Global circulation of atmospheric mercury: a modelling study

This paper presents a comprehensive atmospheric global and regional mercury model and its capability in describing the atmospheric cycling of mercury. This is an on-line model (integrated within the Canadian operational environmental forecasting and data assimilation system) which can be used to understand the role of meteorology in mercury cycling (atmospheric pathways), the inter-annual variability of mercury and can be evaluated against observations on global scales. This is due to the fact that the model uses a combination of actual observed and predicted meteorological state of the atmosphere at high resolution to integrate the model as opposed to the climatological approach used in existing global mercury models. The model was integrated and evaluated on global scale using only anthropogenic emissions. North to south gradients in mercury concentrations, seasonal variability, dry and wet deposition and vertical structure are well simulated by the model. The model was used to explain the observed seasonal variations in atmospheric mercury circulation. The results from this study include a global animation of surface air concentrations of total gaseous mercury for 1997.     

Improved preparation of small biological samples for mercury analysis using cold vapor atomic absorption spectroscopy

Concentrations of mercury in biological samples collected for environmental studies are often less than 0.1 microgram/g. Low mercury concentrations and small organ sizes in many wildlife species (approximately 0.1 g) increase the difficulty of mercury determination at environmentally relevant concentrations. We have developed a digestion technique to extract mercury from small (0.1 g), biological samples at these relevant concentrations. Mean recoveries (+/- standard error) from validation trials of mercury fortified tissue samples using cold vapor atomic absorption spectroscopy for analysis ranged from 102 +/- 4.3% (2.5 micrograms/L, n = 15) to 108 +/- 1.4% (25 micrograms/L, n = 15). Recoveries of inorganic mercury were 99 +/- 5 (n = 19) for quality assurance samples analyzed during environmental evaluations conducted during a 24 month period. This technique can be used to determine total mercury concentrations of 60 ng Hg/g sample. Samples can be analyzed in standard laboratories in a short time, at minimal cost. The technique is versatile and can be used to determine mercury concentrations in several different matrices, limiting the time and expense of method development and validation.     

Mercury cycling and species mass balances in four North American lakes

A mass balance model for mercury based on the fugacity concept is applied to Lake Superior, Lake Michigan, Onondaga Lake and Little Rock Lake to evaluate model performance, analyze cycling of three mercury species groups (elemental, divalent and methyl mercury), and identify important processes that determine the source-to-concentration relationship of the three mercury species groups in these lakes. This model application to four disparate ecosystems is an extension of previous applications of fugacity-based models describing mercury cycling. The model performs satisfactorily following site-specific parameterization, and provides an estimate of minimum rates of species interconversion that compare well with literature. Volatilization and sediment burial are the main processes removing mercury from the lakes, and uncertainty analyses indicate that air-water exchange of elemental mercury and water-sediment exchange of divalent mercury attached to particles are influential in governing mercury concentrations in water. Any new model application or field campaign to quantify mercury cycling in a lake should consider these processes as important.     

Contribution of Spanish-American silver mines (1570-1820) to the present high mercury concentrations in the global environment: a review

In this review I evaluate the contribution of Spanish-American silver mines during the period 1570-1820 (a Spanish colonial period of 250 years) to the present high mercury concentrations in the global environment. The evaluation is based upon the following bibliographic information: (1) total amount of mercury consumed in Spanish-American silver mines between 1570 and 1820; (2) percentage of the total amount of mercury consumed in Spanish-American silver mines that may have been emitted to the atmosphere; (3) global natural input of mercury to the atmosphere; (4) worldwide anthropogenic emissions of mercury to the atmosphere; (5) residence time of mercury in the atmosphere; and (6) capacity of mercury to be deposited in the sediments of aquatic systems. From all this information, and owing to the relatively long time that has passed since Spanish-American silver mines were operational, I conclude that most of the mercury lost during the refining of silver via the patio amalgamation process is now sequestered into the sediments of aquatic systems, mainly in marine sediments. The high mercury concentrations now being reported in the global environment essentially are a consequence of the huge pollution caused by human activities during the past 20th century.     

