Olin Corporation 101
Brandenburg, Ky. on 30-31 March 1977
32 Total Organic Carbon Analysis of Water 103
Samples from Olin Corporation, Brand-
enburg , Ky.
33- Air Sampling at Dow Chemical, Freeport, 112
Tx. on 20-21 June 1977
34 Weather Conditions During Sampling at 114
Dow Chemical, Freeport, Tx.
35 Water Sampling at Dow Chemical, Free- 118
port, Texas, 20-21 June 1977
36 Air Sampling at Jefferson Chemical, 130
Port Neches, Tx, on 22-23 June 1977
37 Weather Conditions During Sampling at 131
Jefferson Chemical, Port Neches, Tx
(Courtesy Weather Bureau, Jefferson
County Airport) 24°C-35°C
38 Water Sampling at Jefferson Chemical, 136
Port Neches, Tx, on 22-23 June 1977
39 Air Sampling at Dow Chemical USA, 153
Plaquemine, La. 27-28 June 1977
40 Weather Conditions During Sampling 154
at Dow Chemical U.S.A., Plaquemine,
La. 22-35°C
41 Water Sampling at Dow Chemical USA, 159
Plaquemine, La. on 27-28 June 1977
42 Air Sampling at Thiokol Corporation, 171
Moss Point, Mississippi on 29-30
June 1977
xx i
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List of Tables (continued)
Table page
43 Weather Conditions During Sampling 173
at Thiokol Corporation, Moss Point,
Miss. 21-35°C
44 Water Sampling at Thiokol Corporation, 176
Moss Point, Mississippi on 29-30 June
1977
45 3-Chloroethers Found in Moss Point 180
Water Samples
46 Weather Conditions During Sampling at 194
Union Carbide, Institute, W. Va.
11-24°C
47 Air Sampling at Union Carbide, Insti- 195
tute, W.Va. on 18-19 August 1977
48 Water Sampling at Union Carbide, 199
Institute, W. Va. on 18-19 August
1977
49 Air Sampling at Milliken Chemical 213
Division, Inman, S.C. 23-24 August
1977
50 Weather Conditions During Sampling at 214
Milliken Chemical, Inman, S.C.
21-31°C
51 Water Sampling at Milliken Chemical 219
Division, Inman, S.C. 23-24 August
1977
52 Air Sampling at Eastman Kodak, Roch- 233
ester, New York on 29-30 August 1977
53. Weather Conditions During Sampling 234
at Eastman Kodak, Rochester, N.Y.,
August 29-30, 1977
54. Water Sampling at Eastman Kodak, 237
Rochester, N. Y. on 29-30 August
1977
xxn
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SECTION 1
SUMMARY
The objective of this study was to develop sampling, workup and
analysis methods for the determination of trace levels of 3-
chloroethers in the environment near potential industrial
emitters. The six 3-chloroethers included in this study were:
chloroethyl vinyl ether, chloroethyl ethyl ether, bis(2-chloro-
ethyl) ether, bis(2-chloroethoxy) methane, bis(2-chloroisbpropyl)
ether and bis(2-chloroethoxy) ethane.
Methods were developed to sample, workup and analyze these six
3-chloroethers in air, water, soil and sediment samples. The
methods were validated both in the laboratory with synthetic
samples and through the analysis of spiked field samples.
Air samples were collected by drawing air through Pyrex sampling
tubes containing Tenax-GC with portable personnel sampling
pumps. Water samples were either 24-hour integrated samples
collected with a peristaltic pump or grab samples. Soil and
sediment samples were collected in glass canning jars.
The Tenax-GC sampling tubes used for air samples were solvent
desorbed with methanol using a procedure developed by MRC. Water,
soil and sediment samples were extracted with methylene chloride.
These methylene chlori'de extracts were concentrated with Kuderna-
Danish evaporators to volumes of 2 to 3 ml.
-------
Analysis of the extracts from the four types of samples was per-
formed by gas chromatography/mass spectrometry. The mass spec-
trometer was operated in the selected ion monitoring (SIM) mode.
Two characteristic ions for each compound were monitored during
the SIM analysis. Average detection limits for the 3-chloro-
ethers in each type of sampling using this method of analysis
were: 7 x 1CT7 g/m3 for air, 2 x 10~7 g/m3 for water, and
4 x 10~9 g/g for soil and sediment.
Eight industrial sites were sampled during the program. During
the sampling three of the six 3-chloroethers were found in at
least one sample. The three ethers were: bis(2-chloroethyl)
ether (BCEE), bis(2-chloroisopropyl) ether (BCIPE), and bis(2-
chloroethoxy) methane (BCEXM). Site one was the Olin Corporation
plant at Brandenburg, Kentucky- None of the 3-chloroethers were
detected in the samples taken at this plant. Sampling site 2
was the Dow Chemical USA plant at Freeport, Texas. BCEE was de-
tected in the downstream water sample closer to the plant outfall.
At site 3, Jefferson Chemical at Port Neches, Texas, BCIPE was
detected in the downstream water sample nearer the plant outfall.
Sampling site 4 was Dow Chemical USA at Plaquemine, Louisiana.
None of the 3-chloroethers were detected at this site. Site 5
was the Thiokol Corporation plant at Moss Point, Mississippi.
BCEXM was detected in two air, five water, one soil and two sedi-
ment samples. Also, BCEE was detected in one water and two
sediment samples. Sampling at site 6, Union Carbide Corporation
at Institute, West Virginia, resulted in the detection of none
of the g-chloroethers. Site 7 was the Milliken Chemical plant
at Inman, South Carolina. BCEE was detected in both downstream
water samples. Finally, at site 8, Eastman Kodak, Rochester,
New York, none of the 3-chloroethers were found in the samples
taken. The samples in which a 3-chloroether was found are listed
in Table 1. Since the sample workup did not result in 100% re-
covery of the 3-chloroethers, a correction factor was computed
for each 3-chloroether in each matrix. These factors were de-
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TABLE 1. SAMPLES IN WHICH B-CHLOROETHERS WERE FOUND
Sample
type
Air
Air
Water
Water
Water
Water
Water
Water
Water
Water
Water
Water
Soil
Sediment
Sediment
Sediment
Sediment
Location
Moss Point, MS
Moss Point, MS
Freeport, TX
Port Neches, TX
Moss Point, MS
Moss Point, MS
Moss Point, MS
Moss Point, MS
Moss Point, MS
Moss Point, MS
Inman, SC
Inamn, SC
Moss Point, MS
Moss Point, MS
,Moss Point, MS
Moss Point, MS
Moss Point, MS
Company
Thiokol
Thiokol
Dow
Jefferson
Thiokol
Thiokol
Thiokol
Thiokol
Thiokol
Thiokol
Milliken
Milliken
Thiokol
Thiokol
Thiokol
Thiokol
Thiokol
Sample
number
A-7
A-10
W-l
W-l
W-l
W-3
W-3
W-4
W-6
W-7
W-l
W-2
S-6
SD-1
SD-1
SD-2
SD-2
Sample
description
Downwind
Downwind
Downstream #1
Downstream #1
Downstream #1
Outfall #1
Outfall ttl
Downstream #2
Upstream
Outfall #2
Downstream #1
Downstream #2
Downwind
Downstream ttl
Downstream ttl
Downstream tt2
Downstream tt2
3-chloroether
BCEXM
BCEXM
BCEE
BCIPE
BCEXM
BCEXM
BCEE
BCEXM
BCEXM
BCEXM
BCEE
BCEE
BCEXM
BCEXM
BCEE
BCEXM
BCEE
Concentration
3.1 x 10- 6 g/m3
8.4 x ID"6 g/m3
T.8 x 10- 6 g/l
2.2 x 10-5 g/l
2*5 x 10-7 g/l
1.5 x 10-1* g/l
6.0 x 10-7 g/l
5.0 x 10-7 g/l
7.5 x 10-7 g/l
1.5 x 10-"* g/l
4.8 x 10- 6 g/l
4.6 x 10~6 g/l
5.8 x 10~7 g/g
1.4 x 10- 7 g/g
6.8 x 10-8 g/g
2.3 x 10-'7 g/g
1.0 x 10- 8 g/g
Ppb
0.44
1.2.
1.8
22.0
0.25
150.
0.6
0.5
0.75
150.
4.8
4.6
580.
140.
68.
23.
10.
-------
termined from results of spiked field samples for air and water
samples and spiked laboratory samples in the case of soil samples.
A complete discussion of the recovery studies is included in
Section 7. The corrected concentrations of 3-chloroethers found
in the four matrices are listed in Table 1.
Additional information is listed in Tables 2 and 3 concerning
other organic compounds present in representative air and water
samples from some of the sampling sites. These data were ac-
quired by making full-scan gas chromatography/mass spectrometry
runs of selected samples.
In addition, three raw water samples were collected in August and
September 1977 at Sioux Falls, South Dakota. These three water
samples were analyzed by GC/MS/SIM for BCEE and BCIPE. Neither
of these compounds was found in the three water samples. The
detection limit for ethers in these samples, for which a larger
volume than normal was extracted, was 3 x 10~8 g/1 (0.03 ppb) .
A final part of this study was devoted to: (1) synthesis of
bis(l-chloromethyl-2-chloroethyl) ether, (2) identification of the
compound in a simulated epichlorohydrin synthesis, and
(3) GC/MS analysis of water samples from the vicinity of the
Dow Chemical USA plant at Freeport, Texas, for the presence of
this compound. Interest in this compound was generated by the
suggestion that the compound could be a by-product of the epi-
chlorohydrin synthesis. Five different synthesis routes were
attempted unsuccessfully. Analysis of the simulated epichloro-
hydrin synthesis by GC/MS did reveal the presence of a compound
whose mass spectra could be interpreted as being bis(1-chloro-
methyl-2-chloroethyl) ether. Analysis of the extracts frpm the
water samples collected in the vicinity of the Dow plant at
Freeport did not show the presence of bis(l-chloromethyl-2-
chloroethyl) ether.
-------
TABLE 2. ORGANIC CHEMICAL COMPOUNDS POUND IN ENVIRONMENTAL
SAMPLES COLLECTED IN THE 3-CHLOROETHER STUDY
Compounds
detected in air
trichlorofluorome thane
methylene chloride
3 -methyl pentane
1 , 2-dichloroethane
trichldroethylene
toluene
chlorobenzene
dibutyl phthlate
benzene
2,2,3, 3-tetramethyl butane
xylene
methyl ethyl benzene
trimethyl benzene
methyl propyl benzene
tetramethyl benzene
acetbphenone
naphthalene
ethyl benzene
isopropyl benzene
benzaldehyde
nitrotoluene
tetrachloroethylene
dichlorobenzene
Freeport,
Texas
X
X
X
X
X
X
X
X
Port Plaque- Moss Point
Neches, Tx. mine, La. Mississippi
XXX
XXX
X X
X
X
X
X
X
X
X
X
Institute
W.Va.
X
X
X
X
X
X
X
X
X
Inman
S.C.
X
X
X
X
X
X
X
X
X
-------
TABLE 3. ORGANIC CHEMICAL COMPOUDS FOUND IN ENVIRONMENTAL
SAMPLES COLLECTED IN THE B-CHLOROETHER STUDY
Compounds Freeport
detected in water Texas
diethyl phthalate x
di-n-butyl phthalate x
triphenyl phosphine x
dioctyl phthalate x
triphenylphosphine oxide x
p-chloro phenol
isothazine
isobutyl phthalate
2,7,11-trimethyl dodeca-2-
trans-6-cis-10-trienol
phenol
diethylene glycol monoethyl ether
OC-caprolactone
p-cresol
triethylene glycol
methyl naphthalene
acenaphthalene or biphenyl
nonyl phenol
1,2 cyclohexane diol
5-n-butyl nonane
2 , 6-ditert-butyl-4-methyl phenol
stilbene
2 , 2-dimethyl-trans-hex-3-ene
diisobutyl phthalate
phenyl dfphenyl phosphinate
1,4 oxathione
methyl-ditert-butyl phenol
dichlorobenzene
diphenyl ether
2,2,4-trimethyl pentadiol
diisobutyrate
butyl carbobutoxymethyl phthalate
Port
Neches, Tx.
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Plaque- Moss Point Insti- Irunan Rochester
mine, La. Mississippi tute, W.Va. S.C. N.Y.
X X
X
x x
X XXX
XX XX
X
X
X XX
X
X
X
X
X
X
X
X
X
X
-------
SECTION 2
INTRODUCTION AND LITERATURE REVIEW
Monsanto Research Corporation (MRC) in response to Research
Request No. 2 of Contract No. 68-01-1980 with the U.S. Environ-
mental Protection Agency's office of Toxic Substances (EPA-OTS)
conducted a study to measure p-chloroether levels in the environ-
ment in the vicinity of potential industrial emitters. 3-Chloro-
ethers are defined as ethers containing a chlorine atom or atoms
attached to a carbon atom bonded to an ether linkage carbon atom.
The original request listed the following compounds for sampling
and analysis:
• bis(2-chloroethyl) ether
• bis(2-chloroisopropyl) ether
• bis(2-chloroethoxy) methane
• 2-chloroethyl vinyl ether
• 1,2-bis(2-chloroethoxy) ethane
• 2-chloroethyl methyl ether
After reviewing literature concerning the B-chloroethers, 2-
chloroethyl methyl ether was removed from the list. Two com-
pounds, 2-chloroethyl ethyl ether and bis(l-chloromethyl-2-chloro-
ethyl) ether were added to the original list. The B-chloroethers
and their abbreviations, chemical formula, structure, boiling
point and density are listed in Table 4.
The remainder of this section is devoted to review of pertinent
literature concerning p-chloroethers. The other sections of
7
-------
TABLE 4. PROPERTIES OF 3"CHLOROETHERS STUDIED
00
Compound
2-chloroethyl. ethyl ether
2-chloroethyl vinyl ether
bis (2-chloroethyl) ether
bis(2-chloroisopropyl) ether
Abbrevi-
ation
CEEE
CEVE
BCEE
BCIPE
Chemical
formula
Ci^HgClO
ClfHyClO
Cl>H8Cl20
C6H12C120
Structure
C1CH2CH2OCH2CH3
C1CH2CH2OCH=CH2
C1CH2CH2OCH2CH2C1
C1CH2CHOCHCH2C1
Boiling
point, °C'
L07-108
108
178
187
Density,
g/cm3
0.9894
1.0475
1.2199
1.1034
bis(2-chloroethoxy) methane
BCEXM
I I
CH3 CH3
C1CH2CH2-OCH2OCH2CH2C1
206
1.225
1,2 bis(2-chloroethoxy) ethane
BCEXE
bis(l-chloromethyl,2-cnloroethvl BCMCEE c6Hi0Cli,O
ether
C1CH2CH2OCH2CH2OCH2CH2C1 230
C1CH2CH-O-CH CH2C1
I I
CH2C1 CH2C1
1.197
-------
this final report, listed below, detail the information con-
cerning the 3-chloroether sampling and analysis.
• Sampling Site Selection
• Sampling Methods
• Sample Workup Methods
• Sample Analysis Methods
• Recovery Studies
• Sampling Site Descriptions and Results
• References
-------
2.1 DESCRIPTION'OF INDUSTRIAL PROCESSES INVOLVING 3-CHLOROETHERS
Most data on the manufacture and uses of 3-chloroethers were
over ten years old and very limited. The available information
pertained primarily to bis(2-chloroethyl) ether and bis(2-
chloroisopropyl) ether. Information on bis(2-chloroethoxy)
methane and 2-chloroethyl vinyl ether was limited. Very little
information was obtained concerning 1,2-bis(2-chloroethoxy)
ethane and almost none was available on 2-chloroethyl methyl
ether.
2.1.1 3-Chloroether Consumption and Uses
Basically.- 3-chloroether usage can be divided into two main cate-
gories: (a) applications that use 3-chloroethers as chemical
intermediates, and (b) applications that use the physical pro-
perties of 3-chloroethers as solvents (1). The consumption and
use of 3-chloroethers is summarized in Table 5.
Related compounds likely to be found with 3-chloroethers are the
a-chloroethers since chlorination first occurs by substitution
of a chlorine atom on -the a position of the ether (30). A
closer study of the a-haloethers indicates that since a-chloro-
ethers hydrolyze very rapidly in water (30-35), their presence
in air, water, or soil for any extended period of time is very
unlikely.
10
-------
TABLE 5. PRODUCTS AND USES OF 3-CHLOROETHERS
3-Chloroether
Bis(2-chloroethyl) ether (1-17)
Chemical intermediate for the synthesis of morpholine,
divinyl ether, plasticizers, synthetic rubber,
Pharmaceuticals, resins, amino ethers, 3-(8-chloro-
ethoxy) phenetole, surfactants, p-chloroethyl vinyl
ether, 4,4-dicarboxyethyl,|5, 3 '-diiododiethyl ether,
tetrahydropyran 4-carbonylic. acid, and 4-cyan tetra-
hydropyran 4-carboxylate.
Dewaxing agent for lubricating oils.
Solvent for the separation of butadiene from butylene.
Penetrant, welting agent, and solvent in the textile
industry.
Insecticide, acaricide, nematocide, soil fumigant and
disinfectant.
Drycleaning agent.
Gasoline additive to scavenge lead deposits.
Replacement for NaOH in Kier boiling.
Impact resistant styrene copolymer.
Water-soluble cation-active polymeric electrolyte in
papermaking industry.
Solvent for fats, oils, waxes, resins, balsams and
dyes.
Process and pickling inhibitor.
-------
TABLE 5 (CONTINUED). PRODUCTS AND USES OF 0-CHLOROETHERS
Bis(2-chloroisopropyl) ether (1-3, 18, 19)
Bis(2-chloroethoxy) methane (20)
l,2-Bis(chloroethoxy) ethane (15, 16,
21-25)
Chemical intermediate for dyes, resins,
and Pharmaceuticals.
Soap additive in the textile industry.
Surfactants, wetting agents, emulsifiers,
and detergents.
Wood preservative (with pentachlorophenol
sodium salt).
Solvent for fats, waxes, and greases in
paints, varnish removers, spotting agents,
and cleaning solutions.
Polysulfide crude rubbers for printing
rollers, hose, gaskets, and gas meter
diaphragms.
Polysulfide liquid polymers for sealants
and adhesives.
Polysulfide latexes.
Chemical intermediate for insecticides
and other organic compounds. .«.->
Cleaning agent.
Polyhydroxy polysulfide polymers in paint,
lacquer or varnish, plastics and resins.
Water-soluble cation-active polymeric
polyelectrolytes used in paper making
industry.
-------
TABLE 5 (CONTINUED). PRODUCTS AND USES OF g-CHLOROETHERS
2-Chloroethyl vinyl ether (26-29)
w
2-Chloroethyl methyl ether
Process and pickling inhibitor in paint
manufacture.
Solvent for hydrocarbon oils, etc.;
extractant.
Water-resistant resins.
Processing chemical in manufacture of
abrasive articles from butadiene polymers
and copolymers.
Soil, oil and water resistant finishing
agent for cotton, wool and polyester
textiles.
Copolymer with maleic anhydride in benzene,
Copolymer with isobutyl vinyl ether.
Copolymer with ethyl acrylate.
No use reported in the literature.
-------
2.1.2 3-Chloroether Production M
Table 6 summarizes the chemical processes available for the syn-
thesis of the B-chloroethers. Only bis (2-chloroethyl) ether and
bis(2-chloroisopropyl) ether are produced in large enough quanti-
ties to warrant inclusion in Stanford Research Institute's
Directory of Chemical Producers.
2.1.3 3-Chloroethers Formed as By-products
2.1.3.1 Bis(2-Chloroethyl) Ether —
Bis (2-chloroethyl) ether is formed as a by-product during the
chlorohydrination process for the manufacture of ethylene chloro-
hydrin, ethylene oxide and ethylene glycol (41, 42) .
Ethylene chlorohydrin — In the manufacture of ethylene chlorohydrin
dilute hypochlorous acid is reacted with ethylene gas (1, 33, 42>
44) .
CH2=CH2 + HOC1 - *-CH2ClCH2OH (1)
Various procedures have been developed for the production of
hypochlorous acid, but it is best produced by the reaction of
chlorine with water (36, 43).
C12 + H9O- »-HOCl + HC1 (2)
The reaction is an equilibrium and may be shifted to the product-
side by using a large amount of water or by neutralizing or other
wise removing HC1 from the reaction zone. Formation of bis
(2-chloroethyl) ether during chlorohydrin synthesis can be rep-
resented by the equation (36, 43),
14
-------
TABLE 6. MANUFACTURING PROCESS OR SYNTHESIS METHODS
FOR PRODUCTION OF 3-CHLOROETHERS
6-chloroether
Manufacturing process or synthesis
Bis(2-chloroethyl) ether
1. Prepared by heating ethylene chlorohydrin
with sulfuric acid at 90-100°C.
2C1CH2CH2OH
C1C"H2CH2OCH2CH2C1 + H2O
Bis(2-chloroisopropyl)
ether
2. Prepared by saturating an aqueous solution
of ethylene chlorohydrin with chlorine and
ethylene (1, 3).
1. Prepared by reacting hypochlorous acid with
propylene. Several reactions occur includ-
ing chlorohydrination. Formation of bis(2-
chloroisopropyl) ether is favored by
high chiorohydrin concentration (36).
2. Prepared from 3-chloroisopropyl alcohol by
the H2SO4 process.
C1CH2CH (CH3 ) OH
C1CH2CH (CH3 ) OCH (CH3 ) CH2Cl
Bis(2-chloroethoxy) methane
1,2-Bis(2-chloroethoxy)
ethane
2-Chloroethyl vinyl ether
2-Chloroethyl methyl
Prepared by the condensation of ethylene
chlorohydrin with anhydrous formaldehyde in
the presence of an azeotroping agent.
2C1CH2C:H.2OH + H€!HO ••
C1CH2CH2OCH2OCH2CH2C1 + H2O
Prepared in the reaction of C12, ethylene
and water. Up to 2% bis(2-chloroethyl)
ether can be added to the reaction mixture
to increase yield (37).
Prepared by the dehydrochlorination of
bis(2-chloroethyl) ether.
C1CH2CH2OCH2CH2C1
JMcLvJcl
C1CH2CH2OCH = CH2
1. Prepared by addition of C12 and MeOH to ethy-
lene. The yields can be greatly increased
by using ethylene oxide, propylene oxide or
epichlorhydrin as acid binding agents (38, 39)
2. Prepared by the action of PCls on MeOCH2CH2OH (40)
15
-------
CH2=CH2 + HO+C1" ^CH2 CH2 + OH~ (3)
/C1\
CH2 CH2 + OH >- OH-CH2-CH2-C1 (4)
CH2— CH2 + OH-CH2-CH2-C1 * Q + HC1 (5)
bis(2-chloroethyl) ether
The amount of bis(2-chloroethyl) ether can be controlled by the
ethylene chlorohydrin concentration (36).
Ethylene oxide (by the chlorohydrin process)—The manufacture
of ethylene oxide by the chlorohydrination of ethylene does not
appear to have been used since 1972 (38). Currently, ethylene
oxide is made by direct oxidation of ethylene over silver
catalyst (1, 42). Facilities for ethylene oxide manufacture by
the chlorohydrin process have been converted to make propylene
oxide. Direct oxidation process being more energy intensive,
energy/economic considerations could lead to a rapid return to
the chlorohydrin route (1). Ethylene oxide is obtained by the
hydrolysis of ethylene chlorohydrin (obtained from ethylene above)
using milk of lime slurry or a solution of sodium hydroxide (1, 42)
Ethylene glycol (by the chlorohydrin process)—The manufacture
of ethylene glycol via the ethylene chlorohydrin process takes
in two basic steps (42):
16
-------
CH2=CH2 + HOC1
~OH-CH2-CH2-C1
(6)
OHJ-CH2-CH2'-C1 Ca (OH) 2
CH2 CH2
O
NaOH
(7)
H2O
CH2-CH2
OH OH
ethylene glycol
Ethylene oxide can readily be converted to ethylene glycol by the
action of a dilute aqueous solution of a strong acid or by reac-
tion with water at elevated temperatures and pressures (42) . A
third alternative is the vapor phase hydrolysis of ethylene oxide
over a silver oxide catalyst (42).
«
Because of the conversion to the direct oxidation process for the
manufacture of ethylene oxide from the chlorohydrin process, plants
using chlorohydrination have been converted to produce propylene
chlorohydrin and propylene oxide. Ethylene glycol is made mainly
from ethylene oxide. Only one plant is currently using the ethy-
a
lene chlorohydrin process to make ethylene chlorohydrin.
2.1.3.2 Bis(2-chloroisopropyl Ether—
Bis(2-chloroisopropyl) ether is formed as a by-product during the
chlorohydrination process for the manufacture of propylene chloro-
hydrin, propylene oxide and propylene glycol (36, 44).
Propylene chlorohydrin—The propylene chlorohydrin route to
propylene oxide still enjoys a competitive economic position (1).
Approximately 70% of the capacity is based on chlorohydrination
as opposed to peroxidation (direct oxidation) (1).
As with ethylene chlorohydrin, propylene chlorohydrin is formed
by reacting hypochlorous acid with propylene. However, two chloro-
17
-------
hydrins are possible with propylene chlorohydrin and as a result
three ethers may be found. The reaction can be represented by
the equation (1, 36, 44) .
CH3-CH=CH2 + HOci~i-»
OH
(8)
CH3- CH —
CH3-CH -
CH3-CIT-CH2 +
OH* Cl
a -chlorohydrin
H-CH2
Cl .OH
3 -chlorohydrin
CH3-CH-CH2
I I
Cl OH
CH3-CH-0 - CH-CH3
CH2C1 CH2C1
CH3-CH-CH2-0-CH-CH3
Cl CH2C1
CH3-CH-CH2-0-CH2-CH-CH3
Cl Cl
(10)
a --Chlorohydrin is the major product, because of the stability
of the secondary carbon atom, but the isomer ratio has been re-
ported to vary from 3:1 to 9:1. The major ether isomer is the
bis(2-chloroisopropyl) ether (1, 36, 44) . Propylene dichloride
is the major by-product being produced in larger quantities with
the ethers (1, 36, 44) .
CH3-CH-C&2
C1
- CH-CH2
Cl Cl
propylene dichloride
18
-------
Propylene oxide^-A typical chlorohydrin plant for manufac-
turing propylene oxide is shown in Figure 1. The haloether would
be found at the same locations as crude propylene dichloride
(e.g., in the chilled caustic soda wash of unreacted gases and
in the aqueous effluent from the steam heat flash hydrolyses
(1, 36, 44).
Propylene oxide is formed from propylene chlorohydrin by the
action of aqueous alkali. Usually the alkali is a lime water
slurry containing 10% in lime (1, 36, 44).
CH3-CH-CH2 + OH~ - » CH3-CH-CH2 + H2O (12)
OH hi 4
CH3-CH-CH2
0
The equilibrium lies well to the right and is driven further in
that direction by the removal of oxide by stripping or by reaction
to glycol (1, 36, 44).
Propylene glycol—Propylene oxide can be rapidly hydrated
to monopropylene glycol by the alkaline condition in the
reactor (1, 36, 44) .
CH3-CH - CH2' + OH" " .CH3-CS-.CH2 (13)
O
-------
Chlorhydrin
tower.
-Pressure
40ins.H20
Distillation
column
Propvlene
Inert gas
bleed
.Crude
propylcnc dichloride
Recycle gas
Crude, .^
propylen* (J\
dichloride YJ
iMilk of limt
(stock tank
Grit Slaker
Recycle
gas booster
Figure 1.
