ABSTRACT
Mercury (Hg) and especially its methylated species (MeHg) are toxic chemicals that contaminate humans via the consumption of seafood. The most recent UNEP Global Mercury Assessment stressed that Mediterranean populations have higher Hg levels than people elsewhere in Europe. The present Critical Review updates current knowledge on the sources, biogeochemical cycling, and mass balance of Hg in the Mediterranean and identifies perspectives for future research especially in the context of global change. Concentrations of Hg in the Western Mediterranean average 0.86 ± 0.27 pmol L-1 in the upper water layer and 1.02 ± 0.12 pmol L-1 in intermediate and deep waters. In the Eastern Mediterranean, Hg measurements are in the same range but are too few to determine any consistent oceanographical pattern. The Mediterranean waters have a high methylation capacity, with MeHg representing up to 86% of the total Hg, and constitute a source of MeHg for the adjacent North Atlantic Ocean. The highest MeHg concentrations are associated with low oxygen water masses, suggesting a microbiological control on Hg methylation, consistent with the identification of hgcA-like genes in Mediterranean waters. MeHg concentrations are twice as high in the waters of the Western Basin compared to the ultra-oligotrophic Eastern Basin waters. This difference appears to be transferred through the food webs and the Hg content in predators to be ultimately controlled by MeHg concentrations of the waters of their foraging zones. Many Mediterranean top-predatory fish still exceed European Union regulatory Hg thresholds. This emphasizes the necessity of monitoring the exposure of Mediterranean populations, to formulate adequate mitigation strategies and recommendations, without advising against seafood consumption. This review also points out other insufficiencies of knowledge of Hg cycling in the Mediterranean Sea, including temporal variations in air-sea exchange, hydrothermal and cold seep inputs, point sources, submarine groundwater discharge, and exchanges between margins and the open sea. Future assessment of global change impacts under the Minamata Convention Hg policy requires long-term observations and dedicated high-resolution Earth System Models for the Mediterranean region.
Subject(s)
Mercury , Methylmercury Compounds , Water Pollutants, Chemical , Animals , Environmental Monitoring , Fishes , Food Chain , Humans , Mediterranean Sea , Mercury/chemistry , Methylmercury Compounds/analysis , Water Pollutants, Chemical/analysisABSTRACT
Seasonal variability of dissolved and particulate methylmercury (F-MeHg, P-MeHg) concentrations was studied in the waters of the Amazon River and its associated Curuai floodplain during hydrological year 2005-2006, to understand the MeHg exchanges between these aquatic systems. In the oxic white water lakes, with neutral pH, high F-MeHg and P-MeHg concentrations were measured during the rising water stage (0.70±0.37pmol/L, n=26) and flood peak (14.19±9.32pmol/g, n=7) respectively, when the Amazon River water discharge into the lakes was at its maximum. The lowest mean values were reported during the dry season (0.18±0.07pmol/L F-MeHg, n=10 and 1.35±1.24pmol/g P-MeHg, n=8), when water and suspended sediments were outflowing from the lakes into the River. In these lakes, the MeHg concentrations were associated to the aluminium and organic carbon/nitrogen changes. In the black water lakes, with acidic pH and reducing conditions, elevated MeHg concentrations were recorded (0.58±0.32pmol/L F-MeHg, n=16 and 19.82±15.13pmol/g P-MeHg, n=6), and correlated with the organic carbon and manganese concentrations. Elevated values of MeHg partition coefficient (4.87Subject(s)
Environmental Monitoring
, Lakes/chemistry
, Methylmercury Compounds/analysis
, Rivers/chemistry
, Water Pollutants, Chemical/analysis
, Brazil
ABSTRACT
Coastal sediments constitute a major reservoir for natural and anthropogenic mercury (Hg) and can be used as geochronological records of past Hg deposition. They may also act as secondary Hg sources for pelagic ecosystems via the efflux of toxic methylmercury (MeHg) diffusing from sediment porewaters and/or mobilized by sediment resuspension. In Toulon Bay sediments, which are known as one of the Hg hot spots of the northwestern Mediterranean Sea, we explored Hg species accumulation and mobility. The total Hg concentrations averaged 0.014 µg g-1 ca. 2000 years ago, then exhibited three major peaks during the Medieval Period, the Early Modern Period of Europe, and the Industrial Era, reaching 0.06, 0.07, and 13 µg g-1, respectively. The Medieval peak is attributed to the massive development of metallurgy in Europe accompanied by the burning of soil and vegetation, the second peak to the optimum of Hg extraction in Europe (Almadén mine), and the resumption of deforestation after the great plague. The third most recent Hg enrichment is associated with Hg-fulminate production, the scuttling of the French navy fleet during World War II, and ship salvaging and removal in the post-war years. Sampling of the dissolved phase at high vertical resolution above and below the sediment-water interface (SWI) enables us to conclude that MeHg was produced in situ by microbiological pathways and its diffusion across the SWI was negligible. On the other hand, ex-situ resuspension experiments showed that sorption and/or photodemethylation restrict MeHg from the dissolved phase.
