United Sti-tej
Environmental Protection
Agency
Office of Pesticide* and
Toxic Substances
V/RftnglM, DC 2C
EPA-560/13-8OO29
December 1980
Toxic Substances
EPA
Acquisition and Chemical
Analysis of Mother's Milk
for Selected Toxic Substances
-------
EPA 560/13-80-029
ACQUISITION AND CHEMICAL ANALYSIS OF MOTHER'S MILK
FOR SELECTED TOXIC SUBSTANCES
by
Mitchell D. Erickson, Benjamin S. H. Harris, III, Edo D. Pellizzari,
Kenneth B. Tomer, Richard D. Waddell and Donald A. Whitaker
Contract No. 68-01-3849
Task 2
Project Officer: Joseph Breen
Field Studies Branch
Exposure Evaluation Division
Office of Pesticides and Toxic Substances
U. S. Environmental Protection Agency
Washington, DC 20460
December 1980
-------
DISCLAIMER
This document has been reviewed and approved for publication by the
Office of Pesticides and Toxic Substances, U.S. Environmental Protection
Agency. Approval does not signify that the contents necessarily reflect the
views and policies of the Environmental Protection Agency, nor does the
mention of trade names or commercial products constitute endorsement or
recommendation for use.
ii
-------
ABSTRACT
Samples of mother's milk were collected from Bayonne, NJ; Jersey City,
NJ; Pittsburgh, PA; Baton Rouge, LA; and Charleston, WV, and analyzed for
volatile (purgeables) and semivolatile (extractable) organics using glass
capillary gas chromatography/mass spectrometry/computer. In the volatile
fraction, 26 halogenated hydrocarbons, 17 aldehydes, 20 ketones, 11 alcohols,
2 acids, 3 ethers, 1 epoxide, 14 furans, 26 other oxygenated compounds, 4
sulfur-containing compounds, 7 nitrogen-containing compounds, 13 alkanes, 12
alkenes, 7 alkynes, 11 cyclic hydrocarbons, and 15 aromatics were found,
including major peaks for hexanal, limonene, dichlorobenzene, and some
esters. The levels of dichlorobenzene appeared to be significantly higher
in the samples from Jersey City and Bayonne than in samples from other
sites. Jersey City samples also appeared to have significantly higher
levels of tetrachloroethylene. Charleston and Jersey City samples appeared
to have significantly higher levels of chloroform; however, chloroform was
observed in the blanks at about 20% of that in the samples. Due to the
small sample size and lack of control over the solicitation of sample donors,
the data cannot be used to extrapolate to the general population.
Fewer semivolatile compounds of interest were found. Polychlorinated
naphthalenes, polybrominated biphenyls, chlorinated phenols, and other
compounds were specifically sought and not detected (limit of detection
about 20-100 ng/mL milk). Polychlorinated biphenyls (PCBs) and DDE were
found.
-------
CONTENTS
Abstract iii
Figures vi
Tables vii
List of Abbreviations and Symbols ix
Acknowledgments x
1. Introduction 1
2. Summary and Conclusions 15
3. Recommendations 16
4. Selection of Sampling Sites 18
5. Sample Collection 32
6. Sample Analysis Methods 35
7. Results 45
References 61
Appendices
A. Data Collection Instruments 68
B. Sampling and Analysis of Volatile Organics in Milk 104
C. Analysis of Semivolatile Organics Compounds in Milk 112
D. Volatile Compounds Identified in Selected Purges of
Mother's Milk 119
E. Semivolatile Compounds Identified in Selected Extracts of
Mother's Milk 144
-------
FIGURES
Number Page
B-l Diagram of headspace purge and trap system 107
D-l Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 1081 (Bayonne, NJ) 122
D-2 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 1040 (Bayonne, NJ) 125
D-3 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 1107 (Jersey City, NJ) 129
D-4 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 1115 (Jersey City, NJ) 132
D-5 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 2048 (Pittsburgh, PA) 135
D-6 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 2071 (Pittsburgh, PA) 138
D-7 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 3053 (Baton Rouge, LA) 141
D-8 Total ion current chromatogram from GC/MS analysis for volatiles
in sample no. 3111 (Baton Rouge, LA) 143
E-l Total ion current chromatogram from GC/MS analysis for semivolatiles
in sample 1032 (Bayonne, NJ) 146
E-2 Total ion current chromatogram from GC/MS analysis for semivolatiles
in sample 2121 (Pittsburgh, PA) 148
E-3 Total ion current chromatogram from GC/MS analysis for semivolatiles
in sample 3095 (Baton Rouge, LA) 150
E-4 Total ion current chromatogram from GC/MS analysis for semivolatiles
in sample 4093 (Charleston, WV) 152
VI
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TABLES
Number Page
1 Comparison Between Human and Cow's Milk 2
2 Levels of Organic Compounds Found in Human Milk in the United
States 5
3 Ranking of Pesticides and PCBs by Reported Concentrations in
Human Milk 9
4 Levels of Organic Compounds Found in Human Milk Outside the
United States 10
5 Summary of PCN Concentrations Found Near Manufacturing and Use
Sites 19
6 Prevalent Halogenated Compounds in Ambient Air and Water of
Rahway/Woodbridge, Boundbrook and Passaic, NJ 22
7 Estimated Daily Intake of Selected Volatile Compounds and Expected
Concentrations in Blood in Northern New Jersey 23
8 Total Daily Intake of Target Compounds, Pesticides, PCBs, BaP and
Metals and Concentrations in Blood in Northern New Jersey . . 24
9 Potential Emissions from Chemical Industry in Baton Rouge, LA. . . 27
10 Prevalent Halogenated Compounds Occurring in Ambient Air and Water
of Baton Rouge, Geismar and Plaquemine, LA 29
11 Potential Emissions from Chemical Industry in Plaquemine, Geismar,
and St. Gabriel, LA 30
12 Method Validation Recovery of Selected Volatile Standards
from Milk 38
13 Method Validation Recovery of Semivolatile Compounds Spiked into
Raw Cow's Milk. 39
14 Operating Conditions for GC/MS Analysis of Purgeables 42
15 Operating Conditions for the GC/MS Analysis of Semivolatiles ... 43
16 Summary of Qualitative Identifications of Volatile Compounds
in Mother's Milk 46
Vll
-------
TABLES CONT'D.
Number Page
17 Volatiles Quantitated in Mother's Milk Samples (ng/mL) 52
18 Summary Statistics for Volatile Compounds by Site 55
19 Significance of the Differences in the Geometric Means by Site . . 56
20 Spearman Correlation Coefficients for Volatile Organics Found
in Mother's Milk 57
21 Quality Control Results for Volatiles in Milk 58
22 DDE and Tetrachlorobiphenyl Levels in Selected Mother's Milk
Samples 60
B-l Instrumental Operating Conditions 108
D-l Volatile Compounds Identified in Purge of Sample No. 1081
(Bayonne, NJ) 120
D-2 Volatile Compounds Identified in Purge of Sample No. 1040
(Bayonne, NJ) 123
D-3 Volatile Compounds Identified in Purge of Sample No. 1107
(Jersey City, NJ) 126
D-4 Volatile Compounds Identified in Purge of Sample No. 1115
(Jersey City, NJ) 130
D-5 Volatile Compounds Identified in Purge of Sample No. 2048
(Pittsburgh, PA) 133
D-6 Volatile Compounds Identified in Purge of Sample No. 2071
(Pittsburgh, PA) 136
D-7 Volatile Compounds Identified in Purge of Sample No. 3053
(Baton Rouge, LA) 139
D-8 Volatile Compounds Identified in Purge of Sample No. 3111
(Baton Rouge, LA) 142
E-l Semivolatile Compounds Identified in Extract of Sample 1032
(Bayonne, NJ) 145
E-2 Semivolatile Compounds Identified in Extract of Sample 3095
(Baton Rouge, LA) 147
E-3 Semivolatile Compounds Identified in Extract of Sample 3095
(Baton Rouge, LA) 149
E-4 Semivolatile Compounds Identified in Extract of Sample 4093
(Charleston, WV) 151
viii
-------
LIST OF ABBREVIATIONS AND SYMBOLS
ABBREVIATIONS
DDT
dpm
ECD
GC
MS
NICIMS
OMB
PBBs
PCBs
PCF
PCN
PLF
SQ
1,1-Bis(£-chlorophenyl)-2,2-trichloroethane
Disintegrations per minute
Electon capture detection
Gas chromatography
Mass spectrometry (electron impact ionization)
Negative ion chemical ionization mass spectrometry
Office of Management and Budget
Polybrominated biphenyls
Polychlorinated biphenyls
Participant Consent Form
Polychlorinated Naphthalene
Participant Listing Form
Study Questionnaire
IX
-------
ACKNOWLEDGMENTS
The authors thank the Project Officer, Dr. Joseph Breen, for his guidance
and advice. Sandra P. Parks, David L. Newton, and Larry C. Michael are
acknowledged for their assistance in the laboratory. Nora P. Castillo and
Kent W. Thomas are thanked for their assistance with mass spectral interpreta-
tion. Pamela A. Gentry, Fred A. McKinney, Stephen P. Burke, and Barbara L.
Bickford are thanked for sample analysis using mass spectrometry.
Personnel who assisted in the milk collection are greatly appreciated:
Elizabeth Bartholomew, Bayonne Hospital, Bayonne, NJ; Jules Rivkind and
Trudy Strunk, Medical Center Hospital, Jersey City, NJ; Ian Holtzman, Magee-
Women's Hospital, Pittsburgh, PA; Lewis Trachtman, Louisiana Health Department,
New Orleans, LA; Maxine Parker, Baton Rouge Area Regional Nursing Consultant,
Baton Rouge, LA; Clementine Martine, Public Health Nursing Supervisor of the
East Baton Rouge Parish Health Unit, Baton Rouge, LA; and N. N. Sehgal,
Charleston Area Medical Center (Memorial Division), Charleston, WV.
Finally we would like to thank the 42 women who so kindly donated the
samples.
-------
SECTION 1
INTRODUCTION
BACKGROUND
It is becoming increasingly important to correlate ambient environmental
pollutant levels with human body burden. Establishment of this correlation
("exposure assessment") may provide a link between pollution and health
effects. This correlation is of interest for both scientific research and
regulatory risk assessment.
Measurement of pollutant body burden levels generally requires invasive
techniques (exceptions are breath and urine sampling) which are undesirable
from the subjects' viewpoint. Some invasive techniques are generally regarded
as acceptable (£.£., blood samples), while others are generally considered
unacceptable from living donors (e.g. adipose tissue, internal organs,
etc.). Mother's milk is an attractive medium for several reasons: (1)
sample collection is reasonably straightforward; (2) milk contains a high
amount of fat (about 3.5 percent, as shown in see Table 1), so fat-soluble
pollutants such as DDT and polychlorinated biphenyls (PCBs) are likely to be
found in higher concentrations in milk than in blood or urine; (3) large
(50-100 ml) volumes are easily collected for analysis, increasing analytical
reliability and detection limit; and (4) the population of nursing mothers
is large relative to pathology samples such as adipose tissue. In addition,
an assessment of pollutant concentrations in mother's milk may be used to
predict the pollutant intake by the nursing infant.
The major disadvantages of mother's milk as a human-sampling medium
relate to the sampling demography: only young-to-middle-aged females are
nursing. Thus, any use of mother's milk in a probability-based sampling
framework extrapolated to the general population would be fraught with
difficulties, such as locating donors.
-------
Table 1. COMPARISON BETWEEN HUMAN AND COW'S MILK
(1)
Parameter
Human Milk
Cow's Milk
Water and solid
content
Calories
Protein
Carbohydrate (in
form of lactose)
Fat(s)
Minerals
Same in both; 87 to 87.5 percent is water
Same in both; 20 calories per ounce
1 to 1.5 percent; 60 percent of this
is lactalbumin and 40 percent casein
6.5 to 7.5 percent
3.5 percent; 15 percent of
this is lactalbumin and
85 percent casein
4.5 to 5.0 percent
Variable, but both have approximately 3.5 percent.
(Differs qualitatively)
Contains more olein, which is
is readily adsorbed
Digestion of fat easy
0.15 to 0.25 percent
Contains more volatile fatty
acids, which are irritat-
ing to the gastric mucosa
Digestion of fat sometimes
difficult
Vitamins
0.7 to 0.75 percent. Con-
tains more of all minerals
with the exception of iron
and copper
Iron content is low in both milks, approximately:
1.5 mg/1 0.5 mg/1
Varies with maternal intake
(continued)
-------
Table 1 (cont'd.)
Parameter Human Milk Cow's Milk
Vitamin A Relative large amounts in both milks
Vitamin B Probably adequate in both milks
Vitamin C More is found in human milk
Thiamine Higher content in cow's milk
Riboflavin Higher content in cow's milk
Vitamin D Relatively small amount in both milks
Vitamin E Satisfactory level in breath milk
Digestion Cow's milk has a higher buffer content and
can therefore adsorb much more gastric acid
than breast milk before it reaches the
acidity necessary for digestion. The large
amount of casein on cow's milk make large,
tough curds in the stomach as compared with
the fine, easily broken down curds of breast
milk
-------
The purpose of this study was to measure levels of environmental pollu-
tants in human milk by gas chromatography/mass spectrometry (GC/MS) and to
evaluate the utility of using this body fluid in specific pollutant studies
for populations in the vicinity of chemical manufacturing plants and/or
industrial user facilities. All routes of exposure, i.e., air, water,
particulate, clothing and food were of interest. Mother's milk samples were
acquired and analyzed for selected industrial chemicals. The chemicals of
interest included: polychlorinated naphthalenes (PCNs), tetrachloroethylene,
trichloroethane, dichloropropanes, benzene, polybrominated biphenyls (PBBs),
chlorinated phenols, toluene, chlorinated benzenes, and chloroform.
Where possible, any other chemicals found in the extracts were identified
and quantitated. The levels of selected organic compounds in mother's milk
were investigated to assess the possibility of using this medium as an
indicator of body burden for a wide range of organic compounds. For this
feasibility study, no attempts were made to develop a statistically valid
sample; sites were selected as having a high probability of pollutant detec-
tion and subjects were selected on a volunteer basis.
LITERATURE REVIEW
A review of the literature concerning pollutants in mother's milk was
conducted. A computer search of MEDLARS II and ORBIT—HI yielded 108
citations. These citations, plus personal contacts and manual searches
yielded the data discussed below.
By far, most of the literature on environmental pollutants in mother's
milk deals with chlorinated insecticides (e.g. DDT). PCBs have also been
studied. Only a few references discuss the presence of other compounds in
milk.
Table 2 lists the levels of pollutants found in mother's milk in the
United States. Table 3 summarizes these findings. Table 4 summarizes
pollutants found in mother's milk outside the United States. With the
(27)
exception of one reference regarding 1,2-dichloroethane exposure, all of
the compounds found in mother's milk are semivolatile (extractable) halogena-
ted compounds.
-------
Table 2. LEVELS OF ORGANIC COMPOUNDS FOUND IN HUMAN MILK IN THE UNITED STATES
Compound
B-BHC
Y-BHC
Total BHC
p_,p_'-DDD
o,p_'-DDE
p_,p_'-DDE
DDE
Sample
Matrix
Milk
Milk
Milk Fat
Milk
Milk
Milk
Milk
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Mean
(ppb)
0.5
83
6.5
7.7
6.2
4.7
10.8
1.0
227
29
84.1
92.4
1766
194
60
30
30
100
Range Number of
(ppb) Determinations Locations
T-10
T-28
30-270
<0.1-20.2
n.d.-37.0
3.6-9.0
<0.1-14
n.d.-30
T-5
<0.1-2.8
10-1720
5.2-981
13.4-236
16.7-138
790-4350
79-386
74-314
20-90
<10-140
_**
70-120
57
40
53
14t
28
7
14t
53
40
14t
57
14t
28
7
53
40
30*
4
5
1**
AR, MS
CO
PA
US
TX
Houston, TX
US
PA
CO
US
AS, MS
US
TX
Houston, TX
PA
CO
AZ
Chicago, IL
Wenatche, WA
Phoenix, AZ
US
References
2
3
4
5
6
6
5
4
3
5
2
5
5
6
4
3
7
8
8
8
8
(continued)
-------
Table 2 (cont'd.)
Sample
Compound Matrix
o,p_'-DDT Milk
Milk
Milk
Milk
p_,p_'-DDT Milk
Milk
Milk Fat
Milk
DDT (unspeci- Milk
fied) Milk
Milk
Milk
Milk
Milk
Total DDT Equiv! Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Mean
(ppb)
92
25
10
29
114
513
100
60
60
70
130
334
70.5
100
170
180
220
170
150
180
447
75
323
130
Range Number of
(ppb) Determinations Locations
10-840
<0. 1-10.8
5-36
T-13
7.8-89
9-383
90-2120
7-109
80-130
<10-220
_**
50-90
10-110
n.d.-770
20-2760
40.4-156
SD=100
SD=130
SD=100
SD=170
SD=150
SD=80
SD=120
59-1899
15-133
185-721
n.d.-770
57
14t
30*
40
14t
30*
53
40
4
5
1
**
40
32
57
14
14
20
19
27
34
6
18
38
14
7
32
AR, MS
US
AZ
CO
US
AZ
PA
CO
Chicago, IL
Wenatche, WA
Phoenix, AZ
US
CO
DC
AR, MS
US
Long Island, NY
Rochester, NY
Chicago, IL
Lexington, KY
Nashville, TN
Memphis, TN
Los Angeles, CA
MS, AK
Nashville, TN
MS, AK
Washington, DC
References
2
5
7
3
5
7
4
3
8
8
8
8
3
9
2
10
10
10
10
10
10
11
11
11
11
9
(continued)
-------
Table 2 (cont'd.)
Compound
Dieldrin
Heptachlor
Epoxide
t-Nonachlor
Oxychlordane
PCBs
Nicotine
Sample
Matrix
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Breast
Fluid
Mean
(ppb)
0.4
6.2
3.3
7.5
4
1.7
160
1
5
T
'vJO
Range Number of
(ppb) Determinations Locations
T-50
2.9-14.6
n.d,-21
1.9-21
T-ll
T-30
<0.1-4.4
40-460
T-5
T-10
T-20
T
<40-100
40-100
n.d.-195
57
14t
28
7
40
57
14t
53
40
57
57
57
39
40
6
AR, MS
US
TX
Houston, TX
CO
AR, MS
US
PA
CO
AR, MS
AR, MS
AR, MS
CO
CO
CA
References
2
5
5
5
3
2
5
4
3
2
2
2
12
3
13
NOTES: BHC = benzenehexachloride (hexachlorocyclohexane)
ODD = 2,2-bis(chlorophenyl)-l,l-dichloroethane
DDE = 1,l-dichloro-2,2-bis(chlorophenyl)ethylene
DDT = l,l,l-trichloro-2,2-bis(chlorophenyl)ethane
Total DDT equiv. = sum of all DDT-related peaks calculated as if all were DDT
PCBs = polychlorinated biphenyls. Quantitation generally based on comparison to an Aroclor
mixture
T = trace
n.d. = not detected
SD = standard deviation
t = 5 women. Separate determinations make total of 14 samples.
* = 6 women. Separate samples makes total of 30 samples.
** = unspecified pool of donors in Denver and other US areas, no range given.
Missing values indicate no data in original article
-------
Table 2 (cont'd.)
NOTES (cont'd.): Mean values were taken from original citation where available; otherwise
arithmetic mean was calculated, counting "ND" values as zero and "T" values
as 0.5 times the lowest reported value.
oo
-------
Table 3. RANKING OF PESTICIDES AND PCBs BY REPORTED
CONCENTRATIONS IN HUMAN MILK&
Compound
DDEC
DDTC
PCBsC
Oxychlordane
Dieldrin
DDDC
Heptachlor epoxide
BHCC
t-Nonachlor
Weighted Mean
Concentration (ppb)
99
94
<10
5
4
4
4
3
1
Number of
Samples
103
100
96
57
92
54
71
106
57
milk only.
Mean value calculated from a weighted mean of values in Table 2.
Where either the mean or number of samples analyzed were unavailable,
the data were excluded from calculation.
£
All isomers summed.
-------
Table 4. LEVELS OF ORGANIC COMPOUNDS FOUND IN HUMAN MILK OUTSIDE THE UNITED STATES
Compound
o-BHC
B-BHC
Y-BHC
4-BHC
Total BHC
E,E'-DDD
ODD
o,£'-DDE
£,p>DDE
Sample
Matrix
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk Fat
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Mean
(ppb)
0.58
4.69
70
200
280
4
2
10.91
-
48
63
10.1
3
1.14
9.4
13
9.9
7
18.02
9.5
65.10
90
21.7
97
30
35
19
35
73
Range
(ppb)
0.1-1.9
1.2-17.8
ND-900
80-910
10-850
1-16
ND-21
1.0-35.8
ND
26-114
40-100
-------
Table 4 (cont'd.)
Compound
DDE
o,p_'-DDT
p_,p_'-DDT
DDT
Sample
Matrix
Milk
Milk Fat
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk Fat
Milk Fat
Milk
Mean
(ppb)
105
3380
3920
61
18.52
7.3
5
3
17.89
90
7.3
32
16
13
6
6
45
36
1060
1760
10
Range
(ppb)
12-450
1930-7950
3420-5970
15-112
1.6-120.9
<1-31
ND-48
2.3-138.3
3-345
10-250
3-344
6-30
<2-ll
?-21a
20-75
7-160
300-2680
1030-2530
2-25
Number of
Determinations
67
22
9
26
SO
28
147
100
50
168
96
29
147
50
6
9
100
19
67
22
9
26
Number of
Positives
67
22
9
26
49
32
SO
167
95
50
6
9
100
19
67
21
9
26
Location
Australia
Vienna
Rural Austria
W. Australia
Norway
Israel
Canada
Canada
Norway
Portugal
Germany
Israel
Canada
Leiden (Neth.)
New Brunswick
Nova Scotia
Canada
England
Australia
Vienna
Rural Austria
H. Australia
Date
1970
1973
1973
1970-1
1975
1975
1967-8
1975
1975
1972
1971
1975
1967-8
1969
1973
1973
1975
1964
1970
1973
1973
1970-1
Reference
21
16
16
25
14
18
19
24
14
22
IS
18
19
17
23
23
24
20
21
16
16
25
(continued)
-------
Table 4 (cont'd.)
Compound
Total DDT
Equiv.
Dieldrin
Aldrin
Heptachlor
Epoxide
Sample
Matrix
Hi Ik
Milk
Milk Fat
Milk Fat
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk Fat
Milk Fat
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Milk
Mean
(ppb)
81.74
186
1390
3480
3480
320
141
139
78
378
128
2.75
40
40
90
90
6
7.0
5
S
3
2
6
21.8
1.57
. 9.1
3
1.2
1
Range
(ppb)
5.2-349.0
< 10- 780
220-2580
330-18800
110-11400
30-870
15-580
10-1020
19-137
3-5868
75-170
0.3-3.6
5-31
<10-80
< 10- 170
<10-2SO
1-29
1-60
3-11
0.1-10.7
ND-6
1-13
0.6-2.6
-------
Table 4 (cont'd.)
Conpound
HCB
PCB
Oxychlordane
trans-
Nonachlor
1,2-Dichloro-
ethane
Sample
Matrix
Milk
Milk Fat
Milk Fat
Milk
Milk
Milk
Milk Fat
Milk Fat
Milk Fat
Milk
Milk Fat
Milk Fat
Milk
Milk
Milk
Milk
Milk
Milk
Mean
(ppb)
9.1
100
1240
3670
25
2
1200
1200
1000
90
1S40
1290
22
18
12
1
1
6000
Range
(ppb)
1.7-60.5
ND-250
260-4360
2140-5110
12-34
ND-21
100-2500
200-3000
700-12000
580-3780
950-1570
15-30
12-32
ND-68
ND-2
ND-2
Number of
Determinations
50
19
22
9
26
100
19
34
48
96
22
9
6
9
100
100
100
1
Number of
Positives
50
22
9
26
81
19
34
48
64
22
9
6
9
100
77
77
1
Location
Norway
Ontario
Vienna
Rural Austria
H. Australia
Canada
Ontario
Ontario
Ontario
Germany
Vienna
New Brunswick
Nova Scotia
Canada
Canada
Canada
Date
1975
1973-4
1973
1973
1970-1
1975
1973-4
1971-2
1969-70
1971
1973
1973
1973
1973
1975
1975
1975
Reference
14
26
16
16
25
24
26
26
26
IS
16
16
23
23
24
24
24
28
NOTES:
BHC = benzenehexachloride (hexachlorocyclohexane)
ODD = 2,2-bis(chlorophenyl)-l,l-dichloroethane
DDE = l,l-dichloro-2,2-bis(chlorophenyl)ethylene
DDT = l,l,l-trichloro-2,2-bis(chlorophenyl)ethane
Total DDT equiv. = sum of all DDT-related peaks calculated as if all were DDT.
PCB = polychlorinated biphenyls. Quantitation generally based on comparison to an Aroclor
mixture.
HCB = hexachlorobenzene
ND = not detected.
Mean values were taken from original citation where available; otherwise arithmetic mean was
calculated, counting "ND" values as zero and "T" values as 0.5 times the lowest reported value.
Missing values indicate no data in original article.
Lowest value not reported.
-------
The literature shows that mother's milk often contains semivolatile
chlorinated organic pollutants (pesticides). Presumably due to lack of
analytical techniques and/or sensitivity, the presence of other pollutants
has apparently not been investigated.