Diagram of a typical chlorohydrin
propylene oxide plant (Fyvie [36], 1964)
(reprinted with permission)
20
-------
2.1.4 3-Chloroether Users
The major commercial applications of 3-chloroethers can be grouped
into two general areas:
• chemical intermediates, and
• solvent use.
Because of the many but limited uses of 3-chloroethers, we will
consider only the commercially important use of bis(2-chloroethoxy)
methane in polysulfide rubbers.
2.1.4.1 Bis(2-chloroethoxy) Methane—
Bis(2-chloroethoxy) methane finds its major application as the
principal monomer in polysulfide polymers (20, 1). The chemical
is manufactured by Thiokol at Moss Point, Mississippi and is
totally consumed in the production of polysulfides (1, 20). These
specialty polymers are used as room-temperature-curing liquid
polymers in the sealant and adhesive markets because of their
good solvent resistance, low-temperature performance, and weathering
and ozone resistance. The polymers are formed by polycondensation
of the bis(2-chloroethoxy) methane with an aqueous polysulfide
solution. Frequently, 1,2,3-trichloropropane is added for
cross-linking and in some instances bis(4-chlorobutoxy) methane
or bis(4-chlorobutyl) ether are used in minor amounts to improve
low-temperature performance (1, 20).
i
2.1.5 Chemical Production Plant Sites With the Potential for
Release of g-Chloroethers
The greatest potential for environmental emission of 6-chloro-
ethers appears to be from the inadvertent production of these
chemicals in other industrial processes such as the chlorohydrin
process. Other likely sources are the production and usage of
e-ohloroethers. Table 7 lists all potential emission sources of
3-chloroethers.
21
-------
TABLE 7. CHEMICAL PRODUCTION PLANT SITES WITH POTENTIAL FOR RELEASE OF g-CHLOROETHERS (45)
g-chloroether
associated
Chemical produced
Company
Plant site
BCEE
BCEE
Ethylene chlorohydrin
Ethylene oxide
to
to
Union Carbide Corp.
Allied Chem. Corp.
Specialty Chem. Div.
BASF Wyandotte Corp.
Indust. Chems. Group
Calcasieu Chem. Corp.
Celanese Corp.
Celanese Chem. Co., Div.
Dow Chem. U.S.A.
Eastman Kodak Co.
Eastman Chem. Products. Inc.
subs. Texas Eastman Co.,
div.
Northern Natural Gas Co.
Northern Petrochem. Co.,
subs.
Polymers div.
Olin Corp.
Design Products Div.
PPG Indust., Inc.
Chem. Div.
Houston Chem. Co. div.
PPG Indust. (Caribe)
Shell Chem. Co.
Base Chems.
SunOlin Chem. Co.
Texaco, Inc.
Jefferson Chem. Co., Inc.
subs.
Institute and South
Charleston, W. Va.
Orange, Texas
(on stand-by)
Geismar, Louisiana
Lake Charles, La.
Clear Lake, Texas
Freeport, Texas
Plaquemine, La.
Longview, Texas
Morris, Illinois
Brandenburg, Kentucky
Beaumont, Texas
Guayanilla, P.R.
Geismar, Louisiana
Claymont, Delaware
Port Neches, Texas
-------
TABLE 7-(CONTrD). CHEMICAL PRODUCTION PLANT SITES WITH POTENTIAL FOR RELEASE'*>F 3-CHLOROETHERS (45)
3-chloroether
associated
Chemical produced
Company
Plant s ite
BCEE
Ethylene oxide (cont'd.)
BCEE
Ethylene glycol
to
to
Union Carbide Corp.
Chems. and Plastics Div.
Union Carbide Caribe,
Inc., subs.
ADD Processing Corp.
Allied Chem. Corp.
Specialty Chems. Div.
BASF Wyandotte Corp.
Indust. Chems. Group
Calcasieu Chem. Corp.
Celanese Corp.
Celanese Chem. Co., div.
Dixie Chem. Co.
Dow Chem. U.S.A.
Eastman Kodak Co.
Eastman Chem. Products,
Inc., subs.
Texas Eastman Co., div.
ICI United States Inc.
Specialty Chems. Div.
Northern Natural Gas Co.
Northern Petrochem. Co.,
subs.
Polymers Div.
01in Corp.
Designed Products Div.
PPG Indust., Inc.
Chem. Div.
Houston Chem. Co., div.
Seadrift, Texas
Taft, Louisiana
Penuelas, P.R.
Abbevilie, Louisiana
*0range, Texas
(on stand-by)
Ge i smar, Louisiana
Lake Charles, La.
Clear Lake, Texas
Bayport, Texas
Freeport, Texas
Plaquemine, La.
Longview, Texas
New Castle, Delaware
Morris, Illinois
Brandenburg, Kentucky
Beaumont, Texas
-------
TABLE 7 (CONT'D). CHEMICAL PRODUCTION PLANT SITES WITH POTENTIAL FOR RELEASE OF 3-CHLOROETHERS (45)
B-chloroether
associated
Chemical produced
Company
Plant site
BCEE
to
BCIPE
BCIPE
Ethylene glycol (cont'd.)
BCEE
Propylene chlorohydrin
Propylene oxide
PPG Indust. (Caribe)
Shell Chem. Co.
Base Chems.
Texaco, Inc.
Jefferson Chem. Co.,
Inc., subs.
Union Carbide Corp. Chem.
and Plastics Div.
Union Carbide (Caribe),
Inc. subs.
Buckman Labs Inc.
J. T. Baker Chem. Co.
Chemical Samples Co.
Eastman Organic Chem.
E. M. Laboratories Inc.
Fisher Scientific Co.
MC&B Manufacturing Chemists
Union Carbide Corp.
Eastman Kodak Co.
Eastman Organic Chems.
RSA Corp.
BASF Wyandotte Corp.
Indust. Chems. Group
Dow Chem. U.S.A.
Guayanilla, P.R.
Geismar, Louisiana
Port Neches, Texas
Seadrift, Texas
Taft, Louisiana
Penuelas, P.R.
Cadet, Missouri
Memphis, Tennessee
Columbus, Ohio
Rochester, New York
Rochester, New York
Ardsley, New York
Wyandotte, Michigan
Freeport, Texas
Plaquemine, Louisiana
-------
TABLE 7.(CONTID). CHEMICAL PRODUCTION PLANT SITES WITH POTENTIAL FOR RELEASE OF 3-CHLOROETHERS (45)
3-chloroether
associated
Chemical produced
Company
Plant site
BCIPE
Propylene oxide (cont'd.)
BCIPE
Propylene glycol
to
BCIPE
BCEM
BCIPE
Polysulfide polymers
Olin Corp.
Designed Products Div.
Oxirane Chem. Co.
Texaco, Inc.
Jefferson Chem. Co./
Inc., subs.
Dow Chem. U.S.A.
Olin Corp.
Designed Products Div.
Oxirane Chem. Co.
Texaco, Inc.
Jefferson Chem. Co.,
Inc., subs.
Union Carbide Corp.
Chems. and Plastics Div.
Dow Chem. U.S.A.
Chemicals Samples Co.
MC&B Manufacturing Chemicals
Diamond Shamrock
The Flamemaster Corp.
Chem-Seal Corp. div.
Products Research &
Chem. Corp.
Eastern Sales & Mfg. Div.
Western Mfg. Div.
Sybron Corp.
Kerr Mfg. Co. Div.
Acco Polymers Div.
Thiokol Corp. Chem. Div.
Brandenburg, Kentucky
Bayport, Texas
Port Neches, Texas
Freeport, Texas
Plaquemine, Louisiana
Brandenburg, Kentucky
Bayport, Texas
Port Neches, Texas
Institute and South
Charleston, W. Va.
Freeport, Texas
Columbus, Ohio
Ashtabula, Ohio
Sun Valley, California
Gloucester City, N. J.
Glendale, California
Romulus, Michigan
Moss Point, Miss.
-------
TABLE 7 (CONT'D). CHEMICAL PRODUCTION PLANT SITES WITH POTENTIAL FOR RELEASE OF 3-CHLOROETHERS (45)
3-chloroether
associated
Chemical produced
Company
Plant site
to
en
BCEM
BCEM
BCOE
Epichlorohydrin
BCEM
BCOE
Dow Chem. U.S.A.
Shell Chem. Co.
Base Chem.
Bio Chemical Labs
K & K Labs
Mide Chem. Corp.
J. T. Baker Chem. Co.
Columbia Org. Chem. Co.
Chemical Procurement
Labs
Chemical Samples Co.
MC&B Manufacturing
Chemists
Polyscience, Inc.
Union Carbide Corp.
Freeport, Texas
Deer Park, Texas
Norco, Louisiana
Smithtown, New York
Bohemia, New York
Columbia, S. Carolina
.College Point, N. Y.
Columbus, Ohio
Warrington, Pa.
-------
2.2 DETECTION OF HALOETHERS IN THE ENVIRONMENT
The vast majority of reports of detection of 3-chloroethers in
the environment have been from water samples. However, a group
of workers at Research Triangle Institute (46) have reported the
detection of BCIPE in ambient, air in Freeport, Texas. The
levels they reported were 27 ng/m3 and 333 ng/m3. Since Rosen,
et al (47) discovered the presence of BCEE in the Kanawha River
of West Virginia in 1964, a number of other government workers
have reported the detection of 3-chloroethers in industrial
wastewater, river water, and drinking water. Table 8 summarizes
the 3-chloroethers found in water, their concentration if
determined, the location where they were found,and the reference
where they were reported. Figure 2 is a map of the United
States showing the locations where 3-chloroethers have been
detected.
2.2.1 Hydrolytic Stability of 3-Chroroethers
A few studies have been conducted to determine the hydrolytic
stability of 3-chloroethers in acid, neutral, and basic aqueous
systems.
Bohme and Sell (32) measured the hydrolysis rate of BCEE in a
dioxane-water mixture (20M water in dioxane) at 100°C. The
half life of BCEE under these conditions was 12.8 days. Van
Duuren and co-workers (31) measured the kinetics of hydrolysis
of microliter quantities of six chloroethers in 10 ml of a water-
formaldehyde (3:1) solution. The hydrochloric acid formed was
titrated with an automatic recording titrator. They found the
half life of all the ethers with alpha-chlbro substituents
was less than 2 minutes, the half life of ethers with no
alpha-chloro substitution was greater than 23 hours,and the BCEE
half life was >23 hours. Salomaa and associates (33) have
studied the hydrolysis of chlorovinyl ethers and chloro-substituted
27
-------
TABLE 8. B-CHLOROETHERS DETECTED IN WATER
Compounds
Concentration
yg/i
Location
Reference
to
00
bis(2-chloroethyl) ether
bis(2-chloroethyl) ether
bis(2-chloroisopropy1) ether
bis(2-chloroethyl) ether
bis(2-chloroisopropyl) ether
bis(2-chloroethyl) ether
bis(2-chloroisopropyl) ether
bis(2-chloroethoxy) methane
bis(2-chloroethyl) ether
bis(2-chloroisopropyl) ether
bis(2-chloroethyl) ether
bis(2-chloroethyl) ether
bis(2-chloroethyl) ether
bis(2-chloroisopropyl) ether
0.5-5.0
2.0
0.07
0.16
0.12
0.18
0.05
0.03
140,000
160
*
10
0.4
0.01-0.36
0.02-0.55
Kanawha River, West Virginia
Jefferson Parish #2
Jefferson Parish #2
Evansville, Indiana Drinking Water
Evansville, Indiana
Carrollton
Jefferson Parish #1
Jefferson Parish #2
Carrollton
Jefferson Parish #1
Jefferson Parish #2
Synthetic Rubber Plant
Synthetic Rubber Plant
Glycol Plant,
Thickening and Sediment Pond
Philadelphia Northeast,
Water Treatment Plant
Delaware River, Philadelphia
Various Cities During NOMS
Various Cities During NOMS
47
48
48
49
49
50
50
50
50
50
50
51
51
51
52
52
53
53
* Detected but not quantified
-------
NJ
IO
A - MOMS
. • OTHER REFERENCES
Figure 2. Sites where B-Chloroethers have been found,
-------
acetals under acid conditions. They found the chlorovinyl ethers
such as chloroethyl vinyl ether are readily hydrolyzed to an
aldehyde and alcohol as shown in equation 15.
C1CH2CH2-0-CH=CH2 H3°^. C1CH2CH2OH + CH3-C-H (15)
Their equations for two hydrolysis pathways for chloro substituted
acetals are shown in equations 16 and 17.
C1CH2CH2OCH2;OCH2CH3 H»» C1CH2CH2O=CH2 + HOCH2CH3 (16)
H+ +
C1CH2CH2;OCH2OCH2CH3 » C1CH2CH2OH + CH2=OCH2CH3 (17)
i
As part of a hazard priority ranking program for the National
Science Foundation, Stanford Research Institute (54) predicted
a half life for BCEE in water at a pH of 7 of 38.2 days. One
other process for catalytically cleaving BCIPE, based on a
patent by Dow Chemical, is shown in equation 18 (55).
(C1CH2CH(CH3))2O •|Cjc^-CH3-CH-CH2Cl and CH3-CH-CH2C1 (18)
U Cl OH
2.3 METHODS FOR THE ISOLATION, CONCENTRATION AND ANALYSIS OF
3-CHLOROETHERS
The isolation, concentration and analysis methods described in
the literature have been directed primarily toward three of the
haloethers, BCEE, BCIPE and BCEXM, of interest to this program.
Descriptions of the methods reported will be divided between air
and water.
30
-------
2.3.1 Air
Two main types of methods, direct analysis and use of sorbants, have
been employed for collection and concentration of 3-chloroethers.
In addition, derivative formation has been used to collect
bis(chloromethyl) ether (BCME) from air. These methods are
included because it was felt early in this program that deri-
vative formation might be a good method for 3-chloroethers.
2.3.1.1 Direct Analysis—
Direct analysis for fumigant gases were performed by Berck (56)
with a 1.8 m x 4 mm stainless steel column packed with 10% SE-30
on Diatoport S. The haloether analyzed for was BCEE and a
thermal conductivity detector was used.
2.3.1.2 Sorbents—
A variety of sorbents have been used to collect 3-chloroethers
from air. The adsorbers are then thermally desorbed onto a gas
chromatographic column, which is connected to a low or high
resolution mass spectrometer. Table 9 cites the haloethers
which were being collected, the sorbant used for collection, the
gas chromatographic column employed and the reference number of
the literature from which these data were taken.
A method based on absorbers for collection makes use of solvent
for desorption purposes. NIOSH traps BCEE from work-place environ-
ments on charcoal. The BCEE is desorbed with carbon disulfide
and analyzed by gas chromatography on 10% FFAP on 80/100 mesh
acid-washed, DMCS-treated Chromosorb W (60).
2.3.1.3 Derivatives—
The third procedure used to collect and analyze BCME in air is
based on derivative formation followed by gas chromatography with
V
an electron capture detector. The derivatives are formed via
the reaction in methanol solution between BCME being scrubbed
31
-------
TABLE 9. ANALYSIS OF HALOETHERS IN AIR WITH SORBENT
GAS CHROMATOGRAPHY/MASS SPECTROMETRY
Gas chromatographic
(3-chloroether Sorbent column . Reference
BCME,BCEE Chromosorb 101 2% DEGS on Chromosorb W 57
Chromosorb 104 (HP) 80/100 mesh 3.6mx2.5mm 58
Tenax GC
Porapak Q
Activated Carbons
20% Carbowax 600
on Chromosorb W
Carbowax 400/Porsail C
Oxypropionitrile/
Porasil C
25% Didecylphthlate
on Chrom. P
20% Tricresyl Phos-
phate on Chrom. W
BCME,BCEE Tenax GC Tenax GC (3.6 m x 2.5 mm) 59
2% DEGS on Supelcoport
(80/100 mesh) (3.6 m x 2.5 mm)
-------
from the air and the sodium salt of 2,4,6 trichlorophenol. Other
sodium salts of alkyl or aryl oxides have been used by other
workers. The materials used to form derivatives, the gas chro-
matographic column used for analysis and the references are
listed in Table 10.
2.3.2 Water
The major methods of isolation and concentration of haloethers
from water have centered around sorption on charcoal or solvent
extraction. Method of analysis is primarily gas chromato-
graphy with different detectors.
Table 11 lists the method of isolation and concentration, the gas
chromatography detector used, and the reference for haloethers in
water. In addition to these standard techniques, Deinzer, et al.
tested the use of a cellulose acetate reverse osmosis membrane
for concentrating BCEE and BCIPE from water (65). They were not
successful in increasing the concentration of these two compounds
in the reject water with the membrane they were using.
33
-------
TABLE'10. DERIVATIVE FORMATION FOR ANALYSIS FOR BCME IN AIR
U)
Derivative reagent
Gas chromatographic
column
Na 2,4,6-trichlorophenate
Na phenate
Na methoxide
Na ethoxide
Na thiophenate
Na 2,4,6-trichlorophenate
0.1% QF-1 and 0.1% OV-17
on 100/120 mesh textured
glass beads (GLC 100)
(1.8 m x 4 mm)
LAC-2R446 + 2% H3PO4
Reference
61
62
Na 2,4,6-trichlorophenate
63
-------
TABLE 11. ANALYSIS OF HALOETHERS IN WATER
Haloethers
BCEE, BCIPE
BCEE, BCIPE
BCEXM
BCEE, BCIPE
Isolation con-
centration techniaue
Carbon chloroform
extraction
Solvent
Carbon chloroform
extraction
Gas chromato-
araph column -
_
4% FFAP on
Chromosorb W
(1.8mx2.1mm or
4mm)
5% SE-30 on
Chromosorb W
Detector
IR
FID, mass
spec.
FID, mass
spec.
Reference
47
51
49
BCEE, BCIPE
BCEM, CEVE
BCIPE, BCEE
BCIPE, BCEE
Extraction with 5%
ethyl ether in hexane
Extraction with 15%
ethyl ether in hexane
Purge and trap
Methylene chloride
extraction
60/80 mesh
(1.8m x 2mm)
5% OV-17 on
Chromosorb W
60/80 mesh
(1.8m x 2mm)
4% SE-30 + 6%
OV-210 on Gas
Chrom. Q (1.8m x
2.1mm)
3% SP 1000 on
Supelecoport
100/120 mesh
(1.8m x 2.1 mm)
0.2% Carbowax
1500 on Carbopak
C (60/80 mesh)
(2.4mx2.1mm) +
Carbowax 1500 on
Chromosorb W
(0.3m x 2.1mm)
1% SP 2250 on
Supelecoport
(100/120 mesh)
(1.8m x 2mm)
OV-17 SCOT
Column
Microconio- 53
metric, electro-
lytic conduc-
tivity
Mass spec.
64
Mass spec.
64
Mass spec.
64
35
-------
SECTION 3
SAMPLING SITE SELECTION
From information in the open literature we were able to determine
19 plant sites where the greatest concentrations of 3-chloroethers
are likely to be found. These plants, the 3-chloroether expected,
the chemical which is being produced and which could result in
the 3-chloroether emission, and the plant site are listed in
Table 12. This list was then reviewed with regard to plant size,
access and other information we were able to gather from state
and local agencies. In addition EPA-OTS contacted Regional EPA
personnel for recommendations as to plants in their region which
were potential 3-chloroether emitters. From these contacts the
Milliken Chemical Company, Inman, S.C. was added to the original
list of 19.
During the time we were sampling these industrial sites and
*?
analyzing the samples, the results of the NOMS survey were pub-
lished (53) . We were requested by EPA-OTS to contact the authors
of the NOMS survey paper. From this contact it was learned that
BCEE and BCIPE were found at Sioux Falls, S.D. Contacts with
regional EPA personnel resulted in our sending cleaned amber jugs
with Teflon-lined caps for use in sampling the Sioux Falls, S.D. water
treatment plant effluent. Four samples were collected, shipped
to MRC, extracted, concentrated and analyzed as described in
Sections 4, 5 and 6. The samples were taken on August 13 and 14
and September 13 and 15, 1977. The September 15, 1977 sample was
broken in transit. Four liters of each sample were extracted and
neither BCEE nor BCIPE were detected in the remaining 3 samples.
36
-------
TABLE 12. LIST OF PREFERRED SAMPLING SITES BY CATEGORIES
I. B -chloroether producers
Chemical
Company
Plant site
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Buckman Labs., Inc.
Dow Chemical USA
Cadet, Missouri
Memphis, Tennessee
Freeport, Texas
II. B-chloroethers as by-products
Chemical
Chemical produced
Company
Plant site
Bis(2-chloroethyl) Ethylene chlorohydrin
ether
Bis(2-chloroiso-
propyl) ether
Propylene chlorohydrin
Propylene oxide
Propylene glycol
Bis(l-chloromethy, Epichlorohydrin
2-chloroethyl) ether
Union Carbide
Corp.
Eastman Kodak
RSA Corp.
BASF
Wyandotte
Corp.
Dow Chemical
USA
Olin Corp.
Oxirane Corp.
Texaco, Inc.
Dow Chemical
USA
Olin Corp.
Oxirane Corp.
Texaco, Inc.
Union Carbide
Corp.
Dow Chemical
USA
Shell Oil Co.
Institute & S.
Charleston,
W. Virginia
Rochester, N.Y.
Ardsley, N.Y.
Wyandotte, Mich.
Freeport, Texas
p^aquemine, La.
Brandenburg, Ky.
Bayport, Texas
Port Neches, Texas
Plaquemine, La.
Freeport, Texas
Brandenburg, Ky.
Bayport, Texas
Port Neches, Tx.
Institute & S.
Charleston,
W. Virginia
Freeport, Texas
Deer Park, Tx.
Norco, Pa.
III. B-chloroether users
Bis(2-chloroethoxy) Polysulfide polymers
methane
Diamond
Shamrock
The Flame
Master Corp.
Product's Re-
search &
Chem. Corp.
Sybron Corp.
Thiokol Corp.
Ashtabula, Ohio
Sun Valley, Ca.
Gloucester City,
New Jersey
Glendale, Ca.
Romulus, Mich.
Moss Point, Miss.
37
-------
The detection limit for BCEE and BCIPE in the samples was
3 x 10~8 g/1.
After this process a final list of eight plants was chosen by
EPA-OTS. The plants sampled are listed in Table 13. The plant
locations are shown graphically on a map of the United States in
Figure 3. The numbers shown are also the order in which the
plants were sampled.
TABLE 13.
PLANT SITES FOR 3-CHLOROETHER
SAMPLING AND ANALYSIS
Company
Plant Site
Number on
Figure 3
Olin Corporation
Dow Chemical USA
Jefferson Chemical
Dow Chemical USA
Thiokol Corporation
Union Carbide
Corporation
Milliken Chemical ;
Eastman Kodak
Brandenburg, Kentucky
Freeport, Texas
Port Neches, Texas
Plaquemina, Louisiana
Moss Point, Mississippi
Institute, West Virginia
Inman, South Carolina
Rochester, New York
1
2
3
4
5
6
7
8
38
-------
CO
vo
Figure 3. 3-chloroethers sampling sites
-------
SECTION 4
SAMPLING METHODS
Four types of samples, air, water, soil and sediment, were
taken in the vicinity of potential 3-chloroether producing
plants. Samples were collected primarily on public lands;
at no time was plant property trespassed upon. The methods
used for sampling each of the four types of samples are des-
cribed in this section.
4.1 AIR
Ambient air samples were drawn through Pyrex sampling tubes
packed with Tenax-GC and then through a backup charcoal sampling
tube with Bendix Model 115 and 130 samplers. Air flow through
the sampling tubes was 1.0 liter/minute. Air sampling times
were ^8 hours during daylight and ^12 hours at night. The
largest concentration of samplers was placed in an arc in the
predominant downwind direction from the plants. Normally
8 samplers were used during daylight. Six of the samplers were
placed downwind and two were placed upwind from the plant com-
plexes. During the night 2 or 3 samplers were employed with
1 upwind and 1 or 2 downwind from the plant. The air samplers
were mounted on 1.25 cm diameter rods 1.5 m above the ground
level. A typical air sampler mounting arrangement is shown
schematically in Figure 4.
40
-------
Tenax - GC Sampling Tube
Tygon Tubing-
1.5M
-SKC Charcoal Sampling Tube
Tape
Flow Meter
Bendix Model Super Sampler
Steel Rod
il,. ,d ,, , ,i I in
Figure 4. Air sampler arrangement,
41
-------
The sampling tubes which were packed with Tenax-GC are shown
schematically in Figure 5. Approximately 2.5-3.0 grams of
Tenax-GC (60/80 mesh) were packed into the center portion of
the sampling tubes. It was important that the glass wool plugs
be placed in the large diameter portion of the tube so the
air flow would not be restricted. The Tenax-GC tubes were con-
ditioned by heating to 300°C in a flow of oxygen-free nitrogen for
sixteen hours, then sealed with stainless steel Swagelok caps
for shipment to the field.
When sampling was completed, the Tenax-GC tubes were removed
and sealed with either stainless steel Swagelok caps or with
polyethylene caps which slip over the glass ends of the sampling
tube. The tubes were then individually wrapped with paper
towels to protect them against breakage during shipment by
air freight back to the laboratory. Upon arrival at the labora-
tory the tubes were stored in a freezer at -20°C until time for
sample workup.
At each site one unused Tenax-GC sampling tube was doped with
^2 x 10~5 grams of each of the six 3-chloroethers. An addi-
tional unused sampling tube was also retained as a control
for the doped sample. Doped and control tubes were treated
in exactly the same manner as sample tubes during shipment,
storage, workup and analysis.
4.2 WATER
Twenty-four-hour water samples were collected at two points
downstream from the potential 3-chloroether producing plant's
outfall and at one point upstream. The water samples were
taken 1.8 m from the bank of the stream being sampled and
20 cm below the water surface. The sampling system used is
shown schematically in Figure 6. Samples were drawn through
Tygon tubing by a peristaltic pump. The end of the sampling
42
-------
LJ
1/4" s.s. Swagelock Cap
1/4" s.s. Swagelock Nut
1/4" Vespel Ferrule
Glass Wool
4mm I.D. X6mmO. D.
15mm I.D. X17 mmO.D.
* *j. cm *
1cm
10cm-
20cm
-*•*.
1cm
Figure 5. Pyrex sampling tube packed with Tenax-GC,
-------
Tygon Tubing
4 Liter Amber
Glass Bottle
\
Motorcycle
Battery
N
Figure 6. Water sampler arrangement,
-------
tube was held up off the bottom by a cork float and below
the water line by a weight. The peristaltic pump was powered
by a motorcycle battery. Both the battery and pump were housed
in a metal toolbox. The water flowed through the pump into
a 4 liter amber glass bottle at a rate of 166 cm3/hr. The
amber glass bottles used were purchased from Burdick-Jackson,
Muskegon, Michigan and had been cleaned and dried by Burdick-
Jackson. These bottles are the same as those bottles used by
Burdick-Jackson for their distilled-in-glass solvents. The
bottles were supplied with screw caps with Teflon liners.
After sampling, a small amount of sample was removed to allow
for volume expansion and the caps were screwed onto the bottles.
The caps were then sealed with plastic tape to prevent their
working loose during shipment. The bottles containing the
water samples were then wrapped with foam padding and placed
in a large picnic ice chest. Remaining space in the ice chests
was filled with ice and the chests were sealed with tape for ship-
ment back to the laboratory by air freight. Upon arrival at
the laboratory the samples were kept at 4°C until analyzed.