ABSTRACT
The accumulation of dissolved mercury (Hg) by phytoplankton is the largest concentration step along aquatic food chains. However, the cell uptake mechanisms remain unclear. In this study, the marine haptophyteTisochrysis lutea, a model phytoplankton species, was examined for its interactions with picomolar levels of dissolved inorganic divalent Hg (iHg) and monomethyl Hg (MMHg). For both these Hg species, the study observed their successive sorption and internalization over time, yielding Hg partition coefficients as well as sorption, uptake, and release rates. These results were integrated into a time-dependent, three-compartment model for marine cellular Hg accumulation that included exposure medium, phycosphere, and internalized mercury. Assuming equilibria and pseudo-first-order kinetics between compartments, this study obtained transfer rates of Hg between compartments. The results provide insight into the phycosphere as an intermediate compartment for Hg species accumulation and quantify its role in the internalization of Hg. Ultimately, the new model and its parametrization were successfully applied to literature data showing Hg cellular accumulation in different groups of marine phytoplankton, lending confidence in its robustness and potential contributions to help model the uptake of Hg in the aquatic food web.
ABSTRACT
Total mercury (Hg(T)) determination requires the addition of concentrated hydrochloric acid solution (≥10 mol L(-1) HCl) in relatively high amounts to preserve the samples and to prepare reagent solutions. A method for the preparation of concentrated HCl with Hg(T) concentration of lower than 5 ng L(-1) is described in this article. It is based on the well-known chemical reaction: 2 NH(4)Cl + H(2)SO(4) â (NH(4))(2)SO(4) + 2 HCl. This method is validated thanks to the US Environmental Protection Agency method 1631 and standard reference materials BCR-579 (mercury in coastal seawater).
Subject(s)
Hydrochloric Acid/chemical synthesis , Mercury/analysis , Water/chemistry , Hydrochloric Acid/chemistry , Seawater/chemistry , SolutionsABSTRACT
Mercury (Hg) contamination in coastal sediments has been widely studied in clay deposits; however, equivalent results on carbonated sediments are scarce. This article aims to study Hg distribution in Lebanese carbonate coastal marine sediments (Eastern Mediterranean) in order to characterize their contamination level and to explore the postdepositional mobility of methylmercury (MeHg) in the deposits. Vertical distribution profiles of total (HgT) and MeHg have been established for the solid phase of sediment cores collected in various near-shore environments chosen for their hypothetical various degrees of anthropization. In addition, dissolved MeHg was determined in sediment pore waters to test its mobility and potential availability for biota. Three sites on the Lebanese coasts--Akkar, Dora, and Selaata--were selected. Akkar is far from any direct contamination source, whereas Dora, located near the Beirut harbor, is a heavily urbanized and industrialized zone including a huge dump site, and Selaata is near a chemical plant that produces phosphate fertilizers. Particulate HgT concentrations in the sediments varied between <0.04 and 0.65 µg/g, with a proportion of MeHg lower than 1%. Based on a sediment quality guideline (MacDonald et al. 2000), we concluded that Dora bay sediments are heavily contaminated by Hg, with concentrations exceeding the "consensus-based threshold effect" level (0.17 µg/g) and almost reaching the "effects range-medium" level (0.71 µg/g). In spite of the low HgT concentration in Akkar and Selaata sediment (similar to natural carbonated sediment: 0.04 µg/g according to Turekian and Wedephol (1961), a closer analysis of the sediment core vertical profile allows one to observe an anthropogenic impact. This impact might be toxicologically insignificant; however, it allows tracing the time increase of Hg diffuse deposition. On the other hand, dissolved MeHg concentrations ranged from 0.04 to 0.09 and from 0.04 to 8.76 ng/l in the Selaata and the Dora sediments, respectively; MeHg vertical profiles in interstitial water enabled us to calculate diffusive fluxes of MeHg from the sediment varying from 0.3 to 1.0 ng/m(2)/day. Thus, the deposited sediments constitute a measurable source of bioavailable Hg for epibenthic organisms.
