Mercury compound distribution and stable isotope composition in the different compartments of seabird eggs: the case of three species breeding in East Greenland.

Mercury (Hg) is a toxic contaminant of global concern and the impact on Arctic ecosystems, particularly in seabirds, is critical due to large-scale Hg transport towards polar regions and its biomagnification in marine trophic systems. While the adverse effects of Hg on reproductive processes in seabirds are established, the understanding of Hg maternal transfer pathways and their control on Hg reproductive toxicity is limited. The combination of Hg compounds speciation (inorganic mercury and monomethylmercury MMHg) and Hg stable isotope composition in the different egg compartments (yolk, albumen, membrane, and shell) before embryo development was investigated to provide information on (i) Hg maternal transfer mechanisms, (ii) influence of egg biochemical composition on Hg organotropism and (iii) proxies of inputs of Hg contamination. Eggs of three seabird species (the common eider, the black-legged kittiwake and the little auk) collected within the same breeding period (summer 2020) in East Greenland were investigated. For all seabirds, albumen and membrane, the most protein-rich compartments, were the most contaminated (from 1.2 to 2.7 µg.g-1 for albumen and from 0.3 to 0.7 µg.g-1 for membrane). In these two compartments, more than 82% of the total Hg amount was in the form of MMHg. Additionally, mass-dependent fractionation values (δ202Hg) were higher in albumen and membrane in the three species. This result was mainly due the organotropism of MMHg as influenced by the biochemical properties and chemical binding affinity of these proteinous compartments. Among the different egg compartments, individuals and species, mass-independent fractionation values were comparable (mean±sd were 0.99±0.11‰, 0.78±0.11‰, 0.03±0.05‰, 0.04±0.10‰ for Δ199Hg, Δ201Hg, Δ200Hg and Δ204Hg, respectively). We conclude that initial MMHg accumulated in the three species originated from Arctic environmental reservoirs exhibiting similar and low photodemethylation extent. This result suggests a unique major source of MMHg in those ecosystems, potentially influenced by sea ice cover.

Dynamics of mercury stable isotope compounds in Arctic seals: New insights from a controlled feeding trial on hooded seals Cystophora cristata.

Accurate interpretation of mercury (Hg) isotopic data requires the consideration of several biotic factors such as age, diet, geographical range, and tissue metabolic turnover. A priori knowledge of prey-predator isotopic incorporation rates and Hg biomagnification is essential. This study aims to assess Hg stable isotopes incorporation in an Arctic species of Phocidae, the hooded seal Cystophora cristata, kept in human care for 24 months (2012-2014) and fed on a constant diet of Norwegian Spring Spawning herring Clupea harengus. We measured THg, MMHg and iHg levels, as well as Hg stable isotope composition with both mass dependent (MDF) and mass independent (MIF) fractionation (e.g. δ202Hg and Δ199,200,201,204Hg) in hooded seal kidney, liver, hair and muscle, in addition to herring muscle. We then calculated Hg MDF and MIF isotopic fractionation between hooded seals and their prey. We found a significant shift in δ202Hg between hooded seal hair (+0.80‰) and kidney (-0.78‰), and herring muscle. In hooded seals tissues δ202Hg correlated positively with MMHg percentage. These findings suggest that tissue-specific Hg speciation is the major driver of changes in Hg isotopic fractionation rates in this Arctic predator. Δ199Hg, Δ200Hg, Δ201Hg and Δ204Hg values did not vary between herring and hooded seal tissues, confirming their utility as tracers of Hg marine and atmospheric sources in top predators. To our knowledge, this represents the first attempt to assess complex Hg isotope dynamics in the internal system of Arctic Phocidae, controlling the effects of age, diet, and distribution. Our results confirm the validity of Hg stable isotopes as tracers of environmental Hg sources even in top predators, but emphasize the importance of animal age and tissue selection for inter-study and inter-species comparisons.

Molybdate inhibits mercury methylation capacity of Pseudodesulfovibrio hydrargyri BerOc1 regardless of the growth metabolism.

