The significance of organic carbon and sediment surface area to the benthic biogeochemistry of the slope and deep water environments of the northern Gulf of Mexico

The bioavailability of metabolizable organic matter within marine sediments is one of the more important driving mechanisms controlling benthic pelagic communities. Interactions between organic material and mineral surfaces within the sediment, such as adsorption, can cause organic matter to be unavailable for degradation by organisms; therefore for this study we have used the relationship of organic carbon-to-sediment surface area as an indicator of available organic carbon in northern Gulf of Mexico sediments. We have determined that these sediment interactions demonstrate a significant association with benthic fauna abundances; however they are not the most dominant environmental variables. It may be the combination of biogeochemical parameters, such as organic carbon content, sediment surface area, grain size, water depth and other geophysical variables, that is the ultimate control on the bioavailability of metabolizable organic matter in the northern Gulf of Mexico

Promoting Uranium Immobilization by the Activities of Microbial Phosphatases

The overall objective of this project is to examine the activity of nonspecific phosphohydrolases present in naturally occurring subsurface microorganisms for the purpose of promoting the immobilization of radionuclides through the production of uranium [U(VI)] phosphate precipitates. Specifically, we hypothesize that the precipitation of U(VI) phosphate minerals may be promoted through the microbial release and/or accumulation of PO4 3- as a means to detoxify radionuclides and heavy metals. An experimental approach was designed to determine the extent of phosphatase activity in bacteria previously isolated from contaminated subsurface soils collected at the ERSP Field Research Center (FRC) in Oak Ridge, TN. Screening of 135 metal resistant isolates for phosphatase activity indicated the majority (75 of 135) exhibited a phosphatase-positive phenotype. During this phase of the project, a PCR based approach has also been designed to assay FRC isolates for the presence of one or more classes of the characterized non-specific acid phophastase (NSAP) genes likely to be involved in promoting U(VI) precipitation. Testing of a subset of Pb resistant (Pbr) Arthrobacter, Bacillus and Rahnella strains indicated 4 of the 9 Pbr isolates exhibited phosphatase phenotypes suggestive of the ability to bioprecipitate U(VI). Two FRC strains, a Rahnella sp. strain Y9602 and a Bacillus sp. strain Y9-2, were further characterized. The Rahnella sp. exhibited enhanced phosphatase activity relative to the Bacillus sp. Whole-cell enzyme assays identified a pH optimum of 5.5, and inorganic phosphate accumulated in pH 5.5 synthetic groundwater (designed to mimic FRC conditions) incubations of both strains in the presence of a model organophosphorus substrate provided as the sole C and P source. Kinetic experiments showed that these two organisms can grow in the presence of 200 μM dissolved uranium and that Rahnella is much more efficient in precipitating U(VI) than Bacillus sp. The precipitation of U(VI) must be mediated by biological activity as less than 3% soluble U(VI) was removed either from the abiotic or the heat-killed cell controls. Interestingly, the pH has a strong effect on growth and U(VI) biomineralization rates by Rahnella. Thermodynamic modeling identifies autunite-type minerals [Ca(UO2)2(PO4)2] as the precipitate likely formed in the synthetic FRC groundwater conditions at all pH investigated. Extended X-ray absorption fine structure measurements have recently confirmed that the precipitate found in these incubations is an autunite and meta-autunite-type mineral. A kinetic model of U biomineralization at the different pH indicates that hydrolysis of organophosphate can be described using simple Monod kinetics and that uranium precipitation is accelerated when monohydrogen phosphate is the main orthophosphate species in solution. Overall, these experiments and ongoing soil slurry incubations demonstrate that the biomineralization of U(VI) through the activity of phosphatase enzymes can be expressed in a wide range of geochemical conditions pertaining to the FRC site

Microbial Community Analysis of a Coastal Salt Marsh Affected by the Deepwater Horizon Oil Spill

