CALCULATIONS

The object of this project is to determine the inputs of PCBs into
Lake Michigan. This is not directly accomplished by determining the
concentration of PCBs in precipitation because the concentration of PCBs in

a precipitation sample is usually inversely proportional to the amount of
precipitation (Hicks 1966; Gatz and Dingle 1971).

To take into account the concentration of PCBs as well as the amount
of precipitation, the volume weighted mean concentration of PCBs was
determined for the samples. This mean is calculated by multiplying the
concentration of PCBs found in the sample (ng/L) by the amount of
precipitation (mm) to give an input of PCBs in ng/m2. The volume weighted
mean for the samples in then calculated by summing the inputs for the

samples and dividing by the total amount of precipiation the samples
represent.

Volume weighted mean PCB concentration = q Concentration X Precipitation
} Precipitation

12


TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)

1, REPORT NO. 2. 3, RECIPIENT'S ACCESSIONMNO.
EPA-600/3-78-071

4. TITLE AND SUBTITLE 5. REPORT DATE
Polychlorinated Biphenyls in Precipitation in the July 1978 issuing date
Lake Michigan Basin. 6. PERFORMING ORGANIZATION CODE

17, AUTHOR(S) i8. PERFORMING ORGANIZATION REPORT NO.

Thomas J. Murphy
Charles P. Rzeszutko

19, PERFORMING ORGANIZATION NAME AND AODRESS 10, PROGRAM ELEMENT NO,
DePaul University 1BA769
1036 W. Belden Avenue TT, CONTRACT/GRANT NO.
Chicago, Illinois 60614 Grant 803 915
12, SPONSORING AGENCY NAME ANDO ADDRESS 13. TYPE OF REPORT AND PERIOD COVERED
Environmental Research Laboratory - Duluth Final Report
Office of Research and Development 14, SPONSORING AGENCY CODE
U.S. Environmental Protection Agency
Duluth, Minnesota 55804 EPA 600/U3

15. SUPPLEMENTARY NOTES

Project Officer: Michael D. Mullin,ERL - Duluth, Grosse Ile, MI 48138

16. ABSTRACT

Rainfall samples were collected in Chicago, Illinois, and on Beaver Island,
Michigan, and analyzed for polychlorinated biphenyls (PCBs). The precipitation
weighted mean concentration of 35 samples of rain was 111 ng/l. (111 parts per
trillion). This would result in the deposition of 4800 kg/yr of PCBs to the Lake
from precipitation. Presently available evidence on other sources of PCBs to the
Lake indicates that precipitation is now the major source of PCBs to the Lake.
The future PCB problems in the Lakes will then be determined mainly by the magni-
tude of atmospheric inputs to the Lake.

The concentrations of PCBs in rainfall were found to be as high on Beaver
Island as in Chicago.

Results obtained from the simultaneous sampling of air and precipitation in-
dicate that PCBs are present in the atmosphere as vapor as well as being present
on particulates. This result raises doubts as to the validity of results for the
dry deposition of PCBs obtained from the use of collectors covered with mineral
oil or other non-polar liquid.

PCB concentrations in the parts per billion range obtained from gas samples
from a vented sanitary landfill, indicate that PCB containing materials incor-
porated into landfills may be an important source of PCBs to the atmosphere.

17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS lb. IDENTIFIERS/OPEN ENDED TERMS |c. COSATI Field/Group
cous 08/H
Precipitation Lake Michigan
Atmospheres Polychlorinated biphenyls
Air Particulates
Rain Landfills
PCB vapor
18, OISTRIBUTION STATEMENT 19. SECURITY CLASS (This Report} 21.NO OF PAGES
Release to the Public Unclassified
20. SECURITY CLASS (This page) 22. PRICE
Unclassified

EPA Form 2220-1 (9-73)
33. eU.5. GOVERNMENT PRINTING OFFICE: 1978-757-140/1421 Region No. 5-1


CHICAGO RAIN SAMPLES

‘SAMPLING INPUT
‘VOLUME, FILTERED NON-F IL TERABLE TOTAL SAMPLE: PCB OF PCBS

BEGUN DURATION RAIN COLLEC % AROCLOR TOTAL. % AROCLOR TOTAL % AROCLOR TOTAL CONC (NG/M2)
YY MM 0D (HR) cm) cL 1242 1254 1260 (NG) 1242 1254 1260 (NG) 1242 1254 1260 (NG) (NG/LD (MG /KM2 )
75 11 09 10.0 8.7 9.0 4.9 32.3 62.6 1030 0.0 0.0 0.0 oO 4.9 32.3 62.6 1030 114.4 0.995
7 1119 24.2 8.8 20.0 74.3 12.7 12.8 1542 0.0 0.0 0.0 O 74.3 12.7 18.8 1541 77.0 (0.678
751205 22.5 10.7 26.7 3.8 57.0 39.1 426 0.0 0.0 0.0 ° 3.8 57.0 39.1 426 15.9 0.170
7S 12 14 5.0 12.8 9.0 22.2 52.6 25.0 541 14.2 35.4 50.3 277 19.5 46.8 33.6 818 90.8 1.163
76 02 20 18.0 37.5 72.0 31.4 35.6 32.9 1122 0.0 0.0 0.0 O 31.4 35.6 32.9 1122 15.5 0. SR4
7 03 29 23.7 2.5 5.5 82.9 13.5 3.4 1194 11.3 72.6 16.2 381 65.6 27.8 6.5 1575 286.3 0.715
76 04 20 13.5 4.3 B.1 70.8 16.5 12.6 547 80.7 15.7 3.3 384 74.9 16.2 8.8 931 114.9 0,494
7 04 20 12.6 8.0 17-1 73.2 13-213.4 216 45.3 34.3 20.3 100 64.4 19.9 15.6 316 18.4 0.147

76 04 24 75 21.8 22.0 62.6 35.4 1.8 3242 0.2 HH 1.8 BO 61.1 37.0 1.8 3323 151.0 3.292
760424 14.0 62.7 77.5 84.2 14.2 1.5 4944 22.2 74.4 2.3 661 76.9 21.3 1.6 5605 72.3 4.554
76 05-05 16.0 54.0 40.0 83.6 11.4 4.9 3392 20.1 54.3 24.9 1124 67.8 e2.1 9.9 4517 112.9 6.097

760513 18.5 3.4 3.2 75.8 21.3 2.8 460 68.6 27.3 3.8 1037 70.8 25.5 3.5 1498 468.1 1,591
7 OS 15 0.5 4.6 2.7 78.7 19.8 1.3 641 37.4 59.8 2.5 213 68.4 29.8 1.6 854 316.2 1.454
70720 19.0 23.5 23.7 70.2 18.2 11.5 1250 25.6 53.1 20.6 804 52.8 31.9 15.1 2053 86.6 2.035

76 07 22 «17.0 12.8 8.3 74.1 19.0 6.7 1411 63.3 33.9 2.4 1055 69.5 25.4 4.9 2466 ao7.t 3.802
76 OF 30 16.0 6.1 6.5 74.3:19.9 5.7 1574 27.4 64.2 8.2 863 57.7 35.6 6.6 2438 375.0 2.287
76 0B 04 40.0 10.0 8.2 64.5 29.4 5.9 1419 14.2 79.2 5.8 970 44.8 49.1 5.9 2335 284.7 2.847

76 O8 11 16.0 5.5 S.7 10.5 38.8 50.5 503 10.1 54.0 35.6 912 10.3 48.6 40.9 1415 248.2 1.365
76 09 OB 0.0 14.0 16.3 S4.7 41.2 4.0 292 18.2 75.2 62 896 27.2 66.9 S.7 1188 72.8 1,020
7% 09 25 15,5 28.6 34.3 27.9 61.9 10.0 630 19.5 63.2 17.0 26% 25.4 62.3 12.1 898 26.5 0. 748

7 10 23 47 12.7 15.2 15.2 50.1 34.6 630 12,0 63.3 24.3 1293 13.1 59.0 27.7 1923 126.5 1.606
76 1004 39.0 33.5 36.7 46.1 5.5 48.3 605 20.6 SH#.4 20.6 B55 31.2 36.5 32.1 1460 33.7 1.33%


analysis. Also, in order to collect remote samples, a means of
concentrating or processing the sample at the collection site, with a
minimum of effort on the part of the sampling personnel, was necessary.

The polyurethane foam collection method for PCBs of Uthe et al.
(1973) was chosen. This method involves passing a liquid or gas stream over
pieces of polyurethane foam coated with a non-polar liquid. The PCBs are
soluble in the liquid and the foam, and are very efficiently scrubbed from
the water or gas stream by the foam. They are then extracted from the foam
in a Soxhlet extractor.

