PROCEEDINGS OF 1995

CANADIAN MERCURY NETWORK WORKSHOP

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MERCURY IN LAKE AND MARINE SEDIMENTS FROM NORTHERN CANADA

W. L. Lockhart, P. Wilkinson, R. Hunt and R. Wagemann

Contaminants Research Section, Fisheries and Oceans Canada, 501 University Crescent, Winnipeg, Manitoba R3T 2N6

Introduction

     Many lakes in northern Canada produce fish with mercury contents
     higher than those recommended for consumption by Health Canada.
     (Health Canada has recommended that mercury in fish sold
     commercially not exceed 0.5 ppm (wet wt) and that the mercury not
     exceed 0.2 ppm in subsistence settings where people consume a lot of
     fish (Health & Welfare Canada, 1978; 1984). There is wide variation
     in natural, geological mercury throughout Canada (Painter et al.,
     1994). At the same time, there is evidence that mercury has been
     increasing in the atmosphere of the northern hemisphere at a rate of
     over 1 per cent per year (Slemr & Langer, 1992), and that mercury
     inputs to lakes in much of central North America have increased as a
     result of atmospheric fallout (Swain et al., 1992). The question in
     the North, then, is the extent to which fish in northern lakes are
     being influenced by natural mercury and by mercury from atmospheric
     pollution.
     
     The only approach we are aware of which might offer insight into the
     question of natural vs. atmospherically transported mercury in
     northern Canada is the record preserved in natural archives in
     integrating media like lake sediments, glacial cores and peat bogs.
     In instances where mercury in recent (last half century or so) media
     exceed those in older media, we may infer that the increase has been
     caused by increased loadings of mercury. This requires the
     assumption that mercury moves very little or not at all after it has
     been deposited. Many studies of lake sediments have been studied and
     most of them from central North America show a basal period with low
     mercury before the present century with a rapid increase in mercury
     during the present century followed by a very recent decline. This
     pattern has been derived as a world summary of the content of heavy
     metals in cores by Valette-Silver, 1992. We opted to examine lakes
     in northern Canada in efforts to estimate current fluxes of mercury
     to them, and to set those inputs in their appropriate historical and
     geological settings.
     
     Methods
     
     Lakes from northwestern Ontario north to the high arctic islands and
     west to the southern Yukon have been sampled since 1986 (Lockhart et
     al., 1993). In addition several cores have been obtained from Hudson
     Bay on the cruises of C.S.S. Hudson in 1993 and M.V. Fogo Isle in
     1993. In lakes, we have usually collected cores late in the winter
     to take advantage of ice as a working platform. Two types of corers
     have been used in lakes, one using circular plastic tubes 10 or 16
     cm in diameter and a larger stainless steel box corer. For cores in
     Hudson Bay and Lake Winnipeg, a large, oceanographic box corer was
     used to collect large boxes of sediment and these were cored by
     pushing 10-cm plastic core tubes into them on the deck of the ship.
     Cores were sliced into either 1-cm or 0.5-cm slices in the field
     just after collection and individual slices were sealed into
     Whirlpak bags. They were kept at as near as possible to 4oC until
     analyzed. Normally slices were analyzed for lead-210 and cesium-137
     before proceeding to more extensive analysis. If the lead-210 showed
     a down-core profile approximating exponential decay, and the
     cesium-137 showed a peak below the surface, the core was accepted as
     one worth further analysis. Periods of deposition of those slices
     with excess lead-210 were estimated by several methods, sometimes
     using mixing models kindly supplied by Dr. John Robbins (NOAA, Ann
     Arbor, MI). Mercury in samples of freeze-dried material from each
     slice was measured using flameless atomic absorption
     spectrophotometry following digestion with aqua regia.
     
     Results and Discussion
     
     The profile of mercury in sediment from Lake 375 from the Experiment
     Lakes Area is presented in Figure 1.

[IMAGE]

     Figure 1. Mercury in slices of sediment from Lake 375, Experimental
     Lakes Area, Northwestern Ontario (Adapted from Lockhart et al.,
     1993).
     
     The results from other lakes in northwestern Ontario were similar,
     showing lower concentrations of mercury in deep slices than in those
     near the sediment-water interface. Three cores have been analyzed
     from Trout lake and they showed a remarkable range of values,
     although the basic shape showing increases in upper slices was
     present in all of them. Further north, lakes on the west shore of
     Hudson Bay showed a similar pattern as did two lakes in Cornwallis
     Island. Two lakes even further north (Buchanan Lake on Axel Heiberg
     Island and Lake Hazen on northern Ellesmere Island) showed no
     obvious pattern but both of these cores were extensively mixed as
     judged by the lead-210 profiles. In the western NWT and southern
     Yukon the increases in mercury in the upper slices were much less
     striking.
     
