Mercury in the River Nura and its floodplain, Central Kazakhstan: I. River sediments and water

The River Nura in Central Kazakhstan has been heavily polluted by mercury originating from an acetaldehyde plant. Mercury in the riverbed is mainly associated with power station fly ash, forming a new type of technogenic deposit. A systematic survey of the bed was carried out to establish the location, extent and nature of the contaminated sediments, and to evaluate the potential for sediment transport. The bed sediments were found to contain very high concentrations of mercury, particularly in the first 15 km downstream of the source of the pollution. Average total mercury concentrations in this section of the river are typically between 150 and 240 mg/kg, falling rapidly with increasing distance downstream. The estimated total volume of silts in the riverbed between Temirtau, the origin of the pollution, and Intumak Reservoir, located 75 km downstream, has been calculated as 463500 m3, containing an estimated 9.4 tonnes mercury. Forty-six percent of the total volume of contaminated silts containing almost 95% of the mercury are located in the upper 25 km of the river, however. The data clearly support the hypothesis that large quantities of polluted sediment are not transported long distances downstream but are removed from the aquatic environment in times of flood and deposited on the low-lying lands adjacent to the river. This process, however, does not stop mercury moving further downstream in the water column.     

Mercury contamination in the vicinity of a derelict chlor-alkali plant. Part I: sediment and water contamination of Lake Balkyldak and the River Irtysh

A mercury-cell chlor-alkali plant operated in Pavlodar, Northern Kazakhstan, for 18 years and caused widespread contamination of the surrounding environment. Untreated wastewater from the plant was discharged to Lake Balkyldak, a shallow impounded lake without an outlet. The nearby River Irtysh was also suspected to be impacted by mercury (Hg) via the transport of contaminated groundwater. We took sediment and water samples from both aquatic systems, and also sampled soils along the shoreline of the lake and in the Irtysh flood plain. Sediments from Lake Balkyldak were found to be very heavily contaminated, with Hg concentrations in the surface layer reaching up to approximately 1500 mg kg(-1) near the wastewater outfall pipe. The contaminated lake sediments are prone to wind-driven resuspension and are acting as a strong source of Hg to the water column. Unfiltered lake water samples taken in shallow areas within 10-15 m from the shoreline contained from 0.11 microg Hg L(-1) in the less contaminated northern part of the lake to 1.39 microg L(-1) near the pollutant outfall in the south (up to 7.3 microg L(-1) on windy days). Sediments from the River Irtysh were only slightly impacted, with maximum Hg concentrations of 0.046 mg kg(-1) in the old river channel and 0.36 mg kg(-1) in floodplain oxbow lakes. In water samples from the River Irtysh, Hg was generally not detected, although trace concentrations (3 to 9 ng L(-1)) were found in some samples taken from oxbow lakes. We conclude that the river is not significantly impacted by Hg, but the highly contaminated Lake Balkyldak poses a threat and is in need of remediation. Potential remediation options for the lake are reviewed and are discussed in the context of experiences made at other Hg-contaminated sites.     

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

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

Mercury contamination in the vicinity of a derelict chlor-alkali plant Part II: contamination of the aquatic and terrestrial food chain and potential risks to the local population

This study investigated the environmental impact and level of risk associated with mercury (Hg) contamination near a derelict chlor-alkali plant in Pavlodar, Northern Kazakhstan. Several species of fish were sampled from the highly polluted Lake Balkyldak and the nearby river Irtysh, to assess the extent of Hg bioaccumulation in the aquatic food chain and potential human health risks. A small number of bovine tissue samples, water samples, soil and plant samples from a nearby village were also investigated in order to make a preliminary assessment of potential impacts on the terrestrial food chain. Mercury levels in fish caught from Lake Balkyldak ranged from 0.16 to 2.2 mg kg(-1) and the majority of fish exceeded current human health criteria for Hg. Interspecies comparisons indicated that Hg is accumulated in the order dace>carp>tench. Site-specific bioaccumulation factors (BAF) were calculated for THg, and were estimated for MeHg. Fish from the river Irtysh and floodplain oxbow lakes contained between 0.075 and 0.159 mg kg(-1) of Hg and can be regarded as uncontaminated. Soils were found to be impacted by past atmospheric emissions of Hg. Cattle grazing in the surroundings of the factory are exposed to Hg from contaminated soils, plants and surface water, but the consumption of contaminated fish from the lake appears to be the main route of exposure for humans.     

