Holocene variations in Lake Titicaca water level and their implications for sociopolitical developments in the central Andes.

Holocene climate in the high tropical Andes was characterized by both gradual and abrupt changes, which disrupted the hydrological cycle and impacted landscapes and societies. High-resolution paleoenvironmental records are essential to contextualize archaeological data and to evaluate the sociopolitical response of ancient societies to environmental variability. Middle-to-Late Holocene water levels in Lake Titicaca were reevaluated through a transfer function model based on measurements of organic carbon stable isotopes, combined with high-resolution profiles of other geochemical variables and paleoshoreline indicators. Our reconstruction indicates that following a prolonged low stand during the Middle Holocene (4000 to 2400 BCE), lake level rose rapidly ~15 m by 1800 BCE, and then increased another 3 to 6 m in a series of steps, attaining the highest values after ~1600 CE. The largest lake-level increases coincided with major sociopolitical changes reported by archaeologists. In particular, at the end of the Formative Period (500 CE), a major lake-level rise inundated large shoreline areas and forced populations to migrate to higher elevation, likely contributing to the emergence of the Tiwanaku culture.

240Pu/239Pu signatures allow refining the chronology of radionuclide fallout in South America.

Atmospheric nuclear tests (1945-1980) have led to radioactive fallout across the globe. French tests in Polynesia (1966-1974) may influence the signature of fallout in South America in addition to those conducted by USA and former USSR until 1963 in the Northern hemisphere. Here, we compiled the 240Pu/239Pu atom ratios reported for soils of South America and conducted additional measurements to examine their latitudinal distributions across this continent. Significantly lower ratio values were found in the 20-45° latitudinal band (0.04 to 0.13) compared to the rest of the continent (up to 0.20) and attributed to the contribution of the French atmospheric tests to the ultra-trace plutonium levels found in these soils. Based on sediment cores collected in lakes of Chile and Uruguay, we show the added value of measuring 240Pu/239Pu atom ratios to refine the age models of environmental archives in this region of the world.

In Situ Photochemical Transformation of Hg Species and Associated Isotopic Fractionation in the Water Column of High-Altitude Lakes from the Bolivian Altiplano.

Photochemical reactions are major pathways for the removal of Hg species from aquatic ecosystems, lowering the concentration of monomethylmercury (MMHg) and its bioaccumulation in foodwebs. Here, we investigated the rates and environmental drivers of MMHg photodegradation and inorganic Hg (IHg) photoreduction in waters of two high-altitude lakes from the Bolivian Altiplano representing meso- to eutrophic conditions. We incubated three contrasting waters in situ at two depths after adding Hg-enriched isotopic species to derive rate constants. We found that transformations mostly occurred in subsurface waters exposed to UV radiation and were mainly modulated by the dissolved organic matter (DOM) level. In parallel, we incubated the same waters after the addition of low concentrations of natural MMHg and followed the stable isotope composition of the remaining Hg species by compound-specific isotope analysis allowing the determination of enrichment factors and mass-independent fractionation (MIF) slopes (Δ199Hg/Δ201Hg) during in situ MMHg photodegradation in natural waters. We found that MIF enrichment factors potentially range from -11 to -19‰ and average -14.3 ± 0.6‰ (1 SE). The MIF slope diverged depending on the DOM level, ranging from 1.24 ± 0.03 to 1.34 ± 0.02 for the low and high DOM waters, respectively, and matched the MMHg MIF slope recorded in fish from the same lake. Our in situ results thus reveal (i) a relatively similar extent of Hg isotopic fractionation during MMHg photodegradation among contrasted natural waters and compared to previous laboratory experiments and (ii) that the MMHg MIF recorded in fish is characteristic for the MMHg bonding environment. They will enable a better assessment of the extent and conditions conducive to MMHg photodegradation in aquatic ecosystems.

Acid volatile sulfides and simultaneously extracted metals: A new miniaturized 'purge and trap' system for laboratory and field measurements.