Molybdate inhibits sulfate respiration in sulfate-reducing bacteria (SRB). It is used as an inhibitor to indirectly evaluate the role of SRB in mercury methylation in the environment. Here, the SRB Pseudodesulfovibrio hydrargyri BerOc1 was used to assess the effect of molybdate on cell growth and mercury methylation under various metabolic conditions. Geobacter sulfurreducens PCA was used as the non-SRB counterpart strain with the ability to methylate mercury. While PCA growth and methylation are not affected by molybdate, 1 mM of molybdate inhibits BerOc1 growth under sulfate respiration (50% inhibition) but also under fumarate respiration (complete inhibition). Even more surprising, mercury methylation of BerOc1 is totally inhibited at 0.1 mM of molybdate when grown under sulfate or fumarate respiration with pyruvate as the electron donor. As molybdate is expected to reduce cellular ATP level, the lower Hg methylation observed with pyruvate could be the consequence of lower energy production. Although molybdate alters the expression of hgcA (mercury methylation marker) and sat (involved in sulfate reduction and molybdate sensitivity) in a metabolism-dependent manner, no relationship with mercury methylation rates could be found. Our results show, for the first time, a specific mercury methylation inhibition by molybdate in SRB.

Organ-specific mercury stable isotopes, speciation and particle measurements reveal methylmercury detoxification processes in Atlantic Bluefin Tuna.

Identifying metabolism and detoxification mechanisms of Hg in biota has important implications for biomonitoring, ecotoxicology, and food safety. Compared to marine mammals and waterbirds, detoxification of MeHg in fish is understudied. Here, we investigated Hg detoxification in Atlantic bluefin tuna Thunnus thynnus using organ-specific Hg and Se speciation data, stable Hg isotope signatures, and Hg and Se particle measurements in multiple tissues. Our results provide evidence for in vivo demethylation and biomineralization of HgSe particles, particularly in spleen and kidney. We observed a maximum range of 1.83‰ for δ202Hg between spleen and lean muscle, whereas Δ199Hg values were similar across all tissues. Mean percent methylmercury ranged from 8% in spleen to 90% in lean muscle. The particulate masses of Hg and Se were higher in spleen and kidney (Hg: 61% and 59%, Se: 12% and 6%, respectively) compared to muscle (Hg: 2%, Se: 0.05%). Our data supports the hypothesis of an organ-specific, two-step detoxification of methylmercury in wild marine fish, consisting of demethylation and biomineralization, like reported for waterbirds. While mass dependent fractionation signatures were highly organ specific, stable mass independent fractionation signatures across all tissues make them potential candidates for source apportionment studies of Hg using ABFT.

Mercury stable isotopes in seabirds in the Ebro Delta (NE Iberian Peninsula): Inter-specific and temporal differences.

Mercury (Hg) is a global pollutant, which particularly affects aquatic ecosystems, both marine and freshwater. Top-predators depending on these environments, such as seabirds, are regarded as suitable bioindicators of Hg pollution. In the Ebro Delta (NE Iberian Peninsula), legacy Hg pollution from a chlor-alkali industry operating in Flix and located ca. 100 km upstream of the Ebro River mouth has been impacting the delta environment and the neighboring coastal area. Furthermore, levels of Hg in the biota of the Mediterranean Sea are known to be high compared to other marine areas. In this work we used a Hg stable isotopes approach in feathers to understand the processes leading to different Hg concentrations in three Laridae species breeding in sympatry in the area (Audouin's gull Ichthyaetus audouinii, black-headed gull Chroicocephalus ridibundus, common tern Sterna hirundo). These species have distinct trophic ecologies, exhibiting a differential use of marine resources and freshwater resources (i.e., rice paddies prey). Moreover, for Audouin's gull, in which in the Ebro Delta colony temporal differences in Hg levels were documented previously, we used Hg stable isotopes to understand the impact of anthropogenic activities on Hg levels in the colony over time. Hg stable isotopes differentiated the three Laridae species according to their trophic ecologies. Furthermore, for Audouin's gull we observed temporal variations in Hg isotopic signatures possibly owing to anthropogenic-derived pollution in the Ebro Delta. To the best of our knowledge this is the first time Hg stable isotopes have been reported in seabirds from the NW Mediterranean.