Two additional 1-liter samples were taken at the upstream
sampling point. One sample was doped with ^2 x 10 5g of each
of the 3-chloroethers. The other 1-liter sample was labeled
as a control. These two samples were subjected to the same
packing, shipment, storage, extraction, concentration, and analysis
procedures as were used for the water samples. These doped
samples were to serve as checks for our methods and to indicate
whether any biological degradation was occurring during shipment
and storage before the water samples were extracted.
4.3 SOIL
Soil samples were 'taken at various points around the sites of
the potential &-chloroether producing plants. One soil sample
45
-------
was taken at each air sampling site. Additional soil samples
were taken in the directions of the points of annual wind rose
charts. Where applicable, samples were also taken in areas
of maximum population density surrounding the sites.
Soil samples were collected using tulip bulb planters. The
vegetation in the area was removed and a core ^ 6 cm in
diameter by 7.5 cm in depth taken. The core was then placed
in a wide-mouthed canning jar (^ 500 cm3 capacity). The jar
lid was then replaced and the sealing ring tightened. Sample
numbers were scribed on the lids of the jars. Each jar was
then wrapped with duct tape to insure retention of the sample
even if the glass jar broke during shipment. The jars were
then returned to their original boxes and when the boxes were
filled, they were sealed and air freighted back to the
laboratory.
Two additional soil samples were taken at a point where maximum
deposition of compounds of interest could occur. One sample
was doped with ^2 x 10 5g of each of the B-chloroethers and
the other sample was held as a control. The recovery results
of the doped sample were checked against recovery data for
samples which had been doped in the laboratory.
4. 4 SEDIMENT
Sediment samples were taken at selected downstream locations
at each site. The samples were collected with a collapsible
shovel, approximately 0.5 meter from the bank of the stream.
The samples were transferred from the shovel to canning jars
and treated in the manner described for the soil samples.
46
-------
SECTION 5
SAMPLE WORKUP METHODS
This section describes the procedures used to recover the g-chloro-
ethers from the samples which were collected at the field sites.
5.1 AIR
All but two of the Tenax-GC sampling tubes from each site were solvent
desorbed with methanol. The remaining two samples (normally one from
a potentially high concentration site sampled during the day and one
sample collected at night) were held for complete characterization
via thermal desorption and gas chromatography/mass spectrometry-
The apparatus used for solvent desorption is shown in Figure 7.
Approximately 4 cm3 of methanol was pumped through the Tenax-GC
sampling tube' in the opposite direction of the air flow during
sampling. The methanol was collected in a tared vial and the
vial was reweighed after desorption from each tube. The
vials were capped with Viton septa and held for analysis.
Analysis was performed by gas chromatography/mass spectrometry.
The mass spectrometer was operating in the selected ion mode (SIM).
5.. 2 WATER
One liter from each water sample was extracted three times in
a separatory funnel with 100 cm3 of methylene chloride. The
methylene chloride extracts were combined and evaporated using
a Kuderna-Danish evaporator to a volume of 1-2 cm3. The solu-
47
-------
00
Milton Roy
Mini - Pump
Solvent
Reservoir
•lenaxlube
Vial (5m\)
Figure 7. Solvent desorption apparatus
-------
COMPANY CONFIDENTIAL
tion remaining in the receiver was then transferred to a tared
vial and the Kuderna-Danish apparatus rinsed with small portions
of methylene chloride. These rinses were then transferred to
the vial and a Viton spectum cap replaced on the vial. The
vials were then reweighed. The samples were held for subsequent
GC-MS-SIM analysis.
. \
5.3 SOIL
Five soil samples from each site were selected. Approximately
50 g of each sample was transferred to an extraction cup. The
samples were then extracted in a Soxhlet apparatus for -v 16
hours. Approximately 200 cm3 of methylene chloride was used
for the extractions. After cooling, the methylene chloride ex-
tracts were then transferred to Kuderna-Danish evaporators and
concentrated to -v 1-2 cm3. Again the Kuderna-Danish apparatus
was rinsed and the washings were combined with the concentrated
solution in tared vials. The vials were sealed with Viton
septa and reweighed. The samples were then held for analysis
via GC-MS-SIM.
5.4 SEDIMENT
Sediment samples were treated in exactly the same way as des-
cribed for soil samples except slightly larger samples were
taken because of water content and samples were weighed before
and after extraction.
49
-------
SECTION 6
ANALYTICAL METHODS
This section concerns the methods used to analyze the samples
collected and worked up as described in the two previous sec-
tions. Subsection 6.1'is devoted to the six haloethers of pri-
mary interest. Subsection 6.2 is a description of efforts to
synthesize bis(l-chloromethyl,2-chloroethyl) ether and to
simulate the synthesis of epichlorohydrin. Subsection 6.3
Is a listing of the other compounds related to the haloethers
for which selected samples were examined. Finally, in Sub-
section 6.4, methods are described which were used to perform
complete characterization of at least one water sample and one air
sample from each site.
6.1 SIX B-CHLOROETHERS
Analyses of the samples described in the sampling and workup sec-
tions were performed via gas chromatography/mass spectrometry-
The mass spectrometer was operated in the selected ion mode (SIM)
so maximum sensitivity could be achieved. The six 3-chloroethers
being quantitated in the samples, their abbreviations, and their
characteristic ion pairs are listed in Table 14.
Before the analysis of the samples by SIM, a high concentration
standard was run with the mass spectrometer operating in a
scanning mode. Table 15 lists the instrumental conditions we
used to run $-chloroether standards and samples. The total ion
chromatogram obtained from the scanned run is shown in Figure 8.
50
-------
TABLE 14. B-CHLOROETHERS ANALYZED FOR BY GC/MS/SIM
H
Materials Belong '
OPPT Library
401 M Street, SW
Washington, DC '.
G**' r~\ O
o> ,
w -~)
8 1
J
Compound
2-chloroethylvinyl ether
2-chloroethylethyl ether
bis (2-chloroethyl) ether
bis (2-chloroisopropyl) ether
bis (2-chloroethoxy) methane
bis (2-chloroethoxy) ethane
*Aldrich Chemical Company, 940
Matheson, Coleman & Bell, 2902
Pfaltz & Bauer, 375 Fairfield
Abbrevi-
ation
CEVE
CEEE
BCEE
BCIPE
BCEXM
BCEXE
W. Saint
Highland
Source*
Aldrich
Aldrich
Ma the son,
Coleman & Bell
Aldrich
Pfaltz &
Bauer
Pfaltz &
Bauer
Paul Avenue, Milwaukee
Avenue , Norwood , Ohio
Avenue, Stamford, Connecticut
Cata- Purity
logue NO. %
10,998-3 99
C, 4120-7 96
BX675
S44368-9
B12370
B12450
, Wisconsin 53233
45212
06902
Masses
63,106
59,108
93,63
45,121
93,63
63,93
-------
TABLE IS. GAS CHROMATOGRAPH/MASS SPECTROMETER
CONDITIONS FOR 3-CHLOROETHER ANALYSIS
Instrument: Hewlett-Packard Model 5983 GC/MS/DS
Column: 1.82 m x 0..21 mm (I.D.) glass packed with
Tenax-GC (60/80 mesh)
Injection Port Temperature: 280°C
Transfer Line Temperature: 280°C
Column Temperature Programming: From 140°C to 260°C at
8°C/min. Hold at 260°C for 5 minutes.
Helium Flow Rate: 30/ml/min
Ion Source Temperature: 150°C
52
-------
** SPECTRUM DISPLAY/EDIT **
BCE 250 PPH IN CH3CL3 3UL
EI-GC 140/S/E60 6' TENAX-GC GAIN 4H
FRN 7840
1ST SC/PGt . 1
X- .50 Y- 1.00
Ul
U)
Figure 8. Total ion chromatogram of 3-chloroethers
-------
Each peak is labeled with the abbrevaiation for the compound
or compounds found in the peak. CEVE and CEEE are not separated
when chromatographed on a Tenax-GC column. The mass spectra for
the B-chloroethers are displayed in Figures 9, 10, 11, 12 and
13.
Actual quantitative data were obtained by running the samples
and standards in SIM. Typical SIM chromatograms are shown in
Figures 14 (a) and 14 (b). The mass spectrometer was not turned
on for 1.5 minutes to allow the solvent to clear before re-
cording data. From 1.5 min. to 7,0 min. masses 59, 108, 63
and 106 were monitored in a repetitive sequence for 250 msec.
each. At 7.0 minutes the masses being monitored were switched
to 93, 63, 45 and 121. Again each mass was monitored in a re-
petitive sequence for 250 msec. After completing the run,
the area for each mass was measured as shown in Figure 14.
An average detection limit using the sample collection, extrac-
tion, concentration, and analysis methods was calculated for the
four types of samples. The detection limits were subject to the
variability of the mass spectrometer on a given day, the volume
of sample collected or extracted, and the volume of the concentra-
ted sample. Even when th'ese variables were taken into considera-
tion, the detection limits only varied by a factor of 4. The
average detection limit for the g-chloroethers of the
mass spectrometer operating in the SIM mode was 8.5 x 10"11 g/vil
of sample injected. This detection limit was taken as the
amount of material required to give a peak with an area three
times the area of a blank run over the same time span.
For air samples the average detection limit was 7.0 x 10~7 g/m3
(0.12 ppb) for samples collected during the day and 3.9 x 10"7
g/m3 (0.07 ppb) for samples collected at night. Water samples
had_ an average detection limit of 2' x 10~7 g/liter (0.2 ppb).
Soil and sediment samples had an average detection limit of
4.1 x 10~9 g/g (4 ppb).
54
-------
UT
FRN 7840 SPECTRUM 62 RETENTION TIME 3.2
LARGST 4: 59.1,100.0 63.0, 69.0 108.0, 27.6 65.0, 23.0
LAST 4J 106.9, l.S 108.0, 27.6 109.0, 1.3 110.0, 7.1
PAGE 1 V - 1.00
100.
80.
60.
40.
: m
20.
0
L00.
80.
60.
f 4U
20.
4
e
1.
..H .1. n 1 ..1
20 40 60 80 100 120 140 160
Ififc ' 200 ' 220 ' 240 ' 260 ' 280 ' 300 ' ^PA
Figure 9 . Mass spectra of 2-chloroethyl vinyl ether and 2-chloroethyl
ethyl ether (CEVE and CEEE).
-------
Ul
F
LAF
LAS
80.
60.
40.
20.
0.
100.
80.
60.
40.
20.
0
•RN 7840 SPECTRUM
?GST 4: 92.9,100.0 *
5T 4: 107.9, .5 1J
20 40 60
180 200 220
240
33.0, 46*5
16. 0, .5
,„
80
240
RETENTION TIME 7.9
95.0, 32.1 65.0, 15.5
142.0, .8 144.0, .5
PAGE 1 V - 1*00
\
III III 1 II M Jin
100 120 140 160
260 ' 280 ' 300 ' 32&
Figure 10. Mass spectrum of bis (2-chloroethyl) ether.
-------
FRN 7840 SPECTRUM 875 RETENTION TIME 8*9
LARGST 4: 45.1,130.0 121.0, 70.3 77.0, 52.0 41.1, 35.0
LAST 4: 108.9, 5.0 1S1.0, 70.3 183.0, 3.7 133.0, 30.8
; PAGE 1 Y • 1.00
L00.
80.
60.
40.
30.
4
0
100.
80.
60.
4
40.
30.
«
0
1111 imiim-mmm illlilln lillj ill
:
i^Li — ~i*L^i^: . L_^ 1 1__ Ti.tl_ V J^ i
30 40 60 80 100 130 140 160
180 200 220 240 260 280 30ft 3PA
Figure 11. Mass spectrum of bis(2-chloroisopropyl)ether (BCIPE).
-------
Ul
00
m
F
LAF
LA<
L00.
80.
i
60.
40.
50.
«
0
100.
80.
60.
«
40.
«
80.
0,
•RN 7840 SPECTRUM
?GST 4: 92.9,100.0 £
5T 4: 133.0* .0 1"
•*v
20 40 60
180 200 820
347
33.0, 43*7
11.0, .0
,!„„,„„ „.
80
24d
RETENTION TIME 10.8
94.9, 32.4 65,0, 14.9
171.0, .7 173.1, .5
PAGE 1 V - 1.00
.
i
1 Iliiiuli Illliliii iiimiUii inn HI in
100 120 140 160
-
• .U>|».k ......... ....|.... .;..|U.l »..(.... ...,| ...,
see aaa x 300 ^Pft
Figure 12. Mass spectrum of bis(2-chloroethoxy)methane (BCEXM).
-------
F
LAP
LA£
f00.
80.
40.
20.
0.
L00.
80.
60.
40.
20.
t
0
•RN 7S40 SPECTRUP1
?GST 4; 63.0,100*0 S
>T 4: 134.9, .1 12
- — * •
20 40 60
\
'
1 S3 200 220
407 RETENTION TIME IS* 4
)3.0, 66*6 65.0, 34.0 107.0, 30.0
J7.0, 4*7 138*0, .3 139.0, 1.4
PAGE 1 V - 1.00
f
80 100 120 140 160
•
1 240 ' 260 ' 2S0 ' 300 ' ^Pft
Figure 13. Mass spectrum of bis(2-chloroethoxy)ethane (BCEXE).
-------
** SELECTED ION CHROMATOGRAm **
~ SPPN.-BCE , DOPE , P . L * S ., 7/i 3/77
EI-GC, 140xS..'a60-5, GN10H, 3u 1, 8/5/77, 1615
106*0
63.
L08*
3106.
CEVE
/\r
21225,
5375.
CEEE
- 30884.
FRN 7856
1ST SC/PG: 1
X' 1.00 Y- 1.00
T I
Figure .14 (a). SIM chromatograms for 3-chloroethers (1.5-7.5 min) .
-------
** SELECTED ION CHROMATOGRAfl **
~5PPN/BCE, DOPE, P. L. S. , 7X13/77
EI-GC,140X8X260-5,GN10H,3uI,8x5x77,1615
FRN 7856
1ST SCXPG* 2-42
X" 1*00 Y- 1.00
121.0
45.0
63.
93.
A- 18716.
BCIPE
A- 3764S.
56106*
BCEE'
98868.
41698.
BCEXM
100231.
A- 80346.
10
i
11
i
12
Figure 14 (b). SIM chromatograms for g-chloroethers (7.5-13.5 min).
-------
6.2 BIS(l-CHLOROMETHYL-2-CHLOROETHYL) ETHER
The potential for formation of three di-beta chloro substituted
ethers during the synthesis of epichlorohydrin was suggested
in the review on haloethers by Syracuse University (1). The
epichlorohydrin synthesis is shown in this equation:
NaOH
H2C=CHCH2C1 + HOC1 -»• ClCH2CHCH2OH + ClCH2CHCH2Cl >• H2C-CHCH2Cl (.18)
Cl OH O
The ethers that could be formed are similar to the propylene
chlorohydrin ethers, except they contain two extra chlorine
atoms (Figure 15). Since the bis(l-chloromethyl-2-chloroethyl)
ether and the other two ethers could be present in some of the
samples taken during this contract and since these ethers are not
commercially available, EPA-OTS suggested that MRC attempt to
synthesize the bis(l-chlormethyl-2-chloroethyl) ether. In addi-
tion we were requested to simulate in the laboratory the synthe-
sis of epichlorohydrin. The synthesis method used for bis-
(l-chloromethyl-2-chloroethyl) of epichlorohydrin ether and epi-
chlorohydrin are described in sections 6.2.1 and 6.2.2. The
_»
synthesis experiments were performed by Dr. A. Y. Gardner of MRC.
CH2C1
CJCH2CHOCHCH2C1 C1CH2CHCH2OCHCH2C1
Cl CH2C1
) VrJL.lVxXiO KS\.*i
CH2C1
bis(l-chloromethyl-2- l-chloromethyl-2-chloro-
chloroethyl) ether ethyl-2',3'-dichloropropyl
(major isomer) ether
CICHo CHCH,OCH2 CHCH2C1
*1 I
Cl Cl
bis(2,3-dichloropropyl)
ether
Figure 15. Potential chloroethers from epichlorohydrin
manufacture.
62
-------
Initial inspection of the reaction mixture from the bis(1-chloro-
methyl-2-chloroethyl) ether synthesis number 5 (Section 6.2.1.5)
by GC/MS indicated the major products were not the desired com-
pound. GC/MS of step 1 of the crude reaction mixture from the
epichlorohydrin synthesis (Section 6.2.2) indicated the presence
of two major compounds with high boiling points. GC/MS of
step 2 of the same synthesis showed the same two compounds.
Neither of the mass spectra was identifiable by either manual or
computer search routines. The earlier eluting of the two peaks
gives a mass spectrum which is similar in some of its fragmenta-
tion patterns to the mass spectrum of bis(2-chloroallyl) ether.
This mass spectrum, which to date defies interpretation, is shown
for future reference in Figure 16. The spectrum of the later elu-
ting compound is shown in Figure 17. It is possible through
examination of fragmentation patterns, including chlorine isotope
clusters, to assign the mass spectrum of this peak as either
bis(l-chloromethyl,2-chloroethyl) ether or this compound plus the
other two isomers shown in Figure 15. The mass fragment assign-
ments for this mass spectrum are illustrated in Figure 18.
Because of the limited amount of effort devoted to this study,
no further purification or characterization of this compound was
attempted. Water and air characterization samples from Freeport,
Texas were, however, carefully examined for the presence of mass
spectra matching Figure 17. No evidence of the presence of
this spectrum was found in the GC/MS run of either sample.
6.2.1 Attempted Synthesis of bis(l-chloromethyl,2-chloroethyl)
ether
Five experiments were performed in attempts to synthesize bis(l-
chloromethyl-2-chloroethyl) ether. Each of the experimental
procedures and results are briefly described in the following
subsections.
63
-------
UORK AREA SPECTRUH FRN 7866 PAGE 1 V • 1.00
LARGST 4: 75.8,100.0 74.9, 92.1 114.8, 76.3 100.8, 69.3
LAST 4: 296.9, .0 297.4, .0 298.5, .0 299.1, .0
-75 + 80
100.
80.
60.
20.
0
100.
80.
60.
40.
20.
0
* V
Jim iiiuilli Hi ilni in III .'..Jill (Lull
20 40 60
Ifrtri
80 ' 100 ' 120 ' 140 ' 160
120 200 220 240 260 2S0 30 « *3Pft
Figure 16. Mass spectrum of earlier eluting compound in epichlorohydrin synthesis mixture,
-------
en
FRN 7S66
SPECTRUn 102 RETENTION TIME 5.5
LARGST 4: 74.
LAST 4: 241.
100.
80.
60.
40.
20.
0
100.
80.
*
60,
40.
80.
0
.
1 20
120
1
1
1
8,100.0 78.8, 47.6 76.8, 38.9 48.8, 33.6
8,
.0 868.5, .0 870.1, .0 280.5, .0
40
'!"" "
10
PAGE 1 V - 1.00
:
I.
60 80 100 180 140 160
...
»
-
220 240 260 280 300 3P^
Figure 17. Mass spectrum of later eluting compound in epichlorohydrin
synthesis mixture [bis(l-chloromethyl-2-chloroethyl)ether?]
-------
CH2C1
m/e=49
CH2C1 CHoCl
\ X
^£H - o - CH
CH2C1 CH2C1
mw=238
CH2C1
ci e
CH=CH
m/e=62
CH2
m/e=75
CH2C1
CH - OH
m/e=7
CHoCl CH2C1 ^ CH2C1 CH2
Vr \ ® v^ /
8 .CH CH - O - CH2 CH - O - C ®
.CH - 0 - CH
CH2C1 CH2C1
m/e=189
CH2C1 CH2C1 CH2C1
m/e=lll . m/e=141 m/e=153
Figure 18. Possible interpretation of mass fragments for
BCMCEE (Figure 7).
66
-------
6.2.1.1 Experiment 1—
OH
2 C1CH2CHCH2C1 + S02C1 »» [ (C1CH2) 2CH] 2O
Heating a mixture of 2 volumes of l/3-dichloro-2-propanol and
1 volume of sulfuryl chloride overnight gave hydrogen chloride
and a black tar.
6.2.1.2 Experiment 2—
OH Cl
C1CH2CHCH2C1 + C1CH2CHCH2C1 —-—>• [(ClCH2)2CH]2O
Heating equal volumes of 1,3-dichloro-2-propanol and 1,2,3-tri-
chloropropane in a steam bath for 3 hours gave no hydrogen
chloride. No change was discerned in the infrared spectrum of
the mixture. Addition of triethylamine and warming gave rise
to olefin absorption in the infrared but no indication of ether
formation.
6.2.1.3 Experiment 3—
?H f1 Na2C03
C1CH2CHCH2C1 + C1CH2CHCH2C1 —^ *- [(C1CH2)2CH]20
Equal volumes of 1,3-dichloro-2-propanol and 1,2,3-trichloropropane
were stirred and heated to 115°C in the presence of anhydrous
Na2CO3 for 3 hours with no reaction. The reaction mixture was
then heated to 135°C for 19 hours. No reaction was detectable by
infrared.
6.2.1.4 Experiment 4—
The addition of pyridine to a reaction mixture of the alcohol
and trichlopropane and heating to 125°C gave a black, tarry
material whose infr.ared spectrum showed olefin and carbonyl
absorptions.
67
-------
OH - OH 0
I V^3 ^f^ I II
C1CH2CHCH2C1 °^S > C1CH2C=CH2 ^ClCH2CCH3
6.2.1.5 Experiment 5—
OH
2 C1CH2CHCH2C1 P-toluenesulfonyl chloride, t(C1CH2)2cH]2O
toluene
Heating of 5 g of the alcohol with 0.5 g of p-toluenesulfonyl
chloride in toluene at reflux overnight gave a mixture of
alcohol and ether according to the infrared spectrum. A scale-
up of the reaction to 43 g (0.33 moles) of alcohol gave one
cm3 of water in the attached Dean-Starke trap and water in the
condenser. The solvent was changed to xylene and heating was
continued under argon for 70 hours. The resultant tarry oil
showed hydroxyl, ether and a trace of carbonyl absorption in its
infrared spectrum.
6.2.2 Simulated Epichlorohydrin Synthesis
The synthesis shown in Section 6.2 was used to simulate the pro-
duction of epichlbrohydrin. The following conditions were em-
ployed for the synthesis. Chlorine gas [35.5 g (0.5 mole)] was
bubbled slowly into a stirred mixture of 38.3 g
(0.5 mole) of allyl chloride and 41 g of H2O in a 250 cm3 round-
bottom, three-necked flask. The reaction of C12 and H2O results
in the in situ generation of HOC1. HOC1 then reacts with allyl
chloride to form the chlorohydrin intermediates. The flask
was equipped with a condenser and a bubbler atop the condenser
to monitor the gas flow. The temperature rose to 73°C during
this addition. A sample of this reaction mixture was analyzed
by gas chromatography/mass spectrometry. The top aqueous phase
of the reaction mixture was removed and a solution of 20 g
68
-------
(0.5 moles) of NaOH in water was added to the cloudy oil that
remained. The mixture turned yellow. This mixture was heated
to 83-88°C for 2 hours. A sample of the cooled reaction mixture
was analyzed by gas chromatography/mass spectrometry (see
Section 6.2.1).
6.3 OTHER COMPOUNDS
At the request of EPA-OTS, a series of six compounds which could
be formed along with the B-chloroethers were analyzed for in
selected samples. The compounds are listed in Table 16 along
with their boiling points and their three most intense mass
spectral ions. The intensities of the mass ion are shown in
parentheses. Each of the water and air characterization
samples described in Section 6.4 were examined for these com-
pounds. None of the six compounds were found in the air or
water samples from the eight sites sampled.
TABLE 16. COMPOUNDS RELATED TO g-CHLOROETHERS
Compound raw
2-chloroethanol 80
1,3-dichloroacetone 126
l,3-dichloro-2-propanol 128
2 , 3-dichloro-2-propanol 128
chloroacetic acid 94
3rchloro-lf2-dihydroxy- 110
propane
Boiling
Point, °C
129
173
174
182
189
213
1
m/e
31(100)
77(100)
79(100)
62(100)
50(100)
44(100)
2
m/e
27(8)
49(67)
43(33)
64(55)
45(71)
61(94)
3
m/e
43(7)
79(32)
81(32)
31(26)
41(64)
43(89)
69
-------
6.4 CHARACTERIZATION. .QF. AIR AND WATER SAMPLES
A complete characterization of one air sample and one water
sample from each of the last seven sites was performed by gas
chromatography/mass spectrometry. Either an outfall or the
#1 downstream water sample was reduced from the volume (2.5-
3.5 cm3) at which SIM analysis was performed to approximately
0.1 cm3. 3 yl of this solution was then injected onto a
1.8 m x 2.1 mm glass column packed with 1% SP2250 on Supelcoport
(100/120 mesh). The outlet of the column was connected to a
Hewlett-Packard'5983 GC/MS. The column was programmed from
50°C to 260°C at 8°C/min. The mass spectrometer was scanned
from 35 to 350 amu with a scan time of ^ 4 sec. The sum of
the ion responses during each scan were recorded as the total
ion chromatogram. The mass spectra of peaks in the chromatogram
were then examined. The mass spectra are then matched either
manually or by computer matching programs.
The air samples were chosen from a point that should have a
high concentration of materials being emitted from the plant.
The Tenax GC tube; was thermally desorbed using the apparatus
shown in Figure 19. Helium was passed through the tube, which
was heated in a modified tube furnace, in the opposite direction
to the direction air was drawn through the tube during sampling.
The components when desorbed were concentrated at the head of a
1.8 m x 2.1 mm glass column packed with Tenax GC (60/80 mesh)
held at -30°C. The desorption temperature was 250°C. The
tubes were desorbed for 5 minutes and then the chromatographic
column was programmed at 30°C/min for 2.67 min then at 10°C/min
to 230°C. The mass spectra were recorded under the mass spectral
conditions listed for the water samples. The mass spectra of
the peaks were again matched to listed mass spectra. (Results
for each of the water and air sample characterizations are
listed in Sections 8-15).
70
-------
PORAPAK - N
COLLECTOR TUBE
CERAMIC
CYLINDER
HEATING TAPE
INSULATION
'f
^
_l
T
INJECTION PORT "B"
INJECTION PORT "A"
Figure 19. Thermal desorption apparatus
71
-------
SECTION 7
RECOVERY STUDIES
The efficiency of the methods described in Sections 5 and 6 for
recovery^of six1e-chloroethers from air, water and soil samples
was determined under laboratory and field conditions. The
procedures and results of these studies are described in the
following subsections.
7.1 LABORATORY RECOVERY STUDIES
Recovery studies were conducted in the laboratory using
3-chloroether standards. These tests were performed
to determine the relative efficiency of the methods which
were to be used for field samples. Matrices similar to those
for field samples; of air, water and soil were spiked with
known amounts of B-chloroethers. These spiked samples were
then subjected to the methods which were used for field
samples.
