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  1. Nanomolar Copper Enhances Mercury Methylation by Desulfovibrio desulfuricans ND132

    Methylmercury (MeHg) is produced by certain anaerobic microorganisms, such as the sulfate-reducing bacterium Desulfovibrio desulfuricans ND132, but environmental factors affecting inorganic mercury [Hg(II)] uptake and methylation remain unclear. We report that the presence of a small amount of copper ions [Cu(II), <100 nM] enhances Hg(II) uptake and methylation by washed cells of ND132, while Hg(II) methylation is inhibited at higher Cu(II) concentrations because of the toxicity of copper to the microorganism. The enhancement or inhibitory effect of Cu(II) is dependent on both time and concentration. The presence of nanomolar concentrations of Cu(II) facilitates rapid uptake of Hg(II) (within minutes) andmore » doubles MeHg production within a 24 h period, but micromolar concentrations of Cu(II) completely inhibit Hg(II) methylation. Metal ions such as zinc [Zn(II)] and nickel [Ni(II)] also inhibit but do not enhance Hg(II) methylation under the same experimental conditions. Furthermore, these observations suggest a synergistic effect of Cu(II) on Hg(II) uptake and methylation, possibly facilitated by copper transporters or metallochaperones in this organism, and highlight the fact that complex environmental factors affect MeHg production in the environment.« less
  2. Characterization of iron oxide nanoparticle films at the air–water interface in Arctic tundra waters

    Here, massive amounts of organic carbon have accumulated in Arctic permafrost and soils due to anoxic and low temperature conditions that limit aerobic microbial respiration. Alternative electron acceptors are thus required for microbes to degrade organic carbon in these soils. Iron or iron oxides have been recognized to play an important role in carbon cycle processes in Arctic soils, although the exact form and role as an electron acceptor or donor remain poorly understood. Here, Arctic biofilms collected during the summers of 2016 and 2017 from tundra surface waters on the Seward Peninsula of western Alaska were characterized with amore » suite of microscopic and spectroscopic methods. We hypothesized that these films contain redox-active minerals bound to biological polymers. The major components of the films were found to be iron oxide nanoparticle aggregates associated with extracellular polymeric substances. The observed mineral phases varied between films collected in different years with magnetite (Fe 2+Fe 2 3+O 4) nanoparticles (<5 nm) predominantly identified in the 2016 films, while for films collected in 2017 ferrihydrite-like amorphous iron oxyhydroxides were found. While the exact formation mechanism of these Artic iron oxide films remains to be explored, the presence of magnetite and other iron oxide/oxyhydroxide nanoparticles at the air–water interface may represent a previously unknown source of electron acceptors for continual anaerobic microbial respiration of organic carbon within poorly drained Arctic tundra.« less
  3. Molecular Insights into Arctic Soil Organic Matter Degradation under Warming

    Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. By using ultrahigh-resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska (United States). EDOM was extracted with 10 mM NH 4HCO 3 from both the organic- and mineral-layer soils during incubation at both -2 and 8°C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classesmore » of compounds, among which lignin-like compounds dominated both the organic and the mineral soils and were the most stable, whereas amino sugars, peptides, and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition in which the ratios of O:C and N:C decreased, while the average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM components, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.« less
  4. Microbial community structure with trends in methylation gene diversity and abundance in mercury-contaminated rice paddy soils in Guizhou, China

    In this paper, paddy soils from mercury (Hg)-contaminated rice fields in Guizhou, China were studied with respect to total mercury (THg) and methylmercury (MeHg) concentrations as well as Bacterial and Archaeal community composition. Total Hg (0.25–990 μg g –1) and MeHg (1.3–30.5 ng g –1) varied between samples. Pyrosequencing (454 FLX) of the hypervariable v1–v3 regions of the 16S rRNA genes showed that Proteobacteria, Actinobacteria, Chloroflexi, Acidobacteria, Euryarchaeota, and Crenarchaeota were dominant in all samples. The Bacterial α-diversity was higher in samples with relatively Low THg and MeHg and decreased with increasing THg and MeHg concentrations. In contrast, Archaeal α-diversitymore » increased with increasing of MeHg concentrations but did not correlate with changes in THg concentrations. Overall, the methylation gene hgcAB copy number increased with both increasing THg and MeHg concentrations. The microbial communities at High THg and High MeHg appear to be adapted by species that are both Hg resistant and carry hgcAB genes for MeHg production. The relatively high abundance of both sulfate-reducing δ- Proteobacteria and methanogenic Archaea, as well as their positive correlations with increasing THg and MeHg concentrations, suggests that these microorganisms are the primary Hg-methylators in the rice paddy soils in Guizhou, China.« less
  5. Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

