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Mercury (Hg), a neurotoxicant released primarily by anthropogenic activity, is present in all the world’s oceans, estuaries, and freshwater bodies (Giang, 2013). In addition to its toxicity to marine biota, Hg bioaccumulates within fish and other seafoods, presenting a threat to human health since fish remain important sources of protein for people across the world (Giang, 2013). Despite improvements in Hg pollution control, levels in commonly consumed marine fish such as bluefin tuna often exceed human health guidelines causing recommendations to limit fish consumption (Giang, 2013). Organic forms of Hg, such as monomethylmercury (MMHg), are more toxic than other forms and are the main causes of concern for human and ecosystem health. Various forms of Hg can transform into MMHg overtime and in certain environments. Elemental mercury (Hg(0)) can transform into different chemical species before becoming MMHg while divalent mercury (Hg(II)) can transform into MMHg through biotic methylation in the water column and sediments under specific chemical and physical conditions (Ming et al., 2019).The U.S. Environmental Protection Agency (EPA) manages approximately 98 ocean dredged material disposal sites (ODMDS) around the country’s federal waters. Disposal sites are used for the disposal of nontoxic sediments that are routinely removed to maintain navigational depths in ports, harbors, and marinas, as well as to support national maritime commerce, commercial fisheries, and recreation (EPA, n.d.). The U.S. Army Corps of Engineers (USACE) is planning to dredge federal channel segments in Newport Bay in Newport Beach, California. Based on sediment samples collected and analyzed for ocean disposal testing, the USACE project sediments were found to be high in Hg contamination (Anchor QEA, LLC., 2020). However, despite the high Hg levels, toxicity tests indicated suitability for ocean disposal at EPA’s LA-3 ODMDS located offshore of Newport Bay (Anchor QEA, LLC., 2020). The current Hg levels at the LA-3 disposal site are low to non-detect, and the effects of disposing of sediments loaded with Hg from the Federal channel in Newport Bay are unknown (Battelle and DAMOSVision, 2015). To address this issue, a literature review of Hg biogeochemical cycling and Hg-methylation was conducted to assist in the understanding of Hg speciation and transport. A policy review was also completed to assess the policies relevant to sediment dredging in California and ocean dumping in federal waters. Related to the policies in place, manuals utilized by USACE and EPA for testing and analysis purposes were reviewed to determine additional sediment and water column tests to minimize the potential risk of Hg contamination in the marine environment. Through the compilation of information, testing and analysis recommendations in addition to current testing were made for the dredge and disposal site locations.

Sediments represent the main reservoir of mercury (Hg) in aquatic environments and may act as a source of Hg to aquatic food webs. Yet, accumulation routes of Hg from the sediment to benthic organisms are poorly constrained. We studied the bioaccumulation of inorganic and methylmercury (HgII and MeHg, respectively) from different geochemical pools of Hg into four groups of benthic invertebrates (amphipods, polychaetes, chironomids, and bivalves). The study was conducted using mesocosm experiments entailing the use of multiple isotopically enriched Hg tracers and simulation of estuarine systems with brackish water and sediment. We applied different loading regimes of nutrients and terrestrial organic matter and showed that the vertical localization and the chemical speciation of HgII and MeHg in the sediment, in combination with the diet composition of the invertebrates, consistently controlled the bioaccumulation of HgII and MeHg into the benthic organisms. Our results suggest a direct link between the concentration of MeHg in the pelagic planktonic food web and the concentration of MeHg in benthic amphipods and, to some extent, in bivalves. In contrast, the quantity of MeHg in benthic chironomids and polychaetes seems to be driven by MeHg accumulation via the benthic food web. Accounting for these geochemical and dietary drivers of Hg bioaccumulation in benthic invertebrates will be important to understand and predict Hg transfer between the benthic and the pelagic food web, under current and future environmental scenarios.

