Photomicrobial Visible Light-Induced Magnetic Mass Independent Fractionation of Mercury in a Marine Microalga

Methylmercury (MeHg), a highly neurotoxic substance, accumulates in aquatic food webs, and is enriched in odd isotopes (i.e., 199Hg and 201Hg), 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 (?199Hgreactant – ?199Hgproduct ~ 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

Variation in Terrestrial and Aquatic Sources of Methylmercury in Stream Predators as Revealed by Stable Mercury Isotopes

Mercury (Hg) is widely distributed in the environment, and its organic form, methylmercury (MeHg), can extensively bioaccumulate and biomagnify in aquatic and terrestrial food webs. Concentrations of MeHg in organisms are highly variable, and the sources in natural food webs are often not well understood. This study examined stable isotope ratios of MeHg (mass-dependent fractionation, as d202HgMeHg; and mass-independent fractionation, as ?199HgMeHg) in benthic invertebrates, juvenile steelhead trout (Oncorhynchus mykiss), and water striders (Gerris remigis) along a stream productivity gradient, as well as carnivorous terrestrial invertebrates, in a forested watershed at the headwater of South Fork Eel River in northern California. Throughout the sampling sites, d202HgMeHg (after correction due to the effect of MeHg photodegradation) was significantly different between benthic (median = -1.40‰; range, -2.34 to -0.78‰; total number of samples = 29) and terrestrial invertebrates (median = +0.51‰; range, -0.37 to +1.40‰; total number of samples = 9), but no major difference between these two groups was found for ?199HgMeHg. Steelhead trout (52 individual fishes) have MeHg of predominantly aquatic origins, with a few exceptions at the upstream locations (e.g., 1 fish collected in a tributary had a purely terrestrial MeHg source and 4 fishes had mixed aquatic and terrestrial MeHg sources). Water striders (seven pooled samples) derive MeHg largely from terrestrial sources throughout headwater sections. These data suggest that direct terrestrial subsidy (e.g., terrestrial invertebrates falling into water) can be important for some stream predators in headwater streams and could represent an important means of transfer of terrestrially derived MeHg (e.g., in situ methylation within forests, atmospheric sources) to aquatic ecosystems. Moreover, these findings show that terrestrial subsidies can enhance MeHg bioaccumulation of consumers in headwater streams where aqueous MeHg levels are very low

Understanding sources of methylmercury in songbirds with stable mercury isotopes: Challenges and future directions

Mercury (Hg) stable isotope analysis is an emerging technique that has contributed to a better understanding of many aspects of the biogeochemical cycling of Hg in the environment. However, no study has yet evaluated its usefulness in elucidating the sources of methylmercury (MeHg) in songbird species, a common organism for biomonitoring of Hg in forested ecosystems. In the present pilot study, we examined stable mercury isotope ratios in blood of 4 species of songbirds and the invertebrates they are likely foraging on in multiple habitats in a small watershed of mixed forest and wetlands in Acadia National Park in Maine (USA). We found distinct isotopic signatures of MeHg in invertebrates (both mass-dependent fractionation [as d202Hg] and mass-independent fractionation [as ?199Hg]) among 3 interconnected aquatic habitats. It appears that the Hg isotopic compositions in bird blood cannot be fully accounted for by the isotopic compositions of MeHg in lower trophic levels in each of the habitats examined. Furthermore, the bird blood isotope results cannot be simply explained by an isotopic offset as a result of metabolic fractionation of d202Hg (e.g., internal demethylation). Our results suggest that many of the birds sampled obtain MeHg from sources outside the habitat they were captured in. Our findings also indicate that mass-independent fractionation is a more reliable and conservative tracer than mass-dependent fractionation for identifying sources of MeHg in bird blood. The results demonstrate the feasibility of Hg isotope studies of songbirds but suggest that larger numbers of samples and an expanded geographic area of study may be required for conclusive interpretation

