NCD980602163_19970211_Warren County PCB Landfill_SERB C_Letter from Terry F. Bidleman of Environment Canada to Bill Meyer re Air Monitoring-OCR

11 l l♦I Environment
Canada
Atmospheric
Environment
Service
4905 Dufferin Street
Downsview, Ontario
M3H 5T4, Canada
Environnement
Canada
Service
de l'environnement
atmospherique
Mr. William L. Meyer, Director
Division of Solid Waste Management
Department of Environment, Health
and Natural Resources, State of North Carolina
P.O. Box 27687
Raleigh , North Carolina 27611-7687
Dear Dr. Meyer:
CANA DAS GRHl'-: Pl.Al'-:
LE Pl.AN \'ERl DU CANADA
Your file Votre reference
Our File Notre ,eterence
February 11, 1997
In early December you sent me a package of information about PCB air monitoring
at the Warren County landfill and asked for my review. I apologize for taking so long to
reply, and hope that the comments below are not too late to be of value. My background
in PCBs goes back to the early 1970s and my research group has published several articles
on aspects of their air sampling techniques, analysis, physicochemical properties and
atmospheric behavior. A short CV is attached.
I've known Bob Lewis for many years. Throughout the 1980s his branch, AREAL,
supported much of our developmental work on air sampling methods for PCBs and
pesticides while I was at the Uni.versity of South Carolina. Bob was one of the first
individuals to use polyurethane foam (PUF) as a sampling medium for PCBs and later
developed a "sandwich" cartridge of PUF and granular sorbents to collect more volatile
compounds. He also recognized, very early, that semivolatile organics are speciated .
between the particle and gas phases in the atmosphere and that glass fiber filters alone
were inadequate for collecting these compounds from air. In short, Bob is one of the leading
experts in the area of sampling methods for PCBs and other organics. In years of
interaction with Bob, I have found him to be totally honest and straightforward in his
dealings.
There are several issues raised by Joel Hirschhorn about the study carried out at the
Warren County landfill and reported by Lewis et al. in Environmental Science and
Technology (1985). In essence, Mr. Hirschhorn has accused EPA of mis-representing the
air concentration data collected at the landfill and for not carrying out a more detailed
investigation following the initial study.
Canada This paper contains a minimum o! 50% recyclec hbfe~ ®
including 10% pos1-co~sumer h~res
Ce papier conhent un minimum de 50% ae !lores recycleE:s ,
dont 10% oe ftt>res recyc!ees apres conso71ma1,or,
(
To put the problem into perspective, it is helpful to consider the origins of PCBs in
ambient air. Present-day sources of PCBs to the atmosphere include volatilization of PCBs
from landfills, leakage of electrical equipment, and "recycling" from contaminated water, soil
and vegetation. Very few measurements have been made on PCB release from landfills.
Recently published mass balance estimates ·for PCBs in the environment (Harrad et al.,
1994; Johnson et al., 1992) quote only two papers, the one by Lewis et al. (1985) and
another by Murphy et al. (1985) on emissions of PCBs from sanitary landfills in the Chicago
area . The database on emissions from the other sources is also not large, but from the
available information release of PCBs from large areas of land and water is substantial.
From a long-term inventory of PCBs in the water column of Lake Superior, Jeremiason et
al. (1994) estimated that 26,500 kg have been volatilized from the lake over a twelve-year
period, or an average of 221 O kg/y. Net volatilization of PCBs from lakes Superior, Michigan
(Hornbuckle et al., 1994, 1995) and Ontario (Hoff et al., 1996) is also implied by fugacities
(partial pressures) of PCBs in surface water which exceed those in the atmosphere. By
comparison, a report to Ontario Ministry of Environment and Energy (Johnson et al., 1992)
estimated that only 1000 kg/y of PCBs was emitted into the air within ·an of eastern North
America by leaking transformers (440 kg/y), stationary fuel combustion (450 kg/y), landfills
(69 kg/y) and incinerators (42 kg/y).
Harrad et al. (1994) estimated that 93% of the contemporary environmental burden
of PCBs in the U.K. is held in soil. Their inventory of current PCB sources to the
atmosphere were : volatilization from soils = 88%, transformer and capacitory leaks = 9%,
refuse-derived fuel = 2% and other industrial sources = 1 %. A model of PCB loss from soils
in the U.K. indicated that concentrations peaked in the late 1960s and have since declined
with a half-time of 10-20 years (Harner et al., 1995). Jones et al. (1995) estimated that
25,000 tonnes of PCBs have been lost from U.K. soils between 1970 and 1990. Clearly re-
emission of PCBs from contaminated water bodies and soil is large compared to releases
from landfills and other point sources.
