Atmospheric mercury distribution in Northern Europe and in the Mediterranean region

Mercury species in air have been measured at five sites in Northwest Europe and at five coastal sites in the Mediterranean region during measurements at four seasons. Observed concentrations of total gaseous mercury (TGM), total particulate mercury (TPM) and reactive gaseous mercury (RGM) were generally slightly higher in the Mediterranean region than in Northwest Europe. Incoming clean Atlantic air seems to be enriched in TGM in comparison to air in Scandinavia. Trajectory analysis of events where high concentrations of TPM simultaneously were observed at sites in North Europe indicate source areas in Central Europe and provide evidence of transport of mercury on particles on a regional scale.     

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model’s ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year^?1 of elemental Hg.     

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.     

Large-scale spatial pollution patterns around the North Sea indicated by coastal bird eggs within an EcoQO programme

To categorize the marine environmental health status, the Oslo and Paris commissions have recently formulated Ecological Quality Objectives (EcoQOs) for many ecological features including the contamination of coastal bird eggs with mercury and organochlorines. In this study, we describe spatial and temporal patterns of egg contamination around the North Sea and compared them to the EcoQOs. Concentrations of mercury, polychlorinated biphenyl (??PCB) congeners, dichlorodiphenyltrichloroethane (??DDT) and derivatives, hexachlorobenzene (HCB) and hexachlorocyclohexane (??HCH) isomers were analysed in two tern species (Sterna hirundo and Sterna paradisaea) and Oystercatcher (Haematopus ostralegus) eggs collected between 2008 and 2010 in a total of 21 sites in seven countries surrounding the North Sea. Hg, ??PCB and HCB were highest in the southern sites, while ??DDT and ??HCH concentrations were greatest in eggs from the western North Sea and the Elbe estuary. There were rarely any consistent decreases over time for any compounds. In the terns, Hg, HCB and ??HCH increased at most sites, ??PCB and ??DDT in Sweden and Norway. In the Oystercatcher, HCB and ??HCH increased at more than the half of the sites, ??PCB, ??DDT and Hg at several German sites. In the terns, Hg, ??PCB and ??DDT exceeded the EcoQO in all, HCB in most years and sites. At most sites, ??HCH fulfilled the EcoQO in some study years. In the Oystercatcher, Hg, ??PCB and ??DDT exceeded the EcoQO in all or most years and sites. HCB and ??HCH fulfilled the EcoQO in some or all years at most sites. The EcoQO was exceeded most frequently in estuaries. We conclude that EcoQOs are suitable for drawing contamination patterns of the coastal North Sea in an easily understandable manner, offering the opportunity to harmonize the EcoQOs with coordinated environmental monitoring programmes.     

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.     

Mercury in lakes and lake fishes on a conservation-industry gradient in Brazil

Mercury contamination in freshwater food webs can be severe and persistent, and freshwater fish are a major source of mercury contamination in humans. Northern hemisphere studies suggest that the primary pathway by which freshwater fish accumulate mercury is the food web, and that atmospheric deposition is the primary route by which mercury enters freshwater systems. Levels of atmospheric deposition are closely linked to proximity to sources of mercury emissions. These propositions have not been tested in the southern hemisphere. In this study, we measured mercury levels at three lakes in southern Brazil and assessed relationships between mercury in precipitation, lake water, sediment and fish tissues at sites close to (industrial and suburban areas) and distant from (protected conservation area) sources of mercury emissions. We also assessed relationships between mercury in fish species and their trophic habits. Mercury concentrations in sediment and lake water did not vary among lakes. In contrast, mercury in precipitation at the study lakes increased with proximity to industrial sources. Mercury in fish tissue generally increased along the same gradient, but also varied with trophic level and preferred depth zone. Atmospheric mercury deposition to these closed lakes may be directly linked to concentrations in fish, with surface-feeding piscivorous species attaining the highest concentrations.     

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.     

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.     