Precipitation was collected on a galvanized steel surface and the
water ran-off to the sampler described below. The surface of the collector
was cleaned before each precipitation event to minimize the amount of dry
fallout incorporated into the sample. The design of the sampler used for
the rain collections on Beaver Island is shown in Figure 2. The collector
used at DePaul worked the same but was slightly different in construction.
The sampler works as follows. When rain is anticipated, the collector is
cleaned and the peristaltic pump is turned on. The pump creates a partial
vacuum in the apparatus. The water from the collector is channeled to the
funnel and drawn through a tared glass fiber filter (GF/A; Gelman
Instruments; Ann Arbor, MI) by the vacuum in the apparatus. This separates
the particulates in the rain from the "soluble" portion, i.e., the
filtrate. The filtrate then flows under gravity through the polyurethane
foam, coated with DC-200 silicone oi1, in the bottom of the sampler. The
water level in the sampler is maintained above the foam by the use of the
siphon tube on the discharge. The water is pumped from the sampler into a
barrel. After a precipitation event, the volume of water in the barrel is
measured to determine the amount of water sampled. The amount of rainfall
jin an event was separately measured with an adjacent rain gage.

Besides making the determination of the PCBs on particulates
possible, the filtration of the rain is necessary since it has been reported
that PCBs on particulate matter pass uncollected through polyurethane foam
(Bedford 1974).

The partial vacuum in the sampler created an additional problem.
Since the water being filtered is saturated with air, it is rapidly degassed
after passing through the filter. A bypass was provided for this air to
prevent it from interfering with the foam extraction. Some of the PCBs in
the water could vaporize at this time. To collect these PCBs, and also any
that evaporate from the particulates when air passes through the filter,
polyurethane foam was placed in the by-pass.

Finally, to ease the remote operation of the sampler, the portions of
the sampler containing the foam are made detachable. Thus, the person
handling the sampler at Beaver Island was supplied a number of filters and
several sets of the interchangeable parts of the sampler, containing clean
foam. After a rain event, the detachable portions of the sampler containing
the foam were wrapped in aluminum foil and mailed to DePaul University for
extraction and analysis. Anew filter and containers with clean foam were


TABLE 3. THE AROCLORR COMPOSITION OF THE DIFFERENT SAMPLE TYPES

Filtered Non-Filterable
Aroclors Aroclors
Sample Type 1242 1254 1260 1242 1254 1260
Rain - Chicago 54 33 13 29 56 15
Beaver Island 34 43 23 31 46 23
Snow - Chicago 54 31 15 24 57 18
Lake Water 16 73 10 42 54 4
Air 85 14 ] 19 34 47
Landfill} 98 2 0 - - -

There is quite a bit of variability between different samples which is
not reflected in the results shown in Tables 1-4. The arithmetic mean and
standard deviation of the concentration of PCBs in the rain samples from
Chicago and Beaver Island are 160 + 125.4 ng/L and 215 + 161 ng/L
respectively. A t-ratio test indicates that the difference between these
means is not significant (t=1.128; N=35). Therefore the PCB concentration
in precipitation in Chicago and Beaver Island are not different. The
geometric means for these sample sets are 109 mg/L and 164 mg/L.

For both the Chicago and Beaver Island rain samples, there was an
inverse correlation, significant at the 5 percent level, between the amount
of precipitation and the concentration of the PCBs in the samples. This is
not an unusual finding and can be explained by a depletion of the
particulates being scavenged by either rainout (Hicks 1966) or washout (Huff
and Stout 1964). See also Gatz and Dingle (1971).

Two precipitation samples were collected simultaneously with air
samples. This permitted the scavenging ratio (ng/kg PCBs in precipitation)/
(ng/kg PCBs in air), and the types of PCBs to’ be simultaneouly determined in
each of these samples. The scavenging ratios found for the two samples were
13 and 37 for a mean of 25.

From the results listed above in Table 1, an input of PCBs from
precipitation to Lake Michigan can be calculated. Since the difference
between the means from the samples from Chicago and Beaver Island was not
statistically significant, the samples from both locations were combined and
a volume weighted mean concentration of 111 ng/L was calculated for all of
the samples. This concentration, when multiplied by the mean precipitation
on the Lake, 740 mm/yr (Jones and Meredith 1973), the area of the Lake
(58,000 km2), and the units corrected, results in an input of 4800 kg/yr
of PCBs to Lake Michigan from precipitation.

16


FOREWORD

The presence of hazardous materials in the environment is a topic of
major interest to the Environmental Protection Agency. Elevated levels of
Polychlorinated bipnenyls (PCBs) in some species of Great Lakes fish have
necessitated the recommendation that persons limit, or eliminate, their die-
tary intake of these fish. In order to develop an understanding of the
pathways by which PCBs move within a lake ecosystem, it is necessary to

determine first the routes and amounts of these pollutants entering the
lake.

This report addresses the input of PCBs from the atmosphere to Lake
Michigan. The differentiation between gaseous and particulate forms are
measured as well as the comparison between urban and rural input rates.

Michael D. Mullin, Ph.D.

Project Officer

Large Lakes Research Station
Environmental Protection Agency-Duluth
Grosse Ile, Michigan

iii


Webb, R. G. and A. C. McCall. 1973. Quantitative PCB standards for
electron capture gas chromatography. J. of Chrom. Sci. 1, 366.

Woodwell, G. W., P. P. Craig and H. A. Johnson. 1971. DDT in the
Biosphere: Where does it go? Science 174, 1101.

Woodwell, G. W., P- P. Craig and H. A. Johnson. 1972. ODT in the
Biosphere: Where does it go? Science 177, 725.

Young, D. R., D. J. McDermott and T. E. Heeson. 1976. Aerial fallout of
DOT in southern California. Bull of Envir. Cont. and Toxic. 16, 604.

27


SECTION 4
RESULTS

The volume weighted mean concentration for all of the samples from
Chicago and Beaver Island which gave useful results are shown in Table 1.

Four of the samples from Chicago collected early in the project, were
not filtered and, based on the results of Bedford (1974), it was presumed
that the particulate matter in these samples and their proportion of the
PCBs, were inefficiently collected. The concentrations of PCBs found for
these samples was then assumed to come only from the filtered portion. From
the other 18 samples, it was determined that 34 + 23 percent of the PCBs
were on the particulates. These four samples were included in the results
shown above by increasing their PCB concentration by 51 percent (1/(1-0.34))
to approximate the inclusion of the particulates.

A number of different types of samples were collected and analyzed for
PCBs during the course of this project. Besides the rain samples, these
include: snow samples, Lake Michigan water samples, air samples and gas
samples collected at the sanitary landfill. The results obtained from the
analyses of these samples are shown in Table 2 along with the percent of the
PCBs which was associated with the filtered, ("soluble") part of the sample.

The composition of the samples with respect to the different PCB
compounds varied considerably from sample to sample. In general, however,
there were ditferent patterns from the ditferent types of samples as shown
in Figure 4 and in Table 3. The compositions shown were calculated from the
sum of the different AroclorsR for al? of the samples of each type. For

TABLE 1. VOLUME WEIGHIED MEAN CONCENTRATION OF PCBs IN RAINFALL

Chicago Beaver Island

Total amount of precipitation (mm) 386.5 110.1
Number of samples 22 13
Volume weighted mean concentration (ng/L) 104 138

13


TABLE 5. INPUTS OF PCBs (KG/YR) 10 LAKE MICHIGAN

Prior to
Sources 1975 1977
Major Industrial DischargesTM (25,000) ---
Precipitation* 4,800 4,800

Streams and Waste Water Effluents® 1,650 1,650
Others> (2,500) (2,500)

Total 33,950 8,950

*This estimate is a lower limit. [he actual amount may be several times
larger.

#This work.

Cuesse, J. L. (1976). Conference Proceedings. National Conference on
Polychlorinated Biphenyls, Nov. 19-21, 1975, Chicago, IL., EPA 560/6-75/004;
NTIS, PB-253 248/9PSX; p. 127.

®leinert, S. (1976). Conference Proceedings. National Conference on
Polychlorinated Biphenyls, Nov. 19-21, 1975, Chicago, IL., EPA 560/6-75-004;
NTIS, PB-253 248/Y9PSX; p. 124; Personal communication.

@schacht, R. A. Pesticides in the Illinois Waters of Lake Michigan. EPA
660/3-74-002, January 1974.

San estimate to attempt to account for dry deposition of PCBs on the Lake
surface and to allow for small industrial discharges not yet identified.

