Formation of dissolved gaseous mercury in a tropical lake (Petit-Saut reservoir, French Guiana)

Formation of dissolved gaseous mercury (DGM) and its volatilization from aquatic systems can be considered as a natural attenuation process, which limits the methylation of mercury (Hg) and Hg accumulation in fish. Although gold-mining activity and erosion of tropical soils lead to increased Hg concentration in aquatic systems, little is known about DGM production and distribution in tropical aqueous systems. Our work explores the vertical distribution and principal sources of DGM in a meromictic Amazonian reservoir. Dissolved gaseous mercury measurements carried out in Petit-Saut reservoir (French Guiana, South America) revealed DGM increase in the surface waters and at the bottom layers of the reservoir during the dry season. As in arctic and temperate lakes, high DGM concentrations in surface waters were attributed to sunlight-mediated photochemical processes. Dissolved gaseous mercury concentrations in the anaerobic hypolimnion were larger than in temperate or arctic lakes. In order to elucidate Hg(II) reduction pathways in the bottom layer of tropical reservoir, laboratory Hg(II) reduction experiments were performed with anoxic aqueous suspensions of surface sediments either untreated or treated by gamma-ray and NaN3. Our results indicated that DGM production at the bottom layer of Petit-Saut reservoir was biologically mediated. Dissolved gaseous mercury formation rates in the surface sediment suspensions were of the same order of magnitude as formation rates in freshwater lakes reported in literature.     

Mercury speciation and exchanges at the air-water interface of a tropical artificial reservoir, French Guiana

The distribution and speciation of mercury (Hg) in air, rain, and surface waters from the artificial tropical lake of Petit-Saut in French Guiana were investigated during the 2003/04 period. In the air, total gaseous mercury (TGM) at the dam station averaged 12+/-2 pmol m(-3) of which >98% was gaseous elemental mercury (GEM). GEM distribution depicted a day-night cycling with high concentrations (up to 15 pmol m(-3)) at dawn and low concentrations (down to 5 pmol m(-3)) at nightfall. Reactive gaseous mercury (RGM) represented <1% of the GEM with a mean concentration of 4+/-3 fmol m(-3). Diel RGM variations were negatively related to GEM. In the rain, the sum of all Hg species in the unfiltered (HgT(UNF)) averaged 16+/-12 pmol L(-1). Temporal distribution of HgT(UNF) exhibited a pattern of high concentrations during the late dry seasons (up to 57.5 pmol L(-1)) and low concentrations (down to 2.7 pmol L(-1)) in the course of the wet seasons. Unfiltered reactive (HgR(UNF)), dissolved gaseous (DGM) and monomethyl (MMHg(UNF)) Hg constituted 20, 5 and 5% of HgT(UNF), respectively. All measured Hg species were positively related and displayed negative relationships with the pH of the rain. In the reservoir surface waters, dissolved total mercury (HgT(D)) averaged 3.4+/-1.2 pmol L(-1) of which 10% consisted of DGM. DGM showed a trend of high concentrations during the dry seasons (480+/-270 fmol L(-1)) and lower (230+/-130 fmol L(-1)) in the course of the wet seasons. Diel variations included diurnal photo-induced DGM production (of about 60 fmol L(-1) h(-1)) coupled to minute to hour oxidation/reduction cycles (of >100 fmol L(-1) amplitude). Finally, calculated atmospheric Hg inputs to the Petit-Saut reservoir represented 14 mol yr(-1) whereas DGM evasion reached 23 mol yr(-1). Apportionment among forms of Hg deposition indicated that up to 75% of the total Hg invasive flux follows the rainfall pathway.     