Origin, Reactivity, and Bioavailability of Mercury in Wildfire Ash

Wildfires are expected to become more frequent and intensive at the global scale due to climate change. Many studies have focused on the loss of mercury (Hg) from burned forests; however, little is known about the origins, concentration, reactivity, and bioavailability of Hg in residual ash materials in postfire landscapes. We examine Hg levels and reactivity in black ash (BA, low burn intensity) and white ash (WA, high burn intensity) generated from two recent northern California wildfires and document that all ash samples contained measurable, but highly variable, Hg levels ranging from 4 to 125 ng/g dry wt. (n = 28). Stable Hg isotopic compositions measured in select ash samples suggest that most Hg in wildfire ash is derived from vegetation. Ash samples had a highly variable fraction of Hg in recalcitrant forms (0–75%), and this recalcitrant Hg pool appears to be associated with the black carbon fraction in ash. Both BA and WA were found to strongly sequester aqueous inorganic Hg but not gaseous elemental Hg under controlled conditions. During anoxic ash incubation with natural surface water, we find that Hg in most ash samples had a minimal release and low methylation potential. Thus, the formation of wildfire ash can sequester Hg into relatively nonbioavailable forms, attenuating the potentially adverse effects of Hg erosion and transport to aquatic environments along with eroded wildfire ash

Feasibility of Sijunzi Tang (Chinese medicine) to enhance protein disulfide isomerase activities for reactivating malate dehydrogenase deactivated by polycyclic aromatic hydrocarbons

The objective of this research is to investigate the enzymatic activities between protein disulfide isomerase (PDI) found in animals and plants and the properties found in a commonly used Chinese medicine called Sijunzi Tang. During the investigation, PDI, which is a monomer with a molecular mass of 57.0 kDa, was used to reactivate malate dehydrogenase (MDH). However, with the interference of polycyclic aromatic hydrocarbons (PAHs), evidence indicates that such chemicals are carcinogenic, mutagenic, and toxic to humans. The enzymatic activity of PDI found in animal’s liver and plant was 1657 folds of purification; 0.284 unit/mg of enzyme activity, and 5694.4 folds of purification; 1.00 unit/mg of enzyme activity, respectively. PDI extracted in treated animal and plant tissue revealed 2.40% and 80.44% of regaining MDH enzymatic activity, respectively. Although in its initial phase of investigation, it is assumed that the properties found in Sijunzi Tang can help regain enzymatic activity in those affected by xenobiotic substances, thus, making it a potential ingredient in assisting with PDI functions

Controls of Methylmercury Bioaccumulation in Forest Floor Food Webs

Compared to the extensive research on aquatic ecosystems, very little is known about the sources and trophic transfer of methylmercury (MeHg) in terrestrial ecosystems. In this study, we examine energy flow and trophic structure using stable carbon (d13C) and nitrogen (d15N) isotope ratios, respectively, and MeHg levels in basal resources and terrestrial invertebrates from four temperate forest ecosystems. We show that MeHg levels in biota increased significantly (p 0.05) from those observed for diverse temperate freshwater systems (0.24 ± 0.07; n = 78), demonstrating for the first time the nearly equivalent efficiencies with which MeHg moves up the food chain in these contrasting ecosystem types. Our results suggest that in situ production of MeHg within the forest floor and efficient biomagnification both elevate MeHg levels in carnivorous invertebrates in temperate forests, which can contribute to significant bioaccumulation of this neurotoxin in terrestrial apex predators

Microbial Pathways of Mercury Methylation During Litter Decomposition

Tree foliage sequesters gaseous elemental mercury (Hg) through stomatal uptake, when the foliage senesces and falls into the water, Hg from leaf litter can be released into the water and/or microbially methylated into a highly toxic form, methylmercury. The dominant groups of microbial communities that can methylate Hg during litter decomposition are, however, less certain. We conducted a microbial inhibition experiment to identify the primary methylators of leaf litter Hg during 28-day decomposition of two litter species of contrasting quality (pine and maple). We demonstrate that sulfate-reducing bacteria are the dominant microbial groups for Hg methylation during anoxic litter decomposition, and our study also indicates that methanogens may have a minor role in mediating Hg methylation during litter decomposition. Thus, aquatic environment with extensive litter accumulation and decomposition (e.g., wetlands, ponds, and river pools) can be hotspots of Hg methylation through sulfate-reduction and, to a lesser extent, methanogenesis

New Insights on Ecosystem Mercury Cycling Revealed by Stable Isotopes of Mercury in Water Flowing from a Headwater Peatland Catchment

Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations through Hg spike addition analysis. We report a relatively large variation in mass-dependent fractionation (d202Hg; from -2.12 to -1.32‰) and a smaller, but significant, variation of mass-independent fractionation (?199Hg; from -0.35 to -0.12‰) during two years of sampling with streamflow varying from 0.003 to 7.8 L s–1. Large variations in d202Hg occurred only during low streamflow (<0.6 L s–1), which suggest that under high streamflow conditions a peatland lagg zone between the bog (3.0 ha) and uplands (6.7 ha) becomes the dominant source of Hg in downstream waters. Further, a binary mixing model showed that except for the spring snowmelt period, Hg in streamwater from the catchment was mainly derived from dry deposition of gaseous elemental Hg (73–95%). This study demonstrates the usefulness of Hg isotopes for tracing sources of Hg deposition, which can lead to a better understanding of the biogeochemical cycling and hydrological transport of Hg in headwater catchments

Methylmercury and methane production potentials in North Carolina Piedmont stream sediments

Methylated mercury (MeHg) can be produced by all microbes possessing the genes hgcA and hgcB, which can include sulfate-reducing bacteria (SRB), iron-reducing bacteria (FeRB), methane-producing archaea (MPA), and other anaerobic microbes. These microbial groups compete for substrates, including hydrogen and acetate. When sulfate is in excess, SRB can outcompete other anaerobic microbes. However, low concentrations of sulfate, which often occur in stream sediments, are thought to reduce the relative importance of SRB. Although SRB are regarded as the primary contributors of MeHg in many aquatic environments, their significance may not be universal, and stream sediments are poorly studied with respect to microbial Hg methylation. We evaluated suppression of methanogenesis by SRB and the potential contributions from SRB, MPA and other MeHg producing microbes (including FeRB) to the production of MeHg in stream sediments from the North Carolina Piedmont region. Lower methanogenesis rates were observed when SRB were not inhibited, however, application of a sulfate-reduction inhibitor stimulated methanogenesis. Greater MeHg production occurred when SRB were active. Other MeHg producing microbes (i.e., FeRB) contributed significantly less MeHg production than SRB. MPA produced MeHg in negligible amounts. Our results suggest that SRB are responsible for the majority of MeHg production and suppress methanogenesis in mid-order stream sediments, similar to other freshwater sediments. Further investigation is needed to evaluate the generality of these findings to streams in other regions, and to determine the mechanisms regulating sulfate and electron acceptor availability and other potential factors governing Hg methylation and methane production in stream sediments

Understanding sources of methylmercury in songbirds with stable mercury isotopes: Challenges and future directions

Mercury (Hg) stable isotope analysis is an emerging technique that has contributed to a better understanding of many aspects of the biogeochemical cycling of Hg in the environment. However, no study has yet evaluated its usefulness in elucidating the sources of methylmercury (MeHg) in songbird species, a common organism for biomonitoring of Hg in forested ecosystems. In the present pilot study, we examined stable mercury isotope ratios in blood of 4 species of songbirds and the invertebrates they are likely foraging on in multiple habitats in a small watershed of mixed forest and wetlands in Acadia National Park in Maine (USA). We found distinct isotopic signatures of MeHg in invertebrates (both massâ dependent fractionation [as δ202Hg] and massâ independent fractionation [as Î 199Hg]) among 3 interconnected aquatic habitats. It appears that the Hg isotopic compositions in bird blood cannot be fully accounted for by the isotopic compositions of MeHg in lower trophic levels in each of the habitats examined. Furthermore, the bird blood isotope results cannot be simply explained by an isotopic offset as a result of metabolic fractionation of δ202Hg (e.g., internal demethylation). Our results suggest that many of the birds sampled obtain MeHg from sources outside the habitat they were captured in. Our findings also indicate that massâ independent fractionation is a more reliable and conservative tracer than massâ dependent fractionation for identifying sources of MeHg in bird blood. The results demonstrate the feasibility of Hg isotope studies of songbirds but suggest that larger numbers of samples and an expanded geographic area of study may be required for conclusive interpretation. Environ Toxicol Chem 2018;37:166â 174. © 2017 SETACPeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141144/1/etc3941.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141144/2/etc3941_am.pd