Total mercury,methylmercury and selenium in mercury polluted areas in the province Guizhou,China

The province of Guizhou in Southwestern China is currently one of the world's most important mercury production areas. Emissions of mercury from the province to the global atmosphere have been estimated to be approximately 12% of the world total anthropogenic emissions. The main objective of this study was to assess the level of contamination with Hg in two geographical areas of Guizhou province. Mercury pollution in the areas concerned originates from mercury mining and ore processing in the area of Wanshan, while in the area of Quingzhen mercury pollution originates from the chemical industry discharging Hg through wastewaters and emissions to the atmosphere due to coal burning for electricity production. The results of this study confirmed high contamination with Hg in soil, sediments and rice in the Hg mining area in Wanshan. High levels of Hg in soil and rice were also found in the vicinity of the chemical plant in Quingzhen. The concentrations of Hg decreased with distance from the main sources of pollution considerably. The general conclusion is that Hg contamination in Wanshan is geographically more widespread, due to deposition and scavenging of Hg from contaminated air and deposition on land. In Quingzhen Hg contamination of soil is very high close to the chemical plant but the levels reach background concentrations at a distance of several km. Even though the major source of Hg in both areas is inorganic Hg, it was observed that active transformation of inorganic Hg to organic Hg species (MeHg) takes place in water, sediments and soils. The concentration of Hg in rice grains can reach up to 569 microg/kg of total Hg of which 145 microg/kg was in MeHg form. The percentage of Hg as MeHg varied from 5 to 83%. The concentrations of selenium can reach up to 16 mg/kg in soil and up to 1 mg/g in rice. A correlation exists between the concentration of Se in soil and rice, indicating that a portion of Se is bioavailable to plants. No correlation between Hg and Se in rice was found. Exposure of the local population to Hg may occur due to inhalation of Hg present in air (in particular in Hg mining area) and consumption of Hg contaminated food (in particular rice and fish) and water. Comparison of intake through these different routes showed that the values of Hg considerably exceed the USA EPA Reference Concentration (RfC) for chronic Hg exposure (RfC is 0.0004 mg/m(3)) close to the emission sources. Intake of Hg through food consumption, particularly rice and fish, is also an important route of Hg exposure in study area. In general, it can be concluded that the population mostly at risk is located in the vicinity of smelting facilities, mining activities and close to the waste disposal sites in the wider area of Wanshan. In order to assess the real level of contamination in the local population, it is recommended that biomonitoring should be performed, including Hg and MeHg measurements in hair, blood and urine samples.     

Mercury contaminations from historic mining to water, soil and vegetation in Lanmuchang, Guizhou, southwestern China

Concentrations of total mercury and methylmercury (MeHg) were measured in soil and vegetation samples collected from a small area with a long history of Hg-mining. Hg distributions were determined in stream-waters during two sampling periods. Total Hg concentrations in soil and vegetation samples were highly elevated ranging from 0.41 to 610 mg kg(-1) and from 0.02 to 55 mg kg(-1), respectively. MeHg concentrations varied from 0.41 to 8.8 microg kg(-1) in soil samples and from 0.65 to 5.5 microg kg(-1) in vegetations. The concentrations of total Hg in stream waters varied from 55.0 to 7020 ng L(-1) in the flood-flow regime and from 24.8 to 679 ng L(-1) in the base-flow regime, respectively. Average dissolved Hg concentration was 15.7 ng L(-1) in the wet season and 21.0 ng L(-1) in the dry season. However, particulate Hg was typically >70% of total Hg in the flood-flow regime. Higher concentrations of particulate Hg primarily originated from summer floods were the major pathway of Hg transportation, which were evidenced by the positive correlation between particulate Hg and total suspended solids (TSS). The contaminated soils and distribution patterns of Hg in the stream-waters may serve as an important source of Hg to the local environment in the study area.     