Photo-induced formation of dissolved gaseous mercury in coastal and offshore seawater of the Mediterranean basin

The first measurements on the daily trend of dissolved gaseous mercury (DGM) concentration determined in coastal and offshore waters of the Mediterranean basin are reported. Marked daily behaviour tracking solar radiation has been observed at the coastal sampling station with DGM values ranging from 11.0 to 38.9 pg/l. Contrary to these observations the DGM values in offshore water samples (11.9-20.0 pg/l) were independent of the sampling time, thus identifying the absence of higher levels during the hours of maximum insolation. The availability of Hg2+ substrate necessary for the photo-reaction processes of DGM formation has been evaluated by measuring the reactive mercury concentration. In offshore waters the lower DGM concentrations are attributable to the substrate as a limiting factor. The highest concentration of DOC measured in coastal seawater with respect to the offshore one could moreover enhance the reaction rates of DGM production through the formation of inorganic mercury complexes and weaker organic associations.     

Dissolved gaseous mercury production in the dark: Evidence for the fundamental role of bacteria in different types of Mediterranean water bodies

It is well established that the dissolved gaseous mercury (DGM) production in waters is mainly driven by photochemical processes. The present paper provides evidence for a significant bacteria-mediated DGM production, occurring also under dark conditions in environmentally different types of coastal water bodies of the Mediterranean basin. The DGM production was laboratory determined in sea, lagoon-brackish and lake water samples, comparing the efficiency of the DGM production processes in darkness and in the light. This latter condition was established by exposing samples at solar radiation intensity in the Photosyntetical Active Radiation region (PAR) of 200 W m^− 2. Mercury reduction rate in the dark was of the order of 2-4% of the DGM production in lightness, depending on the total mercury concentration in the water, rather than the bacterial abundance in it. Support for the active bacterial role in mercury reduction rate under dark conditions was provided by: 1) absence of significant DGM production in sterilized water samples (following filtration treatment or autoclaving), 2) restored DGM production efficiency, following re-inoculation into the same water samples of representatives of their bacterial community, previously isolated and separately cultured. Notwithstanding the low bacteria-mediated vs. the high photo-induced DGM production, whatever natural water body was considered, it is worth stressing the significant contribution of this organismal-mediated process to oceanic mercury evasion, since it occurs continuously along the entire water column throughout the 24 h of the day.     

Changes in the non-protein thiol pool and production of dissolved gaseous mercury in the marine diatom Thalassiosira weissflogii under mercury exposure

Two detoxification mechanisms working in the marine diatom Thalassiosira weissflogii to cope with mercury toxicity were investigated. Initially, the effect of mercury on the intracellular pool of non-protein thiols was studied in exponentially growing cultures exposed to sub-toxic HgCl₂ concentrations. T. weissflogii cells responded by synthesizing metal-binding peptides, named phytochelatins (PCs), besides increasing the intracellular pool of glutathione and γ-glutamylcysteine (γ-EC). Intracellular Hg and PC concentrations increased with the Hg concentration in the culture medium, exhibiting a distinct dose-response relationship. However, considerations of the PCs-SH:Hg molar ratio suggest that glutathione could also be involved in the intracellular mercury sequestration. The time course of the non-protein thiol pool and Hg intracellular concentration shows that PCs, glutathione and γ-EC represent a rapid cellular response to mercury, although their role in Hg detoxification seems to lose importance at longer incubation times. The occurrence of a process of reduction of Hg(II) to Hg° and subsequent production of dissolved gaseous mercury (DGM) was also investigated at lower Hg concentrations, at which the PC synthesis doesn't seem to be involved. The significant (P < 0.01) correlation between the cellular density in solution and the production of DGM suggests that this diatom is capable of directly producing DGM, both in light and dark conditions. This finding has been confirmed by the absence of DGM production in the culture media containing formaldehyde-killed cells. Finally, the relationship between these two different pathways of Hg detoxification is discussed.     