7.1.1 Air
A number of tests were conducted using Tenax tubes spiked
with p-chloroethers. First, 100 yl of a 3-chloroether standard
containing -^2.5 x 10 4 g/cm3 of each of the ethers was injected
onto the end of a Tenax-GC tube. The tube was then solvent
desorbed with methanol using the desorption apparatus shown
in Figure 7 at a rate of 0.5 cm3/min. One-milliliter fractions
were collected. The fractions were then analyzed on a Tenax-GC
column using a flame ionization detector. Results are listed
72
-------
in Table 17. These results show the applicability of the solvent
desorption method for recovery of 3-chloroethers. Then to test
the best method for conditioning the Tenax-GC tubes, two tubes
were spiked with 100 yl of methylene chloride containing
•v2.5 x 10"^ g/cm3 of each of the 3-chloroethers. Tube A was
conditioned by rinsing with 100 ml of methanol and then heating to
100°C for one hour under a flow of nitrogen. Tube B was conditioned
for 16 hours at 300°C with a flow of nitrogen. After spiking/ both
tubes were subjected to an air flow rate of 1 liter/minute for
4 hours. Charcoal tubes were placed in front and behind the
tubes. The charcoal in front was to remove materials from the
laboratory air. The tube in back was to catch any 3-chloro-
ethers passing through the Tenax-GC. Results for these tubes,
again in 1 cm3 increments, are listed in Table 18. Since the
results were very similar, the consistency of the thermally con-
ditioned tube resulted in this b,eing the method of choice for
conditioning. Two other tubes were spiked with 100 yl and
200 yl respectively of the -v>2.5 x 10~k g/cm3 of each 3-chloro-
ether standard solution. Air was then drawn through these tubes
for 6 hours at 1 liter/minute. The total percentage recovery
for each tube is shown in Table 19. Again, the tubes showed a
similar distribution percentage as was seen for the thermally
conditioned tube described in Table 18 for the 1 cm3 increments.
The results for the 100 yl standard may have included contami-
nants from lab air since a charcoal tube was not used in front
of this Tenax-GC tube. Average recovery for the tube B described
in Table 18 and the two tubes in Table 16 were CEVE/CEEE-90%, BCEE-
97% (excluding the 158% value), BCIPE-96%, BCEXM-97%, and BCEXE-
85%. These data show that the efficiency of the desorption
technique is more than adequate for this study- A final experi-
ment was performed to determine whether the volume of methanol
could be reduced from 4 ml to 0.4 ml after desorption using a
micro-Snyder column. The percentage recoveries were
73
-------
TABLE 17. RECOVERY OF 3-CHLOROETHERS FROM TENAX-GC.
100 ul OF ^2.5 x lO"4 g/cm3OF EACH
&-CHLOROETHER ADDED
•" *
cm3
0-1
1-2
2-3
3-4
Total
% Recovery
CEVE/CEEE
68
14
82
BCEE
75
18
93
BCIPE
67
16
83
BCEXM
71
11
82
BCEXE
67
15
82
-------
TABLE 18. RECOVERY OF B-CHLOROETHERS FROM TENAX-GC -
EFFECTS OF CONDITIONING
Tube A - Solvent Conditioned
cm3
0-1
1-2
2-3
3-4
Total
Tube B - Thermally
cm3
0-1
1-2
2-3
3-4
Total
CEVE/CEEE
24
26
15
5
69
Conditioned
CEVE/CEEE
48
25
8
3
85
BCEE
51
35
15
-
101
BCEE
71
18
-
-
89
BCIPE
43
27
12
-
82
BCIPE
64
20
84
BCEXM
40
44
14
-
98
BCEXM
66
26
92
BCEXE
35
32
13
-
80
BCEXE
54
16
70
-------
TABLE 19. RECOVERY OF 3-CHLOROEHERS FROM TENAX-GC -
EFFECTS OF AIR PULLED THROUGH TUBES FOR 6 HOURS
% Recovery
100
200
ul of
yl of
2.
2.
5
5
x 10~u
x 10"4
g/cm3
g/cm3
std.
std.
CEVE/CEEE
87
98
BCEE
158
106
BCIPE
112
91
BCEXM
105
94
BCEXE
97
88
-------
CEVE/CEEE-9%, BCEE-49%, BCIPE-44%, BCEXM-43% and BCEXE-38%.
These results indicated that it would be best not to use the
micro-Snyder system without further study.
7.1.2 --Water
A series of 1 liter samples of deionized water were spiked
with 50, 100 and 200 yl of a standard containing 2.5 x lO
of each of the B-chloroethers. These solutions were then
extracted three times with 100 ml portions of methylene chloride.
The methylene chloride extracts were combined and evaporated
to a volume of ^2 cm3 in a Kuderna-Danish evaporator. The con-
centrates -and rinses were transferred to a septum caped vial
and analyzed on a Tenax-GC column with a flame ionization detector,
The results of these recovery studies are listed in Table 20.
The upper half of the table lists the percent recovery for each
of the spiked samples and the average recovery for the four
samples. These recovery data indicate the extraction and
concentration techniques are more than adequate for this study.
The lower half of the table lists the resultant concentration
of each 3-chloroether in the water after spiking. Earlier
experiments with reducing the volume of the concentrates to
^0.4 cm3 with the micro-Snyder column had shown ^40-50% recovery
of the spiked samples.
7.1.3 Soil
A series of 50 g. samples of soil were Soxhlet extracted twice
for 16 hours with methylene chloride. These soil samples were
then spiked with 25, 50, 100 and 200 yl of a standard containing
^2.5 x lO"4 g/cm3 of each of the 3-chloroethers. The spiked
samples were then re-extracted for 16 hours with methylene
chloride in a Soxhlet extractor. The extracts were combined
and concentrated to ^2 cm3 in a Kuderna-Danish evaporator. The
concentrate and rinses were combined and analyzed on a Tenax-GC
77
-------
TABLE 20. RECOVERY OF 3-CHLOROETHERS FROM WATER
oo
* «f
% Recovery
CEVE/CEEE
50
100
100
200
yl
pi
yl
yl
Average
34.
76.
72.
81.
66.
8
9
0
2
2
CEVE/CE'EE
50
100
200
yl
yl
yl
21...
42.
84.
2
4
8
BCEE
75
91
90
100
89
.0
.0
.7
.3
.3
"BCEE
12
25
50
.7
.4
.8
BCIPE
71
87
89
97
.7
.6
.7
.7
86.7
mi c roar am/ 1
BCIPE
11
23
46
.5
.0
.0
BCEXM
72.
87.
89.
99.
87.
4
5
9
8
4
BCEXM
12
25
50
.5
.0
.0
BCEXE
70.
91.
92.
105.
89.
3
8
0
0
8
BCEXE
12.
25.
51.
8
6
2
-------
column with a flame ionization detector. The results of these
recovery studies are listed in Table 21. The upper half of the
table is the percent recovery for each compound for a given
spike and the lower half is the resultant concentration of each
3-chloroether in the soil after spiking. The average for the
five samples is included at the end of the upper half of the
table. These average recovery data indicate that while recovery
is not optimum it is sufficient for this study. The value of
177.9% for the BCEE 50 yl spike is excluded from the average
calculation. This value is assumed to be due to an interfering
compound which elutes at a retention time similar to the re-
tention time of BCEE. Since a flame ionization detector was
used for this study, specific detection was not possible.
7.2 FIELD RECOVERY STUDIES
Studies were conducted to determine the effects of transportation
and storage as well as the extraction, concentration and analysis
steps on samples taken in the field.
7.2.1 Air
A blank Tenax tube was spiked with a mixture of the six
3-chloroethers in methanol at each of four field sites. The
Swagelok cap was removed from one end of the tube and 100 yl of
the mixture containing ^2.5 x 10"^ g/cm3 of each of the 3-chloro-
ethers was injected onto the Tenax resin. The tube was then
recapped and treated in the same manner as sample tubes with
regard to shipment and storage. Each tube was then solvent
desorbed with 4 ml at the same time that tubes from that site
were desorbed. The desorption was performed using the apparatus
shown in Figure 7. Methanol was collected in 5 cm3 capacity
vials with screw caps. The center of the screw caps was open
and closure was achieved with a Viton spetrum. The solutions
from this spiked tube were then analyzed by GC/MS/SIM at the
79
-------
TABLE 21. RECOVERY OF 3-CHOROETHERS FROM SOIL
oo
o
% Recovery
yl added
25
50
100
100
200
Average
CEVE/CEEE
-
31
25
30
25.4
27.9
BCEE
58.4
179.9
56.1
50.8
53.0
54.6
BCIPE
87.9
96.6
59.9
53.3
55.5
70.6
BCEXM
57.7
64.8
59.4
53.1
51.1
57.2
BCEXE
76.2
77.6
70.9
65.7
59.5
70.0
ug/gram of soil
yl added
25
50
100
200
CEVE/CEEE
0.212
0.414
0.828
1.656
BCEE
0.127
0.254
0.508
1.016
BCIPE
0.115
0.230
0.460
0.920
BCEXM
0.125
0.250
0.500
1.000
BCEXE
0.128
0.256
0.512
1.024
-------
same time as the samples from each site were analyzed. The
results for each of the B-chloroethers from the four sites and
the average for the four are shown in Table 22. The average
recovery for the four field samples was 74.8% as compared with
93% for the laboratory studies. These results indicate an
average loss of 18.2% during transport and storage of the air
samples.
7.2.2 Water
Two extra water samples (approximately 1 liter volume) were
collected at six of the sampling sites at the upstream water
sample location. One sample from each site was spiked with the
mixture of B-chloroethers. The other sample was used as a con-
trol. The concentration of each of the B-chloroethers in the
spiking solution was ^2.5 x ID"1* g/cm3. 100 yl of the spiking
solution was added in the field immediately after sampling to
each of the six water samples. These water samples were then
transported, extracted, concentrated and analyzed along with the
water samples from each site. The samples were in transit and
storage approximately 7 to 10 days before extraction and con-
centration. The samples were extracted three times with 100 ml
portions of methylene chloride. The combined methylene chloride
extracts were then concentrated to a volume of ^2 cm3 in a Kuderna-
Danish evaporator. The concentrates and rinses were transferred
to a septum capped vial and analyzed by GC/MS/SIM. Results for
the field spiked water samples are shown in Table 23. The average
percent recovery for the six B-chloroethers from field doped
samples was 77.3% compared with 83.9% recovery for the laboratory
studies. This 6.6% decrease in recovery reflects the losses due
to transportation, storage, and biological action of the water
samples.
81
-------
TABLE 22.. FIELD RECOVERY STUDIES - AIR
00
Freeport, TX
Compound
CEEE
CEVE
BCEE
BCIPE
BCEXM
BCEXE
Spike,
vg
20.6
21.9
25.4
22.9
25.0
25.5
Amount
measured,
vg
24.4
11.4
18.2
18.6
14.8
15.4
Percent
recovered
118.5
52.2
71.8
81.1
59.3
60.6
Port Neches, TX
Amount
measured.
vg
18.6
7.1
11.8
14.2
7.1
6.1
Percent
recovered
90.4
32.4
46.6
61.9
28.4
24.0
Plaquemine, LA
Amount
measured,
vg
17.3
16.2
23.3
23.2
23.4
29.2
Percent
recovered
83.8
73.9
92.1
101.0
93.3
114.6
Hoss Point, MS
Amount
measured,
vg
15.9
13.9
21.1
21.6
22.4
26.1
Percent
recovered
77.1
63.5
82.9
94.4
89.6
102.2
Average
Amount
measured,
* vg
19.0
12.2
18.6
19.4
16.9
19.2
Percent
recovered
92.5
55.5
73.2
84.7
67.7
75.3
-------
TABLE 23. FIELD BECOVERY STUDIES - WATER
00
Percent recovered
Compound
CEEE
CEVE
BCEE
BCIPE
BCEXM
BXEXE
Spike, ug
20.6
21.9
25.4
22.9
25.0
25.5
Freeport, TX
113.1
92.7
118.5
116.6
113.2
117.3
Fort Neches, TX
86.9
50.2
78.0
113.1
79.3
98.8
Plaquemine, LA
86.7
61.5
76.4
50.3
77.0
91.1
Moss Point, MS
77.0
48.7
72.3
100.3
72.7
86.3
Institute, WV
42.2
50.7
64.6
61.1
66.4
73.7
Rochester, NY
29.6
41.5
70.1
67.6
69.6
68.6
Average
72.6
. 57.6
80.0
84.8
79.7
89.3
-------
7.2.3 Soil
One soil sample taken at Freeport, Texas was spiked in the field
with 100 yl of the 3-chloroether mixture. The concentration of
the six 3-chloroethers in the spiking solution was -^2.5 x 10"4-,
gm/cm3. The sample was then sealed, in the canning jar and transported
back to Dayton. The entire soil sample (^365 g) was then ex-
tracted in a large Soxhlet extractor. The methylene chloride
solution used for the extraction was concentrated in a Kuderna-
\
Danish evaporator to a volume of ~ 2 cm3. This concentrate and
rinses were then transferred to a septum capped vial and
analyzed by GC/MS/SIM. The recoveries for this sample were CEE -
34%, CEVE - 0%, BCEE - 46.5%, BCIPE - 0%, BCEXM - 36.8% and
BCEXE - 41.6%. The nonrecovery of CEVE is not surprising in
view of the hydrolytic instability of the compound particularly
toward acid conditions; however, the reason for the nonrecovery
of BCIPE from this sample is unknown.
7.3 ASSESSMENT OF ERKOR
7.3.1 Sample Collection
»
>
Two sources of error in the collection of air samples are:
(1) the collection efficiency of the Tenax-GC tubes and (2) the
error in measuring the volume of air passed through the tube.
The collection efficiency of Tenax-GC for BCEE has been reported
to be virtually 100%' (59). The error associated with the
measurement of the total volume of air passing through the
Tenax tube is estimated to be ±10%.
For water samples, the source of error in sample collection is
the measurement of the volume of water taken for extraction.
This error is estimated to be ±2.0%.
84
-------
7.3.2 Sample Workup and Analysis
7.3.2.1 Air—
An estimate of the combined error associated with the workup
and analysis of air samples may be determined from the data
concerning the recovery of field-spiked samples. These data
were discussed in detail in Section 7.2.1. Table 24 lists the
average percent recovered for the six 3-chloroethers, the
standard deviation for spiked samples from four sites, and the
percent relative standard deviation (RSD) for each compound.
The average percent RSD for the six compounds was ±33.1% and
represents the average error for sample workup and analysis of
air samples. This potential deviation includes errors associ-
ated with measurement of volume of dopant solution added to the
tubes, solvent desorption, GC/MS analysis, final volume
measurement and volumetric, dilution, and pipetting errors.
7.3.2.2 Water—
In a manner similar to that just described for air samples, the
data related to the recovery of spiked field water samples can
be used to calculate an estimate of error occuring during j
sample workup and analysis of water samples for B-chloroethers.
The recovery of field-spiked water samples and results are
described in Section 7.2.2 Table 25 lists the average percent
recovery for the six 3-chloroethers from spiked water samples,
and standard deviation and percent RSD for each compound. The
average percent RSD for the six compounds was ±29%. This
value represents an estimate of the average error possible
during sample workup and analysis of water samples. Contributing
sources of error for the 3-chloroether water samples include
the reproducibility of extraction Kuderna-Danish evaporation,
GC/MS analysis, addition of doping solution and in determina-
tion of the final sample volume. Also included are the effects
t -\
of biological and chemical action on the 3-chloroethers in the
water samples during transport and storage.
85
-------
TABLE 24.
ASSESSMENT OF ERROR IN B-CHLOROETHER
AIR SAMPLE WORKUP AND ANALYSIS.
3-Chloroether
CEEE
CEVE
BCEE
BCIPE
BCEXM
BCEXE
Average Recover ed,%
92.5
55.5
73.2
84.7
67.7
75.3
Standard
Deviation
18.2
17.8
19.7
17.2
30.3
41.3
Average RSD =
RSDf%
19.7
32.1
26.9
20.3
44.8
54.8
±33.1
TABLE
25. ASSESSMENT OF ERROR IN
V&TER SAMPLE WORKUP AND
B -CHLOROETHER
ANALYSIS.
3 -Chloroether
CEEE
CEVE
BCEE
BCIPE
BCEXM
BCEXE
.»
"Average Recovered, %
72.6
57.6
80.0
84.8
79.7
89.3
Standard
Deviation
31.1
18.4
19.5
28.6
17.1
17.7
RSD,%
42.8
31.9
24.4
33.7
21.5
19.8
Average RSD = ±29.0
86
-------
7.3.2.3 Soil and Sediment—
An estimate of error associated with sample workup of soil and
sediment 3-chloroether samples can be determined from the average
percent RSD for doped laboratory soil samples. The data listed
in Table 26 were compiled from Section 7.1.2. The table includes
the average percent recovered for each of the six 3-chloroethers,
and standard deviation and percent RSD for each ether. The
average percent RSD for the six compounds is ±12.7%.
Since these data were generated with a flame ionization detector,
an estimate of error associated with GC/MS analysis was needed.
This estimate can be made from data rela.ted to the reproducibility
of standard injections. These data are shown in Table 27. The
average percent RSD for the six 3-chloroethers is ±8.3%. Errors
contributing to the estimated errors for 3-chloroether soil and
sediment sample workup and analysis are related to the repro-
ducibility of Soxhlet extraction, Kuderna-Danish evaporation,
and GC/MS analysis. Also, errors in final volume measurement
and addition of standard to the soil contribute to the overall
error.
7.3.3 Total Error
An estimate of the total error can be obtained by summing the
squares of the individual sources of error and the extracting
the square root of this sum. Implicit in this estimation is
the assumption that the individual sources of error are inde-
pendent. The total estimated error for air, water, and soil/
sediment samples is listed in Table 28.
87
-------
TABLE 26. ASSESSMENT OF ERROR IN 6-CHLOROETHER
SOIL AND SEDIMENT WORKUP.
6 -Chloroe ther
CEEE/CEVE
BCEE
BCIPE
BCEXM
BCEXE
Average
Recovered , %
27.9
54.6 4
70.6
57.2
70.0
Standard
Deviation
2.7
2.9
20.1
5.4
7.5
Average
:..RSD,%
9.7
5.3
28.5
9.4
10.7
RSD = ±12.7
TABLE 27. REPODUCIBILITY OF GC/MS ANALYSIS FOR
B-CHLOROETHERS. REPLICATE INJECTIONS
OF A STANDARD B-CHLOROETHER MIX ON
JULY 26, 1977.
Inj.
1
2
3
4
Mean
S.D.
%RSD
CEEE CEVE
Area Area
152659 79072
141018 73969
116401 63463
147918 74276
139499 • 72695
16123 6583
11.6 9.1
BCEE
Area
368941
345212
325876
364755
351196
19796
5.6
BCIPE
Area
288120
266176
237612
284882
269198
23172
8.6
BCEXM
Area
362343
348405
325447
362097
349573
17353
5.0
BCEXE
Area
296448
258510
236424
283743
268781
26719
9.9
Average RSD = ±8.3%
TABLE 28.
Sample Matrix
Air
Water
Soil/Sediment
TOTAL
ESTIMATED
ERROR
Total Error, %
±34.6
±29.0
±15.2
88
-------
SECTION 8
SAMPLING AND ANALYSIS FOR 3-CHLOROETHERS AT
OLIN CORPORATION, BRANDENBURG, KENTUCKY
8.1 PRESAMPLING SURVEY
8.1.1 Description of the Plant Site
Olin Corporation is located on Doe Run Road east of Brandenburg,
Kentucky. The mailing address of the plant is Box 547, Branden-
burg, Kentucky, 40108. The plant produces a variety of indus-
trial organic chemicals. Among the chemicals reported to be
produced at this plant are ethylene oxide and propylene oxide.
Production capacity for propylene oxide which is produced via
the chlorohydrin route is 6.0 x 107 kg/yr. Production capacity
for ethylene oxide production which is reported to be produced
via direct oxidation is 5.1 x 107 kg/yr. A by-product of pro-
pylene oxide production by the chlorohydrin route is bis(2-
chloroisopropyl) ether.
A presurvey of the plant area was performed on 30 April 1977.
The presurvey consisted of visual inspection of the Olin complex,
since contact with plant personnel was not allowed, and selection
of sites for air and water sampling.
The Olin complex site consists of a large number of buildings
including a power plant, open construction facilities, distilla-
tion and cooling towers, storage tanks for liquids and gases and
settling ponds. The wastewater from the plant enters Doe Run and
after traveling a short distance (^ 1 km) enters the Ohio River.
89
-------
The location of the plant is shown on the topographical map of
the area in Figure 20. The plant encompasses an area of 1 km
east to west along Doe Run Road on the S&uth bank of the Ohio
River and 0.8 km north to south from the Ohio River to Doe Run
Road. The overall distance east to west of property owned by
Olin is *\» 3.6 km. A panoramic photograph of the plant taken from
the north bank of the Ohio River is shown in Figure 21. The
plant is bounded on the north by the Ohio River, to the east by
Doe Run Creek, to the south by Doe Run Road and a series of foot-
hills and to the west by the small town of Brandenburg, Ky.
Brandenburg is 4.2 km west of the plant.
8.1.2 Surrounding Area
*
The Brandenburg area is located in northwest Kentucky about 80 km
west of Louisville. The plant site is located in Meade County,
Kentucky. Elevation of the area ranges from 114 m at the Ohio
River to 204 m at the tops of some of the foothills. The plant
site is situated on a flat plain of the Ohio River. Branden-
burg is the only concentration of population in the area of the
plant. The population of Brandenburg, Ky. is 1637.
_»
»
No other industry is located in the area of the Olin plant.
Vegetation in the area consists of a variety of types of deci-
duous trees. The only visible emissions from the plant during
presurvey and sampling were steam vents and the power plant.
No odor was detected in the vicinity of the plant.
8.2 SAMPLING AND ANALYSIS RESULTS
Sampling of the area around Olin Corporation, Brandenburg,
Kentucky for 3-chloroethers was conducted on 30 March - 1
April 1977. The conditions, locations and results for air,
water and soil samples' collected during this sampling trip are
discussed in the following subsections.
90
-------
Figure 20.
Approximate plant boundaries at Olin Corporation,
Brandenburg, Kentucky.
-------
VO
to
Figure 21. Composite panoramic photograph of Olin Corporation, Brandenburg, Kentucky,
-------
8.2.1 Air Samples
Air sampling around Olin, Brandenburg, Ky. was conducted in two.
ways. A sampling array was set up as shown in Figure 22. A
series of perimeter samples was also collected. The locations
of the array samples are shown on the topographical map of the
area in Figure 23. The location of the perimeter samples on the
same map is shown in Figure 24. The sample numbers, location,
compass reading relative to the center of the plant, sampling
start, stop times, duration and volume are shown in Table 29.
Wind speed and direction data are recorded in Table 30. The
sampling was accomplished with stainless tables 20 cm long x 0.45 cm
inside diameter packed with Tenax GC. The sampling was performed
with rotary vane pumps of the type used for EPA method 5 stack
sampling. This pump required propane-fueled electrical generators.
Because of the large pressure drop through these 0.45 cm inside
diameter tubes, even with these large pumps, a sufficient flow
rate was not achieved.
The tubes were analyzed by methanol desorption (1 cm3) followed
by GC/MS/SIM on a HP5982 GC/MS. None of the six B-chloroethers
of interest were found in the samples. Average detection limit
for the array samples was 9.3 x 10"6 g/m3 and average detection
limit for the perimeter samples was 6.3 x 10~6 g/m3. These re-
sults led to the improvements in the sampling and analysis methods
described in Section 4 and 6 of the report.
8.2.2 Water Samples
An upstream, an outfall and two downstream water samples were
collected during 30-31 March 19J7 from Doe Run Creek near Olin
Corporation, Brandenburg, Ky. The samples at the upstream and
downstream locations.were collected with tool box samplers des-
cribed in Section 4. The outfall sample was collected with an
ISCO compositing sampler. Location of the samples is shown in
93
-------
BACKGROUND
WIND
OLIN
Figure 22.
Diagram of array air samplers at
Olin Corporation, Brandenburg, Ky.
94
-------
ID
en
Figure 23. Air sampling sites-array at Olin Corporation, Brandenburg, Ky.
-------
VO
Figure 24. Air sampling sites - perimeter at Olin Corporation,
Br-ancLenlyur-g , Kentucky .
-------
TABLE 29. AIR SAMPLING AT OLIN CORPORATION BRANDENBURG, KY. ON 31 MARCH - 1 APRIL 1977
Sampling
Sample
(Tenax tube)
A-l
A-2
A- 3
A-4
A- 5
P-l
P-2
P-3
P-4
\232)
(243)
(233)
(256)
(246)
(251) (a)
(254) (a)
(235) (a)
(252) (a)
Location
Array #1
Array #2 * 800 m ESE of
Olin
Array 13
Array #4
Background for Array ^ 640 m
WSW of Olin
North bank of Ohio River
N side of service road 0 . 3
km from Doe Run
S side of Doe Run Rd.
E side of Doe Run Rd.
Compass
reading
120
120
120
120
240
0
240
180
120
Time-
Start
1100
1100
loop
1100
1135
1000
1030
1050
1110
(3-31)
(3-31)
(3-31)
(3-31)
(3-31)
(4-1)
(4-1)
(4-1)
(4-1)
Duratioi
End
1830
1830
1830
1830
1923
1800
1820
1850
1910
(3-31)
(3-31)
(3-31)
(8-31)
(3-31)
(4-1)
(4-1)
(4-1)
(4-1)
min
450
450
450
450
468
480
480
480
480
i, Volume,
liter
3.65
85.3
137.0
104.5
105.0
vL20
^120
•v.120
vL20
6 -chlorethers
detected.
None
None
None
None
None
None
None
None
None
(a) Sampling start time, stop time and sampling volume for perimeter samples are approximate due
to loss of sampling data sheets. Estimates shown in table are based on written record of verbal
debriefing after sampling trip.
-------
TABLE 30.
WEATHER CONDITIONS DURING SAMPLING AT OLIN
CORPORATION, BRANDENBURG, KY. 31 MARCH 1977
Wind
Time (Date)
Speed, ktn/hr
Direction, degrees
March 31, 1977
1100
1130
1200
1230
1300
1330
1400
1430
1500
1530
1600
1630
1700
1730
1800
1830
4.8
8.1
3.2
4.8
0
3.2
11.3
8.1
3.2
3.2
1.6
9.7
11.3
0
4.8
0
70
20
250
230
90
340
350
135
340
340
350
320
340
98
-------
Figure 25. The locations, sampling start, stop times, duration
and volume are listed in Table 31. The samples were collected
in polyethylene containers. Photographs of the outfall and two
downstream sampling locations are shown in Figure 26.
The samples were extracted and analyzed as described in Section
5 and 6 except analysis was performed on a HP5982 GC/MS.
None of the 3-chloroethers were detected for these samples.
Average detection limit for the four samples was 5 x 10~6 g/1.
Analysis of the downstream #1 water sample concentrate was
performed by scanned GC/MS. The presence of low levels of
hydrocarbons was detected in the sample. Total organic carbon
analysis of the four samples was also performed and results are
reported in Table 32.
8.2.3 Soil Samples
A total of eleven soil samples were taken in the area of the
01in plant at Brandenburg, Ky. The soil sampling locations are
shown in Figure 27- The samples were composite soil samples
collected from soil cores and stored in polyethylene bags. The
samples (50 g) were Soxhlet extracted with 5% ethyl ether in
hexane and analyzed by GC/MS on a HP5982 GC/MS. None of the
samples contained the six g-chloroethers of interest. Average
detection limit for the soil samples was 8 x 10"~6 g/g.
99
-------
o
o
Figure .25. Water sampling sites at Olin Corporation, Brandenburg, Ky.