Long-term changes in mercury concentrations in fish from the middle Savannah River

Total mercury levels were measured in largemouth bass (Micropterus salmoides), "sunfish" (Lepomis spp.), and "catfish" (primarily Ameiurus spp. and Ictalurus punctatus) from 1971 to 2004 in the middle Savannah River (river km 191 to 302), which drains the coastal plain of the southeastern U.S. Total mercury concentrations were higher in largemouth bass (overall mean of 0.55 mg/kg from 1971 to 2004), a piscivorous (trophic level 4) species than in the other taxa (means of 0.22-0.26 mg/kg), but temporal trends were generally similar among taxa. Mercury levels were highest in 1971 but declined over the next 10 years due to the mitigation of point source industrial pollution. Mercury levels in fish began to increase in the 1980s as a likely consequence of mercury inputs from tributaries and associated wetlands where mercury concentrations were significantly elevated in water and fish. Mercury levels in Savannah River fish decreased sharply in 2001-2003 coincident with a severe drought in the Savannah River basin, but returned to previous levels in 2004 with the resumption of normal precipitation. Regression models showed that mercury levels in fish changed significantly over time and were affected by river discharge. Mercury levels in Savannah River fish were only slightly lower in 2004 (0.3 to 0.8 mg/kg) than in 1971 (0.4 to 1.0 mg/kg) despite temporal changes during the intervening years.     

Heavy metals in urban soils: a case study from the city of Palermo (Sicily), Italy

Concentrations of V, Mn, Cd, Zn, Ni, Cr, Co, Cu, Pb, Hg and Sb were measured on 70 topsoil samples collected from green areas and parks in the city of Palermo (Sicily) in order to: (1) assess the distribution of these heavy metals in the urban environment; (2) discriminate natural and anthropic contributions; and (3) identify possible sources of pollution. Mineralogy, physico-chemical parameters, and major element contents of the topsoils were determined to highlight the influence of 'natural' features on the heavy metal concentrations and their distribution. Medians of Pb, Zn, Cu and Hg concentrations of the investigated urban soils are 202, 138, 63 and 0.68 mgkg(-1), respectively. These values are higher, in some case by different orders of size, than those of unpolluted soils in Sicily that average 44, 122, 34 and 0.07 mg kg(-1). An ensemble of basic and multivariate statistical analyses (cluster analysis and principal component analysis) was performed to reduce the multidimensional space of variables and samples, thus defining two sets of heavy metals as tracers of natural and anthropic influences. Results demonstrate that Pb, Zn, Cu, Sb and Hg can be inferred to be tracers of anthropic pollution, whereas Mn, Ni, Co, Cr, V and Cd were interpreted to be mainly inherited from parent materials. Maps of pollutant distribution were constructed for the whole urban area pointing to vehicle traffic as the main source of diffuse pollution and also showing the contribution of point sources of pollution to urban topsoils.     

A preliminary study on mercury contamination to the environment from artisanal zinc smelting using indigenous methods in Hezhang County, Guizhou, China: Part 2. Mercury contaminations to soil and crop