Importance of the biogenic organic matter in photo-formation of dissolved gaseous mercury in a culture of the marine diatom Chaetoceros sp

Laboratory experiments on DGM production under light/dark cycles in a culture of the marine diatom Chaetoceros sp. spiked with 200 ng l(-1) of mercury have been performed. DGM formation has been investigated also in the cell exudates, obtained by filtration of the cell culture. Results show that the cell culture and the filtrate give the same value of DGM production (2.24+/-0.88 pg min(-1) l(-1) and 2.23+/-0.02 pg min(-1) l(-1), respectively) in the light (40 W m(-2)), values much higher than to those obtained in the medium culture alone. A significant DGM production has been measured in dark conditions both in the cell culture (0.48+/-0.11 pg min(-1) l(-1)) and in the filtrate (0.85+/-0.10 pg min(-1) l(-1)). The results highlight that the organic compounds released by the cell in the culture medium play a fundamental role in the DGM photo-formation processes.     

Continuous analysis of dissolved gaseous mercury in freshwater lakes

The concentration of dissolved gaseous mercury (DGM) in freshwaters changes more quickly than the 40-min processing time of current analytical methods. A new method for continuous field analysis of DGM was developed using a Tekran 2537A to achieve a DGM analysis time of 5 min. Samples were concurrently analyzed for temperature, oxygen, conductivity, pH, and oxidation-reduction potential using a Hydrolab. The detection limit for DGM ranged between 5 and 20 fmolL(-1) with 99% removal efficiency. Control experiments showed that there was no interference due to methyl mercury, which is present in similar concentrations to DGM. Controlled experiments comparing continuous DGM analysis with discrete DGM analysis showed that the results are not significantly affected by typical variations in water temperature (4-30 degrees C), oxidation-reduction potential (135-355 mV), dissolved organic carbon (4.5-10.5 mgL(-1)), or pH (3.5-7.8). The continuous analysis was within 4.5% of the discrete analysis when compared across 12 samples analyzed in triplicate. The field performance of this method was tested over two 48-h periods in two lakes in Kejimkujik Park, Nova Scotia where over 1000 data points were collected.     

Photoreduction and evolution of mercury from seawater

The photoreduction of mercury (Hg2+ to Hg0) in natural seawater was investigated by means of a radiotracer (203Hg2+) solution exposed to natural and simulated sunlight. Different light regimes (dark, natural daylight, and a solar simulator), and dissolved organic carbon (DOC) levels from commercially available humic acids concentrations, were tested in the laboratory to evaluate the possibility of occurrence of the reaction in the environment. The natural seawater prepared accordingly to each experimental condition was continuously purged of the Hg0 formed, which was then re-oxidised in an acid trap and determined. The use of a solar simulator permitted the test of light intensity and wavelength dependence of the process under investigation. The reaction is dependent on the concentration of DOC in the experimental solution, increasing light intensity and decreasing wavelength. Reduction rates were in the range of 0.04-2.2% h(-1) for the DOC concentrations and light regimes tested. The process might have geochemical implications for the cycling of mercury around the air-sea interface.     

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.     

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.     

Diurnal variation of dissolved gaseous mercury (DGM) levels in a southern reservoir lake (Tennessee, USA) in relation to solar radiation

Variations of dissolved gaseous mercury (DGM) concentrations in a southern reservoir lake (Cane Creek Lake, Cookeville, TN, USA) in relation to solar radiation were investigated consecutively from June 2003 to May 2004. The daytime DGM levels in the lake exhibited a two-phase diurnal trend; the DGM concentrations rose in the morning, peaked around noontime and then fell in the afternoon through the evening; these trends followed the general pattern of diurnal solar radiation variations. The morning and afternoon phases appeared to be asymmetrical with the former relatively steep and the latter gradual. A variety of daytime DGM level variations other than the typical two-phase diurnal patterns were also observed. For the time spans studied, the daytime mean DGM concentrations of the lake ranged from 12 to 68 pg L(-1) (60-340 fM). The daytime mean DGM levels in the summertime (June, July, August) showed values above 30 pg L(-1) (150 fM) in most cases and a large number of peak DGM concentrations above 50 pg L(-1) (250 fM). The summer DGM levels in the lake appear to be comparable to those observed in the large northern lakes for the summertime. The daytime DGM levels in the lake were found to correlate with solar radiation to various degrees (cases of r values above 0.8: approximately 12% and approximately 18% of the total sampling days for correlation with global solar radiation and UVA radiation, respectively). Correlating trends are recognizable between the daytime mean DGM concentration and the corresponding mean global solar radiation (r = 0.66, p < 0.0005) and between the daytime mean DGM concentration and the corresponding mean UVA radiation (r = 0.62, p < 0.0005).     