Uptake of atmospheric mercury by deionized water and aqueous solutions of inorganic salts at acidic,neutral and alkaline pH

Mercury (Hg) is well known as a toxic environmental pollutant that is among the most highly bioconcentrated trace metals in the human food chain. The atmosphere is one of the most important media for the environmental cycling of mercury, since it not only receives mercury emitted from natural sources such as volcanoes and soil and water surfaces but also from anthropogenic sources such as fossil fuel combustion, mining and metal smelting. Although atmospheric mercury exists in different physical and chemical forms, as much as 90% can occur as elemental vapour Hg0, depending on the geographic location and time of year. Atmospheric mercury can be deposited to aquatic ecosystems through both wet (rain or snow) and dry (vapour adsorption and particulate deposition) processes. The purpose of the present study was to measure, under laboratory conditions, the rate of deposition of gaseous, elemental mercury (Hg0) to deionized water and to solutions of inorganic salt species of varying ionic strengths with a pH range of 2-12. In deionized water the highest deposition rates occurred at both low (pH 2) and high (pH 12). The addition of different species of salt of various concentrations for the most part had only slight effects on the absorption and retention of atmospheric Hg0. The low pH solutions of various salt concentrations and the high pH solutions of high salt concentrations tested in this study generally showed a greater tendency to absorb and retain atmospheric Hg0 than those at a pH closer to neutral.     

Asturian mercury mining district (Spain) and the environment: a review

Mercury is of particular concern amongst global environmental pollutants, with abundant contaminated sites worldwide, many of which are associated with mining activities. Asturias (Northwest of Spain) can be considered an Hg metallogenic province with abundant epithermal-type deposits, whose paragenetic sequences include also As-rich minerals. These mines were abandoned long before the introduction of any environmental regulations to control metal release from these sources. Consequently, the environment is globally affected, as high metal concentrations have been found in soils, waters, sediments, plants, and air. In this paper, a characterization of the environmental affection caused by Hg mining in nine Asturian mine sites is presented, with particular emphasis in Hg and As contents. Hg concentrations found in the studied milieu are similar and even higher than those reported in previous studies for other mercury mining districts (mainly Almadén and Idrija). Furthermore, the potential adverse health effects of exposure to these elements in the considered sites in this district have been assessed.     

Mercury Concentrations in Lentic Fish Populations Related to Ecosystem and Watershed Characteristics

Predicting mercury (Hg) concentrations of fishes at large spatial scales is a fundamental environmental challenge with the potential to improve human health. In this study, mercury concentrations were examined for five species across 161 lakes and ecosystem, and watershed parameters were investigated as explanatory variables in statistical models. For all species, Hg concentrations were significantly, positively related to wetland coverage. For three species (largemouth bass, pike, and walleye), Hg concentrations were significantly, negatively related to lake trophic state index (TSI), suggestive of growth biodilution. There were no significant relationships between ecosystem size and mercury concentrations. However, Hg concentrations were strongly, positively related to ecosystem size across species. Scores of small or remote lakes that have never been tested could be prioritized for testing using models akin to those presented in this article. Such an approach could also be useful for exploring how Hg concentrations of fishes might respond to natural or anthropogenic changes to ecosystems over time.     

Increasing UV-B radiation at the earth's surface and potential effects on aqueous mercury cycling and toxicity

In the past two decades, a great deal of attention has been paid to the environmental fate of mercury (Hg), and this is exemplified by the growing number of international conferences devoted uniquely to Hg cycling and its impacts on ecosystem functions and life. This interest in the biogeochemistry of Hg has resulted in a significant improvement of our understanding of its impact on the environment and human health. However, both past and current research, have been primarily oriented toward the study of direct impact of anthropogenic activities on Hg cycling. Besides a few indirect effects such as the increase in Hg methylation observed in acid-rain impacted aquatic systems or the reported enhanced Hg bioaccumulation in newly flooded water reservoirs; changes in Hg transformations/fluxes that may be related to global change have received little attention. A case in point is the depletion of stratospheric ozone and the resulting increase in solar UV-radiation reaching the Earth. This review and critical discussion suggest that increasing UV-B radiation at earth's surface could have a significant and complex impact on Hg cycling including effects on Hg volatilization (photo-reduction), solubilization (photo-oxidation), methyl-Hg demethylation, and Hg methylation. Therefore, this paper is written to provoke discussions, and more importantly, to stimulate research on potential impacts of incoming solar UV-radiation on global Hg fluxes and any toxicity aspects of Hg that may become exacerbated by UV-radiation.     