Conceived and designed the experiments: MJB RJM BM PAS. Performed the experiments: MJB RJM SR JP YMP LMT JDVN. Analyzed the data: MJB RJM YMP LMT GLA TCH JDVN JZ PAS. Contributed reagents/materials/analysis tools: GLA TCH JZ BM PAS. Wrote the paper: MJB RJM PAS.Coastal salt marshes are highly sensitive wetland ecosystems that can sustain long-term impacts from anthropogenic events such as oil spills. In this study, we examined the microbial communities of a Gulf of Mexico coastal salt marsh during and after the influx of petroleum hydrocarbons following the Deepwater Horizon oil spill. Total hydrocarbon concentrations in salt marsh sediments were highest in June and July 2010 and decreased in September 2010. Coupled PhyloChip and GeoChip microarray analyses demonstrated that the microbial community structure and function of the extant salt marsh hydrocarbon-degrading microbial populations changed significantly during the study. The relative richness and abundance of phyla containing previously described hydrocarbon-degrading bacteria (Proteobacteria, Bacteroidetes, and Actinobacteria) increased in hydrocarbon-contaminated sediments and then decreased once hydrocarbons were below detection. Firmicutes, however, continued to increase in relative richness and abundance after hydrocarbon concentrations were below detection. Functional genes involved in hydrocarbon degradation were enriched in hydrocarbon-contaminated sediments then declined significantly (p<0.05) once hydrocarbon concentrations decreased. A greater decrease in hydrocarbon concentrations among marsh grass sediments compared to inlet sediments (lacking marsh grass) suggests that the marsh rhizosphere microbial communities could also be contributing to hydrocarbon degradation. The results of this study provide a comprehensive view of microbial community structural and functional dynamics within perturbed salt marsh ecosystems.Yeshttp://www.plosone.org/static/editorial#pee

Nonreductive biomineralization of uranium(VI) as a result of microbial phosphatase activity

Uranium contamination of soils and groundwater at Department of Energy facilities across the United States is a primary environmental concern and the development of effective remediation strategies is a major challenge. Bioremediation, or the use of microbial enzymatic activity to facilitate the remediation of a contaminant, offers a promising in situ approach that may be less invasive than traditional methods, such as pump and treat or excavation. This study demonstrates for the first time the successful biomineralization of uranium phosphate minerals as a result of microbial phosphatase activity at low pH in both aerobic and anaerobic conditions using pure cultures and soils from a contaminated waste site. Pure cultures of microorganisms isolated from soils of a low pH, high uranium- and nitrate-contaminated waste site, expressed constitutive phosphatase activity in response to an organophosphate addition in aerobic and anaerobic incubations. Sufficient phosphate was hydrolyzed to precipitate 73 to 95% total uranium as chernikovite identified by synchrotron X-ray absorption spectroscopy and X-ray diffraction. Highest rates of uranium precipitation and phosphatase activity were observed between pH 5.0 and 7.0. Indigenous microorganisms were also stimulated by organophosphate amendment in soils from a contaminated waste site using flow-through reactors. High phosphate concentrations (0.5 to 3 mmol L-1) in pore water effluents were observed within days of organophosphate addition. Highest rates of phosphatase activity occurred at pH 5.5 in naturally low pH soils in the presence of high uranium and nitrate concentrations. The precipitation of uranium phosphate was identified by a combination of pore water measurements, solid phase extractions, synchrotron-based X-ray spectroscopy, and a reactive transport model. The results of this study demonstrate that uranium is biomineralized to a highly insoluble uranyl phosphate mineral as a result of enzymatic hydrolysis of an organophosphate compound over a wide range of pH, in both aerobic and anaerobic conditions, and in the presence of high uranium and nitrate concentrations. The nonreductive biomineralization of U(VI) provides a promising new approach for in situ uranium bioremediation in low pH, high nitrate, and aerobic conditions that could be complementary to U(VI) bioreduction in high pH, low nitrate, and reducing environments.Ph.D.Committee Chair: Taillefert, Martial; Committee Member: DiChristina, Thomas; Committee Member: Sobecky, Patricia; Committee Member: Van Cappellen, Philippe; Committee Member: Webb, Samue

A Bifunctional Catalyst For Efficient Dehydrogenation And Electro-Oxidation Of Hydrazine