To gage the signiticance of the precipitation inputs of PCBs to the
Lake, the other known and estimated sources of PCBs to the Lake are listed
in Table 5. These include the effluents from waste water treatment plants,
those industries known to have PCBs in their discharges, and tributary
inputs.

If Table 5 is reasonably accurate, and industrial discharges have
greatly decreased, then when the Lake comes to equilibrium with the lower
inputs, the concentration of PCBs in the water and biota should be much less
than the present values. The data here indicate that the atmosphere will be
the major contributor of PCBs and therefore, the levels of PCBs in the Lake
and biota should reflect the magnitude of the inputs from this source.

19


ST

Percent of Total Sample

0 25 50 75 100
| | |

—<——
=

Filterable
RAIN-Chicago Particulates
Total

Filterable
-Beaver Island Particulates ————

Total

Filterable E

SNOW-Chicago Particulates l
Total

—

Filterable =| Tm,
LAKE WATER Particulates
Total

Filterable

AIR Particulates —— TI
ota

NT

LANDFILL Total ]

{ 1

Aroclor 1242 Aroclor 1254 Aroclor 1260

FIGURE 4. THE PCB COMPOSITION OF THE DIFFERENT TYPES OF SAMPLES

47


APPENDIX

Data from the different samples collected and analyzed in this project
are included in the appendix. They include:

1. Rain samples collected in Chicago.
2. Rain samples collected on Beaver Island.

3. Lake Michigan water samples. The May, 1976 sample was
collected in about 0.5 m of water at Beaver Island. The other
samples were collected from a water intake crib of the city of
Chicago in about 10 m of water. All of the samples were
collected from beneath the surface.

4. Snow samples collected in Chicago.

5. Air samples. The Nov., 1975 sample was collected in Mammoth
Cave National Park.

The percent composition of the Aroclors® in the non-filterable
portion of the samples shown in the appendix was calculated from a data base
which included the measured percent composition for the filtered and total
portions only. In those cases where the non-filterable portion of a
particular Aroclor® constitutes only a small portion of the total amount,
there may be significant errors in the percentage shown in the appendix
tables. The results in the report for the non-filterable portions of the

samples were based on the measured values and thus should be free from these
errors.

28


SECTION 3
ANALYSIS

Solvents used were pesticide grade (Burdick and Jackson Laboratories;
Muskegon, MI) or were distilled from glass through a packed column. Drying
agents, cotton, and chromatographic packing materials wepe extracted with
hexane/acetone and dried before use. Activated Florisil” was dried at
130°C before use and stored in a closed bottle at room temperature .
Aroclor” analytical reference standards (U. S. EPA, Health Effects
Research Laboratory, Research Triangle Park, NC) and individual PCB isomers
(Analabs Inc.; North Haven, CN) were used as received. Polyurethane foam
(density = 0.024 or 0.036 gm/cm>) was extracted with water, acetone, and
acetone/hexane before use.

The polyurethane foam plugs from the samplers were extracted with
hexane/acetone in a Soxhlet extractor. The foam from the air bypass was
extracted along with the foam from the filtered ("soluble") water fraction.
The glass fiber filter containing the particulates, the non-filterable
fraction, was separately extracted in a Soxhlet by placing it in a clean,
tared cellulose extraction thimble. The extracts from the particulates were
evaporated to dryness and their weight determined. This weight is reported
as the organic portion of the particulate fraction. The extracts from the
foam contained the silicone coating and thus the weight of the organic
fraction from the filtered portion could not be obtained.

The extracts from the filtered and non-f§1terable fractions in
hexane, were placed on a hexane-washed Florisil‘column. The hexane
fraction was collected and concentrated in a Kuderna-Danish evaporator with
a three-ball Snyder column.

The weight of the non-extractable particulates was determined by
weighing the extraction thimbles containing the filter paper after
extraction and subtracting the weight of the thimble and filter. Since the
extraction thimbles were hygroscopic, the following procedure was followed
to determine gheir weight. The thimbles, with or without contents, are
heated to 110°C for 30-45 minutes in an oven, wrapped quickly in a piece
of aluminum foil, and allowed to cool. The foil-wrapped thimble is weighed,
emptied of its contents, reheated, and reweighed. The weight of the
particulates is obtained by subtracting the weight of the filter and thimble
from the total weight. The tare weight of the thimbles was reproducable to
+2 milligrams.

10


are similar to those of DDT, there was a lot of accumulated experience with
this type of problem to draw on. Thus it was expected that the voluntary
ban on "open" uses of PCBs in 1971 by the sole U. S. manufacturer, would
lead to a decline in PCB levels in the fish similar to that which had
occurred with DDT (Buckley 1972). Unfortunately, this did not happen. PCB
levels in bloaters in 1974 were unchanged from those in 1972 and the levels
in lake trout rose about 50% during the same time period (Willford 1975).

In 1975 then, it was not known why the PCB levels in the fish in Lake
Michigan were continuing to increase. Several possible explanations for
this increase are:

1. The chemistry of the PCBs in the Lake is different from that
of DDT.

2. The slower degradation of many of the PCB isomers increases
the residence time of the PCBs in the Lake.

3. One of the "closed" use of PCBs was the major source of the
PCBs getting into the Lake.

4. The large reservoir of PCBs manufactured before 1971, and
already used or still in use, continue to enter the environment.

Since the measurement of PCBs in tributaries and waste water
treatment plants had shown that only a small amount of PCBs were entering
the Lake by those routes, since the atmosphere had been a major source of
DDT to the Lake, and since PCBs had been identified in precipitation in
other areas (Tarrant and Tatton 1968; Sodergren 1972; 1973), it was thought
that the atmosphere could also be transporting PCBs to the Lake. This
assumes that the fourth explanation above is the cause of the PCB problem in
the Lake.

This study was initiated to determine the amount of PCBs which were
being transported to the Lake by the precipitation scavenging of
PCB-containing particulate matter from the atmosphere, and to make some
Measurements on the concentration of PCBs to the atmosphere. Information on
the distribution of PCBs between the soluble and particulate fraction in
precipiation was obtained and the compostion of the PCBs with respect to the
different isomers present in the samples was determined. Also, the PCB
concentration and composition in gases vented from a sanitary landfill were
measured.

While this project was not directed to the determination of sources
of PCBs to the atmosphere, a convenient opportunity to measure such a source
exists in the Chicago area and such measurements were made.

A potential source of PCBs to the atmosphere is material incorporated
into sanitary landfills. If PCBs in paints, plastics or carbon-less paper,
or in containers such as PCB filled capacitors which have broken open, are


Harvey, G. R. and W. G. Steinhauer. 1974. Atmospheric transport of PCBs to
the North Atlantic. Atm. Envir. 8, 777.

Haile, C. L., G. F. Veith, G. F. Lee and W. C. Boyle. 1975. Chlorinated
hydrocarbons in the Lake Ontario ecosystem. U. S. Environmental Protection
Agency, EPA-660/3-75-022. Grosse Ile, Mich.

Hicks, B. B. 1966. Nucleation and the wet removal of fallout. J. of
Applied Meteor. 5, 169.

Huff, F. A. and G. E. Stout. 1964. Distribution of radioactive rainout in
convective rainfall. J. Appl. Meteor. 3, 707.

Humphrey, H. E. B. 1976. Evaluation of changes of the level of
polychlorinated biphenyls in human tissue. Mich. Dept. of Health; Final
report on U. S. FDA contract.

Ingersoll, B. 1977. The miracle that got away. Chicago, WFMT Inc., 500 N.
Michigan Ave., Chicago, IL 60611. August, p. 100.

International Joint Commission. 1974. Great Lakes Water Quality 1974,
Appendix B, Surveillance Subcommittee Report. p. 161.

International Joint Commission. 1976a. Great Lakes Water Quality 1976.
Appendix B, Surveillance Subcommittee Report. p. 79.

International Joint Commission. 1976b. Great Lakes Water Quality 1976.
Appendix B, Surveillance Subcommittee Report. p. 36.

Jelinek, C. F. and Corneliussen. 1976. Levels of PCBs in the U. S. food
supply. Conference Proceedings. National Conference on Polychlorinated
Biphenyls. Chicago, IL. U. S. Environmental Protection Agency,
EPA-560/6-75-004. p. 147

Jones, D. M. A. and D. D. Meredith. 1972. Great Lakes hydrology by
months. 1946-65. Proc. 15th Conf. of Great Lakes Research. p. 47/.

Junge, C. E. 1977. Basic considerations about trace constituents in the
atmosphere as related to the fate of global pollutants. Proc. ACS Symposium
on the Fate of Pollutants in the Air and Water Environment.
Wiley-Interscience. I. H. Suffet, Ed., p. 7.