-------
TABLE 31. WATER SAMPLING AT OLIN CORPORATION BRANDENBURG, KY. ON 30-31 MARCH 1977
o
Sample
(Tenax tube)
W-l
W-2
W-3
W-4
Sampling
Location
Upstream - Doe Run
of outfall
Outfall - Doe Run
Downstream 11 - Doe
north of outfall
Downstream 12 - Doe
north of outfall.
of Ohio River
Time
Start
*. 0.2
Run i
Run "
30 m
km south
U0 .-4 km
1,0.8 km
south
1635
1613
1510
1533
(3-30)
(3-30)
(3-30)
(3-30)
1817
1100
1639
1615
End
(3-31)
(3-31)
(3-31)
(3-31)
Duration ,
min
1542
1487
1529
1482
Volume ,
liter
•v,4
-\,4
0,4
1,4
B-chloroethers
detected
None
None
None
None
-------
(a) Outfall
(b) Downstream #1
(c) Downstream t2
Figure 26. Photographs of water sampling locations at
Olin Corporation, Brandenburg, Kentucky.
102
-------
TABLE 32. TOTAL ORGANIC CARBON ANALYSIS OF WATER
SAMPLES FROM OLIN CORPORATION, BRANDEN-
BURG, KENTUCKY
Sample Total Organic Carbon, PPM
W-l (upstream) 8.3
W-2 (outfall) 20.7
W-3 (downstream #1) 16.4
W-4 (downstream #2) 14.1
103
-------
Figure 27. Soil sampling sites at Olin Corporation, Brandenberg, Ky,
-------
SECTION 9
SAMPLING AND ANALYSIS FOR 3-CHLOROETHERS AT
DOW CHEMICAL USA, FREEPORT, TEXAS
9.1 PRESAMPLING SURVEY
9.1.1 Description of the Plant Site
Dow Chemical USA, located on Texas Highways 288 and 332 (P.O.
Box K) in Freeport, Texas, 77541 is a huge industrial chemical
complex. Among the chemicals produced at this site are ethylene
oxide (production capacity equals 9.07 x 107 kg/yr via chloro-
hydrin and 9.95 x 107 kg/yr via direct oxidation) and propylene
oxide [production capacity equal 4.15 x 108 kg/yr via chloro-
hydrin (includes 9.07 x 107 kg/yr which is switchable to
ethylene oxide production)]. By-products of the chlorohydrin
processes for producing the oxides are bis(2-chloroethyl)ether
and bis(2-chloroisopropyl)ether, respectively. Also produced
at this location is epichlorohydrin (production capacity is
1.13 x 108 kg/yr). A possible by-product of this material is
bis(l-chloromethyl-2-chloroethyl) ether.
Dow occupies four sites at Freeport, Texas. The four sites are
Dow Chemical Plant A, Plant B and Oyster Creek Division and
Dow Badische Company. The entire complex extends along
Texas 332, 11.3 km from the northwest side of Plant B to the
southeast side of Plant A. Figure 28 is a topographical map
•^
of the Freeport area with the location of the Dow property
for Plants A and B indicated on the map. Telephone contacts
105
-------
Figure 28. Topographical map of Freeport area showing location
of Dow Chemical, Plant A and Plant B.
-------
with Texas air and water pollution control personnel indicated
the ethylene and propylene oxide production facilities were
located at Plant A. Liquid waste from both plants is treated
at Plant B before disposal into the Brazos River.
A presurvey was performed on June 19, 1977. The
presurvey consisted of a visual inspection of the entire
complex, since contact with plant personnel was not allowed,
and selection of sampling sites for air and water samplers.
The entire complex occupies the majority of an area of 11 km
by 3.2 km. Dimensions for the Plant A site are shown on the
topographical map in Figure 29. The Plant A site is a large
number of buildings, oil and gas storage tanks, open construc-
tion distillation columns, cooling towers and flares. A
panoramic photograph of Plant A, taken at the eastern edge of
the Dow property, is shown in Figure 30. Plant A is almost
entirely surrounded by water. All of the land inside the
water is owned by Dow and some of the land outside the waste-
ways is owned by Dow. These circumstances prevented air
samplers being placed closer than 1 km from the center of the
plant.
Dow Chemical, Plant A, is bounded on the north by the Dow
Barge Canal and the East Union Bayou. The Bayou is owned by
Dow up to a small canal which parallels Texas 332. To the
west and southwest the plant is surrounded by the Old Brazos
River and the city of Freeport. To the south, the Old Brazos
River and the Intercostal Waterway form a boundary. On the
east is where the Old Brazos, Intercostal Waterway and the
Dow Barge Canal merge. Also in this area is a Corps of
Engineers storm protection area.
107
-------
o
00
Figure 29. Topographical map showing dimension for
Dow Chemical, Plant A.
-------
Figure 30. Composite panoramic photograph of Dow Chemical Plant A, Freeport, Texas.
-------
9.1.2 Surrounding Area
The Freeport area is on the Texas Gulf coastal plain (130 km south
of Houston). Elevation ranges from sea level to approximately
6 m above sea level. Vegetation in the area is mostly of the
small (1-1.5 m) scrub bush-type with a few trees which are 4-5 m
*.
in height. The population of Freeport is 12,000. Clute, a town
to the northwest, has a population of 6,000. Lake Jackson
(population 13,400) is located northwest of Freeport approximately
12 km and Jones Creek, a small settlement (population 1300), is
located west of Freeport. The other industries in the area are:
A. P- Greene Refractories, Gulf Chemical and Metallurgical Corp.,
the Mill Creek Company, Mineral Research and Development, Nalco
Chemical Company, Red Barn Chemicals, Inc., Rhodia, Inc., Shell
Oil Buccaneer Plant, Shintech, Inc., Stauffer Chemical Co., and
Schenectady Chemical Co. None of these industries are known to
produce, emit or use 3-chloroethers.
9.2 SAMPLING AND ANALYSIS RESULTS
Sampling of Dow Chemical U.S.A., Freeport, Texas was conducted
on June 20-21, 1977. The conditions, locations and results
for the air, water and soil samples collected during this
sampling are contained in the following subsections.
9.2.1 Air Samples
Figure 31 is the topographic map of the Dow Chemical, Plant A
area with the air sampling sites indicated on the map. The
eight samplers employed were of the personnel samplers of the
type described in Section 4.1. Large Tenax tubes described
in the same section were used for sampling this site. Table 33
lists the sample numbers, the Tenax" tube used, a description
of the sampling location, the compass reading for the site
relative to the center of Plant A, the starting and ending
110
-------
Figure 31. Location of air sampling sites at Dow Chemical,
Freeport, Texas, June 20-21, 1977.
-------
TABLE ,33- AIR SAMPLING AT DOW CHEMICAL,' FREEPORT, TX ON 20-21 JUNE 1977
Sample
(Tenax tube)
1— i
H
to
A-l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
(G-18)
(G-42)
(G-12)
(G-10)
(G-25)
(G-14)
(G-39)
(G-30)
(G-5)
(G-38)
Location
Ouintana Island, TX 1495,
1.1 km NE of TX 1495 to the NW
NE side of TX 1495, 1.0 km
NW of Old Brazos River Bridge
E side of TX 523, 30 m from TX 523
0.3 km S of TX 332
S side of TX 332 0.3 km E of
TX 523
S side of TX 332, 20 m S of TX 332,
1.2 km E of TX 523
S side of TX 332, 20 m S of TX 223,
2.3 km E of TX 523
S side of TX 332, 20 m S of TX 332,
2.9 km E of TX 523
S side of TX 332, 20 m S of TX 332,
2.3 km E of TX 523
Spiked - 100 yZ of standard
Control
Compass
reading
180
275
325
325
330
350
15
350
-
-
Sampling
Time
Start
1026
1110
1130
1151
1203
1215
1234
2015
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
-
-
End
1821
1910
1923
1947
2001
2012
2028
1236
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
(6-20)
(6-21)
-
-
Duration ,
min
475
480
473
476
478
477
474
981
-
-
Volume ,
I
475'
480
473
476
478
477
474
981
-
-
g-chloroethers
detected
None
None
None
None
None
None
None
None
See Section 7.2.]
See Section ?-'2-3
-------
sampling times, duration of sampling, volume of gas sampled
and 3-chloroether(s) detected. Seven air samplers were
deployed. Sampler A-l served as a background. Samplers
A-2 and A-7 formed an arc around the west and north side of the
Dow Plant A perimeter. These seven samplers were run for
approximately eight hours at a flow rate of one liter/min. Sample
A-8 was collected at the same location as A-6 overnight. A-8
sampling time was 981 min. Wind speed and direction data
for the sampling periods are listed in Table 34.
Air samples A-l, A-2, A-3, A-4, A-6, A-7, A-9 and A-10 were worked
up by solvent desorbing the tubes with 4 ml of methanol. These
•
samples were analyzed by gas chromatography/mass spectrometry,
with the mass spectrometer operating in the selected ion monitoring
>
-------
TABLE 34. WEATHER,CONDITIONS DURING SAMPLING
AT DOW CHEMICAL, FREEPORT, TEXAS
Date (1977)
and time
20 June
1000-1100
1100-1200
1200-1300
1300-1400
1400-1500
1500-1600
1600-1700
1700-1800
1800-1900
1900-2000
2000-2100
2100-2200
2200-2300
2300-2400
21 June
0000-0100
0100-0200
0200-0300
0300-0400
0400-0500
0500-0600
0600-0700
0700-0800
0800-0900
0900-1000
Wind
Speed, km/hr
22.5
22.5
22.5
24.1
24.1
22.5
16.1
22.5
22.5
24.1
22.5
22.5
25.8
20.9
22.5
24.1
24.1
22.5
22.5
24.1
22.5
20.9
22.5
25.8
Direction
S
S
S
S
S
S
SE
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
114
-------
LI-C,-. 3O •-?
** SFE'JTRUPI
OF FPEEPORT G-
1O 33O-1O 6'TEN^X-GC
DJi-PLAY'-EDIT -» .*
H
OI
FPM 73TM
1ST SC/PG:
V-
I i i i i i i i i
Figure 32. Total ion reconstructed chromatogram of Freeport Sample A-8
-------
toluene
chlorobenzene
dibenzoyl disulfude
dibutyl phthalate
Results for the spiked sample are listed in Section 7.2.1.
9.2.2 Water Samples
Three twenty-four hour composite water samples and 3 grab samples
were collected at Dow Chemical, Freeport, Texas. The water was
extremely clouded by reddish-brown sediment during sampling
at the sites. The composite samples were pumped from the Brazos
River with the toolbox sampler described in Section 4.2. The
effluent from the sampler was collected in brown glass jugs
which held approximately 4 liters of water. Figure 33 shows
the locations where the samples were taken on a topographical
map of the area. An exact description of each location, the
times sampling was started and stopped, the duration of sampling,
the approximate volume collected and B-chloroethers detected are
listed in Table 35. Photographs of the downstream #2 and
upstream locations are shown in Figure 34. The only sample
found to contain a 3-chloroether was the W-l sample taken at
downstream location #1 (nearest downstream point on Brazos
River to Dow Plant B not on Dow property). The concentra-
tion of bis(2-chloroethyl)ether found in this sample was
1.8 x 10~6 g/liter. The concentrate of this same sample
extract was analyzed by GC/MS in the scanned mode. The
total ion chromatogram obtained is shown in Figure 35.
the peaks identified. Compounds found in this sample were:
116
-------
Figure 33. Water sampling sites at Dow Chemical, Freeport, Texas.
-------
TABLE .35. WATER SAMPLING AT DOW CHEMICAL, FREEPORT, TX, 20-21 June 1977
00
Sample
(Tenax tube;
W-l
W-2
W-3
W-4
W-5
W-6
) Location
N bank of Brazos River at Victoria
St., 2.75 km NW of TX 36 bridge
S bank of Brazos River at side
road from Brazos River Rd. , 10.0
km NW of TX 36 bridge
-E bank of Brazos River at TX 36
bridge
Same as W-2, spiked
Same as W-2, control
Same as W-3
Sampling
Time
Start
0822
0930
1000
0930
0930
1000
(6-20)
(6-20)
(6-20)
(6-21)
(6-21)
(6-21)
End
0822 (6-21),
0930 (6-21)
1000 (6-21)
-
-
-
Duration ,
min
1,440
1,440
1,440
Grab
Grab
Grab
Volume , g-chloroethers
I detected
4
4
1
1
1
,.••
Bis(2-chloroethyl) ether
None
None
See Section 7.2.2
Lost
None
-------
Downstream #2 at TX36 bridge.
b. Upstream
Figure 34
Photographs of two water sampling
locations at Dow Chemical, Freeport,
Texas.
119
-------
[,
*.*. 5PEOTRUM DISPLAY/-EDIT
FPEEPOPT ti
GNSH 10/4.'77
TI
7969
1ST SC/PG: 1
X- .50 V- 1.00
7 8
I l I I I I I I 1 I I
11 12 13 14 IS 161718 IS 20 21
1 I I I I I
26 27 2S 23
Figure 35
Total ion reconstructed chromatogam of water sample, W-l,
Dow Chemical USA, Freeport, Texas.
-------
diethyl phthalate
dibutyl phthalate
triphenyl phosphine
dioctyl phthalate
triphenyl phosphine oxide
Detection limit for the 3-chloroethers in the other water samples
was 2 x 10"7 g/liter of water.
Results for the spiked water sample are tabulated in Section 7.2.2
9.2.3 Soil Samples
Figure 36 shows the locations for the soil samples which were
taken at Dow Chemical, Freeport, Texas. The samples were
collected in the downwind direction as indicated, by the annual
wind rose. A soil core 5 cm in diameter by 7.5 cm deep, weighing
•\* 350 g was taken at each site. Samples analyzed were S-4,
S-5, S-6, S-7, and S-8. Fifty gram samples from each site were
extracted. None of the 3-chloroethers was found in these samples.
Detection limits for the 3-chloroethers was 4 x 10~9 g/g of soil.
Results for the spike sample, S-14, are shown in Section 7.2.3.
121
-------
to
to
Figure 36. Soil samples locations at Dow Chemical, Freeport, Texas
-------
SECTION 10
SAMPLING AND ANAYSIS FOR 3-CHLOROETHERS AT
JEFFERSON CHEMICAL CO., INC., PORT NECHES, TEXAS
10.1 PRESAMPLING SURVEY
10.1.1 Description of the Plant Site
Jefferson Chemical Co., Inc. is located on Texas 366 (P. O. Box
847) in Port Neches, Texas, 77651. The plant produces a series
of industrial organic chemicals. Among the materials produced
at this site is propylene oxide (production capacity is
6.8 x 107 kg/yr) produced via the chlorohydrin route. A by-
product of production of this product by the chlorohydrin
process is bis(2-chloroisopropyl)ether. The Jefferson plant
also produces ethylene oxide (production capacity is
2.15 x 108 kg/yr) via direct oxidation.
A presurvey was performed on June 21, 1977. The presurvey
consisted of a visual inspection of the entire complex (since
contact with plant personnel was not allowed) and selection of
sampling sites for air and water samples.
Figure 37 shows the location of the Jefferson Chemical site in
the Port Neches-Groves, Texas area topographical map. The
entire complex occupies an area approximately 2 km square.
The exact dimensions of the site are listed on the topographic
map in Figure 38. Jefferson Chemical at Port Neches is a group
of buildings, both open and closed construction, a large number
123
-------
£l'!ht. - .
- - - - - N* V£
r-vr:-Q- \&
I
jsfi
*—J iff A
n •*&
'n u o
' W
[[] n / JEFFERSON
[)/ CHEMICAL
[OUTTALLMasaas^^
t. / >!£: -
,w
VHL
Ir
-------
Figure 38. Dimension of area around Jefferson Chemical
125
-------
of oil storage tanks> spherical vessels for the storage of gases,
distillation and cooling towers, and flares. The plant site
is bounded on the north by Texas 366, on the east by Hogaboom Rd.,
on the west by Texas 136 and on the south by a wastewater treat-
ment plant and a series of single-family dwellings. Figure 39
is a panoramic photograph of the Jefferson site taken from
Orchard Avenue north of the plant.
As was true for all of the plants sampled during this study,
the operating schedule of the processes of interest were
unknown. The only visible emissions were steam vents and flares.
One of the flares was extremely bright on the night of
June 22, 1977. The entire area was illuminated by the flare
and attempts to take pictures of the flare tower resulted
in totally exposed film. Operations at the plant may have been
abnormal due to the explosion of an ammonia tank truck on the
plant property on June 17, 1977. The explosion destroyed
one flare tower but otherwise did not seem to have interrupted
operations. A slightly sweet odor was present in the area
of the plant. Two large holding ponds are visible from Hogaboom
Road in the Jefferson complex. During the presampling survey
and sampling periods no water effluent was observed to be leaving
the plant via a drainage ditch, which passes under Hogaboom Road,
and parallels Texas 366. The ditch is then joined by a water
flow from the Groves Texas Water Works and passes under Texas 366
and merges with water from other industries to form Left Prong.
Left Prong then passes under Port Neches-Atlantic Road and then
enters the Neches River.
10.1.2 Surrounding Area
The Port Neches-Groves area is on the Texas Gulf coastal plain
in extreme southeastern Texas (approximately 30 km southeast
of Beaumont). The elevation of the area ranges from 2 m to 6 m
126
-------
NJ
Figure 39. Composite panoramic photograph of Jefferson Chemical at Port Neches, Texas
-------
above sea level. Jefferson Chemical is located in Jefferson
ounty, Texas. To the east and southeast are the towns of Port
Arthur (population 57,000) and Groves (18,000); to the west
and north are Port Neches (11,000) and Nederland (16,800).
The other industries in the area include a large Texaco oil
refinery, Bayou Pipe Line System Tank Field and a lumberyard
north of Jefferson. To the east and northwest are Du Pont,
B. F. Goodrich and National Butane plants. The vegatation
in the area consists of small scrub trees, a few large planted
trees,and marshy areas in the region along the Neches River.
«
10.2 SAMPLING AND ANALYSIS RESULTS
Sampling of the area around Jefferson Chemical, Port Neches,
Texas for g-chloroethers was conducted on June 22-23, 1977.
The conditions, locations and results for the air, water,
soil and sediment samples collected during this sampling
are contained in the following subsections.
10.2.1 Air Samples
Figure 40 is a topographic map showing the location of air
sampling sites around the Jefferson Chemical Plant at Port
Neches, Texas. A description of the sampling locations,
compass readings relative to the center of the Jefferson
plant, start and stop times, duration of sampling, sample
volume and 3-chloroethers detected are listed in Table 36.
Sampling was accomplished using portable personnel samplers,
large Tenax tubes and charcoal backup tubes described in
Section 4.1. Weather conditions during the sampling period
were very good. The temperature ranged from 24°C at night to
35°C during the day. The relative humidity was high, but no
rain occurred during the sampling period. Wind speed and
direction data supplied by the weather bureau at Jefferson
County Airport are shown in Table 37. The wind was primarily
from the south to southeast at 9 to 24 km/hr.
128
-------
Figure 40
Air sampling sites at Jefferson
Chemical, Port Neches, Texas.
129
-------
TABLE 36. AIR SAMPLING AT JEFFERSON CHEMICAL, PORT NECHES, TX, ON 22-23 JUNE 1977
Sample
(Tenax tube)
A-l
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A-ll
A-12
(G-34)
(G-28)
tG-41)
(G-23)
(G-41)
(G-24)
(G-26)
(G-17)
(G-6)
(G-32)
(G-21)
(G-13)
Location
W side of TX 136, 1.1 km N of TX 366
E side of Orchard Ave., 0.16 km
N of TX 366
N side of TX 366, 1.29 km E of
TX 136
N side of TX 366, 1.1 km E of
TX 136
N side of TX 366, 0.64 km E of
TX 136
W side of TX 136, 0.16 km S of
TX 366
W side of TX 136, 0.64 km S of
TX 366
NW side of Ho'gaboom Road
E side of Orchard Ave., 0.16 km N
of TX 366
W side of TX 136, 0.64 km S of
TX 366
Spiked tube
Control tube
Compass
reading
0
350
335
320
310
295
280
180
350
280
-
-
Time
Start
1024
1036
1047
1057
1104
1112
1119
1134
1824
1921
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
-
-
Sampling
Duration ,
End
1824
1836
1847
1857
1904
1913
1919
1934
0845
0838
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-22)
(6-23)
(6-23)
-
-
min
480
480
480
480
480
481
480
480
843
797
-
-
Volume ,
I
480
480
480
480
480
481
480
480
843
797
-
-
0-chloroethers
detected
None
None
None
None
None
None
None
None
None
None
See Section
See Section
7.2.1
7.2.1
-------
TABLE 37. WEATHER CONDITIONS DURING SAMPLING AT
JEFFERSON CHEMICAL, PORT NECHES, TEXAS
(COURTESY WEATHER BUREAU, JEFFERSON
COUNTY AIRPORT) 24°C-35°C
Date (1977)
and time
22 June
0955
1056
1158
1255
1356
1455
1555
1655
1755
1855
1955
2055
2155
2253
2347
23 June
0053
0153
0256
0355
0457
0551
0655
0755
0855
Speed , km/hr
11.7
18.5
20.4
22.2
20.4
24.1
22.2
22.2
24.1
20.4
16.7
13.0
11.1
9.3
11.1
13.0
14.8
11.1
13.0
11.1
13.0
11.1
13.0
16.7
Direction, degrees
170
170
170
190
180
160
180
160
180
170
180
180
160
130
120
120
140
150
140
150
130
160
150
150
131
-------
Eight samplers were placed around the perimeter of the plant on
June 22, 1977 and run for eight hours at 1.0 liter/min. Sampler
A-8 was the background sampler. Samples A-l through A-7 were
situated on the rights of way along Texas 136, 366 and Orchard
Avenue to the north and west of the plant. Samples A-9 and A-10
were collected during the night of June 22-23, 1977.
Air samples A-l, A-2, A-3, A-5, A-6, A-7, A-8 and A-10 were de-
sorbed with methanol and analyzed by selected ion monitoring
gas chromatography/mass spectrometry . No responses were
found during the analysis of these seven samples for the six
3-chloroethers of interest (average detection limit =
7 x 10~7 g/m3) . The two remaining air samples A-4 and A-9
were thermally desorbed and analyzed via GC/MS with the
mass spectrometer operating in the scan mode (35-350 amu) .
Sample A-4 was lost during analysis. Sample A-9 showed none
of the 3-chloroethers of interest (average detection limit
x 10~7 g/m3) .
The total ion reconstructed chroma togram for sample A-9 is shown
in Figure 41. Peaks in the chromatogram are also identified in
Figure 41. The compounds found were:
• methylene chloride
• toluene
• chlorobenzene
Results for the spiked sample tube are listed in Section 7.2.1.
10.2.2 Water Samples
Three 24-hour composite water samples and two grab water
samples were collected on June 22 and Jund 23, 1977 at
Jefferson Chemical, Port Neches, Texas. The drainage ditch
from Jefferson was coated with an oily scum and was reddish-
132
-------
** SPECTRUM DISPLAYS-ED IT
THEIRPML D£SORPTION: PORT NECHES A-9, G-6
TEN.-».\ ?0 -^ 1C aOO '30X36O-1O GN3L 10/7/77
**
FRN 7975
1ST SC/PG: 1
X' .35 V- 1.00
H-
U)
U>
Figure 41. Total ion reconstructed chromatogram of Port Neches air sample A-9
-------
brown in color. Figure 42 shows the water sampling sites on
the topographical map of the area. Downstream samples were
taken 6 m north of a bridge on Texas 366 (stream 5 m wide) and
3 m south of a bridge on Port Neches-Atlantic Avenue
(stream 10 m wide). The upstream sample which was taken
from the Neches River at the Port Neches City park was lost
during shipment.
The samples were pumped from the sampling sites using the
toolbox sampler described in Section 4.2. Samples were
collected in amber jugs. The caps of the jugs were teflon
lined. Samples were placed in ice chests with styrofoam
and ice and air freighted to Dayton. A description of the
sampling site, times of sampling, duration, sample volume
and B-chloroethers found for the water samples are listed
in Table 38. Photographs of the outfall, drainage ditch, and
two downstream sampling sites are shown in Figure 43, One
liter of each sample was extracted with three 100 ml portions
of methylene chloride. The methylene chloride extracts were
then combined and evaporated in a Kuderna-Danish evaporator
to * 2.5 ml. Analysis was performed by GC/MS/SIM. Only the
downstream #1 sample (W-l) showed a 3-chloroether of interest.
Bis(2-chloroisopropyl) ether was found in this sample (W-l) at a
concentration of 2.2 x 10~5 g/liter. The detection limit for
the other downstream sample was 2 x 10~7 g/liter for each of
the six B-chloroethers.
The concentrate of the downstream #1 water sample was analyzed
by GC/MS in the normal scanned mode on a SP 2250 column. The
total ion chromatogram obtained is shown in Figure 44. The
peaks in the chromatogram are identified in Figure 44. Com-
pounds found in this sample were:
134
-------
.Figure 42.
Water sampling sites at Jefferson Chemical,
Port Neches, Texas.
135
-------
TABLE 38. WATER SAMPLING AT JEFFERSON CHEMICAL, PORT NECHES, TX, ON 22-23 JUNE 1977
U)
Sampling
Sample
(Tenax tube) Location
W-l
W-2
W-3
W-4
W-5
N side of TX 366, 0.8 km E of
Hogaboom Road
S side of Port Neches - Atlantic
Rd., 4.2 km SE of TX 136
S bank of Neches River at Port
Neches City Park-
Same as 3 Spiked
Same as 3
Time
Start
0857
0919
1012
Grab
Grab
(6-22)
(6-22)
(6-22)
0857
0919
1012
1012
1012
End
(6-23)
(6-23)
(6-23)
(6-23)
(6-23)
Duration ,
min
1,440
1,440
1,440
-
-
Volume ,
I
<\,4
4
<\>4
•x/1
•v.1
(J-chloroethers
detected
BCIPE
None
None
See Section
See Section
7.2.2
7.2.2
-------
a. Outfall
b. Drainage ditch
c* Downstream sampling point #1 d. Downstream sampling point #2
Figure 43. Photograph of Jefferson Chemical, Port
Neches, Texas. Water outfall and
downstream sampling location.
137
-------
** SPECTRUM DISPLAY'EDIT **
•.HARACTERIZATION: PORT NECHES DU-I 3UL
8 260-10 GN6H i0/4-'77
U)
CO
FRN 7968
1ST SCxPG: 1
X- .25 V- 1.00
TI
liiiiiiiiiiiiiiiiiiiiiiiiiiiii
Figure 44. Total ion reconstructed chromatogram of Port Neches downstream
•water sample #1.
-------
• p-chlorophenol
• unknown (11.2 min)
• diethyl phthalate
• unknown (14.1 min)
• isothazine
• unknown (14.8 min)
• unknown (16.0 min)
• isobutylphthalate
• dioctylphthalate
• 2,1,ll-trimethyldodeca-2-trans,6-cis-10-trienol
• triphenylphosphine oxide
Mass spectra for the four unknown compounds are shown in
Figure 45. The results for the spiked water sample are listed
in Section 7.2.2.
The same water sample (W-l, downstream #1) was also analyzed by
GC/MS in the normal scan mode in a Tenax GC column. A series of
polar compounds not identified on the SP 2250 column was identi-
field on the Tenax GC column. The total ion reconstructed chro-
matogram for the Tenax GC characterization and the identity of
the peaks are shown in Figure 46. The compounds identified are
listed below.
