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.
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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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