14
-------
SECTION 2
SUMMARY AND CONCLUSIONS
The results show that sampling and analysis for organic compounds in
mother's milk is feasible. The sample collection technique presented no
significant problems. Analysis of the samples was generally satisfactory.
The use of purge and trap with gas chromatography/mass spectrometry/com-
puter (GC/MS/COMP) analysis for volatile organics was successful, although
the intrusion of contaminants during analysis presented problems with some
compounds. The wide range of volatile compounds found includes common air
and water pollutants and possible metabolites. Thus, it may be possible to
use mother's milk as an indicator of body burden if a correlation between
exposure and mother's milk concentration is established.
The extraction and GC/MS analysis for semivolatile organics was only
marginally successful due to limited sensitivity (about 20-100 ppb milk).
PCBs and DDE were the only halogenated semivolatiles found. The target
semivolatile compounds (PCNs, PBBs, chlorinated phenols, and the higher
chlorinated benzenes) were not present in quantities detectable by the
survey techniques. The use of more sensitive (generally a factor of 100-1000)
and selective methods [GC/electron capture detection (ECD), GC/negative ion
chemical ionization mass spectrometry (NICIMS) or GC/single ion monitoring
MS] may detect these compounds, but was outside the scope of this project.
15
-------
SECTION 3
RECOMMENDATIONS
Further studies of the applicability of mother's milk as a matrix for
assessing the human body burden of pollutants must directly compare human
milk with the other available sample matrices. For example, comparison of
the volatiles in breath, blood, urine, and mother's milk would determine
which matrices are most suitable for measuring these compounds. It may also
be advisable to use animal studies to determine the extent of environmental
exposure-body burden correlation.
In addition, the effects of transport of pollutants to a newborn infant
should be studied. Infants may be uniquely affected by some pollutants due
to their small body weight and different metabolism relative to adults.
The measurement of semivolatile organics in mother's milk requires more
sensitive techniques than those used in this study. For example, chlorinated
compounds could best be detected using GC/ECD or GC/negative ion chemical
ionization mass spectrometry and polynuclear aromatics by GC/photoionization
detection.
Improvement in analytical methodology could occur at several points:
(1) As discussed above, more sensitive, analytical procedures could be
used for specific compound classes.
(2) For volatile organics, background levels could be reduced with an
on-line purge and trap/GC system.
Potential improvements in survey and sampling methodology include:
(1) Addition of questions regarding length of nursing, age of infant,
time since last nursing, etc.
(2) Selection of participants according to a more statistically valid
method (£.£. statistically random sampling).
(3) Closer control over physical collection methodologies (e.g. all
respondents gathered at one location).
16
-------
The 5-month time lag in the study awaiting OMB clearance was seriously
detrimental to the project. The personnel and apparatus used for the valida-
tion studies had to be reassembled once OMB clearance was obtained. Restart-
ing a project following a long dormant period requires retraining analytical
personnel (or training new personnel if original personnel have been reassig-
ned to other research projects), recalibration of instruments, and assembling
the necessary laboratory apparatus and supplies, all of which consume govern-
ment resources. Reducing this time lag is extremely important for execution
of programs involving human testing.
17
-------
SECTION 4
SELECTION OF SAMPLING SITES
Five urban areas were chosen as sampling sites. Each of these cities
is a high-probability area for the presence of one or more of the chemicals
of interest in mother's milk. Since many of the compounds of interest are
probably specific to certain industrial sites, the samples from the other
sites were intended to serve as controls for the site-specific compounds.
Other compounds are considered ubiquitous and their levels in milk was
probably not related to local industrial activity. The rationale for select-
ing the five sampling sites is discussed below.
BRIDGEVILLE, PENNSYLVANIA
PCNs are manufactured by Koppers Company, Inc., of Pittsburgh, PA, at
the Koppers Chemical and Coatings plant in Bridgeville, about 10 km SW of
(29)
Pittsburgh. Reported production levels were 7 million Ib in 1956 and 5
(29)
million Ib in 1972, indicating a potential long-term, relatively constant,
exposure level in the surrounding area. Results from environmental monitoring
in the area immediately (< 1 km) surrounding the plant indicated higher
levels of PCNs in air and soil than those found near five PCN user sites, as
(*5fl Q/ ^
shown in Table 5. Furthermore, fish and apple samples from the same
area were found to contain PCNs, indicating a potential link to the human
food chain.
In addition to PCNs, plants in the Bridgeville area have been reported
(35)
to emit large quantities of phthalic anhydride particulate. At this
plant site, Koppers is reported to manufacture chlorinated naphthalenes,
phthalic anhydride, maleic anhydride, and alkyd resins.
18
-------
Table 5. SUMMARY OF PCN CONCENTRATIONS FOUND NEAR MANUFACTURING AND USE SITES
(32)
Site
PCN manufacturer (Koppers)
Capacitor manufacturing A
Capacitor manufacturing B
Sampling
Period
1
2
1
2
1
2
Air,
Low
25
120
NDb
ND
9.8
9.8
ng/m
High
450
2900
7.3
3.9
31
33
Mean
150
1400
3.1
1.2
19
17
Water, yg/L Soil, yg/kg
Up- Down-
stream stream Low High Mean
0.2 1.4 130 2300 940
a
ND ND ND 7.3 2.0
ND 0.6 ND 470 100
NO water samples collected for period 2.
Not detected.
-------
NORTHERN NEW JERSEY - STATEN ISLAND, NEW YORK, AREA (NNJ)
The Northern New Jersey (NNJ) area was selected as a sampling site on
two bases: production of PBBs and general chemical industrial activity.
(37)
Three facilities are of interest with respect to PBBs: White Chemical
Co., E 22nd St., Bayonne, NJ; Marcor, Inc., Standard T. Chemical Co., subsi-
diary, 2500 Richmond Terrace, Staten Island, NY; and Hexcel Corp., Fine
Organics Division, 880 Main St., Sayreville, NJ. White produced 45,000 kg
of PBBs (specifically octabromobiphenyl and decabromobiphenyl) between 1970
(38) (39)
and 1973. Hexcel is reported to have produced unspecified amounts
of decabromobiphenyl [as well as to have produced or used decabromobiphenyl
oxide, ethylene dichloride, and l,2-bis(2,4,6-tribromophenoxy)ethane].
(39)
Standard T is thought to have been a PBB user up to about 1974. '
Results of environmental sampling in the area surrounding these three
(40 41)
companies ' indicated the presence of PBBs, especially the more highly
brominated homologs, in sediment, water, soil, human hair, fish, turtle, and
plant matter. The findings in human hair oil (18 total samples), which
ranged from undetectable to 310 ppm, are especially relevant to this study,
since they indicate that the PBB manufacturing in this area and the resultant
environmental contamination has resulted in human exposure.
(42)
Northern New Jersey has a high concentration of chemical industries,
many of which use or produce halogenated hydrocarbons. The list of industries
and locations are summarized below. Coastal Industries, Inc. (swimming pool
chemicals), Diamond Shamrock (textile processing chemicals), Scientific
Chemical Processing (chemical waste disposal) and Tenneco Chemicals (synthetic
foam rubbers) are located in Carlstadt. Crompton & Knowles Corp. (dyes,
colors and chemicals) are located in Fairlawn. Fisher Scientific (chemicals),
Conoco Chemicals are in Saddle Brook. In Bayonne are CIBA-Geigy (dyes and
intermediates) and ICI America (organics). In Jersey City are Mallinkrodt
(analytical reagents) and Onya Chemical Co. (textile finish compounds, water
repellants, germicides, and detergents). In Kearney are Standard Chlorine
Chemical Co. (chlorobenzenes), Theobald Industries (bleaches), PPG Industries
(paint) and Monsanto (industrial chemicals). In South Kearney is BASF-
Wyandotte (dyestuffs and vinylidine chloride). In Newark are American Oil
and Supply Co. (surfactants and chemicals), Celanese Plastics (plastics),
20
-------
DuPont (pigments), Inmont (paint), Maas & Waldstein (paint), Otto B. May
(dyes, surfactants), 3M (chemicals), Benjamin Moore (paint), Sherwin-Williams
(paint) and Vulcan Materials (chlororoethanes). In Elizabeth are Perk (chlori-
nated solvents) and Speciality Chemicals Division of Allied Chemical Corp.
Linden Chlorine Products (chlorine) is in Linden. In Rahway are M & T
Chemicals (speciality chemicals) and Merck and Co. (industrial chemicals).
In Edison are Gary Page Chemicals (PVC compounds) and Mobile Chemical (paint).
In Parlin, Hercules manufactures chloroform. In Passaic are Pantasote Co.
of New York (PVC resin film), Stauffer (vinyl sheet and film) and United
Wool Piece Dyeing and Finishing (dyes). In Patterson are several dye manufac-
turers. In Wayne are American Cyanamid (chemicals) and Owens Illinois
(plastics). Many of these and other firms in NNJ undoubtedly manufacture or
use compounds which are of interest to this study.
The levels of general organic pollutants in NNJ have been found to be
high due to intense chemical manufacturing in the area. Environmental
(43-46)
monitoring by RTI under separate contracts, has found a wide variety
of organic pollutants in this area. In addition, preliminary results from
ground and surface water samples indicate measurable levels of a number of
(44 45)
volatile halogenated hydrocarbons. '. These data, summarized in Table
6, are indicative of environmental levels of organics in the NNJ area to
which humans may be exposed and thus are indicative of the types of compounds
(45)
anticipated in mother's milk. Under a separate research project, the
daily intake of some selected organics was roughly estimated. These estimates
are given in Tables 7 and 8. Clearly there is ample exposure to pollutants
which could potentially partition into milk.
The statistics for cancer in two counties of NNJ are very high. '
The overall rate for all malignant neoplasms is significantly above the
national average. This cancer incidence in New Jersey has been partially
linked to the chemical and allied industries located there.
Northern New Jersey is a metropolitan area with a relatively static
population, a well-established chemical industry, known environmental levels
of organics (including PBBs) and abnormally high cancer rates. These factors
make this area especially suited to this study of organics in mother's milk.
21
-------
Table 6. PREVALENT HALOGENATED COMPOUNDS IN AMBIENT AIR AND WATER
OF RAHWAY/WOODBRIDGE, BOUNDBROOK AND PASSAIC, Nj(44)
Occurrence
Medium
Ubiquitous
Mean
Concentration'
Area Specific
Mean
Concentration0
10
Air tetrachloroethylene 210,000
trichloroethylene 125,000
1,1,1-trichloroethane 62,000
1,2-dichloroethane 96,000
chloroform 47,000
carbon tetrachloride 29,000
c^,in,£-dichlorobenzenes 11,000
chlorobenzene 2,700
Water dichlorobenzene 209
trichloroethane 42
chloroform 14
trichloroethylene 7
dichloroethane 5
bromodichlorpethane 5
bromodichloromethane 3.7
tetrachloroethylene 3.6
dibromochloromethane 3.3
1,1,2-trichloroethane
vinyl chloride
1,2-dichloroethylene
1,1,2,2-tetrachloroethane
chloronitrobenzene
methyl trichlorophenoxy acetate
methyl dichlorophenoxy acetate
bromopropylbenzene
bromobenzene
tetrachloroethane
dichloroethylene
9,000
1,200
1,000
750
10
.7
5
3.5
3
3
2.5
1.8
a 3
Concentrations for air expressed in ng/m and for water in yg/L.
-------
Table 7. ESTIMATED DAILY INTAKE OF SELECTED VOLATILE COMPOUNDS AND EXPECTED
CONCENTRATIONS IN BLOOD IN NORTHERN NEW JERSEY (4^)
ro
co
Toxic Chemical
tetrachloroethy 1 ene
trichloroethylene
1,1, 1- trichloroethane
1,2-dichloroethane
chloroform
carbon tetrachloride
dichlorobenzene
chlorobenzene
vinyl chloride
bromodichloromethane
benzene
total
Aira
(ng/day)
2,100,000
1,250,000
620,000
960,000
470,000
290,000
110,000
27,000
12,000
7,500e
Waterb Foodc
(ng/day) (ng/day)
3,600 4,150
7,000 18,660
42,000 5,290
5,000
14,500 14,280
1,000 12,070
209,000
1,000
3,700
300f
Total
(ng/day)
2,108,000
1,276,000
667,000
965,000
499,000
303,000
319,000
28,000
12,000
3,700
7,800
6,188,200
Potential Blood
Concentration^
(ppb)
88
53
28
40
21
13
13
1.2
0.5
0.2
0.2
258.2
From Ref. 44, calculated on basis of 10,000 L/24 h respiration rate.
From Ref. 44, calculated on basis of 1 L/24 h intake.
"From Ref. 47, calculated from FDA standard diet (Ref. 48).
Expected blood concentration is total daily intake divided by blood volume (8.000 mL) assuming 4
half-lives/day.
BFrom Ref. 49, 50.
fFrom Ref. 50.
-------
Table 8. TOTAL DAILY INTAKE OF TARGET COMPOUNDS, PESTICIDES, PCBs, BaP AND METALS AND
CONCENTRATIONS IN BLOOD IN NORTHERN NEW JERSEY
to
Toxic Chemicals
a-BHC
lindane
heptachlor
heptachlor epoxide
chlordane
DDE
DDT/DDD
HCB
PCBs
Total
Halogenated Compounds
benzo(a)pyrene
arsenic
cadmium
lead
'W. 56.
bRef. 57.
Air
(ng/day)
10
60
30
20
70
50
-v.200
440
21
2,800
50
7,500
Water
(ng/day)
0
0
7
0
<60
<67
2
<1,000
<1,000
3,200
Food
(ng/day)
1,100
586
62
640
3,500
2,500
73
388
8,849
7,800
31,300
32,000
105,000
Total
(ng/day)
1,110
646
92
647
20
3,500
2,570
123
648
9,356
7,823
34,100
33,000
115,700
Expected Blood
Concentration
(ppb)
0.14
0.08
0.01
0.08
•vfl
0.44
0.32
0.02
0.08
1.16
1.0
4.4
-------
Table 8 (cont'd.)
Sources:
Pesticides and PCBs in air --
Pesticides in water
Pesticides and PCBs in food --
PCBs in water
BaP in air
Ref. 51 (US)
Ref. 44 (NJ)
Ref. 48 (US)
Ref. 51 (US)
Ref. 52 (US)
BaP in water
BaP in food
Metals in air
Metals in water
Metals in food
-- Ref. 53 (World)
•- Rough estimation
(from Ref. 53 [World])
-- Ref. 54 (NJ)
-- Ref. 55 (NJ)
-- Ref. 48 (N.E. NJ)
-------
BATON ROUGE, LOUISIANA
Baton Rouge was selected on the basis of extensive organic chemical
production (especially volatile halogenated hydrocarbons) as summarized in
(43)
Table 9. In addition, RTI has collected and analyzed ambient air samples
from this area and established the presence of a number of compounds of
(43)
interest in ambient air. ' A summary of the levels of halogenated compounds
found in water and air is presented in Table 10.
In addition to the industrial production in Baton Rouge, industries in
Plaquemine (15 km SSW), St. Gabriel (20 km SSE) and Geismar (27 km SSE) may
emit significant levels of chemicals which may contribute to the levels
observed in mother's milk in Baton Rouge. These industries and their produc-
tion are listed in Table 11.^ '
KANAWHA VALLEY, WEST VIRGINIA
Many manufacturers of organic chemicals are located in the Kanawha
Valley, WV. DuPont, near Belle, WV, has a large chemical complex for the
synthesis of substances such as methylmethacrylate, methylamines, ammonia,
hydrogen cyanide, herbicides, and insecticides. In South Charleston are
production and consumption plants (Union Carbide, and FMC). Plastics, PVC,
antifreeze, chlorine, halogenated organics, carbon disulfide, peroxides,
etc., are the predominant chemicals produced here. The major industrial
facility in the town of Institute is Union Carbide, which also processes a
broad spectrum of compounds, £.£., viscose rayon and phthalate esters.
There is also a large-scale olefin processing complex and a rubber accelerator
plant. A major terminal loading facility in South Charleston handles large
quantities of a variety of organic compounds. Monsanto, FMC, Allied, and
Fike have plants near Nitro for the production of antioxidants, rubber
accelerators, industrial chemicals, and other materials. Several other
chemical manufacturers, consumers, and transporters are located in the
Kanawha Valley, some or all of which may contribute to the presence of
organic materials in the ambient air or water and thus contribute to human
exposure.
Previous RTI sampling^ ' ' ' in the Kanawha Valley found a broad
range of halogenated, ketone, aldehyde, ester, aromatic, and aliphatic
3
compounds. Quantitative results included high values in air of 11,000 ng/m
26
-------
Table 9. POTENTIAL EMISSIONS FROM CHEMICAL INDUSTRY IN BATON ROUGE, LA
a(43)
Chemical
Total Production
(mmlb/yr)
Raw Material
Company
10
chlorodifluoromethane (101)
dichlorodifluoromethane (12)
dichlorotetrafluoroethane (114)
ethylene dichloride
polyethylene resin
trichlorofluoromethane (11)
1,1,2-trichloro-1,2,2-trifluoroethane
(113)
vinyl chloride
ethyl chloride
methyl chloride
perchloroethylene
tetraethyl lead
1,1,1-trichloroethane
trichloroethylene
PVC
benzene
butadiene
n-butyl alcohol
NA
1100
460
NA
480
210
75
100
312
40
32
144
440
428
NA
chloroform
carbon tetrachloride
perchloroethylene
ethylene
ethylene
perchloroethylene
ethylene dichloride
ethylene
methanol
ethylene dichloride
ethyl chloride
1,1-dichloroethane
ethylene
petroleum
ethane, etc.
AC(T
ACC
ACC
ACC, EC
ACC
ACC
ACC
ACC, EC
EC
EC
EC
EC
EC
EC
EC
EXCC
EXCC, CRCC
EXCC
(continued)
-------
Table 9 (cont'd.)
to
oo
Chemical
decanol0
diisodecylphthalate
dodecene
ethylene
isobutylene
isodecanol
isooctyl alcohol
isoprene
isopropanol
neopentanoic acid
nonene
phthalic anhydride
propylene resin
toluene
ethylbenzene
styrene
vinyl toluene
Total Production
(mmlb/yr)
NA
NA
100
700
NA
NA
NA
10
680
5.5
300
90
320
378
900
800
NA
Raw Material
nonene
phthalic anhydride,
isodecanol
propane/propylene
ethane, etc.
petroleum
nonene
neptene
ethylene by-product
propylene
isobutylene
propane/propylene
o-xylene
ethylene
petroleum
benzene
ethylbenzene
toluene, ethylene
Company
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC
EXCC, FGC
FGC
FGC
FGC
aData provided by the Louisiana State Air Board.
ACC = Allied Chemical Corp., EC = Ethyl Corp., EXCC = Exxon
CInvolves production of other alcohols also, C , C , C , C^
NA = not available.
Chem. Corp., FGC = Foster-Grant Co. Inc.
C.^, C16>
-------
Table 10. PREVALENT HALOGENATED COMPOUNDS OCCURRING IN AMBIENT AIR AND WATER
OF BATON ROUGE, GEISMAR AND PLAQUEMINE, LA(44:)
Occurrence
Medium
Ubiquitous
Mean
Concentration'
Area Specific
Mean
Concentration
a
Air
to
vO
Water
chloroform
1,2-dichloroethane
carbon tetrachloride
1,1,1-trichloroethane
trichloroethylene
tetrachloroethylene
1,1-dichloroethane
trichloroethylene
chloroform
trichloroethane
dichloroethane
carbon tetrachloride
d i ch1oroben zene
chlorodibromomethane
tetrachloroethylene
5,500
1,656
811
605
142
118
86
96
20
11
7.7
7.1
4.2
3.5
1.9
1,1,2-trichloroethane
1,2-dichloroethylene
dichlorobutane
1,2-dichloropropane
vinylidene chloride
1,1,2,2-tetrachloroethane
bromobenzene
1,2-dichloroethylene
hexachloroethane
632
472
409
306
78
70
13
4
1.6
a 3
Concentrations for air expressed in ng/m and for water in yg/L.
-------
Table 11. POTENTIAL EMISSIONS FROM CHEMICAL INDUSTRY IN
PLAQUEMINE, GEISMAR, AND ST. GABRIEL, LA(36)
City
Plaquemine
Chemical
chloroform
1 , 2-dichloropropane
ethylene dichloride
methyl chloride
methylene chloride
tetrachloroethylene
vinyl chloride
Annual Capacity
(million pounds)
b
10
1325
150
190
150
450
_ a
Company
Dow
u
u
u
ti
M
II
Geismar
chloroform
ethylene dichloride
methylene chloride
tetrachloroethylene
1,1,1-trichloroethane
phosgene
phosgene
vinyl chloride
vinyl chloride
St. Gabriel phosgene
46
330
80
150
65
55
125
300
300
NA
VCM
BASF
RCC
BOR
MCJ
SCC
aDow = Dow Chem. USA
VMC = Vulcan Materials Co.
BASF = BASF Wyandotte Corp.
RCC = Rubicon Chems., Inc.
BOR = Borden, Inc.
MCI = Monochem, Inc.
SCC = Stauffer Chem Co., Agric. Chem. Div.
200 million pounds combined capacity in Plaquemine and Freeport, TX
plants.
30
-------
3 3
for methylene chloride, 1500 ng/m for tetrachloroethylene, and 72,000 ng/m
for benzene. Compounds identified in the air particulate fraction included
long-chain alkanes, polycyclic aromatic hydrocarbons (PAH) from naphthalene
through anthanthrene (or an isomer), alkyl-PAH derivatives, and nitrogen-con-
taining heterocycles.
31
-------
SECTION 5
SAMPLE COLLECTION
At each of the five sites, arrangements were made to work through
clinical facilities to recruit a suitable panel of respondents. These
facilities included the Bayonne Hospital in Bayonne, NJ; the Medical Center
Hospital in Jersey City, NJ; Magee-Women's Hospital in Pittsburgh, PA;
Charleston Area Medical Center in Charleston, WV; and the East Baton Rouge
Parish Health Clinic in Baton Rouge, LA.
Advance arrangements were made through a contact person at each facility.
This person was responsible for recruiting a professional member of the
facility's staff to serve as the data collector. The data collector was
usually a registered, licensed practical, or public health nurse associated
with the facility.
Respondents were paid $5 for their assistance in providing a milk
sample and completing the survey questionnaire.
The data collection effort is discussed in the following sections.
OMB CLEARANCE
Under the Federal Reports Act, clearance for the study of human subjects
must be obtained from the Office of Management and Budget. This clearance
was obtained on October 18, 1978. The OMB number is 158-578010. This study
was approved with the understanding that: (1) the surveys were conducted as
a pretest of the feasibility of information collection procedures; (2) the
information collected will not be used to generalize to either local areas
or the nation as a whole. These two caveats were invoked since the sample
size was small and a nonprobability sampling method (subject selection) was
used.
32
-------
TRAINING
Before data collection began at a site, a training session was held to
acquaint the facility contact person and data collector(s) with the survey.
The session addressed the study objectives; use of the data collection
instruments; administrative instructions; quality control procedures; and
instructions for collecting, packing, and shipping milk samples to RTI. The
training was conducted by an RTI survey specialist from the Survey Operations
Center. A detailed manual and necessary field reporting forms were developed
for use in these sessions. All training was conducted at the participating
facility and lasted approximately 4 hours.
SURVEY INSTRUMENTS
Three data collection instruments (see Appendix A) were developed for
use by the data collectors. The Participant Consent Form (PCF) was used to
introduce the study, explain the study objectives and requirements of partici-
pation, present the confidentiality procedures, and obtain consent of partici-
pant. This form was signed by the respondent, who retained a copy for her
files. The original was attached to the data collection instrument and a
second copy was filed in the respondent's hospital record.
The Participant Listing Form (PLF) provided a means of assigning unique
numbers to participants at each performance site. The data collector comple-
ted this form as each participant was solicited; the form was returned to
RTI with the completed questionnaires when work at the site was finished.
The Study Questionnaire (SQ) was the primary data collection instrument.
Information concerning participant demographic characteristics, residence
information, health data, use of medications, and personal characteristics
was obtained through this document. The SQ was administered after patients
had been screened and prior to collection of the milk sample.
PARTICIPANT SCREENING
Potential participants (lactating women) were screened by the data
collector to determine whether or not they met certain study criteria, which
included:
33
-------
ability and desire to provide a milk sample of approximately
100 ml.
permanent residence within the area of interest for
at least the preceding 12 months, and
no travel outside the area of interest for the seven days
preceding sample collection.
After potential participants were screened, 10 women who met all the criteria
for participation were asked to provide a milk sample and complete the SQ.
PLF, PCF, AND SQ COMPLETION PROCEDURES
When an eligible person agreed to participate, her name was listed on
the PLF and she was assigned a unique participant number. The data collector
then read the information contained on the PCF to the participant while she
followed along using a second copy. After answering questions or handling
problems, the data collector asked the participant to sign the PCF prior to
administration of the SQ.
The data collector then completed the SQ by asking the questions directly
to the participant. Completion time averaged 15 minutes. An adhesive,
computer-generated ID label was affixed to the SQ; a duplicate label was
provided to be used for identifying the milk sample bottle.
Each participant was a self-respondent unless she was under 18 years of
age, in which case the SQ could have been administered in whole or part to
the parent or guardian, but in the participant's presence.