• phenol
• diethylene glycol monoethyl ether
• a-caprolactone
• p-cresol
• p-chlorophenol
• triethylene glycol
• methyl naphthalene
• acenaphthalene- or biphenyl
• unknown (18.9 min)
• nonyl phenol
139
-------
UORK AREA SPECTRUd FRN 7968 PAGE IV' 1.00
LAR.J5T 4t 70.9,100.0 48.8. 39.8 68.8. 83.3 141.1. 81.6
U*5T 41 231.1. .5 834.1. .3 845.0, .8 880.3. .3
-349 * 344
too
SO
6O.
4<9.
30,
O
100
80.
60
Mill hM
II lltl lIl'N u'liil 'n 'l u Mil h I1 1
80 40 " «8 . SO '180 '180 '140 ' 160
:
Unknown (RT=11.2 min)
WORK AREH SPECTRUM FRN 7968 PMC 1 V - 1.00
LAR05T 41 <«.9,10O.0 70.9, 67.8 84.9. S1.0 48.8. 47.1
LAST 4> 878.4, .7 880.5. 1.0 888.8. 1.9 898.3, .7
-334 * 386
LOO
SO
60v
4O
80
i 01
i
100
i
• 80
60
40
80
0
1
id JLJI| II-.L.HII
.
1 illliHill il^ijJ u j.JLi |||t>.i.ill.iiti . -il bkijiiiln
• • s-"ii''iihg**|i|"li^5f*NHi ^ j-jjjj- • iafe • 14i • 16i
•i. li hhH dHri.i. |||H| inkM-*1 • ii. • i
UORK AREA SPECTRUfl FRN 7968 PAGE 1 V - 1.00
LARGST 41 169.1.100.0 106.9. 88.7 170.0. 81.4 158.1, 63.4
LAST 41 S67.O, 8.0 869.3. 1.8 870.8, 1.1 878.6, .8
toe
80
F»
40
LOO
m
60
40
8*!
I 1
1 L
jl il ll J|ij4L Ml Mll.ll i Ll llldJi'ljl
80 ' 40 ~" 80 "Si ' 100 ' iS r 140" ^ 160
i
ll. .ll,.. .
Unknown (RT=14.1 min)
UORK AREA SPECTRUM FRN 7968 PAGE IV- 1.00
trt»'i?T 41 56.9, 1OO. 0 48.8. 90.4 70.9. 68.6 84.9, 83.8
UifT 41 235. S, .9 289.6, .9 896.5, .8 897.6, .9
ilOO
so
bO
40.
SO.
1O0
80
60
: 40
80.
.
Ill, JILji, lii, ihh Jin iilil. Ji iJui, -a,
80 40 60 80 100 12O 140 160
.._ illilu .11 ll lllilL ihlllli bl 'i lhi.li M.III ULI i u_n
tab ' pae ' aalp ' ^M ' otStt ' »tlat ' 3aa ' tsa
Unknown (RT=14.8 min)
Unknown (RT=16.0 min)
Figure , 45. Mass spectra of unknowns in downstream #1 water sample, Port Nec'hes, Texas.
-------
** SPECTRUN DISPLAY/EDIT *X
PORT NECHES D.S.*1 3UL CHECL2
EI-GC 140/8/280 6' TENAX-GC GAIN 6OR9
FRN 8003
1ST SC/PGJ 1
X- .50 V- 3.00
I I 1 I i i I i i i i i i i
9 10 11 12 13 14 15 16 17 18 19 20 21 22
Figure 46. Total ion reconstructed chromatogram of Port Neches, downstream water
sample - Tenax GC.
-------
The mass spectrum of the unknown compound at 18.9 min. is shown
in Figure 47.
10.2.3 Soil Sampling
Twenty-two soil samples were collected in the vicinity of the
Jefferson Chemical Plant. Figure 48 shows the location of the
soil sampling sites. Samples were primarily sandy loam or clay
loam. The majority of the samples were taken at locations which
would be downwind from the plant. Sampling sites were selected
based on the annual wind rose for the area. All of the samples
were taken with a bulb planter (5 cm diameter by 7.5 cm in
depth). The samples were placed in wide mouthed canning jars.
After air freight shipment back to Dayton, 50 g of selected
samples (S-2, S-3, S-4, S-5, S-7 and S-13) were soxhlet extracted
with methylene chloride. The methylene chloride was then con-
centrated to ^ 2.5 ml and analyzed by GC/MS/SIM. None of the
six g-chloroethers of interest were found in the six soil samples.
Detection limits for the B-chloroethers were 4 x 10"9 g/g of soil.
>
i
10.2.4 Sediment Sampling
A sediment sample..was collected at each of the downstream water
sampling locations. Figure 49 shows the sediment sampling sites
on a topographical map of the area. The sediment samples were
scooped from the bottom of the creeks -\> 0.5 m from the bank
with a collapsible shovel. The samples were transferred to
wide mouthed canning jars. After Soxhlet extraction and con-
centrations to *> 2.5 ml, the samples were analyzed via
GC/MS/SIM. None of the six $-chloroethers of interest were
detected in the two samples. Detection limit for each of
the ethers was 4 x 10"9 g/g of sediment.
142
-------
OJ
UORK AREA SPECTRUM FRN 8003 PAGE 1 Y - 1.00
LARGST 4: 114.0,100.0
LAST 4: 341.2, .0
-356 + 370
100.
80.
60.
40.
«
20.
•
0
L00.
4
80.
4
60.
•
40.
«
20.
<•
0.
20 40
85.9, 98.8 55.9, 31.2 41.9, 14.8
342.4, .2 343.2, .1 345.6, .1
60 80 100 120 140 160
1S0 200 220 S40 260 280 300 320
Figure 47. Unknown (RT=18.9 min) (see Figure 46).
-------
Figure 48.
Soil sampling sites at Jefferson
Chemical, Port Neches, Texas.
144
-------
Figure 49. Sediment sampling sites at Jefferson
Chemical, Port Neches, Texas.
145
-------
SECTION 11
SAMPLING AND ANALYSIS FOR 3-CLOROETHERS AT
DOW CHEMICAL USA, PLAQUEMINE, LOUISIANA
11.1 PRESAMPLING SURVEY
11.1.1 Description of the Plant Site
Dow Chemical USA is located on River Road north of Plaquemine,
Louisiana 70764. The plant's mailing address is P.O. Box 150,
Plaquemine, LA. The plant produces a variety of industrial organic
chemicals. Among the products produced at this plant are ethylene
oxide (production capacity = 2.04 x 108 kg/yr) and propylene oxide
(production capacity = 1.54 x 108 kg/yr). As has been mentioned
earlier the respective by-products of these two chemicals
;»
where they are produced by the chlorohydrin process are bis(2-
chloroethyl) ether and bis(2-chloroisopropyl) ether.
A presurvey of the plant was performed on June 26, 1977. The pre-
survey consisted of visual inspection of the Dow Chemical complex/
since contact with plant personnel was not allowed, and selection
of sites for air and water sampling.
The Dow complex at Plaquemine is a series of buildings of open
and closed construction, distillation and cooling towers, flares
and liquid storage tanks. The location of the complex is shown
in Figure 50 on the topographical map of the area. The main por-
tion of the Dow plant is located in an area roughly 1.5 km by
146
-------
WASTEWATER
^ OUTFALL^
^ ^£&
Figure 50. Dow Chemical location in Plaquemine,
La. area.
147
-------
2.5 km. The entire area owned by Dow encompasses ^2.5 km by
3.0 km. Figure 51 show the dimensions of the area on the topo-
graphical map. The complex is bounded on the east by Louisiana
988, on the south by Louisiana 1148, on the west by Louisiana 1
and on the north by Louisiana 990. Figure 52 is a panoramic
photograph of the Dow complex. The photograph was taken on the
southwest side of the Dow complex.
11.1.2 Surrounding Area
The Plaquemine area is located in south central Louisiana on the
west bank of the Mississippi River approximately 16 km south of
Baton Rouge, La. Elevation of the area ranges from 4.5 m to 7.5 m
above sea level. The area is protected from the Mississippi River
by a levee which is ^7-3 m high. The majority of the Dow plant
proper is in Iberville Parish with part of the land owned by Dow
extending into West Baton Rouge Parish. Due south of the Dow
complex is a small settlement named Turnerville. Further south
is the town of Plaquemine (population 7700). To the northwest
of the plant is a small settlement named Addis (population 700).
The remainder of the area surrounding the plant is farm land.
Industry in the area other than Dow consists of a small plant run
by Copolymer Rubber and Chemical Corporation, a Goodyear Tire and
Rubber Co. plant which adjoins Dow on the east side of the Dow
complex and Sid Richardson Carbon Company on Sid Richardson Road
northwest of the Dow complex.
Vegetation in the area includes locust, cypress and other deciduous
trees and a number of varieties of small bushy plants. The farm
land in the area had recently been plowed.
148
-------
Figure 51.
Dimension of area around Dow Chemical
USA, Plaquemine, Louisiana.
149
-------
en
o
Figure 52. Composite panoramic photograph of Dow Chemical USA, Plaquemine, Louisiana
-------
11.2 SAMPLING AND ANALYSIS RESULTS
Sampling of the area around Dow Chemical, Plaquemine, Louisiana
for 0-chloroethers was conducted on 27-28 June 1977. The condi-
tions, locations and results for air, water, soil and sediment
samples collected during this sampling are contained in the fol-
lowing subsections.
11.2.1 Air Samples
The deployment of the air samplers around the Dow complex is
shown on the topographical map in Figure 53. A total of eight
samplers of the personnel sampler type were used for sampling at
this site. A description of the samplers, the large Tenax tubes
used to collect the 3-chloroethers and the charcoal backup tubes
is included in Section 4.1. Table 39 describes the sample num-
bers, Tenax tube number, a description of the sampling location,
the compass reading for the sampling sites relative to the center
by the Dow plant, the starting and ending sampling times, duration
of sampling, the volume of air sampled and B-chloroether(s) de-
tected. Because of the predominant wind direction (S-SW) during
sampling, samples A-2, A-3 and A-4 were background samples. Sam-
ples A-l, A-5, A-6, A-7 and A-8 formed an arc around the downwind
side of the complex. Sample A-9 was the background sample for
A-10 when these samples were collected during the night of June
27-28, 1977. Table 40 ' lists the wind speed and direction data
for the sampling periods listed in Table 39. Data in Table 40
were recorded by the weather bureau at Ryan Airport, Baton Rouge,
151
-------
Figure 53
Air sampler location at Dow Chemical
USA, Plaquemine, Louisiana.
152
-------
TABLE 39, AIR SAMPLING AT DOW CHEMICAL USA, PLAQUEMINE, LA. 27-28 JUNE L977
Sample
(Tenax Tube)
Al
A2
A3
A4
HJ AS
Ui
W
A6
A7
A8
A9
A10
All
A12
(G-45)
(G-51)
r
(G-50)
{G-44)
(G-46)
(G-15)
(G-49)
(G-48)
(G-47)
(G-20)
(G-43)
(G-19i
Location
NE Side of LA 988,
1.6 km N of LA
1148
E Side of LA 988
at intersection
with LA 1148
SW Side of LA 1148,
0.32 km NW of
Brownie St.
NE Corner of inter-
section of LA 1148
and LA 1
NE Corner of inter-
section of LA 990
and LA 1
S Corner of .inter-
section of LA 990
and LA 988
S Side of LA 988,
0.81 km SE of
LA 990
E.Side of LA 988,
2.6 km SE of LA
990
E Side of LA 988
at intersection
with LA 1148
S Side of LA 998,
0.81 km SE of
LA 990
SPIKED - 100 yl
of Standard
CONTROL
Compass
reading
80
170
185
225
320
355
360
55
170
360
-
-
Sampling
Start
0945
1000
1010
1017
1040
1048
1055
1103
1820
1857
-
-
time
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
End time Duration, min.
1800
1811
1822
1828
1834
1848
1855
1903
0951
1010
-
-
(6-27)
(6-27)
(6-27)
(6-27)
(6-27)
16-27)
(6-27)
(6-27)
(6-28)
(6-28)
495
491
492
491
474
480
480
480
931
913
-
-
Volume , 1
495
491
492
491
474
480
480
480
931
913
-
-
0-Chloroether (s)
detected
None
None
None
None
None
None
None
None
None
None
See Section 7.2.
See Section 7.2.
-------
TABLE 4 0,
WEATHER CONDITIONS DURING SAMPLING AT DOW
CHEMICAL USA, PLAQUEMINE, LOUISIANA 22-35°C
Time (Date)
June 27 , 1977
0853
0955
1053
1153
1251
1354
1456
1552 .
1652
1752
1852
1952
2052
2152
2252
2353
June 28, 1977
0056
0157
0257
0358
0451
0529
0656
0755
0854
0951
1053
Speed , km/hr
16.7
13.0
20.4
18.5
22.4
18.5
25.9
31.5
18.5
22.4
20.4
18.5
16.7
18.5
9.3
11.1
0
0
0
0
0
0
0
5.6
5.6
14.8
13.0
Wind
Direction, degrees
230
200
200
200
230
230
210
240
220
190
230
230
220
200
190
190
_
_
_
_
_
_
.
260
220
230
210
154
-------
La. The temperature during sampling ranged from 22°C at night
to 35°C during the day. The weather was good during the entire
sampling period with no rain occurring.
Air samples A-l through A-7 and A-9 and A-10 were solvent desorbed
with methanol as described in Section 5.1. Four cm3 of methanol
was used for each desorption. The desorbed samples were analyzed
by gas chromatography/mass spectrometry. The mass spectrometer
was operated in the selected ion monitoring mode. None of the
six B-chloroethers of interest were detected in these samples
(average detection limit = 7 x 10 7 g/m3). The average detection
limit for the two samples collected during the night was 3.9 x
10 7 g/m3. One of the air samples, A-8, was thermally desorbed
and analyzed by GC/MS. The mass spectrometer was operating in
the scanned mode. None of the g-chloroethers of interest were
detected in this sample (average detection limit ^2 x 10 7 g/m3).
The total ion reconstructed chromatogram is shown in Figure 54.
The identity of peaks seen in the chromatogram are also listed on
Figure 54. The compounds found in sample A-8 were:
• methylene chloride
• 2,2,3,3-tetramethyl butane
• benzene
• toluene
• chlorobenzene
Results for the spiked sample are listed in Section 7.2.1.
H.2.2 Water Samples
Original plans for the water sampling at Dow Chemical, Plaquemine,
La. called for three 24-hr integrated water samples. However,
during sampling the period the downstream #2 water sampler disap-
peared. Therefore, upstream (W-3) and downstream #1 (W-l) water
samples were 24-hr composite samples and downstream #2 (w-2) was
155
-------
** SPECTRUM DISPLAY/EDIT
THERPIAL DESCRPTICN: PLRQUEmiNE A-S, G-48
TENH.X JO-5 1C '£OO- 3O 26O-1O GN4L 10/9/77
**
FRN 7978
1ST SCxPG: 1
X« .25 Y- 1.00
Ul
TI
\
O
H
•8
I I I
10
I
15
i i i
50
I
25
30
Figure 54. Total ion reconstructed chromatogram of air sample A-8,
thermally desorbed, Dow Chemical USA/ Plaquemine, Louisiana,
-------
a grab sample. The locations of the water samples are shown on
the topographical map of the area in Figure 55. Table 41 lists
the sample numbers, sampling location, sampling times, duration
and volume, and g-chloroethers detected. The upstream location
was '^1.45 km northeast of the plant wastewater outfall. The down-
stream #1 location was 0.8 km south of the outfall and the down-
stream #2 location was ^2.6 km south of the outfall. The Missis-
sippi River ranged from 0.5 km wide at the downstream #2 location
to 1.0 km wide at the upstream location. Photographs of the
drainage ditch to the outfall, downstream #1, downstream #2 and
upstream locations are shown in Figure 56. Caps of the water
sample bottles were taped to insure against leakage. The samples
were placed in picnic coolers with foam padding and ice. The
cooler was then sealed and the samples air freighted to Dayton.
Samples were kept at 4°C until analyzed.
One liter of each sample was extracted three times with 100 cm3
portions of methylene chloride. The extracts for each sample
were combined and concentrated to ^2.5 cm3. These concentrates
were analyzed by GC/MS/SIM. None of the three samples contained
3-chloroethers. The average detections limit for water samples
were 2.0 x 10 7 g/1. The concentrate of the downstream #2 sample
(w-2) was further concentrated to a volume of 0.5 cm3. This sam-
ple was then characterized via GC/MS using an SP 2250 column.
Figure 57 shows the total ion reconstructed chromatogram for
this sample and the compounds identified in the sample. Compounds
found in the sample were:
T
• 1,2-cyclohexanediol
• unknown (RT = 6.0 min.)
• 5-n-butyl nonane
• 2,6-di-tert-buty-4-methyl. phenol
• stilbene
• 2,2-dimethyl-trans-hex-3-ene
• unknown (RT = 15.3 min)
157
-------
"56
WASTEWATERU
OUTFALL
Figure 55. Water sampler location at Dow
Chemical USA, Plaquemine, La.
158
-------
TABLE :-J*L. WATER SAMPLING AT DOW CHEMICAL USA PLAQUEMINE, LA. ON 27-28 JUNE 1977
U1
VO
Sample
W-l
W-2
W-3
W-4
W-5
W bank
S of
Location
Sampling
Start time End time Duration, min
of Mississippi R. 800 M
Dow Waste Water Outfall
W bank of Mississippi R.
N of intersection with
St in Plaguemine, LA.
W bank
S of
St, E
Same as
Same as
of Mississippi R.
intersection with
of LA 988
W-3
W-3
10 M
Court
10 M
Davis
0845
0920
0930
Grab
Grab
(6-27) 0845 (6-28) 1440
Grab Sample
(6-27) 0920 (6-28)
(6-37) 0930 (6-28) 1440
0930
0930
(6-28)
(6-28)
Volume , I B-Chloroether (s)
4 None
4 None
4 None
1 See Section 7.2.1
1 See Section 7.2.1
-------
a. Drainage ditch
b. Downstream #1
c. Downstream #2
d. Upstream
Figure 56. Photographs of drainage ditch and water
sampling locations, Dow Chemical USA,
Plaquemine, Louisiana.
160
-------
.*.* SPECTRUM DISPLAV/EDIT
CHARACTERIZATION: PLAQUEMINE DU-3 3UL
SO S 26O-1O GN?L 10/6x77
FRH 7972
1ST SC/PG: 1
X- .35 V- 1.00
TI
25
i i i r
30
Figure 57. Total ion reconstructed chromatogram for downstream #2
water sample (W-2), Dow Chemical USA, Plaquemine, La.
-------
u
• unknown (RT = 15.7 min)
• diethyl phthalate
• unknown (RT =16.6 min)
• diisobutyl phthalate
• triphenyl phosphine
• dioctyl phthalate
• phenyl diphenyl phosphinate
• triphenyl phosphine oxide
The mass spectra for the four unknown compounds are shown in Fig-
ure 58.. Results .for the spiked water sample (W-5) at this site
are described in Section 7.2.2.
11.2.3 Soil and Sediment Samples
A total 15 soil samples and 2 sediment samples were collected in
the area of the Dow Chemical USA plant, Plaquemine, La. The lo-
cations of these samples are shown in Figure 59. Of-the samples
taken 5 soil samples, S-6, S-7, S-8, S-9 and S-10, and both sedi-
ment samples were analyzed. For details on the sampling procedure
used see Sections 4.3 and 4.4. Fifty grams of each sample were
Soxhlet extracted with methylene chloride. The extracts were
concentrated and analyzed via GC/MS/SIM.
None of the seven soil and sediment samples contained the six
3-chloroethers of interest. The average detection limit for soil
and sediment samples equaled 4 x 10~9 g/g.
162
-------
FRN 7*7a SPECTRUM 127 RETENTION TlPIE 6.O
'^.i.'T -»i »3S.0.1«?O,O 96.e, 48.7 83.9, 25.5 40.0, 13.6
M.VT 4: 332.9, .3 394.3, .4 386.7, .5 369.7, .7
PAGE 1 V • 1.e
LI
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.pa
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4
60 88 100 129 140 ISO
^cft—I. ana.
3PECTRUTI FRN 7972 PAC€ 1 V - 1.0<
iso.=,tee.o ss.e, ss.a aee.o. 77.6 ea.o, se.7
231.0, .9 287.8, 1.0 £88.3, 1.8 891.3, .7
.1 I I I .1... . ,1 i , ll,
1.1 ..I
149 16B
MA gilft
"*^ar^
g"*""^"
(a) Unknown(RT=6.0 min)
(b) Unknown (RT=15.3 min)
to
luOPk HȣH JFECTRUfl FRM 7972 ... WWE
!L«...iT4i 13=.*, 100.0 137.0,94.7 "g-J,'88'?. J
U-r-T 4! 2S3.1, .7 BBS.4, 1.8 89O.8. 1.9 8
I -.TK .395 __ _.
I .
: SO
' 40
• ao.
r6
100
' 80
^60
}
40
80
40 60
4uJ|L
»4S I
»«" aga sae_
(c) Unknown (RT=15.7 min)
UORk. ARE>> SPECTRUM FRN 7?72 P«OE 1 V
UWC.ST 41 ISO.O. IOC.« ISS.e. 76.7 146.«, 59.1 13E.O,
Lrt$T 41 SSS.a. .4 29S.6, .3 297.1, 1.1 B9B.1,
• H20 -413
LOO.
!
' 2J9 40 ' S0
.....
i'0S
140 160
4.
aaa
(d) Unknown (RT=16.6 min)
Figure 58. Mass spectra of unknown compounds in downstream #2
water sample, Plaquemine, Louisiana.
-------
Figure 59. Soil and sediment sampling locations for
Dow Chemical USA, Plaquamine, Louisiana.
164
-------
SECTION 12
SAMPLING AND ANALYSIS FOR &-CHLOROETHERS AT
THIOKOL CORPORATION, MOSS POINT, MISSISSIPPI
12.1 PRESAMPLING SURVEY
12.1.1 Description of the Plant Site
Thiokol Corporation is located at 1640 Elder Ferry Road in
Moss Point, Mississippi. The plant produces synthetic rubber
compounds and chemicals. Among the products they produce are
polysulfide rubbers. An intermediate in the production of
the polysulfide rubbers is bis(2-chloroethoxy) methane.
Bis(2-chloroethoxy) methane is prepared by the condensation
of ethylene chlorohydrin with aqueous formaldehyde in the
presence of an azeotroping agent. A possible byproduct of
the formation bis(2-chloroethoxy) methane is bis(2-chloro-
ethyl) ether. Therefore, two compounds of interest to this
c
research request, which could be present at this site, were
bis(2-chloroethoxy) methane and bis(2-chloroethyl) ether.
A presurvey of the Thiokol plant and surrounding area was
performed on June 29, 1977. The presurvey consisted of a
visual inspection of the plant, since contact with plant
personnel was not allowed, and selection of sampling sites
for air and water samples.
165
-------
1
Figure 60 shows the location of the Thiokol plant site in the
Moss Point, Mississippi area topographical map. Also included
on the figure are dimensions for the area surrounding the plant.
The plant occupies an area ^ 0*4 km square. The plant is located
on the north side of the Escatawpa River. The plant is small by
comparison to the other sites described in this report. One major
building, some open construction pilot plant type structures, some
storage vessels, and a water tower constitute the majority of the
plant. Figure 61 is a panoramic photograph of the Thiokol plant
site. The photograph was taken from the southwest corner of the
Thiokol property.
Wastewater from the plant flows down a concrete-lined drainage
ditch under Elder Ferry Road into an open, unlined ditech which
flows into the Escatawpa River. Distance from the road to the
river is ^ 0.2 km. The water flowing down the ditch was reddish-
brown. A small amount of odor was noticed coming from the plant
when standing on the east side of the plant. The plant is served
by a spur from the Mississippi Export Railroad. The plant is
bounded on the south and east by Elder Ferry Road. To the north
and west of the plant are forest areas.
12.1.2 Surround Area
The Moss Point area is on the Mississippi Gulf coastal plain in
extreme southeasternMissississippi. Moss Point is * 8 km
north of Pascagoula, Mississippi. The elevation of the area
ranges from -\» 3 m to 4.5 m above sea level. Moss Point is
located in Jackson County, Mississippi. The population of
Moss Point, which is located south across the river from the
Thiokol plant, is 19,300. A small community northwest of the
plant is named Escatawpa (population 1700). A larger community
south of Moss Point is Pascagoula (population 27,300). The
area along the Escatawpa River is swampy. A number of types
166
-------
\ C.
Figure 60. Topographical map of the Moss Point, Mississippi area
showing the location of the Thiokol Corporation plant
and dimensions of the area around the plant.
-------
a\
co
Figure 61. Composite panoramic photograph of Thiokol Corporation, Moss Point, Miss
-------
of pine trees, deciduous trees and small bushy plants are
found in the area. Spanish moss grows from a number of the
trees. International Paper Company is located upstream on
the Escatawpa River from the Thiokol plant. International manu-
factures kraft paper and kraft board. Zapata Protein, Inc.
and Standard Products, Inc. located east of the Thiokol plant
are fish processing plants. A company named Halter Marine
is located southwest of the Thiokol plant.
12.2 SAMPLING AND ANALYSIS RESULTS
Sampling of the area around Thiokol Corporation, Moss Point,
Mississippi, for 3-chloroethers was conducted on June 29-30,
1977. The conditions, locations and results for the air,
water, soil and sediment samples collected during this sampling
trip are contained in the following subsections.
12.2.1 Air Samples
Seven air samples were deployed around the Thiokol plant on
June 29, 1977 for daylight sampling. Three air samplers were
used to sample around the plant on the night of June 29-30,
1977. The location of all ten air samplers is shown on the
topographical map in Figure 62." A description of the sampling
locations, compass readings relative to the center of the
Thiokol plant, start and stop times, sampling duration, volume
of air sampled and 3-chloroethers detected are listed in
Table 42.
\
Sampling was accomplished using portable personnel samplers,
large Tenax tubes and charcoal backup tubes described in
Section 4.1. Weather conditions were very good during sampling.
The temperature ranged from 21°C at night to 35°C during the
day. The relative humidity was high, and only one very brief
169
-------
I-1
^J
o
Figure 62. Location of air samplers at Thiokol Corporation, Moss
Point, Mississippi.
-------
TABLE "4-2. AIR SAMPLING AT THIOKOL CORPORATION, MOSS POINT, MISSISSIPPI ON 29-30 JUNE 1977
Sample
.(Tenax Tube)
A-l (G-33)
ft»-2 (G-37)
A-3 (G<-39)
A-4 (G-40)
A-5 (G-ll)
A-6 (G-22
A-7 (G-8)
A-8 (LM-3)
A-9 (G-36)
A-10 (G-9)
A-ll (G-16)
A-12 (G-19)
Location
S Bank of Escatawpa River
N Side of Elder Road,
Moss Point
S Side_of Elder Ferry Rd.,
W. of Thiokol
N Side of Elder Ferry Rd.
