Environmental Protection
Agency
Toxic Substances
Washington DC 20460
EPA-560/13-80-005
February, 1980
Toxic Substances
SEPA Sampling and Analysis of Selected
Toxic Substances
Task 1: Polybrominated Biphenyls in
Air and Soil at User Sites
-------
EPA-560/13-80-005
SAMPLING AND ANALYSIS OF SELECTED TOXIC SUBSTANCES
TASK 1: POLYBROMINATED BIPHENYLS IN AIR AND SOIL AT USER SITES
by
R. A. Zweidinger and E. D. Pellizzari
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, North Carolina 27709
Contract No. 68-01-5020
Task 1
Project Officer
Vincent DeCarlo
Thomas Kopp
Office of Pesticides and Toxic Substances
U. S. Environmental Protection Agency
Washington, D. C. 20460
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
U. S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D. C. 20460
-------
DISCLAIMER
This report has been reviewed by the Office of Pesticides and Toxic
Substances, U. S. Environmental Protection Agency- and approved for pub-
lication. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use.
-------
ABSTRACT
Field sampling for air and soil was conducted in the vicinity of two
Borg Warner Co. facilities, one in Oxnard, CA and the other near Parkersburg,
W.V.
Polybrominated biphenyls (PBBs) were found in all of the soil samples
from Oxnard with the highest levels (36,000 ug/kg) nearest the facility and
the lowest (5 yg/kg) upwind the greatest distance. No PBBs were found in any
of the air samples ( < 3 ng/m ).
Polybrominated biphenyls were confirmed in seven of the thirteen soil
samples from West Virginia, (up to 12 yg/kg) traces detected but not confirmed
in three, and no PBBs were detected in the other three. The highest levels
were from samples collected in the Ohio River basin especially along the
2
eastern bank. No PBBs were confirmed in the air samples { <4 ng/m ).
This report was submitted in fulfillment of Contract No. 68-01-5020,
Research Request No. 1; by Research Triangle Institute under the sponsorship
of the U.S. Environmental Protection Agency. This report covers the period
December 11, 1978 to June 5, 1979 and work was completed as of June 5, 1979.
ill
-------
-------
CONTENTS
Abstract iii
Figures vi
Tables vii
Acknowledgements viii
1. Summary and Conclusions 1
2. Introduction 3
3. Method Validation 4
4. Field Sampling 12
5. Results of the Analysis of PBB's 18
6. Discussion 34
References 36
Appendices
A. Sample Preparation Procedures 37
B. Local Climatological Data, Oxnard, CA 42
C. Local Climatological Data, Parkersburg, WV 44
-------
FIGURES
Number Page
1 Air sampler 5
2 Sampling apparatus configuration for collection of
polychlorinated naphthalenes 6
3 Map of sampling locations Oxnard CA 1/23-28/1979. . . 14
4 Map of sampling locations, Parkersburg, WV
(3/26-30/79) 28
VI
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TABLES
Number Page
1 Intensities of isotopic peaks relative to the molecular
ion for polybrominated compounds 9
2 Ions selected for PBB analysis by SIM 11
3 Sampling Protocol for Borg-Warner, Oxnard, California. 13
4 Sampling protocol for Borg-Warner, Parkersburg, WV . . 16
5 Polybrominated biphenyls in soil samples collected in
Oxnard, CA 1/23/79 - 1/28/79 19
6 Limits of detection for PBBs in air samples 20
7 Polybrominated biphenyls in air samples collected in
Oxnard, CA 1/23/79 - 1/28/79 21
8 Analysis of control and blank soil samples for the
Oxnard, CA sampling trip 1/23/79 - 1/28/79 24
9 Analysis of control and blank polyurethane foam (PUF)
and glass fiber filter (GFF) samples for the Oxnard, CA
sampling trip 1/23/79 - 1/28/79 25
10 Polybrominated biphenyls in soil samples collected near
Parkersburg, WV 3/26/79 - 3/30/79 27
11 Polybrominated biphenyls in air samples collected near
Parkersburg, WV 3/26/79 - 3/30/79 30
12 Analysis of control and blank soil samples for the
Parkersburg, WV sampling trip 3/26/79 - 3/30/79. ... 32
13 Analysis of control and blank polyurethane foam (PUF)
and glass fiber filter (GFF) samples for the Parkersburg,
WV sampling trip 3/26/79 - 3/30/79 33
vii
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ACKNOWLEDGEMENTS
The authors wish to thank Dr. J. T. Bursey and Mr. L. Kelner of the
Research Triangle Institute (RTI), for their assistance with mass spectral
analysis. The technical assistance of Mr. Steve Burke is gratefully acknow-
ledged.
Valuable assistance and discussions were obtained from Mr. J. Rouge,
Ventura County Air Pollution Control District; Dr. V. J. DeCarlo and Mr. T.
Kopp, OPTS, EPA, Washington. Lastly, we wish to thank the many people at
each sampling site who permitted use of their yards, business establishments,
etc. and electricity for our sampling efforts.
viii
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SECTION 1
SUMMARY AND CONCLUSIONS
A field trip to collect air and soil samples in the vicinity of Borg-
Warner Co., Oxnard, CA was executed January 22 through 28, 1979. Access to
suitable sampling locations was severely limited for the air monitoring and
somewhat limited with respect to soil sampling. In all, 14 air samples were
collected over 4 days. The meterological conditions varied over the 4 days
with strong winds on January 24, 1979. Soil samples were taken along an ENE
transect upwind and downwind near (within a block) and far (1 km) from the
facility. Soil was also collected ^1 km in either- direction at right angles
to the first transect.
Polybrominated biphenyls (PBB's) were found in all of the soil samples
with the highest levels (36,000 |Jg/kg) nearest the facility and the lowest (5
|Jg/kg) upwind the greatest distance. No PBBs were found in any of the air
3
samples (<3 ng/m ).
A second field trip to collect air and soil samples in the vicinity of
Borg-Warner Co., Parkersburg, WV was executed March 26 through March 30,
1979. Access to sampling sites was again limited however in this case it was
due to the sparsely populated areas adjacent to the facility for which no
power drops were available and the Ohio River which blocked access to one
side of the facility. In spite of these limitations air sampling sites were
located in an upwind-downwind orientation. Thirteen soil samples were taken
at several distances in all directions up to 3 km from the facility. In all,
16 air samples were collected over 4 days. The meterological conditons were
somewhat more severe than normal for March with temperatures ranging from -1
to 24°C and westerly winds from calm to moderate. Light snow flurries were
encountered during the first sampling period.
Polybrominated biphenyls were confirmed in seven of the thirteen soil
samples, traces detected but not confirmed in three and none were detected
-------
in three other soils. The location of the PBB's follows the Ohio River
basin especially along the eastern bank. No PBB's were confirmed in the air
3
samples (<4 ng/m ).
-------
SECTION 2
INTRODUCTION
Polybrominated biphenyls (PBBs) have been used extensively as flame
retardants for polymers, textiles, and other materials. Although previous
environmental studies have centered around facilities manufacturing PBBs,
little attention has been given to their impact on the environment via user
facilities. Questions about their environmental distribution through wide-
spread use have been aroused by the recent major environmental catastrophes
(2)
in Michigan. The extent to which generalized pollution results from
normal usage of PBBs throughout the United States is still undefined.
The subject of this report is an assessment of the environmental contami-
nation in the vicinity of a user facility, Borg Warner Co. in Oxnard, CA.
To assess the contamination two types of environmental samples were collected,
soil and air. The former represents an environmental sink which for persis-
tant compounds such as PBBs gives a historical picture of PBB contamination.
Since air is the most probable transport medium, air samples were also
taken.
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SECTION 3
METHOD VALIDATION
SAMPLING
Air
Air samples were collected using a custom designed rotary vane pump
(Nutech Corp., Durham, NC), Figure 1, and a glass sampling head, Figure 2,
which holds a glass fiber filter (OFF) and 2 polyurethane foam (PUF) plugs.
The pressure drop imposed by the glass fiber filter and sorbent material
is such that flow rates greater than 300 2/min are not practical. For this
reason, pumps which could operate continuously at about 300 £/min with an
estimated pressure drop of 130 mm of Hg were investigated. Cast rotary vane
pumps satisfied this requirement.
