Markus Meili

Mercury in the Swedish environment : recent research on causes, consequences and corrective methods

ABSTRACTDuring the last decade a new pattern of Hg pollution has been discerned, mostly in Scandinavia and North America. Fish from low productive lakes, even in remote areas, have been found to have a high Hg content. This pollution problem cannot be connected to single Hg discharges but is due to more widespread air pollution and long-range transport of pollutants. A large number of waters are affected and the problem is of a regional character. The national limits for Hg in fish are exceeded in a large number of lakes. In Sweden alone, it has been estimated that the total number of lakes exceeding the blacklisting limit of 1 mg Hg kg-1 in 1-kg pike is about 10 000.The content of Hg in fish has markedly increased in a large part of Sweden, exceeding the estimate background level by about a factor of 2 to 6. Only in the northernmost part of the country is the content in fish close to natural values. There is, however, a large variation of Hg content in fish within the same region, which is basically due to natural conditions such as the geological and hydrological properties of the drainage area. Higher concentrations in fish are mostly found in smaller lakes and in waters with a higher content of humic matter.Since only a small percentage of the total flow of Hg through a lake basin is transferred into the biological system, the bioavailability and the accumulation pattern of Hg in the food web is of importance for the Hg concentrations in top predators like pike. Especially, the transfer of Hg to low trophic levels seems to be a very important factor in determining the concentration in the food web. The fluxes of biomass through the fish community appear to be dominated by fluxes in the pelagic food web. The Hg in the lake water is therefore probably more important as a secondary source of Hg in pike than is the sediment via the benthic food chain.Different remedy actions to reduce Hg in fish have been tested. Improvements have been obtained by measures designed to reduce the transport of Hg to the lakes from the catchment area, eg. wetland liming and drainage area liming, to reduce the Hg flow via the pelagic nutrient chains, eg. intensive fishing, and to reduce the biologically available proportion of the total lake dose of Hg, eg. lake liming with different types of lime and additions of selenium. The length of time necessary before the remedy gives result is a central question, due to the long half-time of Hg in pike.In general it has been possible to reduce the Hg content in perch by 20 to 30% two years after treatments like lake liming, wetland liming, drainage area liming and intensive fishing. Selenium treatment is also effective, but before this method can be recommended, dosing problems and questions concerning the effects of selenium on other species must be evaluated. Regardless how essential these kind of remedial measures may be in a short-term perspective, the only satisfactory long-term alternative is to minimize the Hg contamination in air, soil and water.Internationally, the major sources of Hg emissions to the atmosphere are chlor-alkali factories, waste incineration plants, coal and peat combustion units and metal smelter industries. In the combustion processes without flue gas cleaning systems, probably about 20 to 60% of the Hg is emitted in divalent forms.In Sweden, large amounts of Hg were emitted to the atmosphere during the 50s and 60s, mainly from chlor-alkali plants and from metal production. In those years, the discharges from point sources were about 20 to 30 t yr 1. Since the end of the 60s, the emission of Hg has been reduced dramatically due to better emission control legislation, improved technology, and reduction of polluting industrial production. At present, the annual emissions of Hg to air are about 3.5 t from point sources in Sweden.In air, more than 95% of Hg is present as the elemental Hg form, HgO0. The remaining non-elemental (oxidized) form is partly associated to particles with a high wash-out ratio, and therefore more easily deposited to soils and surface waters by precipitation.The total Hg concentration in air is normally in the range 1 to 4 ng m-3. In oceanic regions in the southern hemisphere, the concentration is generally about 1 ng m−3, while the corresponding figure for the northern hemisphere is about 2 ng m-3. In remote continental regions, the concentrations are mainly about 2 to 4 ng m−3.In precipitation, Hg concentrations are generally found in the range 1 to 100 ng L−1. In the Nordic countries, yearly mean values in rural areas are about 20 to 40 ng L−1 in the southern and central parts, and about 10 ng L−1 in the northern part. Accordingly, wet