    In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less
  6. Microbial community structure with trends in methylation gene diversity and abundance in mercury-contaminated rice paddy soils in Guizhou, China

    Sulfate-reducing bacteria and methanogens are the primary Hg-methylators in Chinese rice paddies.
  7. Influence of Structural Defects on Biomineralized ZnS Nanoparticle Dissolution: An In-Situ Electron Microscopy Study

    The dissolution of metal sulfides, such as ZnS, plays an important role in the fate of metal contaminants in the environment. Here we have examined the dissolution behavior of ZnS nanoparticles synthesized via several abiotic and biological pathways. Specifically, the biogenic ZnS nanoparticles were produced by an anaerobic, metal-reducing bacterium Thermoanaerobacter sp. X513 in a Zn-amended, thiosulfate-containing growth medium, whereas the abiogenic ZnS nanoparticles were produced by mixing an aqueous Zn solution with either H 2S-rich gas or Na 2S solution. For biogenic synthesis, we prepared two types of samples, in the presence or absence of trace silver (Ag). Themore » size distribution, crystal structure, aggregation behavior, and internal defects of the synthesized ZnS nanoparticles were primarily examined using high-resolution transmission electron microscopy coupled with X-ray energy dispersive spectroscopy. The characterization results show that both the biogenic and abiogenic samples were dominantly composed of sphalerite. In the absence of Ag, the biogenic ZnS nanoparticles were significantly larger (i.e., ~10 nm) than the abiogenic ones (i.e., ~3–5 nm) and contained structural defects (e.g., twins and stacking faults). The presence of trace Ag showed a restraining effect on the particle size of the biogenic ZnS, resulting in quantum-dot-sized nanoparticles (i.e., ~3 nm). In situ dissolution experiments for the synthesized ZnS were conducted with a liquid-cell coupled to a transmission electron microscope (LCTEM), and the primary factors (i.e., the presence or absence structural defects) were evaluated for their effects on the dissolution behavior using the biogenic and abiogenic ZnS nanoparticle samples with the largest average particle size. Analysis of the dissolution results (i.e., change in particle radius with time) using the Kelvin equation shows that the defect-bearing biogenic ZnS nanoparticles (γ = 0.799 J/m 2) have a significantly higher surface energy than the abiogenic ZnS nanoparticles (γ = 0.277 J/m 2), suggesting that larger defect-bearing ZnS nanoparticles may be more reactive than the smaller quantum-dot-sized ZnS nanoparticles. These findings provide new insight into the factors that govern the dissolution of metal sulfide nanoparticles in relevant natural and engineered scenarios, and have implication for tracking the fate of zinc at contaminated sites. Moreover, our study exemplified the use of an in situ method (i.e., LCTEM) to investigate nanoparticle behavior (e.g., dissolution) in aqueous solutions.« less
  8. Microbial Community and Functional Gene Changes in Arctic Tundra Soils in a Microcosm Warming Experiment

    Microbial decomposition of soil organic carbon (SOC) in the thawing Arctic permafrost is one of the most important, but poorly understood, processes in determining the greenhouse gases feedback of tundra ecosystems to climate. Here in this paper, we examine changes in microbial community structure during an anoxic incubation at either –2 or 8 °C for up to 122 days using both an organic and a mineral soil collected from the Barrow Environmental Observatory in northern Alaska, USA. Soils were characterized for SOC chemistry, and GeoChips were used to determine microbial community structure and functional genes associated with C degradation andmore » Fe(III) reduction. We observed notable decreases in functional gene diversity (at P < 0.05) in response to warming at 8 °C, particularly in the organic soil. A number of genes associated with SOC degradation, fermentation, methanogenesis, and iron cycling decreased significantly (P < 0.05) after 122 days of incubation, which coincided well with decreasing labile SOC content, soil respiration, methane production, and iron reduction. The soil type (i.e., organic vs. mineral) and the availability of labile SOC were among the most significant environmental factors impacting the functional community structure. In contrast, the functional structure was largely unchanged in the –2 °C incubation due to low microbial activity resulting in less competition or exclusion. These results demonstrate the vulnerability of SOC in Arctic tundra to warming, facilitated by iron reduction and methanogenesis, and the importance of microbial communities in moderating such vulnerability.« less
  9. Demonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO 4 -)