Mass loads of dissolved and particulate mercury and other trace elements in the Mt. Amiata mining district,Southern Tuscany (Italy)

Total dissolved and particulate mercury (Hg), arsenic (As), and antimony (Sb) mass loads were estimated in different seasons (March and September 2011 and March 2012) in the Paglia River basin (PRB) (central Italy). The Paglia River drains the Mt. Amiata Hg district, one of the largest Hg-rich regions worldwide. Quantification of Hg, As, and Sb mass loads in this watershed allowed (1) identification of the contamination sources, (2) evaluation of the effects of Hg on the environment, and (3) determination of processes affecting Hg transport. The dominant source of Hg in the Paglia River is runoff from Hg mines in the Mt. Amiata region. The maximum Hg mass load was found to be related to runoff from the inactive Abbadia San Salvatore Mine (ASSM), and up to 30 g day^?1 of Hg, dominantly in the particulate form, was transported both in high and low flow conditions in 2011. In addition, enrichment factors (EFs) calculated for suspended particulate matter (SPM) were similar in different seasons indicating that water discharge controls the quantities of Hg transported in the PRB, and considerable Hg was transported in all seasons studied. Overall, as much as 11 kg of Hg are discharged annually in the PRB and this Hg is transported downstream to the Tiber River, and eventually to the Mediterranean Sea. Similar to Hg, maximum mass loads for As and Sb were found in March 2011, when as much as 190 g day^?1 each of As and Sb were measured from sites downstream from the ASSM. Therefore, the Paglia River represents a significant source of Hg, Sb, and As to the Mediterranean Sea.     

A mechanistic model for mercury capture with in situ-generated titania particles: role of water vapor

A mechanistic model to predict the capture of gas-phase mercury (Hg) species using in situ-generated titania nanosize particles activated by UV irradiation is developed. The model is an extension of a recently reported model for photochemical reactions by Almquist and Biswas that accounts for the rates of electron-hole pair generation, the adsorption of the compound to be oxidized, and the adsorption of water vapor. The role of water vapor in the removal efficiency of Hg was investigated to evaluate the rates of Hg oxidation at different water vapor concentrations. As the water vapor concentration is increased, more hydroxy radical species are generated on the surface of the titania particle, increasing the number of active sites for the photooxidation and capture of Hg. At very high water vapor concentrations, competitive adsorption is expected to be important and reduce the number of sites available for photooxidation of Hg. The predictions of the developed phenomenological model agreed well with the measured Hg oxidation rates in this study and with the data on oxidation of organic compounds reported in the literature.     

Mercury in Precipitation at an Urbanized Coastal Zone of the Baltic Sea (Poland)

Wet deposition is an important source of metals to the sea. The temporal variability of Hg concentrations in precipitation, and the impact of air masses of different origins over the Polish coastal zone were assessed. Samples of precipitation were collected (August 2008–May 2009) at an urbanized coastal station in Poland. Hg analyses were conducted using CVAFS. These were the first measurements of Hg concentration in precipitation obtained in the Polish coastal zone. Since Poland was identified as the biggest emitter of Hg to the Baltic, these data are very important. In the heating and non-heating season, Hg concentrations in precipitation were similar. Hg wet deposition flux dominated in summer, when the production of biomass in the aquatic system was able to actively adsorb Hg. Input of metal to the sea was attributed to regional and distant sources. Maritime air masses, through transformation of Hg(0), were an essential vector of mercury in precipitation.     

Estimating contribution of precipitation scavenging of atmospheric particulate mercury to mercury wet deposition in Japan