Subject(s)
Mercury/analysis , Methylmercury Compounds/analysis , Water Pollutants, Chemical/analysis , Environmental Monitoring , Geologic Sediments/analysis , Lebanon , Mediterranean Sea , Seawater/analysisABSTRACT
The present study constitutes an in situ investigation of metal kinetics within soft tissue of mussels (Mytilus galloprovincialis), which solves the problem of the decoupling of the effect of animal physiology and metal bioavailability in water. Field experiments were conducted to measure uptake and elimination kinetics for four metals (Hg, Pb, Cd, and Cu) in three Mediterranean sites with different contamination and nutritive levels. At each site, metal concentrations were monitored in soft tissues of mussels and in the surrounding waters. The experimental conditions were completely characterized: Lazaret Bay (located between Nice and Marseille, France) is a hot spot for Hg (6.3 ng/L) and Pb (163 ng/L) concentrations and is an oligotrophic, stable site; Bages Lagoon (located to the west of Montpellier, France) is particularly contaminated by Cd (1.5 ng/L) and Cu (1.5 microg/L) and is a mesotrophic site where variability of trophic and physicochemical parameters is significant; and Port-Cros Island (located in the Hyeres National Park, France) is considered to be a reference site. Those kinetics permit us to decouple physiological, chemical, and environmental interactions. After normalizing mussel metal content for similar physiological conditions, application of the local weighted regression (LOWESS) statistical treatment shows a parallelism between the time trends of metal concentrations in the bivalve and metal concentrations in water. The results enabled us to obtain in situ kinetic parameters and realistic bioaccumulation factors. Their logarithmic values were 4.6 for Hg, 4.3 for Pb, 4.9 for Cd, and 3.9 for Cu. The importance of physiological processes such as spawning is discussed as a factor influencing the bioaccumulation factor. This information may be useful in refining monitoring tools for risk assessment and, more generally, in environmental management strategies.
Subject(s)
Adaptation, Physiological/drug effects , Metals, Heavy/analysis , Mytilus/chemistry , Mytilus/drug effects , Water Pollutants, Chemical/analysis , Water/chemistry , Adaptation, Physiological/physiology , Animals , Biological Availability , Environmental Monitoring/statistics & numerical data , France , Kinetics , Mediterranean Sea , Metals, Heavy/metabolism , Metals, Heavy/pharmacokinetics , Mytilus/growth & development , Tissue Distribution , Water Pollutants, Chemical/metabolism , Water Pollutants, Chemical/pharmacokineticsABSTRACT
This study investigated, on both metric and centimetric scales, mercury (Hg) transformations and dynamics within a water column chemocline of a tropical reservoir. Data collected included conventional measurement of Hg in water samples, diffusive gradients in thin-films (DGT) assessments, and thermodynamic speciation modeling in order to portray the biogeochemical processes that control elemental Hg (EM) and dissolved monomethylated Hg (MeHgD) production. The primary contribution of this study is demonstration that the DGT technique can be successfully implemented to examine labile Hg compound mobilization, and estimation of how local substratum facilitates Hg reduction and methylation reactions. DGT profiles with a resolution of 1cm revealed a fine sequence of prominent Hg reduction/oxidation reactions at the chemocline level. This is interpreted as a manifestation of both: i) kinetic effects capable of arising inside the diffusive layer of DGT devices, and ii) extremely localized production or consumption of reducible and methylable Hg. Another key result obtained at the metric scale is that EM and MeHgD production at a water column chemocline are intricately linked, as both are fueled by nutrients episodically released during the decomposition of falling epilimnetic organic particles or inhibited by dissolved organic matter and inorganic compounds continuously transported from the deeper monimolimnion. Finally, it is worth noting that the chemocline acts as an accumulation and recycling domain for falling MeHg-loaded organic particles, whereas the high primary productivity layer in the epilimnion represents the principal reactor with respect to Hg methylation and reduction.