I have spent a lot of space on this because it is important to recognize that PCBs in
ambient air within Warren County are likely to come from a variety of sources, including
volatilization from soils. Mr. Hirschhorn makes a case about ambient levels of PCBs in four
out of thirty-nine air samples. The positive four were 11, 12, 50, and 71 ng/m3 Aroclor 1260.
Of these, only the last two can really be considered as higher than the LOO of 10 ng/m3•
Were these values actually due to emissions from the landfill? Maybe, and maybe not.
a) PCBs were dumped over a large area of central North Carolina. Even though
efforts were made to clean up the mess, it is likely that some PCBs migrated away
from the immediate sites of contamination by the "grasshoppering" process of
volatilization and redeposition. Indeed, air samples which were taken at a site
where Aroclor-1260 contaminated soils were excavated showed levels of PCBs after
the cleanup operation in the range of 20-90 ng/m3 (Macleod and Lewis, 1980). Is
it possible that the roadway spill sites (even after cleanup) and other soils in the
region contributed to the observed PCBs in ambient air?
b) The levels of PCBs found in ambient air in the vicinity of the Warren County
landfill were not too far above the LOO, and Lewis suggests that they may, in fact,
be "false positives". The analytical work on these samples was done in the early
1980s, by packed-column GC-ECD . PCBs are not well resolved by packed
columns, giving a sort of lumpy chromatogram such as the one displayed by Lewis
et al. (1985), Figure 3. Given the difficulty in quantifying such a chromatogram, it
is possible that other ECO-sensitive compounds, toxaphene and chlordane in
particular, contributed to apparent PCB levels. Both of these organochlorine
pesticides are multicomponent mixtures whose GC retention times overlap those of
Aroclors 1254 and 1260. They can be separated out before analysis by silica gel
chromatography, but this was apparently not done for these air samples.
In the late 1970s we did quite a lot of air sampling in Columbia, South
Carolina for PCBs and pesticides. A paper published by us (Billings and Bidleman,
1980) shows packed and capillary chromatograms of PCBs and toxaphene in
ambient air, after silicic acid separation of the two chemicals. Figures 1 and 3 of
that article clearly show the overlap of the PCB and toxaphene profiles by packed-
column GC. During these years and afterward (toxaphene was banned in 1982 and
remaining stocks were used through 1986), toxaphene was a very abundant
pesticide in southern air. Mean concentrations of toxaphene in Columbia were
about 10 times higher than those of PCBs. Chlordane was in about the same
concentration range as Aroclor 1254. In my view, it is quite likely that PCBs at the
Warren County sites were overestimated because of these analytical interferences.
These arguments show that there is considerable ambiguity about the source --and
even the identity --of the apparent PCBs in ambient air near the Warren County landfill.
On p. 4 of his first statement (Nov. 27), Mr. Hirshhorn compares the concentrations
of PCBs at the main vent of the ToSCA landfill with levels found at uncontrolled landfills:
"However, the paper focused on results from measurements at 120-180 cm for
the other three landfills, which is somewhat analogous to the main vent pipe
condition at the Warren County landfill."
Not really, because vertical profiles of PCBs change greatly with height. This can be seen
from the data in Lewis et al. (1985) Table 3, where PCB concentrations drop by a factor of
about 100 between 2 cm and 180 cm height. In his response letter, Lewis states that the
vents were sampled by placing the intake of the air sampler within the vent pipes, not in the
ambient air around the pipes. This will certainly get the biggest whiff! So if a comparison
is going to be made, it should be the in-pipe measurements at the ToSCA landfill vs. the 2-
cm height measurements at the uncontrolled landfills. In this comparison the main vent pipe
showed 120 µg/m3 (main vent) vs. 271-520 µg/m3 (uncontrolled landfills, October).
Further down on p. 4, and also on p. 4 of his Dec. 1 O statement, Mr. Hirschhorn
states that the vent pipe may have been emitting higher levels of PCBs in the summer, and
cites the summer-fall differences seen at the uncontrolled landfill site as support. I don't
(
think this is likely. Surface emissions at the uncontrolled site will vary with temperature
according to a well-established relationship for semivolatile organics: Log C = mrr + b,
where C is the concentration in ambient air, T is the ambient temperature (Kelvin) and m is
related to the heat of vaporization of the compound. The heat of vaporization of PCBs is
such that C is expected to increase by a factor of three for each 10°C rise in temperature.
So there will be large seasonal differences in PCB levels in ambient air at the uncontrolled
landfills. However the interior of the ToSCA landfill is probably much less sensitive to these
seasonal variations, for the same reason that a cellar maintains a relatively constant
temperature. Thus I wouldn't expect large summer-winter variations in the concentration of
PCBs emitted from the main vent.