In natural environments, Acid Volatile Sulfides (AVS) contained in anoxic waters or sediments, are composed of dissolved sulfides and neo-formed sulfides colloids or particles. Under acidic addition, AVS emit hydrogen sulfide gas and release the so-called simultaneously extracted metals (SEM). The measurement of AVS coupled with that of the SEM enables to evaluate the metal trapping capacity of sulfides in the environment. Because AVS are extremely reactive to oxidation, the most accurate methodology to quantify AVS and SEM requires to be able to process the samples extraction on-site, directly after sampling and avoiding oxygen exposure. However, most of available systems are based on glassware 'purge and trap' techniques developed for the laboratory and are not often adapted to field studies. In these systems, AVS extraction time can range from 30 min to 3 h with relative standard deviation from 7 to 44%. In this study, we developed a new 'purge and trap' system designed for both laboratory use and field AVS/SEM extractions. The system is optimized with a shortened extraction time, miniaturized, unbreakable, easy and reproducible to develop parallel extraction benches. Analytical yields, precision and stability have been improved, allowing to reduce the extraction time to 1 h with an absolute quantification limit of 0.12 µmol S(-II) with a relative standard deviation between 7 and 11% and under a complete extraction efficiency.

High methylmercury uptake by green algae in Lake Titicaca: Potential implications for remediation.

Anthropogenic pressure in the high altitude lakes such as Titicaca and Uru (Bolivia) may favor the production of methylmercury (MeHg) known to accumulate in trophic chains. Periphyton associated with emerged aquatic plants (totoras) from the lake shores accumulates and demethylates MeHg providing a potential cost-effective water treatment technique. In this laboratory study, we measured the MeHg uptake kinetics of a consortium of green algae isolated from Lake Titicaca totora's periphyton. The most abundant algal consortium, composed of Oedogonium spp., Chlorella spp., Scenedesmus spp., was exposed to rising MeHg concentrations (from 5 to 200 ng·L-1) to assess their maximum potential capacity for MeHg accumulation. Various algal biomass concentrations were tested to choose the optimal one. Results provided a net MeHg uptake rate by this algal consortium of 2.38 amol ng-1·h-1·nM-1 (the total uptake was 2863 ng MeHg·g-1) for an initial concentration of 200 ng MeHg·L-1 with an algal biomass concentration of 0.02 g·L-1. This initial MeHg concentration is 1000 times higher than the one measured in the eutrophic Cohana Bay of Lake Titicaca, which shows the high accumulation potential of these green algae. Our data suggest that periphyton has a high potential for the treatment of Hg contaminated waters in constructing wetlands in the Andean Altiplano.

Extreme Arsenic Bioaccumulation Factor Variability in Lake Titicaca, Bolivia.

Latin America, like other areas in the world, is faced with the problem of high arsenic (As) background in surface and groundwater, with impacts on human health. We studied As biogeochemical cycling by periphyton in Lake Titicaca and the mine-impacted Lake Uru Uru. As concentration was measured in water, sediment, totora plants (Schoenoplectus californicus) and periphyton growing on stems, and As speciation was determined by X-ray absorption spectroscopy in bulk and EDTA-extracted periphyton. Dissolved arsenic was between 5.0 and 15 µg L-1 in Lake Titicaca and reached 78.5 µg L-1 in Lake Uru Uru. As accumulation in periphyton was highly variable. We report the highest As bioaccumulation factors ever measured (BAFsperiphyton up to 245,000) in one zone of Lake Titicaca, with As present as As(V) and monomethyl-As (MMA(V)). Non-accumulating periphyton found in the other sites presented BAFsperiphyton between 1281 and 11,962, with As present as As(III), As(V) and arsenosugars. DNA analysis evidenced several taxa possibly related to this phenomenon. Further screening of bacterial and algal isolates would be necessary to identify the organism(s) responsible for As hyperaccumulation. Impacts on the ecosystem and human health appear limited, but such organisms or consortia would be of great interest for the treatment of As contaminated water.

Impact of recent artisanal small-scale gold mining in Senegal: Mercury and methylmercury contamination of terrestrial and aquatic ecosystems.

In Senegal, the environmental impact of artisanal small-scale gold mining (ASGM) using mercury (Hg) is poorly documented despite its intensification over the past two decades. We report here a complete dataset including the distribution and speciation of Hg in soil, sediment, and water in pristine and ASGM impacted sites of the Gambia River ecosystem (Kedougou region - eastern Senegal). Selective extraction showed that soils surrounding ASGM activities were contaminated with elemental Hg [Hg(0)] at concentrations up to 3.9 mg kg-1. In the Gambia River, high total Hg (THg: 1.16 ±â€¯0.80 mg kg-1) and methylmercury (MeHg: 3.2 ±â€¯2.3 ng g-1) were also measured in sediment samples collected at ASGM sites. Along the stream, THg concentrations in sediment decrease with distance from the ASGM sites, while those of methylmercury increase downstream. The study of THg and MeHg partitioning between filtered surface water and suspended particles demonstrate that particulate transport is responsible for the downstream dissemination of the Hg contamination from ASGM sites. Sedimentation of fine particles enriched in Hg downstream ASGM sites likely favors MeHg production and accumulation in sediment. Although elemental Hg is weakly labile, surface soil erosion may also provide important and long-term Hg inputs to downstream aquatic ecosystems, where it can be oxidized and methylated. Finally, the dissemination of THg and MeHg downstream from the ASGM sites in the Gambia River may constitute a long-term source of contamination and can have a large scale impact on the aquatic ecosystem through biomagnification.