Total mercury, organic mercury and selenium in liver and kidney of a South American coastal dolphin

Selenium and total and organic mercury were determined in the liver and kidney of franciscana dolphin (Pontoporia blainvillei) incidentally caught in fishing nets along two Brazilian coastal areas (southeast and south). Regional differences in the concentrations of these contaminants were observed in P. blainvillei. Liver showed the highest organic and total mercury. In general, samples of individuals collected at the southern of Brazil had the highest concentrations of selenium and total and organic mercury. No significant gender differences were observed. Growth stage influenced the accumulation of these contaminants in both organs, and hepatic concentrations increased with the body length, according to the sampling area. Molar mercury and selenium concentrations in liver were significantly correlated, with a Se:Hg ratio close to 4. The among-site differences we found may be related to differences in preferred prey, bioavailability in the marine environment, environmental conditions, or these individuals may belong to distinct populations.     

Wetlands as principal zones of methylmercury production in southern Louisiana and the Gulf of Mexico region

It is widely recognized that wetlands, especially those rich in organic matter and receiving appreciable atmospheric mercury (Hg) inputs, are important sites of methylmercury (MeHg) production. Extensive wetlands in the southeastern United States have many ecosystem attributes ideal for promoting high MeHg production rates; however, relatively few mercury cycling studies have been conducted in these environments. We conducted a landscape scale study examining Hg cycling in coastal Louisiana (USA) including four field trips conducted between August 2003 and May 2005. Sites were chosen to represent different ecosystem types, including: a large shallow eutrophic estuarine lake (Lake Pontchartrain), three rivers draining into the lake, a cypress-tupelo dominated freshwater swamp, and six emergent marshes ranging from a freshwater marsh dominated by Panicum hemitomon to a Spartina alterniflora dominated salt marsh close to the Gulf of Mexico. We measured MeHg and total Hg (THg) concentrations, and ancillary chemical characteristics, in whole and filtered surface water, and filtered porewater. Overall, MeHg concentrations were greatest in surface water of freshwater wetlands and lowest in the profundal (non-vegetated) regions of the lake and river mainstems. Concentrations of THg and MeHg in filtered surface water were positively correlated with the highly reactive, aromatic (hydrophobic organic acid) fraction of dissolved organic carbon (DOC). These results suggest that DOC plays an important role in promoting the mobility, transport and bioavailability of inorganic Hg in these environments. Further, elevated porewater concentrations in marine and brackish wetlands suggest coastal wetlands along the Gulf Coast are key sites for MeHg production and may be a principal source of MeHg to foodwebs in the Gulf of Mexico. Examining the relationships among MeHg, THg, and DOC across these multiple landscape types is a first step in evaluating possible links between key zones for Hg(II)-methylation and the bioaccumulation of mercury in the biota inhabiting the Gulf of Mexico region.     

Mercury in the stomach contents of dab (Limanda limanda) from the North East Irish Sea and Mersey Estuary

A study of mercury concentrations in the stomach contents of fish from the north-east Irish Sea and Mersey Estuary has been shown to provide a means for surveillance of geographical and time-based changes in environmental exposure of fish biota to mercury in marine and estuarine ecosystems. This paper describes data for the flatfish dab (Limanda limanda), caught during the period 1986-1988. The low degree of variability in the data enables confirmation of clear trends in mercury concentration in stomach contents over time. As the inputs of mercury to the sewage sludge dumping ground in Liverpool Bay have decreased, there has been a corresponding decrease in mercury in fish food items. The mean mercury value in stomach contents around the dump site has declined to 100 microg kg(-1) (wet weight) which now predominates over the whole of Liverpool Bay. In 1986, mercury concentrations in stomach contents of fish ranged to over 750 microg kg(-1) although the majority of values were below 200 microg kg(-1). Most of the sites within the Mersey Estuary produced mean concentrations which were similar to those in the open sea, except for Garston which is the site closest to an inland, and principal alternative, source of mercury.     

