Methylmercury degradation by hot spring sulfur-linked microbial communities as a dominant pathway in regulating mercury speciation.

Sulfidic hot springs harbor unique microbial communities and are important in mercury (Hg) species transformations, although the fine scale drivers of these processes remain poorly understood. Here we studied Hg speciation in water, biofilms, and sediment across three sampling seasons in a French sulfidic hot spring with low Hg concentrations. Microbial Hg species methylation and demethylation potentials were evaluated using incubation experiments with species-specific Hg isotope tracers. Temporal variation in inorganic Hg (iHg) and methylmercury (MeHg) concentrations in water, biofilm, and sediment was observed. The incubation of microbial communities in biofilms and sediment under dark conditions exhibited low iHg methylation potentials, whereas a significant extent of biotic MeHg demethylation to oxidized iHg was found in relation to MeHg concentrations. Results from microbial diversity (16S rDNA) and the metabolic inhibition experiments suggest an important role of sulfur-linked bacterial metabolism dynamics. Specifically, sulfate-reducers and anoxygenic phototrophs were important factors in the regulation of MeHg concentrations in our study site. Overall, the observed dominance of microbial MeHg demethylation demonstrates a strong Hg detoxification capacity in sulfidic aquatic environments.

Exploring mercury detoxification in fish: The role of selenium from tuna byproduct diets for sustainable aquaculture.

Exposure to mercury (Hg) through fish consumption poses significant environmental and public health risks, given its status as one of the top ten hazardous chemicals. Aquaculture is expanding, driving a surge in demand for sustainable aquafeeds. Tuna byproducts, which are rich in protein, offer potential for aquafeed production, yet their use is challenged by the high content of heavy metals, particularly Hg. However, these byproducts also contain elevated levels of selenium (Se), which may counteract Hg adverse effects. This study examines the fate of dietary Hg and Se in an aquaculture model fish. Biomolecular speciation analyses through hyphenated analytical approaches were conducted on the water-soluble protein fraction of key organs of juvenile rainbow trout (Oncorhynchus mykiss) exposed to various combinations of Hg and Se species, including diets containing tuna byproducts, over a six-month period. The findings shed light on the dynamics of Hg and Se compounds in fish revealing potential Hg detoxification mechanisms through complexation with Hg-biomolecules, such as cysteine, glutathione, and metallothionein. Furthermore, the trophic transfer of selenoneine is demonstrated, revealing novel opportunities for sustainable aquafeed production. Understanding the interactions between Hg and Se in aquaculture systems is crucial for optimizing feed formulations and mitigating environmental risks. This research contributes to the broader goal of advancing sustainable practices in aquaculture while addressing food security challenges.

First-Time Isotopic Characterization of Seleno-Compounds in Biota: A Pilot Study of Selenium Isotopic Composition in Top Predator Seabirds.

This study pioneers the reporting of Se isotopes in marine top predators and represents the most extensive Se isotopic characterization in animals to date. A methodology based on hydride generation─multicollector inductively coupled plasma mass spectrometry─was established for such samples. The study was conducted on various internal organs of giant petrels (Macronectes spp.), encompassing bulk tissues (δ82/78Sebulk), distinct Se-specific fractions such as selenoneine (δ82/78SeSEN), and HgSe nanoparticles (δ82/78SeNPs). The δ82/78Sebulk results (2.0-5.6‰) offer preliminary insights into the fate of Se in key internal organs of seabirds, including the liver, the kidneys, the muscle, and the brain. Notably, the liver of all individuals was enriched in heavier Se isotopes compared to other examined tissues. In nanoparticle fraction, δ82/78Se varies significantly across individuals (δ82/78SeNPs from 0.6 to 5.7‰, n = 8), whereas it exhibits remarkable consistency among tissues and individuals for selenoneine (δ82/78SeSEN, 1.7 ± 0.3‰, n = 8). Significantly, there was a positive correlation between the shift from δ82/78Sebulk to δ82/78SeSEN and the proportion of Se present as selenoneine in the internal organs. This pilot study proves that Se species-specific isotopic composition is a promising tool for a better understanding of Se species fate, sources, and dynamics in animals.

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.

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.

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.

Synergies of chemodenitrification and denitrification in a saline inland lake.