Mackay, D. and A. W. Wolkoff. 1973. Rate of evaporation of low-solubility
contaminants from water bodies to atmosphere. Envir. Sci. and Tech. 7. 611.

Mackay, D. and P. J. Leinonen. 1975. Rate of evaporation of low-solubility
contaminants from water bodies to atmosphere. Envir. Sci. and Tech. 9, 11/8.

McClure, V. E. 1976. Transport of heavy chlorinated hydrocarbons in the
atmosphere. Envir. Sci. and Tech. 10, 1233.

25


organic fraction and the scavenging efficiency one would expect for such
Particulates. Gatz (1977) has reported a correlation between scavenging
ratios and the mass median diameter (MMD), of the particulates being
scavenged. The smallest scavenging ratio he reported was 76 for lead, with
a MMD of about 0.5 micrometers. Andren (1976) and Strand (1977) have
reported that organic particulates in the atmosphere above Lake Michigan are
less than 2 micrometers in MMD. The scavenging ratio of 25 found in this
Project is, when corrected for the fact that much of the PCBs are present as
vapor, is in good agreement with the sizes found by Andren and Strand.
Although other factors undoubtedly contribute to precipitation scavenging,
the low scavenging ratio found for these samples indicate that the
particulates being scavenged are quite small.

PCBs IN ORGANIC PARTICULATES

In order to be able to account for the distribution of PCBs in the
environment and their movement through the environment, the concentration of
the PCBs in the different compartments of the environment must be known.
Due to their non-polar nature and large n-octanol/water partition
coefficient, PCBs not in the vapor phase are always found associated with
non-polar organic matter. Therefore, if the concentrations of PCBs in this
organic matter, and the movement of the organic matter through the
environment is known, the movement of the PCBs through the environment will
also be known.

Data on the mean amount of hexane/acetone soluble (organic) and
insoluble particulates present in the non-filterable fraction of the
different types of samples collected in the project are in Table 4. Also
shown are the results of calculations based on different assumptions on the
source of the PCBs in the samples. Probably most of the PCBs in
precipitation samples which are filterable are associated with smal]
particulates. Thus the concentration of PCBs in organic material in the
atmosphere may be best represented by the concentration of PCBs in the
organic portion of the particulate fraction of the precipitaion
samples.These results are all close to 100 mg/kg. The similarity of these
values to those found for the concentrations of PCBs in the fat of fish from
Lake Ontario (Heile et al. 1975), may be more than a coincidence.

PCBs IN GASES FROM LANDFILLS

PCBs in landfills have heretofore been considered only as a source of
water pollution. While samples from one day, from a single landfill, allow
no conclusions to be drawn, the high concentration of PCBs found in these
samples (Table 2, p. 13) suggests that landfills may be a source of PCBs to
the atmosphere and that further studies are in order.

PERCHLORINATION

The quantification of PCBs is complicated by the large number of
separate chlorinated biphenyl compounds present in a sample and by the
different sensitivity of the electron capture (EC) detector tot he different

22


CONTENTS

Page
Forward 2. 6 ee ee ee ee ee iii
Abstract 2 6 we ee ee iv
Acknowledgements . 2... 1 ee ee ee ee ee vi
Section:
J. Introduction. ©... ee 1
2. Sampling . 6 6 ee ee ee ee ee 4
3. AmalySis 2. 6 6 ee ee ee ee ee ee 10
Calculations... 1. ee ee 12
4. Results 2... ee 13
5. Discussion . 6. ee ee ee 18
Atmospheric Inputs... 2... 1 2 eee ee ee ee he 18
Distribution of PCBs in the Atmosphere Between Vapor and
Particulates 2. 6 1 1. ee ee te ee 20
PCBs in Organic Particulates... 2... 1 ee eee eee eee 22
PCBs in Gases from Landfills... 2... 2 ee ee ee eee 22
Perchlorination 2... 6 pe ee ee ee ee 22
Bibliography 2 6. ee ee ee 24
Appendix 2 6. ee ee ee 28


ABSTRACT

Event rainfall samples were collected in Chicago, Illinois and on
Beaver Island, Michigan and analyzed for polychlorinated biphenyls (PCBs).
The volume wei ghtgd mean concentration,of 35 samples of rain was 111 ng/L
(111 parts in 10°") of PCBs as Aroclor” 1242 + 1254 + 1260. This would
result in the deposition of 4800 kg/yr of PCBs to Lake Michigan from
precipitation.

The concentrations of PCBs in rainfall were found to be as high on
Beaver Island as in Chicago. This, and the finding of PCBs in the air and
precipitation in remote areas, is interpreted as indicating that the sources
of PCBs to the atmosphere are diffuse and that residence times in the
atmosphere are long.

A comparison of the results obtained from air and precipitation
sampling, including simultaneous sampling, indicates that the majority of
PCBs are present in the atmosphere as vapor with the remainder being present
on particulates. This result, along with the high solubility of PCBs in
non-polar organics, raises doubts as to the validity of measurements for the
dry deposition of PCBs obtained with the use of collectors covered with
mineral oil or other non-polar liquids.

Two gas samples obtained from a vented sanitary landfill had PCB
concentrations in the yg/m> (parts in 10°) range. This indicates that
PCB containing materials incorporated into landfills may be an important
source of PCBs to the atmosphere.

With the decline in the use and discharge of PCBs by major industrial
facilities in the basin, PCB levels in Lake biota may decline by a factor of
four or more. Precipitation is now the major known source of these
materials to the Lake, and the future problems in the Lake with PCBs will be
determined mainly by the magnitude of the atmospheric inputs of PCBs to the
Lake.

iv


The PCBs in the samples were quantified by the method of Webb and
McCall (1973). This involves the use of Aroclor standards and the
percent contribution to these standards of eight or more of their major
components to determine the absolute GC detector response factors (area/ng)
for each of the 23 major peaks which are separated by the GC. These
response factors are then used to determine the amount (ng) of each of the
23 different peaks. Rather than reporting the amount of each of these 23
peaks, they were grouped in a manner very similar to the scheme proposed by
Webb and McCall (1973). The peaks which comprised the di-, tri-,and most of
the tetrachlorobiphenys, were summed and are reported as AroclorTM 1242.
The peaks which comprised the remainder of the tetrachlorobiphenyls, along
the penta-, and most of the hexachlorobiphenyls were summed and reported as
Aroclor® 1254. The peaks which comprised the remainder of the
hexachlorobiphenyls, along with the hepta-, and octachlorobiphenyls were
summed and reported as Aroclor® 1260. Although the PCBs found in the
samples are reported as Aroclors®, in no case did the pattern of PCB peaks
in a sample closely resemble that which occurs in a commercial Aroclor'
sample.

The PCBs were separated on a 1.8m x 2 mm, 3% OV-101 GC column
temperature programmed from 180 to 220°C. The injector was kept at
260°C and the detector at 350°C. A Ni-63 electron capture detector was
used with a pulsed voltage, constant current source. The areas of the
different peaks were obtained with the use of a digital electronic
integrator (Supergrator-1; Columbia Scientific Ind. Corp.; Austin, TX).

The efficiency of the extraction and clean-up of the PCB samples was
checked on several occasions. The efficiency of the recovery of PCBs from
the foam and their clean-up was checked twice by adding 2,3,4,5,6-penta-
chlorobipheny! (740 & 880 ng) to the foam and extracting with a mixture of
hexane/acetone in a Soxhlet for seven hours. The extracts were cleaned-up
and analyzed in the normal manner. The overall recovery was 78 and 84
percent. Further extraction of the foam yielded less than one percent
additional material.

The efficiency of the clean-up procedure was independently checked on
four occasions by adding known amounts of PCB isomers (296 to 840 ng) to the
chromatographic clean-up column and proceeding in the normal manner.
Recoveries of the added PCBs averaged 95 + 11 percent.

On two occasions the three foam plugs from the water sampler were
separately extracted. The bottom foam contained no detectable PCBs on both
occasions.

One one occasion, the two pieces of foam from the air sampler were
separately extracted and analyzed. One fourth of the total PCBs were found
on the second piece of foam indicating an overall sampling efficiency of
about 88%.

In order to be consistent with the reporting procedures followed by
other workers, and to permit easy comparison with other reports, the results
here are uncorrected for analytical efficiency.

ll


SECTION 1
INTRODUCTION

In recent years, fish species in Lake Michigan, especially the
salmonids, have contained high levels of DDT and its degradation products,
and polychlorinated biphenyls (PCBs). In most cases, the large fish are
above the Food and Drug Administration (FDA) limit for these materials of 5
mg/L (Willford 1975). Among the Great Lakes, the levels of DDT and its
degradation products in the late 1960's and then of PCBs in the 1970's, have
been the highest in Lake Michigan (IJC 1974; 1976).