SAMPLE COLLECTION PROCEDURES
After completion of the SQ, the data collector made the necessary
arrangements for the participant to provide the milk sample. A collection
bottle was taken from the shipping box and the adhesive ID label was affixed
to the bottle. The milk was manually expressed directly into the bottle; no
breast pumps or other devices were allowed. Immediately after the milk was
collected, the bottle was capped and the sample frozen until all ten samples
were collected and ready for shipment to RTI. A minimum of 60 mL (half-full
bottle) was required for each sample. If insufficient milk was collected,
the sample was discarded and an additional subject was added to the study.
34
-------
SHIPPING PROCEDURES
Sample bottles were packed in the shipping container, cooled with dry
ice, and sent directly to RTI via Federal Express.
35
-------
SECTION 6
SAMPLE ANALYSIS METHODS
The milk samples were analyzed using gas chromatography/mass spectrome-
try/computer. Due to the broad range of volatilities, the samples were
partitioned into two general classes of compounds: volatiles (e.g. benzene,
chloroform) and semivolatiles (e.g. PCNs, PCBs, pesticides). The analytical
protocols developed for the volatile and semivolatile components in mother's
milk are reproduced in Appendices B and C, respectively. The experiments
conducted which led to these protocols are discussed below.
DEVELOPMENT OF ANALYTICAL PROTOCOL FOR VOLATILES
The headspace purge technique was validated by determining the recovery
of four model compounds from raw cow's milk samples. Compounds labeled with
carbon-14 were chosen in order to examine both the amounts recovered on
Tenax GC and the amounts remaining in purged samples.
Twelve 50 mL cow's milk samples were spiked with methanol solutions of
14
the C-compounds. The analysis for each of the four model compounds was
performed in triplicate. In addition, standards were prepared in triplicate
by adding the appropriate amount of each compound in solution to a scintilla-
tion-counting vial containing 15 mL of Triton X/toluene/Omnifluor scintilla-
tion "cocktail." Milk samples were purged as described in Appendix B; Tenax
cartridges were stored, and aliquots of the purged samples were retained for
oxidation and counting.
Tenax cartridges were desorbed at 270°C and 30 mL/min N» for 10 minutes
into 15 mL of Triton X cocktail in tandem scintillation vials. The vials
were capped and refrigerated until scintillation counting. An aliquot (1
mL) of each purged milk sample was oxidized in the Packard Tricarb Sample
Oxidizer, which converted all carbon-containing compounds to carbon dioxide
14
and water. The C-carbon dioxide was collected in a trapping solution and
36
-------
referenced to a quench correction curve. All standards, Tenax samples and
oxidized milk samples were counted on a Packard Liquid Scintillation Counter
with automatic standardization. Counting data was analyzed by computer to
obtain the number of disintegrations per minute (dpm) for each vial. The
percent recovery was calculated for each milk sample as shown below:
% recoverv = dPm in first vial + dPm in second vial „
average dpm added to triplicate standards
The second of the tandem scintillation vials contained <2 percent of the
14
radioactivity in every case. The amounts of C compounds retained in the
purged sample was calculated:
»/ retained = dpm in oxidized, purged sample IQQ<>.
average dpm added to triplicate standards
The data are tabulated in Table 12. The recoveries for the volatile chloro-
form and carbon tetrachloride were about 90 percent, as expected. The
less-volatile chlorobenzene and bromobenzene exhibited correspondingly
poorer recoveries. These compounds are generally considered only marginally
purgeable from water, so these results from milk are not surprising.
The methodology validation experiment indicated that the proposed
method of analyzing human milk for volatile organic compounds was adequate.
Sensitivity and detection limits were determined by the capabilities of the
GC/MS/COMP system.
DEVELOPMENT OF ANALYTICAL PROTOCOL FOR SEMIVOLATILES
The extraction and cleanup method was validated using six model compounds
(2,4-dichlorophenol, pentachlorobenzene, 1,2,3,4-tetrachloronaphthalene,
4,4'-dibromobiphenyl, 2,2",5,5'-tetrabromobiphenyl, and octachloronaphthalene)
which were representative of the semivolatile (nonpurgeable) compounds of
interest. The compounds were spiked into raw cow's milk at a level of about
1 pg/mL. Raw cow's milk was chosen as the closest readily available analog
to mother's milk.
The results are presented in Table 13. The overall mean recovery was
about 70 percent and the mean of the relative standard deviations was 22
37
-------
Table 12. METHOD VALIDATION RECOVERY OF SELECTED VOLATILE STANDARDS FROM MILK
Compound
14
C-chloroform
14
C- carbon tetrachloride
14
C-chlorobenzene
14
C-bromobenzene
b.p. (°C)
62
76
132
156
Percent ,
Recovered
88
88
63
35
+_ 5
1 6
± 2
± 3
Percent,
Retained
6
3
26
51
+_ 0.3
1 3
1 3
± 13
Percent
Accounted for
94
91
89
86
1 2
1 3
+_ 1
1 10
00
oo
80,000-94,000 dpm added to each sample.
Mean +_ standard deviation of three replicates.
r*
""Sum of percent recovered and percent retained.
-------
Table 13. METHOD VALIDATION RECOVERY OF SEMIVOLATILE COMPOUNDS SPIKED INTO RAW COW'S MILK
VO
Compound mp ("C]
2,4-Dichlorophenol 45
Pentachlorobenzene 85
1,2,3,4-Tetrachloronaphtha- 1Q_
.• J. y /
lene
4,4'-Dibromobiphenyl 164
2 , 2 ' , 5 , 5 ' -Tetrabromobiphenyl
Octachloronaphthalene 198
Concentration
in Milk
) bp (°C) (ng/mL)
207 1.12
277 1.24
1.37
357 1.04
0.93
441 1.08
Mean
Recovery
f 9f "\
I l) 1
59
76
59
58
94C
78C
Standard
Deviation
12
19
15
19
10
14
Relative
Standard ,
Deviation
20
24
25
33
11
17
Seven replicates.
Standard deviation divided by mean multiplied by 100.
f+
"Six replicates.
-------
percent. These results indicated that refinements in the method should be
considered prior to a large-scale study.
Two methods were available for removing fat and other nonvolatile
components of the milk extract: Florisil column chromatography and gel
permeation chromatography (GPC). Evaluation of the two techniques indicated
that the Florisil method was more suitable to this project. The Florisil
method was faster and had greater sample capacity than the GPC. In addition,
the GPC procedure required the use of a pumping system, UV detector, and
expensive, fragile GPC columns. Initial tests with both methods revealed
interference problems, although those with GPC were more severe. Using GPC,
decabromobiphenyl and hexabromobiphenyl eluted with the fat peak. This was
judged totally unsatisfactory. Using Florisil, some fat eluted in the
fraction with the compounds of interest, but repetition of the procedure
yielded samples sufficiently clean for analysis.
DEPARTURES FROM THE ANALYTICAL PROTOCOLS
Emulsions
The formation of an emulsion during the toluene-acetone extraction of
semivolatiles (step 6, Appendix C) was an area of concern. Approximately 80
> percent of the time an emulsion occurred. To eliminate this, three approaches
;. were taken with reasonable success. The first was to avoid the emulsion
x formation by swirling rather than shaking the toluene and acetone extracts.
The second approach was to break the emulsion by adding Na_SO, and waiting.
Both the amounts of Na.SO, and the time required varied. In severe cases
emulsions were broken by filtering through glass wool wetted with toluene.
Lipid Removal Using Florisil
Problems were also encountered during the Florisil cleanup. Some
samples had a tendency to solidify while concentrating the ether/pentane
eluate, apparently due to abnormally high fat content. This usually occurred
when the sample volume reached 1-3 mL. The samples to which this happened
were diluted with pentane and eluted through another Florisil column. The
Florisil cleanup was repeated until the samples remained liquid at small
(<1.0 mL) volumes. Three cleanups was the maximum required for any sample.
40
-------
GC/MS ANALYSIS PROCEDURES
Samples were analyzed by gas chromatography/mass spectrometry using an
1KB 2091 EI/CI GC/MS. Operating conditions for the analysis of purgeables
is given in Table 14 and the operating conditions for the extractables is
given in Table 15. Analysis of the purgeables involved the use of the
desorption apparatus described in Appendix B.
Quantitation of the unknowns was accomplished using relative molar
responses (RMRs) as discussed in Appendices B and C. The RMRs were calculated
from replicate determinations of known amounts of standards and analytes.
Qualitative Analysis
Initial identification of compounds by GC/MS involved comparisons of
unknown spectra with data compiled in the Eight Peak Index of Mass Spectra
If the peaks present in the unknown spectra clearly matched the peaks of the
standard compound in the tables and the intensities were about the same,
then a positive identification was usually made. If peak intensities of
unknowns varied from those of the standards, and there were isomers of the
compounds that were not listed in the Eight Peak Index, then the compound
was listed as an "isomer."
When the background peaks interfered with the spectrum of an unknown to
an extent that made identification uncertain, the compound identification
was labeled as "tentative" (tent.). If no standard spectra similar to those
of the unknowns appeared in the mass spectral references, but fragments
characteristic of a certain class of compounds were identified, tentative
identifications were made on the basis of the characteristic fragments and
apparent molecular weights. These identifications were also labeled "tent".
Usually tentative identifications involved alkyl derivatives or homologs of
classes of compounds that were positively identified in the same sample.
Positive identifications, as well as some tentative identifications,
often required more detailed investigations of standard spectra in the
ff.o\
Registry of Mass Spectral Data or standard spectra found in other
literature such as scientific journals. The Registry of Mass Spectral Data
presents data in the form of histograms rather than as a list of peaks and
their intensities. This type of format allowed more subtle differences in
mass spectra to be considered when several similar standard spectra in the
41
-------
Table 14. OPERATING CONDITIONS FOR GC/MS ANALYSIS OF PURGEABLES
Instrument
Column
Flow
Desorption Temperature
Desorption Time
Desorption Flow
Column Temperature
Scan Range
Scan Speed
Scan Cycle
Injector Temperature
Accelerating Voltage
Ionizing Energy
Trap Current
Source Temperature
1KB 2091
80m - SE-30 WCOT Capillary Column
1.7 mL/min He
270°C
8 min
15 mL/min He
30°C for 2. min programmed to
240°C at A°C/min
5 ->• 490 Dalton
0 •* 670 in 2 sec
1.7 sec
250°C
3500 V
70 eV
50 yA
210°C
42
-------
Table 15. OPERATING CONDITIONS FOR THE GC/MS ANALYSIS OF
SEMIVOLATILES
Instrument
GC Column
Flow
Column Temperature
Scan Range
Scan Speed
Scan Cycle
Injector Temperature
Accelerating Voltage
Ionizing Energy
Trap Current
Source Temperature
LKB 2091
25m SE-52 WCOT capillary column
1.5 mL/min with 15:1 split
80°C for 3 min then 8°C/min to 265°C
5 -»• 530 Dal ton
2 sec 0 •*• 670 Dalton
2.4 sec
240°C
3500 V
70 eV
50 uA
210°C
43
-------
Eight Peak Index appeared to represent possible candidates for unknown
identifications.
A large number of sample components remained unidentified. These unidenti-
fied components were labeled "unknown."
In order to quantify the degree of certainty with which a compound has
been identified, a "level" heirarchy has been established. The compound
identification criteria are listed below:
Level I Computer Interpretation. The raw data generated from the
analysis of samples are subjected to computerized decon-
volution/library search. Compounds identified using this
approach have the lowest level of confidence. In general Level
I is reserved for only those cases where compound verification
is the primary intent of the qualitative analysis.
Level II Manual Interpretation. The plotted mass spectra are manually
interpreted and compared to those spectra compiled in a data
compendium by a skilled interpreter. In general a minimum of
five masses and intensities (±5 percent) should match between the
unknown and the library spectrum. This level does not utilize
any further information such as retention time since the
authentic compound may not be available for establishing
retention times.
Level III Manual Interpretation Plus Retention Time/Boiling Point
of Compound. In addition to the effort described under
Level II, the retention time of the compound is compared to
the retention time that has been derived from previous chro-
matographic analysis. Also the boiling point of the identified
component is compared to the boiling points of other compounds
in the near vicinity of the one in question when a capillary
coated with a nonpolar phase has been used.
Level IV Manual Interpretation Plus Retention Time of Authentic Compounds.
Under this Level, the authentic compound has been chromato-
graphed on the same capillary column using identical operating
conditions and the mass spectrum of the authentic compound is
compared to that of the unknown.
Level V Level IV Plus Independent Confirmation Techniques. This Level
utilizes other physical methods of analysis such as GC/Fourier
transform infrared spectrometry, GC/high resolution mass
spectrometry, or nmr analysis. This Level constitutes the
highest degree of confidence in the identification of organic
compounds.
Unless otherwise stated, all identifications in this report were Level II.
44
-------
SECTION 7
RESULTS
VOLATILES
All 42 of the purged samples were analyzed by thermal desorption/GC/MS.
The mass spectra from selected samples were interpreted manually to deter-
mine which compounds should be quantitated. From these data, selected
compounds were quantitated in all samples. All data were stored on magnetic
tape for subsequent processing and are routinely archived for at least 5
years.
Qualitative Identifications
Eight samples were interpreted. The results are presented in Appendix D.
Samples were selected according to the following criteria. At least two
samples were required from each collection site (Jersey City and Bayonne,
NJ, were counted as two separate sites). The total ion current chromatograms
were inspected and the samples with the greatest number of peaks or those
containing very intense unique peaks (not observed in other samples) were
selected. For those samples selected, all of the mass spectra were printed
and interpreted manually by experienced spectroscopists.
Table 16 summarizes the compounds found and their frequency of occurrence.
It is interesting to note that some compounds (e.g. 1,1,1-trichloroethane
and hydrocarbons) are common air pollutants, others (e.g., dibromochloro-
methane) are common water pollutants, others (dimethyldisulfide, furans,
aldehydes) appear to be metabolites, others (chlorofluorocarbons, siloxanes)
are known background interferents, and others (iodopentane) are of unknown
source.
Quantitation
Based upon the qualitative identifications summarized above, nine com-
pounds were selected for quantitation in all of the samples. The results
for four compounds are summarized in Table 17. As discussed below, the
45
-------
Table 16. SUMMARY OF QUALITATIVE IDENTIFICATIONS OF VOLATILE COMPOUNDS
IN MOTHER'S MILK3
Sample Number
Compound 1081 1040 1107 1115 2048 2071 3053 3111
Halogenated Compounds
chlorodifluoromethane --+_____
chlorotrifluoromethane ++__+_+_
dichlorodifluoromethane -_+__+__
chloromethane ___ + __ + _
chloroethane __+__+__
trichlorofluoromethane + + + + + + - +
dichloroethylene _ + ______
Freon 113 + + + + + + + +
methylene chloride ++++++++
chloroform + + + + + + - +
1,1,1-trichloroethane + + + + + + + +
carbon tetrachloride _+++_+_+
trichloroethylene + + + + + + + +
chloropentane + + ______
dibromochloromethane _____+__
tetrachloroethylene ++++++-+
dichloropropene ___+____
chlorobenzene +_++++__
chlorohexane +++_+---
iodopentane - - . - +
3-methyl-l-iodobutane ++______
chloroethylbenzene ___+____
dibromodichloromethane ___+____
dichlorobenzene + + + + + + + -1-
chlorodecane +_______
trichlorobenzene _____+__
Aldehydes
acetaldehyde +_+_++__
methylpropanal -++_____
n_-butanal +- + + - + + +
methylbutanal _+_+____
crotonaldehyde ___+____
n^-pentanal +- + + + + + +
n^-hexanal + + + + + + + +
furaldehyde ___+__+_
n_-heptanal + + + + + + + -
benzaldehyde ++++++++
ii-octanal +_ + + __ + _
phenyl acetaldehyde ___+____
(continued)
46
-------
Table 16 (cont'd.)
Sample Number
Compound 1081 1040 1107 1115 2048 2071 3053 3111
n-nonanal + + + + ' + - +
methyl furaldehyde _____- + _
n-decanal ___ + __ + _
n-undecanal ___ + __ + _
n-dodecanal ______ + _
Ketones
acetone + + + + + + + +
methyl ethyl ketone ++__+++_
methyl isopropyl ketone _--+-+--
methyl vinyl ketone __+_____
ethyl vinyl ketone ++++__+_
2-pentanone ++++____
methyl pentanone __++____
methyl hydrofuranone ___+____
2-methyl-3-hexanone ___+____
4-heptanone __+_____
3-heptanone +_+_++__
2-heptanone ++++++__
methyl heptanone ___+_+__
furyl methyl ketone ___+____
octanone +__+____
acetophenone ++++++++
2-nonanone +_++_+__
2-decanone ___+____
alkylated lactone ___+____
phthalide - - + - - - -.-
Other Oxygenated Isomers
C5H100
C6H80
C6H100
C1+H602
C6H120
C7H120
C7H100
C7HlttO
C6H602
C8H160
+.
(continued)
-------
Table 16 (cont'd.)
Sample Number
Compound
1081 1040 1107 1115 2048 2071 3053 3111
Other Oxygenated Isomers
(continued)
C^H,00
C10H12°
C10H14°
C10H16°
C10H18°
C10H20°
C10H22°
C9H8°2
C11H20°
C10H10°2
Alcohols
methanol
isopropanol
2-methyl-2-propanol
n-propanol
1-butanol
1-pentanol
a-furfuryl alcohol
2-ethyl-l-hexanol
phenol
2,2,4-trimethylpentyl-
1,3-diol
ot-terpineol
Acids
acetic acid
decanoic acid
Sulfur Compounds
sulfur dioxide
carbon disulfide
dimethyl disulfide
carbonyl sulfide
-I- +
(continued)
48
-------
Table 16 (cont'd.)
Compound
Sample Number
1081 1040 1107 1115 2048 2071 3053 3111
Nitrogen Compounds
nitromethane
C5H6N2
C5H8N2
methyl acetamide
benzonitrile
methyl cinnoline
Esters
vinyl propionate
ethyl acetate
ethyl-n-caproate
methyl caprylate
ethyl caprylate
isoamyl formate
methyl decanoate
ethyl decanoate
Ethers
dimethyl ether
£-dioxane
dihydropyran
Epoxide
1,8-cineole
Furans
furan
tetrahydrofuran
methyl furan
methyl tetrahydrofuran
ethylfuran
dimethyl fur an
2-vinylfuran
furaldehyde
2-ii-butylfuran
2-pentylfuran
methylfuraldehyde
furyl methyl ketone
a-furfuryl alcohol
benzofuran
+ + +
+ + -f
' 4-
49
(continued)
-------
Table 16 (cont'd.)
Compound
Sample Number
1081 1040 1107 1115 2048 2071 3053 3111
Alkanes
C3H8
C4H10
C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24
C12H26
C13H28
C14H30
C15H32
Alkenes
-f
+
C3H6
C4H8
C5H10
C6H12
C7H14
C8H16
C9H18
C10H20
C11H22
C12H24
C13H26
isoprene
Alkynes
•f +
C5H8
C6H10
C7H12
50
(continued)
-------
Table 16 (cont'd.)
Sample Number0
Compound 1081 1040 1107 1115 2048 2071 3053 3111
Alkynes (continued)
C8H14 " + " + ~ " *
r V -4- — — 4-4- — 4- —
C9H16 + + +
C10H18 -- + + ----
r 11 ___ 4-_ ___
C12H22
Cyclic Hydrocarbons
cyclopentane + + + + - + - +
methylcyclopentane + - + - + + + +
cyclohexane + + + - + + --
ethylmethylcyclohexane -- + _____
C10H14isomers + ~ ~ ~ " • "
CnAH,,isomers (other) + + -- + + --
JU ID
limonene + + + + + + + +
methyldecalin -_ + _____
a-pinene -_ + -----
camphene ____- + __
camphor -_-__ + --
Aromatics
benzene + + + + + + + +
toluene + + + + + + + +
ethylbenzene + + + + + + + +
xylene + + -f + -f + + +
phenylacetylene ___+____
styrene + + + + + + + +
benzaldehyde + + + + -f-f- + +
C_-alkylbenzene isomers + + + + -f + + ' 4-
ChalkyIbenzene isomers - + + + + + + -
methylstyrene __4._» + __
dimethylstyrene + + - + + + --
C^-alkylbenzene isomers __4- + ----
naphthalene + + - + + + + -
C,-alkylbenzene isomers -__+-___
Arranged by class in approximate elution order. See Appendix D for sample-
by-sample identifications. + = present; - = not identified in sample.
Q
Participant code number.
51
-------
Table 17. VOLATILES QUANTITATED IN MOTHER'S MILK SAMPLES (ng/mL)
Site
Bayonne, NJ
Jersey City, NJ
Pittsburgh, PA
Baton Rouge, LA
Sample
Number
1016
1032
1040
1057
1073
1081
1024
1107
1115
1123
1164
2014
2022
2048
2055
2063
2071
2089
2097
2105
2113
2121
2139
3012
3020
3038
3046
Chloroform
_d
0.3
0.1
0.7
0.7
1.3
13
17
1.7
20
65
0.9
1.5
0.6
0.8
0.6
1.2
0.7
6.7
2.8
1.2
0.8
0.6
2.9
0.7
0.8
21
Tetrachloro-
ethylene
1.5
1.5
1.1
0.9
3.8
6.3
43
7.4
8.1
17
4.0
0.8
1.8
1.8
1.0
1.6
1.0
26
1.8
1.3
0.7
2.4
0.7
0.1
0.5
1.7
2.5
Chlorobenzene
0.2
0.1
0.1
0.1
0.1
0.1
0.1
0.2
0.3
0.1
0.1
0.2
0.1
0.1
0.05
0.1
0.1
0.2
-
0.4
0.1
TRe
0.1
0.3
0.1
0.2
0.1
Dichloro-
benzenec
6.7
9.1
66
0.2
2.2
32
2.8
68
49
2.2
0.9
0.2
1.1
8.9
0.7
3.1
1.4
0.5
0.3
1.1
0.4
2.0
0.9
4.2
0.6
1.3
2.2
(continued)
-------
• Table 17 (cont'd)
en
Co
Site
Charleston, WVg
Sample
Number3
3053
3079
3087
3095
3103
3111
4010
4028
4036
4051
4069
4085
4093
4101
4119
Chloroform
0.3
0.8
0.7
1.3
0.6
1.8
5.0
7.2
7.5
8.2
-
5.3
12
8.7
11
Tetrachloro-
ethylene
0.4
0.6
0.4
1.0
0.2
0.5
1.2
1.4
3.9
0.6
0.4
0.4
1.0
1.0
>19f
Chlorobenzene
0.2
0.1
0.2
0.3
0.1
-
0.1
0.2
10
0.2
0.1
-
0.1
0.1
0.04
Dichloro-
benzenec
1.8
0.2
5.2
4.2
>22
44
0.7
1.9
0.2
1.1
3.6
3.8
0.04
26
1.4
Participant code number.
See text for caveats with respect to chloroform.
All isomers summed.
w>t detected.
eTrace.
Instrument saturated.
CT
6Sample 4044 lost due to instrumental malfunction.
-------
quantitation of the other five compounds is not reported, since the levels
in milk were not judged sufficiently greater than background to be reliable.
Upon inspection, it is obvious that most values are low relative to
only a few high "outliers." These high values suggest that there is a
range of levels of these compounds which may correlate with exposure.
These results were analyzed statistically to determine if any of the values
correlated significantly. As can be seen in Table 18, the arithmetic mean
and median values generally are quite different. The arithmetic mean is
skewed toward the high end, generally due to one or two relatively high
values. A more realistic representation of the central data is the geometric
mean. These geometric mean values were tested for their significance
(i.e., are the geometric means significantly different from site to site?).
Table 19 summarizes this data. From this table, it appears that samples
from Jersey City have significantly higher levels of chloroform, tetrachloro-
ethylene, and dichlorobenzene than the other study samples. Charleston
samples appear to have significantly higher levels of chloroform, and
Bayonne samples appear to have significantly higher levels of dichlorobenzene.
To test if any of the compound levels were related, the Spearman
correlation coefficients (nonparametric correlation based on the sample,
designed to lessen the weight of a single high outlier) were determined as
shown in Table 20. There does not appear to be any compound-to-compound
correlation among the subjects.
In interpreting these data, it must be remembered that this is a very
small data set. Therefore these data should not be used to extrapolate to
the city or area from which the samples were collected.
Quality Control
Table 21 presents the quality control results for chloroform, tetra-
chloroethylene, chlorobenzene, and dichlorobenzene. The very high recovery
of chloroform from the controls indicates either a miscalculation of the
amount actually spiked or contamination of the samples used as controls.
Since the procedural blanks contained about 15 times less chloroform, the
former explanation is most reasonable. However, the chloroform values
reported in Table 17 must be interpreted subject to the following
54
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Table 18. SUMMARY STATISTICS FOR VOLATILE COMPOUNDS BY SITEa
Site
Bayonne, NJ
Maximum
Meanb
Median
S.D.
n
Jersey City, NJ
Maximum
Meanb
Median
S.D.
n
Pittsburgh, PA
Maximum
Meanb
Median
S.D.
n
Baton Rouge, LA
Maximum
Meanb
Median
S.D.
n
Charleston, WV
Maximum
Meanb
Median
S.D.
n
Overall
Maximum
Meanb
Median
S.D.
n
Chloroform
1.3
0.52
0.5
0.48
6
65
23.34
17
24.3
5
6.7
1.53
0.85
1.74
12
21
3.09
0.8
6.34
10
12
7.21
7.5
3,55
9
65
5.57
1.25
10.9
42
Tetrachloro-
ethylene
6.3
2.52
1.5
2.13
6
43
15.9
8.1
15.9
5
26
3.41
1.45
7.13
12
2.5
0.79
0.5
0.75
10
>19
3.21
1
6.02
9
43
4.10
1.25
8.15
42
Chloro-
benzene
0.2
0.12
0.004
0.1
6
0.3
0.16
0.1
0.089
5
0.4
0.12
0.1
0.11
12
0.3
0.16
0.15
0.096
10
10
1.20
0.1
3.30
9
10
0.37
0.1
1.53
42
Dichloro-
benzene
66
19.37
7.9
25.54
6
68
24.48
2.8
31.69
5 .