Elemental gaseous mercury flux at the water/air interface over the Negro River basin, Amazon, Brazil

The amount of dissolved gaseous mercury (DGM) released annually into the atmosphere by water bodies in each of the 18 major sub-basins of the Negro River tributaries has been estimated for the wet season and adopted for the entire year. Using Remote Sensors (RS) and the Geographic Information System (GIS), an estimate was made for the total flooded area during the period of the wet season (May-July), which corresponds to around 10% of the total basin area. The estimates of DGM evasive flux values were made during four scientific campaigns and ranged from 0.09 to 14 mug m(-2) y(-1). Mercury wet deposition to the same area was estimated using average values of the metal concentration in the rainwater (9.8 ng L(-1)), which varies from 17 to 27 microg m(-2) year(-1). Considering the flooded area of the Negro River Basin as 69,000 km(2), the total amount of mercury emitted by all bodies of water reaches nearly 0.26 ton year(-1), which represents not more than 2% of the total mercury found in wet deposition in this same area.     

Mercury exposure in the population from Wuchuan mercury mining area, Guizhou, China

Mercury (Hg) exposure in the population from Wuchuan mercury mining area (WMMA), Guizhou, China, was evaluated by human hair Hg investigation. Total gaseous mercury (TGM) in the ambient air and Hg in rice were measured to assess human risk of Hg exposure. High TGM concentrations in the ambient air were found near smelting workshop. Rice not only contained high total mercury (T-Hg) which ranged from 6.0-113 ng/g, but also contained highly elevated methylmercury (Me-Hg) which ranged from 3.1-13.4 ng/g. The means of hair T-Hg concentrations were 33.9 microg/g and 21.5 microg/g at YQG and JXC sites, respectively. Residents from other sites also reflected a certain level of Hg exposure. Age had no significant effect on hair Hg levels, but male had higher hair T-Hg concentrations due to occupational exposure and also higher Me-Hg levels which might be related to larger amount of rice consumption. Hair may be a useful tool for monitoring human exposure of Hg vapor in Hg-mining areas. By a preliminary estimation, the inhalation of Hg polluted air was the main route of inorganic Hg exposure to the smelting workers and vicinal residents; but the population in the study area was also at a potential risk of Me-Hg exposure via rice intake.     

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.     

Apparent rates of production and loss of dissolved gaseous mercury (DGM) in a southern reservoir lake (Tennessee, USA)

Apparent rates of dissolved gaseous mercury (DGM) concentration changes in a southern reservoir lake (Cane Creek Lake, Cookeville, Tennessee) were investigated using the DGM data collected in a 12-month study from June 2003 to May 2004. The monthly mean apparent DGM production rates rose from January (3.2 pg L(-1)/h), peaked in the summer months (June-August: 8.9, 8.0, 8.6 pg L(-1)/h), and fell to the lowest in December (1.6 pg L(-1)/h); this trend followed the monthly insolation march for both global solar radiation and UVA radiation. The monthly apparent DGM loss rates failed to show the similar trend with no consistent pattern recognizable. The spring and summer had higher seasonal mean apparent DGM production rates than the fall and winter (6.8, 9.0, 3.9, 5.0 pg L(-1)/h, respectively), and the seasonal trend also appeared to closely follow the solar radiation variation. The seasonal apparent DGM loss featured similar rate values for the four seasons (5.5, 4.3, 3.3, and 3.9 pg L(-1)/h for spring, summer, fall, and winter, respectively). Correlation was found of the seasonal mean apparent DGM production rate with the seasonal mean morning solar radiation (r=0.9084, p<0.01) and with the seasonal mean morning UVA radiation (r=0.9582, p<0.01). No significant correlation was found between the seasonal apparent DGM loss rate and the corresponding afternoon solar radiation (r=0.5686 for global radiation and 0.6098 for UVA radiation). These results suggest that DGM production in the lake engaged certain photochemical processes, either primary or secondary, but the DGM loss was probably driven by some dark processes.     