Artisanal zinc smelting using indigenous method in Hezhang County, Guizhou, China has posed seriously environmental pollution to the local environment. Within less than 150 km2 area in Hezhang, a few metric tons of mercury were released into the atmosphere each year since 1989 due to artisanal zinc smelting, and the surface waters were seriously contaminated with mercury. For the first time, we investigated the mercury contamination to the local soil and crop compartments due to mercury emissions from artisanal zinc smelting activities in this area. Mercury distribution patterns in 5 soil profiles collected in artisanal zinc smelting area showed that the top soils were seriously contaminated with mercury. The soils from agriculture land close to the zinc smelting areas were also contaminated with mercury due to the deposition of mercury species that emitted from artisanal zinc smelting processes. Total mercury concentrations in top soils decrease exponentially with distance from the zinc smelting area. Corn plants that were cultivated in agriculture land close to the zinc smelting area were also contaminated with mercury. Mercury concentration in corn plant tissue increased in the order of grains相似文献   

Modelling transport and transformation of mercury fractions in heavily contaminated mountain streams by coupling a GIS-based hydrological model with a mercury chemistry model

Many heavily polluted areas are located in remote regions that lack routine hydrologic monitoring. A modelling method that can produce scenarios of water chemistry trends for regions that lack hydrological data is therefore needed. The Wanshan mining area, in Guizhou province in south-western China, is such a region, as it is heavily polluted with mercury (Hg). In order to model Hg transport in a stream draining the Wanshan mining area, a Geographic Information System (GIS) hydrologic model (HEC-HMS) was coupled with a simulation model for Hg fractions in water (WASP Hg). Hydrological variations in the stream flow can thereby be simulated based on readily available precipitation data. The WASP 7 MERC Hg model was used for simulating variations in total Hg, dissolved Hg and methyl-Hg concentrations.The results of HEC-HMS modelling of flow show clear seasonal variation. Winter (Oct-Dec) constitutes the dry season with low flow, while the summer season (Jun-Aug) is rainy with high flow. 48% of total annual precipitation happens in the three summer months. The stream flows at the high flow events were several times higher than normal flow. The modelled total suspended solids and Hg concentrations were tested against monitoring data from two sampling campaigns conducted in September 2007 and August 2008. The model produced reasonable simulations for TSS, THg, DHg and MeHg, with relative errors generally around 10% for the modelled parameters. High flow events are the main contributors for release of both suspended particles and Hg. The three high flow events account for about 50% of annual discharge of THg. The annual total discharge of Hg was 8.8 kg Hg high up in the stream and 2.6 kg where the stream meets a large river 20 km downstream of the pollution source. Hence, about 70% of Hg is retained in the stream through sedimentation.     

The delivery of mercury to the Beaufort Sea of the Arctic Ocean by the Mackenzie River

Very high levels of mercury (Hg) have recently been reported in marine mammals and other higher trophic-level biota in the Mackenzie Delta and Beaufort Sea of the western Arctic Ocean. To quantify the input of Hg (particulate, dissolved and methylated) by the Mackenzie River as a potential source for Hg in the ecosystem, surface water and sediment samples were taken from 79 sites in the lower Mackenzie Basin during three consecutive summers (2003-2005) and analyzed for Hg and methylmercury (MeHg). Intensive studies were also carried out in the Mackenzie Delta during the freshets of 2004 and 2005. Large seasonal and annual variations were found in Hg concentrations in the river, coincident with the variations in water discharge. Increased discharges during spring freshet and during the summers of 2003 and 2005 compared to 2004 were mirrored by higher Hg concentrations. The correlation between Hg concentration and riverflow suggests additional Hg sources during periods of high water, potentially from increased surface inundation and increased bank erosion. The increase in the Hg concentration with increasing water discharge amplifies the annual Hg and MeHg fluxes during high water level years. For the period 2003-2005, the Hg and MeHg fluxes from the Mackenzie River to the Beaufort Sea averaged 2.2 tonnes/yr and 15 kg/yr, respectively, the largest known Hg source to the Beaufort Sea. More than half of the mercury flux occurs during the short spring freshet season which coincides with the period of rapid growth of marine biota. Consequently, the Mackenzie River input potentially provides the major mercury source to marine mammals of the Beaufort Sea. The Hg and MeHg fluxes from the Mackenzie River are expected to further increase with the projected climate warming in the Mackenzie Basin.     

