Search NASA⌕ Search

Engineering topics

Gu, Baohua

Publications and source records attributed to Gu, Baohua.

At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Isotopic discrimination of natural and anthropogenic perchlorate sources in groundwater in a semi-arid region of northeastern Oregon (USA)

Perchlorate (ClO 4 - ) has synthetic and natural sources. Synthetic ClO 4 - is released to the environment from its use as an oxidant in military and aerospace applications, and from its presence in a variety of common commercial products, such as safety flares, chlorate herbicides, and fireworks. Natural sources of ClO 4 - in the environment include imported nitrate fertilizers derived from salt deposits in the Atacama Desert of Chile and indigenous natural ClO 4 - that accumulates in unsaturated soils and groundwaters in other arid and semi-arid environments, largely from atmospheric deposition. The stable isotope ratios of chlorine ( 37 Cl/ 35 Cl) and oxygen ( 18 O/ 16 O, 17 O/ 16 O) and the isotopic abundance of radioactive 36 Cl in ClO 4 - can be used to discriminate these different sources. Perchlorate was previously detected at relatively high concentrations (3.8–34.7 μg/L) in groundwater from many wells in the Boardman-Umatilla area near the Columbia River in northeastern Oregon, which is a semi-arid, highly agricultural, heavily irrigated area that includes several past and current military installations. Eight representative groundwater wells were sampled throughout this region and isotopic characteristics of ClO 4 - collected from each well were measured along with other chemical and isotopic parameters including tritium and other groundwater age indicators. We report isotopic data indicate that indigenous natural ClO 4 - was present in groundwater from all sampled wells and was the predominant source in five of the wells. Synthetic ClO 4 - was present in the three remaining wells with natural ClO 4 - , and a minor fraction of Atacama-fertilizer-derived ClO4- was indicated in one of the wells. Data from this study expand the geographic area of the USA in which indigenous natural ClO 4 - has been detected to include the semi-arid northwest. This study also illustrates the role of irrigation recharge as a mechanism for producing relatively high concentrations of indigenous natural ClO 4 - in groundwater by flushing accumulated salts from the unsaturated zone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Unravelling biogeochemical drivers of methylmercury production in an Arctic fen soil and a bog soil

Arctic tundra soils store a globally significant amount of mercury (Hg), which could be transformed to the neurotoxic methylmercury (MeHg) upon warming and thus poses serious threats to the Arctic ecosystem. However, our knowledge of the biogeochemical drivers of MeHg production is limited in these soils. Using substrate addition (acetate and sulfate) and selective microbial inhibition approaches, we investigated the geochemical drivers and dominant microbial methylators in 60-day microcosm incubations with two tundra soils: a circumneutral fen soil and an acidic bog soil, collected near Nome, Alaska, United States. Results showed that increasing acetate concentration had negligible influences on MeHg production in both soils. However, inhibition of sulfate-reducing bacteria (SRB) completely stalled MeHg production in the fen soil in the first 15 days, whereas addition of sulfate in the low-sulfate bog soil increased MeHg production by 5-fold, suggesting prominent roles of SRB in Hg(II) methylation. Without the addition of sulfate in the bog soil or when sulfate was depleted in the fen soil (after 15 days), both SRB and methanogens contributed to MeHg production. Analysis of microbial community composition confirmed the presence of several phyla known to harbor microorganisms associated with Hg(II) methylation in the soils. Lastly, the observations suggest that SRB and methanogens were mainly responsible for Hg(II) methylation in these tundra soils, although their relative contributions depended on the availability of sulfate and possibly syntrophic metabolisms between SRB and methanogens.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Removable, Sequestration Coatings for Mitigating Hazardous Contaminants Related to Deactivation and Decommissioning Activities