PCBs are a serious health hazard to many species of animals and to
man. It has been shown that the cause of the reproductive failures in ranch
mink fed Lake Michigan fish during the middle 1960's, was due to PCBs in the
fish (Aulerich et al. 1973). Fish are now practically the sole source of
PCBs in the human diet (Jelinek and Corneliussen 1976). Breast fed infants
throughout the country (Savage et al. 1973; Musial et al. 1974; Grant et al.
1976) are now exposed to 10% of the dosage of PCBs which has been shown to
cause serious health problems in rhesus monkeys (Allen and Norback 1976;
Barsotti et al. 1976). A correlation between the number of Lake Michigan
fish consumed and the blood levels of PCBs in humans has been reported
(Humphreys 1976). The public press has reported the case of one fisherman
who developed the symptoms of PCB poisoning, Yusho disease, after having
eaten large quantities of Lake Michigan fish (Ingersoll 1977).

The cause of the DDT problem was probably the use of this insecticide
in the agricultural regions around the Lake, and for Dutch Elm disease
control in the urban areas at the south end of the Lake. It is believed
that an important route for the dissemination of DDT and its metabolites is
atmospheric transport as vapor, mist and material adsorbed on particulate
matter (Woodwell et al. 1971; 1972). This material could then enter the
Lake by both wet and dry deposition.

When the use of DDT was halted in Wisconsin and Michigan, and then
natiowide in the late 1960's, the levels of DDT and its metabolites in the
fish dropped rapidly over the next several years. For instance, the level
in bloaters (chubs, Coregonus hoyi) dropped 87 percent from 1970 to 1975,.
and the level in Lake Trout (Salvelinus namaycush) dropped 53 percent during
the same time period. This indicates a relatively short residence time in
the Lake for these materials.

The problem with PCBs became apparent during the time of the problems
with DDT. Since many of the chemical and physical properties of the PCBs


TABLE 4. THE CONCENTRATION OF PCBs IN ORGANIC MATTER

Sample Type

Rain Snow Lake Air
Chicago Beaver Is. Water
Number of Samples 7 W ~~ 2 3 4
Particulates per Sample (mg)
Organics 8+8.4 545.3 9.8 3.8 1044
Total 260 + 195 76 + 56 140 82 58
PCB Concentration in Particulates
Total PCBs per Sample (mg/kg) «
Organic Particulates 340 240 220 140 600
Total Particulates 8 16 0 5.5 200%
Non-Filterable PCBs per Sample (mg/kg)
Organic Particulates 88 120 150 100 18*
Total Particulates 2.5 7.5 5.5 4 3*

*Biased by the fact that most of the PCBs on air particulates are
collected as vapor.

7


Laboratory
Duluth MN 55804

SEPA Polychlorinated
Biphenyls
in Precipitation

in the Lake Michigan
Basin

> Dy»


SECTION 2
SAMPLING

To meet the objectives of this project, air and event precipitation
samples were collected in Chicago, Illinois at DePaul University (41
55.4'N; 87° 39.9'W) from July 1975 jhrough January 1977, and rain samples
were collected on Beaver Island (45° 40'N; 85° 31'W), 500 km from
Chicago, from May through October 1976. The sampler in Chicago was located
about 15 meters above the ground on the roof of a building, 2 km west of
Lake Michigan, 4 km north of the central business district of Chicago in a
densely populated urban area which also contained some light manufacturing.
The sampler on Beaver Island (Figure 1), 500 km north of Chicago, was one
meter above the ground and about 30 meters from the shore on the east side
of the Island on the grounds of the Biological Station of Central Michigan
University.

Air samples were collected in Chicago at the aboye location, and
within the boundaries of Mammoth Cave National Park (37> 13'N; 86° 03'W).
In addition, several water samples from Lake Michigan were collected and
some samples obtained of gases vented from a sanitary landfill.

When possible, samples were filtered upon collection, and thus
separate samples of PCBs associated with the non-filterable as well as the
filterable portions were obtained. The samples were cleaned-up and analyzed
for the PCBs present. Since the commercial PCB products, the Aroclors’,
contain mixtures of different PCB compounds, the weight of the individual
PCB compounds found in the samples was determined, summed, and Reported as
the Aroclor” in which they predominately occurred. The Aroclor
mixtures reported here are 1242, 1254 and 1260. In no case did the relative
amounts of the different PCB,compounds found in the samples approximate the
ratios found in the Aroclors’.

Polychlorinated biphenyls (PCBs) are liquids or solids at room
temperature. They are non-polar, slightly soluble in water (56,g/L for
Aroclor” 1254 at 258C3 Haque et al.,1974) and they have a slight vapor
pressure (7.7 x 10° mm for AroclorTM 1254 at 25°C; Mackay and Wolkoff
1973). Thus PCBs in the environment can be expected to be present in the
air, water and solid phases, which greatly complicates the sampling for them.

In addition, the concentration of PCBs in gost environmental samples
was expected to be less than 1 ng/g (1 part in 10°). Thus the collection
and handling of large samples is necessary to get sufficient PCBs for


present in a landfill, they can evaporate. Since gases are generated by the
anerobic decomposition of organics within landfills, and continually escape
to the atmosphere, PCBs which evaporate in the landfill would be carried out
along with these gases.

An above ground landfill has been constructed in a suburb of Chicago
and is used for recreational purposes. The landfill has been carefully
sealed with clay, and several gas wells have been put in place to vent gases
generated within the landfill to the atmosphere. These gases have been
sampled by the I1linois Geological Survey and, on a volume basis, consist
mostly of methane (69%), and carbon dioxide (29%).


BIBLIOGRAPHY

Allen, J. R. and D. H. Norback. 1976. Pathobiological Responses of
Primates to Polychlorinated Biphenyl Exposure. National Conference on

Polychlorinated Biphenyls. Conference Proceedings, EPA-560/6-75-004, U. S.
Environmental Protection Agency, Washington, D. C., Chicago, IL. p. 43.

Andren, A. A. 1976. 1Uth Great Lakes Regional Conference, American

Chemical Society, June, 19/6, Evanston, IL. Quoted by J. J. Delfino, Envir.
Sci. and Tech., 10, 986.

Armour, J. A. 1973. Quantitative perchlorination of PCBs as a method for

confirmatory residue measurement and analysis. J of the Assoc. of Off. Anal
Chem., 56, 987.

Aulerich, R. J., R. K. Ringer and S. Iwamoto. 1973. Reproductive failure

ang mortality in mink fed on Great Lakes fish. J. Reprod. Fert. Suppl., 19,

Barsotti, D. A., R. J. Martar and J. R. Allen. 1976. Reproductive
dysfunction in rhesus monkeys exposed to low levels of polychlorinated
biphenyls (Aroclor 1248). Fd. Cosmet. Toxicol. 14, 99.

Bedford, J. W. 1974. The use of polyurethane foam plugs for extraction of
PCBs from natural waters. Bull. Envir. Contam. and Tox., 12, 622.

Bidleman, T. F. and C. E. Olmey. 1974. High volume collection of
atmospheric PCBs. Bull. Envir. Cont. and Tox., ll, 44.

Buckley, J. L. 1972. Polychlorinated biphenyls; Still prevalent but less
of a problem. Quoted by T. H. Maugh, II, Science 178, 388.

Gatz, D. F. and A. N. Dingle. 1971. Trace substances in rain water:

concentration variations during convective rains, and their interpretation.
Tellus 23, 14.

Gatz, D. J. 1977. Scavenging ratio measurements in METROMEX.
Precipitation Scavenging 1974. Champaign, IL, Symposium Series #41, ERDA
(CONF-741003), p. 71

Grant., D. L., J. Mes, and R. Frank. 1976. PCB residues in human adipose
tissue and milk. Conference Proceedings; National Conference on
Polychlorinated Biphenyls, Chicago, IL. U. S. Environmental Protection
Agency, EPA-560/6-757-004; p. 144.

Greenfield, S. M. 1957. Rain scavenging of radioactive particulate matter
from the atmosphere. J. of Meteor. 14, 115.

Haque, R., D. W. Schmedding and V. H. Freed. 1974. Aqueous solubility,
adsorption and vapor behavior of AroclorR 1254. Envir. Sci. and Tech. 8,
139.