Total and organic Hg concentrations in cephalopods from the North Eastern Atlantic waters: influence of geographical origin and feeding ecology

Total (T-Hg) and organic (O-Hg) mercury concentrations and tissue distribution were examined in 20 species of cephalopods (n=278) from the north eastern Atlantic waters, i.e. from the Bay of Biscay to the Faroe Islands. Concentrations of T-Hg in whole cephalopods showed elevated variations among species, i.e. from 40 to 3560ng g(-1) dwt, but a low variability within each species (mean CV%=39%). With the exception of oceanic squids, the digestive gland globally displayed higher T-Hg concentrations than the remaining tissues. In contrast, O-Hg concentrations determined in selected species were generally higher in the remaining tissues. Despite higher T-Hg concentrations, the digestive gland weakly contributed to the total body burden of both T-Hg and O-Hg (<25% and <15%, respectively). In fact, from 75% to 95% of the T-Hg and O-Hg were contained in the muscular remaining tissues. Therefore, O-Hg may have a strong affinity to proteins in cephalopods. Sex and size only significantly influenced the bioaccumulation of Hg for the Loliginidae family. T-Hg and O-Hg concentrations were also influenced by geographical origin: Celtic Sea>Bay of Biscay>Faroe Islands, corresponding to the seawater Hg concentrations in these areas. In the Faroe Islands and the Celtic Sea, benthic cephalopods contained significant higher Hg concentrations compared to pelagic ones. This suggests that diet is not the main pathway of Hg uptake in cephalopods as pelagic species were expected to be more exposed to O-Hg through fish consumption than benthic ones.     

Air-soil exchange of mercury from background soils in the United States

The air-surface exchange of mercury (Hg) was measured, using a dynamic polycarbonate flux chamber, for soils with low or "background" Hg concentrations (<0.1 mg/kg) at eleven locations across the contiguous United States. Sampling locations included agricultural, desert, grassland, mixed and pine forest ecosystems (n=1326 soil flux measurements at 46 individual sites). An overall soil Hg flux of 0.9+/-0.2 ng/m2/h for these background soils was obtained by averaging the means for the different locations. Soil Hg fluxes were significantly lower in dark conditions than in the light for all but the grassland sites. Mean inlet air Hg concentrations were 1.0+/-0.1 ng/m3 in the dark and 1.3+/-0.2 ng/m3 in the light. Soil temperature inside and outside of the chamber, air temperature, relative humidity, and irradiance were measured concurrently with soil Hg flux. Soil-air Hg exchange was weakly predicted by environmental variables (R2 from 0.07 to 0.52). For a single location, flux was better correlated with soil moisture than other measured environmental parameters, suggesting that soil moisture might be an important driver for Hg emissions from background soils. In addition, based on data collected we suggest some quality control measures for use of Tekran 2537A analyzers when measuring low mercury fluxes. Using basic scaling procedures, we roughly estimate that natural emissions from soils in the contiguous U.S. release approximately 100 Mg/yr of Hg to the atmosphere.     