Use of Stable Isotopes to Identify Sources of Mercury in Sediments: A Review and Uncertainty Analysis

Mass-dependent and mass-independent mercury isotope fractionation potentially generates unique source signatures that can be used to apportion contributions to sediment contamination. This article reviews findings from previous investigations that have used mercury isotopes to identify sources. It also discusses a mass balance mercury isotope fractionation model that simulates changes in isotopic source signatures in aquatic systems caused by natural biogeochemical cycling. According to the model, the extent of source signature alteration depends on chemical speciation, with more labile forms exhibiting greater isotopic fractionation. Apportionment is tractable when differences between δ²⁰²Hg of sources are larger than potential changes in isotopic signatures following the release of mercury into the environment.     

Carbon storage in Amazonia during the last glacial maximum: secondary data and uncertainties

The Amazonian forest is, due to its great size, carbon storage capacity and present-day variability in carbon uptake and release, an important component of the global carbon cycle. Paleo-environmental reconstruction is difficult for Amazonia due to the scarcity of primary palynological data and the mis-interpretation of some secondary data. Studies of lacustrine sediment records have shown that Amazonia has known periods in which the climate was drier than it is today. However, not all geomorphological features such as dunes, and slope erosion, which are thought to indicate rainforest regression, date from the time of the Late Glacial Maximum (LGM) and these features do not necessarily correspond to episodes of forest regression. There is also uncertainty concerning LGM carbon storage due to rainforest soils and biomass estimates. Soil carbon content may decrease moderately during the LGM, whereas rainforest biomass may change considerably in response to changes in the global environment. Biomass per unit area in Amazonia has probably been reduced by the cumulative effects of low CO2 concentration, a drier climate and lower temperatures. As few paleo-vegetation data are available, there is considerable uncertainty concerning the amount of carbon stored in Amazonia during the LGM, which may have corresponded to 44-94% of the carbon currently stored in biomass and soils.     

Mercury methylation in aquatic systems affected by acid deposition

Recently, it has been noted that fish in acidified lakes may contain elevated levels of mercury. While there is correlation among lakes between depressed pH and high mercury concentrations in fish, the cause of this problem is unknown. A number of hypotheses have been advanced in explanation, including increased mercury deposition, changes in mercury mobility due to acidification, pH dependent changes in mercury uptake by biota, and alterations in population size and/or structure which result in increased bioaccumulation in fish. Because fish accumulate mercury mainly in an organic form, methylmercury, changes in the biogeochemical cycling of this compound might account for elevated bioaccumulation. Mercury methylation is predominantly a microbial process which occurs in situ in lakes. This review focuses on microbiological and biogeochemical changes that may lead to increased levels of methylmercury in fresh waters impacted by acid-deposition. In particular, we focus on the hypothesis that sulfate-reducing bacteria are important mediators of metal methylation in aquatic systems and, moreover, that sulfate-deposition may stimulate methylmercury production by enhancing the activity of sulfate-reducing bacteria in sediments.     

Trends in air concentration and deposition of mercury in the coastal environment of the North Sea Area

An evaluation of mercury observations from North Sea coastal stations during 1995–2002 has been performed. The mercury data originate from EMEP/OSPAR stations in Ireland, Netherlands, Germany, Norway and Sweden where mercury in precipitation and Total Gaseous Mercury (TGM) have been measured. A decreasing trend in mercury wet deposition is observed. The decrease is sufficiently large to be significant considering measurement precision and appears to occur at all the studied sites. The reduction in deposition is 10–30% when comparing the two periods 1995–1998 and 1999–2002. The trend is likely to be due to emission controls in Europe. In contrast, no decreasing trend in TGM could be observed during the same time periods. A plausible explanation is that the TGM concentration measured in the OSPAR area to a larger extent than before is dominated by the hemispherical background concentration of TGM.     

Periphyton as a bioindicator of mercury pollution in a temperate torrential river ecosystem

Mercury presents a potential risk to the environment and humans, especially in its methylated form. It is among the highest priority environmental pollutants. River Idrijca (Slovenia) is highly contaminated with mercury due to past mercury mining. The aim of this work was to investigate whether the periphyton community in rivers such as Idrijca is a suitable indicator of Hg pollution and of changes in mercury methylation and could serve as an early warning system of increased input of MeHg in the food chain. Periphyton is the only site of primary production in temperate torrential rivers such as Idrijca and is therefore an important link in the food chain. It is also a potential site of Hg accumulation and its introduction to higher trophic levels. Our aim was to assess the response of the periphyton to seasonal and spatial variations in mercury levels and to evaluate its potential as an early warning system of changes in mercury reactivity and mobilization The results indicate that periphyton in a torrential river is too complex and unpredictable to be used as a sole indicator of mercury concentrations and changes in the river. Nevertheless, it can complement environmental measurements due to its importance in the riverine food web.     