This project is a collaborative effort between InnoSense LLC (ISL) and Oak Ridge National Laboratory (ORNL) aimed at mitigating the mercury (Hg) contamination problem at the Y-12 National Security Complex (NSC). The report summarizes the research and technology development work of the Phase IIB Project, led by Dr. Uma Sampathkumaran at ISL for the period of July 31, 2017–October 31, 2021. The Y-12 site cleanup includes technologies for safe and cost-effective facility demolition, soil remediation, and on-site treatment and disposal of mercury bearing wastes. One of the technology demonstration goals was a reactive strippable coating for targeted pre-demolition and de-contamination to limit Hg mobilization and the volume of debris requiring treatment for disposal. Toward this, ISL has developed a water-based reactive strippable coating (Trap & See-Hg™) to sequester elemental Hg(0) and mercuric Hg(II) species in the coating. The coating provides multiple benefits including (1) Hg vapor suppression, (2) sealing in the hazardous contaminants, (3) visually locating the contaminant through color changes, and (4) remediating the contaminated surfaces upon coating removal. Through collaboration between ORNL and ISL in Phase II work, the team successfully demonstrated the Trap & See-Hg technology to (1) visually locate the presence of Hg on concrete, soil and drywall surfaces, (2) effectively sequester all mercury species (elemental, soluble and insoluble Hg) from lab-generated and ex-situ soil and brick/rubble samples collected from the Y 12 site with 80 to 95% efficiency to capture/reduce Hg vapor concentration, (3) be applied by manual and robotic spray applicators and cure at room ambient, (4) remain a cohesive and peelable coating upon drying, and (5) sequester Hg0 from walls in the alpha-2 building basement at Y-12 during a small scale in-situ field trial. In Phase IIB, ISL’s effort was focused on refining the coating formulations with additives containing passive and reactive sorbents, colorimetric indicator, and thixotropic agents to achieve the desired performance. The paints were then evaluated at ORNL for applicability to metal and concrete surfaces of different sizes and shapes, and soil rubble, Hg-sorption capacity and achieving sag-free coating on surfaces when applied by a manual spray applicator. Ambient cure of the coating resulted in a dry thickness of 16–20 mil. The coatings were removed from smooth or rough surfaces with low to moderate force. Both lab-generated Hg-contaminated samples and soil and brick/rubble samples containing a range of Hg concentrations (collected from the Y-12 site by UCOR) were used in this project. Optimized formulations were applied to these samples and evaluated for ability to suppress Hg vapors, sequester Hg 0 and Hg(II) species and color mapping of mercury species on the test surface. The ORNL team initially identified three to four potential sites at Y-12 and ORNL for potential demonstration. However, the pandemic closed any possible avenues for on-site demonstration of the robotic spray applicator. The metal and concrete samples with low to high Hg content provided by UCOR from an ongoing demolition were subsequently used for ex-situ sample characterization and analysis at ORNL over a period of 25 days. The coatings suppressed Hg vapors with an efficiency of 95–99% from heavily contaminated metal and 60% from concrete substrate. Analysis of total Hg in the peeled paints indicates sorption capacities ranging from 12 µg Hg/g of paint from concrete to 1.2 mg Hg/g of paint from the metal substrates while peeled paints from soil samples could capture a total Hg from 2.3 mg Hg/g to 66 mg/g paint. Toxicity characteristic leaching procedure (TCLP) tests recovered total mercury leached at 0.15±0.0008 µg/L for concrete to 126.81±0.67 µg/L and 377.25±5.67 µg/L for the two metal substrates, to allow for informed decisions on downstream disposal considerations. Together, this Phase IIB demonstrated the potential value of the Trap & See-Hg for Hg uptake, vapor suppression, and color mapping, and may thus be used to enhance worker safety during site cleanup, facility demolition, and downstream waste disposal at Y-12 NSC.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Origin of the isotopic composition of natural perchlorate: Experimental results for the impact of reaction pathway and initial ClO x reactant