8.9
1.71
1
2.41
12
44
8
3.2
13.98
10
26
4.30
1.4
8.25
9
68
9.15
1.95
17.3
42
Maximum, mean and median values are ng/mL.
Arithmetic mean.
55
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Table 19. SIGNIFICANCE OF THE DIFFERENCES IN THE GEOMETRIC MEANS BY SITE
Geometric Mean (ng/mL)
Site
Bayonne
Jersey City
Pittsburgh
Baton Rouge
Charleston
Significance
Chloroform
0.45
14.7
1.23
1.53
5.92
0.01
Tetrachloroethylene
2.09
11.5
1.82
0.67
1.65
0.01
Chlorobenzene
0.12
0.16
0.12
0.15
0.42
N.S.b
Dichlorobenzene
8.33
8.55
1.21
3.83
1.98
0.05
0.01 implies 99 percent confidence that the numbers are statistically different, while 0.05
implies 95 percent confidence.
Not significant.
-------
Table 20. SPEARMAN CORRELATION COEFFICIENTS FOR VOLATILE ORGAN!CS
FOUND IN MOTHER'S MILK
_,- - Tetrachloro- _., , Dichloro-
Chloroform , , Chlorobenzene ,
ethylene benzene
Chloroform
Tetrachloro-
ethylene
Chlorobenzene
Dichloro-
benzene
1.0 0.373 -0.02b -0.13b
1.0 0.007b 0.05b
1.0 0.03b
1.0
Significant at 0.05 level (95 percent confidence).
b Not significant
Sample size = 42
57
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Table 21. QUALITY CONTROL RESULTS FOR VOLATILES IN MILK
Type of Sample
Chloroform
Tetrachloroethylene
Chlorobenzene
Dlchlorobenzene
Blanks
n
Mean (ng/mL)D
S.D.
RSD (%)
Controls0
7
1.2
1.3
108
7
0.22
0.11
49
7
0.03
0.025
84
17
0.12
0.19
159
in
00
n
Mean Recovery6
S.D.
RSD (%)
8 ,
14. 02*
8.20
58
8
1.12
0.41
37
8
0.62
0.34
55
0
-
—
Blanks consisted of two field water blanks and five water blanks purged with the milk samples to monitor
procedural background. No difference between the two types of blanks was observed.
Arithmetic mean.
Controls consisted of two spiked raw cow's milk samples carried to the field and returned, two spiked
raw cow's milk samples stored in the laboratory, two spiked water samples carried to the field and
returned, and two spiked water samples stored in the laboratory. No major differences were observed
between the four types of samples. Samples were spiked at 30-90 ng/volume purged (or about 1 ng/mL).
Not included in control spiking solution.
1.0 = 100 percent recovery.
Extremely high recovery probably a result of improper loading of controls.
-------
considerations: the mean reported levels in the samples were only 4.9 times
the blank levels; the recovery from controls was about 1400 percent, invali-
dating the recovery study; and chloroform is known to be a laboratory atmos-
pheric contaminant.
The compounds presented in Table 17 represented significant levels
above the background in blanks. Several other compounds were quantitated
that did not exhibit substantial concentrations. These compounds, with the
ratio of the mean in the samples to the mean in the background given in
parenthesis, were: 1,1,1-trichloroethane (1:1), benzene (2:1), toluene
(2:4), trichloroethylene (1:2) and carbon tetrachloride (1:4). These levels
in the samples cannot be reliably assigned to either the milk sample or to
laboratory contamination. If these compounds are present in milk, they are
very low and cannot be regarded as significant, given the limitations of the
technique employed. Apparently, mother's milk does not represent a bioconcen-
tration matrix for these compounds.
SEMIVOLATILES
Three samples were fully interpreted, as presented in Appendix E. As
can be seen from the data, few compounds of interest were observed in the
mass spectra. The data were searched on the GC/MS data system for target
compounds (PCNs, PBBs and PCBs) using single ion plots called up from the
full data set. No evidence for any of these compounds was observed at a
detection limit of about 20 ppb. DDE was quantitated in five samples as
shown in Table 22. These values were in the range generally reported by
previous investigators (see Tables 2 - 4). Since none of the target compounds
were present in detectable quantities, no further identification or quantita-
tion was attempted.
59
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Table 22. DDE AND TETRACHLOROBIPHENYL LEVELS IN SELECTED
MOTHER'S MILK SAMPLES
Site
Pittsburgh
Pittsburgh
Charleston, WV
Charleston, WV
Charleston, WV
Sample
Number
2105
2121
4069
4085
4093
d
Mean
S.D.
RSD (%)
Median
ng/mL Milk
DDE Tetrachlorobiphenyl
45 NDb
73 TC
107 ND
38 ND
91 ND
71
29
42
73
Samples selected as having the most intense total ion current
chromatograms.
Not detected.
Trace.
Arithmetic mean.
60
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12. Savage, E. P., e_t al., "A Search for Polychlorinated Biphenyls in Human
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19. Ritchy, W..R., G. Savary and K. A. McCulley, "Organochlorine Insecticide
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20. Egan, H., R. Goulding, J. Roburn and J. O'G. Tatton, "Organo-chlorine
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69 (1965).
21. Newton, K. G. and N. C. Greene, "Organochlorine Pesticide Residue
Levels in Human Milk — Victoria, Australia 1970," Pest. Mon. J., 6,
4-8 (1972).
22. Graca, I., A. M. S. Silva Fernandes and H. C. Mourao, "Organochlorine
Insecticide Residues in Human Milk in Portugal," Pest. Mon. J., 8,
148-156 (1974).
23. Musial, C. J., 0. Hutzinger, V. Zitko and J. Crocker, "Presence of PCB,
DDE, and DDT in Human Milk in the Providences of New Brunswick and Nova
Scotia, Canada," Bull. Environ. Contamin. Toxicol., 12, 258-267 (1974).
62
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24. Mes. J. and D. J. Davies, "Presence of Polychlorinated Biphenyl and
Organocblorine Pesticide Residues and the Absence of Polychlorinated
Terphenyls in Canadian Human Milk Samples," Bull. Environ. Contain.
Toxicol., 21, 381-387 (1979).
25. Stacey, C. I. and B. W. Thomas, "Organochlorine Pesticide Residues in
Human Milk, Western Australia — 1970-71," Pest. Mon. J., 9, 64-66
(1975).
26. Van House Holdrinet, M., H. E. Braun, R. Frank, G. J. Stopps, M. S.
Smout, and J. W. McWade, "Organochlorine Residues in Human Adipose
Tissue and Milk from Ontario Residents," Can. J. Pub. Health, 68,
74-80 (1977).
27. Winter, M., M. Thomas, S. Wernick, S. Levin and M. T. Farver, "Analysis
of Pesticide Residues in 290 Samples of Guatemalan Mother's Milk,"
Bull. Environ. Contamin. Toxicol., 16, 652-657 (1976).
28. "Criteria for a Recommended Standard...Occupational Exposure to Ethylene
Bichloride (1,2-dichloroethane)," HEW Publ. No. (NIOSH) 76-139 (March
1976).
29. Kover, F. D., Environmental Hazard Assessment Report. Chlorinated
Naphthalenes. EPA 560/8-75-001 (December 1975).
30. Erickson, M. D., R. A. Zweidinger, L. C. Michael and E. D. Pellizzari,
"Environmental Monitoring Near Industrial Sites: Polychloronaphthalenes,"
EPA-560/6-77-019 (1977).
31. Erickson, M. D., L. C. Michael, R. A. Zweidinger, and E. D. Pellizzari,
"Development of Methods for Sampling and Analysis of Polychlorinated
Naphthalenes in Ambient Air," Environ. Sci. Technol., 12, 927-931
(1978).
32. Erickson, M. D., L. C. Michael, R. A. Zweidinger and E. D. Pellizzari,
"Sampling and Analysis for Polychlorinated Naphthalenes in the Environ-
ment," JAOAC, 61, 1335-1346 (1978).
33. Erickson, M. D., L. C. Michael, R. A. Zweidinger, and E. D. Pellizzari,
"Development of Methods for Sampling and Analysis of Polychlorinated
Naphthalenes in Ambient Air," 1977 Annual Meeting, American Chemical
Society, Chicago, IL (August 31, 1977).
63
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34. Erickson, M. D., L. C. Michael, R. A. Zweidinger, and E. D. Pellizzari,
"Sampling and Analysis for Polychlorinated Naphthalenes in the Environ-
ment," 1977 Annual Meeting AOAC, Washington, DC (October 20, 1977).
35. Unpublished data, E. Roessler, Borough of Bridgeville, PA (1976).
36. 1977 Directory of Chemical Producers-USA, Chemical Information Services,
Stanford Research Inst., Menlo Park, CA (1977).
37. Environmental Sciences and Engineering, "Trip Report for Sampling of
Polybrominated Biphenyls (PBBs)," submitted to OTS, EPA, Washington, DC,
Contract No. 68-01-3248 (April 1977)).
38. Mumma, C. E. and D. D. Wallace, "Survey of Industrial Processing Data.
Task I - Pollution Potential of Polybrominated Biphenyls," EPA-560/3-
75-004 (June 1975).
39. Unpublished data, E. J. Londres, New Jersey Dept. of Environmental
Protection via G. E. Parris, OTS, EPA, Washington, DC (1977).
40. Erickson, M. D., R. A. Zweidinger, and E. D. Pellizzari, "Analysis of a
Series of Samples for Polybrominated Biphenyls (PBBs)," EPA-560/6-77-020
(August 1977).
41. Environmental Science and Engineering, "Data Report for Polybrominated
Biphenyl Near Manufacture (sic) in the Northeast," submitted to OTS,
EPA, Washington, DC Contract No. 68-01-3248 (June 16, 1977).
42. 1974 New Jersey State Industrial Directory, New Jersey State Industrial
Directory, 2 Perm Plaza, NY, 10001 (1974).
43. Pellizzari, E. D., "The Measurement of Carcinogenic Vapors in Ambient
Atmospheres," EPA-600/7-77-055 (June 1977).
44. Pellizzari, E. D., M. D. Erickson, and R. A. Zweidinger, "Formulation of
a Preliminary Assessment of Halogenated Organic Compounds in Man and
Environmental Media," EPA-560/13-79-006 (July 1979).
45. Pellizzari, E. D., M. D. Erickson, T. D. Hartwell, S. R. Williams, C. M.
Sparacino and R. D. Waddell, "Preliminary Study on Toxic Chemicals in
Environmental and Human Samples. Part I: Formulation of an Exposure
and Body Burden Monitoring Program," submitted to U. S. Environmental
Protection Agency, Washington, DC, Contract No. 68-01-3849 (June 1980).
64
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68. Eight Peak Index of Mass Spectra. Vol. I (Tables 1 and 2) and II
(Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading,
RG74PR, UK (1970).
67
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APPENDIX A
DATA COLLECTION INSTRUMENTS
68
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46. Pellizzari, E. D., "Analysis of Organic Air Pollutants by Gas Chromato-
graphy and Mass Spectroscopy," Publication No. EPA-600/2-77-100,
Contract No. 68-02-2262, (June 1977).
47. McDonnell, G., D. M. Ferguson and C. R. Pearson, "Chlorinated Hydrocar-
bons and the Environment," Endeavour, 34, 13-18 (1975).
48. FDA Compliance Program, Evaluation, "FY 74 Total Diet Studies (7320.08),"
Date accepted: January 21, 1977.
49. State of New Jersey Department of Environmental Protection, "Initial
Report on the Findings of the State Air Monitoring Program for Selected
Volatile Organic Substances in Air," (October 1979).
50. Zweidinger, R. A., A. Sherdon, B. S. Harris, III, H. Zelon, T. Hartwell,
and E. D. Pellizzari, "Measurement of Benzene Body Burden of Potentially
Environmentally Exposed Individuals," Final Report, EPA Contract No.
68-01-3849, Task 1 (May 1980).
51. Hartwell, T., P. Piserchia,.S. White, N. Gustafson, A. Sherdon, R.
Lucas, D. Lucas, D. Myers, J. Batts, R. Handy, and S. Williams, "Analysis
of EPA Pesticide Monitoring Networks," Office of Toxic Substances,
Washington, DC. Draft Report (1979).
52. U.S. Environmental Protection Agency, Office of Research and Development,
"Health Assessment Document for Polycyclic Organic Matter," (May 1978).
53. Stanford Research Institute, "The Environmental Fate of Selected Poly-
nuclear Aromatic Hydrocarbons," Prepared for U. S. Environmental Pro-
tection Agency (February 1976).
54. State of New Jersey Department of Environmental Protection, "Initial
Report on the Findings of the State Air Monitoring Program for Selected
Heavy Metals in Air," (October 1979).
55. Unpublished data, William J. Librizzi, U.S. Environmental Protection
Agency, Region II (October 1977).
56. Fribers, L., M. Piscator, G. F. Nandberg and T. Kjellstrom, "Cadmium in
the Environment," CRC Press, Cleveland, OH (1974).
65
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57. National Academy of Sciences, "Lead," Washington, DC (1972).
58. Mason, T. J., F. W. McKay, "U.S. Cancer Mortality by County: 1950-69,"
DHEW Publ. No. (NIH), 74-615, Washington, DC, U.S. Govt. Printing Office
(1974).
59. Mason, T. J., F. W. McKay, J. R. Hoover, W. Blot and J. F. Fraumeni,
Jr., "Atlas of Cancer Mortality for U.S. Counties: 1950-69," DHEW Publ.
No. (NIH) 75-780, Washington, DC, U.S. Govt. Printing Office (1975).
60. Greenberg, Michael R., "The Spacial Distribution of Cancer Mortality and
of High and Low Risk Factors in the New Jersey-New York-Philadelphia
Metropolitan Regions, 1950-1969, Part I," New Jersey Dept. of Environ-
mental Protection, Program on Environmental Cancer and Toxic Substances
(January 1979).
61. Greenberg, M., F. McKay, and P. White, "A Time-Series Comparison of
Cancer Mortality Rates in the New Jersey-New York-Philadelphia Metropoli-
tan Region and the Remainder of the United States, 1950-1969," Am. Jour.
of Epidemiology, 111, 166 (1980).
62. Greenberg, M. R., P. W. Preuss, and R. Anderson, "Clues for Case Control
Studies of Cancer in the Northeast Urban Corridor," Soc, Sci. & Med.,
14D, 37-43 (1980).
63. Greenberg, M. R., J. Caruana, B. Holcomb, G. Greenberg, R. Parker, J.
Louis, and P. White, "High Cancer Mortality Rates from Childhood Leukemia
and Young Adult Hodgkin's Disease and Lymphoma in the New Jersey-New
York-Philadelphia Metropolitan Corridor, 1950-1969," Cancer Research,
40, 439-443 (1980).
64. Cross, J. and G. B. Wiersma, "Preliminary Analysis of Cancer Rates in
Organic Chemical-Producing Counties," EPA-600/1-79-022 (June 1979).
65. Pellizzari, E. D., and M. D. Erickson, "Analysis of Organic Air Pollutants
in the Kanawha Valley, WV and the Shenandoah Valley, VA," Publication
No. EPA-903/9-78-007, Contract No. BOA 68-02-2543 (June 1978).
66. Erickson, M. D., S. P. Parks, D. Smith and E. D. Pellizzari, "Sampling
and Analysis of Organic Air Pollutants in Two Industrialized Valleys,"
FACSS V, Boston (October 30 - November 3, 1978.
67. McLafferty, F. W., E. Stenhagen, and S. Abrahammson, Ed., Registry of
Mass Spectral Data, John Wiley and Sons, New York (1974).
66
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STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK
EPA Contract No. 68-01-3849
RTI Project No. 31U-1521-22
DATA COLLECTION INSTRUCTIONS
Performed for
Office of Toxic Substances
Environmental Protection Agency
Washington, DC 20460
69
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1.0 Introduction
Under contract to the Office of Toxic Substances, Environmental
Protection Agency (EPA), the Research Triangle Institute (RTI) is
conducting a limited study designed to measure environmental pollutant
levels in human milk and to evaluate the utility of using this body
fluid in specific pollutant studies for populations in the vicinity of
manufacturing plants and/or industrial user facilities. RTI is responsible
for all phases of the study, including study design, subject recruitment,
chemical analysis of milk samples, and report writing. RTI is a not-for-profit
contract research organization located in North Carolina's Research Triangle
Park between Raleigh, Durham, and Chapel Hill. The Institute was incorporated
as a separate operating entity in 1958 by the University of North Carolina
(UNC) at Chapel Hill, Duke University at Durham, and North Carolina State
University at Raleigh, and is still closely affiliated with the three
universities.
2.0 Overview
Four urban areas have been chosen as performance sites; they are
Bridgeville, Pennsylvania; the area which includes Linden and Bayonne,
New Jersey and western Staten Island, New York; Baton Rouge, Louisiana;
and South Charleston and Nitro, West Virginia. These sites represent
high-probability areas for the presence of one or more of the chemicals
of interest in human milk. The selected industrial chemicals of interest
include polychlorlnated naphthalenes, tetrachlorethylene, trichloroethane,
dichloropropane, benzene, polybrominated biphenyls, chlorinated phenols,
toluene, chlorinated benzenes, and chloroform.
70
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At each of the four sites, arrangements will be made to work through
clinical facilities such as hospitals, clinics, or physician's offices,
in order to recruit a panel of respondents. At each site ten participants
will be recruited, for a total of 40. Potential participants (lactating
females) will be screened to determine that they live in one of the areas
of interest and are willing and able to provide the milk sample.
A questionnaire will be administered for each participant to obtain
information on demographic variables, residence histories, and potential
exposure situations; for each participant, a sample of milk will be collected
and analyzed for the compounds of interest by gas chromatography/mass
spectrometry or high pressure liquid chromatography. A professional member
of the facility's staff, such as a registered nurse, will be trained in the
proper procedures to administer the questionnaire and obtain the milk sample.
To try to reduce the non-participation rate due to refusals, and to reimburse
the subject for the time spent on the study, volunteers will be offered a
$5.00 incentive for participating.
3.0 Data Collection
3.1 General Remarks
Data collection for this research effort consists of the following
steps:
1. Screening of potential participants (lactating women) to
determine that they live in one of the areas of interest
(see below), that they have resided in that area for at
least the preceding 12 months, that they have remained in
that area continuously for the preceding week, and that they
are willing and able to provide a milk sample.
71
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2. When an eligible person is encountered, the nature and
purpose of the study will be explained and their partici-
pation solicited.
3. When an eligible person agrees to participate, the person
will be required to sign a Participant Consent Form (FCF)
in order to participate in the study.
4. Once the participant has signed the PCF, the person should'
be listed on the Participant Listing Form (PLF), a Patient
Number assigned, and the data collector will proceed to
administer the Study Questionnaire (SQ) and collect the
milk sample.
5. Once the SQ has been administered and the milk sample collected,
the participant will be offered a $5.00 incentive for
participating.
*
6. Milk samples and completed data collection instruments will
be returned to RTI.
3.2 Survey Instruments
As indicated in the preceding section, there are 3 data collection
instruments for this research effort, the PCF, the PLF, and the SQ; subsequent
sections contain instructions for the use of each instrument as well as
item-by-tiem explanations for their completion, and general descriptions
are provided below. The survey instruments have been designed hopefully
to provide an efficient means of collecting and recording the requisite
data for the study. It is imperative that all survey instruments be completed
accurately. The success and reliability of the study and its results are
dependent upon the quality of data collected, which will be fully dependent
72
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on the accuracy of your execution of your assignment. As you complete
a form, conduct a thorough edit to verify that required data have been
entered and entered correctly. Copies of the data collection instruments
appear in Attachment 1.
3.2.1 Participant Consent Form (PCF)
. Purpose; The purposes of the PCF are to introduce
the study; explain its objectives, sponsorship (the
relationship and roles of RTI and EPA), and require-
ments of and risks, burdens, and benefits to partici-
pants; and stress that participation is completely
voluntary and that all data collected will be kept
confidential.
. General Description: The PCF is a single page form
printed on special paper which makes three copies from
a single impression. The survey title appears at the
top, along with the name of RTI; spaces for necessary
identifying information appear at the bottom.
. Administration; The PCF will be signed by the partici-
pant and contains an agreement to provide the necessary
information and milk sample. Participants may freely
withdraw from the study at any time; however, in order
to encourage participation RTI offers an incentive of
five dollars to each participant to be paid after each
data set (PCF, SQ, and milk sample) is obtained. Again,
confidentiality of data is stressed, including steps
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taken to disassociate the name of the participant
from the data once collected; for example, the PCF
is the only data collection instrument which bears
the name of the participant and allows its association
to study identification numbers, but will be maintained
in hard copy only and stored in a restricted area.
To further emphasize this disassoclation, the incentive
will be paid in cash rather than by check or money order,
although the participant will sign the PCF indicating
that the incentive was received. A signed PCF must be
obtained for each participant before proceeding with
Study Questionnaire (SQ) administration and collection
of the milk sample.
. Disposition; The top (white) copy will be attached
to the appropriate SQ until it is received at RTI and
verified; the yellow copy will be provided to the
participant; the pink copy will be retained by the data
collector.
3.2.2 Participant Listing Form (PLF)
. Purpose: The purpose of the PLF is to provide a means
of assigning unique numbers to participants at each
performance site.
. General Description; The PLF is a single page form
printed on pink paper; space for Comments is provided
on the reverse side. The survey title appears at the
top, along with the names and addresses of RTI and EPA/OTS
and a confidentiality statement.
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. Administration; As each participant is enlisted up
to the required number (10), that participant should
be listed on the PLF.
. Disposition; When data collection at a site or facility
is completed, the PLF (or a copy) should be sent to RTI.
3.2.3 Study Questionnaire (SQ)
. Purpose; The purpose of the SQ is to obtain information
on participants, including demographic characteristics
such as age, sex, race, and occupation; residence infor-
mation; health information such as current health status
and prescription medications; and personal characteristics
such as hobbies.
. General Description; The SQ is divided into six sections,
dealing respectively with demographic characteristics,
occupation, health and personal habits, residence and
household information, information on the interviewer and
respondent, and information regarding the milk sample,
including an indication as to whether or not the milk
sample was obtained, the date and time of acquisition
of the sample, and the date the sample was shipped to RTI.
Participants will be identified by a unique study number
used to correlate and cross-identify the questionnaires
and samples by way of pre-printed self-adhesive labels.
The SQ is 5 pages long, with space provided for comments.
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. Administration; An SQ is to be completed for each
participant for whom a signed PCF is obtained.
. Disposition: The SQ's are to be sent to RTI as instructed.
3.3 Screening
As indicated in section 3.1, potential participants (lactating women)
should be screened to determine that they meet certain study criteria for
participation:
1. That they are willing and able to provide a milk sample of
sufficient quantity (approximately 100 ml.),
2. That they live in one of the areas of interest (see below),
3. That they have resided in that area for at lea'st the preceding
12 months, and
A. That they have remained in that area continuously for the
preceding 7 days.
As indicated in section 2.0, four areas have been chosen as perfor-
mance sites, with a specific Site Number assigned to each which will remain
constant for each site and is to be entered where appropriate on data
collection instruments as follows:
Site Site Number
Northern New Jersey/Staten Island, New York 1
Bridgeville, Pennsylvania 2
Baton Rouge, Louisiana 3
Nitro/South Charleston, West Virginia 4
With the exception of Bridgeville, Pennsylvania, participants residing in
some areas at each site are of considerably more interest to the study than
those living in others, as discussed in the following sections.
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3.3.1 Northern New Jersey/Staten Island, New York
Within the Northern New Jersey/Staten Island area, potential
participants residing in some communities are of more interest than those
residing in others, more or less in the order listed below:
1. Bayonne, NJ 9. Elizabeth, NJ
2. Northern Staten Island 10. Sayreville, NJ
(Port Richmond), NY
3. Linden, NJ > NJ
4. Carlstadt, NJ > NJ
5. Saddle Brook, NJ ^ passaiC) NJ
6. Jersey City, NJ ^ Patterson, NJ
7. Kearney, NJ ^ Wayne> NJ
8. Newark, NJ
3.3.2 Baton Rouge, Louisiana
Potential participants residing in Baton Rouge are of primary
interest to this study; other communities in the Baton Rouge area of interest
are Placquemine, St. Gabriel, and Geismar.
3.3.3 Nitro /South Charleston. West Virginia
Potential participants residing in Nitro and South Charleston
are of primary interest to this study; other communities of interest in the
area are Belle and Institute.
3.4 Participant Listing Form
When an eligible person is encountered who agrees to participate,
that person should be listed on a PLF in order to be assigned a unique
Participant Number. The PLF is completed by entering the appropriate Site
Number (see section 3.3 above); then, each time that an eligible participant
is encountered who agrees to participate, up to the number required, enter the
Participant's Name (Last, First, Middle) on the PLF and assign a Participant
Number in the left-hand column, beginning with 0001 at each site unless other-
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wise instructed. Assign Participant Numbers consecutively for all study
participants. Where appropriate, enter the participant's Medical Record
Number in the right-hand column. When making numerical entries, right-adjust
and enter leading zeros.