     In each lake we have tried to estimate the tendency of the core site
     to focus sediments so that the core represents an accumulation from
     more area than its actual area. This has been done using the flux of
     lead-210 at the site and comparing it either to the flux estimated
     from soil samples within the drainage or to the flux expected based
     on the latitude of the site. Using this factor to calculate focusing
     factors, the concentrations of mercury in the top and bottom slices
     have been converted to estimates of fluxes calculated from the
     product of mercury concentration and sedimentation rate. The fluxes
     have then been adjusted by the focusing factors and these new
     estimates of corrected fluxes have been compared for tops and
     bottoms of cores. The flux at the top is taken as a measure of the
     total net mercury flux, comprising contributions from natural and
     anthropogenic sources, and the flux at the bottom is taken as a
     measure of the natural, geological flux. The difference in these is
     taken as the anthropogenic contribution. The results of these
     calculations are shown in Figure 2. The pattern suggests that
     mercury in lakes in northwestern Ontario and in the eastern NWT
     originates mainly from anthropogenic sources while that in the
     western NWT and Yukon Territory originates mainly from natural
     sources.
     
     [IMAGE] Recently the above interpretation of core profiles (and of
     other indications that anthropogenic sources exist) has been
     challenged (Rasmussen, 1994). It has been suggested that natural
     geochemical gradients rather than increases in deposition result in
     mercury profiles which show increased mercury in the upper slices.
     One case which offers a test of this is that of Clay Lake in
     northwestern Ontario. This lake received mercury from a chlor-alkali
     plant until 1969 and a core taken in 1971 showed the peak of mercury
     at the surface of the sediments. A second core taken in 1978 showed
     the peak a few cm deeper and a third core taken in 1995 showed the
     peak a few cm deeper yet. This series of cores indicated that the
     mercury did not move to the surface in response to post-depositional
     processes but rather became buried deeper and deeper. Similar
     results from a chlor-alkali plant in eastern Canada were reported by
     Smith and Loring (1981).
     
     Conclusions
     
     We conclude that cores can and often do preserve records of changing
     inputs of mercury and that a regional pattern of mercury impacts
     exists in northern Canada with eastern sites influenced more by
     anthropogenic sources of mercury than western sites.
     
     References
     
     1. Health Welfare Canada. 1978. Methylmercury in Canada. Exposure of
     Indian and Inuit Residents to Methylmercury in the Canadian
     Environment. 200 pgHealth and Welfare Canada, Medical Services
     Branch.
     
     2. ____. 1984. Methylmercury in Canada. Exposure of Indian and Inuit
     Residents to Methylmercury in the Canadian Environment. 164 pgHealth
     and Welfare Canada, Medical Services Branch.
     
     3. Lockhart, W. L., P. Wilkinson, B. N. Billeck, G. J. Brunskill, R.
     V. Hunt, and R. Wagemann. 1993. Polycyclic Aromatic Hydrocarbons and
     Mercury in Sediments From Two Isolated Lakes in Central and Northern
     Canada. Wat. Sci. Tech. 28, no. 8-9: 43-52.
     
     4. Painter, Scott, Eion M. Cameron, Rod Allan, and Jeremy Rouse.
     1994. Reconnaissance Geochemistry and Its Environmental Relevance.
     J. Geochem. Explor. 51: 213-46.
     
     5. Rasmussen, Pat E. 1994. Current Methods of Estimating Atmospheric
     Mercury Fluxes in Remote Areas. Environ. Sci. Technol. 28, no. 13:
     2233-41.
     
     6. Slemr, F, and E. Langer. 1992. Increase in Global Atmospheric
     Concentrations of Mercury Inferred From Measurements Over the
     Atlantic Ocean. Nature 355: 434--437.
     
     7. Smith, John M., and Douglas H. Loring. 1981. Geochronology for
     Mercury Pollution in the Sediments of the Saguenay Fjord, Quebec.
     Environ. Sci. Technol. 15: 944-51.
     
     8. Swain, Edward B., Daniel R. Engstrom, Mark E. Brigham, Thomas A.
     Henning, and Patrick L. Brezonik. 1992. Increasing Rates of
     Atmospheric Mercury Deposition in Midcontinental North America.
     Science 257: 784-7.
     
     9. Valette-Silver, Nathalie. 1992. Historical Reconstruction of
     Contamination Using Sediment Cores: a Review, Technical Memorandum
     NOS/ORCA 65. NOAA, Rockville, Maryland.

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