Natural perchlorate (ClO 4 - ) exists in many places on Earth, in lunar regolith, meteorites, and on the surface of Mars. Terrestrial natural ClO 4 - has widely variable Cl and O stable isotopic compositions (δ 37 Cl, δ 18 O, Δ 17 O). The δ 18 O and Δ 17 O values of ClO 4 - from the most hyper-arid locations co-vary. ClO 4 - from less arid areas has relatively little 17 O excess and poor Δ 17 O-δ 18 O correlation. ClO 4 - from the Atacama Desert has unusually low δ 37 Cl (<-10‰) and exhibits a positive correlation between δ 37 Cl and δ 18 O, while the δ 37 Cl of ClO 4 - from all other locations varies between -5 and +7‰ with no δ 37 Cl-δ 18 O covariation. To evaluate the impact of different precursors (ClO x ) and reaction pathways on the isotopic composition of ClO 4 - , we measured the isotopic composition of ClO 4 - produced in the laboratory by UV or O 3 mediated aqueous oxidation of Cl-, OCl-, ClO2-, and ClO2° as well as O 3 mediated oxidation of dry NaCl. ClO x oxidation in aqueous or dry systems enriched in O 3 produced ClO 4 - with Δ 17 O values that generally increased with the number of O atoms required and included evidence that the site-specific 17 O anomaly in O 3 was preferentially transferred to ClO 4 - . Based on the inferred number of O atoms sourced from O 3 , and known Cl and O reaction pathways, it appears that ClO 2 ° and ClO 3 * were required intermediates in the production of ClO 4 - in the O 3 experiments. ClO x aqueous oxidation by UV irradiation produced ClO 4 - with a large range of δ 18 O values and little or no 17 O anomaly. ClO 3 - was produced to a much greater extent than ClO 4 - in all experiments except dry oxidation of NaCl by O 3 . The isotopic composition of ClO 3 - was distinct from that of ClO 4 - produced from the same initial reactants. Combined results of O 3 and UV mediated reactions largely bracketed the range of natural ClO 4 - δ 18 O and Δ 17 O values as well as δ 37 Cl values of non-Atacama natural samples, but no conditions produced the low δ 37 Cl values of Atacama ClO 4 - . Finally, our results indicate that variation in production mechanisms, possibly combined with isotopically variable precursors, could be responsible for much of the observed isotopic variation in natural ClO 4 - and ClO 3 - .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Spectroscopic and computational investigations of organometallic complexation of group 12 transition metals by methanobactins from Methylocystis sp. SB2

Methanotrophic bacteria catalyze the aerobic oxidation of methane to methanol using Cu-containing enzymes, thereby exerting a modulating influence on the global methane cycle. To facilitate the acquisition of Cu ions, some methanotrophic bacteria secrete small modified peptides known as “methanobactins,” which strongly bind Cu and function as an extracellular Cu recruitment relay, analogous to siderophores and Fe. In addition to Cu, methanobactins form complexes with other late transition metals, including the Group 12 transition metals Zn, Cd, and Hg, although the interplay among solution-phase configurations, metal interactions, and the spectroscopic signatures of methanobactin-metal complexes remains ambiguous. In this study, the complexation of Zn, Cd, and Hg by methanobactin from Methylocystis sp. strain SB2 was studied using a combination of absorbance, fluorescence, extended x-ray absorption fine structure (EXAFS) spectroscopy, and time-dependent density functional theory (TD-DFT) calculations. We report changes in sample absorbance and fluorescence spectral dynamics, which occur on a wide range of experimental timescales and characterize a clear stoichiometric complexation dependence. Mercury L3-edge EXAFS and TD-DFT calculations suggest a linear model for Hg--S coordination, and TD-DFT suggests a tetrahedral model for Zn 2+ and Cd 2+ . We observed an enhancement in the fluorescence of methanobactin upon interaction with transition metals and propose a mechanism of complexation-hindered isomerization drawing inspiration from the wild-type Green Fluorescent Protein active site. Collectively, our results represent the first combined computational and experimental spectroscopy study of methanobactins and shed new light on molecular interactions and dynamics that characterize complexes of methanobactins with Group 12 transition metals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

Competitive exchange between divalent metal ions [Cu(II), Zn(II), Ca(II)] and Hg(II) bound to thiols and natural organic matter

