Observations of the chemistry and concentrations of reactive Hg at locations with different ambient air chemistry.

The Hg research community needs methods to more accurately measure atmospheric Hg concentrations and chemistry. The Reactive Mercury Active System (RMAS) uses cation exchange, nylon, and PTFE membranes to determine reactive mercury (RM), gaseous oxidized mercury, and particulate-bound mercury (PBM) concentrations and chemistry. New data for Atlanta, Georgia (NRGT) demonstrated that particulate-bound Hg was dominant and the chemistry was primarily N and S HgII compounds. At Great Salt Lake, Utah (GSL), RM was predominately PBM, with NS > organics > halogen > O HgII compounds. At Guadalupe Mountains National Park, Texas (GUMO), halogenated compound concentrations were lowest when air interacting with the site was primarily derived from the Midwest, and highest when the air was sourced from Mexico. At Amsterdam Island, Southern Indian Ocean, compounds were primarily halogenated with some N, S, and organic HgII compounds potentially associated with biological activity. The GEOS-Chem model was applied to see if it predicted measurements at five field sites. Model values were higher than observations at GSL, slightly lower at NRGT, and observations were an order of magnitude higher than modeled values for GUMO and Reno, Nevada. In general, data collected from 13 locations indicated that N, S, and organic RM compounds were associated with city and forest locations, halogenated compounds were sourced from the marine boundary layer, and O compounds were associated with long-range transport. Data being developed currently, and in the past, suggest there are multiple forms of RM that modelers must consider, and PBM is an important component of RM.

Phase partitioning of mercury, arsenic, selenium, and cadmium in Chlamydomonas reinhardtii and Arthrospira maxima microcosms.

As the global human population increases, demand for protein will surpass our current production ability without an increase in land use or intensification. Microalgae cultivation offers a high yield of protein, and utilization of wastewater from municipal or agricultural sources in place of freshwater for microalgae aquaculture may increase the sustainability of this practice. However, wastewater from municipal and agricultural sources may contain contaminants, such as mercury (Hg), cadmium (Cd), selenium (Se), and arsenic (As). Association of these elements with algal biomass may present an exposure risk to product consumers, while volatilization may present an exposure hazard to industry workers. Thus, the partitioning of these elements should be evaluated before wastewater can be confidently used in an aquaculture setting. This study explored the potential for exposure associated with Arthrospira maxima and Chlamydomonas reinhardtii aquaculture in medium contaminated with 0.33 µg Hg L-1, 60 µg As L-1, 554 µg Se L-1, and 30 µg Cd L-1. Gaseous effluent from microalgae aquaculture was analyzed for Hg, As, Se, and Cd to quantify volatilization. A mass balance approach was used to describe the partitioning of elements between the biomass, medium, and gas phases at the end of exponential growth. Contaminants were recovered predominantly in medium and biomass, regardless of microalgae strain. In the case of Hg, 48 ± 2% was associated with A. maxima biomass and 55 ± 8% with C. reinhardtii when Hg was present as the only contaminant, but this increased to 85 ± 11% in C. reinhardtii biomass when As, Se, and Cd were also present. A small and highly variable abiotic volatilization of Hg was observed in the gas phase of both A. maxima and C. reinhardtii cultures. Evidence presented herein suggests that utilizing wastewater containing Hg, Cd, Se, and As for microalgae cultivation may present health hazards to consumers.

Comparison and calibration of methods for ambient reactive mercury quantification.

Gaseous oxidized mercury (GOM) is the dominant form of atmospheric mercury (Hg) deposited and sequestered within ecosystems. Thus, accurate, calibrated measurements of GOM are needed. Here, two active membrane-based collection systems (RMAS) were used to determine GOM and particulate-bound Hg (PBM), as well as reactive Hg (RM = GOM + PBM), and compared with two dual-channel systems (DCS) and a Tekran 2537/1130 speciation system. The DCS measured operationally defined GOM by difference, using concentrations of gaseous elemental Hg (GEM) and total gaseous Hg. One DCS was linked to a custom-built, automated calibration system that permeated GEM, HgBr2, or HgCl2. The five systems were co-located for one-year to develop a dataset that would allow for understanding limitations of each system, and assessing measurement accuracy and long-term precision of the calibrator. The Tekran system measured ~14.5 % of the GOM measured by the other systems. The USU and UNR DCS and RMAS were significantly correlated, but the DCS was 50 and 30 % higher, respectively, than the RMAS. The calibrator performed consistently in the field and lab, and the DCS fully recovered GOM injected by the calibrator. Since the uncalibrated DCS measured the same concentrations as the calibrated DCS, they are both accurate methods for measuring RM and/or GOM. Some loss occurred from the RMAS membranes. SYNOPSIS: Accurate and calibrated measurements of atmospheric reactive mercury using membranes and two dual-channel systems.