Binding of mercury in soils and attic dust in the Idrija mercury mine area (Slovenia)

Total Hg concentrations and Hg speciation were determined in soils and attic dust in a 160 km2 area around Idrija mercury mine. Attic dust as well as a sample of soil was collected at 100 locations. Mercury phases were separated into cinnabar and non-cinnabar compounds via a thermo-desorption technique. The amount of the non-cinnabar fraction is important since it is potentially bioavailable and results are needed for further risk assessment studies. The concentrations of Hg in attic dust are many times higher than in surrounding soils and the attic dust/soil ratio changes with distance. The highest concentration ratios were identified at the greatest distance from the source of pollution and the lowest close to the source of pollution. This confirms the impact of air emissions on the wider area around Idrija. Furthermore the spatial mercury distribution in the attic dust shows that the influence of atmospheric emissions caused by the Idrija smelter resulted in impacts on the environment on a regional scale. The portions of non-cinnabar compounds increase with distance from the mercury source in both sampling media. Non-cinnabar fractions were found to be enriched in distant areas where fine grained material was deposited. There were two different transport mechanisms of dust particles and gaseous Hg(0) during the mercury production period. Obviously coarse grained particles, with mostly cinnabar-bound Hg settled in the immediate vicinity of the smokestack of the smelter, whereas the fine grained fraction could be dispersed further ahead. This is represented by the percentage of cinnabar-bound Hg in attic dust and soil decreasing with distance from the smelter. Gaseous Hg(0) is probably bound to fine and ultrafine aerosols with longer residence time against deposition. The consequence is that fine grained material with Hg2+ and Hg0 prevails in remote localities and is bound in soils and dust with matrix and organic matter as non-cinnabar mercury compounds. The distributions of mercury species in attic dust and soils along the Idrijca River show that in the region from Idrija to Spodnja Idrija the portions of cinnabar and non-cinnabar are about equal, while in the upper and in the lower Idrijca valley non-cinnabar bound mercury prevails. The applicability of attic dust for tracing the mercury halo in the Idrija area was successfully shown.     

The Almadén district (Spain): anatomy of one of the world's largest Hg-contaminated sites

We present data from an early reconnaissance survey (stream sediments, soil, and water Hg chemistry; plants and water crustaceans Hg intake) of the Almadén district (central Spain), that was carried out to establish the potential environmental hazards derived from the anomalous mercury concentrations measured in this realm. The Almadén mercury district (approximately 300 km2) can be regarded as the largest geochemical anomaly of mercury on Earth. The district includes a series of mercury mineral deposits, having in common a simple mineralogy (dominant cinnabar: HgS, and minor pyrite: FeS2). The ore deposits have been mined for more than 2000 years, and the main mine of the district (Almadén), has been active from Roman times to present day with almost no interruptions. The mercury distribution in soils of the district reveals the existence of high, and extremely high mercury values (up to 8889 microg g(-1)), whereas concentrations in stream sediments and waters reach exceptional values of up to 16,000 microg g(-1) and 11,200 ng l(-1) respectively. On the other hand, very high concentrations of methylmercury (MeHg) have been detected in calcines (up to 3100 ng g(-1)), sediments (0.32-82 ng g(-1)), and waters (0.040-30 ng l(-1)). Mercury gets incorporated to edible river crustaceans and plants. The red swamp crayfish Procambarus clarkii, has Hg concentrations of up to 9060 ng g(-1) (muscle) and 26,150 ng g(-1) (hepatopancreas). Regarding plants, the local wild asparagus (Asparagus acutifolius) yields values of up to 298 microg g(-1) Hg. Mercury also escapes to the atmosphere, and mineral deposits, together with metallurgical activities, generate strong anomalies of atmospheric Hg. The most important concentrations relate to the emissions from the Almadén metallurgical roaster, in the order of 14,000 ng Hg m(-3). Additionally, large open pit operations also contribute to the district atmospheric pool of mercury, with high concentrations above 1000 ng Hg m(-3). Thus, no system (rocks, soils, sediments, waters, atmosphere, biota) in the Almadén district is free from strong Hg contamination.     