-v 0.3 km N.E. of Thiokol
N Side of Elder Ferry Rd. ,
•v 0.2 km N.E. of Thiokol
N Side of Elder Ferry Rd.,
^ 0.1 km N of Thiokol
W Side of Elder Ferry Rd. ,
<\- 33 m E of Thiokol
S Side of Elder Ferry Rd. ,
W of Thiokol
N Side of Elder Ferry Rd.,
•v, 0.2 km N.E. of Thiokol
W side of Elder Ferry Rd.,
A, 33 m E of Thiokol
Spiked with 100 ul of BCE
Standard
Control
Compass
Reading
115
210
245
60
55
10
10
245
55
90
-
-
Sampling
Start time
0914(6-29)
0934(6-29)
0953(6-29)
1012(6-29)
1027(6-29)
1035(6-29)
1040(6-29)
1845(6-29)
1900(6-29)
1907(6-29)
-
-
End time Duration, mm
1720(6-29)
1744(6-29)
1838(6-29)
1856(6-29)
1859(6-29)
1902(6-29)
1905(6-29)
0908(6-30)
0925(6-30)
0930(6-30)
-
-
486
490
525
524
502
507
505
863
865
863
-
-
VO 1 . , I
486
490
525
524
502
507
505
863
865
863
-
-
B-chloro-
ethers
detected
_
_
_
_
_
—
BCEXM
_
BCEXM
BCEXM
Section
7.2.1
Section^
7.2.1
-------
shower K5 min) occurred during the sampling. Wind speed and
direction data supplied by the weather bureau at Mobile, Alabama
Airport are shown in Table 43. The wind was primarily from
the south to south-southwest at 5 to 30 km/hr.
Air samples were capped, wrapped to protect against breakage,
and returned by air freight to Dayton. Air samples A-l
through A-5, A-7, A-8 and A-10 were solvent desorbed with metha-
nol. Four cm3 of methanol was used to desorb each tube. The
methanol solutions were then analyzed by GC/MS/SIM. Air
samples A-7 and A-10 were found to contain bis(2-chloroethoxy)
methane. These two samples were located close to the plant
(^ 33 m from the plant) and downwind from the plant. The
concentrations of BCEXM found in these samples were
3.1 x 10~6 g/m3 for A-7 and 8.4 x 10"6 g/m3 for A-10. No res-
ponses were recorded for the six 3-chloroethers in the other
samples analyzed by solvent desorption (average detection limit =
7 x 10~7 g/m3 for day samples and 3.8 x 10"~7 g/m3 for night sample
Air sample A-6 was lost during transit. Air sample A-9 was
thermally desorbed and characterized by GC/MS. A trace of
BCEXM was detected in this sample when the m/e 93 and 63 ions
for BCEXM were recalled for this sample. (Average detection
limit for this sample was 2 x 10~7 g/m3). The total ion chroma-
togram for this sample is shown in Figure 63. The identity of
the peaks in the chromatogram are also included in the same
figure. Compounds found to be present in this sample were:
• methylene chloride
• benzene
• toluene
• xylene
• methyl ethyl benzene
172
-------
TABLE 43.
WEATHER CONDITIONS DURING SAMPLING AT THIOKOL
CORPORATION, MOSS POINT, MISS. 21-35°C
Time (Date)
June 29, 1977
0854
0941
1055
1155
1257
1336
1355
1453
1557
1657
1757
1854
1954
2058
2156
2254
2355
June 30, 1977
0057
0152
0255
0352
0453
0556
0656
0754
0855
0954
Speed , km/hr
20.4
14.8
9.3
13.0
16.7
22.2
24.1
29.6
27.8
27.8
14.8
11.1
7.4
25.9
5.6
16.7
14.8
9.3
11.1
7.4
7.4
7.4
11.1
16.7
14.8
14.8
9.3
Wind
Direction/ degrees
230
250
310
210
200
220
190
190
180
200
200
190
190
080
060
190
200
200
200
180
200
180
220
240
230
250
180
173
-------
** SPECTRUM DISPLftV/EDIT **
THERMAL DESORPTIONt MOSS POJNT A-9, G-36
TENrtX 3O-51O-aOO-30-260-10 GN4L 10/9x77
FRN 7977
1ST SC/PG: 1
X- .35 V- 1.00
TI
I I I I I T I I I I I I I I I I I
10 15 50
I I I I I I
25 30
Figure 63. Total ion reconstructed chromatogram of air sample A-9,
Thiokol Corporation, Moss Point, Mississippi.
-------
• trimethyl benzene
• methyl propyl benzene
• tetramethyl benzene
• acetophenone
• napthalene
Results for the spike samples are described in Section 7.2.1.
12.2.2 Water Samples
A total of seven water samples were collected in the area of
Thiokol Corporation, Moss Point, Mississippi. Two 24-
hour composite (one upstream and one downstream) were collected.
Three 4-liter grab samples (one downstream and two at the
outfall) were also collected. Two 1-liter grab samples were
taken at the upstream location (one sample was spiked with a
mixture of the 3-chloroether and one served as a control). A
complete description of the sample location, times, volumes and
3-chloroethers found are listed in Table 43. The sample loca-
tions are also shown on the topographical map of the area on
Figure 64. The river was ^ 75 m wide at the downstream #1
site, ^ 100 m at downstream #2, -v 75 m at the upstream site,
and the outfall was ^ 2 m wide. Photographs of the drainage
ditch, outfall ditch and downstream #1 site are shown in
Figure 65. The samples were sealed, placed in an ice chest
with foam and ice and the chest was sealed and shipped to MRC-
Dayton.
One liter of each sample was extracted three times with 100 cm3
portions of methylene chloride. These three extracts were com-
bined, concentrated to a volume of -\» 2.5 cm3 in a Kuderna-
Danish evaporator and analyzed by GC/MS/SIM. The 3-chloroethers
found in the samples' and their concentrations are listed in
Table 44. Figure 66 is the SIM chromatogram showing the off-
175
-------
TABLE Uk . WATER SAMPLING AT THIOKOL CORPORATION, MOSS POINT, MISSISSIPPI ON 29-30 JUNE 1977
I-1
-O
Sample
W-l
W-2
W-3
W-4
W-5
W-6
W-7
Location
Downstream 11 from Thiokol outfall, N side
of Escatawpa River, O.I km downstream from
outfall
Upstream from Thiokol, S side of Escatawpa
River, 0.1 km W of International Paper Co.
Thiokol outfall at Elder Ferry Rd.
Downstream 12 at MS 63 bridge, S side of
Escatawpa River
Same as W-2 spiked
Same as W-2 control
Thiokol outfall at Elder Ferry Rd.
Start time
0810 (6-29)
0090 (6-29)
1030 (6-29)
Grab
1200 (6-29)
X3rab
940 (6-30)
Grab
940 (6-30)
Grab
1000 (6-30)
Grab
Sampling
End time Duration, min Volume, I
0920 (6-30) 1510 4
0940 (6-30) 1420 4
4
_ - 4
1
-1
-4
6-chloroethers
detected
BCEXM
none
BCEXM
BCEE
BCEXM
See Section
7.2.2
BCEXM
BCEXM
-------
-J
-J
Figure 64. Location of water samplers at Thiokol Corporation,
Moss Point, Mississippi.
-------
a. Drainage ditch
b. Outfall ditch
c. Downstream #1
Figure 65.
Photographs of water sampling locations at
Thiakol Corporation/ Moss Point, Miss.
178
-------
** SELECTED ION CHROmATOGRAfl **
MOSS PT. OUTFALL *1 2.4481g
Et-GC 1-40/8/260-5 6'TENAX 3UL GN10H 7-80
FRN 7750
1ST SC/PG* 222
X- 1.00 Y- 1.00
vo
63.0
93.i
A- 463266*
.BCEXM
565532.
I
9
I
10
I
11
12
Figure 66. SIM chromatogram of Thiokol Corporation outfall sample #1
(W-3), Moss Point, Mississippi showing BCEXM ions.
-------
scale peaks for BCEXM ions m/e 93 and 63 for outfall sample #1
(W-3). The reason for BCEXM being detected in the control sample
upstream can be explained when it is remembered that the
Escatawpa River is subject to tidal currents due to the proxi-
mity to the Gulf of Mexico.
Table 45- B-CHLOROETHERS FOUND IN MOSS POINT WATER SAMPLES
Sample
W-l
W-2 v
W-3
W-4
W-6
W-7
Description BCEE
Downstream #1
Upstream #1
Outfall #1 6 x 10~7 g/1.
Downstream #2
Control-upstream
Outfall #2
BCEXM
2.5 x 10~7 g/1
-
1.4 x 10"1* g/1
5 x 10-7 g/1
7.5 x 10~7 g/1
1.5 x ICT1* g/1
Outfall sample #1 (W-3) was also analyzed by GC/MS with the MS
operating in the scanned mode. The total ion reconstructed
chromatogram for this sample when chromatographed on a 1% SP 2250
column is shown in Figure 67. Peaks in the chromatogram were
identified as shown in the figure. Compounds found were:
• 1,4 oxathione
• bis(2-chloroethoxy) methane
• unknown (RT=10 min)
• methyl-di-tert-butyl phenol
• unknown (RT=14.5 min)
• hydrocarbon (probably C10 alkane RT=19.7 min)
• hydrocarbon (RT=21.2 min)
• hydrocarbon (RT=22.4 min)
• unknown (RT=22.6 min)
• triphenyl phosphine oxide
• unknown (RT=26 min)
The mass spectra for BCEXM and the unknown at a retention time
of 10.0 minutes are shown in Figure 68. Results for the
spiked samples are reported in Section 7.2.2.
180
-------
V-1
00
SRETCTRUn
OF MOSS PT. OUTFALL*! rtSIS 5UL
EI-GC 6-SP3250 50/8/SS0 GN6H 8/37/77
1ST SC/PGs 1
X« ,25 Y» 1.00
Figure 67. Total ion reconstructed chromatogram of Thiokol
Corporation outfall sample #1, Moss Point, Mississippi,
-------
00
NJ
FRN 7S59 SPECTRUM 162
LARGST m 93.8,100.0 88.8, S7.9
LAST 4« 133.9. .3 141.8, .1
100.
80.
60.
40.
20.
. RETENTION TICIE 6.5
94.8, 31.3 64.8, 18.5
170.9, .7 173.0, .1
PAGE 1 V • l.e
100 180 140 160
niiHll iii
ana aaa a«a gsa
190
80
60,
40.
80
WORK AREA SPECTRUM FRN 7859
LARGST -»t 59.8,100.0 166.0, 96.8
LAST 4« 167.0, 6.1 167.9, 9.8
-264 + 370
PAGE 1 V - 1.00
91.8, 76.9 121.8, 49.a
169.1, .8 ssa.9. ,1
60.
40.
30.
0,
30 40
tee ise 1-40 iee
(a) bis(2-chloroethoxy) methane
(b) unknown (RT=10.0 min)
Figure 68.
Mass spectra from Thiokol Corporation outfall sample #1 (W-3),
Moss Point, Mississippi (see Figure 67) .
-------
12.2.3 Soil and Sediment Samples
Soil samples were taken at the locations shown on Figure 69.
in the area around Thiokol Corporation, Moss Point, Mississippi,
Also sediment samples were taken at the locations shown on
Figure 70. The samples were worked up as described in
Section 5. Soil samples S-3, S-4, S-5, S-6, S-8 and S-9 and
the three sediment samples were analyzed by GC/MS/SIM. Soil
sample, S-6, the sample closest to the plant was found to
contain 5.8 x 10~7g/g of BCEXM. Two of the sediment samples,
SD-1 the outfall sample and SD-2 the upstream location, were
both found to contain BCEE and BCEXM. The concentrations were
SD-1, BCEE=6.8 x 10~8 g/g and BCEXM=1.4 x 10~7 g/g and
and SD-2, BCEE=1.0 x 1CT8 g/g and BCEXM=2.3 x 10~7 g/g.
183
-------
00
Figure 69. Location of soil samples at Thiokol Corporation, Moss
Point, Mississippi.
-------
H
00
Ul
Figure 70. Location of sediment samples at Thiokol Corporation,
Moss Point, Mississippi.
-------
SECTION 13
SAMPLING AND ANALYSIS FOR 3-CHLOROETHERS AT
UNION CARBIDE CORPORATION, INSTITUTE, WEST VIRGINIA
13.1 PRESAMPLING SURVEY
13.1.1 Description of the Plant Site
Union Carbide Corporation is located on West Virginia Route
25 West of Institute, West Virginia. The plant produces a
wide variety of industrial organic and inorganic chemicals.
Among the compounds reported to have been produced at the
site over the years are ethylene chlorohydrin, ethylene
oxide, bis(2-chloroethyl) ether, 2-chloroethyl vinyl ether,
propylene oxide, bis(2-chloroisopropyl) ether, and 1,2-
bis(2-chloroethoxy) ethane (1, 45). While most recent reports
tended to indicate ethylene oxide and propylene oxide are
no longer produced at this site or the Union Carbide South
Charleston plant, the production status of the 3-chloroethers
was unknown.
A presurvey of the plant area was performed on August 18,
1977. The presurvey consisted of visual inspection of the
Union Carbide complex, since contact with plant personnel
was not allowed, and selection of sites for air and water
sampling.
The Union Carbide complex at Institute is a series of
buildings of open and closed construction, distillation
186
-------
towers, cooling towers, liquid storage tanks and a power
plant. The ^Location of the complex is illustrated on the
topographical map of the area in Figure 71. Union Carbide
occupies the area between West Virginia 25 and the
Kanawha River at the west edge of Institute, West Virginia.
The plant property encompasses an area ^2.4 km long (NW
to SE) and ^0.5 km wide (NE to SW). Figure 72 shows the
dimensions of the area on the topographical map. The complex
is bounded on the north by WV 25, on the east by the West
Virginia Rehabilitation Center, on the south by the Kanawha
River and on the west by a scrap iron company and open fields.
Figure 73 is a panoramic photograph of the Union Carbide
complex. The photograph was taken from a hill north of the
complex.
»
13.1.2 Surrounding Area
The Institute area is located on the north bank of the Kanawha
River in west central West Virginia approximately 10 km west
of Charleston, W. Va. Elevation of the area ranges from 175 m
at the river to 325m at the tops of surrounding hills. The
whole area is a series of hills and valleys enclosing the
entire Kanawha River valley- To the east of the plant are
the towns by Institute (pop. 2700), Dunbar (pop. 9151) and
the city of Charleston (pop.71,505). Southwest of the plant
is Saint Albans (pop.14,356). To the west is of the complex is
Nitro (pop. 8019). Directly north of the Union Carbide
site is a series of steep hills with a very few single family
dwellings.
Industry in the immediate area of the Union Carbide complex
included Appalachian Power's Turner station, Criss and
Shaver and Kim Ballard Machine. Other major chemical plants
upstream from Carbide are Du Pont, FMC and the Union Carbide
South Charleston plant.
187
-------
00
00
IQ^^SW
^ •'•M-rrffsfs-s^i'. • •>• M- TT"^-,-.^
Figure 71. Location of Union Carbide Corporation plant on topographical
map of Institute, W. Va. area.
-------
00
UNITKC
PEPARTMENT
GEOLOGIC
45'
Figure . 72.
Dimensions of the Union Carbide complex and location of
upstream water samples at Institute, W. Va.
-------
Figure 73. Composite panoramic photograph of Union Carbide Corporation,
Institute, West Virginia.
-------
Vegetation in the area includes a number of species of
deciduous trees (including oaks and elms), bushes and weedy
ground cover. The banks on the south side of the Kanawha River
downstream from the Union Carbide plant are extremely steep.
In addition the north bank of the river is completely lined
with private single family dwellings.
Visible emissions from the plant included steam from various
vents and stacks, gray smoke from the power plant and a very
dense white smoke tinged yellowish brown from a small plant
on the north side of WV 25. This plume had a very strong
nitric acid odor. Also a very strong, indistinct odor was
coming from the Carbide plant proper.
13.2 SAMPLING AND ANALYSIS RESULT
Sampling of the area around Union Carbide Corporation,
Institute, West Virginia for p-chloroethers was conducted on
18-19 August 1977. The conditions, locations and results for
air, water, soil and sediment samples collected during this
sampling trip are contained in the following subsections.
13.2.1 Air Samples
Air samplers were placed around the Union Carbide plant in the
configuration shown in Figure 74. Seven samplers of the
personnel sampling type described in Section 4.1, were
used for sampling for g-chloroethers in the air around Carbide
during the day light on 18 August 1977. B-Chloroethers were
collected on the large style Tenax GC tubes; a charcoal
tube was used as backup. Three samples were collected using
the same type samplers during the night of 18-19 August 1977.
Weather was good during daylight hours with winds light and
variable and a high temperature of 24°C. At night a fog
occurred and wind was almost non-existent. Weather data for
191
-------
vo
Figure 74. Air sampling locations at Union Carbide, Institute, W. Va.
-------
the sampling periods are shown in Table .46. After sampling
the tubes were capped with polyethylene slip-on type caps
and wrapped with paper towels to insure against breakage.
Table 47 lists the sample numbers, sampling location, compass
reading relative to the center of the plant, sampling start
and stop time, duration of sampling, volume of air sampled
and 3-chloroethers detected.
The tubes were returned to the laboratory and desorbed and
analyzed as described in Sections Sand 6. Air samples A-l,
A-2, A-4, A-5, A-6, A-8, A-9, and A-10 were solvent desorbed
and analyzed by GC/MS/SIM for the six 3-chloroethers. Average
detection limit for day samples was 7 x 10~7 g/m3 and
3.9 x 10"7 g/m3 for. night samples. Air sample A-3 was
thermally desorbed for characterization by scanned mass
spectrometry. Air sample A-7 was lost during thermal
analysis. The total ion reconstructed chromatogram for
A-3 is shown in Figure -75. The compounds identified by
their mass spectra are shown in the same figure and listed
below.
• trichloromonofluoromethane
• methylene chloride
• benzene
• toluene
• chlorobenzene
• ethyl benzene
• isopropyl benzene
• methyl ethyl benzene
• benzaldehyde
• nitrotoluene
193
-------
TABLE 46. WEATHER CONDITIONS DURING SAMPLING AT
UNION CARBIDE, INSTITUTE, W. V. 11-24°C
Wind
Time (DATE) Speed, km/hr Direction, degrees
August 18, 1977
1055 5.6 350
1155 3.7 050
1255 11.1 360
1355 9.3 300
1455 9.3 200
1555 5.6 300
1655 11.1 310 -
1755 11.1 330
1855 9.3 350
1955 5.6 350
2055 5.6 100
2155 0
2255 0
2355 0
August 19, 1977
0055 , 0
0155 * 0
0255 3.7 080
0355 5.6 040
0455 5.6 090
0555 5.6 090
0655 3.7 050
0755 0
0855 0
0955 • 0
1055 5.6 340
194
-------
TABLE
AIR SAMPLING AT UNION CARBIDE, INSTITUTE, W.V. ON 18-19 AUGUST 1977
Sampling
Sample
(Tenax Tube)
Al XG-37)
A2 (G-49)
A3 (G-14)
\ A4 (G-13)
H A5 (G-24)
VO
Ui
A6 (G-10)
A7 (G-ll)
A8 (G-41)
A9 (G-31)
A10 (G-12)
Compess
Location Reading
S side of W 25, 3 km W of
1-64
S side of WV 25, 1.6 km W of
1-64
N side of W 25, 0.4 km W of
1-64
WV Rehabilitation Center
Campus in Institute, WV -
0.75 km SE of Plant Center
S side of WV 25 at inter-
section with Ave. A, 75m E
of 1-64 0.85km NE of plant
E side of Ave in West Vir-
ginia State College campus,
10m from Kanawha R. , 0.95
km SE of plant center
S side of US 60, 0.35 km W
of Kanawha Terrace in St.
Albans, W.V., 0.87 km SW of
plant
N side of WV 25, 0.4 km W
of 1-64
S side of WV 25 at inter-
section with Ave. A, 75m E
of 1-64 0.85m NE of plant
S side of US 60, 0.35 km W
of Kanawha Terrace in St.
Albans, W.V., 0.87 km SW
of plant
270
300
20
130
90
140
210
20
90
210
Time
Start
1111
1125
1135
1150
1200
1219
1245
1950
2023
2040
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
End
1920
1930
1940
1957
2012
2005
2035
1000
1010
930
Duration , Volume ,
min liter
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-18)
(8-19)
(8-19)
(8-19)
489
485
485
487
492
466
470
850
827
770
489
485
485
487
492
466
470
850
827
770
6 -Chloroethers
detected
None
None
None
None
None
None
None
None
None
None
-------
THERMAL DESORPTION:
TEMH.X 3O-? "1C.
* SPECTRUM DISPLAY/EDIT **
INSTITUTE A-3,G-14
lO GN4L
FRM 7979
1ST SC/PG: 1
X- .85 V- 1.00
vo
Figure 75. Total ion reconstructed chromatogram of air sample A-3,
thermally desorbed, Union Carbide, Institute, W. Va.
-------
13.2.2 Water Samples
Because of the steep south banks of the Kanawha River, which were
heavily covered with thorny bushes, and the large population
of single family dwellings along the north bank, we were
unable to obtain the two downstream and one upstream 24-hour
composite water samples desired. One composite 24-hour sample
was taken downstream -^5 km from the Union Carbide outfall. The
locations of the other grab water samples taken for the site
are shown on the topographical map in Figure 76 for the
outfall and downstream samples and Figure 72 for the upstream
samples. A description of all of the water sampling sites is
included in Table 48- Included in this table are sampling
times, volume of sample collected and 3-chloroethers detected.
Sample W-l, downstream #1, was taken at Mitch's Marina in St.
Albans, W.V. on the south bank of the Kanawha. The surface
of the river was covered with an oily film. Water sample W-2
was taken as a 24-hr composite sample on the north bank of the
Kanawha, behind a Pentacostal church. Water samples W-3,
W-4, and W-5 were taken as upstream samples from the north
bank of the Kanawha River at 17th Street in Dunbar, W.V.,
Sample W-4 was spiked &-chloroether standard solution. Water
sample W-6 was collected from a boat, 6 m from the north -bank of the
Kanawha just downstream from the Union Carbide Environmental. Center.
Sample W-7 was also obtained from the boat 1.5. m downstream
from the farthest downstream visible Union Carbide outfall.
The Kanawha River was muddy and contained numerous branches,
logs and other debris. Local residents stated that areas
in the Kanawha watershed had had heavy rains recently.
Photographs of the outfalls and the sampling location just
downstream from the Union Carbide Environmental Center are
shown in Figure .77.
197
-------
vo
00
£WW$
ti&SFW. Kit
> / f f^L. >K/ f\ f'f * .£. * j •'• ^^Sk N' ^ II •/ /
~-^.^V\XN. V^la,'* ^\ ^JH£»:'-.;n ^vt/
Figure ,76. Downstream and outfall water sampling locations at Union
Carbide, Institute, W. Va.
-------
TABLE ^8.. WATER SAMPLING AT UNION CARBIDE, INSTITUTE, W. V. en 18-19 AUGUST, 1977
Sample
W-l
W-2
W-3
W-4
W-5
W-6
W-7
Location
0.1 km E of 3rd St. bridge
at Marina
0.3 km W of 3rd St. bridge
behind Nazairene Church
17th St. N bank of Kanawha
River - Dunbar, WV
17th St. N bank of Kanawha
River - Spike
17th St. N bank of Kanawha
River - Control
Outfall 12 just downstream
from Union Carbide En-
vironmental plant
Outfall #1 1.5 m down-
stream from farthest
downstream Union Carbide
outfall
Sample
Time Duration ,
1315
1010
1030
1030
1030
1330
1325
Start
(8-18)
(8-18)
(8-19)
(8-19)
(8-19)
(8-18)
(8-18)
End min
GRAB
945 (8-18) 1415
GRAB
GRAB
GRAB
GRAB
GRAB
Volume ,
liter
4
4
4
1
1
4
4
B -chloroethers
detected
None
None
None
See Section
See Section
None
None
7.2.2
7.2.2
-------
River downstream from
Union Carbide Center
Outfall downstream #2
c. Outfall downstream #3
d. Outfall downstream #1
Figure 77. Photographs of water sampling locations and
outfall at Union Carbide, Institute, West
Virginia.
200
-------
The samples were extracted, concentrated and analyzed as
described in Sections 5 and 6. None of the samples except
the spiked upstream sample, W-4, were found to contain g-
chloroethers. Results for sample W-4 are reported in Section
7.2.2. The extract of water sample W-7, the sample taken
1.5m from the farthest downstream of the visible outfalls,
was characterized by GC/MS in the scanned mode. The total ion
reconstructed chromatogram for this sample is shown in Figure
78. Compounds identified are listed on the figure and below.
A series of silicones characterized by m/e ions of 73 and
147 are indicated on Figure 78 by S's. .These mass-to-charge
ions are characteristic of a series of silicones having the
structure shown below (66).
C
H
CH-Si— IO-Si-
n=0,l,2,3
m/e n
73
147
221
295
0
1
2
3
Figure 79 shows the total ion chromatogram and single ion traces
for masses 73 and 147 of the silicones.
• dichlorobenzene
• phenyl ether
• 2,2,4-trimethyl penta-l,3-diol diisobutyrate
• diethyl phthalate
• unknown (RT=13.9 min)
• di-h-butyl phthalate
• dioctyl phthalate
• unknown (RT=25 min)
201
-------
CHARACTERIZATION:
.*.* SPECTRUM DISPLAY' ED IT **
INSTITUTE OUT R-l 3UL
GM6H 10/3/77
FRU
1ST
7367
Y-
to
o
TI
I I I I I 1
PC;
Figure 78. Total ion reconstructed chromatogram of water sample
W-7, Union Carbide, Institute, West Virginia.
-------
CHARACTERIZATION
SO.'S 2
•147.0
to
o
U)
** SPECTRUM DISPLAY/ EDIT **
INSTITUTE OUT R-I SUL
GN6H 10x3/77
FRN 7967
1ST SC/PG: 1
' .35 V" 1.00
»v4-JljJUill^^
i i i i i I I
Figure 79
Total ion reconstructed chromatogram and single ion
chromatograms for m/e ions 73 and 147 for water sample
W-7, Union Carbide, Institute/ West Virginia.
-------
Figure 80 is the mass spectra of unknown compounds at retention
times 13.9 and 25.0 min.
13.2.3 Soil and Sediment Samples
A total of eight soil samples and one sediment sample were
collected at the locations shown in Figure 81 in the area
surrounding Union Carbide, Institute, W.V. The samples were
collected in 500 cm3 capacity canning jars. These samples
were extracted, concentrated and analyzed as described in
Sections 5 and 6. None of the six $-chlorethers of interest
were found in any of these nine samples. Average detections
limit for soil and sediment samples for the 8-chloroethers was
4 x 10~9 g/g.
204
-------
UORK AREA SPECTRUM FRN 7967 PA6E 1 V - 1.06
LARGST 41 353.1. 100. O 254. 1, 31.8 255.1. 13.1 195.1. 11.1
L«*T 4: 337.0. .5 295. 9. .3 397.6, .4 299.3, .4
-291 + 29S
IOO
SO
60.
4O.
20.
0
109
to ! '
O 80.
Ul
'
60.
40.
30.
0
*
' 30 ' 40 ' 60 ' 80 ' 100 ' 130 ' 140 ' 160
1
ll'l III llljl- II ll'lllt 1 lllll-UI Irmiml llllllli uiHlJI'illlmii inlllni lililuli ilii|ii HIM 1 |
1 ifl« ' pee ' PP*» ' a4e ' pea ' ana aea zsi
UORk AREA SPECTRLjm FRN
LAC-T"4! 283 !a^ l!0
«• PSO -S57
too
SO
1 60
40.
2O.
0
100
80
. 60
! 40.