These air samplers have been used for the collection of chloronaph-
thalenes in ambient air. The sampler shown schematically in Figure 1
uses a Gast oilless rotary vane vacuum pump model No. 1022. This pump is
rated to deliver 280 £/min air flow at no pressure drop and 250 £/min air
flow at 130 mm Hg. The selection of this model was based in part on the
fact that it has a motor mounted drive rather than belt drive which results
in a more compact, lighter unit for field sampling.
The flow rate is monitored at the pump exhaust to avoid the problems
associated with correcting for pressure changes during the sampling period.
The pressure at the pump was monitored with a vacuum gauge which serves to
signal possible malfunctions.
The sorbent material, PUF, was prepared from Olympic 2315 polyether
type polyurethane foam (Olympic Products Company, Greensboro, NC). These
plugs, 5 cm diameter x 13 cm long were cut from sheets of polyurethane foam
with an electric knife. The plugs were cleaned by five successive extractions
with toluene at 100°C for approximately 10 min per extraction. After
-------
VACUUM
GAUGE
Q.
COLLECTION MODULE
ROTARY VANE VACUUM
PUMP
EXHAUST
FLOW METER
Figure 1. Air sampler.
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GLASS FIBER FILTER
WIRE MESH SUPPORT
POLYUR ETHANE
FOAM PLUGS
STAINLESS STEEL
COUPLING
COUPLING BOLTS
WIRE MESH SUPPORT
SCALE lcm=4cm
Figure 2. Sampling apparatus configuration for collection
of polychlorinated naphthalenes.
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extraction individual plugs were placed in 9 oz. glass jars and dried in
vacuo at 50°C for ~12 hr. After drying, the jars were capped and wrapped
with aluminum foil to prevent photodegradation of the foam. This procedure
was shown to give a relatively low background when used for polychlorinated
naphthalene (PCN) sampling and analysis.
The performance of this sampling medium was previously evaluated for
PCNs which as a group are more volatile than the PBBs analyzed here. The
highest molecular weight PCN, octachloronaphthalene, has a volatility between
that of pentabromobiphenyl and hexabromobiphenyl based on gas chromatographic
elution times. Monobromobiphenyl has a volatility similar to di- or trichloro-
naphthalene. In the previous validation experiment, all of the PCNs were
well retained on the tandem PUF plugs with the exception of the monochloro-
naphthalene.
Control and blank samples for both the GFF and PUF media were prepared
and analyzed. That data is included in Section 5.3.
Soil
Soil samples are collected using a common garden bulb planter. A 2.5
cm deep core of soil was taken in 5 points approximately 5 m apart and
arrayed so as to represent an area ^10 M in diameter. Each such area is
referred to as a location. The soil was placed in precleaned glass jars,
capped with foil-lined caps and labeled. The arrangement of these locations
is discussed in Section 4.1. The cores from each location were composited
before analyzing.
The extraction procedure used for soils was an adaptation of a method
for
(14)
(12 13)
reported for pesticides, PCBs and PCNs ' and tested for its applicability
to PBBs.
EXTRACTION AND WORKUP
The extraction and work-up procedures had previously been validated for
other halogenated compounds (i-e_. polychlorinated naphthalenes ). These
procedures were validated in this work by the use of controls and blanks
prepared in each media, GFF, PUF, and soil. These controls and blanks were
analyzed by the protocol in Appendix A. The results are given in Section
5.0 along with the field controls and blanks.
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GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS) ANALYSIS
Analytical methodology was validated by GC/MS by a consistent policy of
use of standards. Each day the mass spectrometer was tuned using perfluoro-
tributylamine (FC-43) as a reference compound. Peak resolution was checked
daily, as were relative abundances of peaks in the reference compound. This
provided a check only for the mass spectrometer, however. To monitor the
performance of the entire system, a solution containing known quantities of
pure isomers of certain of the polybrominated biphenyls (2-bromobiphenyl,
4.99 ng/|Jl; 4,4'-dibromobiphenyl, 4.56 ng/|Jl; 2,4',5-tribromobiphenyl, 10.08
ng/|Jl; 2,2' ,5 ,5 '-tetrabromobiphenyl, 9.90 ng/(Jl; 2,2',4,5',6-pentabromobi-
phenyl, 10.03 ng/pl; and 2,2',4,4',6,6'-hexabromobiphenyl, 9.98 ng/(Jl) and
internal standards (octachloronaphthalene, 3.72 ng/(Jl; and decachlorobiphenyl,
3.96 ng/pl) was used. The standard was used as the first and last analysis
of the day. Also, during the course of the day, every fifth injection was
an analysis of the standard solution. Samples were analyzed by the selective
ion monitoring (SIM) technique. Ratios of peak areas were calculated and
standard deviations of these ratios observed to monitor stability of the
system. Also, each sample contained two internal standards, octachloronaph-
thalene and decachlorobiphenyl, at a level of approximately 2 ng/|jl each.
These standards were monitored in every determination. A second standard
mixture (containing decachlorobiphenyl, 88 ng/jjl; 2,2',4,4',6,6'-hexabromobi-
phenyl, 116 ng/jjl; and 2,2',3,3 ' ,5 ,5 ' ,-6,6 '-octabromobiphenyl, 80 ng/(Jl) was
used in the analysis of the hepta- through deca-isomers.
The columns used in the analyses were a 180 cm x 0.2 cm i.d. glass
column, 2% OV-101 on 80/100 Gas Chrom Q for monobromo-through
hexabromobiphenyl and a 42 cm x 0.2 cm i.d. glass column with the same
packing for hexabromo-through decabromobiphenyl. The temperature range was
190° to 280°C, programmed at 12°/min with a helium flow rate of 30 cc/min
for the longer column. For the shorter column, a temperature range of 240°
to 280°C programmed at a rate of 8°/min was employed. The separator was
maintained at 250°C, the injector at 280°C.
Intensities of isotopic peaks relative to a molecular ion (calculated
79
for Br) for polybrominated compounds are shown in Table 1.
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Table 1. INTENSITIES OF ISOTOPIC PEAKS RELATIVE TO THE MOLECULAR ION FOR
POLYBROMINATED COMPOUNDS
Degree of
Bromination
Br
Br2
Br3
Br4
Br5
Br6
Br7
Br8
Br,
Brio
M
100
100
100
100
100
100
100
100
100
100
M + 2
97.8
195
293
391
489
587
685
783
881
979
M + 4
95
286
575
958
1436
2011
2682
3440
4310
M + 6
93
375
937
1875
3280
5249
7873
11247
M + 8
92
459
1376
3210
6421
11557
19262
M + 10
90
539
1885
5027
11310
22620
M + 12 M + 14 M + 16 M + 18 M + 20
88
615 86
2460 687 84
7379 3095 757 82
18447 10315 3786 823 81
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Using this table as a guide, the most intense ion of a given isotope
cluster was selected to monitor for the presence of a given isomer. An
approximate time window for elution could be derived from the elution times
of the known isomers comprising the standard solution. The ions monitored
in PBB analysis are shown in Table 2.
When a primary ion was observed at an appropriate time, identification
of the compound as a polybrominated biphenyl was confirmed by a subsequent
determination monitoring both the primary and secondary ions. An identifica-
tion was considered "confirmed" when both ions were present, maximized at
the same point, and occurred in the correct intensity ratio.
10
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Table 2. IONS SELECTED FOR PBB ANALYSIS BY SIM
PBB Isomers
C12H9Br
C18H8Br2
C12H7Br3
C12H6Br4
C12H5Br5
C12H4Br6
C12H3Br7
C12H2Br8
C12HBr9
C12Br10
M = nominal
Ma
232
310
388
466
544
622
700
778
856
934
molecular weight based on Br = 79.