Linking Microbial Activities and Low-Molecular-Weight Thiols to Hg Methylation in Biofilms and Periphyton from High-Altitude Tropical Lakes in the Bolivian Altiplano.

The sources and factors controlling concentrations of monomethylmercury (MMHg) in aquatic ecosystems need to be better understood. Here, we investigated Hg transformations in sediments, periphyton associated with green algae's or aquatic plants, and benthic biofilms from the Lake Titicaca hydrosystem and compared them to the occurrence of active methylating microorganisms and extracellular Hg ligands. Intense Hg methylation was found in benthic biofilms and green algae's periphyton, while it remained low in sediments and aquatic plants' periphyton. Demethylation varied between compartments but remained overall in the same range. Hg methylation was mainly carried out by sulfate reducers, although methanogens also played a role. Its variability between compartments was first explained by the presence or absence of the hgcAB genes. Next, both benthic biofilm and green algae's periphyton exhibited a great diversity of extracellular low-molecular-weight (LMW) thiols (13 or 14 compounds) present at a range of a few nmol L-1 or µmol L-1 but clearly dominated by cysteine and 3-mercaptopropionic acid. Hg methylation was overall positively correlated to the total thiol concentrations, albeit to different extents according to the compartment and conditions. This work is the first examining the interplay between active methylating bacterial communities and extracellular ligands in heterotrophic biofilms and supports the involvement of LMW thiols in Hg methylation in real aquatic systems.

Spatial variation and risk assessment of trace metals in water and sediment of the Mekong Delta.

The Mekong Delta, is home to 17 million inhabitants and faces numerous challenges relating to climate change, environmental degradation and water issues. In this study, we assess trace metals concentrations (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Hg, Pb) in the water, suspended particulate matter and surface sediments of the Tien River, the Northern branch of the Mekong Delta, during both dry and rainy seasons. Metal concentrations in the dissolved and suspended particle phases remain in the low concentration range of the main Asian Tropical River. During transportation in the riverine part, we evidenced that V, Cr, Co, As and Pb are dominant in the particulate phase while Mo, Ni and Cu dominate in the dissolved fraction. In the salinity gradient, dissolved U, V, Mo exhibit conservative behaviour while Ni, Cu, As, Co and Cd showed additive behaviour suggesting desorption processes. In the surface sediment, metal concentrations are controlled by the particle-size, POC contents and Fe, Al and Mn - oxy(hydr)oxides. Calculated Enrichment Factor and Geoaccumulation Index evidenced As enrichment while the calculated mean effect range median quotients evidenced a low to medium ecotoxicological potential effects range in the surface sediments.

Baseline seasonal investigation of nutrients and trace metals in surface waters and sediments along the Saigon River basin impacted by the megacity of Ho Chi Minh (Vietnam).

The Saigon River, Southern Vietnam, crosses one of the most dynamic developing Megacity in Southeast Asia: Ho Chi Minh City (HCMC). The increased economic, industrial, and domestic developments may affect the environmental quality of water and halieutic resources. In this study, we evaluated the seasonal (dry and wet seasons) biogeochemical state of the Saigon River during two snapshot campaigns conducted along the river basin upstream from HCMC; the Saigon River was characterized by slightly acidic (pH 5.7-7.7) and oxygen-depleted water (dissolved oxygen (DO), 0.36-5.18 mg l-1). Nutrients (N-NH4 = 0.01-2.41, N-NO3 = 0.14-2.72, and P-PO4 = ~0-0.42 mg l-1), DOC (2.2-8.0 mg l-1), POC, and trace metal(oid) (As, Cd, Cr, Cu, Zn, and Hg) concentrations were low showing a good quality of the upstream river. In the urban center area, DO dropped to 0.03 mg l-1 accompanied with a rise of nutrient concentrations (e.g., N-NH4, up to 17.7 mg l-1) likely originating from wastewater discharges. Trace metal concentrations also rose sharply (e.g., Cr and Hg rose up to 10-fold higher) in both water and sediments but remained under the World Health Organization (WHO) and Vietnamese concentration guidelines. In the downstream estuarine area, the intrusion of marine waters diluted water flowing from HCMC, leading water quality to return close to the state observed upstream from HCMC. In general, levels of nutrient and metal contaminations along the Saigon River during both seasons appear moderate regarding to Vietnamese and WHO guidelines although the urban area is highlighted as the major contributor for metal(oid) emissions. Finally, we showed that apart from wastewater and industrial discharges that affect the river quality, metal(oid) partitioning between solid and solution is controlled by the change in water geochemistry along the continuum during both seasons, such as DO (e.g., for As and Cr) and pH (e.g., for Pb) which drives their sorption/dissolution dynamics.