In shallow aquatic environments, sediment is a significant source of monomethylmercury (MMHg) for surface water (SW). High-altitude aquatic ecosystems are characterized by extreme hydro-climatic constraints (e.g., low oxygen and high UV radiation). We studied, during two seasons, the diel cycles of MMHg in SW and sediment porewaters (PW) of Lake Uru Uru (3686 m a.s.l, Bolivia) contaminated by urban and mining activities. Our results show that diel changes in SW MMHg concentrations (up to 1.8 ng L&minus, 1) overwhelm seasonal ones, with higher MMHg accumulation during the night-time and the dry season. The calculation of MMHg diffusive fluxes demonstrates that the sediment compartment was the primary source of MMHg to the SW. Most MMHg efflux occurred during the dry season (35.7 &plusmn, 17.4 ng m&minus, 2 day&minus, 1), when the lake was relatively shallow, more eutrophicated, and with the redoxcline located above the sediment&ndash, water interface (SWI). Changes in MMHg accumulation in the PWs were attributed to diel redox oscillations around the SWI driving both the bacterial sulfate reduction and bio-methylation. Finally, we highlight that although MMHg loading from the PW to the SW is large, MMHg photodegradation and demethylation by microorganisms control the net MMHg accumulation in the water column.

Mercury (Hg) in the Arctic Ocean is a concern due to unusually high concentrations of monomethylmercury (MMHg) in fish and marine animals. Increased human exposure from consumption of these animals is a significant health concern that is related to Hg contamination in nature. Most Arctic marine Hg research has investigated the amounts, distributions, and cycling in animals, snow, and ice, while few studies have examined the aqueous behavior and fate of Hg in the polar ocean. Here we present the most comprehensive dataset published to date detailing Hg speciation and distribution of elemental Hg (Hg0), dimethylmercury (DMHg), and filtered and particulate total Hg and MMHg in the western Arctic Ocean. This data was obtained as part of the U.S. Arctic GEOTRACES cruise (GN01) in 2015. Many water masses sampled appeared to be enriched with anthropogenic Hg. The Transpolar Drift supplied HgT and Hg0 to the central Arctic Ocean, but not methylated Hg. Gaseous Hg0, but not DMHg, was elevated in surface waters under the ice cover. Monomethylmercury levels, which averaged 0.054 ± 0.050 pM, are lower than other major ocean basins, suggesting ambient MMHg levels in western Arctic Ocean seawater do not by themselves explain anomalously high Hg in Arctic animals.

We discuss three methods of analysis of methyl and inorganic mercury in sediments and water and present new results for one of these. The methods used are (1) solvent extraction and derivatization to CH 3 HgBr (with separate analysis of inorganic mercury) with determination by electron capture gas chromatography, (2) aqueous phase derivatization using NaB(C 2 H 5 ) 4 with detection by atomic absorption spectroscopy and (3) derivatization with NaBH 4 with detection of CH 3 Hg and inorganic mercury by atomic absorption and mass spectroscopes. We present new results on the analytical stability of CH 3 HgH and discuss errors arising in the methods.

We examined Hg biogeochemistry in Baihua Reservoir, a system affected by industrial wastewater containing mercury (Hg). As expected, we found high levels of total Hg (THg, 664-7421 ng g(-1)) and monomethylmercury (MMHg, 3-21 ng g(-1)) in the surface sediments (0-10 cm). In the water column, both THg and MMHg showed strong vertical variations with higher concentrations in the anoxic layer (>4m) than in the oxic layer (0-4 m), which was most pronounced for the dissolved MMHg (p < 0.001). However, mercury levels in biota samples (mostly cyprinid fish) were one order of magnitude lower than common regulatory values (i.e. 0.3-0.5 mg kg(-1)) for human consumption. We identified three main reasons to explain the low fish Hg bioaccumulation: disconnection of the aquatic food web from the high MMHg zone, simple food web structures, and biodilution effect at the base of the food chain in this eutrophic reservoir.

