Total mercury and methyl mercury levels in British estuarine sediments—II

Results from a large-scale study of Mersey Estuary, U.K. sediments are discussed. Correlations are drawn between total mercury, methyl mercury, silt and organic carbon contents of the sediments. These correlations are compared to earlier results, and coefficients range from 0.55 to 0.94.The influence of redox potential and the sulphide content of a sediment on both the ambient level of methyl mercury and the extent of a growth and decay effect in methyl mercury levels in sediments after sampling is discussed. The results show that in an esturary (Clyde, U.K.) where sulphide levels vary from 0 to 8.5 mg g⁻¹ there is a maximum level of methyl mercury found at approximately 5.8 mg g⁻¹ sulphide, suggesting that sulphide concentrations may control methyl mercury levels.     

Mercury distribution in a polluted marine area, ratio of total mercury, methyl mercury and selenium in sediments, mussels and fish

Total mercury, methyl mercury and selenium concentrations were determined in sediments and organisms from the Kaštela bay in the Central Adriatic, polluted with inorganic mercury by a chlor-alkali plant. Sediments and mussels (Mytilus galloprovincialis) contained high total mercury concentrations, especially in the vicinity of the source of pollution. The percentage of mercury in the methyl form increased from surface sediments (up to 1.37%) to the edible parts of mussels (0.1–27%, negatively correlated with total mercury concentrations) and to the fish, in which methyl mercury accounted for most of the mercury in the muscle tissue.     

Mercury distribution in a polluted marine area. Concentrations of methyl mercury in sediments and some marine organisms

Methyl mercury concentrations were measured in various parts of Kastela Bay in the Central Adriatic, which is polluted with inorganic mercury. The values obtained, on a wet weight basis, for sediments were from 2 to 20 micrograms methyl mercury kg-1; for the mussel Mytilus galloprovincialis from 10 to 110 micrograms kg-1; and for various species of fish from 102 to 1448 micrograms kg-1. The methyl mercury content increases by three orders of magnitude going from sediment to fish. The distribution of methyl mercury in relation to the depth of the sediment and the different organs of the mussel is presented. On the basis of the results obtained, it may be concluded that non-migratory species of fish are more suitable for methyl mercury monitoring in the marine environment than are sediment and mussels.     

Distribution of total and methyl mercury in sediments along Steamboat Creek (Nevada, USA)

In the late 1800s, mills in the Washoe Lake area, Nevada, used elemental mercury to remove gold and silver from the ores of the Comstock deposit. Since that time, mercury contaminated waste has been distributed from Washoe Lake, down Steamboat Creek, and to the Truckee River. The creek has high mercury concentrations in both water and sediments, and continues to be a constant source of mercury to the Truckee River. The objective of this study was to determine concentrations of total and methyl mercury (MeHg) in surface sediments and characterize their spatial distribution in the Steamboat Creek watershed. Total mercury concentrations measured in channel and bank sediments did not decrease downstream, indicating that mercury contamination has been distributed along the creek's length. Total mercury concentrations in sediments (0.01-21.43 microg/g) were one to two orders of magnitude higher than those in pristine systems. At 14 out of 17 sites, MeHg concentrations in streambank sediments were higher than the concentrations in the channel, suggesting that low banks with wet sediments might be important sites of mercury methylation in this system. Both pond/wetland and channel sites exhibited high potential for mercury methylation (6.4-30.0 ng g(-1) day(-1)). Potential methylation rates were positively correlated with sulfate reduction rates, and decreased as a function of reduced sulfur and MeHg concentration in the sediments. Potential demethylation rate appeared not to be influenced by MeHg concentration, sulfur chemistry, DOC, sediment grain size or other parameters, and showed little variation across the sites (3.7-7.4 ng g(-1) day(-1)).     

Bioaccumulation of mercury in benthic communities of a river ecosystem affected by mercury mining

The presence of mercury in the river Idrijca (Slovenia) is mainly due to 500 years of mercury mining in this region. In order to understand the cycling of mercury in the Idrijca ecosystem it is crucial to investigate the role of biota. This study is part of an ongoing investigation of mercury biogeochemistry in the river Idrijca, focusing on the accumulation and speciation of mercury in the lower levels of the food chain, namely filamentous algae, periphyton and macroinvertebrates. Mercury analysis and speciation in the biota and in water were performed during the spring, summer and autumn seasons at four locations on the river, representing different degrees of mercury contamination. Total (THg) and methyl mercury (MeHg) were measured. The results showed that the highest THg concentrations in biota correlate well with THg levels in sediments and water. The level of MeHg is spatially and seasonally variable, showing higher values at the most contaminated sites during the summer and autumn periods. The percentage of Hg as MeHg increases with the trophic level from water (0.1-0.8%), algae (0.5-1.3%), periphyton (1.6-8.8%) to macroinvertebrates (0.1-100%), which indicates active transformation, accumulation and magnification of mercury in the benthic organism of this heavily contaminated torrential river.     