Investigation of the biochemical controls on mercury uptake and mobility in trees.

Atmospheric elemental mercury (Hg(0)) enters plant stomata, becomes oxidized, and is then transferred to annual growth rings providing an archive of air Hg(0) concentrations. To better understand the processes of Hg accumulation and translocation, the foliage of quaking aspen and Austrian pine were exposed to Hg(0), and methylmercury (MeHg) or Me198Hg via roots, in controlled exposures during the summer. Isotopic measurements demonstrated, in a laboratory setting, that the natural mass-dependent fractionation observed was the same as that measured in field studies, with the lighter isotopes being preferentially taken up by the leaves. Hg was measured in plant tissues across seasons. Aspen trees moved Hg into new growth immediately after exposure, resorbed Hg in the fall, and then distributed Hg to new growth tissues in the spring. Austrian pine did not reallocate Hg. Mercury measured in aspen leaf fractions of trees exposed to Hg(0) demonstrated that 85 % of Hg was in the cell wall. It was also found that redox-active molecules, such as H2O2, could potentiate the release of cell wall-bound Hg from aspen leaves, providing a potential mechanism for remobilization. Regardless of the mechanism, the ability of aspen to reallocate Hg to new tissues indicates that Hg distribution in tree rings from aspen do not provide a reliable record of yearly changes in atmospheric Hg(0).

Evidence against Rapid Mercury Oxidation in Photochemical Smog.

Mercury pollution is primarily emitted to the atmosphere, and atmospheric transport and chemical processes determine its fate in the environment, but scientific understanding of atmospheric mercury chemistry is clouded in uncertainty. Mercury oxidation by atomic bromine in the Arctic and the upper atmosphere is well established, but less is understood about oxidation pathways in conditions of anthropogenic photochemical smog. Many have observed rapid increases in oxidized mercury under polluted conditions, but it has not been clearly demonstrated that these increases are the result of local mercury oxidation. We measured elemental and oxidized mercury in an area that experienced abundant photochemical activity (ozone >100 ppb) during winter inversion (i.e., cold air pools) conditions that restricted entrainment of air from the oxidized mercury-rich upper atmosphere. Under these conditions, oxidized mercury concentrations decreased day-upon-day, even as ozone and other pollutants increased dramatically. A box model that incorporated rapid kinetics for reactions of elemental mercury with ozone and OH radical overestimated observed oxidized mercury, while incorporation of slower, more widely accepted reaction rates did not. Our results show that rapid gas-phase mercury oxidation by ozone and OH in photochemical smog is unlikely.

Using a next-generation sequencing approach to DNA metabarcoding for identification of adulteration and potential sources of mercury in commercial cat and dog foods.

Studies have demonstrated that some commercial pet (i.e., cat and dog) food products contain high concentrations of mercury (Hg), and some products have Hg concentrations that are higher than expected based on the ingredients included in the package ingredient list. Additionally, concentrations of methylmercury, a particularly toxic form of Hg commonly associated with fish-based ingredients, are largely unstudied despite the widespread use of such ingredients in pet food products. This study aimed to quantify total Hg and methylmercury in a variety of commercial pet food products (n = 127), and use genetic tools to determine if specific ingredients contributed to high Hg concentrations in the final product. Results indicate that total Hg concentrations were above suggested maximum tolerable limits in three of the tested pet food products, and that methylmercury concentrations were at safe levels in all tested products. Next-generation amplicon sequencing using ten barcode primers was conducted to target distinct taxa and to determine if one primer set outperformed the others in amplifying the often heavily degraded DNA found in pet food products. The 16sUniF_16sUniR primer set generated a relatively higher number of reads across the broadest set of taxa, although several of the primer sets were useful in identifying common animal- and plant-based ingredients in commercial pet food products. Combined with the Hg results, it was demonstrated that pet food product ingredients are consistent among and between product lots. However, these results also revealed that adulteration is prevalent in pet food products.