SIM
232,
312,
390,
470,
548,
628,
706,
788,
866,
942,
Ions
234
310
392
472
550
630
708
784
862
946
Ions listed in order of "primary" and "secondary",
11
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SECTION 4
FIELD SAMPLING
SAMPLING NEAR THE BORG-WARNER FACILITY IN OXNARD, CA
General Description of the Meterology of the Area
An excerpt from the Local Climatological Data - Annual Summaries for
1974 is included as Appendix B. This excerpt describes the climatological
conditions of Los Angeles, CA. Since Oxnard is on the coastal plain west
and a little north of Los Angeles (^75 km), the same influences of ocean
(west and south) and mountains (north and east) are operative and determine
the climatology of Oxnard. Winds are usually light and variable depending
on time of day and season. The predominant wind direction in spring, summer
and early fall is on-shore (westerly). In the fall, winter and early spring
months, strong winds descend from the mountains to the northeast. These are
referred to as the Santa Ana winds and can pick up considerable amounts of
dust. Thermal inversions during periods of low air movement at times extends
air pollution outward from Los Angeles to Oxnard.
Sampling Protocol
The sampling protocol is given in Table 3 for both air and soil samples.
The locations of each of these samples is shown in Figure 3. The local
inhabitants were in general not inclined to cooperate and security was very
poor. Almost all residences and business establishments had high fences or
walls around any private yards. We were informed at the fire station that
even with personnel present nearly 24 hours a day they could not assure the
security of their fenced areas. Despite these problems, samplers were
deployed in nearly the desired array for 4 days as indicated in Table 3.
Discussions with local inhabitants highlighted a factor which may be
important in the dispersion of PBBs from such an apparently innocuous
source as the Borg-Warner facility in Oxnard. That is the Santa Ana winds
which blow out of the mountains in November and December at speeds of 55-80
12
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Table 3. SAMPLING PROTOCOL FOR BORG-WARNER, OXNARD, CALIFORNIA
Period Cycle
1/23,24/79 CI
PI
1/24,25/79 CI
P2
1/25,26/79 CI
P3
1/26,27/79 CI
1/28/79 CI
Location
LI
L2
L4
LI
L2
L3
L4
L5
L6
L7
LB
LI
L2
L3
L4
L2
L3
L4
L9
L10
Sampling
Time Sample
(PST) Volume (m3)
1442-1223
1740-1253
1620-1314
1245-1205
1308-1234
1205-1136
1344-1302
-
_
-
-
1224-1134
1245-1155
1151-1102
1317-1213
1207-1120
1118-1055
1232-1134
_
-
257
215
226
271
264
260
241
_ c
_ c
_ c
c
260
254
254
247
262
253
250
_ c
_ c
Type of
Sample
alra
air
air
alra-b
air
air
air
aoll
soil
Boll
soil
air
air
air
air
air
air
air
soil
soil
Meteorological Conditions
T(*C) Mind Dlr. /Speed (krnph) Other
4-lBd 31/2-3
calm
2/2-3
32/2-5
19f 32-26/3-7h
8-19 unknown
31°/B-10
19£ 27V8-10 C16
3-108 29/6-9h
unknown
2-3/3
6/3-4
4-16d 27/4-5
3-216 2-6/3£
unknown
1-4/5-7
(2 hrs)6 overcast-broken
(13 hrs) clouds In a.m.
(2 hrs)
(3 hrs)
(9 hrs) scattered clouds-clear
(8 hra)
(7 hrs)
(8 hrs) clear
(4 hrs)
(8 hrs)
(3 hra)
(3 hra)
(6 hra) clear
(4 hra)
(8 hra)
(6 hrs)
Nutech Corporation custom designed high volume samplers were used. Sample intake 1-2 m elevation
except as noted.
Sampler placed on roof ^5 m elevation.
Each soil sample was comprised of 5 cores 5.5 cm in diameter and 2.5 cm in depth.
From the National Weather Service.
^From the Oxnard Airport Weather Station. 8 hrs from 2145 to 0600 PST were not recorded.
Manual temperature reading at location 4.
?MRI monitor at location 4.
.MRI readings indicated calm.
MRI readings indicated wind direction was NNE under light winds.
-------
Figure 3. Map of sampling locations Oxnard, CA 1/23-28/1979.
14
-------
kmph. These winds frequently fuel brush fires in the surrounding hills
filling the coastal region where Oxnard is located with dense particulate
from the smoke. Similarly dust and other particulates may be transported by
these winds.
The meterological recording instrument (MRI) was set up at Location 4
on 1/24/79. The wind run indicator was operating erratically and hence
airport data was used. Wind directions between the two sources were identical
SAMPLING NEAR THE BORG-WARNER FACILITY IN PARKERSBURG, WV
General Description of the Meterology of the Area
An excerpt from Local Climatological Data - Annual Summaries for 1974
(Part II) is included in Appendix C which describes the average climatological
conditions of Parkersburg, WV. The Borg-Warner facility is located in a
low, flat area known as Washington Bottom situated on the inside of a right-
angle bend in the Ohio River approximately 10 kilometers west of Parkersburg.
Weather in the Parkersburg area is generally mild for the region, presumably
moderated by the proximity of the Ohio River. For the month of March,
average temperatures are in the range 5-8°C and light winds (^12 KMPH) are
prevalent. During the actual sampling period (3/26-30/79) the weather was
less mild than normal with temperatures from -1 to 24°C and westerly winds
from calm to moderate (up to 22 KMPH). Light snow flurries were also encoun-
tered during the first sampling period (3/26,27/79). Despite the below
freezing temperatures encountered early in the trip, the ground remained
thawed thus posing no difficulty in the collection of soil samples. Although
an MRI Meterological Weather Station was set up close to the Borg Warner
facility at Location 1, the unit functioned erratically. Specific weather
data for the sampling period was therefore obtained from the National Weather
Service office located in downtown Parkersburg, WV.
Sampling Period
The sampling protocol is given in Table 4 for both air and soil samples.
A map showing the locations of these samples is given in Figure 4. Four air
samples (24 hr period) were collected at each of four separate locations
(total of 16 air samples) under a variety of meterological conditions. A
15
-------
Table 4. SAMPLING PROTOCOL FOR BORG-WARNER, PARKERSBURG, WV
Period Cycle
3/26,27/79 Cl
PI
3/27,28/79 Cl
P2
3/28,29/79 Cl
P3
3/29,30/79 Cl
PA
Location
LI
1,2
L3
LA
LI
LI
L2
L2
L3
L3
L4
LA
L5
L6
L7
L8
L9
LI
L2
L3
LA
L10
Lll
LI 2
L13
LI
L2
L3
LA
Sampling
Time
(PST)
1055-1035
1155-lion
1315-1225
1AOO-1300
1050-1035
_
1110-1055
_
12AO-11AO
_
1315-1200
-
-
-
-
_
-
10A5-1000
1110-1035
1150-1125
1220-11AO
_
_
_
_
1025-0940
1055-1310
1135-10A5
1155-1055
Sample 3
Volume (m )
282
252
185
2A7
28A
_
265
_
196
_
2A9
-
-
-
-
-
-
277
2A6
198
225
_
_
_
_
26A
253
166
233
Type ofa'b Meteorological CondltlonaC Other
Simple T(°C)
air -1-2''
air
air
air
air -3-8
soil
air
soil
air
soil
air
•-oil
soil
soil
soil
soil
soil
air 11-23
air
air
air
soil
soil
soil
soil
air 17-2A
air
air
air
Wind Dir. /Speed (KMPH)
W/21-22'
SW/5-71
SU/8-1A
NW/5
Calm
N/5
E/5-8
Calm
SE/5-11
SE/10-1A
S/16
SW/1A-21
S/13
SE/1A-18
S/1A-16
SE/1A-16
S/ll-16
SW/16-21
SW/19-22
SE/2-8
3/11-13
S'l/1/,-21
(2 hr) Heavy cloud,
(?7 hr) • 3now
(10 hr) cloudy-clear
(1 hr)
(3 hr)
(1 hr)
(3 hr)
(A hr)
(2 hr)
(A hr) clear
(1 hr)
(3 hr)
(1 hr)
(2 hr)
(2 hr)
(2 hr)
(A hr)
(5 hr)
(7 hr) clear
(6 hr)
(8 hr)
(3 hr)
Air samples were collected with a Nutech Corporation custom designed high volume samplers. Sam-
pie intake 1-2 M elevation.
Each soil sample was comprised of 5 cores 5.5 cm in diameter and 4 cm in depth.
From the National Weather Services, Parkersburg, WV given in 24 hr periods from 1000-1000 EST.
Manual temperature reading at location 1 was 0° at 1100 EST.