Atmospheric mercury in Norway: contributions from different sources

The environmental loadings of national Norwegian mercury emissions compared to the loadings of atmospheric long range transported mercury have been estimated using national emission data and EMEP model data. The results indicate that atmospheric long-range transport to Norway is somewhat larger than the national Norwegian emissions of mercury. Atmospheric deposition of mercury has been studied using data from Norwegian monitoring programs on mercury in precipitation, mosses, natural surface soils, and lake sediments. Precipitation data show no significant time trend during 1990-2002, whereas moss samples show similar concentrations from 1985 to 1995, but a 30% decrease from 1995 to 2000. Concentrations of mercury in peat cores and reference sediments indicate that the current mercury levels measured in surface sediments, surface soils and mosses at background sites in Norway are substantially affected by long-range atmospheric transport.     

Horizontal and vertical variability of mercury species in pore water and sediments in small lakes in Ontario

Mary Lake, St. George Lake, and Philips Lake are located in the Greater Toronto Area, Ontario, Canada. These lakes are relatively small and have no direct inflow and outflow channels. Mercury (Hg) input to the lakes comes mainly from atmospheric deposition. Sediment cores from the points of the maximum lake depth and surface sediment samples from the points of maximum lake depth to the bank of each lake were collected in October 2005. Total and methyl mercury concentrations in the pore water and sediments of these samples were determined. In these small lakes with high organic content, there was no correlation between organic content and total mercury (THg) in the samples throughout the entire sediment cores while strong positive correlation between these two parameters was observed in all the surface sediments. Compared with typical methylmercury (MeHg) depth-profiles of sediment cores in other studies, where MeHg concentrations and methylation rates decreased sharply with increasing depth, MeHg distributions in the sediment cores in this study showed that MeHg might have been produced not only in the upper sediment but also in the deeper sediments, which resulted in a larger MeHg reservoir in the sediment. Organic matter, to some extent, affected MeHg distributions in the samples throughout the entire sediment cores. Concentrations of MeHg in all the surface sediments, however, were not controlled by organic matter, whereas they were largely a function of water column depths. Total mercury concentrations in pore water were relatively homogenous in both the sediment cores and surface sediment while MeHg in pore water generally deceased with increasing depth in the sediment cores and increasing distance from the centre of the lakes in surface sediments. Methylmercury contributed 1% to 76% of THg in the pore water samples. Concentrations and distributions of MeHg in overlying water and sediment-surface water in Mary Lake and St. George Lake suggested that both in situ production of MeHg in lake water and the release of MeHg from sediment contributed to high MeHg in deep anoxic water.     

Climate induced thermocline change has an effect on the methyl mercury cycle in small boreal lakes

We conducted a whole-lake experiment by manipulating the stratification pattern (thermocline depth) of a small polyhumic, boreal lake (Halsjärvi) in southern Finland and studying the impacts on lake mercury chemistry. The experimental lake was compared to a nearby reference site (Valkea-Kotinen Lake). During the first phase of the experiment the thermocline of Halsjärvi was lowered in order to simulate the estimated increase in wind speed and in total lake heat content (high-change climate scenario). The rate of methyl mercury (MeHg) production during summer stagnation (May-August) was calculated from water profiles before the treatment (2004), during treatment (2005, 2006) and after treatment (2007). We also calculated fluxes of MeHg from the epilimnion and from the hypolimnion to the sediments using sediment traps. Experimental mixing with a submerged propeller caused a 1.5-2 m deepening of the thermocline and oxycline. Methyl mercury production occurred mostly in the oxygen free layers in both lakes. In the experimental lake there was no net increase in MeHg during the experiment and following year; whereas the reference lake showed net production for all years. We conclude that the new exposed epilimnetic sediments caused by a lowering of the thermocline were a major sink for MeHg in the epilimnion. The results demonstrate that in-lake MeHg production can be manipulated in small lakes with anoxic hypolimnia during summer. The climate change induced changes in small boreal lakes most probably affect methyl mercury production and depend on the lake characteristics and stratification pattern. The results support the hypothesis that possible oxygen related changes caused by climate change are more important than possible temperature changes in small polyhumic lakes with regularly occurring oxygen deficiency in the hypolimnion.     