Mercury wet deposition is dependent on both the scavenging of divalent reactive gaseous mercury (RGM) and atmospheric particulate mercury (Hg(p)) by precipitation. Estimating the contribution of precipitation scavenging of RGM and Hg(p) is important for better understanding the causes of the regional and seasonal variations in mercury wet deposition. In this study, the contribution of Hg(p) scavenging was estimated on the basis of the scavenging ratios of other trace elements (i.e., Cd, Cu, Mn, Ni, Pb and V) existing entirely in particulate form. Their wet deposition fluxes and concentrations in air, which were measured concurrently from April 2004 to March 2005 at 10 sites in Japan, were used in this estimation. The monthly wet deposition flux of mercury at each site correlated with the amount of monthly precipitation, whereas the Hg(p) concentrations in air tended to decrease during summer. There was a significant correlation (P<0.001) among the calculated monthly average scavenging ratios of trace elements, and the values in each month at each site were similar. Therefore, it is assumed the monthly scavenging ratio of Hg(p) is equivalent to the mean value of other trace elements. Using this scavenging ratio (W), the wet deposition flux (F) due to Hg(p) scavenging in each month was calculated by F=WKP, where K and P are the Hg(p) concentration and amount of precipitation, respectively. Relatively large fluxes due to Hg(p) scavenging were observed at a highly industrial site and at sites on the Japan Sea coast, which are strongly affected by the local sources and the long-range transport from the Asian continent, respectively. However, on average, at the 10 sites, the contribution of Hg(p) scavenging to the annual mercury deposition flux was 26%, suggesting that mercury wet deposition in Japan is dominated by RGM scavenging. This RGM should originate mainly from the in situ oxidation of Hg⁰ in the atmosphere.     

Mercury chemistry in the MBL: Mediterranean case and sensitivity studies using the AMCOTS (Atmospheric Mercury Chemistry over the Sea) model

The atmospheric oxidation of mercury in the Mediterranean marine boundary layer (MBL) has been studied using the Atmospheric Mercury Chemistry over the Sea (AMCOTS) model. The model results have been compared to measured data obtained during an oceanographic research campaign in 2000, with more success than previous modelling attempts. In light of the often high concentrations of ozone present in the Mediterranean boundary layer, seasonal case studies using typical meteorological conditions and average ozone concentrations have been performed to identify the main oxidants of elemental mercury. The sensitivity of the modelled reactive gaseous mercury (RGM) concentrations to the Hg+O₃ rate constant has been assessed using the two most recent rate determinations. The results using the higher of the two literature values gives results inconsistent with measured values of RGM when the reaction between Hg and O₃ is assumed to give a gas phase product. This does not necessarily indicate that the rate constant is incorrect but possibly that other rate constants in the model are overestimated or indeed that there may be reduction reactions occurring in the atmosphere which have yet to be identified. Alternatively, when the reaction product of Hg and O₃ is assumed to be a solid and therefore not contribute to RGM the modelled and measured results are comparable. The deposition rates calculated by the model when compared with calculated and measured sea surface emission fluxes available in the literature indicate that dry deposition flux of RGM is comparable to the sea surface emission flux. The calculated lifetime of Hg⁰ in the Mediterranean MBL is between one and two weeks.     

Trace metals in seagrass, algae and molluscs from an uncontaminated area in the Mediterranean

The concentrations of Cd, Cr, Cu, Pb and Zn were measured in specimens of four marine organisms--the seagrass Posidonia oceanica (L.) Delile, the brown algae Padina pavonica (L.) Thivy, and the two gastropod molluscs Monodonta turbinata Born and Patella caerulea L.--selected as possible cosmopolitan biomonitors of trace metals in the Mediterranean area. The organisms were collected at five coastal sites in Favignana Island (Sicily, Italy), an area virtually uninfluenced by anthropogenic activities. In order to gain a more complete picture of both the environmental conditions of the experimental area and the bioaccumulation patterns of the selected organisms, soluble and total metal concentrations were determined in coastal water samples collected at the same stations. The picture of bioavailable metal loads in the different sites of the selected area provided by the four species was rather univocal. An overall trend of increased metal concentrations at the station in which the local harbour is located was clear. On the other hand, the metal concentrations recorded at the 'clean' stations generally fall in the range of the lowest values available in the literature and may be considered as useful background levels to which to refer for intraspecific comparison within the Mediterranean area. Implications in biomonitoring of the observed accumulation patterns, especially in the different tissues of Posidonia oceanica, are discussed.     

Does salt water intrusion constitute a mercury contamination risk for coastal fresh water aquifers?