ABSTRACT
The Petit-Saut hydroelectric reservoir was filled in 1994 on the Sinnamary River in French Guiana (Amazonian basin). Flooding of the equatorial rain forest led to anoxia in most of the water column and enhanced mercury methylation in the reservoir hypolimnion. We selected the benthivorous/omnivorous fish species Curimata cyprinoides to investigate total mercury and methylmercury (MeHg) bioavailability and bioaccumulation capacities in the reservoir and downstream in the Sinnamary River. Mercury concentrations in the dorsal skeletal muscle were 10-fold higher in fish from the downstream zone. Stomach contents and stable nitrogen and carbon isotope ratios showed that biofilms and the associated invertebrate communities represented important food sources at the two sites. The delta 13C measurements indicated that biofilms in the flooded forest zone of the reservoir consist of endogenous primary producers; downstream, they are based on exogenous organic matter and microorganisms, mainly from the anoxic layers of the reservoir. Total mercury and MeHg concentrations in the biofilms and associated invertebrates were much higher at the downstream site compared to concentrations at the reservoir. Our results clearly show the importance of MeHg export from the anoxic layers of this tropical reservoir. We conclude that differences between biofilm composition and MeHg concentrations in the ingested food could explain the marked differences observed between mercury levels in fish.
Subject(s)
Mercury/pharmacokinetics , Animals , Biofilms , Feeding Behavior , Fishes , France , Fresh WaterABSTRACT
The mussel, Brachidontes variabilis, and the limpet, Patella sp., were used as indicators to monitor cadmium, lead and mercury concentrations along the Lebanese coast. Studies were carried out in order to define the best strategy for assessing and minimizing the effects of size and physiological condition on the metal contents of the molluscs, and corrective models were constructed. Metal concentrations in surface water were measured to estimate bioconcentration factors (BCFs). The BCFs varied from 8.3 x 10(3) to 3.4 x 10(4), from 7.5 x 10(3) to 8.0 x 10(3) and from 3.0 x 10(4) to 3.2 x10(4), for Cd, Pb and Hg, respectively. For limpets, BCFs varied from 1.7 x 10(4) to 7.4 x 10(4) for Cd, from 2.5 x 10(3) to 6 x 10(3) for Pb and remained fairly constant at around 10(4) for Hg. The highest BCFs were associated with lowest contamination levels. The results of the geographical survey exhibited a similar large-scale spatial pattern for the two species and followed the metal concentration distributions measured in the waters.
Subject(s)
Environmental Monitoring/methods , Metals, Heavy/analysis , Shellfish/analysis , Water Pollutants, Chemical/analysis , Animals , Cadmium/analysis , Lead/analysis , Lebanon , Mercury/analysis , Mollusca/chemistry , SeawaterABSTRACT
Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in this paper include a clear gradient of Hg concentrations between the Northern and Southern hemispheres, confirming that the gradient observed is mostly driven by local and regional sources, which can be anthropogenic, natural or a combination of both.
ABSTRACT
Mercury and its speciation were studied in surface and deep waters of the Adriatic Sea. Several mercury species (i.e. DGM dissolved gaseous Hg, RHg reactive Hg, THg total Hg, MeHg monomethyl Hg and DMeHg dimethylmercury) together with other water parameters were measured in coastal and open sea deep water profiles. THg concentrations in the water column, as well as in sediments and pore waters, were the highest in the northern, most polluted part of the Adriatic Sea as the consequence of Hg mining in Idrija and the heavy industry of northern Italy. Certain profiles in the South Adriatic Pit exhibit an increase of DGM just over the bottom due to its diffusion from sediment as a consequence of microbial and/or tectonic activity. Furthermore, a Hg mass balance for the Adriatic Sea was calculated based on measurements and literature data.