Mercuric Hg(II) ion forms exceptionally strong complexes with various organic ligands, particularly thiols and dissolved organic matter (DOM) in natural water. Few studies, however, have experimentally determined whether or not the presence of base cations and transition metal ions, such as Ca(II), Cu(II), and Zn(II), would compete with Hg(II) bound to these ligands, as concentrations of these metal ions are usually orders of magnitude higher than Hg(II) in aquatic systems. Different from previous model predictions, a significant fraction of Hg(II) bound to cysteine (CYS), glutathione (GSH), or DOM was found to be competitively exchanged by Cu(II), but not by Zn(II) or Ca(II). About 20–75% of CYS-bound-Hg(II) [at 2:1 CYS:Hg(II)] and 14–40% of GSH-bound-Hg(II) [at 1:1 GSH:Hg(II)] were exchanged by Cu(II) at concentrations 1–3 orders of magnitude greater than Hg(II). Competitive exchange was also observed between Cu(II) and Hg(II) bound to DOM, albeit to a lower extent, depending on relative abundances of thiol and carboxylate functional groups on DOM and their equilibrium time with Hg(II). When complexed with ethylenediaminetetraacetate (EDTA), most Hg(II) could be exchanged by Cu(II) and Zn(II), as well as Ca(II) at increasing concentrations. Furthermore, these results shed additional light on competitive exchange reactions between Hg(II) and coexisting metal ions and have important implications in Hg(II) chemical speciation and biogeochemical transformation, particularly in contaminated environments containing relatively high concentrations of Hg(II) and metal ions.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Mechanistic Investigation of Dimethylmercury Formation Mediated by a Sulfide Mineral Surface

Mercury (Hg) pollution is a global environmental problem, but many key transformations among 29 various Hg species are not well understood. Although anaerobic microorganisms are the primary 30 producers of monomethylmercury (MMeHg), the abiotic formation of dimethylmercury (DMeHg) 31 from MMeHg have been suggested to account for a large portion of DMeHg in the ocean. It has 32 been shown that abiotic formation of DMeHg from MMeHg can be facilitated by reduced sulfur 33 groups on mineral surfaces. However, a detailed mechanistic understanding of this reaction is 34 lacking. Here we perform density functional theory (DFT) calculations to explore mechanisms of 35 DMeHg formation on the 110 surface of a CdS(s) (hawleyite) nanoparticle. We show that 36 coordination of MMeHg substituents to adjacent reduced sulfur groups protruding from the surface 37 facilitate DMeHg formation and that the reaction proceeds through direct transmethylation from 38 one MMeHg substituent to another. Solvation effects were found to play an important role in the 39 surface reconstruction of the nanoparticle and in decreasing the energetic barrier for DMeHg 40 formation. We also investigate DMeHg formation from MMeHg mediated by organic dithiols and 41 compare the results to those mediated by the mineral surface. In contrast to the surface reaction, 42 the calculations suggest that dithiol-mediated formation of DMeHg instead proceeds through a 43 mechanism in which Hg–Hg interactions activate a methyl group from one MMeHg substituent 44 for intramolecular transfer to the adjacent MMeHg substituent. These findings refine previously 45 proposed mechanisms of abiotic DMeHg formation and fill gaps in our understanding of global 46 Hg cycling in the environment.

Lian, Peng↗
DOE OSTI2021

Temporal, Spatial, and Temperature Controls on Organic Carbon Mineralization and Methanogenesis in Arctic High-Centered Polygon Soils

Warming temperatures in continuous permafrost zones of the Arctic will alter both hydrological and geochemical soil conditions, which are strongly linked with heterotrophic microbial carbon (C) cycling. Heterogeneous permafrost landscapes are often dominated by polygonal features formed by expanding ice wedges: water accumulates in low centered polygons (LCPs), and water drains outward to surrounding troughs in high centered polygons (HCPs). These geospatial differences in hydrology cause gradients in biogeochemistry, soil C storage potential, and thermal properties. Presently, data quantifying carbon dioxide (CO 2 ) and methane (CH 4 ) release from HCP soils are needed to support modeling and evaluation of warming-induced CO 2 and CH 4 fluxes from tundra soils. This study quantifies the distribution of microbial CO 2 and CH 4 release in HCPs over a range of temperatures and draws comparisons to previous LCP studies. Arctic tundra soils were initially characterized for geochemical and hydraulic properties. Laboratory incubations at −2, +4, and +8°C were used to quantify temporal trends in CO 2 and CH 4 production from homogenized active layer organic and mineral soils in HCP centers and troughs, and methanogen abundance was estimated from mcrA gene measurements. Results showed that soil water availability, organic C, and redox conditions influence temporal dynamics and magnitude of gas production from HCP active layer soils during warming. At early incubation times (2–9 days), higher CO 2 emissions were observed from HCP trough soils than from HCP center soils, but increased CO 2 production occurred in center soils at later times (>20 days). HCP center soils did not support methanogenesis, but CH 4 -producing trough soils did indicate methanogen presence. Consistent with previous LCP studies, HCP organic soils showed increased CO 2 and CH 4 production with elevated water content, but HCP trough mineral soils produced more CH 4 than LCP mineral soils. HCP mineral soils also released substantial CO 2 but did not show a strong trend in CO 2 and CH 4 release with water content. Knowledge of temporal and spatial variability in microbial C mineralization rates of Arctic soils in response to warming are key to constraining uncertainties in predictive climate models.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Methanotrophic-Mediated Methylmercury Transformation: Characterization of Products, Mechanism, and Environmental Significance (Final Technical Report)