Moreover, the emissions from vent pipes may become less with time. Landfills
"breathe" by production of methane and also by the in-and-out movement of air due to
changes in barometric pressure (Murphy et al., 1985). It is, of course, the "out" movement
from both processes that pumps PCBs into the air. So as decay of vegetation tapers off,
one of the processes (methane emission) will be of less consequence.
The main vent pipe was releasing PCBs out of one small point source, whereas PCBs
from the uncontrolled landfills were volatilizing over a wide area. This is evident from the
description in the Lewis et al. (1985) paper of the uncontrolled sites as being strewn with
leaking capacitors with visibly leaking askarels. Thus the emissions from the uncontrolled
landfills were surely much greater than from the ToSCA landfill. At the emission rate of
the main vent (12 ng/s), a dispersion model predicted very low downwind concentrations of
4 x 10-6 to 1 x 10·1 ng/m3 --far lower than any of the measured ambient air concentrations.
To me, this is an indication that PCBs found in ambient air near the ToSCA site were
probably emanating from an area source, such as volatilization from contaminated soils.
Mr. Hirschhorn is speaking for a community of citizens who have a right to have their
concerns taken seriously. We know a lot more about the sources of PCBs and how to
measure them than we did in the early 1980s. Clearly, it would be beneficial to carry out
a subsequent investigation of PCBs in the region using today's greatly improved analytical
methodology. Such a study should include on-site and off-site measurements of PCBs in the
landfill vicinity, along the roadsides where PCBs were initially dumped, and in other regions
of the state for comparison. If such an investigation does indeed implicate the landfill,
corrective action should be swift. This is the best way to respond to the concerns of the
community, and I believe that Mr. Hirschhorn would agree. It is unfortunate, however, that
he seems more intent on fixing blame than getting on with it.
Si rely~,~/
(,U,~4 ~~ erry f;. 1 leman
Rese rch Scientist
(
I . References
Billings, W.N. and T.F. Bidleman, 1980. Field comparison of polyurethane foam and Tenax-
GC resin for high volume air sampling of chlorinated hydrocarbons. Environ. Sci. Technol.
14:, 679-683.
Harrad, S.J., A. Sewart, R.E. Alcock, R. Boumphrey, V. Burnett, R. Duarte-Davidson, C.
Halsall, G. Sanders, K.S . Waterhouse, S.R. Wild and K.C. Jones (1994). Polychlorinated
biphenyls in the British environment: sinks, sources and temporal trends. Environ. Pollut.
85: 131-146.
Lewis, R.G., B.E. Martin, D.L. Sgontz and J.E. Howes, Jr., 1985. Measurement of fugative
atmospheric emissions of polychlorinated biphenyls from hazardous waste landfills. Environ.
Sci. Technol. 19:, 986-991.
Macleod, K.E. and R.G . Lewis, 1980. Measurement of contamination from PCB sources.
Sampling and Analysis of Toxic Organics in the Atmosphere. ASTM Special Pub. 721, 56-
69.
Murphy, T.J., L.J. Formanski, B. Brownawell and J.A. Meyer, 1985. Polychlorinated biphenyl
emissions to the atmosphere in the Great Lakes region. Municipal landfills and incinerators.
Environ. Sci. Technol. 19:, 942-946.
Harner, T. D. Mackay and K.C . Jones, 1995. Model of the long-term exchange of PCBs
between soil and the atmosphere in the southern U.K. Environ. Sci. Technol. 29:, 1200-
1209.
Hoff, R.M ., W.M.J. Strachan, C.W. Sweet, C.H. Chan, M. Shackleton, T.F . Bidleman, K.A .
Brice, D.A. Burniston, S. Cussion, D.F. Gatz, K. Harlin and W.H. Schroeder, 1996.
Atmospheric deposition of toxic chemicals to the Great Lakes: a review of data through
1994. Atmos. Environ. 30: 3505-3527.
Hornbuckle, K.C., J.D. Jeremiason, C.W. Sweet and S.J. Eisenreich, 1994. Seasonal
variations in air-water exchange of polychlorinated biphenyls in Lake Superior. Environ. Sci.
Technol. 28: 1491-1501.
Hornbuckle, K.C ., C.W. Sweet, R.F. Pearson, D.L. Swackhamer and S.J. Eisenreich, 1995.
Assessing annual air-water fluxes of PCBs in Lake Michigan. Environ. Sci. Technol. 29:
869-877.
Jeremiason, J.D., K.C. Hornbuckle and S.J. Eisenreich, 1994. PCBs in Lake Superior,
1978-1992: Decreases in water concentration reflect loss by volatilization. Environ. Sci.
Technol. 28: 903-913.
Johnson, N.D., M.T. Scholtz, V. Cassaday, K. Davidson and D. Ord, 1992. MOE Toxic
Chemical Emission Inventory for Ontario and Eastern North America, final report to Air
Resources Branch, Ontario Ministry of the Environment, report no. P.92-T61-5429/OG.