24


compounds. It has been reported (Armour 1973) that, upon reaction with
antimony pentachloride, PCBs are quantitatively perchlorinated to the fully
chlorinated biphenyl, decachlorobiphenyl (DCB). Thus all of the different
PCBs present are converted into one compound, and of all of the PCBs, the EC
detector has the greatest sensitivity to DCB. It was hoped that the use of
this reaction would greatly simplify the quantification of the PCBs.

While some initial control experiments using AroclorR 1254 were
satisfactory, further experiments with AroclorR 1242 gave only about 25
percent conversion to the DCB. Careful attention to the evaporation of the
samples raised this to 38 percent.

To check on the possibility that the perchlorination of the pure PCB
standards was not different from the perchlorination of samples which
contained large amounts of other organics, the following standard addition
experiment was carried out. A portion of a precipitation sample was
perchlorinated and the DCB produced was determined. A known amount of
Aroclor® 1242 was then added and the sample again perchlorinated. Only 40
percent of the theoretical amount of DCB was formed.

Since the yield of DCB was a function of the composition of the PCBs
in the sample, and the percent of Aroclor 1242 in the different types of
samples varied from 9 percent to 98 percent, it was decided that this method
was not suitable for the quantification of the PCBs in the samples collected
in this project.

23


ACKNOWLEDGEMENTS

The authors would like to express their thanks and appreciation to
Dr. Matthew C. Hohn, director of the Central Michigan University Biological
Station on Beaver Island for his conscientious help in collecting the
Precipitation samples on Beaver Island.

We would like to acknowledge the help of Cunera Buys, Edwardine
Nodzenski and Guiseppe Paolucci for their able assistance with some of the
analytical work on this project.

We wish to thank the Illinois Geological Survey for the use of a
recording rain gage for this project; Mr. George Bottoms and the Forest
Preserves of DuPage County for permitting the collection of the landfill gas
samples at Roy C. Blackwell Forest Preserve; Mr. Thomas Ward and the City of
Chicago Department of Waters and Sewers for their permission and
co-operation in collecting the water samples from the 68th Street (Dunne)
water intake crib; and the National Park Service at Mammoth Cave National
Park for their permission to sample and the Cave Research Foundation for
their co-operation in the sampling in the National Park.

We would like to acknowledge the partial support of this project by
DePaul University.

vi


TABLE 2. THE MEAN CONCENTRATION OF PCBs

Arithmetic Percent PCBs in

Sample Type Number of Mean PCB Filtered
Samples Concentration Portion
Rain (ng/L) Chicago 22 160 66
Beaver Island 13 215 53
Snow (ng/L) Chicago 4 212 36
Lake Water (ng/L) Chicago 2 4l 30
Beaver Island 1 30 : 43
Air (ng/m3) Chicago 4 7.6 97
Mammoth Cave NP 1 6.7 95
Landfill Gases (ng/m3) 2 3240 -

the rain samples, a volume weighted mean distribution of the PCBs was also
calculated. The results showed little difference from the arithmetic mean.
To be consistent, the arithmetic mean of the rain samples is included in
Table 3.

For a number of the rain samples, the amount of the hexane/acetone
extractable material, the organic fraction, of the particulate portion of
the sample was derermined. If it is presumed (see Discussion) that all of
the PCBs in the rain samples came from particulates scavenged by the
precipitation, then the concentration of PCBs on the particulates and in the
organic fraction of the particulates can be determined.

Shown in Table 4 are the results of calculations which show the
concentration of PCBs in the total particulates and organic particulate
fractions if it is assumed that 1) either all of the PCBs present in the
sample were associated with the particulate organics; or 2) that only the
particulate PCBs were associated with the particulate organics. For
instance, the mean amount of PCBs found on particulates in the rain samples
in Chicago was 697 nanograms/sample. If these PCBs are assumed to be
associated only with the organics in the particulate matter (8 milligrams/
sample), the PCB concentration in the organics is 88 mg/kg. Also, the PCB
concentration in the total particulates (260 milligrams/sample) then is 2.6
mg/kg.

Since the organic fraction is small, the errors in their determination
are large. Therefore, the weights of this fraction and the calculations
based on them are not very precise and should be treated only as
approximations.

14


Té€

L4KE MICHIGAN

SAMPLING
DATE VOLUME
BEGUN DURATION COLLEC
YY MM DD CHR? aL)
76 05 22 0.0 14.7
76 09 22 0.0 15.5
76 09 22 0.0 13.5
SAMPLING
DATE VOL.UME
BEGUN DURATION COLLEC
YY MM DD CHR) «L)
75 1229 «425.0 12.7
7 O1 21 3.0 10.5
76 12 06 17.0 6.0
77 01 10 0.0 8.7

FILTERED
_% AROCLOR TOTAL
1e42 1254 1260) (NG)

19.8 68.6 11.5 191
14.4 76.4 91 195

14.3 75.7 9.9 160

WATER SAMPLES

NON-F Il. TERABLE
% AROCLOR TOTAL
1242 1254 1260 (NG)

66.4 27.6 5.8 249
24.1 71.4 4.2 473
49.4 48.1 2.1 362

CHICAGO SNOW SAMPLES

FILTERED
% AROCLOR TOTAL,
1242 1254 1260 (NG)
83.7 9.5 6.6 546
57.0 36.0 6.9 66
33.3 35.2 31.3 764
47.5 40.7 11.6 576

NON-F IL. TERABLE
% AROCLOR TOTAL.
1242 1254 1260 (NG)

4.4 55.6 39.7 ape

29.4 58.9 11.5 1414
25.2 55.3 19.2 64
21.9 57.4 20.3 2a71

TOTAL SAMPLE

% AROCLOR TOTAL
1242 1254 1260) (NG)
46.2 45.4 8.3 440
21.3 72.9 5.7 668
38.7 56.6 4.5 See

TOTAL SAMPLE
% AROCLOR TOTAL
1242 1254 1P60 (NG)

60.5 23.0 16.3 772

33.1 50.9 3.3 e1KO

29.3 45.3 25.3 1527

27.1 54.1 18.6 aBa7

PCB
CONC
(NG/L)
23.9
43.0

3B.6


ce

4IR SAMPLES

SAMPLING

DATE VOLUME FILTERED NON-F Tl. TERABLE TOTAL SAMPLE PCB

BEGUN DURATION COLLEC % ARGCLOR ‘TaTAL % AROCLOR TOTAL % ARGCL.AR TOTAL CONC
YY MM DD CHR) (M3) 1242 1254 1260 (NG) 1242 1254 1260 (NG) 1242 1254 1260 (NG) (NG/M3)
75 11 a7 32.0 178e 80.3 19.1 0.5 11469 45.2 54.2 2.6 S47 78.7 20.7 0.6 12017 6.7
751205 2.7 1106 93.2 62 0.6 7517 0.7 12.6 85.5 771 84.6 6.8 8.5 8abh 7.4
7 02 20 21.4 1072 86.4 10.2 3.4 3646 14.3 36.6 46.0 266 81.5 12.0 6.3 3912 3.6
7603 29° 20.0 1138 75.3 24.4 0.2 11275 75.3 42.6 0.2 62 75.3 24.5 0.2 11337 3.9

7604 19 PR.9 954 94.7 4.7 0.5 10385 28.4 48.8 15.2 1430 93.8 5.3 0.7 10528 11.0


; The most recent information on the concentration of PCBs in Lake
Michigan fish indicates that levels in chubs and coho salmon have declined
by a statistically significant amount below the maximum values of recent
years (Seelye 1977). Thus, it seems as if the concentration of PCBs in Lake

biota are now beginning to respond to the decreased inputs of PCBs to the
Lake.

The data in Table 3 and Figure 4 indicate that the different
compartments associated with the Lake contain very ditferent compositions of
PCBs. For instance, the PCBs in air are 84 percent AroclorR 1242 while
the Lake water is only 34 percent; and 66 percent of the PCBs in rain are
filterable while only 33 percent of the PCBs in the Lake are. There are too
few samples in most cases to give reliable information, and many of the
compartments in the Lake are not represented, but it seems clear from these
different compositions that, in the past, sources other than the air and
precipitation have contributed PCBs to Lake Michigan.

DISTRIBUTION OF PCBs IN THE ATMOSPHERE BETWEEN VAPOR AND PARTICULATES

At the present, it has not possible to determine the extent to which
PCBs are present as vapor and on particulates in the atmosphere. This is
because PCBs on particulates, captured on the filter paper of high volume
air particulate samplers, evaporate into the air stream and are collected as
vapor. Thus, the total amount of PCBs present in the atmosphere can be
readily determined, but their distribution between vapor and particulate
forms can not be. The information obtained in this project, however, leads
to a tentative resolution of this problem.