Previous work in the laboratories of the PIs found that methanotrophs, through the production of a novel metal chelator called methanobactin (MB), can bind inorganic mercury (Hg[II]). By doing so, methanotrophs substantially reduce Hg[II] toxicity. We have also recently shown that MB can bind a much more toxic form of mercury, the neurotoxin methylmercury (MeHg). MeHg bioaccumulates and biomagnifies in biota such as fish, and is of significant concern. Further, certain methanotrophs expressing MB are able to demethylate significant amounts of MeHg despite lacking merB, the organomercurial lyase. Further, unlike the canonical organomercurial lyase, methanotrophs take up and degrade MeHg at environmentally relevant pH and Hg concentrations (i.e., picomolar to nanomolar), suggesting that methanotrophs likely play a critical role in controlling net MeHg production and toxicity in situ. However, although MB is necessary for methanotrophic-mediated MeHg degradation, it is not sufficient as purified MB binds, but does not degrade MeHg. That is, MB appears to serve as binding device leading to demethylation of MeHg by an as yet unknown mechanism. The major goals of this project were to extend this initial work and characterize the mechanism of methanotrophic-mediated MeHg demethylation and how methanobactin production may affect net methylmercury production in situ.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Isotope Exchange between Mercuric [Hg(II)] Chloride and Hg(II) Bound to Minerals and Thiolate Ligands: Implications for Enriched Isotope Tracer Studies

Enriched mercury (Hg) stable isotopes have been widely used as tracers in field and laboratory investigations of Hg(II) biogeochemical transformations such as methylation and demethylation. Few studies, however, have considered concurrent isotope exchange reactions between newly spiked and pre-existing Hg(II) in environmental matrices, which may alter redistribution and thus transformation of the spiked and pre-existing Hg(II). Using enriched 198 Hg [as mercuric Hg(II) or HgCl n species], this study investigated isotope exchange between 198 Hg and pre-existing Hg(II) bound to metacinnabar (β-HgS), sediments, low-molecular-weight (LMW) thiols, and dissolved organic matter (DOM). The impact of isotope exchange on methylmercury production in the presence of organic ligands was also evaluated with an iron-reducing bacterium Geobacter sulfurreducens PCA in a phosphate buffered solution (pH 7.4). Here, we found that spiked 198 Hg readily exchanged with mineral-bound ambient Hg(II) despite concurrent Hg(II) adsorption and immobilization on the solids. Rapid exchange (<3 min) was also observed between spiked 198 Hg and 200 Hg pre-equilibrated with LMW thiols and DOM in solution. While the exchange did not cause net changes in Hg(II) chemical speciation, it resulted in redistribution of Hg(II) isotopes bound to the ligands and thus an apparently similar methylation rate and magnitude of the spiked 198 Hg and pre-existing 200 Hg by PCA cells when 198 Hg and 200 Hg were added at 1:1 ratio. These observations underscore the importance of isotope exchange when an enriched Hg isotope is applied in environmental matrices, as the exchange could potentially lead to biased rate calculations of Hg(II) transformation and bioaccumulation and thus risk assessments of new Hg(II) input to the natural ecosystems.

