Impact of forest fire on the mercury stable isotope composition in litter and soil in the Amazon.

Mercury (Hg) emissions from forest fires, especially tropical forests such as the Amazonian forest, were shown to contribute significantly to the atmospheric mercury budget, but new methods are still necessary to improve the traceability and to reduce the great uncertainties related to this emission source. Recent studies have shown that the combustion process can result in Hg stable isotope fractionation that allows tracking coal combustion Hg emissions, as influenced by different factors such as combustion temperature. The main goal of the present study was, therefore, to investigate for the first time the potential of Hg stable isotopes to trace forest fire Hg emissions and pathways. More specifically, small-scale and a large scale prescribed forest fire experiments were conducted in the Brazilian Amazonian forest to study the impact of fire severity on Hg isotopic composition of litter, soil, and ash samples and associated Hg isotope fractionation pathways. In the small-scale experiment, no difference was found in the mercury isotopic composition of the samples collected before and after burning. In contrast, the larger-scale experiment resulted in significant mass dependent fractionation (MDF δ202Hg) in soils and ash suggesting that higher combustion temperature influence Hg isotopic fractionation with the emission of lighter Hg isotopes to the atmosphere and enrichment with heavier Hg in ashes. As for coal combustion, mass independent fractionation was not observed. To our knowledge, these results are the first to highlight the potential of forest fires to cause Hg isotopic fractionation, depending on the fire severity. The results also allowed to establish an isotopic fingerprint for tropical forest fire Hg emissions that corresponds to a mixture of litter and soil Hg isotopic composition (resulting atmospheric δ202Hg, Δ200Hg and Δ199Hg were -1.79 ± 0.24‰, -0.05 ± 0.04‰ and -0.45 ± 0.12‰, respectively).

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.

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.

Role of the floodplain lakes in the methylmercury distribution and exchanges with the Amazon River, Brazil.

Seasonal variability of dissolved and particulate methylmercury (F-MeHg, P-MeHg) concentrations was studied in the waters of the Amazon River and its associated Curuai floodplain during hydrological year 2005-2006, to understand the MeHg exchanges between these aquatic systems. In the oxic white water lakes, with neutral pH, high F-MeHg and P-MeHg concentrations were measured during the rising water stage (0.70±0.37pmol/L, n=26) and flood peak (14.19±9.32pmol/g, n=7) respectively, when the Amazon River water discharge into the lakes was at its maximum. The lowest mean values were reported during the dry season (0.18±0.07pmol/L F-MeHg, n=10 and 1.35±1.24pmol/g P-MeHg, n=8), when water and suspended sediments were outflowing from the lakes into the River. In these lakes, the MeHg concentrations were associated to the aluminium and organic carbon/nitrogen changes. In the black water lakes, with acidic pH and reducing conditions, elevated MeHg concentrations were recorded (0.58±0.32pmol/L F-MeHg, n=16 and 19.82±15.13pmol/g P-MeHg, n=6), and correlated with the organic carbon and manganese concentrations. Elevated values of MeHg partition coefficient (4.87

Mercury speciation in plankton from the Cabo Frio Bay, SE--Brazil.

Mercury (Hg) is considered a global pollutant, and the scientific community has shown great concern about its toxicity as it may affect the biota of entire systems, through bioaccumulation and bioamplification processes of its organic form, methylmercury (MeHg), along food web. However, few research studies deal with bioaccumulation of Hg from marine primary producers and the first-order consumers. So, this study aims to determine Hg distribution and concentration levels in phytoplankton and zooplankton in the Cabo Frio Bay, Brazil, a site influenced by coastal upwelling. The results from Hg speciation analyses show that inorganic mercury Hg(II) was the predominant specie in plankton from this bay. The annual Hg species distribution in plankton shown mean concentration of 2.00 ± 1.28 ng Hg(II) g(-1) and 0.15 ± 0.08 ng MeHg g(-1) wet weight (phytoplankton) and 2.5 ± 2.03 ng Hg(II) g(-1) and 0.25 ± 0.09 ng MeHg g(-1) wet weight (zooplankton). Therefore, upwelling zones should be considered in the Hg biogeochemical cycle models as a process that enhances Hg(II) bioaccumulation in plankton, raising its bioavailability and shelf deposition.