The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.

The photochemical reduction of Hg(II) is an important pathway in the environmental Hg cycle because it competes with Hg methylation and potentially limits the formation of bioaccumulative methylmercury. Hg stable isotope systematics have proven to be an effective tool for investigating the transport, transformation, and bioaccumulation of Hg. The dominant cause of mass independent isotope fractionation (MIF) of Hg in nature is the photochemical reduction of various species of Hg(II). However, it is difficult to fully interpret Hg stable isotope signatures due to the lack of mechanistic information about which Hg compounds are susceptible to MIF and why. This study investigates Hg isotope fractionation during the photochemical reduction of Hg(II) complexed to organic ligands, which are representative of the available binding sites in natural dissolved organic matter. The photochemical reduction of Hg(II) in the presence of cysteine resulted in both negative and positive MIF in residual Hg(II), where the sign depended on pH and dissolved oxygen level. In the presence of serine, either nuclear volume or magnetic isotope effects were observed depending on the wavelength of light and the extent of Hg(II) complexation by serine. In the presence of ethylenediamine, MIF was negative. Our Hg stable isotope results suggest that MDF and MIF are induced at different steps in the overall photochemical reduction reaction and that MIF does not depend on the rate-determining step but instead depends on photophysical aspects of the reaction such as intersystem crossing and hyperfine coupling. The behavior of Hg isotopes reported here will allow for a better understanding of the underlying reaction mechanisms controlling the Hg isotope signatures recorded in natural samples.

Methylmercury (MeHg), a highly neurotoxic substance, accumulates in aquatic food webs, and is enriched in odd isotopes (i.e., 199 Hg and 201 Hg), purportedly as a result of abiotic photodegradation in surface waters. Here, we highlight the potential role of phytoplankton in the mass independent fractionation (MIF) of MeHg in marine food-webs by providing evidence of (1) degradation of intracellular MeHg and reduction of intracellular inorganic mercury (Hg(II)) in the marine microalga, Isochrysis galbana; (2) a large, positive MIF (Δ 199 Hg reactant − Δ 199 Hg product ∼ 5−10‰) during intracellular degradation of MeHg in cells exposed to visible light with no UVB, consistent with the accumulation of odd isotope-enriched MeHg in marine food-webs; and (3) a negative MIF (−1‰) during intracellular reduction of Hg(II) in the presence of UVB light. If representative of the photochemical reactivity of MeHg in marine phytoplankton, our results indicate that algal cell-mediated demethylation of MeHg by visible light could account for 20 to 55% of the total photochemically driven demethylation in the open ocean and transparent freshwater ecosystems with deep euphotic zones. Thus, our results extend the importance of phytoplankton (and possibly other light permeable microorganisms) in mercury biogeochemistry beyond their role as accumulators of MeHg and/or reducers of Hg(II) at the base of the food chain to include MeHg degradation and MIF of Hg in sunlit layers of the ocean and other aquatic systems.

Mercury isotopic compositions of amphipods and snailfish from deep-sea trenches reveal information on the sources and transformations of mercury in the deep oceans. Evidence for methyl-mercury subjected to photochemical degradation in the photic zone is provided by odd-mass independent isotope values (Δ199Hg) in amphipods from the Kermadec Trench, which average 1.57‰ (±0.14,n= 12, SD), and amphipods from the Mariana Trench, which average 1.49‰ (±0.28,n= 13). These values are close to the average value of 1.48‰ (±0.34,n= 10) for methyl-mercury in fish that feed at ∼500-m depth in the central Pacific Ocean. Evidence for variable contributions of mercury from rainfall is provided by even-mass independent isotope values (Δ200Hg) in amphipods that average 0.03‰ (±0.02,n= 12) for the Kermadec and 0.07‰ (±0.01,n= 13) for the Mariana Trench compared to the rainfall average of 0.13 (±0.05,n= 8) in the central Pacific. Mass-dependent isotope values (δ202Hg) are elevated in amphipods from the Kermadec Trench (0.91 ±0.22‰,n= 12) compared to the Mariana Trench (0.26 ±0.23‰,n= 13), suggesting a higher level of microbial demethylation of the methyl-mercury pool before incorporation into the base of the foodweb. Our study suggests that mercury in the marine foodweb at ∼500 m, which is predominantly anthropogenic, is transported to deep-sea trenches primarily in carrion, and then incorporated into hadal (6,000-11,000-m) food webs. Anthropogenic Hg added to the surface ocean is, therefore, expected to be rapidly transported to the deepest reaches of the oceans.

Mercury is a globally distributed atmospheric pollutant, which travels long distances in the form of gaseous elemental mercury (Hg 0 ). Gaseous Hg 0 is removed from the atmosphere via the foliar uptake (Demers et al., 2013;Zhou et al., 2021) or via oxidation to Hg 2+ , which is readily deposited to the biosphere following sorption to particles (Hg P ) and/or precipitation (Selin, 2009). Since industrialization, anthropogenic activities alone have increased mercury emission by a factor of approximately 5 (Streets et al., 2017). Increased mercury loading to aquatic ecosystems can enhance microbial production of monomethylmercury (MeHg) (Benoit et al., 2003;Lindberg et al., 2007), which is a bioaccumulative toxin in food webs (Mergler et al., 2007). Humans are primarily exposed to MeHg via the consumption of fishery products (Sunderland, 2007).In 2017, the Minamata Convention on Mercury (MC), a multilateral agreement to mitigate anthropogenic mercury emissions and human health from mercury pollution, has entered into force (UNEP, 2019). As a part of the MC, provisions have been established for a global monitoring program and a convention effectiveness evaluation (Article 19, 22) to understand spatiotemporal changes in mercury levels as well as its sources, processes, and fate in various environmental media. Since then, numerous studies have assessed temporal trends of mercury in diverse atmospheric samples (Hg 0 , Hg 2+ , Hg P , precipitation) (Cheng et al., 2017;Dommergue et al., 2016) and biota (fish, bird eggs, polar bear) (Blukacz-Richards et al., 2017;Lee et al., 2016;McKinney et al., 2017) to gather insights on the changes in emissions, deposition, and ecosystem fate of mercury. Natural archives of sediment, peat, and ice cores have also been used to quantify long-term changes in the deposition of various atmospheric mercury species (Engstrom et al., 2014;Enrico

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Different theoretical approaches for the calculation of 237 Np Mossbauer isomer shifts are investigated. The traditional contact density route is compared to a previously proposed alternative approach that uses energy derivatives with respect to the nuclear radius. Both approaches yield similar results as long as suitable basis sets augmented with large exponents and relativistic methods are used. Density functional theory (DFT) calculations do not show a strong dependency of the 237 Np isomer shift on the chosen functional. Wavefunction calculations show that dynamic electron correlation can be important when covalent bonding influences the isomer shift. Effects from spin−orbit coupling are small. The isomer shifts of ionic solids and Np(III) organometallic complexes are largely governed by the oxidation state of Np. Isomer shifts of organometallic Np(IV) complexes are strongly affected by donation bonding. Detailed analysis of the wavefunction results with different active spaces demonstrates that correlation among the outer core Np and occupied ligand frontier orbitals contributes significantly to isomer shifts of Np(IV) compounds.

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