Discovery of methyl mercury compound in dry batteries

The mercury compounds used in dry cell batteries are inorganic mercurials. This report clarifies the possible formation of methyl mercury compounds in the contents of batteries obtained on the market. Using gas chromatography-mass spectrometry it was confirmed that the substance extracted from the ingredients is methyl mercury chloride.     

Isolation of mercury resistant bacteria and influence of abiotic factors on bioavailability of mercury -- a case study in Pulicat Lake North of Chennai, South East India

Pulicat Lake sediments are often severely polluted with mercury compounds and other toxic heavy metals. Several mercury-resistant bacteria were isolated and identified from the sediments and all the isolates exhibited broad spectrum resistance (both organic and inorganic mercuric compounds). Mercury volatilization showed that four of the isolated Bacillus cereus strains were able to reduce water soluble ionic form of mercury into volatile form via the well known enzymatic reduction. The effect of increasing concentration of mercuric chloride and phenyl mercuric acetate in the growth of this mercury reducing strain was also determined. To study the native physico-chemical parameters, which influence the bioavailability of mercury to bacteria in Pulicat Lake ecosystem, a total of 60 water and 30 sediment samples were collected and analyzed for pH, temperature, dissolved oxygen, salinity, nitrate, nitrite, silicate, phosphate, organic matter and organic carbon. Increased levels of phosphate, nitrite, nitrate, silicate, organic matter and organic carbon during the post monsoon reduce the bioavailability of mercury by forming complexes which may increase the concentration of mercury in the sediments during post monsoon.     

Tests of the fidelity of lake sediment core records of mercury deposition to known histories of mercury contamination

There has been recent controversy over the discrimination between natural and anthropogenic loadings of mercury to lakes. Sediment core profiles have been interpreted as evidence that inputs to lakes have increased. Some investigators have argued, however, that mercury may be sufficiently mobile in sediments to generate profiles that are misinterpreted as historical records. This argument can be tested where the histories of inputs of mercury are known independently from other kinds of information. We have such cases in Canadian lakes and we have been able to assemble sediment core records for comparison with known source histories. Three cases are represented by Clay Lake in Ontario where the source was a chlor-alkali plant with a known history of mercury discharges, Giauque Lake in the Northwest Territories where mercury was used at a gold mine to extract gold from ore, and Stuart Lake in British Columbia where a mercury mine operated for a known period at Pinchi Lake, the lake immediately upstream from Stuart Lake. In these cases lake sediment cores were dated using lead-210 and cesium-137 and then slices were analysed for mercury. The histories of mercury deposition derived from the cores agreed well with the known histories of inputs.     

The poison chain for mercury in the environment

The toxic effects of mercury in specific population groups, for example following occupational exposure or therapeutic application, has long been known, but mercury as a general environmental hazard has followed comparitively recent technological development. Contamination with both inorganic mercury and organic mercury compounds has resulted from industrial waste and from the use of the latter compounds as fungicides. Deposited eventually in rivers and lakes, this has led to raised levels of mercury in fish. Under appropriate conditions, methylation of mercury may occur in the natural environment, converting less toxic inorganic and aryl mercury compounds into the more toxic alkyl mercury form. In certain predominantly fish eating populations this has led to an increase in the body burden for organic mercury, resulting in localized outbreaks of methyl mercury poisoning. Raised levels of mercury in eggs and bird tissues have resulted from feeding on mercury contaminated fish and on organomercury treated seed. This has contributed to a reduction in some species of birds in certain areas. In addition to the direct toxic action of mercury, limited evidence suggests that methyl mercury compounds may possibly exert mutagenic and teratogenic effects, at levels below those usually associated with poisoning. Methyl mercury concentration should be monitored in exposed groups and where this is raised, epidemiological studies performed to evaluate a possible hazard.     

Abiotic methylation of mercury in the aquatic environment

Methylation of inorganic mercury in the aquatic environment has been considered to be largely the result of biological processes, primarily involving sulfate-reducing bacteria. However, these processes cannot account for all of the methylmercury that is formed naturally. A growing body of evidence suggests that chemical reactions represent another possible pathway for mercury methylation in the aquatic environment. In order to assess the abiotic contribution to mercury methylation in the water column, and specifically the conditions under which this contribution may be significant, the current state of knowledge about environmentally significant methylation reactions is reviewed. Results of our laboratory-based investigations of aqueous mercury reactions with some potential methyl donors, including MeCo(dmg)(2)(H2O), a simple model for methylcobalamin, various methyltin compounds and methyl iodide, are presented. In each reaction, the yield of methylmercury and the rate of methylation depend strongly on environmental factors such as pH, temperature, and the presence of complexing agents, especially chloride.     