^
"MRI readings taken at location 1 indicated wind direction was WSW at 5 KMPH from 1100-1530 EST
during this period.
-------
total of thirteen composite soil samples were collected with each composite
made up of 5 samples plugs taken approximately 2 meters apart.
The Borg-Warner facility is located 10 kilometers west of Parkersburg
at a bend in the Ohio River known as Washington Bottom. The hilly terrain
and sparse population near the facility severely limited the choice of
adequate air sampler locations. We were able to locate one sample site
approximately 0.2 kilometers east of the facility corresponding to the
general downwind transect. A second sampling site was also located in the
river bottom area directly across the Ohio River from the facility Ol
kilometer west). The third and fourth sample sites were located on ridges
overlooking the river bottom from the east and west in the residential areas
of Washington, WV and Little Hocking, OH, respectively.
Composite soil samples were taken at each air sample site as well as
sites distributed around the Borg-Warner facility in all directions up to a
distance of 2 kilometers. The 5 core samples from each location were composi-
ted immediately upon collection. Each composite was mixed thoroughly before
removal of a portion for extraction and analysis.
17
-------
SECTION 5
RESULTS OF THE ANALYSIS OF PBB's
SAMPLES FROM OXNARD, CA
Soils
The results for the analysis of soil samples taken in Oxnard are given
in Table 5. Only hexabromobiphenyl was found in all of the soil samples.
Small OlO% of the total PBBs) amounts of pentabromobiphenyl were found in
the two samples containing the largest amount of PBB's. Heptabromobiphenyl
(3% of the total PBBs) was found in the sample containing the greatest
amount of PBB's. No nona- or decabromobiphenyl was detected in any sample.
In two samples P2/C1/L5 and P2/C1/L7, material with a retention time similar
to that of monobromobiphenyl and possessing the two ions characteristic of
this compound in the proper ratio was observed. In this mass range, one
cannot be certain that these GC/MS peaks are due to monobromobiphenyl, and
the amounts observed were treated as upper limits of PBB concentration.
Air
All of the glass fiber filters from the air sampling in Oxnard were
analyzed for all of the PBB's (1 through 10 bromines) and none were confirmed
to be present. The limit of detections, exclusive of collection efficiency
and recovery, are given in Table 6 by isomer. Table 6 also contains the
limit of detection for the analysis of PUF samples for PBB's (1 through 6
bromines). The analysis of the actual samples is given in Table 7- Where
"not confirmed" is listed, the two ions monitored for confirmation showed
peaks(s) at the same retention time in the appropriate retention window for
that isomer, but the intensity ratio was different from theoretical values.
Such a finding does not preclude the presence of a PBB isomer, but fails to
confirm its presence. There is a high frequency of interference in the
determination of monobromobiphenyl especially in the PUF samples. The
o
highest possible concentration of monobromobiphenyl was 3.4 ng/m in the
18
-------
Table 5. POLYBROMINATED BIPHENYLS IN SOIL SAMPLES COLLECTED IN OXNARD, CA
1/23/79 - 1/28/79
Compound (pg/Kg)
C12H9Bri C12H8Br2 C^B^
P2/C1/L5* <7.2*| NDC ND
±0.8d
P2/C1/L6 ND ND ND
P2/C1/L7
-------
Table 6. LIMITS OF DETECTION FOR PBB'S IN AIR SAMPLES
Compound
C12H9Br
C12H8Br2
C12H7Br3
C12H6Br4
C12H5Br5
C12H4Br6
C12H3Br?
C12H2Br8
C12HlBr9
C12Br10
Total
L/D GFF
(ng/m3)
0.03
0.02
0.02
0.08
0.15
0.6
0.6
0.6
0.6
0.6
3.3
L/D PUF
(ng/m3)
0.5
0.01
0.01
0.04
0.07
0.3
-
-
-
-
0.44a
1-6 bromines.
20
-------
Table 7. POLYBROMINATED BIPHENYLS IN AIR SAMPLES COLLECTED IN OXNARD, CA
1/23/79 - 1/28/79
Compound (ng/m )
Sample
P1/C1/L1 -
P1/C1/L2 -
P1/C1/L4 -
P2/C1/L1 -
P2/C1/L2 -
P2/C1/L3 -
P2/C1/U -
P3/C1/L1 -
P3/C1/L2 -
P3/C1/L3 -
P3/C1/U. -
P4/C1/L2 -
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
GFF
PUF
C12H,Bria
ND
NC
NC
NC
NC
NC
ND
NC
NC
NC
ND
NC
ND
NC
NC
NC
NC
NC
ND
ND
ND
NC
ND
NC
C12,,8Br2b
ND
NC
ND
NC
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
NC
ND
ND
ND
NC
ND
ND
ND
ND
C12H7Br3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H6Br4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H5Br5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H4Br6 C12H3Br9 C12H2Br8
ND ND ND
ND
ND ND ND
ND
ND ND ND
ND
ND ND ND
ND
ND ND NC
ND
ND ND ND
ND
ND ND NC
ND
ND ND ND
ND
ND ND NC
ND
ND ND ND
ND
ND ND ND
ND
ND ND ND
ND
C^HBr, C12Br1Q
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
ND ND
(continued)
-------
Table 7 (cont'd.)
Compound (ng/m )
Sample
P4/C1/L3 -
-
PA/C1/L4 -
-
GFF
PUF
GFF
PUF
C12»9Bria
NC
NC
NC
NC
C12H8Br2
ND
ND
ND
ND
C12,l7Br3
ND
ND
ND
ND
C12H6BrA
ND
ND
ND
ND
C12H5Br5
ND
ND
ND
ND
C12"«Br6 C12H3Br9 C12"2Br8C C12HBr9 C12Br10
ND ND ND ND ND
ND
ND ND NC ND ND
ND
ND - not detected.
NC - not confirmed.
a 3
No value could exceed 3.A ng/m .
No values could exceed 0.03 ng/m .
c 3
No values could exceed 0.6 ng/m .
-------
P4/C1/L3 PUF. Polyurethane foam blanks gave backgrounds equivalent to 0.5
3
ng/m . Occasional interference in the determination of the dibromobiphenyl
occurred. However the maximum concentration which could be present is <_ 0.03
3
ng/m . Octabromobiphenyl is noted as not confirmed in several of the GFF
samples, however it must be noted that the maximum that could possibly have
been present was below the stated limit of detection.
Quality Control/Quality Assurance
In preparation for the field sampling, control and blank samples were
prepared for each medium sampled. Half of the samples were stored in the
laboratory and the other half sent to the sampling site and returned in order
to evaluate the rigors of transportation. These controls and blanks were
intermingled with the samples and analyzed along with the samples. The
results of the analysis of the soil samples is given in Table 8. The instru-
mental sensitivity to the higher brominated compounds drops off rapidly and
octabromobiphenyl could not be detected at 23 Mg/kg either in the soil
control samples or in a reference standard prepared from the spiking solution.
Determinations were all performed at least in duplicate. A standard
mixture of known pure polybrominated biphenyl isomers was analyzed at the
start and end of each day. In the course of the day, every fifth injection
was a determination of the standard solution. Every sample contained two
internal standards at a level of 2 ng/pl each, and these standards were
monitored with every determination. Solvent washes were done between sample
and standard injections.
Blank and control PUF and GFF samples were analyzed; the results are
given in Table 9. The absence of hexabromobiphenyl in the control samples
was due to technical difficulties in preparing the spiking solution. Subse-
quent analysis of control samples from the Parkersburg sampling trip showed
adequate recoveries of hexabromobiphenyl.