58 GEOSCIENCES↗
DOE OSTI2020

Molecular Dynamics Simulation of the Structures, Dynamics, and Aggregation of Dissolved Organic Matter

Dissolved organic matter (DOM) plays a significant role in the transport and transformation of pollutants in the aquatic environment. However, the experimental characterization of DOM has been limited mainly to bulk properties, and the molecular-level interactions among various components of DOM remain to be fully characterized. In this study, we use molecular dynamics (MD) simulations to probe the structural properties of model DOM systems at atomic detail. The 200 ns simulations, validated by available experimental data, reveal processes and mechanisms by which chemical species (cations, peptides, lipids, lignin, carbohydrates, and some low-molecular-weight aliphatic and aromatic compounds) aggregate to form complex DOM. The DOM aggregates are dynamic, consisting of a hydrophobic core and amphiphilic exterior. The lipid tails and other hydrophobic fragments form the core, with hydrophilic and amphiphilic groups exposed to water, making DOM accessible to both polar and nonpolar species. Thus, the lipid component acts as a nucleator, whereas cations (especially Ca 2+ ) connect the molecular fragments on the surface by coordinating with the O-containing functional groups of DOM. The structural details revealed here provide new insights including surface accessible atoms, overall assemblage, and interactions among the molecules of DOM for understanding the kinetics and mechanisms through which DOM interacts with metal and other contaminants.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Anaerobic respiration pathways and response to increased substrate availability of Arctic wetland soils

The availability of labile carbon (C) compounds in Arctic wetland soils is expected to increase due to thawing permafrost and increased fermentation as a result of decomposition of organic matter with warming. How microbial communities respond to this change will affect the balance of CO 2 and CH 4 emitted during anaerobic organic matter decomposition, and ultimately the net radiative forcing of greenhouse gas emissions from these soils. While soil water content limits aerobic respiration, the factors controlling methanogenesis and anaerobic respiration are poorly defined in suboxic Arctic soils. In this study, we conducted incubation experiments on two tundra soils from field sites on the Seward Peninsula, Alaska, with contrasting pH and geochemistry to determine the pathways of anaerobic microbial respiration and changes with increasing substrate availability upon warming. In incubation of soils from the circumneutral Teller site, the ratio of CO 2 to CH 4 dropped from 10 to <2 after 60 days, indicating rapid depletion of alternative terminal electron acceptors (TEAs). Addition of acetate stimulated production of CO 2 and CH 4 in a nearly 1:1 ratio, consistent with methanogenesis, and the composition of the microbial community shifted to favor clades capable of utilizing the added acetate such as the Fe(III)-reducing Geobacter and the methanogenic archaea Methanosarcina. In contrast, both CO 2 and CH 4 production declined with acetate addition during incubation of soils from the more acidic Council site, and fermentative microorganisms increased in abundance despite the high availability of fermentation products. These results demonstrate that the degree to which increasing substrate availability stimulates greenhouse gas production in tundra wetlands will vary widely depending on soil pH and geochemistry.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Influences of Hillslope Biogeochemistry on Anaerobic Soil Organic Matter Decomposition in a Tundra Watershed

In this work, we investigated rates and controls on greenhouse gas (CO 2 and CH 4 ) production in two contrasting water-saturated tundra soils within a permafrost-affected watershed near Nome, Alaska, United States. Three years of field sample analysis have shown that soil from a fen-like area in the toeslope of the watershed had higher pH and higher porewater ion concentrations than soil collected from a bog-like peat plateau at the top of the hillslope. The influence of these contrasting geochemical and topographic environments on CO 2 and CH 4 production was tested in soil microcosms by incubating both the organic- and mineral-layer soils anaerobically for 55 days. Additionally, nitrogen (as NH 4 Cl) was added to half of the microcosms to test potential effects of N limitation on microbial greenhouse gas production. We found that the organic toeslope soils produced more CO 2 and CH 4 , fueled by higher pH and higher concentrations of water-extractable organic C (WEOC). Our results also indicate N limitation on CO 2 production in the peat plateau soils but not the toeslope soils. Together these results suggest that the weathering and leaching of ions and nutrients from tundra hillslopes can increase the rate of anaerobic soil organic matter decomposition in downslope soils by (1) increasing the pH of soil porewater; (2) providing bioavailable WEOC and fermentation products such as acetate; and (3) relieving microbial N limitation through nutrient runoff. We conclude that the soil geochemistry as mediated by landscape position is an important factor influencing the rate and magnitude of greenhouse gas production in tundra soils.