Preliminary investigation of the mercury saturation in the Baltic Sea winter surface water

A new experimental measuring system for the total gaseous mercury saturation in the sea surface water has been developed. The technique applied to the system is based on equilibrating water-air mercury partial pressures at the air-sea interface. First data using this system were collected in the Baltic Sea on 13-22 January 2000. Measurements were completed from the research vessel 'Alexander von Humboldt' on the way from the Gotland Sea to the Mecklenburg Bight. In general the results showed domination of supersaturated winter sea surface waters with respect to gaseous mercury. Two areas with distinctly elevated mercury saturation were found: one in the east-west shipping route, south of Bornholm, where the equilibrated gaseous Hg content of water was approximately 9.2-fold higher, and another over the ammunition disposal region south-east of Hoburgs Bank, where the Hg content of water was approximately 3.8-fold higher than that in air. In general, the data indicate that the south-western Baltic Sea, and in particular both maritime areas identified with elevated mercury saturation, can emit gaseous mercury from surface waters into the atmosphere and contribute to long-range atmospheric transport.     

Electrochemically enhanced oxidation reactions in sandy soil polluted with mercury

For remediation of soils contaminated with heavy metals, the electrodialytic remediation (EDR) method is a highly relevant method, see e.g. Hansen et al. (Hansen HK, Ottosen LM, Kliem BK, Villumsen A. Electrodialytic remediation of soils polluted with Cu, Cr, Hg, Pb, and Zn. J Chem Tech Biotechnol 1997;70:67-73). During the process the heavy metals are transferred to the pore water in dissolved form or attached to colloids and move within the applied electric field. The method is found to be useful in many soil types, but has its strength in fine-grained soils. It is exactly in such soils that other remediation methods fail. Four cell experiments were made in order to investigate how relevant the method is for a more sandy soil and if it is suitable for non-ionic heavy metals such as elemental mercury. The duration was 27 days for two of the experiments and two experiments lasted 54 days, and the mercury within the soil was initially 1200-1900 mg kg(-1), of which 84% was elemental Hg. To monitor the process the pseudo-total mercury concentration was distinguished between elemental mercury and non-metallic mercury species by thermodesorption. During the electrodialytic treatment an increase of the content of non-metallic mercury occurred and a corresponding decrease of the content of elemental mercury which indicates a transformation of the latter species into any other non-metallic species. Generally, oxidation of Hg by dissolved oxygen in a solution is kinetically inhibited and thus quite slow. The redistribution of Hg was closely connected to a decrease of soil pH during the experiments. This corresponds very well to the thermodynamic calculations from which it was found that a decrease in the pH of the soil will result in an increase in the oxidation rate of elemental Hg. Results from this investigation show that the electrodialytic remediation method alone is not efficient in situations with sandy soils containing elemental mercury. As a solution for this problem it is suggested to add chloride to the soil system. Chloride would act as a complexing agent avoiding precipitation and enhancing the dissolution of precipitates as well as elemental mercury.     

Quantification and speciation of mercury in soils from the Tripuí Ecological Station, Minas Gerais, Brazil

Contents of total mercury, organic carbon, total sulfur, iron, aluminum and grain size and clay mineralogy were used along with Pearson's correlation and Hg thermal desorption technique to investigate the presence, distribution and binding behavior of Hg in soils from three depths from the Tripuí Ecological Station, located near Ouro Preto, Minas Gerais State, Brazil. The soils studied had predominantly medium and fine sand texture (0.59-0.062 mm), acid character and Hg contents ranging from 0.09 to 1.23 microg/g. The granulometric distribution revealed that Hg is associated with coarse sand (2-0.59 mm) and silt and clay (<0.062 mm) and presents similar Hg concentrations in both fractions. Mercury distribution in soil profiles showed that Hg was homogeneously distributed throughout the depths at most sites. Hg thermal desorption curves show that mercury occurs not only as Hg2+ predominantly bound to organic components in most of the samples, but also in the form of cinnabar in some. Pearson's correlation confirmed that mercury is associated with organic matter and sulfur and possibly with sulfur-bearing organic matter in most samples.