RESULTS OF THE ANALYSIS OF SAMPLES TAKEN NEAR PARKERSBURG, WV
Soils
The results of the GC/MS analysis of soil samples taken near Parkersburg,
WV are given in Table 10. Hexabromobiphenyl was confirmed and quantitated in
seven of the thirteen soil samples and traces detected but not confirmed in
three additional samples. Three samples contained no detectable levels
23
-------
Table 8 . ANALYSIS OF CONTROL AND BLANK SOIL SAMPLES FOR THE OXNARD, CA SAMPLING TRIP
1/23/79 - 1/28/79
Compound, (Jg/Kg (0/0)
Sample
Laboratory 1
Control
2
Blank 1
2
Field 1
Control
2
Blank 1
2
C12H9Brl C12H8Br2
2.8 + 0.6° 90+2
(76 + 2)
ND 78 + 10
(66 + 8)
NCe ND
NC ND
NC 44 + 14
(36 + 12)
NC 68 + 22
(58 + 19)
ND ND
ND ND
O O Ti-v- f* U B** f~* 14 B t~
C12H7Br3 C12H6Br4 C12H5Br5
105 +
(81 +
102 +
(80 +
ND
ND
44 +
(34 +
90 +
(69 +
ND
ND
0.4
0.3)
10
8)
12
9)
10
8)
174 +
(85 +
178 +
(87 +
ND
ND
64 +
(32 +
154 +
(75 +
ND
ND
14
8)
18
8)
36
18)
8
4)
196 +
(108 +
218. +
(120 +
ND
ND
52 +
(36 +
202 +
(111 +
ND
ND
60
31)
16
9)
26
18)
22
12)
C12H4Br6 (
118 + 70
(120 + 71)
168 + 16
(172 + 17)
ND
ND
ND
178 + 60
(182 + 62)
ND
ND
: 2H Br Total
NDd
ND
ND
ND
ND
ND
ND
ND
686 +
(89 +
744 +
(105 +
<1
<1
204 +
(34 +
692 +
(99 +
<1
<1
93
25)
32
42)
48
2)
69
50)
Percent recovery in parenthesis.
This compound was added at 23 pg/kg and could not be detected in either the control sample pr the
calibration standard at that level.
None added.
ND
not detected at more than 1 pg/kg.
"NC = not confirmed by proper ion ratios.
-------
Table 9. ANALYSIS OF CONTROL AND BLANK POLYURETHANE FOAM (PUF) AND GLASS FIBER FILTER (GFF)
SAMPLES FOR THE OXNARD, CA SAMPLING TRIP, 1/23/79 - 1/28/79
10
Cn
Compounds
C12H9Br
ng
HIE b
Laboratory 1 £32
Control
Blank 1 £128
Field £44
Control 1
Control 2 £2
Blank 1 £48
Blank 2 £115
GFF
Laboratory 1 QI ND
Control
QIII ND
C}2H8Br2
ng (0/0)
94 + 4°
(78 + 3)
NCe
93 + 6
(78 + 4)
6560 + 360
(111 + 6)
NC
NC
38 + 5
(32 + 4)
960 + 130
(16 + 2f)
C12H7Br3
ng (0/0)
110 + 17
(85 + 13)
ND
101 + 5
(78 + 4)
7050 + 440
(107 + 7)
ND
ND
77 + 2
(59 + 2)
2100 + 30
(32 + lf)
ng (0/0)
156 + 8
(76 + 4)
ND
144 + 16
(71 + 8)
10,150 + 480
(100 + 5)
ND
ND
160 + 10
(79 + 5)
6,460 + 100f
(63 + lf)
C12H5Br5
ng (0/0)
229 + 34
(127 + 19)
ND
183 + 16
(102 + 9)
12,900 + 550
(142 + 6)
ND
ND
100 + 0
(56 + 0)
3,980 + 10f
(44 + lf)
ng (0/0)
d
ND
(<17)
ND
ND
(<17)
216
(4)
ND
ND
ND
(<2)
ND
Total3
589 + 39
(91 + 24)
521 + 24
(82 + 14)
36,660 + 900
(115 + 18)
375 + 12
56 + 19
13,500 + 167
39 + 20
Blank
ND
ND
ND
ND
ND
ND
(continued)
-------
Table 9 (cont'd.)
Compounds
C12H9Br
Sample ng
Field 1 QI ND
Control
QIII NC
Blank 1 ND
C12H8Br2
ng (0/0)
116 + 25
(97 + 21)
948 + 17
(16 + 0.3)
ND
C12H7Br3
ng (0/0)
250 + 14
(192 + 11)
2027 + 250
(31 ± 4)
ND
C12H6Br4
ng (0/0)
193 + 21
(96 + 10)
5457 + 444
(54 + 4)
ND
C12H5Br5
ng (0/0)
171 + 18
(95 + 10)
3830 + 218
(42 + 2)
ND
ng (0/0) Totala
ND 730 + 40
120 + 48
ND 12,262
36 + 16
ND
Exclusive of C H Br .
Limit of detection due to background interferences.
Standard deviation of 3 or more determinations.
ND
not detected - Technical difficulties in the preparation of the spiking solution.
"NC = not confirmed in ion ratios of 2 or more ions not correct for this compound.
Deviation of a measured value from the average of two determinations.
-------
Table 10. POLYBROMINATED BIPHENYLS IN SOIL SAMPLES COLLECTED NEAR PARKERSBURG, WV
3/26/79 - 3/30/79
Compound (ug/kg)
Sample
P2/C1/L18
P2/C1/L2
P2/C1/L3
P2/C1/L4
P2/C1/L5
P2/C1/L6
P2/C1/L7
P2/C1/L8
P2/C1/L9
P3/C1/L10
P3/C1/L11
P3/C1/L12
P3/C1/L13
C12H9Br1
ND
ND
<5d
ND
ND
ND
ND
ND
ND
ND
ND
NC
ND
C12H8Br2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H7Br3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H6Br4
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H5Br5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
<0.4°
ND
C12H4Br6
35 + 3b
<0.3C
<0.8C
<0.5C
3.2 + 0.3e
1.9 + O.lb
ND
ND
0.73 + 0.03b
1.86 + 0.02b
2.4 + O.lb
10.6 + 0.4e
ND
C12H3Br7
ND
ND
ND
ND
ND
ND
. ND
ND
ND
ND
ND
1
ND
C12,,2Br8
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C^HBr,
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12Br10
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Total
35 + 3
<0.3
<0.8
<0.5
3.2 + 0.3
1.9
ND
ND
0.73
1.86
2.4
12.0 + 0.4
ND
aRefer to Table 4 and Figure 4 .
Trace detected but not confirmed.
c
+ indicates range of duplicate measurements.
Not confirmed, may be background.
Q
+ indicates standard deviation of three or more measurements.
-------
00
Figure 4, Map of sampling locations, Parkersburg, WV (3/26-30/79).
-------
of any PBB. One sample, P3/C1/L12, showed small proportions of pentabromobi-
phenyl and heptabromobiphenyl along with the hexabromobiphenyl. The soil
extracts from those samples were submitted to the optional Florisil column
cleanup (see Appendix A). This clean-up reduced the background interference
with the detection of monobromobiphenyl as well as shortening instrumental
analysis time. In only two samples were the m/z, 232 and 234 ions observed
and in neither case was the ratio near the theoretical for monobromobiphenyl.
Air
No air samples could be confirmed to contain PBB's (Table 11). Some
trace amounts may have been detected but could not be confirmed. Where this
occurred the upper limit of the quantity is listed as a 5 amount. For the
limits of detection see Table 6- There was some background interference with
the detection of monobromobiphenyl however the maximum amount which could
3
have been present in any sample was <0.1 ng/m .
QUALITY CONTROL/QUALITY ASSURANCE
Control and blank samples were prepared for each medium sampled. Half
of the samples were stored in the laboratory (laboratory controls and blanks)
and half were sent to the field and returned (field controls and blanks).
The controls and blanks were intermingled with the samples and analyzed along
with the samples. The results of the soil samples are given in Table 12.
Octabromobiphenyl was added at 104 M8/kg aQd could be detected but quantitation
was not possible.
Determinations were all performed at least in duplicate. A standard
mixture of known pure PBB isomers was analyzed at the start and end of each
day. In the course of the day, every fifth injection was a determination of
the standard solutions. Every sample contained two internal standards at a
level of 2 ng/(Jl each, and these standards were monitored with each determina-
tion. Solvent washes were performed between standard and sample injections.
Blank and control PUF and GFF samples were analyzed and the results are
given in Table 13.