58 GEOSCIENCES↗
DOE OSTI2020

Microbial Communities Associated with Methylmercury Degradation in Paddy Soils

Bioaccumulation of the neurotoxin methylmercury (MeHg) in rice has raised worldwide concerns because of its risks to human health. Certain microorganisms are able to degrade MeHg in pure cultures, but the roles and diversities of the microbial communities in MeHg degradation in rice paddy soils are unknown. Using a series of microcosms, we investigated MeHg degradation in paddy soils from Hunan, Guizhou, and Hubei provinces, representing three major rice production regions in China, and further characterized one of the soils from the Hunan Province for microbial communities associated with MeHg degradation. Microbial demethylation was observed in all three soils, demonstrated by significantly more MeHg degraded in the unsterilized soils than in the sterilized controls. More demethylation occurred in water-saturated soils than in unsaturated soils, but the addition of molybdate and bromoethanesulfonic acid as the respective inhibitors of sulfate reducing bacteria and methanogens showed insignificant effects on MeHg degradation. However, the addition of Cu enhanced MeHg degradation and the enrichment of Xanthomonadaceae in the unsaturated soil. 16S rRNA Illumina sequencing and metatranscriptomic analyses of the Hunan soil consistently revealed that Catenulisporaceae, Frankiaceae, Mycobacteriaceae, and Thermomonosporaceae were among the most likely microbial taxa in influencing MeHg degradation in the paddy soil, and they were confirmed by combined analyses of the co-occurrence network, random forest modeling, and linear discriminant analysis of the effect size. Furthermore, our results shed additional light onto the roles of microbial communities in MeHg degradation in paddy soils and its subsequent bioaccumulation in rice grains.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Synergistic Effects of a Chalkophore, Methanobactin, on Microbial Methylation of Mercury

Microbial production of the neurotoxin methylmercury (MeHg) is a significant health and environmental concern, as it can bioaccumulate and biomagnify in the food web. A chalkophore or a copper-binding compound, termed methanobactin (MB), has been shown to form strong complexes with mercury [as Hg(II)] and also enables some methanotrophs to degrade MeHg. It is unknown, however, if Hg(II) binding with MB can also impede Hg(II) methylation by other microbes. Contrary to expectations, MB produced by the methanotroph Methylosinus trichosporium OB3b (OB3b-MB) enhanced the rate and efficiency of Hg(II) methylation more than that observed with thiol compounds (such as cysteine) by the mercury-methylating bacteria Desulfovibrio desulfuricans ND132 and Geobacter sulfurreducens PCA. Compared to no-MB controls, OB3b-MB decreased the rates of Hg(II) sorption and internalization, but increased methylation by 5- to 7-fold, suggesting that Hg(II) complexation with OB3b-MB facilitated exchange and internal transfer of Hg(II) to the HgcAB proteins required for methylation. Conversely, addition of excess amounts of OB3b-MB or a different form of MB from Methylocystis strain SB2 (SB2-MB) inhibited Hg(II) methylation, likely due to greater binding of Hg(II). Collectively, our results underscore the complex roles of microbial exogenous metal-scavenging compounds in controlling net production and bioaccumulation of MeHg in the environment. Some anaerobic microorganisms convert inorganic mercury (Hg) into the neurotoxin methylmercury, which can bioaccumulate and biomagnify in the food web. While the genetic basis of microbial mercury methylation is known, factors that control net methylmercury production in the environment are still poorly understood. Here, it is shown that mercury methylation can be substantially enhanced by one form of an exogenous copper-binding compound (methanobactin) produced by some methanotrophs, but not by another. This novel finding illustrates that complex interactions exist between microbes and that these interactions can potentially affect the net production of methylmercury in situ .

54 ENVIRONMENTAL SCIENCES↗