Calculation of the mercury accumulation in the Idrijca River alluvial plain sediments

From the historic literature on the Idrija mercury mine, it is evident that part of the smelting and mining waste was dumped into the Idrijca River. This waste was transported downstream during floods. The amount of mercury which has accumulated in the alluvial sediments of the Idrijca River until the present was studied. Mapping of Holocene river terraces of the Idrijca River was performed in order to estimate the volume of the alluvial sediment. For the purpose of the assessment of the mercury concentration, we sampled the alluvial sediments on different levels and performed an analysis of variance. The greatest variability is between the floodplain and terraces inside the same alluvial plain. Considering this fact, which determined the methodology employed for calculation, we estimated that about 2029 tons of mercury is stored in the Idrijca River alluvial sediments.     

A preliminary study of mercury contamination in the surface soil and river sediment of the Roscio District, Bolivar State, Venezuela

The present study constitutes a comparison of mercury in surface soil and river sediments of a contaminated and an uncontaminated area of Venezuela. In the contaminated area, gold prospectors have been using mercury to separate gold from auriferous sand and rock powders for many years. The baseline level of mercury in the river sediments of the uncontaminated area (Manzanares River, Sucre State) was 0.06 micrograms g-1, while in the contaminated area in the Roscio District of Bolivar State the concentration varied from 0.12 to 129 micrograms g-1. In the river sediments the average level of mercury was 0.71 micrograms g-1 and in the surface soil of the working areas 37 micrograms g-1, which shows a significant increase in the mercury level in the contaminated areas. This high level of mercury in the soil and sediments constitutes a serious risk to public health in the contaminated area, where the local people use the water for drinking and other domestic purposes; moreover, they also consume fish from these rivers.     

Lead, cadmium, mercury and selenium in Greenland marine biota and sediments during AMAP phase 1

Lead, cadmium, mercury and selenium levels in the Greenland marine environment from the first phase of the AMAP are presented. Samples were collected in 1994-1995 covering four widely separated regions in Greenland. Samples included sediments, soft tissue of blue mussel; and liver of polar cod, shorthorn sculpin, glaucous gull, Iceland gull and ringed seal. Concentrations of lead were found to increase with the size of blue mussel, but not with the age of gulls or ringed seal. Both cadmium and mercury concentrations were found to increase with the size/age of all species. Selenium concentrations decreased with increasing size of blue mussel, but increased with the age of gulls and ringed seal. Element levels found are within the range of those found in previous studies in Greenland. Relative to global background levels, lead levels must be considered low, whereas levels of cadmium, mercury and selenium in Greenland marine biota are high. Significant differences in element levels in sediments and biota among regions in Greenland were seen in several cases. There was a tendency for the highest lead and mercury concentrations to be found in east Greenland, whereas the highest cadmium concentrations were found in central west Greenland. However, the geographical differences among the media did not show a consistent pattern.     

Potential effects of forest fire and storm flow on total mercury and methylmercury in sediments of an arid-lands reservoir

A study was conducted from July 1995 to June 1996 to examine the spatial and temporal changes of mercury concentrations in sediments of an arid-lands reservoir. Prior to the first sample collection in July, a forest fire burned 2930 ha of mixed conifer and ponderosa pine in the watershed of Caballo Reservoir in south-central New Mexico. The fire was eventually extinguished by summer rains and storm runoff resulting in the mobilization and transport of charred vegetative material into an intermittent tributary (Palomas Creek) that drains the watershed into Caballo Reservoir. Concentrations of total mercury (THg), monomethlymercury (MMHg), and total organic carbon (TOC) in surficial sediments revealed fire, followed by storm runoff, enhanced the transport of mercury and organic matter to the reservoir. Concentrations of THg in sediments increased from 7.5 etag/g in July to 46.1 etag/g by November 1995 at one site (Palomas) nearest the outflow of Palomas Creek. No other spatial or temporal trends were observed for THg at other sites throughout the remainder of the study. Concentrations of MMHg in sediments at the Palomas site increased from 0.428 etag/g in July to 12.46 etag/g by October 1995 compared to concentrations in sediments at the remaining sites which ranged from 0.11 to 1.50 etag/g throughout the study. The ratio of MMHg to THg (a gross index of methylation activity) was greatest in sediments from the Palomas site (5.4-33.8%) compared to the remaining sites (0.01-3.60%). The ratio was mirrored by elevated TOC in sediments at the Palomas site (2.5-11.8%) that remained elevated throughout the study. Fire and subsequent late-summer rains may have had a twofold effect on mercury concentrations in Caballo Reservoir. The storm-driven runoff following the forest fire carried mercury complexed to organic matter which resulted in elevated levels of mercury as well as providing a carbon source for microbial methylation processes in sediment.     