20
0
|
""' 20' '""
(InpUf,
1 1
ll
taa '
40
III! 1 ll
pea
7967
179.0, 88.7
291.3, • 2.3
Hinntiliiiliiinnn 1
60 '
illl'lili|illl uil|lilrt
80
llllll
40 '
PAGE i v - i.ee
187.0, 7S.3 134.9. 47.9
397.3. 11.8 399.3, 8.1
ill iiiltm|l|lli|iiiillritim illllllil
100 120
1 1.Jl,,!,,,.!,,,,,,.,!!!!,,!,,,
aee ssa
lilf|hn-Mi|llH
L
140 160
||
-tea* ' -K?R
(a) Unknown (RT=13.9 min)
(b) Unknown (RT=25.0 min)
Figure 80. Mass spectra of two unknowns in water sample W-7
extract (see Figure F-8 for chromatogram).
-------
N>
O
Figure 81. Soil and sediment sampling locations at Union Carbide,
Institute, W. Va.
-------
SECTION 14
SAMPLING AND ANALYSIS FOR g-CHLOROETHERS
MILLIKEN CHEMICAL, INMAN, SOUTH CAROLINA
14.1 PRESAMPLING SURVEY
14.1.1 Description of the Plant Site
Milliken Chemical Division is located on Campton Road southwest
of Inman, South Carolina. The plant's mailing address is P.O.
Box 817, Inman, SC 29349. The plant specializes in the produc-
tion of high quality, organic chemicals widely used in the
textile and related industries and as intermediates in the
synthesis of dyestuff and other chemical intermediates. Sampling
by EPA Region IV revealed the presence of bis(2-chloroethyl) ether
and 1,2-bis(2-chloroethoxy) ethane in the wastewater effluent
from this plant. The plant was required in their NPDES permit
issued by the South Carolina Department of Health and Environ-
mental Control to monitor bis(2-chloroethyl) ether and 2-
chloroethanol for the period 18 March 1976 through 30 June 1977.
A presurvey of the plant area was performed on 23 August 1977.
The presurvey consisted of a visual inspection of the Milliken
plant site, since contact with plant personnel was not allowed,
and selection of sites for air and water sampling.
207
-------
The Milliken Chemical Division at Inman consists of two large
buildings and a number of small buildings. Only one main stack
^ 12 m high was present at the plant site. The only visible
emissions were a number of steam vents. No odor was present in
the area during presurvey or sampling. The wastewater treatment
and outfall of the plant were not visible from areas accessible
around the plant. It was known from the NPDES permit that the
water effluent of the plant was received by Lawsons Fork Creek.
The location of the Milliken plant and surrounding area known
to be owned by Milliken are shown in Figure 82. The dimensions
of the site are also indicated on Figure 82. The site occupies
a triangular area 0.37 km x 0.3 km x 0.5 km. The short side of
the triangle fronts on Campton Road. A road at one time ran
through the property, butr.ij. has since been closed and fenced.
The plant site is bounded on the NE by Campton Road, on the south
and northwest by pine forests. Only a few houses along Campton
Road near the plant. A panoramic photograph of the plant is
shown in Figure 83.
14.1.2 Surrounding Area
The Inman area is located in northwest South Carolina, ^ 8 km
north northwest of the city of Spartanburg, S.C. Elevation of
the area ranges from 260-290 m above sea level. The population
of Inman is 1661. Two other small towns in the area are
Campobello (pop. 530) and Boiling Springs (pop. 600). The
population of Spartanburg is 44,546. The Milliken plant is
located in Spartanburg County, S. C.
Industry in the area of the Milliken Plant included Byars
Asphalt Terminal, which was 0.6 km southeast and Carolina
Frozen Food, 0.3 km to the northeast. Vegetation in the area
consisted of pine trees, 6 to 9 m high and 0.1 m in diameter,
deciduous trees including maples and creek willows, and a
number of bushy plants and vines along Lawsons Fork Creek.
208
-------
to
o
VD
Figure 82. Location and dimensions of the Milliken Chemical
Division plant, Inman, S. C. on the topographical
map of the area.
-------
4101-25
to
M
O
Figure 83.
Panoramic photograph of Milliken Chemical Division, Inman, S. C. and
a photograph of the main entrance to the plant.
-------
14.2 SAMPLING AND ANALYSIS RESULTS
Sampling of the area around Milliken Chemical Division, Inman
South Carolina for 3-chloroethers was conducted on 23-24 August
1977. The conditions, locations and results for air, water,
soil and sediment samples collected during this sampling are
contained in the following subsections.
14.2.1 Air Samples
Air samplers were placed around the Milliken plant in the con-
figuration shown in Figure 84. Seven personnel type samplers
were employed for this sampling trip. A description of the
samples, the Tenax tubes used to adsorb the B-chloroethers and
the charcoal backup tubes are included in Section 4.1 of the
main body of this report. Two samples were obtained the
evening of 23-24 August 1977 and seven samples were collected
during daylight hours on 24 August 1977. Table 49 lists the
samples, where they were located, the compass reading relative
to the center of the plant, sampling start, stop, duration and
volume and 3-chloroethers detected. Wind speed and direction,
supplied by the weather bureau at Greenville-Spartanburg
Airport, Greer, S.C. are listed in Table 50. The temperature
during sampling ranged from 21°C to 31°C. A light rain shower
occurred during air sampling on 24 August from 1130 to 1230.
The winds during sampling, except during the shower, were very
light and variable in direction. After sampling the tubes
were capped with polyethylene slip-on caps and wrapped for
shipment to Dayton.
211
-------
NJ
t->
NJ
\>
Figure 84. Air sampling locations at Milliken Chemical
Division, Inman, S. C.
-------
TABLE 49. AIR SAMPLING AT MILLIKEN CHEMICAL DIVISION, INMAN, S.C. 23-24 AUGUST 1977
W
Sampling
Sample
(Tenax tube)
A-l
A-2
A- 3
A-4
(G-45)
(G-52)
(G-15)
(G-40)
Location
Compass
reading
0.05 km E of Milliken, 20 m
from Campton Road 60
0.05 km E of Milliken, 30 m
from Campton Road 80
0.05 km E of Milliken, 20 m
from Campton Road 60
0.05 km E of Milliken, 30 m
from Campton Road
A-S
A-6,
A-7
A- 8
A-9
(G-50)
(G-51)
(G-27)
(G-17)
(G-20)
0.10
0.30
0.20
0.60
0.60
km SE of Milliken
km SE of Milliken
km NE of Milliken
km NW of Milliken
km W of Milliken
80
110
140
30
340
270
Time
Start
1935
1950
1020
1035
1045
1055
1110
1125
1140
(8-23)
(8-23)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
Duration,
End
1010
1027
1740
1840
1845
1852
1900
1906
1924
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
(8-24)
min
875
877
440
485
480
477
470
461
464
Volume ,
liter
1225
965
616
485
480
477
470
461
464
B -chlorethers
detected
None
None
None
None
None
None
None
None
None
-------
TABLE 50. WEATHER CONDITIONS DURING SAMPLING AT
MILLIKEN CHEMICAL, INMAN, S. C., 21-31°C
Time (Date)
August 23, 1977
1855
1957
2055
2155
2255
2355
August 24, 1977
0055
0156
0257
0356
0455
0555
0655
0757
0857
0956
1057
1155
1255
1355
1455
1555
1655
1755
1855
1955
Speed , km/hr
0
7.4
0
0
0
7.4
7.4
7.4
0
0
0
7.4
9.3
9.3
9.3
7.4
25.9
7.4
14.8
13.0
7.4
5.6
7.4
7.4
0
0
Wind
Direction, degrees
-
150
—
—
—
160
170
190
-
—
—
180
170
200
220
220
140
340
040
340
270
350
330
190
—
—
214
-------
The tubes upon return to the laboratory were desorbed and
analyzed as described in Sections 5 and 6. Air samples A-2
through A-9 were solvent desorbed and analyzed for the six
B-chloroethers of interest by GC/MS/SIM. None of the samples
contained 3-chloroethers. Average detection limit for samples
collected during daylight was 7 x 10~7 g/m3 and 3.9 x 10~7 g/m3
f9r sample A-2 collected at night. Air sample A-l was thermally
desorbed for characterization by scanned GC/MS. The total in
reconstructed chromatogram for A-l is shown in Figure 85 and
the compounds identified by their mass spectra are shown on
the same figure and listed below.
• 1,2-dichloroethane
• trichloroethylene
• toluene
tetrachloroethylene
• ethylbenzene
• chlorobenzene
• benzaldehyde
dichlorobenzene
• acetophenone
• nitrotoluene
Detection limit for the 3-chloroethers for sample A-l were
•\> 2 x 10"7 g/m3.
14.2.2 Water Samples
Three 24-hour composite water samples were taken during
sampling at Milliken Chemical, Inman, S. C. Wastewater
from the Milliken plant was known to flow into Lawsons Fork
Creek, which eventually empties into the Pacolet River near
Spartanburg, S.C. The locations of the one^upstream and two
downstream water sampling sites are shown in Figure 86.
215
-------
TEHHN 3
tt SPECTRUM DISPLAY 'CD IT
DESORPTION: INMAN A-I,
30-260-10
FPH 7980
1ST SCXPG: 1
.» .as v- 1.00
to
TI
10
T I I
T I I
15
T I I
T I I
T I I
Figure .85. Total ion reconstructed chromatogram of thermally desorbed air
sample, A-l, Milliken Chemical, Inman, S.C.
-------
K)
H1
Figure 86. Water sampling locations at Milliken Chemical,
Inman, S. C.
-------
Lawsons Fork Creek at all three locations is -v» 6-9 m wide. At
the upstream location the water had a slight froth on top. At
the two downstream locations, the water was darker than at the
upstream location and had a slight petroleum odor. The sample
numbers, locations, sampling start, stop, duration and volume,
and the 3-chloroethers detected are listed in Table 51. At
all three sampling locations the banks of Lawsons Fork Creek
i
were overgrown with bushes, trees and vines.
The samples were extracted, concentrated and analyzed as
described in Sections 5 and 6. The two downstream locations were
found to contain bis(2-chloroethyl) ether. Water sample W-2,
downstream #1, was found to contain 4.8 x 10~6 g/1 of BCEE.
Figure 87 is the SIM chromatogram for W-2 showing the m/e 93
and 63 ions of BCEE. Water sample W-3, downstream #2, was found
to contain 4.6 x 10"6 g/1 of BCEE. Figure 88 is the SIM
chromatograms for W-3 showing the m/e 93 and 63 ions of BCEE.
The extract of water sample, W-2, downstream #1, was characterized
further by scanned GC/MS. The total ion reconstructed
chromatogram for this sample is shown in Figure 89. The peaks
for which mass spectra were identified are shown in the same
figure and the compounds are listed below.
• 2,6-di-tert-butyl-4-methyl phenol
• bis-(2-chloroethyl) phthalate
• unknown (RT=19.9 min)
• unknown (RT=22.1 min)
• dioctyl phthalate
• triphenyl phosphine oxide
i
The mass spectra of the two unknown compounds are shown in
Figure 90.
218
-------
KJ
H
VO
TABLE 51. WATER SAMPLING AT MILLIKEN CHEMICAL DIVISION, INMAN, S.C. 23-24 AUGUST 1977
Sampling
Sample
W-l
W-2
W-3
Time
Location
Upstream, 1.2
Downstream fl
Milliken
Downstream #2
Milliken
km
, 1.
, 2.
W
0
0
of
km
km
Milliken
SSE of
SE of
Start
1757
1845
1910
(8-23)
(8-23)
(8-23)
1755
1815
1830
End
(8-24)
(8-24)
(8-24)
Duration , Volume ,
min liter
1438 ^4
1410 ~4
1400 '*4
B -chloroe ther s
detected
None
BCEE
BCEE
-------
to
to
o
SELECTED ION CHROMATGGRAm **
INMAN DU-1 3UL
TENrtX 14O'S'£6O GNliH 9/13/77
J121.O
45.0
63.0
93.01
1 1
FPN 7898
1ST SC/PG: 233
" 1.00 V" 1.00
ia
Figure 87. SIM chromatograms of water sample, W-2, Milliken Chemical, Inman, S.C.
-------
to
fO
SELECTED ION C
DU-E 3UL
45.0
63.
93.0
GNUH 9x is/77
i
10
** FPN 7899
1ST SC/PGi 333
X- 1.00 Y- 1.00
11
i
13
Figure 88. SIM chromatogram of water sample, W-3, Milliken Chemical, Inman, S.C,
-------
CHARACTERIZATION
so S
** SPECTRUM DISPLACED IT
inn AN DU-I 3UL
**
... .. ...
10
to
ro
TI
FRN 7971
1ST SC/PG* 1
» .as v- 1.00
IS
I I
I T
20
I I I
Figure 89.
Total ion reconstructed chromatogram of water sample,
W-2f Milliken Chemical, Inman, S.C.
-------
UOF
LAP
LA;
100
SO
60
40
50
0
100
60
40
30.
0
!K AREA SPECTRUM FRM
'GST 4! 12S.P, 1OO.0
?T 4: 395.9, .5
IS + 5«>9
r nlid A HIM
iae
,-,l,l,
,1 ,.J|
see
i,,.,,,
J
7971
63.1, 84.7
397.1, .5
' J
. J ..ii, h. tin.
60 80
,,,,,,,i, i
2P0 540
43.0, 55.
397.7,
JL
1,11
100
260
Lu
PAGE 1 V - 1.00
3 105.9, 51.3
8 399.0, .3
i. . • ill ... .it .LI i.i
130 1-40 160
'•'•''•'a^S ^a£ sS,
(a) Unknown (RT=19.9 min)
UOF:
LAS
too.
SO
40.
30,
0
100.
30.
60.
•K AREA SPECTRUM FRN 7971
'•35T •»: 149.1.1OO.O 55.0
-T •): 391.1, 1.8 392.9
••= + 5TO
40.
30.
„'
ll.
• Illll 1 1 I I 1
30 40
1 'I'niiijilili 1* ill Mih
Unit
ini
60
PAGE IV- 1.00
, 56.9 63.0, 47.3 166.8, 43.0
, 1.4 393.7, .6 397.7, 3.1
I'll IlllllilPllllllllll lUllllll'Ill 1 'ill I'll
, . 1.1.
80 100 130 140 160
(b) Unknown (RT=22.1 min)
Figure 90. Mass spectra of two unknown compounds,
(see Figure 89).
223
-------
14.2.3 Soil and Sediment Samples
Eight soil samples and three sediment samples were collected
as described in Sections 4.3 and 4.4 around the Milliken Chemical
plant, Inman, S. C. The sampling locations were shown in Figure
91. The samples were analyzed as described in Sections 5 and 6.
None of the eleven samples contained the six g-chloroethers of
interest. Average detection limit for these samples was
4 x 10~9 g/g.
224
-------
NJ
Figure 91. Soil and sediment samples locations around Milliken
Chemical, Inman, S. C.
-------
SECTION 15
SAMPLING AND ANALYSIS FOR 3-CHLOROETHERS AT
EASTMAN KODAK COMPANY, ROCHESTER, NEW YORK
15.1 PRESAMPLING SURVEY
15.1.1 Description of the Plant Site
Kodak Park Division of Eastman Kodak Company is located along
Ridge Road in northwest Rochester, New York. The address for
the location is 1669 Lake Avenue, Rochester, New York 14615.
Kodak manufactures a large variety of chemicals for both
industrial and photographic purposes. Among the chemicals
reported to be manufactured at Kodak is propylene chlorohydrin,
which has as a by-product bis(2-chloroisopropyl) ether.
A presurvey of the Kodak Park complex was performed on
29 August 1977. The presurvey consisted of visual inspection
of the complex,.since contact with plant personnel was not
allowed, and selection of sites for air and water sampling.
The Eastman Kodak complex at Rochester is a huge facility
occupying nine distinct locations. Chemical manufacture is
performed at Kodak Park Division, 200 Ridge Road and Distilla-
tion Products Industries, 2255 Mt. Read Blvd. Well over 300
buildings are included in the site. Stacks and vents are too
numerous to cite specifically. The location of the Kodak Park
complex is shown on the topographical map of the area in
226
-------
Figure 92. The water used by the complex is treated at the
Kings Landing Waste Treatment Facility and flows into the
Genesee River. Figure 93 shows a number of photographs of the
waste treatment facility taken from Seneca Park across the
Genesee River gorge. In the background of these photographs can
be seen a few of the major buildings of Kodak Park. Figure 94
shows the dimension of the Kodak Park area. Kodak Park is
bounded on all sides except the east by residencial housing
and small businesses. On the east the site is bounded by the
Genesee River.
15.1.2 Surrounding Area
The city of Rochester is located in northwest New York state
along both sides of the Genesee River. Rochester is located
in Monroe County, New York, 15 km from Lake Ontario. Elevation
of the area ranges from 76 m at the lower level of the Genesee
River to 160 m. The area is fairly flat except for the area
around the Genesee River. The banks of the Genesee River gorge
drop almost 50 m in a distance of less than 50 m at the down-
stream #1 water sampling location. Population of Rochester is
282,000. Vegetation in the area includes a number of species
of deciduous trees. No visible emissions, other than those from
power plants, and no odors were found at the Kodak site during
presurvey or sampling.
15.2 SAMPLING AND ANALYSIS RESULTS
Sampling of the area around Eastman Kodak, Rochester, New York
for 3-chloroethers was conducted on 29-30 August 1977. The
conditions, locations and results for air, water, soil and sedi-
ment samples collected during this sampling trip are included
in the following subsections.
227
-------
EASTMAN KODAK
KODAK
Figure 92.
Topographical map showing Kodak Park
Division, Eastman Kodak, Rochester,
N. Y.
228
-------
"3T '
Figure 93. Photographs of Kings Landing Waste Treatment Facility and portions of
Kodak Park Division of Eastman Kodak, Rochester, New York.
-------
Figure 94. Dimensions of the Kodak Park Division
of Eastman Kodak, Rochester, N.Y.
230
-------
15.2.1 Air Samples
A total of seven air samples were collected around the Eastman
Kodak complex using methods described in Section 4. The loca-
tions at which samples were collected are shown on the topographi-
cal map of the area in Figure 95. Two samples, A-l and A-2 were
collected during the night of 29-30 August 1977. Five samples
were collected during the day of 30 August 1977. Table 52
describes the samples, their locations, sampling start, stop times,
duration and volume, and 3-chloroethers detected. Weather con-
ditions during sampling were supplied by the weather bureau at
Rochester-Monroe County Airport. The temperature ranged from
18 to 25°C. Wind speed and direction data are shown at hourly
intervals in Table 53. Weather during the sampling period
was very good except for light rains between 2300 on 29 August
and 0100 on 30 August 1977. The sampling tubes were capped
with polyethylene slip-on caps and wrapped for shipment back to
Dayton.
The samples were desorbed and analyzed by GC/MS/SIM as described
in Sections 5 and 6. Samples A-l, A-3 through A-7 were solvent
desorbed. None of these samples contained 3-chloroethers of
interest. Average detection limit for A-3 through A-7 was
7 x 10~7 g/m3 and 3.9 x 10~7 g/m3 for air sample A-l. Sample
A-2 was lost during thermal desorption analysis for characteri-
zation -purposes.
15.2.2 Water Samples
Two 24-hour composite water samples were collected by
the method described in Section 4 from the Genesee River down-
stream from the Kodak Kings Landing Waste Treatment Plant. Also,
one 4-liter and two 1-liter grab samples were taken at a
Rochester Light and Power Station upstream from Kodak on the
231
-------
Figure 95. Air sampling locations at Eastman Kodak,
Rochester, N.Y.
232
-------
TABLE 52 . AIR SAMPLING AT EASTMAN KODAK, ROCHESTER, NEW YORK ON 29-30 AUGUST 1977
Sample
(Tenax tube)
to
U)
CO
A-l (G-19)
A- 2 (G-29)
A- (G-32)
A-4 (G-36)
A-5 (G-8)
A-e' (G-38)
A-7 (G-42)
10 IT V» Of
of NY 104
20 m N of
of NY 18
20 m N of
of NY 18
10 m W of
of NY 104
Location
Lake Ave.
NY 104, 0
NY 104, 0
Lake Ave.
, 1.1 km N
.53 km W
.53 km W
, 1.1 km N
5 m from entrance to Kodak
Waste Treatment Plant
10 m E of
of NY 104
E side of
NY 18, 0.
Maplewood
23 km S
Park Dr . ,
Compass
Reading
60
330
330
60
100
180
120
Start time
1615
1640
900
920
940
1000
1015
8-29)
(8-39)
(8-30)
(8-30)
(8-30)
(8-30)
(8-30)
Sampling
End time
900 (8-30)
850 (8-30)
1745 (8-30)
1717 (8-30)
1730 (8-30)
1738 (8-30)
1725 (8-30)
Duration ,
min
1005
970
525
475
470
458
430
Volume i
liter
1005
970
525
475
470
458
430
P-chloroethers
detected
None
Lost
None
None
None
None
None
0.2 km N of NY 104
-------
TABLE 53
WEATHER CONDITIONS DURING SAMPLING
AT EASTMAN KODAK, ROCHESTER, N. Y.,
AUGUST 29-30, 1977
Date (1977)
and time
August 29
1555
1652
1751
1850
1950
2050
2154
2251
2350
August 30
0051
0150
0251
0352
0450
0550
0650
0755
0858
0953
1055
1155
1252
1355
1454
1555
1650
1753
Speed, km/hr
24.1
20.4
20.4
20.4
13.0
5.6
16.7
11.1
9.3
9.3
13.0
11.1
11.1
14.8
14.8
16.7
14.8
13.0
13.0
7.4
13.0
7.4
11.1
14.8
14.8
13.0
14.8
Wind
Direction, degrees
250
250
240
250
260
140
350
010
280
300
320
290
290
280
290
290
260
260
240
270
320
030
050
010
020
030
050
234
-------
Genesee River. The locations of these water sampling sites are
shown on Figure 96. Table 54 lists the sampling locations,
sampling start, stop, duration and volume, and 3-chloroethers
detected. Downstream #1 water sample, W-2, was obtained by
climbing down the 50 m sides of the Genesee River behind
St. Bernard's Seminary to reach the side of the river. The
river at this point was ^ 100 m wide. Downstream #2 water
sample, W-l, was taken at the Old Genesee River Docks. The
river at this point was ^ 150 m wide. Photographs of the
Genesee River gorge and the downstream #2 sampling location are
shown in Figure 97.
The water samples were analyzed by methods described in
Sections 5 and 6. None of the six B-chloroethers of interest
were found in any of the water samples except the spiked sample,
W-4. Results for the spiked sample are listed in Section 7.2.2.
Downstream #1 water sample concentrate, W-2, was also characterized
by scanned GC/MS. The total ion reconstructed chromatogram for
this sample is shown in Figure 98. The identity of the peaks
is shown on the figure and the compounds are listed below.
• 2,6 di-tert-butyl-4-methyl phenol
• unknown (RT=14.1 min)
• unknown (RT=15.0 min)
• butyl carbobutoxymethyl phthalate
• unknown (RT=18.0 min)
• triphenyl phosphine
• dioctyl phthalate
• triphenyl phosphine oxide
I
Mass spectra of the three unknown compounds are shown in
Figure 99 for future reference.
235
-------
tZL-JL -...-:-fa*.-...-.lETi*;.
Fiqure 96 Water sampling locations at Eastman
Kodak, Rochester, N.Y.
236
-------
TABLE 5lf. WATER SAMPLING AT EASTMAN KODAK, ROCHESTER, N. Y. ON 29-30 AUGUST, 1977.
to
OJ
Sampling
Sample Time Duration, Volume,
(Tenax tube) Start End min liter
W-l W Bank of Genesee River 1336 (8-29) 1615 (8-30) 1599 4
at Old Genesee Docks
W-2 W bank of Genesee River 1430 (8-29) 1645 (8-30) 1575 4
behind St. Bernard's
seminary
B-chloroethers
detected
None
None
W-3
W-4
W-5
E bank of Genesee River 1530 (8-29)
at Rochester Light &
Power
E bank of Genesee River 1530 (8-29)
at Rochester Light &
Power - spike
E bank of Genesee River 1530 (8-29)
at Rochester Light &
Power - control
Grab
Grab
Grab
None
See Section 7.2.2
See Section 7.2.2
-------
NJ
LO
00
Figure 97. Photographs of the Genesee River gorge and downstream #2, W-l, water
sampling location at Rochester, New York.
-------
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Total ion reconstructed chromatogram of downstream #1,
W-2, water sample at Eastman Kodak, Rochester, New York
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240
-------
15.2.3 Soil and Sediment Samples
A total of six soil samples and one sediment sample were collected
during the sampling trip to Eastman Kodak, Rochester, New York.
The samples were collected as described in Section 4. Sampling
locations are shown in Figure 100 on the topographical map of
the area. The samples were worked up and analyzed by the methods
described in Sections 5 and 6. None of the samples contained the
six 3-chloroethers of interest. Average detection limit was
4 x 10"9 g/g.
241
-------
Figure 100.
Soil and sediment sampling locations
at Eastman Kodak, Rochester, N.Y.
242
-------
SECTION 16
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248
-------
TECHNICAL REPORT DATA
(Please read Instructions on the revene before completing)
V REPORT NO.
EPA-560/6-78-003
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Environmental Monitoring Near Industrial Sites;
3-Chloroethers
6 REPORT DATE
June 1978
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Paul L. Sherman, A. Melvin Kemmer, Leroy Metcalfe,
Harlan D. Toy
8. PERFORMING ORGANIZATION REPORT NO
MRC-DA-779
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Monsanto Research Corporation
P. 0. Box 8 (Station B)
Dayton, Ohio 45497
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-1980
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Toxic Substances
Washington, B.C. 20460
13. TVPE Or REPORT AND PERIOD COVERED
Task Final 5/76-6/78
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA project officer for this study is Dr. John Smith (TS 793)
401 M Street, S.W., Washington, D.C. 20460
16. ABSTRACT
Sampling, workup and analysis methods were developed for six 3-chloroethers in air, water
soil and sediment samples to evaluate possible environmental contamination by this class
of compounds. The six ethers were chloroethyl ethyl ether, chloroethyl vinyl ether, bis-
(2-chloroethyl) ether, bis(2-chloroisopropyl) ether, bis(2-chloroethoxy) methane and
bis(2-chloroethoxy) ethane.
Four types of samples were collected near eight industrial sites which were potential
emitters of 3-chloroethers. The sites included four plants where propylene oxide is
produced via the chlorohydrin route. One plant produced propylene chlorohydrin; one
plant produced both ethylene chlorohydrin and propylene chlorohydrin, and had produced
various 3-chloroethers previously; one plant produced intermediates and surfactants for
the textile industry; and one plant produced polysulfide rubbers.
Air samples were collected by drawing air through Pyrex tubes packed with Tenax-GC using
personnel sampling pumps. Water samples were collected either as grab samples or inte-
grated 24-hour samples with a peristaltic pump. Soil and sediment samples were
transported in glass canning jars. Air sampling tubes were desorbed with methanol with
a procedure developed at MRC. Water samples were solvent extracted with methylene
chloride. Soil and sediment samples were Soxhlet extracted with methylene chloride. The
methylene chloride extracts from the water, soil and sediment, samples were each concen-
trated with a Kuderna-Danish evaporator to a volume of 2-3 ml.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
bis(2-chloroethyl) ether
bis(2-chloroisopropyl) ether
bis(2-chloroethoxy) methane
bis(2-chloroethoxy) ethane
2-chloroethylvinyl ether
2-chloroethylethyl ether
GC/mass spectrometer
3-chloroethers
industrial sites
sampling
analysis
4esorption
air
soil
wastewater
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
:. DISTRIBUTION STATEMENT
Releaste Unlimited
19 SECURITY CLASS (THIt Report)
Unclassified
21. NO. OF PAGES
271
20 SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220-1 (t-73)
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