3.5 Participant Consent Form
Potential participants must understand exactly -what is involved in
participation in the study and what benefits may be realized by participation;
this understanding and agreement must be documented by a signed PCF. In the
event that the potential participant is under the age of 18 years, the person's
parent or other legal guardian must sign the PCF in order for the designated
eligible to participate.
More specifically, the potential participant and/or that person's
parent, guardian or other spokesman, must understand that full participation
in the study consists of providing answers to a questionnaire related to
environmental exposure, part of which relates to the individual's household
in general and part of which is related to the individual participant (be
prepared to show the person the SQ), and providing a milk sample of approximately
100 ml. (be prepared to show the person one of the collection bottles.)
The individual must further understand that she will only enjoy certain limited
benefits in return for her time and inconvenience, primarily a $5.00 incentive
to be disbursed after administration of the questionnaire and collection of
the milk sample. The individual must understand that participation in the
study is completely voluntary and that she may withdraw at any time, but that
payment of the incentive is dependent on full participation. The individual
must also understand that all data collected in the study will be held
strictly confidential, and that names will not be disclosed.
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I£. the participant or that perons's parent, guardian or other
spokesman agrees to participate, read through the FCF with them and make
entries where appropriate. At the bottom, record the Date (month, day, and
year) that the PCF is signed and print the Participant's full Name (First,
Middle or Maiden, Last - do not abbreviate); record the appropriate Site
Number (see section 3.3 above) and Participant Number (from the PLF); have
the participant (or other appropriate person) sign the PCF; enter your signa-
ture as witness; and record the participant's home Address (Street Number and
Name, City, State, and Zip Code) in the spaces provided.
After data collection (administration of SQ and collection of milk
sample) is completed, the participant (or that person's parent or guardian)
should be given $5.00. The recipient must sign in the space provided at the
bottom of the PCF to indicate receipt of the incentive. Should the signatures
on the PCF for Participant and Recipient be other than the participant's,
please explain in the Comments section of the SQ.
Finally, as indicated in section 3.2.1, the top (white) copy of
the PCF is to be attached to the appropriate SQ; the yellow copy is to be
provided to the participant or her guardian; and the pink copy is to be
retained by the data collector.
3.6 Study Questionnaire
Before proceeding with administration of the SQ, read the justifi-
cation and confidentiality statement in the box on the cover. Enter the
appropriate Site (see section 3.3 above) and Participant (from the PLF)
Numbers. Stapled inside the SQ you will find a set of pre-printed, self-
adhesive labels which are necessary to identify corresponding SQs and samples.
Each label contains a unique Study Number, which should be the same on all
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labels in a set, and an indication of what the label is for. You should
also have some labels that have only a Study Number and a few that are
completely blank; these are for your use in the event that a label is
damaged or missing. If you use a label that has a Study Number only,
you will have to write on the label what it is intended for, such as MILK;
if you use a blank label, you must write on the label the Study Number and
what it is intended for. Check to be sure that all the labels in a given
SQ contain the same Study Number; if not, do not use the SQ and return it
to RTI. If the Study Number is the same on all labels, remove the one for
the QUESTIONNAIRE and place it on the cover of the SQ over the spaces
provided for the Study Number. Space for Comments is provided on page 5.
If the. participant is under 18 years of age, the SQ may have to
be administered in whole or part to the parent or guardian, and must be
administered in that person's presence. If the participant suffers from a
speech or hearing deficit, or is otherwise incapacitated, the SQ may have
to be administered to the spouse or some other spokesman.
Item 1 - Race: Indicate the participant's race by placing an X
in the appropriate box. This question may be answered by
observation; however, if there is any doubt whatsoever, ask.
Item 2 - Age; Determine and enter the participant's age in years
as of the last birthday.
Item 3 - Birthdate: Determine and enter the participant's exact
birthdate (month, day and year). Again, remember to right-
adjust and enter leading zeros. A note on dates: accept and
record partial dates, if that is all that the respondent can
provide; in that case, indicate missing elements of the date
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with a dash (-) — for example, April 1977 would be
recorded as |0 j A| - H-l - |7 |7l .
Item 4 - Weight; Determine and enter the participant's approxi-
mate weight in pounds (to the nearest pound—no fractions!)
or kilogramsf in which case observe the decimal.
Item 5 - Height; Determine and enter the participant's approximate
height in inches or centimeters.
Item 6 - Current Employment; Determine if the participant is currently
employed in any capacity and place an X in the appropriate box.
If the answer is Yes, continue to Item 7; if the answer is
No, skip to Item 10.
Item 7 - Length of Present Employment; Determine and record the
length of time that the participant has been employed by
her present employer; enter the units in the spaces provided
and then place an X in the appropriate box to indicate whether
the units represent days, months, or years.
Item 8 - Occupation Away From Home; Determine if the participant's
occupation usually takes her away from home and place an X in
the appropriate box. If Yes, continue to Item 9; if No, skip
to Item 11. This question, and Item 9 below, are aimed at
eliciting information regarding the location of the participant's
various exposure to the environment.
Item 9 - Location of Present Employment; If the participant is
currently employed, determine the nature (not the name) and
location (street address, city, state, and Zip Code, if known)
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of the employer. By nature, we mean the type of business,
such as service station, school, hospital, grocery store,
doctor's office, hotel, restaurant, etc.
Item 10 - Employment Status; If the participant is not presently
employed, determine which of the provided categories best
describes the participant's status and place an X in the
appropriate box. If the response is choice 1 or 2, skip
to Item 15; if the response is choice 3-5, continue to Item 11.
Item 11 - Usual Occupation: Determine and record the participant's
usual (or most common) occupation (when employed); be succinct -
e.g., high school coach, waitress, hotel desk clerk, taxi driver.
Item 12 - Present Occupation: Determine if the participant is
presently employed in her usual occupation (indicated in Item
11) and place an X in the appropriate box. Items 12 and 13
may be skipped for unemployed, retired and disabled persons.
Item 13; If the response to Item 12 was positive, determine how
long the participant has been employed in her usual occupation
(recorded in Item 11) and record; enter the units in the spaces
provided and then place an X in the appropriate box to indicate
whether the units represent days, months or years.
Item 14; Determine if the participant presently works at or in any
of the listed occupations or establishments and place an X
in each appropriate box.
Item 15 - Present Smoking Status; Ascertain if the participant
currently smokes cigarettes, and place an X in the appropriate
box. If YES, continue to Item 16; if NO, skip to Item 18.
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Item 16 - Age at First Smoke; If the participant is a smoker
(a positive response to Item 15), ascertain the age (in years)
at which the participant started smoking and record in the
spaces provided.
Item 17 - Smoking Frequency; Ascertain how many cigarettes the
participant smokes per day, on the average, and place an X
in the appropriate box. If the participant uses tobacco in
some form other than cigarettes, such as snuff, record in the
space provided.
Item 18 - Time Outdoors; Ascertain the average number of hours
that the participant spends out of doors each day and record
in the spaces provided — another indication of environmental
exposure.
Item 19 - Time Away From Home; Determine how many hours of the day
on the average the participant normally spends more than 2
miles away from home, and record in the spaces provided. This
determination should be done separately for weekdays and
weekends.
Item 20 - General Health Status; Using the four qualifiers provided,
ascertain the participant's general current health status and
place an X in the appropriate box.
Item 21 - Prescription Medications; Inquire as to whether the
participant is currently taking any prescription medication(s)
on a regular daily basis and place an X in the appropriate
box; if YES, determine and record the drug name - e.g., penicillin,
oral contraceptives, Valium, phenobarbital, etc.
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.Item 22 - Non-prescription Medications: Inquire as to whether
the participant has taken any non-prescription medications
in the past 24 hours, and place an X in the appropriate box;
If YES, determine and record the drug name -e.g., aspirin,
vitamins, Dristan, Bufferin, Alka-Seltzer, etc.
Item 23 - Gasoline; Inquire as to whether the participant pumps
her own gasoline, for example at self-service pumps, and place
and X in the appropriate box.
Item 24 - Egg Consumption; Determine and record the approximate
number of -eggs that the participant has eaten in the past
48 hours. Again, in recording numerical entries, remember
to right-adjust and enter leading zeros.
Item 25 - Hobbies; Determine if the participant pursues any of
the listed avocations and place an X in each appropriate box.
Item 26; Determine if the participant pursues any activity that
includes regular use of solvent glue or model airplane cement,
and place an X in the appropriate box.
Item 27 - Length of Residence in Area; Determine how many years
the participant has lived in the area of interest, and record
in the spaces provided. Round to the nearest year, except
that if the response is less than one year record as | < | 1 |
and terminate the interview; the individual is ineligible to
participate further in the study. This situation should be
detected during the screening process.
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Item 28 - Length of Residence at Current Address: Determine how
long the participant has lived at her current address;
record the units in the spaces provided and place an X in
the appropriate box to indicated whether the units represent
days, months, or years. Use the most appropriate units and
round to the nearest appropriate unit. For example, more
than 28 days should be expressed in months and more than 11
months should be expressed in years. If the participant has
resided at her current address for less than 12 months, but
has lived in the area of interest for at least 12 months,
record any previous addresses during the preceding 12 months
(city and state is sufficient) in the Comments section.
Item 29 - Cooling Appliances: Determine whether any of the indicated
appliances or others, in which case specify, are used to cool
the participant's home and place an X in the appropriate box(es)
for all that apply.
Item 30 - Home Garden; Determine if the participant's household
consumes food grown in a home garden and indicate the response
by placing an X in the appropriate box. If a positive response
is obtained, determine the location of the garden and record.
Location could be participant's backyard, or another community,
in which case specify city and state; be as specific as
possible.
Item 31 - Commercial Food Source; Determine where the participant's
household usually obtains fruit and/or vegetables and record.
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a*..- ... Again, be as specific as possible. For example, if
the city or town has more than one store by the sane name,
the store name alone would not be an adeuqate answer; as a
matter of course, record the name and location of the store,
market, or vendor.
Items 32-34 - Water Sources; In Item 32, try to determine the
primary source of drinking water for the participant's
household and place an X in the appropriate box. In Item
33, determine if the same primary drinking water source
indicated in Item 32 is used for drink mixes such as coffee
and tea; if it differs, indicate how. In Item 24, try to
determine the primary source of water for cooking in the
participant's household and place an X in the appropriate box.
For example, some households in some areas of the country
use bottled water for drinking and drink mixes but tap water
(from whatever source) in cooking.
Item 35 - Other Household Tobacco Use: Inquire as to whether
other members of the participant's household smoke, and place
an X in the appropriate box; if YES, determine if the other
members smoke cigarettes, cigars, a pipe, etc. and place an
X in each appropriate box.
Item 36 - Occupation of Other Household Members: Determine if any
other members of the participant's household work at any of
the listed occupations or businesses, and place an X in each
appropriate box.
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Item 37 - Hobbies of Other Household Members; Determine if any
other members of the participant's household pursue any of
the listed avocations, and place an X in each appropriate box.
Respondent/Interviewer Information
Item 38 - Respondent; Indicate, by placing an X in the appropriate
box, whether the person who served as the primary respondent was
the participant or some other person, in which case specify
in the space provided.
Item 39 - Interviewer Number; Enter your assigned 3-digit
Interviewer identification Number.
Item 40 - Date of Interview; Enter the date (month, day and year)
that the interview was conducted and the questionnaire completed.
Item 41 - Interviewer Name; The name of the person administering
the questionnaire should be printed in the space provided.
Sample Information
Item 42; Indicate, by placing an X in the appropriate box, whether
or not a milk sample was collected; if not, explain in the
Comments section below.
Item 43 - Date and Time of Milk Sample Collection; If a milk sample
is collected, record the date (month, day and year) and
approximate time (using a 24-hour clock) of such collection.
The time should correspond to the time that collection was
completed; on a 24-hour clock, add 12 to the p.m. hours - e.g.,
1:00 p.m. would be 13:00, 5:30 would be 17:30, etc.
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Item 44 - Date Shipped to RTI; Record the date (month, day ami
year) that the respective milk sample was shipped to RTI, or
turned over to an RTI representative.
3.7 Collection of the Milk Sample
3.7.1 General Remarks
As indicated in section 1.0 above, the milk samples are
being collected for chemical analysis by RTI as part of an EPA study to
measure pollutant levels in human milk and evaluate the utility of using this
body fluid in specific pollutant studies. The chemical compounds for which
the samples will be analyzed are present in extremely low levels, so the
utmost care and cleanliness must be used to prevent either contamination or
loss. The instructions below are designed to preserve the integrity of the
sample and should be followed precisely.
3.7.2 Sample Collection Instructions
1. The bottles provided have been thoroughly cleaned and
should be kept tightly closed, except during sampling;
do not wash or otherwise clean them.
2. Remove the MILK SAMPLE label from the sheet of labels
in the appropriate SQ and place on one of the collection
bottles.
3. The milk should be manually expressed directly into the
the bottle; do not use breast pumps or other devices as
the plastics in such devices would contaminate the sample.
Hands should be cleaned and thoroughly rinsed to remove
any residual soap; do not use rubber gloves.
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4. Collect as much milk as possible. Unless the mother
has recently nursed her infant, at least half a bottle
should be easily obtainable. Less than half a bottle
is unuseable and does not constitute a sample. The
ability of the participant to provide an adequate sample
should be determined during the screening process.
5. Immediately cap the bottle and double check to see that
the study numbers on the bottle and questionnaire match.
6. The milk sample should be immediately frozen following
collection and remain so until shipping.
7. Note any deviations from this procedure in the Comments
. section of the appropriate SQ.
3.7.3 Shipping Instructions
1. Pack the container as it was received.
2. Fill the can with dry ice.
3. Make sure that there is adequate padding to prevent
breakage, that all excess space is filled with packing
material.
4. Fill out enclosed Federal Express forms, attach to
the outside of the box, and seal the box.
5. Call Federal Express and have them pick up the package.
6. When Federal Express picks up the package, call Dr. Mitch
Erickson at RTI (see below) to notify him that Federal
Express has picked up the package; if Dr. Erickson is out,
leave an appropriate message with his secretary.
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7. Mail the corresponding questionnaires to RTI in one of
the envelopes provided.
8. When the questionnaires are in the mail, call Ben Harris
at RTI (see below) to notify him that the questionnaires
are in the mail; if Mr. Harris is out, leave an appropriate
message with his secretary.
4.0 Confidentiality
All survey research conducted by RTI is based on highest ethical standards,
including those related to confidentiality. These standards are applied from
the earliest steps of deciding whether or not RTI should participate in a
proposed survey to the final steps of analyzing and reporting the information
obtained. Strict precautions must be observed at all times to protect
the rights of those whom we interview or about whom we collect data. Such
•
precautions are built into the study design, so that promises of confidentiality
and anonymity will be upheld during all phases of data handling and analysis.
No amount of effort to insure confidentiality will be successful,
however, unless those responsible for data collection in the field maintain
equally rigid standards, treating with utmost confidence all information offered
or observed during data collection. Successful and meaningful survey research
is dependent on the establishment of trust between individuals engaged in data
collection and sources of information, and maintaining this sense of responsibilit
to the public throughout all survey activities.
Each data collector will be required to sign in duplicate a contractual
agreement which includes provisions on confidential treatment of data. This
agreement is designed to protect you as well as RTI and participating institu-
tions and individuals. A copy of this agreement appears in Attachment 2.
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The importance of total confidentiality cannot be over-emphasized. Any
breach of confidence could result in litigation.
5.0 Contacts with Project Staff
During the data collection period it will be necessary for data
collectors to maintain regular contact with RTI project staff by telephone.
While you are collecting data, problems or confusing issues may arise that
are not addressed in these instructions. You are encouraged to telephone
RTI whenever you experience a problem or encounter a situation which you
feel you cannot adequately handle.
All supplies required for data collection will be furnished by RTI.
Should you require additional supplies during the conduct of data collection,
inform your RTI contact so that proper arrangements can be made. Need for
additional supplies should be anticipated so that your work will not be delayed
while you await receipt of needed items. All study-related items that are
in your possession at the conclusion of data collection are to be returned
to RTI or disposed of according to instructions from your RTI contact.
Calls to RTI should be made between the hours of 8:30 a.m. and 5:00 p.m.
(Eastern Time), Monday through Friday, to RTI's toll-free number, 800-334-8571.
Request to speak to the appropriate project staff member listed below:
Dr. Mitch Erickson Extension 6505
(regarding milk sample collection)
Mr. Ben Harris Extension 6055
(regarding participant selection and questionnaire administration)
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If the problem is particularly acute, and you have trouble getting through
on-the toll-free line, call collect 919-541-6505 (Dr. Erickson) or 919-541-60!
(Mr. Harris). After 6:00 p.m. Eastern Time you may call Mr. Harris collect
at work (919-541-6055) or person-to-person at home (919-942-6988).
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Attachment 1
Data Collection Instruments
93
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OMB No. 1S8-S7801
Approval Expirei Stpttmbcr 198
RESEARCH TRIANGLE INSTITUTE
STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK
PARTICIPANT CONSENT FORM
I understand that Research Triangle Institute it engaged in e nudy of various organic compounds as they appear
in human milk. I underrtand that the survey is being conducted in order to measure the levels of various organic
compounds in human milk, and is limited to the purpose stated. I further understand that the survey is being
conducted under the auspices of the United States Environmental Protection Agency in cooperation with
[Name of Local Agency] • .
I do hereby freely consent to participate in this study of organic compounds in human milk and understand that
my participation will consist of providing answers to a questionnaire related to environmental exposure and pro-
viding a milk sample of approximately 100 ml. I underrtand that an agent of Research Triangle Institute will
administer the questionnaire and collect the milk sample, after which I will receive an incentive of five dollars for my
participation.
I understand that my name will not be voluntarily disclosed, or referred to in any way when compiling and
evaluating the results of the study. I understand that participation in this study may result in no direct benefits to
me. other than those described herein, and that I am free to withdraw from this study at any time. It has been
explained to me that there are no significant risks to me from participation in this study. I further understand that
while participating in the study I will be free to ask any questions concerning the study; if I have any further
questions about the project, I know that I am free to contact
telephone mimbtr .
or Mr. Benjamin S. H. Harris, III, Survey Operations Center, Research Triangle Institute, Research Triangle Park,
North Carolina 27709, telephone number 919-541-6055.
.: m-m-
Participent'i Name:
Month) IDtyl (Yttrl (Prim)
Site Number: | | Perricipem Number:
SIGNATURES:
Participant: Witneu:
(Stntt Nurnttrtnd Hunt I
ICItyl ISaal (Zip Cod*)
Incentive Received:
CSfcnetui* of ftecjpi'entJ
94
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STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK
Sponaorad by:
Offica of Toxic Subroncai
Environmental Prottetion Aoancy
Washington, O.C. 30460
Conducndby:
Raatarcn Tranajt Irmftuta
P.O. Box 12194
Rnurch Triingli Park. North Carolina 27709
PARTICIPANT LISTING FORM
NOTICE: AM information racordad on tfiit decumant wfiiefi would oarmit idantificarion of an individual or an arabliirimant will
ba hald in ftrin coMidanea, oil) ba uiad only by panont angaoad in and for tna purpom nattd for thii nudv, and will not taa
diacloiad or ralaaaM to otnar oanoni or umi for any othar purpoai.
Sin Numbar
D
Numbar
Participant Nama ILttt. f/m. Miaaltl
Madieal Raeord Numbar
95
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COMMENTS
96
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OMB No. 1S8-S780
Approvil Expim Swnmber 19
STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK
Spomorid by:
Off let of Toxfc SufarancM
Environmtmal Protection Agmcy
Wunington. D.C. 20460
Conducted by:
RMMrch Transit IntttaiM
P.O. Bon 121B4
RiiMrch Triangl* Ptrk. Nor* Ccrolint 27709
QUESTIONNAIRE
THE RESEARCH TRIANGLE INSTITUTE OF RESEARCH TRIANGLE PARK, NORTH CAROLINA. IS
UNDERTAKING A RESEARCH STUDY FOR THE U.S. ENVIRONMENTAL PROTECTION AGENCY
OF LEVELS OF VARIOUS ORGANIC COMPOUNDS IN HUMAN MILK. THE INFORMATION
RECORDED IN THIS QUESTIONNAIRE WILL BE HELD IN STRICT CONFIDENCE AND WILL BE
USED SOLELY FOR RESEARCH INTO THE EFFECTS OF ENVIRONMENTAL FACTORS ON PUBLIC
HEALTH. ALL RESULTS WILL BE SUMMARIZED FOR GROUPS OF PEOPLE; NO INFORMATION
ABOUT INDIVIDUAL PERSONS WILL BE RELEASED WITHOUT THE CONSENT OF THE INDI-
VIDUAL. THIS QUESTIONNAIRE IS AUTHORIZED BY LAW (P.L. 94-469). WHILE YOU ARE NOT
REQUIRED TO RESPOND. YOUR COOPERATION IS NEEDED TO MAKE THE RESULTS OF THIS
SURVEY COMPREHENSIVE. ACCURATE. AND TIMELY.
Study number:
Sitt number:
Participant number:
97
-------
•2-
Fint, I would lika to atk toma ganartl quettiom about you.
1. Raca:
l>
f7~| American Indian/
I I Alartan Natlva
'• What U your binhdna?
Slack. net of
Hl«p«nic origin
I 4 I Ailan/PacHIc
I I lilandar
Hwhlta. not 0« I . I Otn.r
Hlvanic origin I' I ISpKifyl
IMontil IB*yl (Yuri
-m-m
2. What wai your agt in yaan at l«ft birthday? J | Yaar»
5. What If your (Might? I
4. What it you r appro* imata waight?
rrn.
Naxt, I would lika to aik torn* quaitioni about your occupation.
6. Art you praiantly amployad in any capacity? | ' | Vtt (Contfnutl \ 3 \ He IGo to 0. 101
7. How long hava you baan amployad by your praaant amplovtr? [_|__jUnta | 1 | Dayi | 3 [Monthi
& Don your occupation tnually taka you away from homa? | 1 | Vaa tContinutl
t. What ll tha natura and location (itratt addran) of tha company for which you work?
ISfHCifyl
a in
lantly amployad
i| Houiawifa
i
*l Studant
which of tha following bat
j
((Go to a 151
\
(Zip Codtl
t datcribat your ttatut?
1 3 | Unamployad
L*jRatinjd
(Cominufl
11. What it/wai your uual occupation?
12. Art you praiantly amployad in tha occupation? | 1 | Vat | » [ No
13. If yat to abeva quaition. how long hava you baan amployad in that occupation?
| | | Unto flj Oayt [*] Montht
IQutttioni 12 tnd 13 miy bt ttipptti for
untmp/OYtd. mind, tnd dittbltdptnontl
14. Do you work at or in any of tha following occupation or attabliihmanti? IChKktll tfittipply.l
\ 1 I Painting | » | Chtmiea) plant | » | Strvict mtion/Baraga/angina rapair
| * I Dry claaning | * | Patrolaum plant | * | Furnirurt rafiniahing or rapair
Vaan
98
-------
Naxt. I would Ilka to aik »oma quntioru regarding your health and personal habits.
15. Do you amoka? jjj Yai ICeminutl \* \ No lOo to a III
16. How old wan you whan you flnt nanad amoklng? | | | Yaan
17. On ttia avaraga, how many ckjarenai do you amok* par day?
Qj Lan than K pack (1-4 clgartmt) [*J About 1H packi (25-34 cigwattai)
\3\ About H pack (5-14 cJgaranaf) [ »] About 2 packi (3649 cigarettes)
[»| About 1 pack (IB-24 clgaranai) (*| Mora than 2 packi (50 or mor* cigarattatl
NOTE: If th* ptniciptnt out rooacco in torn* otnar form fotncr Man njaafaitai «.». muff!.
ncortf nara;
IB. What 'a tha avaraga numbar of noun that you a^and out of doom aach day? | [ | Houn
19. How many noun of tha day. on tha avaraga. do you nomully oand away from homa? (Ar»af» ueirwn/r for w***ltiYi
Houn Houn
Waakdayi
Waakandt
20. What do you eoraidar tha currant ratui of your haaltti? (ttac* em.1
Q] Eneallant Q] Good Q] Fair [*] Poor
21. Am you currently taking any pra«=rlptk>n madlcatlondl on a ragular dally ball? [jj Vat [j] No
If ym. tpteify: -
22. Hava you tafcan any non-prwcription madlcatlona hi tha pen 48 hourt? | < | Yai
No
23. Do you pump your own ga>? ' l | Yai | a | No
24. How many agoi hava you aatan In tha pan 48 hours?
25. Do you punua any of tha following hobbk»? ICfitct M Out ieely.t
JJJ Fumrura raflnlatiing [»[ fainting Q>J Scala modali | « | Careening
28. Do you puraua any activity that indudai ragular uaa of aolvafR glua or modal aliplana camam?
Q] Vaa \J\ No
99
-------
, I would likt to nk tornt question* (bout your roidmca Bid houuhold.