Temporal mercury dynamics throughout the rice cultivation season in the Ebro Delta (NE Spain): An integrative approach.

During the last few decades, inputs of mercury (Hg) to the environment from anthropogenic sources have increased. The Ebro Delta is an important area of rice production in the Iberian Peninsula. Given the industrial activity and its legacy pollution along the Ebro river, residues containing Hg have been transported throughout the Ebro Delta ecosystems. Rice paddies are regarded as propitious environments for Hg methylation and its subsequent incorporation to plants and rice paddies' food webs. We have analyzed how Hg dynamics change throughout the rice cultivation season in different compartments from the paddies' ecosystems: soil, water, rice plants and fauna. Furthermore, we assessed the effect of different agricultural practices (ecological vs. conventional) associated to various flooding patterns (wet vs. mild alternating wet and dry) to the Hg levels in rice fields. Finally, we have estimated the proportion of methylmercury (MeHg) to total mercury in a subset of samples, as MeHg is the most bioaccumulable toxic form for humans and wildlife. Overall, we observed varying degrees of mercury concentration over the rice cultivation season in the different compartments. We found that different agricultural practices and flooding patterns did not influence the THg levels observed in water, soil or plants. However, Hg concentrations in fauna samples seemed to be affected by hydroperiod and we also observed evidence of Hg biomagnification along the rice fields' aquatic food webs.

Assessing comparability and uncertainty of analytical methods for methylated mercury species in seawater.

BACKGROUND: The relative distribution and importance of monomethylmercury (MMHg) and dimethylmercury (DMHg) in seawater is still under debate. A lack of comparability between measurements at sub-picomolar levels hampered the further understanding of the biogeochemical Hg cycle. To overcome this, we assessed the relative standard measurement uncertainties (Uex,r) for direct measurements of MMHg and DMHg by species-specific isotope dilution ICP-MS and cryo-focusing GC-ICP-MS at femtomolar concentrations. Furthermore, Uex,r was determined for the indirect determination of DMHg (DMHgcalc = MeHg - MMHg) and MeHg (MeHgcalc = MMHg + DMHg) to compare the two methodologies. RESULTS: Expanded Uex,r (confidence interval of 95%) for cryo-focusing GC-ICP-MS was 14.4 (<50 fM) and 14.2% (>50 fM) and for SS-ID GC-ICP-MS 5.6 (<50 fM) and 3.7% (>50 fM). For concentrations above 50 fM, Uex,r for DMHgcalc was always lower than for direct measurements (14.2%). For MeHgcalc, on the other hand, Uex,r was always higher for concentrations above 115 fM (range: 3.7-13.9%) than for direct measurements (3.7%). We evaluated the comparability of directly measured and calculated DMHg and MeHg concentrations based on Hg speciation measurements for two vertical profiles in the Mediterranean Sea. We show that directly measured and indirectly determined DMHg and MeHg concentrations yield comparable results. SIGNIFICANCE: Our results validate the application of the indirect method for the determination of DMHg if a direct measurement method with a low Uex,r such as isotope dilution is used for MMHg and MeHg measurements. The validation of the indirect measurement approach opens new possibilities to generate more precise and accurate DMHg data in the global ocean.

Mercury Sources and Fate in a Large Brackish Ecosystem (the Baltic Sea) Depicted by Stable Isotopes.