Three-dimensional modelling of mercury cycling in the Gulf of Trieste

The Gulf of Trieste (Northern Adriatic) is subject to mercury pollution from a former mercury mine in Idrija, located along a river which transports mercury-contaminated sediments into the Gulf. Concentrations in suspended and bottom sediments are up to two orders of magnitude higher than in the central and southern Adriatic. Extensive research has been carried out on measurements and modelling of the transport and fate of mercury in the Gulf. Two- and three-dimensional models have been developed to include the influence of the significant advective transport due to currents. Wind, thermohaline forcing, and the Soca river momentum are the most important forcing factors. A two-dimensional model simulated the transport of non-methylated and methylated mercury in dissolved, particulate and plankton fractions. Mercury processes included the input of atmospheric mercury, sedimentation, reduction, methylation and demethylation. The model simulations gave basically what were proper trends of the phenomena; quantitatively the measured and computed results are mainly within a factor of three. To simulate the non-uniform distribution of parameters over the depth, an existing three-dimensional (3D) hydrodynamic and transport-dispersion (TD) model, PCFLOW3D, was adapted and applied. As it was found that most mercury transport is related to suspended sediment particles, a new 3D sediment transport module was also developed and included in the model. Three cases are presented: one describing the simulation of TD of dissolved total mercury; another the simulation of the TD of particulate mercury in the Gulf during a river flood; and the third simulating sediment transport in the Gulf during a period of strong ENE wind. Comparison with measurements was only partly possible, but mainly the computed and measured results were within a factor of two and proper trends of the phenomena were obtained by the simulations. The combination of modelling and measurements has resulted in some interesting conclusions about the phenomenon of the transport and fate of mercury in a coastal sea.     

Urinary mercury in people living near point sources of mercury emissions

As part of the European Mercury Emissions from Chlor Alkali Plants (EMECAP) project, we tested the hypothesis that contamination of ambient air with mercury around chlor alkali plants using mercury cells would increase the internal dose of mercury in people living close to the plants. Mercury in urine (U-Hg) was determined in 225 individuals living near a Swedish or an Italian chlor alkali plant, and in 256 age- and sex-matched individuals from two reference areas. Other factors possibly affecting mercury exposure were examined. Emissions and concentrations of total gaseous mercury (TGM) around the plants were measured and modeled. No increase in U-Hg could be demonstrated in the populations living close to the plants. This was the case also when the comparison was restricted to subjects with no dental amalgam and low fish consumption. The emissions of mercury to air doubled the background level, but contributed only about 2 ng/m(3) to long-term averages in the residential areas. The median U-Hg levels in subjects with dental amalgam were 1.2 microg/g creatinine (micro/gC) in Italy and 0.6 microg/gC in Sweden. In individuals without dental amalgam, the medians were 0.9 microg/gC and 0.2 microg/gC, respectively. The number of amalgam fillings, as well as chewing, fish consumption, and female sex were associated with higher U-Hg. The difference between the countries is probably due to higher fish consumption in Italy, demethylated methyl mercury (MeHg) being partly excreted in urine. Post hoc power calculations showed that if the background mercury exposure is low it may be possible to demonstrate an increase in U-Hg of as little as about 10 ng/m(3) as a contribution to ambient mercury from a point source.     

Land-sea mercury transport through a modified watershed, SE Brazil

River management has altered the land-sea transport of water, sediments, and chemical compounds with profound impacts on the structure of continental and costal ecosystems. Understanding riverine transport across modified watersheds allow for better assessment of the influence of river management on material fluxes to coastal waters. Here, we assess the quantitative and qualitative aspects of mercury (Hg) transport across a modified watershed by diversion of Paraíba do Sul River waters into Sepetiba Bay, Brazil. We measured concentrations and speciation of Hg in water samples collected at sites within the modified watershed. These data, together with water discharge and sediment load from numerical models and measurements were used to estimate mass balances. In the Sepetiba watershed, mercury is mainly associated with suspended sediments (90%) and therefore Hg flux displayed the characteristic trend of downstream reduction due to trapping efficiency of particulate load by successive reservoirs. The mass balance suggests that the major source of mercury to Sepetiba Bay is the erosion of soil-derived particles from the drainage basin rather than mercury diverted from Paraíba do Sul River watershed.