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.

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.

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 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.