Use of Membranes and Detailed HYSPLIT Analyses to Understand Atmospheric Particulate, Gaseous Oxidized, and Reactive Mercury Chemistry.

The atmosphere is the primary pathway by which mercury enters ecosystems. Despite the importance of atmospheric deposition, concentrations and chemistry of gaseous oxidized (GOM) and particulate-bound (PBM) mercury are poorly characterized. Here, three membranes (cation exchange (CEM), nylon, and poly(tetrafluoroethylene) (PTFE) membranes) were used as a means for quantification of concentrations and identification of the chemistry of GOM and PBM. Detailed HYSPLIT analyses were used to determine sources of oxidants forming reactive mercury (RM = PBM + GOM). Despite the coarse sampling resolution (1-2 weeks), a gradient in chemistry was observed, with halogenated compounds dominating over the Pacific Ocean, and continued influence from the marine boundary layer in Nevada and Utah with a periodic occurrence in Maryland. Oxide-based RM compounds arrived at continental locations via long-range transport. Nitrogen, sulfur, and organic RM compounds correlated with regional and local air masses. RM concentrations were highest over the ocean and decreased moving from west to east across the United States. Comparison of membrane concentrations demonstrated that the CEM provided a quantitative measure of RM concentrations and PTFE membranes were useful for collecting PBM. Nylon membranes do not retain all compounds with equal efficiency in ambient air, and an alternate desorption surface is needed.

Improvements to the Accuracy of Atmospheric Oxidized Mercury Measurements.

We developed a cation-exchange membrane-based dual-channel system to measure elemental and oxidized mercury and deployed it with an automated calibration system and the University of Nevada, Reno-Reactive Mercury Active System (UNR-RMAS) at a rural/suburban field site in Colorado during the summer of 2018. Unlike oxidized mercury measurements collected via the widely used KCl denuder method, the dual-channel system was able to quantitatively recover HgCl2 and HgBr2 injected by the calibrator into the ambient sample air and compared well with the UNR-RMAS measurements. The system measured at 10 min intervals and had a 3-h average detection limit for oxidized mercury of 33 pg m-3. It was able to detect day-to-day variability and diel cycles in oxidized mercury (0 to 200 pg m-3) and will be an important tool for future studies of atmospheric mercury. We used a gravimetric method to independently determine the total mercury permeation rate from the permeation tubes. Permeation rates derived from the gravimetric method matched the permeation rates observed via mercury measurement devices to within 25% when the mercury permeation rate was relatively high (up to 30 pg s-1), but the agreement decreased for lower permeation rates, probably because of increased uncertainty in the gravimetric measurements.

Use of Multiple Lines of Evidence to Understand Reactive Mercury Concentrations and Chemistry in Hawai'i, Nevada, Maryland, and Utah, USA.

To advance our understanding of the mercury (Hg) biogeochemical cycle, concentrations and chemistry of gaseous oxidized Hg (GOM), particulate-bound Hg (PBM), and reactive Hg (RM = GOM + PBM) need to be known. The UNR-RMAS 2.0 provides a solution that will advance knowledge. From 11/2017 to 02/2019, the RMAS 2.0 was deployed in Hawai'i, Nevada, Maryland, and Utah to test system performance and develop an understanding of RM at locations impacted by different atmospheric oxidants. Mauna Loa Observatory, Hawai'i, impacted by the free troposphere and the marine boundary layer, had primarily -Br/Cl RM compounds. The Nevada location, directly adjacent to a major interstate highway and experiences inputs from the free troposphere, exhibited -Br/Cl, -N, -S, and organic compounds. In Maryland, compounds observed were -N, -S, and organic-Hg. This site is downwind of coal-fired power plants and located in a forested area. The location in Utah is in a basin impacted by oil and natural gas extraction, multiday wintertime inversion episodes, and inputs from the free troposphere. Compounds were -Br/Cl or -O, -N, and -Br/Cl. The chemical forms of RM identified were consistent with the air source areas, predominant ion chemistry, criterion air pollutants, and meteorology.

Comparison of 4 Methods for Measurement of Reactive, Gaseous Oxidized, and Particulate Bound Mercury.