How many yaui ham you liwd In mis ana? \ \ \ Yaart
28. How long havi you livid n your curnm addrus?
Units 0«y» Won** Yaan
29. Do you cool your horn, with «ny of th« (allowing appliircM? (One* ill Oat tpply.l
[_jj Central air conditioning | « | Window tend) J_JJ Nont of these
[a] Window • cinirn
[_Sj Tip • municipil wpply |*| T«p • priviti will ]*] Do not know
Qj Othir tSmeifyl
3& Don invent riw In your houwhold imoki? [ ' | Vn | 3 \ No | » | Do not know
W K«. e*«e* •// tt*r vply: [jj Clginmn |JJ Ggin [Tj Plp»|_«J Othr
36. Don inyom •)>• in your hounhoW work n iny of tht following oceupitioru/tauiinMan? ICtitck §11 ttiit tpply.i
[jj Piintlng [jj Oivniul ptant Qj Swvlci rution/gangt/mgiiM npilr
[ * I Dry duning | 4 [ PnrolBim olini | » [ Fumhura rafinWiing or npiir
37. DOM myorn */u in your hounhold punui iny of tin following hobbta? (Ottct ill Oitt tpply.l
|1 | Painting |_2J.Furniturt raflniahlng | * | Soli modali \*\ Oardaning
RESPONDENT/INTERVIEWER INFORMATION
3a Ra^wndam: QJ Participant [»
38. Intarvlawar numtaar:
41.
40. Data of imarviaw:
(Dtyl (Yuri
-m-m
100
-------
•6-
SAMPLE INFORMATION
42. W« « milk
|M
No
43. If v«, dro
-DD -
timt
Noun
Minuat
(Month! (0»Y>
"
44. Out *>ipQ«l to RTI:
COMMENTS
101
-------
Attachment 2
Research Triangle Institute
Data Collection Agreement
102
-------
Research Triangle Institute Ft>r Pr°J«ct
DATA COLLECTION
AGREEMENT
Project No.
I, , agree to provide, as an
employee of Poverforce Company, Inc., field data collection services for
Research Triangle Institute in connection with the project named above.
a. I agree to provide services within the guidelines and specifica-
tions for project data collection activities provided by Research
Triangle Institute;
b. I am avare that the research being conducted by the Institute is
being performed under contractual arrangement with
I
c. I agree to treat as confidential all information secured during
interviews or obtained in any project-related way during the
period I am providing services to the Institute;
d. I shall at all times recognize and protect the confidentiality
of all information secured while providing my services throughout
the conduct of this research project;
e. I am aware that the survey instruments completed form the-basis
from which all the analysis will be drawn, and therefore agree
that all work for which I submit invoices will be of high quality
•and in accordance with project specifications; and
f. .1 fully agree to conduct myself at all times in a manner that
will obtain the respect and confidence of all individuals from
whom data will be collected and I will not betray this confidence
by divulging information obtained to anyone other than authorized
representatives of Research Triangle Institute.
Dated at
(City/Town) (State)
this day of 19_
Employee
For Research Triangle Institute
Disposition: Original to RTI; yellow copy retained by Employee.
103
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APPENDIX B
SAMPLING AND ANALYSIS OF VOLATILE ORGANICS IN MILK
104
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SAMPLING AND ANALYSIS OF VOLATILE ORGANICS IN MILK
1.0 Principle of the Method
Volatile compounds are recovered from an aqueous or solid sample by
wanning the sample and purging helium over it. The vapors are then trapped on
a Tenax cartridge which can be introduced by thermal desorption directly into
the GC/MS for analysis. This protocol is the result of extensive development
efforts.(1'9)
2.0 Range and Sensitivity
For a typical organic compound approximately 30 ng is required to
obtain mass spectral identification using high resolution gas capillary
GC/MS analysis. Based on a 50 g milk sample, a detection limit of about 0.6
pg/kg would be possible. The dynamic range (limit of detection to saturation
4
on the mass spectrometer) for a purged sample is M.O ; however, smaller
samples may be purged and the upper end of the range increased commensurately.
3.0 Interferences
Two possible types of interferences must be considered: (1) material
present in the sample which physically prevents the effective purge of the
sample, and (2) material which interferes with the analysis of the purged
sample. In the former case, several techniques have been developed to
handle such problems (e.g., foaming) by diluting and stirring the sample.
The second case is minimized by the use of GC/MS for the analysis, since
unique combinations of m/z and retention time can be selected for most
compounds. This permits the evaluation of compounds even though chromatogra-
phic resolution is not obtained.
4.0 Precision and Accuracy
The purge and trap technique has been evaluated for a variety of
matrices using model compounds which are expected to be typical of volatile
halogenated compounds.
105
-------
The recovery of the purge step was validated using cow's milk samples
14 14 14
spiked with C-chloroform, C-carbon tetrachloride, C-chlorobenzene and
14
C-bromobenzene. The average recoveries were 88, 88, 63, and 35 percent,
respectively. The recoveries correlate roughly with volatility (inversely
with boiling point), so anticipated recovery for other compounds may be
interpolated from these data.
5.0 Apparatus
5.1 Purge Apparatus
The purge apparatus is shown in Figure 1.
5.2 Sampling Cartridges
The sampling tubes are prepared by packing a 10-cm long x 1.5-cm i.d.
glass tube containing 6 cm of 35/60 mesh Tenax GC with glass wool in the ends
(2 3)
to provide support. ' Virgin Tenax is extracted in a Soxhlet extractor for
a minimum of 24 h with redistilled methanol and pentane prior to preparation
(2 3)
of cartridge samples. ' After purification of the Tenax GC sorbent and
drying in a vacuum oven at 100°C for 2-3 h all of the sorbent material is
meshed to provide a 35/60 mesh-size range. Sample cartridges are then prepared
and conditioned at 270°C with helium flow at 30 mL/min for 30 minutes. The
®
conditioned cartridges are transferred to Kimax (2.5 cm x 150 cm) culture
tubes, immediately sealed using Teflon-lined caps, and cooled. This procedure
(2 3)
is performed in order to avoid recontamination of the sorbent bed. '
5.3 GC/MS/COMP
The volatile halogenated hydrocarbons purged from water are analyzed on
either an 1KB 2091 GC/MS with an 1KB 2031 data system or a Varian MAT CH-7
GC/MS with a Varian 620/i data system. The sample, concentrated on a Tenax GC
(2 4)
cartridge, is thermally desorbed using an inlet manifold system. ' The
operating conditions for the thermal desorption unit and the analysis Tenax GC
cartridges are given in Table 1.
6.0 Materials
6.1 Sampling
Clean, 120 ml, wide-mouth glass bottles with Teflon-lined caps are used
for the collection of milk samples.
106
-------
THERMOMETER
-20tol50°c
THERMOMETER ADAPTER
with 0—ring
9 10/18
TENAX CARTRIDGE
HELIUM
'PURGE
HELIUM INLET
TUBE
LIQUID LEVEL
KX> ml ROUND BOTTOM FLASK
MAGNETIC STIRRING BAR
Figure B-l. Diagram of headspace purge and trap system.
107
-------
Table B-l. INSTRUMENTAL OPERATING CONDITIONS
LKB 2091
Varian HAT CH-7
o
00
Deaorption ehaaber tetipenature
Deaorptlon chamber He flow
Deaorption tl«e
Capillary trap temperature during deaorption
Temperature of capillary trap during injection
onto coluan
Time of He flow through capillary trap
Re flow through coluam (aweep time]
Carrier flow
Capillary column
Coluan temperature
Scan range
Scan rate
Scan cycle time
Scan mode
Trap current
Filament current
Accelerating volatage
270
IS wL/min
8.0 mln
-196»C
265
10 ml/min
8.0 aio
-196-C
-196°C to 250*C - then held at 190*C
12 3/4 Bin
9.5 «ln
2.0 aL/ain
100 • SE-30 SCOT
30°C for 2 «in,
then 4°/a>in to 240*
5-490 dalton
2 tec full acale
2.4 aec
parabolic
4A
50|iA
3.5 kV
12 3/4 »in
4 «in
1.0 «V»in
20 • SE-30 WCOT
20 •» 240° at 4%aln
20 •» 500 dalton
1 «ec/decade
4.5 aec
exponential
300|iA
2kV
-------
6.2 Purge
Tenax cartridges - 16-mm o.d. x 10.5 cm glass tubes filled with 6 cm of
Tenax with 1-cm glass-wool plugs in each end.
Charcoal cartridges - 16-mm o.d. x 6 cm filled with 4 cm of charcoal
and glass-wool plugs in each end.
Glass culture tubes with Teflon-lined screw caps.
7.0 Procedure
7.1 Collection of Field Samples
Milk (60-120 ml) is expressed directly into the wide-mouth bottle,
capped tightly, and frozen for shipment and storage. To preserve the inte-
grity with respect to volatiles, handling and transfer must be minimized.
7.2 Purging of Volatiles
The apparatus is assembled as depicted in Figure 1, including the Tenax
GC cartridges (1.5-cm diameter x 6.0-cm length). A carbon cartridge 1.5-cm
diameter x 4.0-cm length is connected to the effluent end of the Tenax
cartridge to prevent contamination of the cartridge by laboratory vapors.
The milk sample is cooled to ~4°C, shaken vigorously and 100 ml diluted with
350 ml distilled water. The pH of the solution is adjusted to 4.0 with
sulfuric acid. A glass-wool plug is inserted into the center neck of the
flask just above the level of the solution and, with the flask in a heating
mantle, the solution is heated to 70°C while it is stirred with a magnetic
stirrer. The sample is purged at 15 ml helium/min and 70°C for 90 minutes.
The loaded cartridge is removed and stored in a culture tube containing 1-2 g
CaSO, desiccant for 2-12 h. The desiccant is removed from the culture tube
and the dry, loaded cartridge stored at -20°C.
7.3 Analysis of Sample Purged on Cartridge
The instrumental conditions for the analysis of volatile compounds of
(2-9)
the sorbent Tenax GC sampling cartridge are shown in Table 1. The
thermal desorption chamber and six-port valve are maintained at 270°C and
200°C, respectively. The helium purge gas through the desorption chamber is
adjusted to 15-20 mL/min. The nickel capillary trap at the inlet manifold
is cooled with liquid nitrogen. In a typical thermal desorption cycle a
sampling cartridge is placed in the preheated desorption chamber and helium
gas is channeled through the cartridge to purge the vapors into the liquid
109
-------
nitrogen cooled nickel capillary trap. After desorption the six-port valve
is rotated and the temperature on the capillary loop is rapidly raised; the
carrier gas then introduces the vapors onto the high resolution GC column.
The glass capillary column is temperature programmed from 20°C to 240°C at
4°/min and held at the upper limit for a minimum of 10 minutes. After all
of the components have eluted from the capillary column, the analytical
column is cooled to ambient temperature and the next sample is processed.
7.4 Quantitation
All data are acquired in the full scan mode. Quantitation of the
halogenated compounds of interest is accomplished by utilizing selected ion
plots (SIPs), which are plots of the intensity of specific ions (obtained
from full scan data) versus time. Using SIPs of ions characteristic of a
given compound in conjunction with retention times permits quantitation of
components of overlapping peaks. Two external standards, perfluorobenzene
and perfluorotoluene, were added to each Tenax GC cartridge in known quanti-
ties just prior to analysis. In order to eliminate the need to construct
complete calibration curves for each compound quantitated, the method of
relative molar response (RMR) is used. In this method the relationship of
the RMR of the unknown to the RMR of the standard is determined as follows:
A . /moles .
RMR „ = Unk UDk
std
A , /g ./GMW ,
unk feunk' unk
unk/std ~ A . ./g . ,/GMW . .
' std 6std' std
where A = peak response of a selected ion,
std = standard
unk = unknown
g = number of grams present, and
GMW = gram molecular weight.
Thus, in the sample analyzed:
(Aunk"GMWunk)(«.td)
110
-------
The value of an RMR is determined from at least three independent analyses
of standards of accurately known concentration prepared using a gas permeation
(3)
system. The precision of this method has been determined to be generally
±10 percent when replicate sampling cartridges are examined.
8.0 References
1. Michael, L. C., M. D. Erickson, S. P. Parks, and £. D. Pellizzari,
Anal. Chem., 52, 1836-1841 (1980).
2. Pellizzari, E. D., "Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors," Publication No. EPA-600/2-
76-076, Contract No. 68-02-1228, 185 (November 1975).
3. Pellizzari, E. D., "Development of Analytical Techniques for Measuring
Ambient Atmospheric Carcinogenic Vapors," EPA 600/2-75-075, 187, (Novem-
ber 1975).
4. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal.
Chem., 48, 803 (1976).
5. Pellizzari, E. D., J. E. Bunch, B. H. Carpenter and E. Sawicki, Environ.
Sci. Tech., 9, 552 (1975).
6. Pellizzari, E. D., B. H. Carpenter, J. E. Bunch, and E. Sawicki, Environ.
Sci. Tech., 9, 556 (1975).
7. Pellizzari, E. D., Quarterly Report No. 1, EPA Contract No. 68-02-2262,
February, 1976.
8. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal.
Lett., 9, 45 (1976).
9. Pellizzari, E. D., Analysis of Organic Air Pollutants by Gas Chromato-
graphy and Mass Spectroscopy. EPA-600/2-79-057, 243 pp., March, 1979.
Protocol Prepared, June, 1980
111
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APPENDIX C
ANALYSIS OF SEMIVOLATILE ORGANIC COMPOUNDS IN MILK
112
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ANALYSIS OF SEMIVOLATILE ORGANIC COMPOUNDS IN MILK
1.0 Principle of the Method
Milk samples are collected from nursing mothers and frozen until ready
for analysis. An aliquot of the thawed sample is then extracted, cleaned up
by Florisil column chromatography and analyzed by GC/MS/COMP.
The extraction procedure used here is preferable to that used by the
AOAC , since both polar and nonpolar compounds are extracted from the
milk. The AOAC method is designed for pesticide residues and would not
efficiently extract polar and/or acidic compounds.
Open column chromatography is a necessary prerequisite to GC/MS/COMP
analysis. Although some loss of sample may occur during the extraction and
cleanup, these procedures remove proteins and fats from the sample which
would otherwise create overwhelming interferences for GC/MS/COMP analysis.
Since the compounds of interest in these fractions cover such a broad
range of volatilities, the GC/MS/COMP analysis can be rather complex. The
higher PBBs of interest in the extracted fraction must be chromatographed on
a very short column (45 cm x 0.2-cm i.d., 2 percent OV-101 on Gas-Chrom Q)
at high temperatures to elute them as sharp peaks which may be identified
and quantitated. These chromatographic conditions are not applicable to
more volatile compounds since they are not resolved from the solvent. Thus,
the extracted fraction is analyzed a second time using a nonpolar SCOT
capillary column (either OV-101 or SE-30 liquid phase) to separate and
identify semivolatile constituents (e.g. chlorobenzenes, PCNs, pesticides,
etc.). The chromatographic conditions are typically 60°C initially, program-
med to 2AO°C (or the column limit) at 6°/min.
The mass spectral data are stored on magnetic tape. The mass spectra of
interest will be printed out by the instrument operator for qualitative
analysis. Quantitation from this data may be achieved by integrating the
area of selected ions and comparing them to the area of the external standard.
113
-------
The sensitivity of the determination may be significantly improved for
quantitative purposes by using the technique of selected ion monitoring
(SIM), also known as multiple ion detection (MID). This technique monitors
up to 9 ions at a sensitivity 10-100 greater than the normal operating mode.
This technique is used for quantitation of compounds in samples where the
increased sensitivity is necessary for detection or accurate determination.
2.0 Range and Sensitivity
The detection limit of the GC/MS/COMP system has been determined to be
about 5-50 ng/pL for pesticides such as Y'BHC, p_,p_'-DDE, atrazine, trifluralin
and heptachlor using a 40 m SE-30 capillary column. When SIM was used, the
detection limit was about one order of magnitude less (i.e., 0.5-5 ng/pL).
The detection limit for tetrabromobiphenyl is about 1 ng/pL in the SIM mode
using 45 x 0.2-cm i.d. column packed with 2 percent OV-101 coated on Gas-
Chrom Q.
For an instrumental detection limit of 1 ng/(Jl, the overall sensitivity
of the method should be about 6 ng/mL (6 ppb) milk assuming a 50 ml milk
sample extracted and extract concentrated to 0.3 ml. This detection limit may
be improved by using SIM and may be worsened by background interferences.
3.0 Precision and Accuracy
When electron capture gas chromatography (GC/ECD) was used, the mean
recoveries from cow's milk for seven replicates ranged from 57 to 93 percent
for six model compounds. Thus, the results obtained may be as little as
half the actual amount in the sample. The relative standard deviations
(RSD) for the above replicates ranged from 11 to 33 percent, with the average
RSD at 21.7 percent. Thus the precision of the method is about + 20 percent.
It is anticipated that accuracy and precision will improve with experience
with the method.
4.0 Apparatus
4.1 Gas Chromatograph
3
A Fisher-Victoreen 4400 gas chromatograph with an H electron capture
-13
detector, a 10 AFS electrometer, and a 1.0 mV recorder is used.
4.2 Gas Chromatography Column
For most compounds, separation is achieved using a 40 m SCOT glass
capillary column coated with 1 percent SE-30 and 0.32 percent Tullanox. For
114
-------
the compounds of very low volatility (e.g. the higher PBBs) which will not
chromatograph on the capillary column, a 45- x 0.2-cm i.d. glass column
packed with 2 percent OV-101 on Gas-Chrom Q is used.
4.3 Liquid Chromatography Column
A 24-mm i.d. glass column with a Teflon stopcock is used.
4.4 Gas Chromatography/Mass Spectrometer
An LKB 2091 gas chromatograph/mass spectrometer with 2 PDF 11/4 computer
is used. The system is equipped with a glass jet separator and is used with
either glass capillary or packed glass column.
5.0 Materials
Kuderna-Danish evaporators:
5 mL receivers
250 mL KD flasks
Snyder columns
500 mL flat-bottom boiling flasks
250 mL separatory funnels
Clean glass wool
Whatman 1 P/S .filter paper
Florisil
Sodium sulfate (anhydrous)
Acetone "Distilled in Glass", redistilled
Pentane "Distilled in Glass", redistilled
Toluene "Distilled in Glass", redistilled
Ethyl ether "Distilled in Glass"
6.0 Procedure
6.1 Extraction
(1) Mix 50 mL (or volume available up to 50 mL) of a milk sample with
clean glass wool and 150 mL of acetone to precipitate the proteins.
(2) Decant and filter the acetone/water layer.
(3) Repeat steps 1 and 2 with two 50 mL acetone fractions.
(4) Concentrate to about 20 mL using a Kuderna-Danish evaporator.
(5) Extract the precipitate with 40 mL of toluene; decant and filter
the toluene layer.
115
-------
(6) Combine the toluene extract and the acetone extract with shaking.
(7) Let the layers separate and draw off toluene (top) layer.
(8) Repeat Steps 5-7 with 40 mL toluene and then with 10-20 mL toluene.
(9) Discard the lower water layer.
(10) Dry the organic layer with anhydrous sodium sulfate and concentrate
to desired volume using a flat-bottom boiling flask and Snyder
column. Quantatively transfer to a vial and concentrate to 5-10
mL under a gentle stream of nitrogen.
6.2 Florisil Column Chromatography
(1) Prepare Florisil by heating to 130°C for at least 5 hours.
(2) Prepare a 24-mm i.d. column so that the Florisil is 10 cm high
after settling.
(3) Place about 1 cm of anhydrous sodium sulfate on top of the Florisil.
(4) Rinse column with 40-50 mL pentane, never allowing the solvent to
go below the Na2SO, layer, as channeling may result.
(5) Add up to 10 mL of sample to column.
(6) Elute with 200 mL of 6 percent ethyl ether/pentane solution at £5
mL/min.
(7) Collect and concentrate in a Kuderna-Danish evaporator.
(8) Evaporate under nitrogen stream to •*• 1.5 mL. Quantitatively
transfer to a vial, store in a freezer.
(9) If sample solidifies after concentration, repeat the Florisil
cleanup (Steps 1-8).
6.3 Standards
Standards are spiked into the sample following the extraction and
workup (d..-pyrene was used at 200 ng/mL).
6.4 Analysis .
6.4.1 GC/MS/COMP Analysis for Semivolatiles
Inject 0.2 pL onto a 40 m SE-30 SCOT capillary at 60°C initially,
program at 6°/min to 240°C, then hold until no more peaks are observed.
Collect mass spectral data at 2 sec/scan from m/z 20-500. Compounds amenable
to this analysis include organic compounds with volatility lower than that
for purgeable compounds. Only the very low volatile compounds (e.g. higher
PBBs) will not elute from the capillary.
116
-------
6.A.2 GC/MS/COMP Analysis for Low Volatile Compounds
6.4.2.1 Normal Procedure
Inject 1.0 pL onto a 45 x 0.2-cm i.d. glass column packed with 2 percent
OV-101 on GasChrom Q at 220°C initially, program to 300° at 12°/min and hold
until all peaks have eluted. A helium flow rate of 20 mL/min is used. The
mass spectrometer is scanned from m/z 20-1000 at 2 sec/scan.
6.4.2.2 Alternate Procedure
Using the same chromatographic conditions analyze the sample by SIM.
Preselect up to 8 ions characteristic of the compound(s) of interest and one
ion characteristic of the standard. Retention times provide qualitative
identifications. Peak areas may be used for quantification as discussed
below. This alternate procedure has 10-100 times better sensitivity than
the full scan mode and provides faster quantitative results. The main
disadvantage is that only preselected compounds may be identified.
In addition, if specific halogenated compounds are found to be present
with little interference in most samples, they may be analyzed by GC/ECD.
This procedure improves the sensitivity and reduces the analysis time (since
GC/MS/COMP requires an offline data output). If GC/ECD is used, approximately
10 percent of the analyses are verified by GC/MS/COMP.
6.4.3 Qualitative Data Interpretation
Spectra are interpreted by visual comparison with standard spectral
(2 3)
reference collections ' where possible. Where standard spectra are not
available, tentative identifications are made based upon interpretation of
the mass spectrum. Where possible, the GC retention time is also used to
assist in the identification procedure.
All identifications and interpretations are checked independently by
other experienced chemists or spectroscopists to assure that the interpreta-
tions are correct.
6.4.4 Quantitative Analysis
In order to eliminate the need to construct complete calibration curves
for each compound to be quantified, the method of relative molar response
(RMR) is used. Successful use of this method requires information on the
exact amount of standard added and the relationship of RMR (unknown) to the
RMR (standards). In general, the RMR for a compound is determined for a
117
-------
characteristic ion (parent or fragment) in its mass spectrum. The integrated
ion current may also be used, but is generally less precise. The value of
RMR is determined from at least three independent analyses. The method of
calculation is as follows:
A . /moles ,
m RMR = unk unk
unknown/standard A ,/moles ,
A = peak area, determined by integration or triangulation
of the total ion current or for a selected mass of each
compound
unk/std
A = peak area, as above
g = number of grams present
GMW = gram molecular weight
Thus, in the sample analyzed:
Astd/GMWstd/RMRunk/std
7.0 References
1. Horowitz, W. , ed., AOAC Methods of Analysis, 12th ed., Association of
Official Analytical Chemists, Washington, DC. (1975).
2. McLafferty, F. W. , £. Stenhagen, and S. Abrahammson, ed., "Registry
of Mass Spectral Data," John Wiley and Sons, New York (1974).
3. Eight Peak Index of Mass Spectra. Vol. I (Tables 1 and 2) and II
(Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading,
RG74PR, UK (1970).
Protocol Prepared, June, 1980
118
-------
APPENDIX D
VOLATILE COMPOUNDS IDENTIFIED IN SELECTED PURGES
OF MOTHER'S MILK
119
-------
Table D-l. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 1081
(Bayonne, NJ)
Chroma to-
graphic
Peak No.
1A
IB
2
3
4
5
6
7A
78
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23A
23B
24
25
26
27
28A
28B
29
30
31A
31B
32
33
34
35
36
37
38
39
40
Elution
leaf.
CC)
58
58
61
65
66
67
73
73
74
76
77
79
60
83
83
87
89
91
92
94
95
96
97
99
102
102
104
105
108
112
113
114
115
116
119
119
122
126
129
134
135
138
143
145
147
Conpound
carbon dioxide
chlorotrlfluoroae thane
propylene
C4Hg leomer
C4H10 UoIBer
C.Hg laomei
acetaldehyde
acetone
trlchlorofluoroae thane
ii-pentane
laopropanol
•ethylene chloride
freon 113
carbon diiulfide
n-butanal
cyclopentane
C4H6°2 leoner
•ethyl ethyl ketone
C6H12 UoBer
bexafluorobenzene (int. atd.)
n_-hexane
chloroform
C?H14 iaomer
C,Hj_ iaomer
perfluoro toluene (int. ltd.)
Be thy Icyclopen tane
1(1! 1-trlchloroe thane
C-Bj, laomer
benzene
cyclohexane
ethyl vinyl ketone
2-pentanone
C.H.,0 /tent.)
0 If
£-pentanal
t rl chloroe thy lene
C7H12 or CjHgO iaomer
n_-heptane
CgH16 iaomer
C.B. , laomer
1-chloropentane
unknovn
toluene
C0H12° iaomer (tent.)
£-hexanal
C8H16 i*aael
Chroma to-
graphic
Peak No.
41
42A
42B
43
44
45
46
47
48
49
50
51
52
S3A
S3B
S3C
53D
54
55
56
57
58A
58B
59
60A
60B
61A
61B
62
63
64
65
66
67
68
69A
69B
70
71A
71B
72
73A
73B
73C
74
Elution
Temp.
CO
150
152
152
154
156
159
161
163
166
168
171
171
173
173
173
174
174
175
178
179
181
183
164
188
189
189
191
191
193
194
195
196
197
199
200
201
202
203
204
205
206
210
210
210
211
Compound
n-occane
tetrachloroethylene
CgH16 laomer (tent.)