Surface sediments and sediment cores were collected in a mercury (Hg)- contaminated lagoon, namely Largo do Laranjo – Ria de Aveiro, Portugal and analysed in order to establish the monomethylmercury (MeHg) behaviour in this kind of environment. In surface sediments, this compound was only detected in one place (13.2 ng g-1 (dry weight)). In this site, it was determined one of the lowest redox potentials (22 mV), indicative of oxic/anoxic conditions, which favours Hg methylation by enhancing the sulphate-reducing bacteria activity. However, the MeHg percentage obtained was low, namely less than 0.1% of the total Hg. This is probably due to Hg deposition with organic matter and iron oxyhydroxides, decreasing Hg availability to methylation. At the deeper layers, MeHg was also determined, reaching 46.4 ng g-1 (dry weight) and representing less than 0.1% of the total Hg. The higher MeHg percentages were observed near the surface, where Hg seems to be faster methylated as a result of the lower sulphide concencentrations that render bioavailable the inorganic Hg. At depth the low MeHg percentages obtained are due to the formation of HgS and to the adsorption of Hg to iron monosulphides.

International audience; This work presents the simultaneous online determination of the isotopic composition of different Hg species in a single sample by the hyphenation of gas chromatography (GC) with multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS). With the use of commercially available instrumentation, precise and accurate species-specific Hg isotope delta values (per mil deviation of the Hg isotope ratio in the sample relative to a reference standard) have been obtained online from consecutive GC transient signals. The use of isothermal temperature programs to extend the elution of the Hg species, the proper selection of the peak integration window, as well as the preconcentration of real samples are critical to provide optimal counting statistics. Also, isotope ratio drift during transient signal elution was overcome by iritroducing a mixed Hg(II) and MeHg standard bracketing scheme and expressing all results using the delta-notation relative to SRM NIST-3133. Using the proposed methodology, we have obtained an external 2SD precision of 0.56 %. for delta Hg-202 that is more than 10 times smaller than the overall Hg stable isotope variation thus far observed in terrestrial samples. The measurement of species-specific Hg isotopic composition relative to SRM NIST-3133 has been validated versus two other analytical techniques, i.e., conventional nebulization (CN) of Hg(H) solution and cold vapor (CV) generation of Hg-0 vapor. A good agreement between the species-specific 6 values obtained by the different techniques has been obtained in secondary fractionated reference standard (UM-Almaden) and environmental matrixes, i.e., BCR-CRM 464 (tuna fish) and IAEA-085 (human hair). The results show mass-dependent and mass-independent fractionation in environmental samples, i.e., mass-independent fractionation of odd isotopes Hg-199 and Hg-201 in tuna fish was observed. This methodology provides new possibilities for the future study of species-specific stable isotope geochemistry of Hg and other trace metals.

The sequestering capacity of synthetic and naturally occurring polycarboxylate ligands towards mono- methylmercury(II) was evaluated by stability quantitative data on the interaction of CH3Hgþ with different molecular weight synthetic polyacrylates (2 and 20 kDa average M.wt) and alginate (70– 100 kDa) extracted from brown algae Macrocystis pyrifera. The influence of ionic medium was evaluated by measurements on the CH3Hgþ-polyacrylate systems in NaNO3 medium at different ionic strengths (0.10, 0.25, 0.50 and 0.75mol Lÿ1), and a Debye–Hu¨ ckel type equation was used for the dependence of complex formation constants on ionic strength. Measurements on the CH3Hgþ - alginate system were carried out at I ¼0.10mol Lÿ1 in NaNO3 medium. By using the stability data, the sequestering capacity of both ligands towards monomethylmercury(II) was determined at different pH values. Results obtained show that the binding ability of polyacrylic ligands (PAA) is stronger than the alginate (AA), following the trend PAA (20 kDa)4PAA (2 kDa)4AA.