deposition is about 20 (10 to 35) g km−2 yr−1 in southern Scandinavia and 5 (2 to 7) in the northern part. Calculations of Hg deposition based on forest moss mapping techniques give similar values.The general pattern of atmospheric deposition of Hg with decreasing values from the southwest part of the country towards the north, strongly suggests that the deposition over Sweden is dominated by sources in other European countries. This conclusion is supported by analyses of air parcel back trajectories and findings of significant covariations between Hg and other long range transported pollutants in the precipitation. Apart from the long range transport of anthropogenic Hg, the deposition over Sweden may also be affected by an oxidation of elemental Hg in the atmosphere.Atmospheric Hg deposited on podzolic soils, the most common type of forest soil in Sweden, is effectively bound in the humus-rich upper parts of the forest soil. In the Tiveden area in southern Sweden, about 75 to 80% of the yearly deposition is retained in the humus layer, chemically bound to S or Se atoms in the humic structure. The amount of Hg found in the B horizon of the soils is probably only slightly influenced by anthropogenic emissions. In the deeper layers of the soil, hardly any accumulation of Hg takes place. The dominating horizontal flow in the soils takes place in the uppermost soil layers (0 to 20 cm) during periods of high precipitation and high groun water level in the soils. The yearly transport of Hg within the soils has been calculated to be about 5 to 6 g km−2.The specific transport of total Hg from the soil system to running waters and lakes in Sweden is about 1 to 6 g km−2 yr1. The transport of Hg is closely related to the transport of humic matter in the water. The main factors influencing the Hg content and the transport of Hg in run-off waters from soils are therefore the Hg content in soils, the transport of humic matter from the soils and the humus content of the water. Other factors, for example acidification of soils and waters, are of secondary importance. Large peatlands and major lake basins in the catchment area reduce the out-transport of Hg from such areas. About 25 to 75% of the total load of Hg of lakes in southern and central Sweden originates from run-off from the catchment area. In lakes where the total load is high, the transport from run-off is the dominating pathway.The total Hg concentrations in soil solution are usually in the range 1 to 50, in ground water 0.5 to 15 and in run-off and lake water 2 to 12 ng L−1, respectively. The variation is largely due to differences in the humus content of the waters. In deep ground water with a low content of humic substances, the Hg concentration is usually below 1 ng L−1.The present amount and concentrations of Hg in the mor layer of forest soils are affected by the total anthropogenic emissions of Hg to the atmosphere, mainly during this century. Especially in the southern part of Sweden and in the central part along the Bothnian coast, the concentrations in the mor layer are markedly high. In southern areas the anthropogenic part of the total Hg content is about 70 to 90%. Here, the increased content in these soils is mainly caused by long-range transport and emissions from other European countries, while high level areas in the central parts are markedly affected by local historical emissions, mainly from the chlor-alkali industry.When comparing the input/output fluxes to watersheds it is evident that the present atmospheric deposition is much higher than the output via run-off waters, on average about 3 to 10 times higher, with the highest ration in the southern parts of Sweden. Obviously, Hg is accumulating in forest soils in Sweden at the present atmospheric deposition rate and, accordingly, the concentrations in forest soils are still increasing despite the fact that the emissions of Hg have drastically been reduced in Sweden during the last decades. The increased content of Hg in forest soils may have an effect on the organisms and the biological processes in the soils. Hg is by far the most toxic metal to microorganisms. In some regions in Sweden, the content of Hg in soils is already today at a level that has been proposed as a critical concentration.To obtain a general decrease in the Hg content in fish and in forest soils, the atmospheric deposition of Hg has to be reduced. The critical atmospheric load of Hg can be defined as the load where the input to the forest soils is less than the output and, consequently, where the Hg content in the top soil layers and the transport of Hg to the surface waters start to decrease. A reduction by about 80% of the present atmospheric wet deposition has to be obtained to reach the critical load for Scandinavia.