Subject(s)
Environmental Monitoring , Mercury/analysis , Seawater/chemistry , Water Pollutants, Chemical/analysis , Italy , Methylmercury Compounds , MiningABSTRACT
Chemical contamination levels and stable isotope ratios provide integrated information about contaminant exposure, trophic position and also biological and environmental influences on marine organisms. By combining these approaches with otolith shape analyses, the aim of the present study was to document the spatial variability of Hg and PCB contamination of the European hake (Merluccius merluccius) in the French Mediterranean, hypothesizing that local contaminant sources, environmental conditions and biological specificities lead to site-specific contamination patterns. High Hg concentrations discriminated Corsica (average: 1.36 ± 0.80 µg g(-1) dm) from the Gulf of Lions (average values<0.5 µg g(-1) dm), where Rhône River input caused high PCB burdens. CB 153 average concentrations ranged between 4.00 ± 0.64 and 18.39 ± 12.38 ng g(-1) dm in the Gulf of Lions, whatever the sex of the individuals, whereas the highest values in Corsica were 6.75 ± 4.22 ng g(-1) dm. Otolith shape discriminated juveniles and adults, due to their different habitats. The use of combined ecotracers was revealed as a powerful tool to discriminate between fish populations at large and small spatial scale, and to enable understanding of the environmental and biological influences on contamination patterns.
Subject(s)
Environmental Monitoring/methods , Gadiformes/metabolism , Water Pollutants, Chemical/metabolism , Animals , France , Mercury/metabolism , Otolithic Membrane/chemistry , Polychlorinated Biphenyls/metabolismABSTRACT
Methylmercury (MeHg) is a neurotoxic compound that threatens wildlife and human health across the Arctic region. Though much is known about the source and dynamics of its inorganic mercury (Hg) precursor, the exact origin of the high MeHg concentrations in Arctic biota remains uncertain. Arctic coastal sediments, coastal marine waters and surface snow are known sites for MeHg production. Observations on marine Hg dynamics, however, have been restricted to the Canadian Archipelago and the Beaufort Sea (<79 °N). Here we present the first central Arctic Ocean (79-90 °N) profiles for total mercury (tHg) and MeHg. We find elevated tHg and MeHg concentrations in the marginal sea ice zone (81-85 °N). Similar to other open ocean basins, Arctic MeHg concentration maxima also occur in the pycnocline waters, but at much shallower depths (150-200 m). The shallow MeHg maxima just below the productive surface layer possibly result in enhanced biological uptake at the base of the Arctic marine food web and may explain the elevated MeHg concentrations in Arctic biota. We suggest that Arctic warming, through thinning sea ice, extension of the seasonal sea ice zone, intensified surface ocean stratification and shifts in plankton ecodynamics, will likely lead to higher marine MeHg production.
Subject(s)
Methylmercury Compounds/analysis , Water Pollutants, Chemical/analysis , Arctic Regions , Biota , Environmental Monitoring , Ice Cover , Mercury/analysis , Oceans and SeasABSTRACT
Filtered and non-filtered natural waters from French Guyana were irradiated with lamps emitting within the wavelength range 300-450 nm for 4 days with and without oxygen. Dissolved gaseous mercury (DGM) evolution was observed and quantified in the course of the irradiation. Measurements of total mercury in waters prior to and after the irradiations were also performed. The mass balance in the various mercury species (Hg(total), Hg(reactive) and DGM) proves the capability of the light to extract the mercury linked to the organic matter. DGM evolvement was greater in N2- than in air-saturated solutions, and the formation of volatile oxidized species can account for the inhibiting effect of oxygen. Filtration did not affect the mercury photoreduction, but reduced the formation of DGM in the dark. Great care has to be taken with regard to the following artifact: it was found that DGM originated not only from the natural waters, but also from the experimental device itself when exposed to the light. These non-expected DGM entries were quantitatively evaluated. This stresses the difficulty in measuring mercury at environmental concentrations.