Mercury tissue residue approach in Chironomus riparius: Involvement of toxicokinetics and comparison of subcellular fractionation methods.

Along with the growing body of evidence that total internal concentration is not a good indicator of toxicity, the Critical Body Residue (CBR) approach recently evolved into the Tissue Residue Approach (TRA) which considers the biologically active portion of metal that is available to contribute to the toxicity at sites of toxic action. For that purpose, we examined total mercury (Hg) bioaccumulation and subcellular fractionation kinetics in fourth stage larvae of the midge Chironomus riparius during a four-day laboratory exposure to Hg-spiked sediments and water. The debris (including exoskeleton, gut contents and cellular debris), granule and organelle fractions accounted only for about 10% of the Hg taken up, whereas Hg concentrations in the entire cytosolic fraction rapidly increased to approach steady-state. Within this fraction, Hg compartmentalization to metallothionein-like proteins (MTLP) and heat-sensitive proteins (HSP), consisting mostly of enzymes, was assessed in a comparative manner by two methodologies based on heat-treatment and centrifugation (HT&C method) or size exclusion chromatography separation (SECS method). The low Hg recoveries obtained with the HT&C method prevented accurate analysis of the cytosolic Hg fractionation by this approach. According to the SECS methodology, the Hg-bound MTLP fraction increased linearly over the exposure duration and sequestered a third of the Hg flux entering the cytosol. In contrast, the HSP fraction progressively saturated leading to Hg excretion and physiological impairments. This work highlights several methodological and biological aspects to improve our understanding of Hg toxicological bioavailability in aquatic invertebrates.

Total and methylmercury partitioning between colloids and true solution: From case studies in sediment overlying and porewaters to a generalized model.

Tangential flow ultrafiltration was used to determine the partitioning of total mercury (THg) and monomethylmercury (MMHg) between colloids and true solution in sediment overlying and porewaters collected in Lake Geneva (Switzerland and France), Venice Lagoon (Italy), and Baihua Reservoir (China). Overlying water and porewater spanned different ranges of THg and MMHg concentrations, redox conditions, and salinity. Total Hg, MMHg, and dissolved organic carbon (DOC) concentrations were measured in filter-passing (<0.45 µm), colloidal (3 kDa-0.45 µm), and truly dissolved (<3 kDa) fractions. The percentages of filterable Hg and MMHg associated with colloids (arithmetic means ±1 standard deviation [SD]) were 29 ± 11% for THg (range, 4-60%) and 44 ± 17% for MMHg (range, 15-65%). Ultrafiltration DOC mass balances were often not satisfactory. However, this was apparently without consequences on THg/MMHg fractionation, suggesting that only a part of total DOC controlled THg/MMHg partitioning in overlying water and porewater. Linear relationships existed between filter passing and truly dissolved concentrations of THg and MMHg, suggesting that mechanisms controlling their partitioning are, at least partly, similar across aquatic systems. These linear relationships could be extended to data from published studies and ultrafilterable concentrations often could be predicted, within a factor of 2, from the measurement of filter-passing ones. The possibility to easily model THg/MMHg partitioning across aquatic systems will facilitate its consideration in general biogeochemical THg/MMHg models.

Mercury mobilization and speciation linked to bacterial iron oxide and sulfate reduction: A column study to mimic reactive transfer in an anoxic aquifer.