    Costs for environmental analysis and monitoring are increasing at a rapid rate and represent a significant percentage of the total and future remedial expenses at many U.S. Department of Defense (DoD) contaminated sites. It has been reported that about 30 to 40% of the remediation budget is usually spent on long-term monitoring (LTM), of which a large percentage represents laboratory analytical costs. Energetics such as perchlorate (ClO 4 -) are among the most frequently detected contaminants in groundwater and surface water at or near military installations due to their persistence and mobility. Currently, the standard protocol entails collecting samples inmore » the field, packaging them, and shipping them overnight to a designated laboratory for analysis. This process requires significant sample preparation and handling, and analytical results may not be available for several days to weeks. In this project, we developed and demonstrated a portable Raman sensor based on surface enhanced Raman scattering (SERS) technology to detect ClO 4 - in contaminated water. We summarize major accomplishments as follows: • A SERS sensor based on elevated gold (Au) nano-ellipse dimer architectures was designed and developed for ClO 4 - with a detection limit of ~10 -6 M (or 100 μg/L); The performance of these sensors was evaluated and optimized through variation of their geometric characteristics (i.e., dimer aspect ratio, dimer separation, etc.). • Large-scale commercial production of SERS substrate sensors via nanoimprinting by Nanova Inc. and Nanoimprint lithography (NIL) technology was successfully demonstrated. This is a substantial step forward toward the commercialization of the SERS sensors and may potentially lead to significantly reduced fabrication costs of SERS substrates. • Commercially produced SERS sensors were demonstrated to detect ClO 4 - at levels above 10 -6 M using a portable Raman analyzer. The performance of the commercial SERS sensors for ClO 4 - detection in the presence and absence of interferences was determined for a series of standard solutions. Sulfate (SO 4 2-) was found to exhibit the greatest interference for the anions tested, which included Cl-, NO 3 -, and SO 4 2-. • Field demonstration of the portable Raman sensor with commercially produced SERS substrates was completed at two Department of Defense (DoD) sites; twice at the Indian Head Naval Surface Warfare Center, Indian Head, MD, and once at Redstone Arsenal, Huntsville, AL. Multiple wells were sampled at both DoD sites, where a standard addition method was employed using the sensor to determine the ClO 4 -4 - and possibly other energetics that are both important for environmental monitoring and of interest for national security. However, we point out that SERS technology is also prone to interferences due to its sensitivity and responses to other ionic species, such as NO 3 -, SO 4 2-, and dissolved organics or co-contaminants present in the groundwater, which could potentially mask the SERS signal of the target analyte (i.e., ClO 4 -). As such, SERS analysis was subject to significant variations (e.g., ±20% or more), and its detection limit for ClO 4 --8 M) and was substantially higher than what we anticipated from laboratory studies. However, despite these complications, the portable Raman sensor developed in this project could be used as a rapid screening tool for ClO 4 - at concentrations above 10 -6 M. Future studies are warranted to further develop the technology and to optimize its performance, and eventually to bring the technology to the market. With additional development and demonstration, the sensor has the potential to reduce analytical costs by eliminating shipping and typical costs associated with laboratory analysis. A cost savings of 30–45% may be realized during a typical sampling event and, more importantly, the technology could allow rapid turn-around of information to decision makers for site characterization and remediation.« less
  10. Identification of Mercury and Dissolved Organic Matter Complexes Using Ultrahigh Resolution Mass Spectrometry

    The chemical speciation and bioavailability of mercury (Hg) is markedly influenced by its complexation with naturally dissolved organic matter (DOM) in aquatic environments. To date, however, analytical methodologies capable of identifying such complexes are scarce. Here, we utilize ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) coupled with electrospray ionization to identify individual Hg-DOM complexes. The measurements were performed by direct infusion of DOM in a 1:1 methanol:water solution at a Hg to dissolved organic carbon (DOC) molar ratio of 3 × 10 -4. Heteroatomic molecules, especially those containing multiple S and N atoms, were found to bemore » among the most important in forming strong complexes with Hg. Major Hg-DOM complexes of C10H21N2S4Hg+ and C8H17N2S4Hg+ were identified based on both the exact molecular mass and patterns of Hg stable isotope distributions detected by FTICR-MS. Density functional theory was used to predict the solution-phase structures of candidate molecules. These findings represent the first step to unambiguously identify specific DOM molecules in Hg binding, although future studies are warranted to further optimize and validate the methodology so as to explore detailed molecular compositions and structures of Hg-DOM complexes that affect biological uptake and transformation of Hg in the environment.« less
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