Subject(s)
Mercury/analysis , Mercury/chemistry , Ultraviolet Rays , Water Pollutants/analysis , Environmental Monitoring , Photochemistry , Reproducibility of Results , Tropical ClimateABSTRACT
The study of trace elements (Cu, Zn, Pb, As, Hg) and butyltin concentrations in the sediments of Port Camargue enabled assessment of the levels and history of the contamination of the largest European marina linked with the use of antifouling paints. Surface sediments near the boat maintenance area were heavily contaminated with up to 1497 µg g(-1) of Cu, 475 µg g(-1) of Zn, 0.82 µg g(-1) of Hg, 94 µg g(-1) of Pb and over 10,000 ngSn g(-1) of tributyltin (TBT). High concentrations of Hg and TBT indicate ongoing sources of these elements despite the ban on their use as biocides in paints. Sediment cores provided records of contamination since 1969. The peak concentrations of As, Hg, Pb and TBT in the sediment profile reflect their presence on boat hulls when the marina was built at the end of the 1960s. Degradation of TBT in the sediments near the boat maintenance area is slow compared to other less contaminated area of the marina.
Subject(s)
Environmental Monitoring , Geologic Sediments/chemistry , Trace Elements/analysis , Water Pollutants, Chemical/analysis , France , Mercury/analysis , Ships , Trialkyltin Compounds/analysis , Water Pollution, Chemical/statistics & numerical dataABSTRACT
Consumption of marine organisms represents one of the main exposure sources of contaminants for human populations. To obtain a global view of the contamination in commercial fish in the NW Mediterranean Sea, we analysed four types of priority contaminants (PCBs, PBDEs, Hg and (137)Cs) in the European hake, Merluccius merluccius, from the Gulf of Lions in relation with organism's trophic level (δ(15)N). All contaminants presented a significant increase in concentration in hake muscle with trophic level. However, obvious differences between contaminants were evidenced. Biomagnification factors (BMF and FWMF) along the hake food web were higher for Hg and CB-153 than for BDE-47 and (137)Cs, and increase in contaminant concentration with trophic level occurred at different rates depending on contaminants. Such differences of biomagnification patterns can be related to physico-chemical properties of the different contaminants.
Subject(s)
Cesium Radioisotopes/metabolism , Gadiformes/metabolism , Halogenated Diphenyl Ethers/metabolism , Mercury/metabolism , Polychlorinated Biphenyls/metabolism , Water Pollutants, Chemical/metabolism , Animals , Aquatic Organisms/metabolism , Cesium Radioisotopes/analysis , Female , Food Chain , Halogenated Diphenyl Ethers/analysis , Male , Mediterranean Sea , Mercury/analysis , Polychlorinated Biphenyls/analysis , Water Pollutants, Chemical/analysisABSTRACT
Under stratified oligotrophic conditions (May-November), the surface mixed layer of the Northwestern Mediterranean constitutes a homogeneous water volume of 10-30 m depth. In other respects, the mean residence time of Ligurian surface waters (0-200 m) is 102 days. It is therefore possible to quantify the extent to which atmospheric deposition of trace metals affects surface waters. On the basis of literature data on anthropogenic and natural trace metals, we demonstrate that the ratios between total seawater labile atmospheric deposition during 102 days (Δc) and dissolved TM concentrations in Ligurian surface waters (c) illustrate the impact of atmospheric deposition on surface seawater (Δc/c). High ratios indicate surface TM enrichments, while low ratios indicate surface TM depletion, due to the quasi-complete sorption and removal of TMs by plankton during spring bloom. The simple box model proposed here may be used for other marine regions where hydrodynamical and physico-chemical constraints are well defined.