Identifying Hg sources to aquatic ecosystems and processes controlling the levels of monomethylmercury (MMHg) is critical for developing efficient policies of Hg emissions reduction. Here we measured Hg concentrations and stable isotopes in sediment, seston, and fishes from the various basins of the Baltic Sea, a large brackish ecosystem presenting extensive gradients in salinity, redox conditions, dissolved organic matter (DOM) composition, and biological activities. We found that Hg mass dependent fractionation (Hg-MDF) values in sediments mostly reflect a mixing between light terrestrial Hg and heavier industrial sources, whereas odd Hg isotope mass independent fractionation (odd Hg-MIF) reveals atmospheric inputs. Seston presents intermediate Hg-MDF and odd Hg-MIF values falling between sediments and fish, but in northern basins, high even Hg-MIF values suggest the preferential accumulation of wet-deposited Hg. Odd Hg-MIF values in fish indicate an overall low extent of MMHg photodegradation due to limited sunlight exposure and penetration but also reveal large spatial differences. The photodegradation extent is lowest in the central basin with recurrent algal blooms due to their shading effect and is highest in the northern, least saline basin with high concentrations of terrestrial DOM. As increased loads of terrestrial DOM are expected in many coastal areas due to global changes, its impact on MMHg photodegradation needs to be better understood and accounted for when predicting future MMHg concentrations in aquatic ecosystems.

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).

Influence of oxygen, UV light and reactive dissolved organic matter on the photodemethylation and photoreduction of monomethylmercury in model freshwater.

The key factors which affect the abiotic photodemethylation process of monomethylmercury (MMHg) in the freshwaters has remained unclear. Hence, this work aimed to better elucidate the abiotic photodemethylation pathway in a model freshwater. Anoxic and oxic conditions were implemented to investigate the simultaneous photodemethylation to Hg(II) and photoreduction to Hg(0). MMHg freshwater solution was irradiated through exposure to three wavelength ranges of full light (280-800 nm), without short UVB (305-800 nm), and visible light (400-800 nm). The kinetic experiments were performed following dissolved and gaseous Hg species concentrations (i.e., MMHg, iHg(II), Hg(0)). A comparison between two methods of post-irradiation purging and continuous-irradiation purging confirmed MMHg photodecomposition to Hg(0) is mainly induced by a first photodemethylation step to iHg(II) followed by a photoreduction step to Hg(0). Photodemethylation under full light extent normalized to absorbed radiation energy showed a higher rate constant in anoxic conditions at 18.0 ± 2.2 kJ-1 compared to oxic conditions at 4.5 ± 0.4 kJ-1. Moreover, photoreduction also increased up to four-fold under anoxic conditions. Normalized and wavelength-specific photodemethylation (Kpd) and photoreduction (Kpr) rate constants were also calculated for natural sunlight conditions to evaluate the role of each wavelength range. The relative ratio in wavelength-specific KPAR: Klong UVB+ UVA: K short UVB showed higher dependence on UV light for photoreduction at least ten-fold compared to photodemethylation, regardless of redox conditions. Both results using Reactive Oxygen Species (ROS) scavenging methods and Volatile Organic Compounds (VOC) measurements revealed the occurrence and production of low molecular weight (LMW) organic compounds that are as photoreactive intermediates responsible for MMHg photodemethylation and iHg(II) photoreduction in the dominant pathway. This study also supports the role of dissolved oxygen as an inhibitor for the photodemethylation pathways driven by LMW photosensitizers.

In Vivo Mercury (De)Methylation Metabolism in Cephalopods under Different pCO2 Scenarios.

This work quantified the accumulation efficiencies of Hg in cuttlefish, depending on both organic (MeHg) and inorganic (Hg(II)) forms, under increased pCO2 (1600 µatm). Cuttlefish were fed with live shrimps injected with two Hg stable isotopic tracers (Me202Hg and 199Hg(II)), which allowed for the simultaneous quantification of internal Hg accumulation, Hg(II) methylation, and MeHg demethylation rates in different organs. Results showed that pCO2 had no impact on Hg bioaccumulation and organotropism, and both Hg and pCO2 did not influence the microbiota diversity of gut and digestive gland. However, the results also demonstrated that the digestive gland is a key organ for in vivo MeHg demethylation. Consequently, cuttlefish exposed to environmental levels of MeHg could exhibit in vivo MeHg demethylation. We hypothesize that in vivo MeHg demethylation could be due to biologically induced reactions or to abiotic reactions. This has important implications as to how some marine organisms may respond to future ocean change and global mercury contamination.