29
-------
Table 11. POLYBROMINATED BIPHENYLS IN AIR SAMPLES COLLECTED NEAR PARKERSBURG, WV
3/26/79 - 3/30/79
Compound (ng/m
Sample
P1/C1/L1
P1/C1/L2
P1/C1/L3
P1/C1/L4
P2/C1/L1
P2/C1/L2
P2/C1/L3
OJ
O
P2/C1/L4
P2/C1/L1
P3/C1/L1
P3/C1/L2
P3/C1/L3
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
C12»9Bria
ND
ND
NC
NC
NC
NC
NC
NC
ND
NC
ND
NC
NC
NC
NC
<0.03
ND
NC
ND
NC
NC
ND
NC
ND
C12HBBr2b
ND
ND
ND
ND
ND
10.02
<0.03
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H7Br3
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H6Br4
ND
ND
ND
ND
ND
ND
ND
10.02
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12H3Br5
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
C12"^6
ND
ND
ND
ND
ND
ND
-------
Table 11 (cont'd)
Compound (ng/m )
Sample
P3/C1/L4
P4/C1/L1
P4/C1/L2
P4/C1/L3
P4/C1/U
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
- GFF
- PUF
C12Vrl"
NA
ND
ND
ND
ND
<0.2
ND
ND
NA
ND
C12H8Br2b
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12H7Br3
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12V'4
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12H3Br5
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
cnV'6
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12U3Br7
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12H2Br8
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12llBr,
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
C12Br10
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
Total
NA
ND
ND
ND
ND
ND
ND
ND
NA
ND
ND = not detected.
NC = not confirmed.
"-1 ^o values could exceed 0.4 ng/m .
TSIo values could exceed 0.03 ng/m .
CTrace detected but not fully confirmed.
-------
N>
Table 12 . ANALYSIS OF CONTROL AND BLANK SOIL SAMPLES FOR THE PARKERSBURG, WV SAMPLING TRIP,
3/26/79 - 3/30/79
Compound, Mg/Kg (0/0)"
Sample
Laboratory
Control - 1
- 2
Blank - 1
- 2
Field
Control - 1
- 2
Blank - 1
- 2
C12H9Br1
NDcd
ND
ND
ND
ND
ND
ND
ND
C12H8Br2
284 + 12*
(95 + 4)
242 + 4*
(81 + 1)
ND
ND
500 + 16*
(168 + 5)
403 + 10*
(135 + 3)
ND
ND
C12H?Br3
182 + 7
(107 + 4)
144 + 4*
(85 + 2)
ND
ND
270 + 0*
(159 + 0)
251 + 6*
(148 + 4)
ND
ND
C12H6Br4
NDC
ND
ND
ND
ND
ND
ND
ND
C12H5Br5
46 + 4
(90 + 8)
47 + 6
(92 + 12)
ND
ND
60+5
(118 + 10)
84 + 3
(165 + 6)
ND
ND
C12H4Br6 C12H2Bra
444 + 18 >27
(73 ± 3)
466 + 16 >37
(76 + 3)
ND ND
ND ND
484 + 30 >66
(79 + 5)
799 + 56 >53
(131 + 9)
ND ND
ND ND
Total
956 + 23
(91 ± 14)
899 + 18
(84 + 7)
ND
ND
1314 + 34
(131 + 41)
1537 + 56
(145 + 15)
ND
ND
ft
Percent recovery In parenthesis.
This compound was added at 112 yg/kg the values listed are lower limits of the amount recovered
based on the M-Br (m/z = 706) ion and an estimate of the RMR.
Q
None added.
ND = not detected.
-------
Table 13. ANALYSIS OF CONTROL AND BLANK POLYURETHANE FOAM (PUF) AND GLASS FIBER FILTER (GFF)
SAMPLES FOR THE PARKERSBURG, WV SAMPLING TRIP 3/26/79 - 3/30/79
u>
CO
Compound, ng (0/0)
Sample C12H9Br
PUF
Laboratory
Control - 1 NCC
Blank - 1 <16f
-2 <4
Field
Control - 1
- 2 Trace
Blank - 1 <7
-2 <6
GFF
Laboratory
Control - Ql ND
- Q3 ND
Blank NDd
Field
Control - Ql NC
- Q3 NC
Blank - 1 <0.4
C12H7Br2
48 + 6°
(21 + 2.5)
ND
ND
92 + 2e
do ± i)
4000
(27)
ND
ND
10
(4)
2080
(14)
66 + 2C
(28 + 1)
1880
(13)
ND
C12H7Br3
96 + 2C
(73 + 2)
ND
ND
148 + 2°
(113 + 2)
5240
(62)
ND
ND
21
(16)
1510
(18)
ND
160 + 6°
(122 + 4)
2120 + 8C
(25)
ND
C12H5Brs
12 + 5°
(25 + 10)
ND
ND
46 + 1°
(96 + 1)
1620 + 65
(63)
ND
ND
ND
0
700
(27)
ND
30 + 1°
(62 + 2)
960 + 50°
(38)
ND
C12H4Br6
390 + 1C
(81 + 1)
ND
ND
707 + 39
(147 + 8)
" 17,000
(56)
ND
ND
ND
0
10,000
(33)
no
302 + llc
(63 + 2)
14500 + 900°
(48 + 3)
ND
C12H2Br8
ND
ND
ND
NQ8
ND
ND
ND
NQ8
ND
ND
ND
Totalb
456 + 8
(50 + 31)a
ND
ND
993 + 39 .
(99 ± 44)d
27,860 + 65 .
(56 + 17)
30
3
14,390
(23 + 7)"
558 + 14 .
(69 + 39)
19,460 + 900
(31 + 15)"
ND
Percent recovery in parenthesis.
Total exclusive of C,0H_Br0 which could not be quantitated.
12 2 o
°The deviation of the mean from the measured values for two measurements.
Standard deviation of the percent recoveries for each isomer.
eNC = not confirmed by ion ratio.
Maximum amount which could be present given the background of the sample.
^Detected but not quantitated.
-------
SECTION 6
DISCUSSION
OXNARD, CA
The soil samples all contained some detectable hexabromobiphenyl. The
highest concentration (P2/C1/L6) was found across the street from a loading
dock storage area at the Borg-Warner facility. This was downwind with respect
to the Santa Ana winds (from the mountains ENE). The second highest (P2/C1/L7)
was taken ~1 block NNE of the Borg-Warner facility, however this sample
showed a 30 fold lower PBB concentration. The samples L5 and L8 were nearly
equidistant from the facility yet there is a 5 fold difference in PBB levels.
This would tend to indicate the Fall and Winter northeasterly winds have a
larger role in the dispersion of the PBB's than the prevailing Westerlies.
Residents mentioned the large amount of airborne particulate during the
winter wind storms. It would appear that these winds may play a role in the
spread of PBB contamination.
The mass of the soil PBB burden may be estimated by converting (Jg/kg to
2
g/km . The conversion factor for the Oxnard soil samples if 4.64. The
estimation of soil burden may best be done in two stages using the average
level of the 2 "near" samples as representative of the first 0.1 km and the
remaining samples for the area from 0.1 to 1.0 km. This gives a burden of
~2,500 g for the first 0.1 km and ^400 g for the 0.1 to 1.0 km distance for
a total of approximately 3000 g of PBB's. Obviously this is only an order to
magnitude estimate since it assumes a step change in concentration between
the two circles where very large concentration differences are observed.
No air samples were found to contain PBB's. This is not surprising
since airborne PBB's at this time would be expected to arise from the suspen-
sion of contaminated soil. Even at the highest soil contamination (33,000
O
(Jg/kg) , the PBB's would not be detected at a particulate level of 100 (Jg/m
(values for Los Angeles of 93 ng/m have been reported ).
34
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PARKERSBURG, WV
The polybrominated biphenyl levels in the soil samples from Parkersburg,
WV ranged from 35 Hg/kg to not detectable. The distribution of the PBB's is
not as straight forward as is the case for Oxnard due in part to the hilly
terrain and the Ohio River. The detection of PBB's follows the river contours
both upstream and downstream (N and NE and S of the Borg-Warner facility).
The highest levels were found due east of the facility before a ridge blocks
the air flow. No PBB's were found west of the facility. The closest access
west of the facility was across the river however PBB's were found more
distant in other directions. East winds are uncommon in this area relative
to the NW, W, and SW winds and that may account for the distribution of the
PBB's. Another factor which must at least be considered when interpreting
this data are the transportation routes which may have been used to bring
PBB's to the facility. Several of the samples were taken on road sides
although only P2/C1/L1 and P3/C1/L11 are the only ones which are clearly on
trucking routes. The other roadside samples were taken on back roads with
little or no trucking traffic.