Where do the PCBs found in the precipitation come from? Either from
PCBs present as vapor which dissolved in the precipitation, or as PCBs
adsorbed on particulates which were scavenged by precipitation. The
scavenging of PCB vapor by rain can be ruled out on theoretical and
experimental grounds. On theoretical grounds, the distribution constant for
the partition of PCBs between air and water, the Henry's Law Constant (HLC),
is about 20 for AroclorR 1242 and 1254 (Junge 1977; Mackay and Leinonen
1975; Mackay and Wolkoff 1973). It should be similar for Aroclor 1260.
Since the data in Table 2 indicate that the the concentration in
precipitation is about 400 times that calculated using the mean
concentration in air and the HLC, PCB vapor is not an important source of

PCBs to precipitation. McClure (1976) has arrived at similar conclusions
for DDT.

Experimentally, the scavenging of PCB vapor by the precipitation also
can not explain the amounts of Aroclor 1260 found in the precipitation
samples. From the summaries of the compositions of the air and
precipitation samples in Table 2 and Figure 4, the air samples contain about
3 percent Aroclor® 1260, while the precipitation samples contain more than
20 percent. The lower water solubility of the AroclorR 1260 compared to
the other AroclorsR studied here, would preclude the factor of six
enhancement in the precipitation as compared to the air. The greater
percentages of the AroclorR 1260 in the precipitation samples can only be
explained by the air particulates being higher in Aroclor® 1260, and the

20


DISCLAIMER

This report has been reviewed by the Office of Research and Development,
Environmental Protection Agency and approved for publication. Approval does
not signify that the contents necessarily reflect the views and policies of
the Environmental Protection Agency, nor does mention of trade names or com-
mercial products constitute endorsement or recommendation for use.

ii


Gas
Weill

Filter

24/40
Foam

Pump

24/40

#55/50

Foam

18/9

FIGURE 2. PCB SAMPLER FOR WATER SAMPLES.

—T
_

Le

Foam

AH

FIGURE 3.

7

Pump

SAMPLER SET-UP FOR SAMPLING GASES FROM A LANDFILL.


The flow rate of the gases which passed through the sampler was
measured by passing this gas through three rotometers connected in
parallel. The rotometers had been calibrated by connecting the intact
sampling train to a closed 216 L (55 gal) drum which had a manometer
connected to it. The sampler was operated for short periods, and volume of
air pumped from the drum was calculated from the known volume of the drum
and the pressure change caused by the pumping. This permitted the flow rate
to be determined. The system was calibrated at several different flow rates.


EPA-600/3-78-071
July 1978

POLYCHLORINATED BIPHENYLS IN PRECIPITATION IN THE
LAKE MICHIGAN BASIN

by

Thomas J. Murphy
Charles P. Rzeszutko
DePaul University

Chicago, I]linois 60614

Grant No. 803915

Project Officer

Michael D. Mullin
Large Lakes Research Station
Environmental Research Laboratory - Duluth
Grosse Ile, Michigan 48138

ENVIRONMENTAL RESEARCH LABORATORY

OFFICE OF RESEARCH AND DEVELOPMENT

U.S. ENVIRONMENTAL PROTECTION AGENCY
DULUTH, MINNESOTA 55804


o€

SAMPLING

DATE

BEGUN DURATION
YY MM OD (HR)
76 05 09 5.7
76 06 13 9.5
76 06 15 3.7
76 06 18 2.3
TE 06 24 13.0
7% O7 29 0.0.
76 O08 OO 0.2
76 08 27 0.0
7 O08 31 16.0
76 09 14 7.0
76 09 29 5.0
76 10 04 13.0
76 10 14 3.0

cnn)
12.2
5.0
2.3
5.6
0.9
5.8
14.7
12.2
13.2
4.5
5.2
26.7
1.8

VOLUME
RAIN COLLEC

iis)
15.8
6.1
a1
6.5
1.3
We
7S
4.8
16.5,
5.2
6.5
28.3

1242
37.4
42.0
19.2
20.7
43.3
51.3
19.6
40.0
4.1
58.0
22.5
37.0
29.8

BEAVER

ISLAND RAIN

FILTERED
% AROCLOR

1254
52.7
46.1
69.9
43.3
40.0
33.4
46.3
55.3
73.5
32.6
56.5
34.1

44.5

1260

9.8
11.6
10.8
35.9
16.5
15.2
33.9

4G

2.3

9.2
20.8
e8.8
25.6

NON-FILTERABLE
% AROCLOR
1242 1254 1260

26.2 55.7 17.7

32.0

5.8
37.5
24.4
25.1
52.2
18.4
26.2

9.6
35.9
22.6

39.9

60.2
68.4
42.7
43.4
S7.6
4h
51.7
Sat
50.0
31.8
37.7
27.9

14
25.9
139.5
aL.
WA

Oo.
22.6
15.7
40.7
B1.R
32.2

BLL

TOTAL.
(NG)

1401
504
174

sai
151
S77
Sé3
757

SAmeP. Ss

TOTAL SAMPLE
% AROCLOR

1242
28.7
38.4
14.1

23.8
34.7
41.8
34.4
29.0
25.4

38.2
30.5
34.4

35.9

1254 1260
58.1 16.0
51.3 10.3
69.2 16.5
43.2 32.9
41.6 23.6
218.9

46.9 18.6
53.5 17.4
66.1 8.7
39.6 22.0
41.9 27.4
35.4 30.0

34.6' 29.4

TOTAL
(NG)

1793
1382
460

INPUT
PCB OF PCHY
CONC (ING /Me?
(ING/L) (NG /KDI2
113.4 1. 3e4
226.5 1.137
219.0 0.503
134.0 0.750
485.3 0.436.
311.8 1,808
82.1 1.207
285.4 3.482
66.1 0.873
71.5 0.321
149.5 0.777
56.4 1.506
601.4 1.082


SECTION 5

DISCUSSION
ATMOSPHERIC INPUTS

Extent of the Problem

An unexpected result, and a significant finding, of this study was the
finding that the concentration of PCBs in precipitation was as high on
Beaver Island as in Chicago. This means that either there is a local source
of PCBs to the atmosphere in the vicinity of Beaver Island, which is
unlikely, or that PCBs are being very widely distributed by the atmosphere.

There is other evidence to support the wide distribution of PCBs by
the atmosphere. Concentrations of 230 ng/L of PCBs have been found in snow
samples collected on Isle Royale National Park in Lake Superior (Swain
1977), 800 km north of Chicago. Also, the air sample collected in this
project in Mammoth Cave National Park, which is located in a rural area
remote from centers of population and industry, and 650 km south of Chicago,
had concentrations of PCBs similar to those found in Chicago (Table 2).
Strachan et al. (1977) report lower concentrations of PCBs found in
precipitation in the Lake Ontario basin.

Effects on Lake Michigan

The results of the measurements made in this project are that 4800
kilograms of PCBs are coming into Lake Michigan in precipitation per year.
To gage the significance of these inputs, the other known and estimated
sources of PCBs are listed in Table 5. It can be seen that precipitation is
now the major source of PCBs to Lake Michigan.

The industrial use of PCBs for such uses as heat transfer fluids,
hydraulic fluids, in die casting operations, etc., has greatly decreased
since 1971 when they ceased to be sold for those purposes. As there was
little or no control over the use or discharge of PCBs prior to 1971, it is
not known how much of these materials were discharged and reached Lake
Michigan, or where these discharges occurred. An illustration of the
possible magnitude of these sources to the Lake, is a manufacturer in
Waukegan, Illinois, who used a commercial hydraulic fluid containing PCBs.
The water effluents from this plant go mostly to Waukegan harbor, but some
go to a ditch leading directly to the Lake. The manufacturer estimated that
of the 3.8 X 106 kilograms of PCBs they purchased over a twenty year
period, as much as 15% to 20% could have been discharged with their water
effluents (Thomas 1976). Sediment samples taken in the harbor in 1976 show
concentrations of PCBs as high as 4 mg/gm, and sediments from the ditch were
as high as 0.6 mg/gm (IJC 19/6b).

18


RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency. have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields
The nine series are:

Environmental Health Effects Research

Environmental Protection Technology

Ecological Research

Environmental Monitoring

Socioeconomic Environmental Studies

Scientific and Technical Assessment Reports (STAR)
Interagency Energy-Environment Research and Development
“Special” Reports

Miscellaneous Reports.