Mercury levels in Oryza sativa cultivated in Philippine small-scale mining villages

Soil physico-chemical parameters and total mercury concentrations were measured in soil and rice plant samples collected over a cropping period grown in areas near mine tailings ponds in two Philippine small-scale mining (SSM) communities. Step-wise regression analysis relating environmental parameters to Hg uptake showed that pH has a highly significant effect on Hg content in the samples (p < 0.001) while temperature, contrary to previous studies, had no significant effect. The mean total Hg concentrations appeared to be significantly lower in rice plant parts sampled in control sites than in the contaminated sites in both SSM communities: 0.020 and 2.832 mg/kg, respectively in Aroroy, Masbate and 0.004 and 0.016 mg/kg, respectively in Fidelisan, Sagada. Harvested rice grains from the Masbate sampling sites further revealed total Hg concentration at 0.1331 mg/kg, exceeding the maximum permissible limit of 0.02 mg/kg Hg contamination. The study shows that Hg use in SSM activities and the cumulative effects of prolonged exposure to the metal through regular consumption of the village-cultivated rice may put the local residents at risk of health problems related to mercury.     

Mercury in the Mackenzie River delta and estuary: Concentrations and fluxes during open-water conditions

Estimates of mercury (Hg) loadings to the Arctic Ocean from circumpolar rivers have not considered biogeochemical changes that occur when river water is temporarily stored in large deltas (delta effect). There are also few data describing Hg changes across the freshwater-saltwater transition zone (FSTZ) of these rivers. We assessed temporal changes in unfiltered total mercury (THg) and methylmercury (MeHg) concentrations during open-water 2004 in the Mackenzie River upstream of the Mackenzie River delta, and in 6 floodplain lakes across an elevation gradient. These data were used to calculate Hg fluxes from the Mackenzie River and to evaluate a delta effect on Hg using an estimate of delta river water storage and a mixing analysis. Mean THg concentrations were highest in river water (9.17 ± 5.51 ng/L) and decreased up the lake elevation gradient. Mean MeHg concentrations were highest in lakes periodically connected to the river (0.213 ± 0.122 ng/L) and MeHg concentrations in elevated lakes showed a mid-summer peak. Results from the mixing analysis showed that the delta effect may be large enough to affect Hg loadings to the Arctic Ocean. THg concentrations exiting the delta (10.2 ng/L) were 16% lower than those entering (12.1 ng/L), whereas MeHg showed little change. We calculated 2.5-month (open-water) THg and MeHg fluxes from the Mackenzie River of 1208 and 8.4 kg. These fluxes are similar in magnitude to previous annual estimates in the arctic literature suggesting that previously published annual Hg fluxes from the Mackenzie River may be large underestimates. We also assessed changes in Mackenzie River water THg and MeHg concentrations as it crossed the FSTZ during an open-water cruise. THg decreased non-conservatively across the estuary from 3.8-0.6 ng/L, possibly due to mixing and particle settling. MeHg concentrations were variable and near detection. Our results show that the Mackenzie River estuary is a dynamic environment and may have important controls on Hg delivered to the Arctic Ocean.     

Historical perspective of heavy metals contamination (Cd, Cr, Cu, Hg, Pb, Zn) in the Seine River basin (France) following a DPSIR approach (1950-2005)

The Driver-Pressures-State-Impact-Response approach is applied to heavy metals in the Seine River catchment (65,000 km(2); 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930-2000 for floodplain cores, 1980-2003 for suspended particulate matter (SPM) and bed-sediments, 1994-2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg(-1) for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1.8 mg kg(-1)), Hg (1.08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970's and the metal monitoring in the catchment that started in the early 1980's. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990's, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very specific: there is a marked decontamination from 1970 to 2000, but the leakage ratio remains very high (10 to 20%) during this period. Drivers and Pressures are poorly known prior to 1985; State evolution since 1935 has been reconstructed from flood plain cores analysis; Impacts were maximum between 1950 and 1970 but remained unknown due to analytical limitation and lack of awareness. Some Responses are lagging 10 y behind monitoring and have much evolved in the past 10 y.     