CgH16 iaomer (tent.)
ailoxane
CgHlft laomer (tent.)
chlorobenzene
1-chlorohexane (tent.)
ethylbenzene
zylene laomer
3-heptanone
2-heptanone
atyrene
C9H16 iioner
CjH20 laomer
n_-heptanal
xylene iaomer
C10H22 1'OBer
CL-aoaane
C10H22 1'omer
3-me thy 1-1-iodobutane
iaopropylbenzene
C10E22 I80mer
C11H24 llOIDer
C10H16 1SOmer
C-H,,0 laooer (tent.)
0 ID
benzaldehyde
n-propyl benzene
C.-alkyl benzene
CjHjQ iaomer (tent.)
C9H18 llomer
C11H24 1>ooer
octanone iaomer
C11H24 I80mer
2-pentylfuran
C11H2ft iaowr
n-octanal
ailoxane
C10H22 Uomer
dlchlorobenzene
C11H24 1>01*r
C10H14 it
-------
Table D-l (cont'd.)
Chromato-
Qraphic
Peak No.
75
76
77A
77B
78 "
79A
79B
80
81
82
83
84
85
Elution
Teop.
CC)
212
215
215
216
218
219
219
221
222
224
225
227
230
Compound
liaonene
•at. hydrocarbon
unaat. hydrocarbon
C.,H,. leomer (tent.)
11 24
•onochlorodecane (tent.)
C9H18°
acetophenone
•at. hydrocarbon
•at. hydrocarbon
2-nonanone
dioethylatyrene
ti-nonanal
n-undecane
Chroma to-
graphic
Peak No.
86
87
88
89
90
91
92
93
94
95
96
97
Elution
Temp.
CC)
240
240
240
240
240
240
240
240
240
240
240
240
Compound
uncit . hydrocarbon
•lloxane
naphthalene
C10E20° 1>DBer (tent.)
ii-dodecane
unknown
unsat. hydrocarbon
•lloxane
C11B22 lBOBer
•iloxane
unknown
•lloxane
121
-------
»
65
Figure D-l. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 1081
(Bayonne, NJ).
-------
Table D-2. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO.
(Bayonne, NJ)
1040
diromato-
iraphlc
Peak No.
1
2
3 .
4
SA
SB
5C
5D
6A
6B
6C
6D
6E
7
8
9
10
11
12
13
14
15
16
17
18
19
20A
20B
21
22
23
24A
24B
25A
25B
26
27A
28B
28A
28B
29
30
31
32
33
Elutlon
Temp.
CC)
58
59
60
67
74
74
75
75
77
78
78
79
79
81
82
84
85
87
90
92
94
96
97
98
101
104
106
107
109
110
111
113
113
113
115
115
117
121
123
124
127
130
132
136
138
Compound
carbon dioxide
ehlorotrifluorooe thane
dlaethyl ether
C4B10 lson*r
laopentane
trlchlorofluoroae thane
acetone
C5H10 i"aet
nr-pentane
iaoprene
laopropaool
C,H,, laoner
o a
vlnylldlne chloride
•ethylane chloride
Freon 113
carbon dlaulflde
2-mc thylpropanal
cyclopentaue
unknown
•ethyl ethyl ketone
C6H12 1"OIDer
hexafluorobenzene (int. (td.)
Er-hexane
chloroform
C,H, , iaomer
O 14
perfluorotoluene (int. atd.)
1,1, 1-trlchloroethane
3-oethylbutanal (tent.)
2-*ethylbutanal
benzene
carbon tetrachloride
cyclohexane
•ethyltetrahydrofuran (tent.)
C7H14
ethyl vinyl ketone
2-pentanone
vinyl proplonate (tent.)
trlchloroethylene
C7H12 °r W
unknown
C?H14 laoner
C7H14 laoner
dimethyl diaulfide
1-chloropentane
unknown
Chroma to-
graphic
Peak No.
34
35A
35B
36
37
38
39A
39B
40A
40B
41
42A
42B
42C
43
44A
44B
45
46A
46B
47
48
49
50
51
S2A
52B
S3A
53B
54
55
56
57
58A
58B
S9A
S9B
60
61
62
63
64
65
66
67A
Elutlon
Temp.
CO
140
141
142
145
146
149
150
151
152
153
153
154
154
154
155
157
157
161
162
162
163
165
167
169
173
174
175
175
176
177
179
181
181
182
183
184
185
189
190
190
191
192
194
196
196
Compound
toluene
1-pentanol
unknown
C.H. . laooer
7 16
n-hexanal
C8H16 Uoner
unknown
C8H16 I800er
C.H... laoaer
o 4O
trana-4-octene
tetracbloroethylene
CgH-Q iaoner
•at . hydrocarbon
unaat. hydrocarbon
C8B16 1'omer
CBH14 Uomer
•lloxane
unaat. hydrocarbon
•at. hydrocarbon
unsat. hydrocarbon
unknown
chlorohexane
ethylbenzene
xylene Iaomer
2-heptanone
•tyrene
2-n-butylfuran (tent.)
n-h«p canal
sylene iaomer
CjHjg laoner
C9H2() Homer
•at. hydrocarbon
CjH18 Iaomer
3-oethyl-l-iodobutane
C.H.g iaomer
iaopropylbenzene
•at. hydrocarbon
hydrocarbon
C10H16 UoBer
unaat. hydrocarbon
benzaldahyde
n,-propylbenzene (tent . )
trlaethylbenzene laoaer
laoamyl t ornate (tent.)
unknown
- Continued -
123
-------
Table D-2 (cont'd.)
Chroma to-
graphic
Peak No.
67B
68A
6BB
69
70 ~
71
72
73
74
75
76
77
78
79
80
ei
82
83
Elation
Temp.
CC)
197
198
199
200
201
203
203
204
206
207
209
211
212
213
216
216
217
219
Compound
•at. hydrocarbon
C9U20 i""Ber
C.-alkyl benzene
•at. hydrocarbon
2-peotyl furan
C.-alkyl benzene
C10H20
•ilnxane
dichlorobenzene
C.-alkyl benzene (tent.)
C8H14
dlmethylethylbenzene Isoner
aentbene (tent.)
linonene
C11H22 leo"er
uncat. hydrocarbon
•at. hydrocarbon
•unknown
Chroma to-
graphic
Peak No.
84
85
86
87
88
89
90A
90B
91
92
93
94
95
96
97
98
99
100
Elution
Temp.
CO
220
222
223
225
226
228
230
231
234
239
240
240
240
240
240
240
240
240
CoMpound
unknown
acetophenone
•at. hydrocarbon
C10H22 itmeT
dlBethylstyrene
£-nonanal
•lloxane
•lloxane
tetraaethylbenzene (tent.)
•lloxane
•lloxane
naphthalene
C12H26 lBOBer
unknown
•lloxane
2-undecanone
C13H28
•lloxane
124
-------
V"" •' •' f V !,' !,'' "-~~r-"-"~T'" ~, ~Y" ' ">T'--fc- ' ''£'" ••••"t--"-"'" C" '
Issssssissss
Figure D-2. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 1040
(Bayonne, NJ).
-------
Table D-3. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO.
(Jersey City, NJ)
1107
Chroma to-
graphic
Peak No.
1
2
3A
3B
4
5A
56
5C
50
6A
7
8A
SB
8C
9A
9B
10A
10B
IOC
100
10E
10F .
11A
11B
12A
12B
13A
13B
14A
14B
14C
15
16A
16B
16C
17A
17B
17C
18A
IBB
19A
19B
19C
19D
20A
Elution
Tenp.
CC)
64
65
67
67
69
70
71
72
73
74
75
76
78
78
79
79
81
83
85
86
86
86
88
89
90
91
92
93
94
97
98
100
101
102
102
104
105
106
108
109
110
110
111
112
112
Conpound
xenon
carbon dioxide
freon 22
dichlorodifluorone thane
ii-propane
butene iaoner
n-butane
ace t aldehyde
butene laoner
chloroethane
tetranethylailane
trlchlorofluorone thane
1-pentene
acetone
laopropanol
ti-pentane
•ethylene chloride
Preon 113
carbon dlaulfide (trace)
•ethyl vinyl ketone (trace)
•ethyl propanol
nit rone thane (tent.)
cyclopentane
2-Bethyl pentane
vinyl acetate
n_-butanal
3-nethyl pentane
CfcH12 iaoner
perfluorobencene (int. atd.)
n-hexane
chloroform
dihydrofuran
te trahy drof uran
perfluorotoluene (int. atd.)
•ethylcyclopentane
n_-»ethyl acetaalde
1,1, 1-trlchloroe thane
3. 3-dlaethyloxetan (tent.)
benzene
carbon tetrachlorlde
1-butanol
cyclohexane
CJBIO° iaoner
ethyl vinyl ketoae (teat.)
2-pentanone
Chroma to-
graphic
Peak No.
20B
21
22A
22B
22C
220
23
24
25
26A
26B
26C
27
28
29
30A
30B
31
32A
32B
33A
33B
34
35
36
37
38A
38B
38C
39A
39B
40A
40B
40C
41A
41B
42A
42B
43
44A
44B
44C
45A
45B
46
Elution
Tea^.
CC)
113
114
116
117
118
118
120
123
124
125
127
127
128
129
131
134
137
139
141
143
146
147
148
149
151
154
156
156
156
158
159
160
161
161
162
163
164
165
166
167
168
168
169
170
172
CoBpound
vinyl proplonate
n-pentanal
C.HJ4 laoner
trlchloroethylene
p_-dioxane
ethyl furan (tent.)
n-heptane
2,2,4- trine thyl-1-pentene
laohexenal
C6H10° l80"er
4-nethyl- 2-pentanone
C8H16 l801Ber
dimethyl dlsulflde
dlhydropyran
chloropentane
toluene
C8H18 i8omer
C6H12° i80Ber
ii-hexanal
C-E.g laoner
ii-octaae
C8H16 im
-------
Table D-3 (cont'd.)
Chroma to-
graphic
Peak No.
47
48
49A
49B
49C
49D
50A
SOB
51
52A
52B
52C
53
54
55A
55B
Sf
57
58A
58B
59
60A
60B
61A
61B
62
63A
63B
63C
63D
64A
64B
64C
640
64E
65
66A
66B
66C
660
67A
67B
67C
68A
68B
Elutlon
Temp.
CO
173
174
175
175
176
176
176
177
178
181
182
182
184
186
187
187
187
188
190
190
192
193
193
194
194
195
196
196
197
198
200
200
201
201
201
202
203
203
204
204
205
206
206
207
207
Conpound
•at. hydrocarbon
C10H20 1§OBer
•at. hydrocarbon
•thyl methyl cyclohexane
unknovn
C7H100 i.o«r
liopropyl benzene
C ~H . iioaer
10 22 «-*
CgH^O icooer (tent.)
trana-2-heptenal
a-pinene
benzaldehyde
n_-propylbenzene
xylene iaoaer
•at. hydrocarbon
C10H22 Is00er
benzonltrlle (trace)
•at. hydrocarbon
phenol
trlaethylbenzene
pentyl furan
nj-octanal
benzofuran
trlaethylbtnzene iaoners
C10H20 1§00er
•lloxane
C7H10°
nj-decane
dlchlorobenzene
C11H22 UoBer
unknovn
trloethyl benzene iaoaer
unknovn
C^-alkylbenzene
•at. hydrocarbon
C11H25 *•«•"
•at. hydrocarbon
liaonene
C11H22 1>0»er.
•ethyl atyrene
•at. hydrocarbon
C11H22 Uo«"
dlethylbenzene liner
•at. hydrocarbon
•c* tophi none
Chroaato-
graphic
Peak No.
69A
69B
70
71A
71B
72A
72B
73A
73B
73C
74
75A
75B
76A
76B
77
78A
78B
79A
79B
80
81
82A
82B
83
84A
84B
84C
85
86A
86B
86C
86D
86E
B6F
86C
87
88
89
90
91
92
93
94
95
Elutlon
Teap.
CO
208
209
210-
210
211
211
212
212
212
213
213
214
215
215
216
217
218
219
220
220
221
222
223
224
224
225
226
226
226
228
228
229
229
229
230
230
230
230
230
230
230
230
230
230
230
CoBpouod
C,-alkylbenzene
C11H22 UoBier
C11H22 lto~r
C11H22 1>0""
phthallde (tent.)
aat. hydrocarbon
decalin (tent.)
•at. hydrocarbon
C11H24 UoBer
C^-alkylbenzene laoeer
2-nonanone
C11H22 i'"ner
C.-alkyl benzene Icoaer
•at. hydrocarbon
ii-nonanal
C11H22 Uoner
C10H12° Uoner
n-undecane
•lloxane
C11H22 lMBer
f H 4 mntnar
C10H18 Uoner
C^-alkylbenzene lioner
C12H26 1OBCT (trace)
C12H24 Uomer
C10H12° Uom"
C10H18° ttaKt
unknovn
C11H16 ltmel
•lloxane
•at. hydrocarbon
•at. hydrocarbon
•at. hydrocarbon
•at. hydrocarbon
naphthalene
unaat. hydrocarbon
o-dodeccne
•at. hydrocarbon
- Continued -
127
-------
Table D-3 (cont'd.)
Chroma to-
graphic
Peak No.
96
97
96
99
100
101
102
103
104
Elution
Temp.
CO
230
230
230
230
230
230
230
230
230
Compound
slloxane
2-undecaoone
Bat . hydrocarbon
unknown
siloxane
Bat. hydrocarbon
unknown
dlphenyl ether
eat. hydrocarbon
Chroma to-
graphic
Peak No.
105
106
107
108
109
110
111
112
Elution
Temp.
(*c)
230
230
230
230
230
230
230
230
Conpound
unknown
2-trldecanone
sat. hydrocarbon
slloxane
phthalate
lactone Isomer (tent.)
dilsobutyrate Isomer
CUH22° lsooer
128
-------
Figure D-3. To til ion current chromatogram from GC/MS analysis for volatiles in sample no. 1107.
(Jersey City, NJ).
-------
Table I>-4. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 1115
(Jersey City, NJ)
Chroma to-
graphic
Peak No.
1A
IB
2
3A
3B
4A
4B
5A
5B
6A
6B
6C
6D
7
8A
8B
ec
9
IDA
10B
11A
11B
12
13
14A
14B
14C
15
16A
16B
16C
17
ISA
18B
19
20A
20B
20C
21A
21B
21C
22A
22B
22C
23A
23B
Elution
Temp.
CC)
62
«3
65
67
68
76
76
77
78
80
81
82
82
83
86
87
89
90
92
92
94
94
96
98
99
100
100
102
104
105
105
106
107
107
108
109
110
no
111
112
112
114
114
115
116
117
CoBpound
carbon dioxide
xenon (trace)
carbonyl aulflde (tent.)
chlorome thane
unknown
trlchlorofluoronethane
acetone
iaopentane
laopropanol
•ethylene chloride
Freon 113
carbon diaulflde (trace)
unknovn
unknown
cyclopentane
•ethyl isopropyl ketone
n-but»nal
1-hexene (tent.)
bexafluorobenzene (int. »td.)
ii-hexane
chlorofonn (trace)
•ethyl furan
unsat. hydrocarbon
perfluorotoluene (Int. atd.)
crotonaldehyde (tent . )
1,1, 1-trichloroe thane
3-«ethylbutanal
2-tDethylbutanal (tent.)
benzene
carbon tetrachloride (trace)
1-butanol (tent.)
unknown
•tbyl vinyl ketone
2-pentanone
vinyl propionate
nj-pentanal
•at. hydrocarbon
•ethylhexane (tent.) (trace)
1-hexene
trichloroethylene
•thylfuran (tent.)
2,5-dlaethylfuran
n-beptaae
C,B. iaoner
D D
unknown
C5H6K2 (tent.) (trace)
Chromato-
graphic
Peak Ho.
24
25
26
27
28
29A
29B
30
31
32A
32B
33
34A
34B
34C
35A
35B
36
37A
37B
38A
38B
39
40
41A
41B
42A
42B
42C
43A
43B
44A
44B
44C
44D
45
46
47
48
49
SO
S1A
51B
51C
51D
52A
-Continued*
Elution
Temp.
CO
120
122
122
124
126
128
129
131
134
136
137
138
140
140
141
142
142
143
146
147
148
149
151
151
152
152
153
153
155
155
156
157
158
158
159
159
160
162
165
166
170
171
172
172
173
174
CoBpound
C7H14 --OBer
dioethyldlaulflde
dlhydropyran
chloropentane
unknown
toluene
1-pentanol
4-oethyl-2-pentanone
nj-bexanal
C8H16 iBO*er
furaldehyde (tent.) (trace)
n_-octane
tetrachloroethylene
dichloropropene (trace)
unknown
C5H8N2
C8H16 1'oaer
•lloxane
2-hexanal
chlorobenzene
C8H14 t>OBer
5-nethyl-3-hydrofuran-2-one (tent.)
a-furfuryl alcohol
•thylbenzene
CgBjg laoner
C4H4K20 (tent.)
zylene leaner
phenylacetylene
5-«ethyl-3-bexanone
2-beptanone
C7H12°
C9H20 (trace)
•tyrene
n-heptanal
mylene laooer
C9H18 iaoaer
2-furyl aethyl ketone (tent.)
n-conane
lodopentane
unknown
trana-2-heptenal
benzaldehyde
5-Mtbyl-2-furfural
unknown
o-propylbenzene
xylene iaoaer
130
-------
Table D-A (cont'd.)
Chromato-
graphic
Peak No.
S2B
52C
52D
52E
53A
53B
53C
53D
53E
53F
54
55
56
57A
57B
57C
57D
58
59
60
61
62A
62B
62C
63A
63B
63C
64
65A
65B
66A
66B
67
68
69
70A
70B
Elution
Temp.
CO
175
175
175
176
176
176
176
177
177
177
178
180
180
181
182
182
182
182
184
184
187
188
188
188
190
190
191
192
192
193
194
195
196
196
197
198
198
Compound
benzonitrile
octanone
C10H22
C.-alkylbenzene
l-chlorc-3-ethylbenzene (tent.)
dibromodichloromethane (tent.)
phenol
sat. hydrocarbon
5-methyl-3-heptanone (tent.)
unknown
6-methyl-2-heptanone
pentyl furan
ri-octaoal
benzofuran (trace)
C.-alkylbenzene
C10H20 i80ner
C.H..O Isomer
siloxane
i>-decane
dlchlorobenzene
C9H16
C.-alkylbenzene
phenylacetaldehyde
C10H20 lsoner
limonene
1,8-cineole
C10H18 (trace)
unsat. hydrocarbon
sat. hydrocarbon
acetophenone
n-butylbenzene (tent.)
C7Bg02 (tent.)
C..B.. Isomer
unknown
unknown
C10H18 isooer
sat. hydrocarbon
Chroma to-
graphic
Peak No.
71A
71B
71C
71D
72
73
74
75
76A
76B
77
78
79A
79B
80
81
82
B3A
83B
84
85
86
87
88
89
90
91A
91B
92
93
94
95
96
97
98
99
100
Elution
Temp.
CO
199
200
200
200
201
204
212
213
214
215
216
218
220
220
221
223
225
226
227
228
231
233
237
238
239
240
240
240
240
240
240
240
240
240
240
240
240
Compound
2-nonanone
dimethylstyrene (trace)
C.-alkylbenzene (trace)
C10H16° I8oner
£-nonanal
undecane
unsat. hydrocarbon
C10H18° isomer
ii-pentylbenzene
siloxane
sat. hydrocarbon
2-decanone
naphthalene
C12H22 I80ner
ii-decanal
ii-dodecane
sat. hydrocarbon
unknown
methyl clnnollne (tent.) (trace)
lactone Isomer (tent.)
oxygenated hydrocarbon
phenyl hexane
C10H16° (tent')
unknown
undecane
C10H16° )
unknown
siloxane
unsat. hydrocarbon
sat. hydrocarbon
2,2,4-trimethylpenta-l, 3-diol
dl-isobutyrate (BKG)
•at. hydrocarbon
C14H30 lBOner
unsat. hydrocarbon
sat . hydrocarbon
C..B.. Isomer
sat. hydrocarbon
131
-------
•I' L' i.' V L'
S S S 2 S
Figure D-4. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 1115
(Jersey City, NJ).
-------
Table D-5. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO.
(Pittsburgh, PA)
2048
Chroma to-
graphic
Peak No.
1A
IB
2
3
4A
4B
SA
SB
6A
6B
7A
7B
8
9A
9B
10
11A
11B
12A
12B
13
14A
14B
ISA
15B
16
17
ISA
18B
18C
19
20A
20B
21
22
23
24A
24B
25
26
27
28
29
30
31
32
Elutlon
lenp.
CO
58
58
64
66
70
70
71
72
73
74
77
77
79
83
83
84
87
87
89
89
91
96
96
98
98
102
104
106
107
109
109
112
112
115
119
126
126
127
130
131
133
134
136
138
140
143
Conpound
carbon dioxide
cblorotrlfluorone thane
C^Hg laoner
CU 1 • n« • T-
jB.. xaoner
4 10
acetaldehyde
C.H.. laoner
trlchlorofluorone thane
acetone
nj-pentane
laopropanol
Freon 113
•etbylene chloride
carbon diaulfide
CjHJO lioner
C,B, . laoner
o 14
CjB1Q0 laoner (tent.)
•ethyl ethyl ketone
C.Hj, laoner
hexafluorobenzene (Int. atd.)
n_-hezane
chloroform
perfluorotoluene (Int. atd.)
•ethylcjrclopentane
1 ,1 , 1-trlchloroe thane
1-butanol (tent.)
benzene
eyclobexane
C6H12 laoner
CjH.pO laoner
C»HIQ laoner
n-pentanal
trlchloroethylene
CjHj. iaoner
unknown
C7B14
C.B..O laoner
uoaat. hydrocarbon
chloropentane
unaat. hydrocarbon (tent.)
toluene
1-pentanol
C,B, laomer
D O
CfiH120 Uo»r
£-hexanal
C8H16 Uomer
n-octane
Chroma to-
graphic
Peak No.
33A
33B
34
35
36A
36B
37
38
39A
39B
39C
39D
40
41
42A
42B
42C
43A
43B
44
45
46
47
48A
48B
49
SOA
SOB
51A
SIB
SIC
52A
S2B
53
54
55
S6A
56B
57
58
59
60A
60B
61
62A
62B
-Continued-
Elutlon
tenp.
CO
145
146
147
149
153
154
156
159
161
161
162
162
164
165
166
167
167
168
168
169
170
173
175
177
177
181
182
183
184
184
184
186
186
187
189
190
190
192
192
194
194
195
195
197
198
198
Conpound
tetrachloroethylene
C.B., laoner
o 16
C7H14° 1>0"er
alloxane
CjHjjO laoner
chlorobenzene (trace)
chlorohexane (trace)
•thylbenzene
aat. hydrocarbon
xylene laoner
unknown
CjH2() laoner
3-heptanone
2-heptanone
atyrene
CgB., laoner (tent.)
aat. hydrocarbon
n_-heptanal
xylene laoner
£-00 nane
C10E20 lsoner
C10H22 1*°°er
C-.H,, laoner (tent.)
10 22
laopropylbenzene
C10H22 1*°"er
C. • HA , XSOOCT
C10H16 imOKT
CgBj.O laoner
unaat. hydrocarbon
benz aldehyde
n-propylbenzene
C10H16 lsOIDer
C.-alkyl benzere laoner
aat. hydrocarbon
unaat. hydrocarbon
C11H24 1§oi*r
C8B16° 1>ODer
C10H22 1«°"er
C11H24 lto~r
2-pentylfuran
C11H24 UoBer <"nt->
C.-alkylbenzene iaoner
C10H20 *"***
•lloxane
•at. hydrocarbon
dlchlorobenzene
133
-------
Table D-5 (continued)
Chroma to-
graphic
Peak No.
63A
63B
64
65
66A
66B
67
68
69
70
71
72
73
74A
74B
75A
75B
76
77
78
79
80A
SOB
81
Elutlon
Temp.
CO
200
200
202
203
206
206
208
209
211
212
213
214
215
216
217
218
219
220
222
223
226
226
227
229
Compound
unsat. hydrocarbon
sat. hydrocarbon (tent.)
unsat. hydrocarbon
2-e thy 1- 1-hexanol
linonene
C10H18° iBOmer
sat. hydrocarbon (tent.)
sat. hydrocarbon
C,-alkylbenzene
acetophenone
sat. hydrocarbon
sat. hydrocarbon
sat. hydrocarbon
C,-alkylbenzene
C9H18° l80Iner
dlmethylstyrene
sat. hydrocarbon
n-nonanal
nr-undecane
slloxane
C,-alkylbenzene
C,-alkylbenzene
unknown
sat. hydrocarbon
Chromato-
graphlc
Peak No.
82
83
84
85A
85B
85C
86
87
88A
88B
89A
89B
90
91
92
93
94
95
96
97
98
99
100
101
Elutlon
Temp.
(*c)
231
232
233
235
236
236
238
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
Cottpound
unsat . hydrocarbon
CUH20 laomeT
C10H18° iBOTer
siloxane
C10H18° lsomer
C10H14° i801Ber
uneat. hydrocarbon
sat. hydrocarbon
naphthalene
CnnH,,0 Isomer (tent.)