Mercury (Hg) mobility and speciation in subsurface aquifers is directly linked to its surrounding geochemical and microbial environment. The role of bacteria on Hg speciation (i.e., methylation, demethylation and reduction) is well documented, however little data is available on their impact on Hg mobility. The aim of this study was to test if (i) Hg mobility is due to either direct iron oxide reduction by iron reducing bacteria (IRB) or indirect iron reduction by sulfide produced by sulfate reducing bacteria (SRB), and (ii) to investigate its subsequent fate and speciation. Experiments were carried out in an original column setup combining geochemical and microbiological approaches that mimic an aquifer including an interface of iron-rich and iron depleted zones. Two identical glass columns containing iron oxides spiked with Hg(II) were submitted to (i) direct iron reduction by IRB and (ii) to indirect iron reduction by sulfides produced by SRB. Results show that in both columns Hg was leached and methylated during the height of bacterial activity. In the column where IRB are dominant, Hg methylation and leaching from the column was directly correlated to bacterial iron reduction (i.e., Fe(II) release). In opposition, when SRB are dominant, produced sulfide induced indirect iron oxide reduction and rapid adsorption of leached Hg (or produced methylmercury) on neoformed iron sulfides (e.g., Mackinawite) or its precipitation as HgS. At the end of the SRB column experiment, when iron-oxide reduction was complete, filtered Hg and Fe concentrations increased at the outlet suggesting a leaching of Hg bound to FeS colloids that may be a dominant mechanism of Hg transport in aquifer environments. These experimental results highlight different biogeochemical mechanisms that can occur in stratified sub-surface aquifers where bacterial activities play a major role on Hg mobility and changes in speciation.

High methylmercury production under ferruginous conditions in sediments impacted by sewage treatment plant discharges.

Sewage treatment plants (STPs) are important point sources of mercury (Hg) to the environment. STPs are also significant sources of iron when hydrated ferric oxide (HFO) is used as a dephosphatation agent during water purification. In this study, we combined geochemical and microbiological characterization with Hg speciation and sediment amendments to evaluate the impact of STP's effluents on monomethylmercury (MMHg) production. The highest in-situ Hg methylation was found close to the discharge pipe in subsurface sediments enriched with Hg, organic matter, and iron. There, ferruginous conditions were prevailing with high concentrations of dissolved Fe(2+) and virtually no free sulfide in the porewater. Sediment incubations demonstrated that the high MMHg production close to the discharge was controlled by low demethylation yields. Inhibition of dissimilatory sulfate reduction with molybdate led to increased iron reduction rates and Hg-methylation, suggesting that sulfate-reducing bacteria (SRB) may not have been the main Hg methylators under these conditions. However, Hg methylation in sediments amended with amorphous Fe(III)-oxides was only slightly higher than control conditions. Thus, in addition to iron-reducing bacteria, other non-SRB most likely contributed to Hg methylation. Overall, this study highlights that sediments impacted by STP discharges can become local hot-spots for Hg methylation due to the combined inputs of i) Hg, ii) organic matter, which fuels bacterial activities and iii) iron, which keeps porewater sulfide concentration low and hence Hg bioavailable.

Human exposure to mercury in artisanal small-scale gold mining areas of Kedougou region, Senegal, as a function of occupational activity and fish consumption.

We investigated mercury (Hg) exposure of food web and humans in the region of Kedougou, Senegal, where Hg is used for gold amalgamation in artisanal small-scale gold mining (ASGM). For this purpose, total mercury (THg) concentration was determined in eight fish species and two shellfish species from Gambia River and in human hair from 111 volunteers of different age and sex, living in urban locations (Kedougou and Samekouta) or in ASGM areas (Tinkoto and Bantako). THg concentrations in fish samples range from 0.03 to 0.51 mg kg(-1) wet weight (ww) and 0.5 to 1.05 mg kg(-1) ww for shellfish. THg concentrations in fish are below the WHO guideline of 0.5 mg kg(-1) ww, whereas 100 % of shellfish are above this safety guideline. In the entire set of fish and shellfish samples, we documented a decrease of THg concentrations with increasing selenium to mercury (Se:Hg) ratio suggesting a protection of Se against Hg. However, local population consuming fish from the Gambia River in the two ASGM areas have higher THg concentrations (median = 1.45 and 1.5 mg kg(-1) at Bantako and Tinkoto) in hair than those from others localities (median = 0.42 and 0.32 mg kg(-1) at Kedougou town and Samekouta) who have diverse diets. At ASGM sites, about 30 % of the local population present Hg concentrations in hair exceeding 1 mg kg(-1), defined as the reference concentration of Hg in hair. We also evidence a higher exposure of women to Hg in the Tinkoto ASGM site due to the traditional distribution of daily tasks where women are more involved in the burning of amalgams. The discrepancy between the calculated moderate exposure through fish consumption and the high Hg concentrations measured in hair suggest that fish consumption is not the only source of Hg exposure and that further studies should focus on direct exposure to elemental Hg of population living at ASGM sites.