Jones, K.C., A.E. Johnston and S.P. McGrath, 1995. The importance of long-and short-
term air-soil exchange of organic contaminants. lnternat. J. Environ. Anal. Chem. 59: 167-
178.
,
TERRY F. BIDLEMAN
Atmospheric Environment Service
4905 Dufferin Street, Downsview, Ontario, Canada M3H 5T4
Phone: [phone] FAX: [phone]
EDUCATION
B.Sc. 1964. Chemistry, Ohio University, Athens, OH, U.S.A.
Ph .D. 1970. Analytical Chemistry, University of Minnesota, Minneapolis, MN, U.S.A.
Postdoctoral 1970-72. Dalhousie University, Halifax, Nova Scotia, Canada.
POSITIONS
1994-present: Adjunct Professor, Dept. of Chemical Engineering & Applied Chemistry,
University of Toronto, Toronto, Ontario, Canada.
1992-present: Research Scientist, Atmospheric Environment Service, Environment
Canada, Downsview, Ontario, Canada.
1975-92: Professor (1989-92), Associate Professor (1981-89), Assistant Professor
(1975-81 ), Department of Chemistry and Biochemistry , and Marine Science Program,
University of South Carolina, Columbia, SC, U.S.A.
1983-84: Visiting Scientist, Swedish Environmental Protection Board, Solna, Sweden.
1972-75: Research Associate, Dept. of Food Science, Technology, Nutrition and
Dietetics, University of Rhode Island, Kingston, RI , U.S.A.
PROFESSIONAL SOCIETIES
American Chemical Society (Div. of Environmental Chemistry and Agrochemicals),
Society for Environmental Toxicology and Chemistry (SETAC), International
Association for Great Lakes Research.
, . .. I .
SELECTED PUBLICATIONS (out of 109)
Bidleman, T.F., Olney, C.E., 1974. Chlorinated hydrocarbons in the Sargasso Sea
atmosphere and surface water. Science 183: 516-518.
Bidleman, T.F., Matthews, J.L., Olney, C.E., Rice, C.P., 1978. Separation of
polychlorinated biphenyls, chlordane and p,p'-DDT from toxaphene by silicic acid column
chromatography. J. Assoc. Offic. Anal. Chem . 61 : 820-828.
Billings, W.N ., Bidleman, T.F., 1980. Field comparison of polyurethane foam and Tenax-
GC resin for high volume air sampling of chlorinated hydrocarbons. Environ. Sci. Technol.
14:, 679-683.
Bidleman, T.F., 1985. High volume collection of organic vapors using solid adsorbents.
In : J.F. Lawrence (ed.), Trace Analysis, Vol. 4, Academic Press, NY, 51-100.
Bidleman, T.F., 1988. Atmospheric processes: wet and dry deposition of organic
compounds are controlled by their vapor-particle partitioning. Environ. Sci. Technol. 22:
361-367.
Foreman, W.T., Bidleman, T.F., 1990. Semivolatile organic compounds in the ambient
air of Denver, Colorado. Atmos. Environ. 24A, 2405-2416.
Hinckley, D.A., Bidleman, T.F., Foreman, W.T., Tuschall , J.R., 1990. Determination of
vapor pressures for nonpolar and semipolar organic compounds by capillary gas
chromatography. J. Chem. Eng. Data 35, 232-237.
Bidleman, T.F., Patton, G.W., Hinckley, D.A., Walla, M.D., Cotham, W.E., Hargrave, B.T.,
1990. Chlorinated pesticides and polychlorinated biphenyls in the atmosphere of the
Canadian Arctic. In: Kurtz, D.A. (ed .) Atmospheric Transport of Pesticides, Lewis
Publishers, Chelsea, Michigan, 332-387.
Falconer, R.L., Bidleman, T.F., 1994. Vapor pressures and predicted particle/gas
distributions of polychlorinated bi phenyl congeners as functions of temperature and ortho-
chlorine substitution. Atmos. Environ. 28, 547-554.
Falconer, R.L., Bidleman, T.F., 1995. Preferential sorption of non-and mono-ortho
polychlorinated biphenyls to urban aerosols. Environ. Sci. Technol. 29: 1666-1673.
Cotham, W.E., Bidleman, T.F., 1995. Polycyclic aromatic hydrocarbons and
polychlorinated biphenyls in air at an urban and rural site near Lake Michigan. Environ.
Sci. Technol. 29 : 2782-2789.
Harner, T. and Bidleman, T.F., 1996. Measurement of octanol-air partition coefficients
for polychlorinated biphenyls. J. Chem. Eng. Data 41 : 895-899.