10 22
a-terplneol (tent.)
unsat. hydrocarbon
n-dodecane
slloxane
unsat. hydrocarbon
slloxane
2~undecanone
slloxane
C13H28 I80mer
slloxane
decanolc acid (tent.)
C14B30 I80mer
unsat. hydrocarbon
slloxane
134
-------
10
C/i
\' .
Ill
fcBP
! k i
I i I I
Figure D-5. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 2048
(Pittsburgh, PA).
-------
Table D-6. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 2071
(Pittsburgh, PA)
Chronato-
graphic
Feak No.
1
2A
2B
3A
3B
4A
4B
5
6
7
8A
SB
9A
9B
9C
10
11A
11B
11C
12
13A
13B
14
ISA
15B
16
17
18
19
20
21
22
23A
23B
24
25A
25B
26
27A
27B
28 .
29
30A
30B
31
32
Elutloo
Temp.
(*c)
59
60
61
62
63
64
65
66
68
71
73
73
75
75
76
77
78
79
80
81
82
83
85
86
87
87
88
89
90
91
93
94
94
95
96
100
100
101
102
103
106
107
108
108
111
113
Coapound
carbon dioxide
propylene (trace)
dichlorodifluoronethane (trace)
dimethyldifluorosilane
laobutane
C4H8 1">IDer
ii-butane (trace)
acetaldebyde
chloroechene (crace)
•ethanol
acetone
trlchlorofluorone thane
laopropanol
o-pentane
C.Hg isoner
C6H12 lsoBer
•ethylene chloride
2 -me thyl-2-propanol
Freon 113
C6H14
carbon dlsulfide
w
o-propanol (tent.)
cyclopentane
C6H12 *"***
P 11 f ai Tiinm
C6H14 "OIDer
vinyl acetate •
n-butanal
•ethyl ethyl katone
C6H12 i"met
hexafluorobenzene (Int. ltd.)
ir-hexane
ethyl acetate
chloroform
C7H laoner
7 14
perfluorotolueoe (lot. atd.)
•etbylcyclopantane
C,BU iaoner
1,1, 1-trlchloroe thane
cjB100 iaoner (tant.)
benzene
carbon tetrachlorlde (trace)
n-butanol (cant.)
cyclohexane
•ethyl propyl ketooe
o- pen canal
Chrona to-
graphic
Feak No.
33
34A
34B
35
36
37
38
39
40
41
42
43
44
45A
45B
46
47A
47B
48
49
50A
SOB
S1A
SIB
52A
52B
53
54
55
56
57
S8A
SBB
59
60
61
62A
62B
63A
63B
64
65
66
67A
67B
68A
- continued -
Elutloo
Tenp.
CC)
116
118
119
122
124
126
127
129
133
138
139
141
144
145
146
147
149
149
152
153
158
159
160
160
162
163
164
166
167
169
170
173
174
176
177
179
180
180
162
182
184
185
185
186
186
187
CoBpound
tr 1 chloroe thy lene
o-heptane
C7B14 1>0"er
C8HU l.oner
C7B,4 laoner
dinethyl dlaulfide
unknown
C.Hj, laoner (tent.)
toluene
dlbronochloronethane (trace)
n_-hexaoal
C8H16 lsoffler
o.-octane
tetrachloroethylene
CgB16 iaoner (tent.)
unknown
unaat. hydrocarbon
alloxane
C.lLg laoner
chlorobenzene
athylbenzene
CjB18 laoner
xylene laoner
phenylacatylene
3-heptanone
2-heptanone
atyrene
sylene laoner
n_-heptanal
n-nonane
C10H22 *•«•"
laopropylbenzene
C10H22 ltm"
C10H16 itmel
C,.H,. laoner
10 20
O-plnene
banzaldehyde
£-propylbenzene
C10B16 1'°ner
C.-alkylbenzene
trlnethylbenzene laoner
C10H22 1>M*r
baozonltrile
•ethylheptanone laover
d-tcthylatyraoe
trlnethylbenzene laoner
136
-------
Table D-6 (continued)
Chroma to-
graphic
Peak No.
68B
692
69B
70A
70B
70C
70D
71
72A
72B
72C
72D
73
74
75A
75B
76
77
78
79A
79B
80
61
82
Elution
Temp.
CO
187
188
188
190
190
190
191
192
192
193
193
194
194
196
196
197
199
201
203
205
205
207
208
210
Compound
•at. hydrocarbon
ethyl ii-caproate
pentylfurao (tent.)
benzofuran (tent.)
C,-alkylbenzene
trimethylbenzene itomer
phenol (trace)
•lloxane
C10H22 lsonier
di chlorobenzene
unknown
C10H16 l80Ber
sat. hydrocarbon
C10H16 isomer (tent')
C10H16 lsoner
C,-alkylbenzene
limonene
unknown
cat. hydrocarbon
acetophenone
C10H16 lsomer
•at. hydrocarbon
unknown
2-nonanone
Chroma to-
graphic
Peak No.
83
84
85
86
87
88
89
90
91
92
93
94A
94B
95
96
97
98A
98B
99
100
101
102
103
104
Elution
Temp.
CO
211
211
212
214
215
216
222
223
225
227
230
231
232
235
239
240
240
240
240
240
240
240
240
240
Coapound
dloethylstyrene
•at . hydrocarbon
camohene (tent.)
•lloxane
•at . hydrocarbon
methyl caprylate
• lloxane
camphor
C10H18° (trace) <"«•)
•lloxane
trlchlorobenzene (trace)
ethyl caprylate
naphthalene
ri-dodecane
unset, hydrocarbon (tent.)
•lloxane
2-undecanone
sat . hydrocarbon
•at. hydrocarbon
methyl decanoate
siloxane
C14H30 (tent')
ethyl decanoate
unsat. hydrocarbon
137
-------
co
oo
i
I'.
Hi
.1
to
1 1
11 1
\ f i m
4
,
.1 .J . - Hi
>
«9
Ml
.AjJiM^ ^. 1
L. ft . * .ft 1 ft-
I...
10]
1 I k i
\ \ \ \
Figure D-6. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 2071
(Pittsburgh, PA).
-------
Table D-7. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO.
(Baton Rouge, LA)
3053
Chroma to-
graphic
Peak No.
1A
IB
2
3
4
5A
SB
5C
6
7
8A
BB
9
10
11
12
13A
13B
14A
14B
14C
ISA
1SB
16
17A
17B
18
19
20
21
22A
22B
23
24
25A
25B
25C
26A
26B
27
28
29
30
31
32
33
Elution
temp.
CO
57
58
62
63
68
70
71
72
73
74
76
77
79
80
85
86
87
88
90
90
90
92
93
94
97
97
98
100
104
106
108
108
109
110
113
113
114
116
117
120
122
123
125
126
133
134
Compound
carbon dioxide
chlorotrlfluoromethane
chlorome thane
C4H10 Uo"er
dlmethyldlfluoroallane
acrylaldehyde
acetone
furan
n-pentane
^-propanol
methylene chloride
Freon 113
carbon disulfide (trace)
C,B_0 laomer
C,H]00 laomer
ii-butanal
methyl ethyl ketone
C,H. , iaomer
hexafluorobenzene (int. atd.)
2-methylfuran
£— hexane
unknown
3-methylfuran
C,Bj_ iaomer
perfluorotoluene (int. atd.)
•ethylcyclopentane
C.H.O iaomer .
4 o
. 1,1,1-trlchloroe thane
benzene
C6B12 1>OBeI
athyl vinyl ketone
C5H10° lsoner
C6H12° Uomer
£-pentanal
C7H14 1M""
trlchloroctbylene
C6H8°
n-heptane
acetic acid
2-vlnylfuran
C-Bj. laomer (tent.)
C7H14 *«0-r
dimethyl diaulflde
dlhydropyran (tent.)
toluene
C7»14 *— «
Chroma to-
graphic
Peak Mo.
34
35
36
37
38
39
40
41
42A
42B
43A
43B
44
4SA
4SB
45C
45D
45E
46
47
48A
48B
48C
49A
49B
50
51A
51B
52
S3
54
55
56
57A
57B
58
S9A
59B
59C
60
61
62A
62B
63A
63B
64
- continued -
Elution
Tamp.
Cc)
136
139
141
144
145
147
149
150
153
153
155
156
158
159
159
160
161
161
164
165
166
166
167
169
170
172
173
173
175
176
178
180
181
182
182
184
186
187
188
189
190
191
191
192
193
194
Compound
C6H12° lgomer
ii-hexanal
C.B., laomer
o ID
it-octane
C6H10° Uol>er
furaldehyde laomer
C8H16 ito*"
alloxane
C8H16 Uoner
C,H,.0 laomer (tent.)
O i.U
C8H14 1*01>er
C6B100 laomer
unknown
ethylbenzene
C?HJ2 laomer (tent.)
o-furfuryl alcohol
xylene laomer
C8H18 Uo""
C7H14° Uo-er
C8H16 1>OBer
atyrene
C7D10°2 1"mr
n_-heptanal
C6H6°2 lsomer
unknown
£-nonane
CBH16 lBOIDer
C.H , laomer
8 14
unknown
C9H18 ltol*r
C0Hlg laomer
C10H20 i"*er
C9B18 laomer (tent.)
•ethylfuraldehyde laomer
benzaldehyde
methylfuraldehyde laomer
£-propylbenzene
C10H20 ito«r
C10H22 i*°*er
C11H24 Uo>"
C9H180>1*0"er
unknown
C..B,2 laomer (tent.)
C11H24 U"er
2-pentylfuran
£-octanal
139
-------
Table D-7 (continued)
Chroma to-
graphic
Peak No.
6SA
65B
66
67A
67B
68
69
70
71
72A
72B
73A
73B
74A
74B
75
76
77A
77B
77C
77D
78A
78B
79
80
81
82
83
84
85
86
87A
Elution
Temp.
194
194
196
197
198
199
201
202
204
204
204
207
207
208
209
210
211
212
212
213
213
214
215
217
218
221
222
224
226
227
228
229
Compound
C-alkyl benzene isoner
unknown
slloxane
i-decane
dichlorobenzene
unsac. hydrocarbon
CgHjg isoaer
C^-alkylbenzene (ten t . )
C.H,0, isomer
o O *
llnonene
sat. hydrocarbon
unsat . hydrocarbon
C11H24 l80Ber
sat. hydrocarbon
acetophenone
C.-alkylbenzene
M
C11H24 I80mer
C11H24 isamt
unsat. hydrocarbon
sat. hydrocarbon
C9H8°2 iaoael
CjHgO. isomer (tent.)
C11H24 lsomer
C10H16° i80mer
n_-nonanal
n_-undecane
unsat, hydrocarbon
sat . hydrocarbon
C12H2fc isomer
sat. hydrocarbon
C,2H2, isomer
siloxane
Chroma to-
graphic
Peak No.
87B
8BA
88B
89
90
91
92A
92B
93A
93B
94A
94 B
95
96
97
98A
98B
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
Elution
Temp.
Cc)
231
234
234
235
236
237
238
239
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
240
Compound
C.nH,.. iso&er
12 24
slloxane
C.-H,nO- (tent.)
10 10 2
sat. hydrocarbon
C12H26 I80ffler
C12H26 l80n"
C10H20° l80Iner
unsat. hydrocarbon
naphthalene (trace)
C12H22 isomer
ii-decanal
C12H24 istmer
nj-dodecane
C13H28 i80mer
sat. hydrocarbon
C,,H,, Isomer
13 26
C11H20° i8OTier
C13H28 i80mer
C. ,H-g Isomer
C13H28 isonier
C10H16° I80ffier
C13H24 lsomer
n-undecanal
ii-tridecane
C10H16° isoner
siloxane
unsat. hydrocarbon
unsat. hydrocarbon
n-dodecanal
Ei-tetradecane
unsat. hydrocarbon
i^-pentadecane
140
-------
to
M
e .
ii!
5 S I I
Figure D-7. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 3053
(Baton Rouge, LA) .
-------
Table D-8. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 3111
(Baton Rouge, LA)
Chromato-
graphlc
Peak No.
1
2
3A.
3B
4
5A
5B
6A
6B
6C
7A
7B
6
9
10A
10B
11
12A
12B
13
14
15
16A
16B
17A
17B
18
19
20
21
22
23
24
25
26
27
28
29
30
31A
31B
32
33A
Elution
Temp.
CO
59
61
65
65
71
73
74
76
76
77
80
81
82
84
87
88
89
91
92
94
95
96
101
101
104
104
106
108
109
110
111
112
114
117
120
123
126
128
135
142
144
146
148
CoBpound
carbon dioxide
dlchlorodlfluoromethane
aulfur dioxide
{• u 4matn*Y
C4H8 1>01D"
C5H1Q Loner
trichlorofluoronethane
acetone
laopropanol
il-pentane
C.Hg iaoner
kethylene chloride
Freon 113
carbon dLulfide
n-butanal
cyclopentane
CgH., Loner
C5H1()0 Loner
C5H1Q0 Loner
CfiH12 Loner
hexafluorobenzene (int. ltd.)
o-hexane
chloroform
perfluorotoluene (int. ltd.)
•e thy 1 cy clopentane
1,1, 1-trichloroe thane
C5H1Q0 Loner (tent.)
C6H120 Loner.
benzene
carbon tetracbloride
C6H12 iaoner
CjH120 Loner (tent.)
CgH120 Loner (teat.)
n-pentanal
trlchloroethylene
n_-beptane
C8H16 1*oner
P 11 4miMnpr
C7H14 ±me*Kr
dimethyl dLulfide
toluene
n_-hexanal
CBH16 1*oner
n-octane
tetrachloroethylene
Chroma to-
graphic
Peak Ho.
33B
34
35
36A
36B
37
38A
38B
39A
39B
40
41
42
43A
43B
44
45
46
47
48
49
50
51
52
53
54A
S4B
55A
55B
56
57
58
59
60
61A
61B
62
63
64
65
66
67
68
Elution
Temp.
(*C)
148
150
152
155
155
161
163
164
168
168
169
170
173
177
177
178
179
181
183
186
189
189
191
192
193
194
195
196
197
198
202
204
206
208
212
213
214
217
221
233
240
240
240
Compound
unaat. hydrocarbon
CgHlfi Loner (tent.)
•iloxane
C9B18 Loner
CjB20 iaoner (tent.)
ethylbenzene
xylene Loner
C9B20 Loner
•tyrene
CjHjQ Isoner
xylene Isoner
CgH20 Isoner
CjH20 Loner
•at . hydrocarbon
Cyalkyl benzene (tent.)
C10B22 i'OBer
C10U22 lsoner
•at. hydrocarbon
•iloxane
benzaldehyde
unknown
C11H24 I801ner
C,-alkyl benzene
C11H24 lsoner
C11H24 i§OBer
C11B24 Uomer
C.~alkyl benzene
•iloxane
C11B24 1*omer
dlchlorobenzene
C.-alkyl benzene
linonene
•at. hydrocarbon
•at. hydrocarbon
•cetophenone
•at. hydrocarbon
•at. hydrocarbon
•at. hydrocarbon
£-undecane
•Iloxane
nj-dodecane
unaat. hydrocarbon
•iloxane
142
-------
Figure D-8. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 3111
(Baton Rouge, LA).
-------
APPENDIX E
SEMIVOLATILE COMPOUNDS IDENTIFIED IN SELECTED
EXTRACTS OF MOTHER'S MILK
144
-------
Table E-l. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 1032
(Bayonne, NJ)
Chromato- Elution
graphic Temp.
Peck No. (*C)
1A
IB
2
3"
4
5
6
7
8
9
10
11A
US
12
13
14
IS
16
17
16
19
20
21
22
23
24
Coopound
toluene
syleoe isoner
•iloxane
•Iloxane
•Iloxane
•Iloxane
•iloxane
•lloxaoe
•Iloxane
dlaethylbiphenyl (tent.)
•Iloxane
•Iloxane
unknovn
•Iloxane
•at. hydrocarbon
•iloxane
•Iloxane
•at. hydrocarbon
•at. and unaat. hydrocarbons
•Iloxane
•Iloxane
•iloxane
•at. hydrocarbon
phthalate (tent.)
•Iloxane
•at. and unaat. hydrocarbons
Chrooato- Elution
graphic Temp.
Peak No. CO
25
26
27
26
29
30
31
32
33
34A
34B
35
36
37
38
39
40
41
42
43
44
45
46
47
46
Covpound
unknown
unknovn
•Iloxane
•iloxane
djp-pyrene (atd.)
•at. and unsat. hydrocarbons
•Iloxane
DDE
unknown
•ilnxane
unknown
unknown
•at. and unaat. hydrocarbons
•Iloxane
•at. and unsat. hydrocarbons
•at. and unaat. hydrocarbons
•Iloxane
•Iloxane
•Iloxane
•Iloxane
•iloxane
•Iloxane
lycopersene
choleateryl acetate
•iloxane
145
-------
Ill
DC
Figure E-l. Total ion current chromatogram from GC/MS analysis for Semivolatiles in sample 1032
(Bayonne, NJ).
-------
Table E-2. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 2121
(Pittsburgh, PA)
Chromito- Elution
graphic Temp.
Peak Ho. CC)
Compound
Chromato- Elution
graphic Temp.
Peak Ho. CO
COBDOU&d
i
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
toluene
•Iloxane
•iloxane
•Iloxane
ailoxane
2,6-dl-ter t-buty1-4-ae thy1phenol
•ethyl dodecanoate
ethyl butyrate (tent.)
•lloxane
aat. hydrocarbon
ailoxane
slloxane
aat. hydrocarbon
•iloxane
•iloxane
ailoxane
•at. and unsat. hydrocarbons
•at. hydrocarbon
unknown
•iloxane
•at. and unaat. hydrocarbons
unknown
unknown
•iloxane
•iloxane
d^Q-pyrenc (int. *td.)
•iloxane
28
29A
29B
30
31
32
33
34
35
36
37
38
39
40
41A
41B
42
43
44
45
46
47
48
49
50
51
uniat. hydrocarbon
unaat. hydrocarbon
DDE
••t. and unaat. hydrocarbons
ailoxane
pentachloroblphenyl
•at. and unsat. hydrocarbons
•Iloxane
••t. and unsat. hydrocarbons
hexachlorobiphenyl
•Iloxane
aat. hydrocarbon
•iloxane
•at. and unsat. hydrocarbons
•at. and unsat. hydrocarbons
heptachlorobiphenyl
ailoxane
•at. and unsat. hydrocarbons
•iloxane
•Iloxane
•iloxane
•iloxane
•Iloxane
lycopercene
•Iloxane
choleiteryl acetate
147
-------
Figure E-2. Total ion current chromatogram from GC/MS analysis for semivolatiles in sample 2121
(Pittsburgh, PA).
-------
Table E-3. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 3095
(Baton Rouge, LA)
Chrooato- Elutlon
graphic Temp.
Peak No. CO
1
2
3
4 "
5
6
7
B
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27A
27B
28
29
30
31
Compound
•ethylene chloride
toluene
•lloxane
••t. hydrocarbon
•at. hydrocarbon (tent.)
•lloxane
•at. hydrocarbon (tent.) .
•lloxane
•at. hydrocarbon (tent.)
•lloxane
•at. hydrocarbon
••t. hydrocarbon
unknovn
unknown
•at. hydrocarbon
•lloxane
••t. hydrocarbon
•iloxane
•iloxane
•at. hydrocarbon
•at. hydrocarbon:
•lloxane
•lloxane
•lloxane
aat. hydrocarbon
•iloxane
•at. hydrocarbon
unaat. hydrocarbon
unknown
unknown
•lloxane
•lloxane
Chronato- Elutlon
graphic Temp.
Peak No. CO
32
33A
33B
34
35
36A
36B
37A
37B
38
39
40
41
42
43
44
45
46A
46B
47
48
49
SOA
SOB
51
52
53A
53B
54
55
56
57
Compound
d10-pyr«ne
•at. hydrocarbon
unsat. hydrocarbon
•lloxane
DDE
unknown
uneat. hydrocarbon
ailoxane
unknown
•ac. hydrocarbon (tent.)
•lloxane
unsat. hydrocarbon (tent.)
ailoxane
•at. hydrocarbon (tent.)
•lloxane
••t. hydrocarbon
•at. hydrocarbon
•at. hydrocarbon
•lloxane
•lloxane
•at. hydrocarbon
•lloxane (tent.)
•lloxane
•at. hydrocarbon
•at. hydrocarbon
lycoperaene
•lloxane
cboleiteryl acetate
•lloxane
•at. hydrocarbon
unknown
•lloxane
149
-------
s
in
5
UJ
m
i
-------
Table E-4. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 4093
(Charleston, WV)
Chronato- Elutlon
graphic Tenp.
Peak No. (*C)
vOSJpOUOfl
ChroBato- Elutlon
graphic Tenp.
Peak Ho. CO
Coopound
1
2
3
4 A
4B
5
6
7
8
9A
9B
10
11
12
13
14
IS
16
17
18
19
20
21
22
23A
23B
24
25
26
27
28
29
toluene
•Iloxane
•Iloxane
•Iloxane
•at. hydrocarbon
•Iloxane
•iloxane
butyric •rhydride (tent.)
aat. hydrocarbon
^9^20 ^*°*er
unknown
•iloxane
aat. hydrocarbon
•at. hydrocarbon
•iloxane
•Iloxane
•at. hydrocarbon
aat. hydrocarbon
•at. hydrocarbon
•at. hydrocarbon
unknown
•Iloxane
•at. hydrocarbon
•at. and unaat. hydrocarbon
•Iloxane
•at. and unaat. hydrocarbons
•Iloxane
•at. and unsat. hydrocarbons
•iloxane
unknown
•at. and unaat. hydrocarbon*
•at. and unaat. hydrocarbons
30
31
32
S3
34
35
36
37A
37B
38
39
40
41
42A
42B
43
44
45
46
47
48
SO
51
52
53
54
55
56
57
58
59
•Iloxane
•Iloxane
d^-pyrene (int. atd.)
•at. and unaat. hydrocarbons
•iloxane
aat. and unaat. hydrocarbons
•at. and unaat. hydrocarbons
aat. and unaat. hydrocarbons
DDE
•at. and unsat. hydrocarbons
•iloxane
•iloxane
aat. and unsat. hydrocarbons
•Iloxane
•ethyl dthydroabletate (tent.)
•iloxane
•at. hydrocarbon
•iloxane
•at. and unsat. hydrocarbons
•Iloxane
pbtbalate
•Iloxane
unknown
•Iloxane
•Iloxane
•iloxane
lycoperaane
•Iloxane
cholesteryl acetate
aat. and unaat. hydrocarbons
•iloxane
et-tacopherol (vltaaln)
151
-------
8
s
tn
to
tl
X
u.
19
26
2
UIUJ
_JUI
•" Q.
u. in
Figure E-A. Total ion current chromatogram from GC/MS analysis .for semivolatiles in sample 4093
(Charleston, WV).
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
560/13-80-029
2.
t
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
ACQUISITION AND CHEMICAL ANALYSIS OF MOTHER'S MILK FOR
SELECTED TOXIC SUBSTANCES
6. REPORT DATE
December, 1980
6. PERFORMING ORGANIZATION CODE
31U-1521-21 + 22
[7TAUTHOR(s)Mitchell D. Erickson, Benjamin S. H. Harris,
III, Edo D. Pellizzari, Kenneth B. Tomer, Richard D.
Waddell and Donald A. Whitaker
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-01-3849 - Task 2
12. SPONSORING AGENCY NAME AND ADDRESS
Field Studies Branch, Exposure Evaluation Division
Office of Pesticides and Toxic Substances, U. S.
Environmental Protection Agency, Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
Task Final 1/23/78-4/18/80
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Project Officer: Joseph Breen
16. ABSTRACT
Samples of mother's milk were collected from Bayonne, NJ; Jersey City, NJ; Pitts-
burgh, PA; Baton Rouge, LA; and Charleston, WV, and analyzed for volatile (purgeables)
and semivolatile (extractable) organics using glass capillary gas chromatography/mass
spectrometry/computer. In the volatile fraction, 26 halogenated hydrocarbons, 17
aldehydes, 20 ketones, 11 alcohols, 2 acids, 3 ethers, 1 epoxide, 14 furans, 26 other
oxygenated compounds, 4 sulfur-containing compounds, 7 nitrogen-containing compounds,
13 alkanes, 12 alkenes, 7 alkynes, 11 cyclic hydrocarbons, and 15 aromatics were found,
including major peaks for hexanal, limonene, dichlorobenzene, and some esters. The
levels of dichlorobenzene appeared to be significantly higher in the samples from
Jersey City and Bayonne than in samples from other sites. Jersey City samples also
appeared to have significantly higher levels of tetrachloroethylene. Charleston and
Jersey City samples appeared to have significantly higher levels of chloroform; how-
ever, chloroform was observed in the blanks at about 20% of that in the samples. Due
to the small sample size and lack of control over the solicitation of sample donors,
the data cannot be used to extrapolate to the general population.
Fewer semivolatile compounds of interest were found. Polychlorinated naphtha-
lenes, polybrominated biphenyls, chlorinated phenols, and other compounds were specifi-
cally sought and not detected (limit of detection about 20-100 ng/mL milk). Poly-
chlorinated biphenyls (PCBs) and DDE were found.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b. IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Mother's Milk
Purge and Trap
GC/MS
Sampling
Milk
Chlorinated Organics
18. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (This Report)
UNCLASSIFIED
21. NO. OF PAGES
164
20. SECURITY CLASS (THtspagej
22. PRICE
EPA Form 2220-1 (R«». 4-77)
PREVIOUS COITION I* OBSOLETE
153
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