Atmospheric mercury incorporation in soils of an area impacted by a chlor-alkali plant (Grenoble, France): contribution of canopy uptake.

This study focused on the fluxes of mercury (Hg) and mechanisms of incorporation into soils surrounding a chlor-alkali plant suspected to have emitted up to ~600 kg Hg year(-1) for decades into the atmosphere. Comparison of vertical Hg soil profiles with As, Cu, Ni and Zn (which were not emitted by the plant) support Hg enrichment in surface horizons due to atmospheric Hg inputs from the chlor-alkali plant. Based on chemical extractions and elemental correlations, Hg was found to be weakly leachable and bio-available for plants, and most probably strongly bound to organic matter. In contrast, other trace elements were probably associated with phyllosilicates, iron oxides or with primary minerals. Hg stocks in the surface horizon of a forested soil (1255 mg Hg m(-3)) were two-fold higher than in an agricultural soil (636 mg Hg m(-3)) at a similar distance to the plant. The difference was attributed to the interception of atmospheric Hg by the canopy (most likely gaseous elemental Hg and reactive gaseous Hg) and subsequent litterfall incorporation. Some differences in the ability to trap atmospheric Hg were observed between tree species. The characterization of the litter showed an increasing Hg concentration in the plant material proportional to their degradation stage. In agricultural soils, very low Hg concentrations found in corn leaves and grains suggested a limited uptake via both the foliar and root pathways. Thus, the short-term risk of Hg transfer to agricultural crops and higher levels of the trophic chain appeared limited. A possible risk which remains to be evaluated is the possible transfer of Hg-rich particles from the forest topsoil to downstream aquatic ecosystems during rain and snowmelt events.

Insights into low fish mercury bioaccumulation in a mercury-contaminated reservoir, Guizhou, China.

We examined Hg biogeochemistry in Baihua Reservoir, a system affected by industrial wastewater containing mercury (Hg). As expected, we found high levels of total Hg (THg, 664-7421 ng g(-1)) and monomethylmercury (MMHg, 3-21 ng g(-1)) in the surface sediments (0-10 cm). In the water column, both THg and MMHg showed strong vertical variations with higher concentrations in the anoxic layer (>4m) than in the oxic layer (0-4 m), which was most pronounced for the dissolved MMHg (p < 0.001). However, mercury levels in biota samples (mostly cyprinid fish) were one order of magnitude lower than common regulatory values (i.e. 0.3-0.5 mg kg(-1)) for human consumption. We identified three main reasons to explain the low fish Hg bioaccumulation: disconnection of the aquatic food web from the high MMHg zone, simple food web structures, and biodilution effect at the base of the food chain in this eutrophic reservoir.

Amazonian former gold mined soils as a source of methylmercury: evidence from a small scale watershed in French Guiana.

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.

Mercury distribution in tropical soil profiles related to origin of mercury and soil processes.

The aim of the study is to improve our understanding of the vertical and lateral variations in the mercury content [Hg] of tropical soils. In addition to the distance to anthropogenic sources of Hg, the most frequently evoked determining factor is the abundance of Hg-bearing phases. Soil processes (weathering, mass or water transfer) determine the abundance of carrier phases. We assume that soil processes also have a direct impact on the distribution of Hg and that the impact is different according to the lithogenic or atmospheric origin of this element. We compare two types of soil (oxisol and ultisol) in the French Guiana forest, at localities a few tens of metres apart and exhibiting very different Hg contents. We show that vertical profiles of [Hg] are strongly related to the variations of [Hg(atmospheric)], whereas [Hg(lithogenic)] varies little. The penetration of Hg(atmospheric) from the surface deposits is favoured down to a depth of 3 m in the oxisol and limited to the upper horizons of the ultisol because of contrasted hydraulic conductivity between the two soils. Hg is primarily of lithogenic origin in the alteritic horizons of the ultisol. The relative accumulation of Hg(lithogenic) during the progressive weathering of parental material is limited near the soil surface by the disequilibrium of secondary minerals. Remobilization of Hg(atmospheric) or Hg(lithogenic) stored in the soil is a function of the chemical or particulate erosion of Hg-bearing phases, particularly active in the upper horizons of the ultisol, where lateral flow occurs during rain events. The correlations observed between the iron or clay contents and [Hg] can be caused by the affinity of Hg for these carrier phases, but may also reflect the weathering and the transfer processes which affect together the fate of Hg and the mineralogical and chemical composition of the soil.