A century of mercury: Ecosystem-wide changes drive increasing contamination of a tropical seabird species in the South Atlantic Ocean.

Mercury (Hg) is a highly toxic metal that adversely impacts human and wildlife health. The amount of Hg released globally in the environment has increased steadily since the Industrial Revolution, resulting in growing contamination in biota. Seabirds have been extensively studied to monitor Hg contamination in the world's oceans. Multidecadal increases in seabird Hg contamination have been documented in polar, temperate and subtropical regions, whereas in tropical regions they are largely unknown. Since seabirds accumulate Hg mainly from their diet, their trophic ecology is fundamental in understanding their Hg exposure over time. Here, we used the sooty tern (Onychoprion fuscatus), the most abundant tropical seabird, as bioindicator of temporal variations in Hg transfer to marine predators in tropical ecosystems, in response to trophic changes and other potential drivers. Body feathers were sampled from 220 sooty terns, from museum specimens (n = 134) and free-living birds (n = 86) from Ascension Island, in the South Atlantic Ocean, over 145 years (1876-2021). Chemical analyses included (i) total- and methyl-Hg, and (ii) carbon (δ1³C) and nitrogen (δ15N) stable isotopes, as proxies of foraging habitat and trophic position, respectively, to investigate the relationship between trophic ecology and Hg contamination over time. Despite current regulations on its global emissions, mean Hg concentrations were 58.9% higher in the 2020s (2.0 µg g-1, n = 34) than in the 1920s (1.2 µg g-1, n = 107). Feather Hg concentrations were negatively and positively associated with δ1³C and δ15N values, respectively. The sharp decline of 2.9 ‰ in δ1³C values over time indicates ecosystem-wide changes (shifting primary productivity) in the tropical South Atlantic Ocean and can help explain the observed increase in terns' feather Hg concentrations. Overall, this study provides invaluable information on how ecosystem-wide changes can increase Hg contamination of tropical marine predators and reinforces the need for long-term regulations of harmful contaminants at the global scale.

Upside down sulphate dynamics in a saline inland lake.

The sulphur cycle has a key role on the fate of nutrients through its several interconnected reactions. Although sulphur cycling in aquatic ecosystems has been thoroughly studied since the early 70's, its characterisation in saline endorheic lakes still deserves further exploration. Gallocanta Lake (NE Spain) is an ephemeral saline inland lake whose main sulphate source is found on the lake bed minerals and leads to dissolved sulphate concentrations higher than those of seawater. An integrative study including geochemical and isotopic characterization of surface water, porewater and sediment has been performed to address how sulphur cycling is constrained by the geological background. In freshwater and marine environments, sulphate concentration decreases with depth are commonly associated with bacterial sulphate reduction (BSR). However, in Gallocanta Lake sulphate concentrations in porewater increase from 60 mM at the water-sediment interface to 230 mM at 25 cm depth. This extreme increase could be caused by dissolution of the sulphate rich mineral epsomite (MgSO4·7H2O). Sulphur isotopic data was used to validate this hypothesis and demonstrate the occurrence of BSR near the water-sediment interface. This dynamic prevents methane production and release from the anoxic sediment, which is advantageous in the current context of global warming. These results underline that geological context should be considered in future biogeochemical studies of inland lakes with higher potential availability of electron acceptors in the lake bed compared to the water column.

Dynamics, distribution, and transformations of mercury species from pyrenean high-altitude lakes.