Mercury distribution in waters and fishes of the upper Madeira rivers and mercury exposure in riparian Amazonian populations

In this paper, the results of mercury concentrations in two abiotic compartments (river water and suspended particles) and two biotic compartments (fish and human hair) from the upper Madeira rivers of the Bolivian Amazon basin are presented. Because of the local hydrological regimes and a high deposition rate in the plain, due to the presence of a subsidence zone at the bottom of the Andean piedmont, in the dry season, the highest mercury concentrations and fluxes were not found in rivers where mining activities took place (2.25–6.99 ng l⁻¹; and 1.07–8.67 mg Hg d⁻¹ km⁻²), but at the outlet of the Andean basins exploited for their alluvial gold (7.22–8.22 ng l⁻¹; and 9.47–9.52 mg Hg d⁻¹ km⁻²). The total mercury concentrations measured in surface waters of the upper Beni basin varied during the dry season, from 2.24 to 2.57 ng l⁻¹ in the glacial waters of the Zongo river, to 7.00 ng l⁻¹ in the Madeira River at Porto Velho and 9.49–10.86 ng l⁻¹ at its confluence with the Amazon. The results obtained from fish indicate, on one hand, that 86% of the piscivorous fishes collected in the Beni river were contaminated, and, on the other hand, their high mercury concentrations could exceed by almost four times the WHO (1976) safety limit. In the Beni River, the mercury concentrations found in omnivorous and mud-feeding fish ranged from 0.02 to 0.19 μg g⁻¹ (wet wt.), and in piscivorous fish, from 0.33 to 2.30 μg Hg g⁻¹ (wet wt.). The mercury accumulated by carnivorous fishes was mainly present in its organic form; methylmercury represented 73–98% of the total mercury analysed. Eighty persons were studied in the entire Bolivian Amazonian basin. Unlike the gold miners, who are more affected by tropical diseases, such as malaria and yellow fever, the indigenous people living on the banks of the Beni river, present elevated levels of mercury (9.81 μg g⁻¹ on average). We observed an increase in contamination in young children still being breast-fed, confirming that hair mercury concentration in babies was significantly affected by maternal mercury contamination during pregnancy. These results show that the major health impacts caused by mercury affect people who are not working directly in gold mining activities but who have a regular fish diet.     

Impacts of mercury contaminated mining waste on soil quality, crops, bivalves, and fish in the Naboc River area, Mindanao, Philippines

Rice paddy fields in the Naboc area, near Monkayo on the island of Mindanao, Philippines, have been irrigated four times a year over the last decade using Naboc River water contaminated with mercury (Hg) by artisanal gold mining in the Diwalwal area. Silt containing up to at least 90 mg Hg/kg (d.w.) has been deposited in rice paddy fields during the 1990s and this has been repeatedly mixed into the rice root zone through ploughing. Hg in the rice paddy field soils averages 24 mg Hg/kg and generally exceeds the UK and Canadian soil quality thresholds for agricultural soils as well as the proposed Dutch Intervention value and the USEPA soil ingestion Soil Screening Level (SSL) for inorganic Hg. Much lower Hg concentrations (0.05-0.99 mg/kg) within the range expected for uncontaminated soils, characterise soils on which corn and bananas are cultivated, largely because these are not irrigated with Hg-contaminated water from the Naboc River. The estimated total weekly MeHg intake for a person living in the Naboc area related to the weekly consumption of 2.1 kg of rice grown on Hg-contaminated soils (15 microg MeHg) in conjunction with 1 kg of fish (220 microg MeHg) and 100 g of mussels (50 microg MeHg) from the Naboc River, would total 285 microg MeHg (equivalent to 4.75 microg/kg bw for a 60 kg adult), which is nearly three times the JECFA PTWI of 1.6 microg/kg bw. This will significantly contribute to the population mercury exposure and might explain why 38% of the local inhabitants were classified as Hg intoxicated during a mercury toxicity assessment [Drasch GS, B?se, O'Reilly S, Beinhoff C, Roider G, Maydl S. The Mt. Diwata study on the Philippines 1999-assessing mercury intoxication of the population by small scale gold mining. Sci Total Environ 2001; 267(1-3): 151-168.].     