The interconnection between biotic and abiotic pathways involving the nitrogen and iron biogeochemical cycles has recently gained interest. While lacustrine ecosystems are considered prone to the biotic nitrate reduction (denitrification), their potential for promoting the abiotic nitrite reduction (chemodenitrification) remains unclear. In the present study, batch incubations were performed to assess the potential for chemodenitrification and denitrification in the saline inland lake Gallocanta. Sulfidic conditions are found in top sediments of the system while below (5-9 cm), it presents low organic carbon and high sulfate and ferrous iron availability. Anoxic incubations of sediment (5-9 cm) and water from the lake with nitrite revealed potential for chemodenitrification, especially when external ferrous iron was added. The obtained isotopic fractionation values for nitrite (ɛ15NNO2) were -6.8 and -12.3 ‰ and therefore, fell in the range of those previously reported for the nitrite reduction. The more pronounced ɛ15NNO2 (-12.3 ‰) measured in the experiment containing additional ferrous iron was attributed to a higher contribution of the chemodenitrification over biotic denitrification. Incubations containing nitrate also confirmed the potential for denitrification under autotrophic conditions (low organic carbon, high ferrous iron). Higher reaction rate constants were found in the experiment containing 100 µM compared to 400 µM nitrate. The obtained ɛ15NNO3 values (-8.5 and -15.1 ‰) during nitrate consumption fell in the range of those expected for the denitrification. A more pronounced ɛ15NNO3 (-15.1 ‰) was determined in the experiment presenting a lower reaction rate constant (400 µM nitrate). Therefore, in Gallocanta lake, nitrite generated during nitrate reduction can be further reduced by both the abiotic and biotic pathways. These findings establish the significance of chemodenitrification in lacustrine systems and support further exploration in aquatic environments with different levels of C, N, S, and Fe. This might be especially useful in predicting nitrous oxide emissions in natural ecosystems.

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.

Precise measurement of Fe isotopes in marine and biological samples by pseudo-high-resolution multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS).

This paper introduces an enhanced technique for analyzing iron isotopes in complex marine and biological samples. A dedicated iron purification method for biological marine matrices, utilizing three ion exchange columns, is validated. The MC-ICPMS in pseudo-high-resolution mode determines precise iron isotopic ratios, with sensitivity improved through the DSN-100 desolvating nebulizer system and Apex-IR. Only 2 µg of iron on DSN versus 1 µg on Apex is needed for six replicates (30-60 times improvement) while 10 to 20 µg is required for a single measurement on a wet system considering the resolution power (Rp) is maintained at 11,000-13,000. The Ni-doping method with a Fe/Ni ratio of 1 yields more accurate isotopic ratios than standard-sample bracketing alone. Measurement reproducibility of triplicate samples from marine biological experiments on MC-ICPMS is ± 0.03‰ (2SD) for δ56Fe and ± 0.07‰ for δ57Fe (2SD). This study introduces a novel iron purification process specifically designed for marine and biological samples, enhancing sensitivity and enabling more reliable measurements with smaller sample sizes and reduced uncertainties. It proposes iron isotopic compositions for biological reference materials, offering a valuable reference dataset in diverse scientific disciplines.

Assessment of dietary Selenium and its role in Mercury fate in cultured fish rainbow trout with two sustainable aquafeeds.

This study enhances the current limited understanding of the interaction between mercury (Hg) and selenium (Se) species in fish. Rainbow trout (Oncorhynchus mykiss), a model aquaculture fish, was exposed to Hg and Se species through controlled dietary conditions. Over a 6-month feeding trial, the impact of dietary Se on Hg bioaccumulation in fish, including flesh, brain, and liver, was tracked. Twelve dietary conditions were tested, including plant-based diets (0.25 µgSe g-1) and tuna byproduct diets (0.25 µgHg g-1, 8.0 µgSe g-1) enriched with methylmercury and/or Se as selenite or selenomethionine. The tuna byproduct diet resulted in lower Hg levels than the plant-based diets, with muscle Hg content below the European Commission's safe threshold. This study highlights the significant impact of specific Se compounds in the diet, particularly from tuna-based aquafeed, on Hg bioaccumulation. These promising results provide a strong recommendation for future use of fisheries byproducts in sustainable aquafeeds.

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.

Revisiting the mercury cycle in marine sediments: A potential multifaceted role for Desulfobacterota.

Marine sediments impacted by urban and industrial pollutants are typically exposed to reducing conditions and represent major reservoirs of toxic mercury species. Mercury methylation mediated by anaerobic microorganisms is favored under such conditions, yet little is known about potential microbial mechanisms for mercury detoxification. We used culture-independent (metagenomics, metabarcoding) and culture-dependent approaches in anoxic marine sediments to identify microbial indicators of mercury pollution and analyze the distribution of genes involved in mercury reduction (merA) and demethylation (merB). While none of the isolates featured merB genes, 52 isolates, predominantly affiliated with Gammaproteobacteria, were merA positive. In contrast, merA genes detected in metagenomes were assigned to different phyla, including Desulfobacterota, Actinomycetota, Gemmatimonadota, Nitrospirota, and Pseudomonadota. This indicates a widespread capacity for mercury reduction in anoxic sediment microbiomes. Notably, merA genes were predominately identified in Desulfobacterota, a phylum previously associated only with mercury methylation. Marker genes involved in the latter process (hgcAB) were also mainly assigned to Desulfobacterota, implying a potential central and multifaceted role of this phylum in the mercury cycle. Network analysis revealed that Desulfobacterota were associated with anaerobic fermenters, methanogens and sulfur-oxidizers, indicating potential interactions between key players of the carbon, sulfur and mercury cycling in anoxic marine sediments.

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.