The atmosphere is an important (1) pathway by which mercury (Hg) is transported around the globe and (2) source of Hg to ecosystems. Thus, understanding Hg atmospheric chemistry is critical for understanding the biogeochemical cycle and impacts to human and ecosystem health. Work over the past 13 years has demonstrated that the standard instrument used to measure atmospheric Hg does not accurately quantify gaseous oxidized mercury (GOM) or particulate bound mercury (PBM). This study focused on comparing four methods for quantifying atmospheric Hg and identifying Hg(II) compounds. Data from two automated systems, the Tekran 2537/1130 system and the University of Nevada, Reno-Dual Channel System (DCS), were compared with two University of Nevada, Reno-Reactive Mercury Active Systems (RMAS 2.0). One RMAS 2.0 included cation exchange membranes (CEMs) and nylon membranes, and the second included a polytetrafluoroethylene (PTFE) membrane upstream of the CEM and nylon membranes. The Tekran system and the DCS underestimated GOM concentrations with respect to that measured using the RMAS 2.0. The RMAS 2.0 with the upstream PTFE provided a means of distinguishing GOM and PBM. Thermal desorption of nylon membrane data identified a variety of GOM and PBM compounds present.

What is in commercial cat and dog food? The case for mercury and ingredient testing.

Commercial pet foods should be safe for long-term feeding. However, recent recalls and lawsuits have eroded public trust in pet food companies and products. Recent studies have identified high concentrations of mercury, a potent neurotoxin, in pet food products. Here we posit that pet food products require independent testing to verify safety and compliance with developed Food and Drug Administration and Association of American Feed Control Officials standards, and initiate a discussion as to why including quantification of mercury and methylmercury, as well as the identification of adulteration, are important to such testing protocols. The outcomes of these discussions will be multi-faceted: initiating the impetus to investigate the quality and label accuracy of pet foods; ensuring product safety; promoting transparency within the pet food industry; informing veterinary practices regarding pet food recommendations; providing data for evidence-based policy and regulatory enforcement; and working toward fulfilling the National Research Council's call for research that identifies levels of contaminants in animal feeds and residues in human foods.

Biogeochemical fate of ferrihydrite-model organic compound complexes during anaerobic microbial reduction.

Associations of organic carbon (OC) with iron (Fe) oxide minerals play an important role in regulating the stability of OC in soil environments. Knowledge about the fate and stability of Fe-OC complexes is impaired by the heterogeneity of OC. Additional biogeochemical variables in soil environments, such as redox conditions and microbes, further increase complexity in understanding the stability of mineral-associated soil OC. This study investigated the fate and stability of model organic compounds, including glucose (GL), glucosamine (GN), tyrosine (TN), benzoquinone (BQ), amylose (AM), and alginate (AL), complexed with an Fe oxide mineral, ferrihydrite (Fh), during microbial reduction. During a 25-d anaerobic incubation with Shewanella putrefaciens CN32, the reduction of Fe followed the order of Fh-BQ > Fh-GL > Fh-GN > Fh-TN > Fh-AL > Fh-AM. In terms of OC released during the anaerobic incubation, Fh-GN complexes released the highest amount of OC while Fh-AM complexes released the lowest. Organic carbon regulated the reduction of Fe by acting as an electron shuttle, affecting microbial activities, and associating with Fh. Benzoquinone had the highest electron accepting capacity, but potentially can inhibit microbial activity. These findings provide insights into the roles of different organic functional groups in regulating Fe reduction and the stability of Fh-bound OC under anaerobic conditions.

Aerobic respiration of mineral-bound organic carbon in a soil.

Associations with minerals can potentially augment soil organic carbon (SOC) stability by reducing the bioavailability and degradation of SOC. However, few studies have directly measured aerobic respiration of mineral-bound SOC. In this study, we investigated the microbial aerobic respiration and bioavailability of ferrihydrite-sorbed glucose (Fh-GLU) and ferrihydrite-sorbed formic acid (Fh-FA) by adding 13C-labeled compounds to a soil. During an 11-day incubation, 30.2% of free, non-Fh-sorbed glucose (GLU) and 61.8% of free formic acid (FA) were respired, whereas 4.2% and 27.9% of Fh-GLU and Fh-FA were respired, respectively. Our results demonstrated that Fh-bound GLU/FA had lower bioavailability compared to free organic compounds. Associations with Fh led to greater inhibition in the bioavailability of GLU than that for FA. The priming effects of added compounds on the respiration of native SOC were decreased by their association with Fh. Our results demonstrated that the bioavailability and priming effect of organic compounds depend on their interactions with minerals.