Subject(s)
Air Pollutants/analysis , Atmosphere/chemistry , Seawater/chemistry , Trace Elements/analysis , Water Pollutants, Chemical/analysis , Environmental Monitoring , Mediterranean Sea , Metals/analysis , Models, ChemicalABSTRACT
Total mercury (HgT) and monomethylmercury (MMHg) were investigated in a tropical head watershed (1 km(2)) of French Guiana. The watershed includes a pristine area on the hill slopes and a former gold mined flat in the bottomland. Concentrations of dissolved and particulate HgT and MMHg were measured in rain, throughfall, soil water and at three points along the stream. Samples were taken in-between and during 14 storm events at the beginning and middle of the 2005 and 2006 rainy seasons. Dissolved and particulate HgT concentrations in the stream slightly increased downstream, while dissolved and particulate MMHg concentrations were low at the pristine sub-watershed outlet (median = 0.006 ng L(-1) and 1.84 ng g(-1), respectively) and sharply increased at the gold mined flat outlet (median = 0.056 ng L(-1) and 6.80 ng g(-1), respectively). Oxisols, which are dominant in the pristine area act as a sink of HgT and MMHg from rain and throughfall inputs. Hydromorphic soils in the flat are strongly contaminated with Hg (including Hg(0) droplets) and their structure has been disturbed by former gold-mining processes, leading to multiple stagnant water areas where biogeochemical conditions are favorable for methylation. In the former gold mined flat high dissolved MMHg concentrations (up to 0.8 ng L(-1)) were measured in puddles or suboxic soil pore waters, whereas high dissolved HgT concentrations were found in lower Eh conditions. Iron-reducing bacteria were suggested as the main methylators since highest concentrations for dissolved MMHg were associated with high dissolved ferrous iron concentrations. The connection between saturated areas and stagnant waters with the hydrographic network during rain events leads to the export of dissolved MMHg and HgT in stream waters, especially at the beginning of the rainy season. As both legal and illegal gold-mining continues to expand in French Guiana, an increase in dissolved and particulate MMHg emissions in the hydrographic network is expected. This will enhance MMHg bio-amplification and present a threat to local populations, whose diet relies mainly on fish.
Subject(s)
Methylmercury Compounds/analysis , Soil Pollutants/analysis , Water Pollutants, Chemical/analysis , Environmental Monitoring , French Guiana , Gold , Mining , Rain/chemistry , Rivers/chemistry , Seasons , WildernessABSTRACT
Total mercury (THg) and monomethylmercury (MMHg) concentrations were determined in the tissues of demersal shark (Order Squaliformes and the Families: Scyliorhinidae, Hexanchidae) and chimaera species (Families: Chimaeridae and Rhinochimaeridae) from continental shelf and slope waters off southeast Australia, including embryos, juveniles and adults. The distribution of THg in various tissues (muscle, liver, kidney and skin), examined in ten species, shows higher levels in the muscle tissue (1.49+/-0.47mgkg(-1), ww), which accounted for between 59% and 82% of the total body burden of mercury and in the kidney (0.93+/-0.14mgkg(-1), ww) and liver (0.61+/-0.25mgkg(-1), ww) with lower levels observed in the skin (0.12+/-0.06mgkg(-1), ww). Additional THg determinations were performed in the muscle tissue of five other species allowing geographical and inter-specific comparisons. Speciation analysis demonstrated that more than 90% mercury was bound in muscle tissue as MMHg with higher percentages (>95%) observed in sharks species occupying deeper environments. Species differences were observed. Highest THg levels in the muscle tissue (up to 6.64mgkg(-1) wet weight, ww) were recorded in Proscymnodon plunketi and Centrophorus zeehaani (mean values; 4.47+/-1.20 and 3.52+/-0.07mgkg(-1), ww, respectively). Consistent with the ongoing paradigm on mercury bioaccumulation, we systematically observed THg concentrations increasing with animal size from the embryos to the larger sharks. Embryos of Etmopterus baxteri and Centroselachus crepidater had average levels 0.28 and 0.06mgkg(-1) (ww), while adult specimens reached 3.3 and 2.3mgkg(-1) (ww), respectively. THg concentrations in Australian sharks were compared with the same genus collected in other world regions. Levels were closer to data reported for East Atlantic than for the epicontinental Mediterranean margins. At a smaller geographical scale, the habitat effect on mercury concentration in sharks seems less clear. Squalid sharks occupying shelf waters showed higher mean mercury levels relative to their size (body weight, bw) than mid-slope species (0.4-6.7mgkg(-1) bw and 0.3-2.2mgkg(-1) bw, respectively). However, local regional differences (East and South Tasmania vs. Victoria) in Hg levels were not detected for the majority of taxa examined. All species, with the exception of Figaro boardmani showed values greater than 0.5mgkg(-1) (ww) and all but four were above many international regulatory thresholds (1.0mgkg(-1), ww).