OMNDAOSLWN=

This report has been assigned to the ECOLOGICAL RESEARCH series. This series
describes research on the effects of pollution on humans, plant and animal spe-
cies, and materials. Problems are assessed for their long- and short-term influ-
ences. Investigations include formation, transport, and pathway studies to deter-
mine the fate of pollutants and their effects. This work provides the technical basis
for setting standards to minimize undesirable changes in living organisms in the
aquatic, terrestrial, and atmospheric environments.

This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161


Musial, C. J., 0. Hutzinger and V. Zitko. 1974. Presence of PCB, DDE and
DDT in human milk in the provinces of New Brunswick and Nova Scotia,
Canada. Bull. of Envir. Contam. and Toxic. 12, 258.

Neely, W. B., D. R. Branson and G. E. Blau 1974. Predicting
bioconcentration potentials. Envir. Sci. and Tech., 8, 1113.

Reed, N. P. 1976. U. S. Federal Agency Roles and Actions: The Department
of the Interior. National Conference on Polychlorinated Biphenyls.
Conference Proceedings, EPA-560/6-75-004, U. S. Environmental Protection
Agency, Washington, D. C. p. 434.

Savage, E. P., J. 0. Tessari, J. W. Malberg, H. W. Wheeler and J. R. Bagby.
1973. A search for polychlorinated biphenyls in human milk in rural
Colorado. Bull. of Envir. Contam. and Toxic. 9, 222.

Seeyle, J. 1977. Results of Fish Contaminant Monitoring. Personal

Gonmun ication. Great Lakes Fishery Laboratory, 1451 Green Road, Ann Arbor,
\ 48105.

Sedergren, A. 1972. Chlorinated hydrocarbon residues in airborne fallout.
Nature 236, 395.

Sedergren, A. 1973. Transportation, distribution and degradation of DDT
and PCBs in a south Swedish Lake ecosystem. Vatten 2, 90.

Strachan, W. M. J., F. C. Elder, H. Huneault and W. M. Schertzer. 1977.

Presented at the 20th Conference on Great Lakes Research; Ann Arbor. MI;
May. 1977.

Strand, J. W. 1977. Polyaromatic hydrocarbons and total organic carbon
aerosol content above Lake Michigan. 20th Conference on Great Lakes
Research. May, 1977, Ann Arbor, MI.

Swain, W. R. 1977. Persistant organic compounds in the vicinity of Isle
Royale. J. of Great Lakes Research, in the press.

Tarrant, K. R. and J. O'G. Tatton. 1968. Organochlorine pesticides in
rainwater in the British Isles. Nature 219, 725.

Thomas, H. T. 1976. Letter to Mr. James McDonald; Chief, Enforcement
Division, Region V, U. S. EPA; March 15.

Uthe, J. F., d. Reinke and H. Gesser. 1972. Extraction of organochlorine
pesticides from water by porous polyurethane coated with selective
adsorbants. Envir. Letters 3, 117.

°

Willford, W. A., R. J. Hesselburg and L. W. Nicholson. 1976. Trends of
polychlorinated biphenyls in three Lake Michigan fishes. Conference
Proceedings, National Conference on Polychlorinated Biphenyls, Chicago, IL.
U. S. Environmental Protection Agency, EPA-560/6-75-004, p. 177.

26


PCBs in precipitation coming chiefly from the scavenging of these
particulates. The greater proportions of the lower molecular weight
AroclorsR found in the air samples must then be due to material present in
the atmosphere as vapor.

Precipitation then is providing the solution to the sampling dilemma
which exists for PCBs in the atmosphere. If all of the PCBs in the
non-filterable fraction of the precipiation samples, and most, if not all,
of the PCBs in the filtered portion are coming from air particulates, then
precipitation is serving as a selective sampler for air particulates. And,
while a rain droplet may have a ditferent scavenging efficiency for
different sized air particulates, this would make a difference only if the
PCB composition of ditferent sized particulates were different.

A comparison of the air and rain samples collected permits an
approximate resolution ot the PCBs present in the atmosphere into vapor and
part icujate forms. As mentioned before, the air samples show a mean
Aroclor® 1260 concentration of about 3 percent, while the rain samples
show a mean AroclorTM 1260 composition of 20 percent. Thus, a mass balance
based on AroclorTM 1260 indicates that only about 15 percent of the PCBs in
the atmosphere are on particulates. These results are in accord with the
predictions of Junge (1977) that compounds with vapor pressures of about
10° mm of Hg, should be present in the atmosphere chiefly as vapor, even
in urban atmospheres.

The data in Table 4, page 17, support this conclusion. The values
shown for the total PCB concentration in air particulates are clearly high
by a factor of 2 to 4, if it is assumed that all of the PCBs found in the
vapor and particulate phases were on the particulates. The simple explana-
tion for this is that not all of the PCBs collected were on particulates,
but rather were present in the atmosphere as vapor. The low value for the
non-filterable PCBs/sample for the air samples, is due to the evaporation of
the PCBs from the filter and their collection as filtered PCBs.

The evidence that much of thé PCBs in the atmosphere in the Lake
Michigan region are present as vapor has important ramifications for the
validity of methods recently reported for the collection of the dry fallout
of PCBs (Sdédergren 1973; McClure 1976) and DDT (Young et al. 1976). These
methods all utilize collectors coated with a non-polar liquid to capture and
hold particulate matter. But, since PCBs are quite soluble in non-polar
liquids, the partition coefficient into the liquid would be such that the
equilibrium concentration on PCBs would be in the milligrams per liter
range. Thus, PCBs present in the atmosphere as vapor would be expected to
be efficiently scavenged by the liquid coating. The deposition results
reported from the use of these sampling techniques would include not only
PCBs from dry deposition, but also from vapor scavenging. In fact, the
scavenging of PCBs in the vapor state by non-polar liquids is so efficient
that it is the basis for a method for the collection of PCB vapor (Harvey
and Steinhauer 1974).

Further evidence that the PCBs in precipitation are coming from the
scavenging of air particulates comes from measurements of the size of the

21


(>

‘Sle Royale

x Mammoth Cave NP

FIGURE 1. MAP OF SAMPLING LOCATIONS.


Placed on the sampler. About 200 mL of 70% ethanol were added to cover the
foam in he bottom of the sampler in order to force the air out of the foam
and to permit the water to flow freely thru it.

A final complication with this sampler is that the flow rate is fixed
by the pumping rate, one liter/minute for the pumps used in this project.
Thus, during a rain storm when the rainfall rate is high, not all of the
water will be sampled. Also, as the filter becomes clogged with
particulates, the filtering rate decreases. Fortunately, much of the
particulates are in the early part of the rain when the filtering efficiency
of the sampler is high. Loss of sample due to overflow of the filter will
affect the results only if the concentration of PCBs in the portion which
overflows is different from that which is sampled.

The interception area of the collectors was 1.29 mat DePaul and
1.2 m° at Beaver Island. A rain rate of 0.8 mm/min (1.9 in/hr) then
corresponds to about one liter/minute of water. The average rainfall
intensity for most rain events is much less than this, but many contain
periods of high rainfall intensity.

To determine the severity of the problem, a recording rain gage
(Belfort Instrument Co.) was used in Chicago in addition to the standard
accumulation type gage. Inspection of the records for 20 rain events showed
that while a significant amount of rain from some events occurred during
periods of high rainfall rates, the rainfall rate for most of the water
which fell was below 0.8 mm/min. With some variability, the average volume
of sample per unit of precipitation was 1.06 L/mm in Chicago and 0.98 L/mm
on Beaver Island.

This problem could be minimized further or corrected for in several
ways: the area of the collector could be decreased; the area of the funnel
could be increased to lower its flow resistance and spread the particulates
over a larger area; the volume of the funnel could be increased for more
storage capacity; and finally, an overflow could be incorporated on the
funnel to collect excess water in an adjacent container which would then be
manually poured through the sampler after the rain event.

Air samples were collected with a standard high volume air sampler
(General Metal Works; Cleves, 0H) modified to permit plugs of polyurethane
foam (Bidleman and Olney 1974) to be inserted in the air stream after the
filter paper. Glass fiber filters (GF/A; Gelman Inst.; Ann Arbor, MI) were
used to collect the particulates. Five to 7.5 cm of foam was used. The
foam was coated with DC-200 silicone fluid (Uthe et al. 1972).

The gases discharged from the landfill vent were sampled at the exit
port of the vent pipe. The apparatus used is shown on Figure 3. It
permitted different sample tubes containing polyurethane foam to be
connected to the vent. The extra piping on the sampler permitted excess gas
to be vented, and the pressure in the vent monitored to insure that there
was always positive pressure in the vent pipe so that outside air was not
drawn into the sampler.