The coupling of mercury and organic matter in the biogeochemical cycle — towards a mechanistic model for the boreal forest zone

In boreal forest lakes, high Hg concentrations in fish are common, even in remote areas. In this paper, the effects of atmospheric Hg pollution in Sweden are synthesized and related to a concept based on the strong interaction of Hg with biogenic matter (Hg/B). Based on this concept, a compartment model is developed to predict concentrations, pool sizes, flux rates and turnover times of Hg along the biogeochemical cycle, including atmosphere, forest soils, surface runoff, lake waters, and aquatic biota. The aim is to provide a conceptual framework, both for a comprehensive mechanistic model, and for predictions from readily available information, such as regional data on acid deposition, air temperature and surface runoff, and local data on the trophic status of lakes with respect to humus and nutrient concentrations. The model is in good agreement with observations from recent Swedish field studies in all compartments. It suggests a strong influence of climate on the susceptibility of soil and lake ecosystems in the boreal region to Hg contamination. The high Hg concentrations in fish from forest lakes can be largely attributed to the low productivity of both terrestrial and aquatic biota. The impact of historical point sources of Hg is considered, as well as the slow turnover of Hg in forest soils, both resulting in elevated fish Hg levels in humic lakes for centuries following atmospheric deposition.

Mercury net methylation in five tropical flood plain regions of Brazil: high in the root zone of floating macrophyte mats but low in surface sediments and flooded soils.

Mercury net methylation in five tropical flood plain regions of Brazil: high in the root zone of floating macrophyte mats, but low in surface sediments and flooded soils

Sources, concentrations and characteristics of organic matter in softwater lakes and streams of the Swedish forest region

18 Swedish forest lakes covering a wide range of dystrophy were studied in order to quantify and characterize the organic matter in the water with respect to origin (allochthonous or autochthonous), physical state (particulate or dissolved) and phosphorus content. Samples were collected repeatedly during a two-year period with unusually variable hydrological conditions. Water from three different depths and from tributaries was analysed with standard monitoring methods, including water colour, Secchi disk transparency, total organic carbon (TOC), CODCr, CODMn, total phosphorus and molybdate reactive phosphorus. Interrelationships were used to compare different methods and to assess the concentration and composition of organic matter. It is estimated that in remote softwater lakes of the Swedish forest region, autochthonous carbon is typically 200 g Pt m−3) the proportion can exceed 90%. Secchi depth readings were related similarly to organic matter from both sources and provided good estimates of TOC with a single optical measurement. Water colour was used to distinguish allochthonous and autochthonous matter. High concentrations of phosphorus were found in humic waters, most of it being molybdate reactive, and probably associated with humic matter rather than as dissolved free inorganic forms. CODMn yielded only 25–60% of TOC and appears to include mainly truly dissolved substances of low molecular weight.

Hg methylation in sediments and floating meadows of a tropical lake in the Pantanal floodplain, Brazil

Potential net 203Hg methylation was assayed in different substrates and conditions in Fazenda Ipiranga Lake, 30 km downstream from gold mining fields near Pocone, Pantanal, Brazil, during the dry season. Samples and acidified controls of surface sediments and roots of dominant floating macrophytes (Eichhornia azurea, Salvinia sp.) were incubated in situ for 3 days with approx. 43 ng Hg.g−1 (dry weight), added as 203HgCl2. Methylmercury (Me203Hg) was extracted in toluene and measured by beta counting. Net methylation was about 1% in sediments under floating macrophytes, both at an open lake site and at a littoral site. Parallel incubations of sulphate or molybdate amended samples suggest that sulphate reducing bacteria may be important Hg methylators at both sites, and that their activity is sulphate-limited in particular at the littoral site. In laboratory experiments, net methylation in the same sediments was highest at temperatures in the 33–45°C range but was completely inhibited at 55°C. NaCl addition had a strong inhibiting effect on net methylation. In an intact open-lake sediment core, spiked with 203Hg in the overlying water and incubated for 3 days, total 203Hg was detectable down to a depth of 14–16 cm, coinciding with the depth reached by the galleries of chironomid larvae present in the core. Swimming insects caused 203Hg penetration down to 4 cm. Me203Hg was detected only in the upper layers (0–2 cm) of the sediment, with concentrations reaching 0.47–0.75% of total Hg. This suggests an important role for bioturbation in the exchange of Hg and MeHg between sediment and water. Methylation was up to nine times more intense in floating macrophyte roots than in the underlying surface sediments: an average of 10.4% of added Hg was methylated in samples of Salvinia sp. roots during the 3-day incubation, and 6.5% in E. azurea roots. This adds to previous findings on the role of such macrophyte stands, a distinctive feature of tropical rivers and lakes, as potentially important sites for the production of highly available MeHg.

