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  1. 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
  2. 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
  3. 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
  4. 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
  5. 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 in this paper, 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, weremore » found to be among the most important in forming strong complexes with Hg. Major Hg–DOM complexes of C 10H 21N 2S 4Hg + and C 8H 17N 2S 4Hg + 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. Finally, 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
  6. Atmospheric deposition of mercury (Hg) to surface water is one of the dominant sources of Hg in aquatic environments and ultimately drives methylmercury (MeHg) toxin accumulation in fish. It is known that freshly deposited Hg is more readily methylated by microorganisms than aged or preexisting Hg; however the underlying mechanism of this process is unclear. Here we report that Hg bioavailability is decreased by photochemical reactions between Hg and dissolved organic matter (DOM) in water. Photo-irradiation of Hg-DOM complexes results in loss of Sn(II)-reducible (i.e. reactive) Hg and up to an 80% decrease in MeHg production by the methylating bacteriummore » Geobacter sulfurreducens PCA. Loss of reactive Hg proceeded at a faster rate with a decrease in the Hg to DOM ratio and is attributed to the possible formation of mercury sulfide (HgS). Lastly, these results suggest a new pathway of abiotic photochemical formation of HgS in surface water and provide a mechanism whereby freshly deposited Hg is readily methylated but, over time, progressively becomes less available for microbial uptake and methylation.« less
  7. The rapid temperature rise in Arctic permafrost concerns not only the degradation of stored soil organic carbon (SOC) and climate feedback, but also the production and bioaccumulation of methylmercury (MeHg) that may endanger humans, as well as wildlife in terrestrial, aquatic, and marine ecosystems. Decomposition of SOC provides an energy source for microbial methylation, although little is known how rapid permafrost thaw affects Hg methylation and how SOC degradation is coupled to MeHg biosynthesis. We describe rates of MeHg production in Arctic soils from an 8-month warming microcosm experiment under anoxic conditions. MeHg production increased >10 fold in both organic-more » and the mineral-rich soil layers at a warmer temperature (8 C) compared to a sub-zero temperature ( 2 C). MeHg production was positively correlated to methane and ferrous ion concentrations, suggesting that Hg methylation is coupled with methanogenesis and iron reduction. Labile SOC, such as reducing sugars and alcohol, were particularly effective in fueling the initial rapid biosynthesis of MeHg. In freshly amended Hg we found that there was more bioavailable than existing Hg in the mineral soil. Finally, the data indicate that climate warming and permafrost thaw could greatly enhance MeHg production, thereby impacting Arctic aquatic and marine ecosystems through biomagnification in the food web.« less

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