Four different sampling surveys were carried out in 1998 to evaluate the possible causes of severe mercury contamination involving many wells spread over a vast territory along the coast of southern Tuscany (Italy). Several samples of groundwater and coastal sea water were collected to determine the Hg, Cl, Ar, He and N contents. Anthropogenic or deep-seated sources of the Hg involved in the contamination event can be excluded. The observed coupling of Hg pollution with progressive salt water intrusion along the coastal aquifer indicates a close causal relation between these two phenomena.     

Mercury in flounder (Platichthys flesus L.) from estuaries and coastal waters of the north-east Irish Sea

This paper reports concentrations of mercury in muscle tissue of flounder (Platichthys flesus L.) from various estuaries and coastal waters of north Wales and north-west England that encompass the north-east Irish Sea. Mercury concentrations were highest within and offshore the Ribble Estuary (0.476 +/- 0.037 mg kg(-1)) but were also high within the Mersey (0.389+/-0.042 mg kg(-1)) and Dee Estuaries (0.295+/-0.065) and at coastal sites in the vicinity. Values for all three estuaries and their near coastal sites were significantly higher than for sites in the north and central sectors of the study area. Regressions of mercury concentration against fish length showed significant relationships and age accumulation for the majority of sites, particularly within or in close proximity to the Mersey, Dee and Ribble Estuaries.     

Trace metals assessment in water, sediment, mussel and seagrass species--validation of the use of Posidonia oceanica as a metal biomonitor

The accumulation of trace metals (Cd, Co, Cr, Hg, Ni and Pb) was measured in water, sediment, the mussel Mytilus galloprovincialis and the seagrass Posidonia oceanica. Samples were collected in three locations of the north-western Mediterranean (Canari, Livorno and Porto-Torres) which present different levels and sources of human impact. Analyses in the different compartments (water, sediment, M. galloprovincialis and P. oceanica) have allowed to identify Canari as the most Cd, Co, Cr and Ni contaminated site; Livorno as the most Hg contaminated and Porto-Torres as the most Pb contaminated. Furthermore, for the first time, metal concentrations found in P. oceanica have been compared with those found in the water column, in the sediment and in the recognized metal bio-indicator species M. galloprovincialis and the results obtained have led to the same conclusions. Thus, this study allows to validate the use of P. oceanica as metal biomonitor of coastal waters.     

Spatial and temporal variations of trace metals in bottom sediments of Peter the Great Bay, the Sea of Japan

New data on trace metal distribution in bottom sediments of Peter the Great Bay (the Sea of Japan) are presented. Much higher concentrations were detected near the most likely anthropogenic sources of trace metal inputs (waste water discharges from Vladivostok and Nakhodka, and the Vladivostok coastal landfill). Sediments in these contaminated areas were up to 700 ppm in Zn, 530 ppm in Pb, 7 ppm in Cd and 3 ppm in Hg. River runoff is of minor importance as a metal source in the investigated areas. The spatial distribution of trace metals outside the areas directly influenced by sewage discharges is regulated by natural processes such as sediment sorting by grain size. Based on radiometric dating of sediment cores, increases in the trace metal content of bottom sediments near Vladivostok begun in approximately 1945.     

Preparation of mercury emissions inventory for eastern North America

Point and area inventories of anthropogenic mercury emissions documented by US and Canadian environmental agencies have been aggregated into a single archive for analysis and air pollution modeling work. For 5341 point sources and 1634 aggregated area sources, mercury emissions are apportioned among elemental gaseous [Hg(0)], reactive gaseous[Hg(II)], and particulate [Hg(p)] emissions using speciation factors derived from available monitoring measurements. According to this inventory, 4.82 x 10(5) mol of mercury were emitted in calendar year 1996 in the latitude range 24-51 degrees north, and longitude range 64-91 degrees west, which covers most of North America east of the Mississippi River. Using speciation factors consistent with past emission source studies, we find the relative emission proportions among Hg(0):Hg(II):Hg(p) species are 47:35:18. Maps of the various mercury species' emissions patterns are presented. Gridded emission patterns show local mercury emission extremes associated with individual cement production and municipal incineration facilities, and in contrast to past inventories, population centers do not stand out. Considerable uncertainties are still present in estimating emissions from large point sources, as are methods of apportioning emissions among various mercury species.     

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.