Mercury in the surface water of Swedish forest lakes —concentrations, speciation and controlling factors

Concentrations of total Hg and five operationally defined Hg species were determined in the surface water of 25 Swedish forest lakes of different type. Regional and seasonal variations were studied during the ice-free season of 1986. The concentration of total Hg was usually in the range of 2 to 10 μg m-3. Hg concentrations were highly correlated to the concentration of humic matter measured as water color. Hg concentrations were about twice as high in acidic lakes (pH 5) than in circumneutral lakes, which is attributed basically to the acidity of humic compounds acting as Hg carriers in boreal waters. Significant seasonal variations were caused by hydrological processes. During periods of high water flow, Hg concentrations increased dramatically, especially in humic lakes. Between spring and autumn, chemically reactive Hg compounds were gradually replaced by more inert species. Hg/C ratios were higher than in surface runoff from forest watersheds, indicating a significant impact of direct deposition of Hg on lake surfaces during summer. Regional differences were small despite differences in Hg contamination.

Fish mercury concentration in the Alto Pantanal, Brazil: influence of season and water parameters

The tropical flood plain Pantanal is one of the worlds largest wetlands and a wildlife sanctuary. Mercury (Hg) emissions from some upstream gold mining areas and recent findings of high natural Hg levels in tropical oxisols motivated studies on the Hg cycle in the Pantanal. A survey was made on total Hg in the most consumed piscivorous fish species from rivers and floodplain lakes in the north (Cáceres and Barão de Melgaço) and in the south part of Alto Pantanal (around the confluence of the Cuiabá and Paraguai rivers). Samples were collected in both the rainy and dry seasons (March and August 1998) and included piranha (Serrasalmus spp.), and catfish (Pseudoplatystoma coruscans, pintado, and Pseudoplatystoma fasciatum, cachara or surubim). There was only a small spatial variation in Hg concentration of the 185 analyzed fish samples from the 200 x 200 km large investigation area, and 90% contained total Hg concentration below the safety limit for regular fish consumption (500 ng g(-1)). Concentration above this limit was found in both Pseudoplatystoma and Serrasalmus samples from the Baia Siá Mariana, the only acid soft-water lake included in this study, during both the rainy and dry seasons. Concentration above this limit was also found in fish outside Baia Siá Mariana during the dry season, especially in Rio Cuiabá in the region of Barão de Melgaço. The seasonal effect may be connected with decreasing water volumes and changing habitat during the dry season. The results indicate that fertile women should restrict their consumption of piscivorous fishes from the Rio Cuiabá basin during the dry season. Measures should be implanted to avoid a further deterioration of fish Hg levels.

Relationship of mercury with aluminum, iron and manganese oxy-hydroxides in sediments from the Alto Pantanal, Brazil

Sediments from nine floodplain lakes in Pantanal were analyzed for a large-scale (300 km) survey of mercury (Hg) load in sediments and soils of the Alto Pantanal and to study the relationship between Hg and reactive aluminum, iron, and manganese oxy-hydroxides. The results were compared with the Hg content in river and stream sediments from the Poconé gold mining area, where Hg has been extensively used and still is in use. The results indicate that the Hg concentrations were elevated in river sediment close to the mining area in Bento Gomes river basin (average in the < 74-microm fraction 88.9 ng Hg g(-1) dry wt.; interquartile range 50.3-119.5), but there was no clear indication that the local Hg emissions have contaminated the remote floodplain lakes, where concentrations were surprisingly low (average in the < 74-microm fraction 33.2 ng Hg g(-1) dry wt. sediment; interquartile range 18.4-46.8), in particular when considering geochemical characteristics of the sediment. The sediment from the floodplain lakes contained less Hg-tot and more reactive iron oxy-hydroxides than soils from the Tapajós area in the Amazon basin. This resulted in a mass ratio between Hg and amorphous oxy-hydroxides of only 5 x 10(-6) for Hg-tot/Fe-oxa (interquartile range 3-7 x 10(-6).

The influence of humic substances on the speciation and bioavailability of dissolved mercury and methylmercury, measured as uptake by Chaoborus larvae and loss by volatilization.