Mercury in the Mediterranean. Part 2: processes and mass balance

Mass balance of contaminants can provide useful information on the processes that influence their concentrations in various environmental compartments. The most important sources, sinks and the equilibrium or non-equilibrium state of the contaminant in individual environmental compartments can also be identified. Using the latest mercury speciation data, the results of numerical models and the results of recent studies on mercury transport and transformation processes in the marine environment, we have re-evaluated the total mercury (HgT) mass balance in the Mediterranean Sea. New calculations have been performed employing three distinct marine layers: the surface layer, the thermocline and the deep sea. New transport mechanisms, deep water formation and density-driven sinking and upwelling, were included in the mass balance calculations. The most recent data have even enabled the calculation of an approximate methylmercury (MeHg) mass balance. HgT is well balanced in the entire Mediterranean, and the discrepancies between inputs and outputs in individual layers do not exceed 20 %. The MeHg balance shows larger discrepancies between gains and losses due to measurement uncertainties and gaps in our knowledge of Hg species transformation processes. Nonetheless, the main sources and sinks of HgT (deposition and evasion) and MeHg (fluxes from sediment, outflow through the Gibraltar Strait) are in accordance with previous studies on mercury in the Mediterranean Basin. Mercury in the Mediterranean fish harvest is the second largest MeHg sink; about 300 kg of this toxic substance is consumed annually with sea food.     

Bioaccumulation of mercury in the trophic chain of flatfish from the Baltic Sea

Mercury concentrations in three flatfish species - flounder (Platichtys flesus), plaice (Pleuronectes platessa), and Baltic turbot (Scophthalmus maximus), netted in the southern Baltic Sea were assessed and compared to concentrations of this metal in sediments, sea water, and flatfish food - bivalve Macoma balthica, isopod Saduria entomon, and sprat (Sprattus sprattus). Collected simultaneously with flatfish in 2009 and 2010. Different concentrations of mercury depending on species, tissue or organ, sex, individual length, kind of food, and region were determined. The muscle tissues of turbot had the highest concentrations of the metal. The bioaccumulation (BF) and biomagnification (BMF) factors has been counted showing that the muscle tissues of turbot have maximum affinity for mercury, and thus best reflected the metal contamination of the Baltic Sea environment. The data suggest that the common Baltic turbot (S. maximus) is an important model species, suitable and cost-effective to biomonitor environmental mercury pollution for ecological research.     

Ecological effects, transport, and fate of mercury: a general review

Mercury at low concentrations represents a major hazard to microorganisms. Inorganic mercury has been reported to produce harmful effects at 5 μg/l in a culture medium. Organomercury compounds can exert the same effect at concentrations 10 times lower than this. The organic forms of mercury are generally more toxic to aquatic organisms and birds than the inorganic forms. Aquatic plants are affected by mercury in water at concentrations of 1 mg/l for inorganic mercury and at much lower concentrations of organic mercury. Aquatic invertebrates widely vary in their susceptibility to mercury. In general, organisms in the larval stage are most sensitive. Methyl mercury in fish is caused by bacterial methylation of inorganic mercury, either in the environment or in bacteria associated with fish gills or gut. In aquatic matrices, mercury toxicity is affected by temperature, salinity, dissolved oxygen and water hardness. A wide variety of physiological, reproductive and biochemical abnormalities have been reported in fish exposed to sublethal concentrations of mercury. Birds fed inorganic mercury show a reduction in food intake and consequent poor growth. Other (more subtle) effects in avian receptors have been reported (i.e., increased enzyme production, decreased cardiovascular function, blood parameter changes, immune response, kidney function and structure, and behavioral changes). The form of retained mercury in birds is more variable and depends on species, target organ and geographical site. With few exceptions, terrestrial plants (woody plants in particular) are generally insensitive to the harmful effects of mercury compounds.