Accumulation of organotin compounds and mercury in harbour porpoises (Phocoena phocoena) from the Danish waters and West Greenland

The concentrations of butyltin (summation operatorBT=TBT+DBT+MBT) and mercury (Hg) were determined in the liver of 35 harbour porpoises (Phocoena phocoena), which were found dead along the coastlines or caught as by-catch in the Danish North Sea and the Inner Danish waters. In addition, three harbour porpoises hunted in West Greenland were analysed. High levels of butyltin and mercury, within the range of 68-4605 mg BT/kg ww and 0.22-92 mg Hg/kg ww, were found in the liver of the Danish harbour porpoises and both substances tend to accumulate with age. The levels in the harbour porpoise from West Greenland were 2.0-18 mg BT/kg ww and 6.3-6.9 mg Hg/kg ww, respectively. The concentrations of butyltin and mercury were both found to be higher in stranded than in by-caught harbour porpoises but only the butyltin concentration was significantly higher in stranded porpoises in the age group 1-5 years. These substances are suspected of inducing adverse effects on immune and endocrine systems in mammals and they may thereby pose a threat to the animals. This study suggests that organotin compounds are also important, when assessing the risks of contaminants on the health and viability of harbour porpoises in Danish waters.     

Mercury and methylmercury in the Gulf of Trieste (northern Adriatic Sea)

The distribution, sources and fate of mercury (Hg) in the water column of the Gulf of Trieste (northern Adriatic Sea), affected by the Hg polluted river Soca/Isonzo for centuries draining the cinnabar-rich deposits of the Idrija mining district (NW Slovenia), were studied in terms of total and dissolved Hg, reactive Hg, total and dissolved methylmercury (MeHg), mesozooplankton Hg and MeHg, and sedimentation rates of particulate Hg. Higher total Hg concentrations in the surface layer were restricted to the area of the Gulf in front of the river plume expanding in a westerly direction. Higher concentrations in bottom water layers were the consequence of sediment resuspension. Dissolved Hg exhibited higher concentrations in the surface layer in the area in front of the river plume. Higher bottom concentrations of dissolved Hg observed at some stations were probably due to remobilization from sediments, including resuspension and benthic recycling. The relationship between dissolved Hg in the surface layer and salinity showed nonconservative mixing in June 1995 during higher riverine inflow and nearly conservative mixing in September 1995 during lower riverine inflow. Both mixing curves confirm the river Soca/Isonzo to be the most important source of total and dissolved Hg, which are significantly correlated, in the Gulf. Reactive Hg is significantly correlated with dissolved Hg, indicating that the majority of dissolved Hg is reactive and potentially involved in biogeochemical transformations. The higher total MeHg in the bottom layer is the result of remobilization of MeHg from sediments including benthic fluxes. Strong seasonal variation of sedimentation rates of particulate Hg was found during a 2-year study in the central part of the Gulf. These variations followed those of total sedimented matter, indicating that sedimented Hg is mostly associated with inorganic matter. About a 2.5-fold higher fluxes of particulate Hg were observed at the depth of 20 m relative to 10 m which is attributed to bottom sediment resuspension. Temporal variability of mesozooplankton Hg and MeHg is the consequence of biomass and species variations, and grazing behaviour. From the preliminary Hg mass balance it appears that the Gulf is an efficient trap for total Hg and a net source of MeHg.