The influence of dissolved humic substances (HS) on the bioavailability of dissolved inorganic and methyl mercury (Hg) was quantified by measuring the direct uptake of 203Hg in Chaoborus larvae using laboratory microcosms containing artificial freshwater. The animals were exposed individually in triplicate aquaria at 10 different concentrations of HS covering the whole range found in natural freshwaters (0-110 mg C l(-1)). Mercury-203 concentrations were monitored repeatedly in the same individuals and in their ambient water during up to 10 days. Near-steady state Hg concentrations in Chaoborus were usually reached within 5 days. The bioconcentration factor (BCF, direct uptake only) for the larvae in the absence of HS was 0.55+/-0.09 (S.E.) ml individual(-1) for inorganic Hg and 5.3+/-0.7 ml individual(-1) for methyl Hg, thus showing a 10-fold difference. Normalizing to the organic carbon content of the larvae yields a BCF(OC) in the absence of HS of 2.8+/-0.4 x 10(3) ml (gC)(-1) for inorganic Hg and 2.7+/-0.3 x 10(4) ml (gC)(-1) for methyl Hg. The uptake of both inorganic and methyl Hg decreased markedly with increasing concentration of HS. For inorganic Hg, the decrease in uptake was most pronounced at HS concentrations below 0.2 mg C l(-1). For methyl Hg, the relationship between uptake and log([HS]) was sigmoid, showing a reduction by > 90% when increasing HS concentrations from 1 to 50 mg C l(-1). Similar patterns were observed for losses of Hg from the water phase, mainly through volatilization. These results have implications for both the biouptake and the abiotic cycling of Hg in natural ecosystems and suggest that most dissolved inorganic Hg is bound to dissolved organic matter in most natural freshwaters, whereas dissolved methyl Hg is bound only in humic waters. Assuming that only free aqueous Hg is taken up by the organisms, the rather simple methodology employed here can be used for estimating distribution coefficients (K(OC)) for Hg between HS and water. In this study, the K(OC) values were 2.5+/-0.7 (S.E.) x 10(7) ml (gC)(-1) for inorganic Hg and 1.5+/-0.6 x 10(5) ml (gC)(-1) for methyl Hg. Values of similar magnitude were derived from observed losses of Hg from the water phase, supporting the assumption of an immobilization of both inorganic and methyl Hg by HS. The strong negative influence of dissolved HS on the bioavailability of both inorganic and methyl Hg in freshwater suggests that the high Hg levels often found in fish from humic lakes in the boreal forest zone cannot be explained alone by direct uptake of methyl Hg from the water phase into biota at low trophic levels.

Fluxes, pools, and turnover of mercury in Swedish forest lakes

In boreal forest lakes, high Hg concentrations in fish are common, even in remote areas. Data from recent Swedish surveys were synthesized to assess sources, sinks, fluxes and turnover rates of Hg in headwater lakes of different type, to determine and quantify controlling factors and their relative influence, and to discuss implications for the contamination of fish and potential remedial actions. In humic lakes, annual input of Hg is dominated by the transport from forest soils, whereas in clearwater lakes, direct deposition on the lake surface is often more important. Direct deposition is more likely to dominate during the growing season when the water discharge in forest streams is low. Sedimentation of Hg is largely controlled by the water residence time and is related to water quality. In clearwater lakes, most of the Hg load is deposited in the sediment, which is in contrast to humic lakes, and which partly explains the susceptibility of headwater lakes to atmospheric Hg pollution. The fish community contains about half or more of the methylmercury pool in the water column, and internal recycling in the food web may be important. However, only a minor fraction of the total annual Hg load to lakes is channeled through the fish community. As this allows large variations in the ecological fractionation and bioavailability of Hg, differences in Hg fluxes can only partly explain the wide range of Hg concentrations found in fish from different lakes. The annual Hg load to headwater lakes exceeds the total Hg pool in the water column by a factor of up to 20. Single remedial measures aiming at the removal of Hg from the water column are therefore likely to have little success. Local actions should aim primarily at reducing the bioavailability of the Hg entering the lakes and need to be repeated continuously.