While mercury (Hg) is a major concern in all aquatic environments because of its methylation and biomagnification pathways, very few studies consider Hg cycling in remote alpine lakes which are sensitive ecosystems. Nineteen high-altitude pristine lakes from Western/Central Pyrenees were investigated on both northern (France) and southern (Spain) slopes (1620-2600 m asl.). Subsurface water samples were collected in June 2017/2018/2019 and October 2017/2018 for Hg speciation analysis of inorganic mercury (iHg(II)), monomethylmercury (MMHg), and dissolved gaseous mercury (DGM) to investigate spatial and seasonal variations. In June 2018/2019 and October 2018, more comprehensive studies were performed in four lakes by taking water column depth profiles. Besides, in-situ incubation experiments using isotopically enriched Hg species (199iHg(II), 201MMHg) were conducted to investigate Hg transformation mechanisms in the water column. While iHg(II) (0.08-1.10 ng L-1 in filtered samples; 0.11-1.19 ng L-1 in unfiltered samples) did not show significant seasonal variations in the subsurface water samples, MMHg (<0.03-0.035 ng L-1 in filtered samples; <0.03-0.062 ng L-1 in unfiltered samples) was significantly higher in October 2018, mainly because of in-situ methylation. DGM (0.02-0.68 ng L-1) varies strongly and can exhibit higher levels in comparison with other pristine areas. Depth profiles and incubation experiments highlighted the importance of in-situ biotic methylation triggered by anoxic conditions in bottom waters. In-situ incubations confirm that significant methylation, demethylation and photoreduction extents are taking place in the water columns. Overall, drastic environmental changes occurring daily and seasonally in alpine lakes are providing conditions that can both promote Hg methylation (stratified anoxic waters) and MMHg photodemethylation (intense UV light). In addition, light induced photoreduction is a major pathway controlling significant gaseous Hg evasion. Global warming and potential eutrophication may thus have direct implications on Hg turnover and MMHg burden in those remote ecosystems.

Assessing and predicting the changes for inorganic mercury and methylmercury concentrations in surface waters of a tidal estuary (Adour Estuary, SW France).

Total and dissolved concentrations of inorganic mercury (IHg) and methylmercury (MeHg) in water (Adour Estuary) were determined during three sampling campaigns and related to biogeochemical variables (nutrients, organic matter). Factors (sampling time, sample type) were included in analysis of covariance with effect separation. The urban estuary suffered historically from anthropogenic sources, however, decreased emissions have reduced Hg concentrations. Total IHg (0.51-3.42 ng L-1) and MeHg (25-81 pg L-1) concentrations are additively described by suspended particulate matter and particulate organic carbon. Higher total concentrations, carried by organic-rich particles, were found near specific discharge points (0.79-8.02 ng L-1 and 34-235 pg L-1 for IHg and MeHg, respectively). The associated high dissolved MeHg concentrations could not be explained only by biogeochemical variables. Better efficiency of the models is found for total than for dissolved concentrations. Models should be checked with other contaminants or with estuaries, suffering from downstream contamination.

Effect of exogenous and endogenous sulfide on the production and the export of methylmercury by sulfate-reducing bacteria.

Mercury (Hg) is a global pollutant of environmental and health concern; its methylated form, methylmercury (MeHg), is a potent neurotoxin. Sulfur-containing molecules play a role in MeHg production by microorganisms. While sulfides are considered to limit Hg methylation, sulfate and cysteine were shown to favor this process. However, these two forms can be endogenously converted by microorganisms into sulfide. Here, we explore the effect of sulfide (produced by the cell or supplied exogenously) on Hg methylation. For this purpose, Pseudodesulfovibrio hydrargyri BerOc1 was cultivated in non-sulfidogenic conditions with addition of cysteine and sulfide as well as in sulfidogenic conditions. We report that Hg methylation depends on sulfide concentration in the culture and the sulfides produced by cysteine degradation or sulfate reduction could affect the Hg methylation pattern. Hg methylation was independent of hgcA expression. Interestingly, MeHg production was maximal at 0.1-0.5 mM of sulfides. Besides, a strong positive correlation between MeHg in the extracellular medium and the increase of sulfide concentrations was observed, suggesting a facilitated MeHg export with sulfide and/or higher desorption from the cell. We suggest that sulfides (exogenous or endogenous) play a key role in controlling mercury methylation and should be considered when investigating the impact of Hg in natural environments.