The concentration of PBB's in the soil may be converted to concentration
2
per unit soil surface area by multiplying by 4.64 kg/m . If one estimates
2
the area contaminant as 5 to 10 km and takes the average PBB level found, 8
2
(Jg/kg, (disregarding trace and not detected samples) convert it to g/km to
2
obtain 37 g/km . The total soil burden may be estimated to be on the order
of 180-400 g.
No PBB's could be confirmed in any of the air samples. The same consi-
derations apply here as in Oxnard concerning resuspension of PBB laden
particulate with even lower soil levels of PBB's.
35
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REFERENCES
1. G. Sundstrom, 0. Hutzinger, S. Safe and V. Zitko, The Science of
The Total Environment, 6, 15 (1976).
2. I. J. Selikoff, "Health Effects of Exposure to Polybrominated Bi-
phenyls: Results of a Clinical Field Survey November 4-10, 1976".
Interim Summary Report to NIEHS ES 00928.
3. Pest. Tox. Chem. News, February 9, 1977, p. 25.
4. Michigan Chemical Corporation, St. Louis, Michigan.
5. W. H. Gutenmann and D. J. Lisk, J. Agr. Food Chem., 23, 1005 (1976).
6. N. V. Fehringer, J. Assoc. Offic. Anal. Chem., 5_8, 978 (1975).
7 N. V. Fehringer, J. Assoc. Offic. Anal. Chem., 58, 1206 (1975).
8. L. W. Jacobs, S. F- Chou and J. J. Tiedje, J. Agr. Food Chem.,
24, 1198 (1976).
9. A. B. Filanow, L. W. Jacobs, and M. M. Mortland, J. Agr. Food
Chem., 24, 1201 (1976).
10. S. Whitlock and C. Stratton, Survey of Polybrominated Biphenyls
Near Sites of Manufacture and Use in Northeastern New Jersey, EPA
68-01-3428, Dec. 1977-
11. M. D. Erickson, R. A. Zweidinger, L. C. Michael and E. D. Pellizzari,
Environmental Monitoring Near Industrial Sites: Polychloronaphtha-
lenes. EPA 560/6-77-019.
12. D. F. Goerlitz and L. M. Law, J. Assoc. Offic. Anal. Chem., 57_, 176
(1974).
13. Official Methods of Analysis of the AOAC, W. Horwitz Ed., 12th Edi-
tion, A.O.A.C. Washington, DC (1975).
14. M. D. Erickson, R. A. Zweidinger, E. D. Pellizzari. Analysis of
A Series of Samples for Polybrominated Biphenyls (PBBs). EPA 68-
01-1978, August 1977.
15. National Air Surveillance Network Observations (1969).
36
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APPENDIX A
SAMPLE PREPARATION PROCEDURES
37
-------
PROCEDURE FOR CLEANTUP OF POLYURETHANE FOAM PLUGS
®
1. Cut 5 cm diameter x 13 cm long plugs from sheet of Olympic 2315
polyurethane foam.
2. Mark each plug with an identification number in the top using a hot
wire.
3. Place four plugs in bottom of clean four liter beaker, add 500 ml
hot toluene (100°C).
4. Compress the plugs 10 times using a one liter Erlenmeyer flask.
5. Let sit five minutes on steam bath.
6. Repeat Steps 4 and 5.
7. Compress the plugs and decant the toluene.
8. Add 250 ml fresh, hot toluene and repeat steps 4 through 7-
9. Repeat Step 8 three times (total of five extractions).
10. Using clean tweezers, transfer each plug into a foil-wrapped wide-
mouthed jar and cover loosely with a foil-lined cap.
11. Dry in vacuo at 50° for 12 hours.
12. Remove from oven, tighten cap and store away from potential contami-
nants .
PROCEDURE FOR EXTRACTION OF POLYBROMINATED BIPHENYLS FROM POLYURETHANE
FOAM PLUGS
1. Using cleaned tongs, remove foam plugs from storage jars and place
them in 400 ml beakers.
2. Add 150 ml of toluene to beakers containing foam plugs.
3. Compress the foam plugs 10 times to the bottom of the beakers with a
125 ml Erlenmeyer flask, soak for five minutes and compress an
additional 10 times.
38
-------
4. Squeeze the toluene out of the plug and decant into a flat bottom
boiling flask.
5. Repeat steps 2 through 4 two more times.
6. Concentrate in a flat bottom boiling flask topped with a Snyder
column to approximately 15 ml.
7- Transfer and concentrate to 1 ml under nitrogen stream.
8. Add internal standards and submit to GC/MS analysis.
PROCEDURES FOR EXTRACTION OF FILTERS
1. Cut filter in 2 equal pieces and analyze one piece as below.
2. Cut with a clean scalpel into pieces which will fit into a micro
Soxhlet extractor (extractor volume 10 ml).
3. Place a small plug of glass wool in the bottom of the extractor
and insert filter pieces.
4. Fill a 50 ml round bottom flask with 30 ml of solvent. Assemble
Soxhlet extractor and extract overnight.
5. Evaporate to 1 ml under nitrogen stream.
6. Add internal standards and submit to GC/MS analysis.
PROCEDURE FOR EXTRACTION OF POLYBROMINATED BIPHENYLS BIPHENYLS FROM SOIL
SAMPLES*
1. Weigh 50 g of soil into a 1 quart screw cap jar.
2. Add 50 ml of diethyl ether, shake and allow to stand overnight.
3. Remove diethyl ether in vacuo at room temperature.
4. Add 5 ml of distilled-deionized water to dampen soil.
5. Add 40 ml of acetone and shake for 20 minutes.
6. Add 80 ml of toluene and shake an additional 10 minutes.
&.
"Procedure adapted from D. F. Goerlitz and L. M. Law, J. Assoc. Offic.
Anal. Chem., 5_7, 176-181 (1974).
39
-------
7. Decant acetone-toluene extract through glass wool into a one
liter separatory funnel.
8. Repeat Steps 5 through 7 two more times.
9. Extract combined organic fractions with 500 ml water.
10. Back extract water three times with 25 ml portions of toluene.
11. Dry combined organic extracts with sodium sulfate.
12. Concentrate to 15 ml in a flat bottom boiling flask topped with a
Snyder column. Evaporate to 1 ml under nitrogen.
13. Add internal standards and submit to GC/MS analysis.
OPTION COLUMN CLEANUP
Reagents
Hexane - suitable for use in pesticide residue analysis or distilled
in glass
Florisil (60/100 mesh) PR grade - store at 130°C until used
Sodium sulfate - anhydrous, granular, Mallinckrodt No. 8024 or
equivalent. Store at 130°C in glass stoppered
bottle.
Procedure:
1. Prepare columns in Chromoflex glass columns with 6 mm i.d. Plug
with a small wad of clean glass wool and add 1.6 g of Florisil.
Top Florisil with a 2 cm layer of anhydrous sodium sulfate.
2. Prewash column with 5 mL of hexane. Drain, but do not let
liquid level drop below the top of the sodium sulfate.
3. Transfer concentrated extract, in hexane solvent, to top of
column and follow with three hexane rinsings of ~0.5 mL each.
Drain until liquid level is near top of the sodium sulfate. At no
point allow the liquid level to drop below the top of the sodium
sulfate. Elute PBB's with 15 mL of hexane.
40
-------
4. Concentrate sample in Kuderna-Danish evaporator to a small volume
^0.5 ml. Transfer sample to a conical vial with hexane rinses, add
10 |Jl toluene and evaporate to M).l ml under a nitrogen stream.
NOTE: The column cleanup may be performed after the internal standard
is added since both octachloronaphthalene and decachlorobiphenyl coelute
with PBB's on Florisil.