Arsenic Analysis in the Petroleum Industry: A Review.

The presence of arsenic in natural gas and liquid hydrocarbons is of great concern for oil companies. In addition to health risks due to its toxicity as well as environmental issues, arsenic is responsible for irreversible poisoning of catalysts and clogging of pipes via the accumulation of As-containing precipitates. To address these problems and to better design treatment units, robust methods for the analysis of arsenic and its compounds in oil streams are required. In addition, the use of feedstocks as a novel source of energy is becoming increasingly important. Most biomasses used as feedstocks are contaminated with arsenic. To avoid problems related to the presence of this element, it is therefore also necessary to have reliable methods for the analysis of arsenic and its compounds in these new fluids. This review outlines the sampling techniques, sample preparation methods, and arsenic analysis techniques developed during recent decades and commonly used in the oil industry and in the new feedstock energy domain.

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.

Selenium distribution and speciation in waters of pristine alpine lakes from central-western Pyrenees (France-Spain).

The speciation of both redox reactive and volatile selenium (Se) compounds, barely reported in pristine aquatic environments, has never been investigated in remote alpine lakes, considered as sensitive ecosystems to detect the effect of global change. This work presents an integrated investigation on Se distribution and speciation conducted in 20 high altitude pristine lakes from the central-western Pyrenees. Five seasonal sampling campaigns were carried out after snowmelt (June/July) and in early fall (October) for the period 2017-2019. Concentrations of total dissolved Se (TDSe) ranged from 7 to 78 ng L-1, with selenate being ubiquitously observed in most cases (median of 61% of TDSe). Selenite was only occasionally detected up to 4 ng L-1, therefore a fraction of TDSe was presumably in the forms of elemental Se(0) and/or selenides. Depth profiles obtained in different lakes showed the occurrence of such Se(-II, 0) pools in bottom hypoxic to anoxic waters. The production of volatile Se compounds presented a low median total concentration (TVSe) of 33 pg L-1 (range 3-120 pg L-1), mainly in the form of dimethylselenide in subsurface samples (median of 82% of TVSe). The Se concentration in lake waters was significantly correlated with the sulphate concentration (ρ = 0.93, p < 0.0001), demonstrating that it is influenced by erosion and dissolution of Se and S-enriched parent bedrocks. In addition, for Se depleted alpine lake-bedrock systems, long-range transport and wet atmospheric depositions represent a major source of Se for lake waters.

Determination of the Intracellular Complexation of Inorganic and Methylmercury in Cyanobacterium Synechocystis sp. PCC 6803.

Understanding of mercury (Hg) complexation with low molecular weight (LMW) bioligands will help elucidate its speciation. In natural waters, the rate of this complexation is governed by physicochemical, geochemical, and biochemical parameters. However, the role of bioligands involved in Hg intracellular handling by aquatic microorganisms is not well documented. Here, we combine the use of isotopically labeled Hg species (inorganic and monomethylmercury, iHg and MeHg) with gas or liquid chromatography coupling to elemental and molecular mass spectrometry to explore the role of intracellular biogenic ligands involved in iHg and MeHg speciation in cyanobacterium Synechocystis sp. PCC 6803, a representative phytoplankton species. This approach allowed to track resulting metabolic and newly found intracellular Hg biocomplexes (e.g., organic thiols) in Synechocystis sp. PCC 6803 finding different intracellular Hg species binding affinities with both high and low molecular weight (HMW and LMW) bioligands in the exponential and stationary phase. Furthermore, the parallel detection with both elemental and molecular ionization sources allowed the sensitive detection and molecular identification of glutathione (GSH) as the main low molecular weight binding ligand to iHg ((GS)2-Hg) and MeHg (GS-MeHg) in the cytosolic fraction. Such a novel experimental approach expands our knowledge on the role of biogenic ligands involved in iHg and MeHg intracellular handling in cyanobacteria.