41
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APPENDIX B
LOCAL CLIMATOLOGICAL DATA
OXNARD, CA
42
-------
oal Climatological Data
.iinual Summary With Comparative Data
1974
LOS ANGELES, CALIFORNIA
CIVIC CENTER
Narrative Climatological Summary
The climate of Los Angeles is normally pleasant
and mild through the year. The Pacific Ocean is
the primary moderating influence, but coastal
mountain ranges lying along the north and east
sides of the Los Angeles coastal basin act as a
buffer against extremes of summer heat and
winter cold occurring in desert and plateau
regions in the interior. A variable balance be-
tween mild sea breezes, and either hot or cold
winds from the interior, results in some variety
in weather conditions, but temperature and humid-
ity are usually well within the limits of human
comfort. An important, and somewhat unusual,
aspect of the climate of the Los Angeles metro-
politan area, is the pronounced difference in
temperature, humidity, cloudiness, fog, rain, and
sunshine over fairly short distances.
These differences are closely related to the dis-
tance from, and elevation above, the Pacific
Ocean. Both high and low temperatures become
more extreme and the average relative humidity
becomes lower as one goes inland and up foot-
hill slopes. On the coast and in the lower coastal
plain, average daily temperature ranges are about
15° in summer and 20° in winter, but in foothill
and inland valley communities these ranges in-
crease to about 30° in summer and 25° in winter.
Relative humidity is frequently high near the
coast, but may be quite low along the foothills.
During periods of high temperatures, the relative
humidity is usually below normal so that dis-
comfort is rare, except for infrequent periods
when high temperatures and high humidities occur
together.
Like other Pacific Coast areas, most rainfall
comes during the winter with nearly 85 percent
of the annual total occurring from November
through March, while summers are practically
rainless. As in many semiarid regions, there
Is a marked variability in monthly and seasonal
totals. Annual precipitation may range from less
than a third of the normal value to nearly three
times normal, while some customarily rainy
months may be either completely rainless, or
receive from three to four times the average for
the month. Precipitation generally increases with
distance from the ocean from a yearly total of
around 12 inches in coastal sections to the south
of the City up to over 20 inches in foothill areas.
Destructive flash floods occasionally develop in
and below some mountain canyons. Snow is often
visible on nearby mountains in the winter, but is
extremely rare in the coastal basin. Thunder-
storms are infrequent.
Prevailing winds are from the west during the
spring, summer, and early autumn, with north-
easterly wind predominating the remainder of
the year. Average wind speeds are rather low.
At times, the lack of air movement, combined
with a frequent and persistent temperature in-
version, is associated with concentrations of air
pollution in the Los Angeles coastal basin and some
adjacent areas. In fall, winter, and early spring
months, occasional foehn- like descending (Santa
Ana) winds come from the northeast over ridges
and through passes in the coastal mountains.
These Santa Ana winds may pick up considerable
amounts of dust and reach speeds of 35 to 50
m.p.h. in north and east sections of the City, with
higher speeds in outlying areas to the north and
east, but rarely reach coastal portions of the City.
Sunshine, fog, and clouds depend a great deal on
topography and distance from the ocean. Low
clouds are common at night and in the morning
along the coast during spring and summer, but
form later and clear earlier near the foothills
so that average annual cloudiness and fog fre-
quencies are greatest near the ocean, and sun-
shine totals are highest on the inland side of the
City. The sun shines about 75 percent of day-
time hours at the Civic Center. Light fog may
accompany the usual night and morning low clouds,
but dense fog is more likely to occur during the
night and early morning hours of the winter
months.
noaa
NATIONAL OCEANIC AND
ATMOSPHERIC ADMINISTRATION
ENVIRONMENTAL / NATIONAL CLIMATIC CENTER
DATA SERVICE
43
ASHEVILLE, N.C.
-------
APPENDIX C
LOCAL CLIMATOLOGICAL DATA
PARKERSBURG, WV
44
-------
Local Climatological Data
Annual Summary With Comparative Data
1974
PARKERSBURG, WEST VIRGINIA
*
c.
\
Narrative Climatological Summary
The climate of Parkersburg can well be described as moderate. Located on the south bank of the
Ohio River and in the extreme north of the "upper south," Parkersburg is in the farthest
north area where tender vegetation, such as magnolias, is able to survive most of the winters.
In summers, prolonged hot weather is infrequent. During the period of record, there have been
only 24 days with a temperature of 100" or more. Likewise, prolonged cold weather is in-
frequent; temperatures 'Of -10° or lower have occurred on only 13 days. Precipitation is usual-
ly ample for the locality's needs; the Ohio is a well-watered valley. The heaviest rains are
in June and July. The lightest amounts are in October. On the average of once every four or
five years, a dry spell in July or August does some damage to crops in the vicinity. Frequent
rainfall in late May and in June may cause difficulty in harvesting early hay. Days with
measurable snowfall average about 25 for the year; the average annual snowfall is about 24
inches. However, total snowfall amounts vary greatly from winter to winter, ranging from over
55 inches to less than 4 Inches.
Within 2 miles of the Weather Service Office, there is a locally-famous early vegetable-pro-
ducing district. Presumably because of the moderating influence of the nearby Ohio River, the
character of the soil and its southern exposure, the district produces vegetables about three
weeks earlier in the spring than do other places in the Parkersburg area. Since 1950 the
mean latest and earliest occurrences of 32° are April 18 and October 23. Lower temperatures are
prevalent in the area on clear, calm nights.
Parkersburg is not a windy City, the winds being light most of the time. However, once in a
while -a winter storm may be accompanied by winds up to gale force and, also infrequently, the
squall winds of a summer thunderstorm may blow about as hard.
Parkersburg is located at the confluence of the Little Kanawha with the Ohio River. A rather
closely spaced series of wooded ridges more or less paralleling the Ohio or Little Kanawha
River, and rising to as much as 100 to 150 feet above the valley floor, gives the local terrain
a hilly character. There are two principal hills near the station; one about 0.6 mile to the
southwest and rising to an elevation of about 820 feet m.s.l., and the other about 1/4 mile
east-northeast and rising to an elevation of about 765 feet m.s.l.
Situated near the path taken by the average storm moving eastward across the country, Parkers-
burg is subject to the stimulating influence of rather frequent changes in weather. During warm
periods in the summer with the circulation from the Gulf, the humidity may be depressingly high
with dew points in the mid-seventies. Being relatively free from extremes of temperature, pre-
cipitation, and wind, Parkersburg's moderate climate is very favorable to man and his varied
activities In this area.
NATIONAL OCEANIC AND / ENVIRONMENTAL / NATIONAL CLIMATIC CENTER
ATMOSPHERIC ADMINISTRATION/ DATA SERVICE / ASHEVILLE, N.C.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
. REPORT NO.
EPA-560/13-80-005
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Sampling and Analysis of Selected Toxic Substances
Task 1: Polybrominated Biphenyls in Air and Soil at
User Sites
5. REPORT DATE
January 1Q8Q
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R. A. Zweidinger and E. D. Pellizzari
8. PERFORMING ORGANIZATION REPORT NO.
Task 1 - Final Report
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Research Triangle Institute
Post Office Box 12194
Research Triangle Park, NC 27709
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
EPA 68-01-5020
12. SPONSORING AGENCY NAME AND ADDRESS
Office of Pesticides and Toxic Substances
U. S. Environmental Protection Agency
Washington, DC 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
Final 12/28/78 - 6/5/79
15. SUPPLEMENTARY NOTES
Project Officers are Vincent DeCarlo and Thomas E. Kopp
16. ABSTRACT
Field sampling for air and soil was conducted in the vicinity of two Borg
. Warner Co. facilities, one in Oxnard, CA and the other near Parkersburg, WV.
Polybrominated biphenyls (PBBs) were found in all of the soil samples from
Oxnard with the highest levels (36,000 yg/kg) nearest the facility and the
lowest (5 ug/kg) upwind the greatest distance. No PBBs were found in any of the
air samples (<3 ng/m3).
Polybrominated biphenyls were confirmed in seven of the thirteen soil samples
from West Virginia (up to 12 pg/kg) traces detected but not confirmed in three,
and no PBBs were detected in the other three. The highest levels were from samples
collected in the Ohio River basin especially along the eastern bank. No PBBs were
confirmed in the air samples (<4 ng/m3).
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
Polybrominated biphenyls
PBB
Air analysis
Soil analysis
STATEMENT
19. SECURITY CLASS (ThisReport)
21. NO. OF PAGES
20. SECURITY CLASS (Thispage)
22. PRICE
EPA Form 2220-1 (9-73)
46
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