The chemical energy stored in energetic materials may often be utilized in various ways, which motivates the development of multifunctional catalysts for flexible and efficient utilization of the chemical energy. Hydrazine is a promising energy carrier due to its high energy density and high hydrogen content, which can be utilized as a chemical hydrogen storage medium or a fuel for direct fuel cells. Herein, we propose a bifunctional catalyst for efficient dehydrogenation and electro-oxidation of hydrazine. As a proof-of-concept study, a carbon-black-supported Pt0.2Ni0.8 nanoparticle catalyst has been developed with high activity and durability for both complete dehydrogenation (with a turnover frequency of 673 h-1 and a H2 generation rate of 188 L h-1 gmetal-1) and electro-oxidation (with a mass activity of 132 mA mgmetal-1) of hydrazine under mild conditions, outperforming other catalysts including Pt, Ni, Pd0.2Ni0.8, and Au0.2Ni0.8 nanoparticles. Such a bifunctional catalyst can enable the utilization of hydrazine as a promising energy carrier for both on-demand hydrogen generation and electricity generation via direct hydrazine fuel cells, enhancing its flexibility for future onboard applications

NATURAL ABUNDANCES OF CARBON ISOTOPES ( 14 C, 13 C) IN LICHENS AND CALCIUM OXALATE PRUINA: IMPLICATIONS FOR ARCHAEOLOGICAL AND PALEOENVIRONMENTAL STUDIES

ABSTRACT. Radiocarbon ages of calcium oxalate that occurs naturally on rock surfaces have been used recently in archaeological and paleoenvironmental studies. Oxalate rock coatings are found globally, with most appearing to be residues from epilithic lichens. To explore the source(s) of carbon used by these organisms for the production of oxalate we measured the natural abundances of 14 C and 13 C in 5 oxalate-producing lichen species, 3 growing on limestone in southwestern Texas and 2 on sandstone in Arkansas. We also examined the distribution of the isotopes between the calcium oxalate and lichen tissues by separating these components and measuring the 13 C/C independently. The results demonstrate that the limestone species were slightly enriched in 14 C, by 1.7‰, relative to the sandstone species, which suggests that &quot;dead&quot; carbon from the limestone substrate does not constitute a significant source of carbon for the production of oxalate. The calcium oxalate produced by the lichens is also enriched in 13 C by 6.5‰ compared to the lichen tissues, demonstrating that there is a large carbon isotope discrimination during oxalate biosynthesis. These results support the reliability of 14 C ages of calcium oxalate rock coatings used for archaeological and paleoclimate studies

Biomineralization Of U(Vi) Phosphate Promoted By Microbially-Mediated Phytate Hydrolysis In Contaminated Soils

The bioreduction of uranium may immobilize a significant fraction of this toxic contaminant in reduced environments at circumneutral pH. In oxic and low pH environments, however, the low solubility of U(VI)-phosphate minerals also makes them good candidates for the immobilization of U(VI) in the solid phase. As inorganic phosphate is generally scarce in soils, the biomineralization of U(VI)-phosphate minerals via microbially-mediated organophosphate hydrolysis may represent the main immobilization process of uranium in these environments. In this study, contaminated sediments were incubated aerobically in two pH conditions to examine whether phytate, a naturally-occurring and abundant organophosphate in soils, could represent a potential phosphorous source to promote U(VI)-phosphate biomineralization by natural microbial communities. While phytate hydrolysis was not evident at pH 7.0, nearly complete hydrolysis was observed both with and without electron donor at pH 5.5, suggesting indigenous microorganisms express acidic phytases in these sediments. While the rate of hydrolysis of phytate generally increased in the presence of uranium, the net rate of inorganic phosphate production in solution was decreased and inositol phosphate intermediates were generated in contrast to similar incubations conducted without uranium. These findings suggest uranium stress enhanced the phytate-metabolism of the microbial community, while simultaneously inhibiting phosphatase production and/or activity by the indigenous population. Finally, phytate hydrolysis drastically decreased uranium solubility, likely due to formation of ternary sorption complexes, U(VI)-phytate precipitates, and U(VI)-phosphate minerals. Overall, the results of this study provide evidence for the ability of natural microbial communities to liberate phosphate from phytate in acidic sediments, possibly as a detoxification mechanism, and demonstrate the potential utility of phytate-promoted uranium immobilization in subsurface environments. These processes should be investigated in more detail with pure cultures isolated from these sediments

Natural Abundance of Carbon Isotopes (14C, 13C) in Lichens and Calcium Oxalate Pruina: Implications for Archaeological and Paleoenvironmental Studies

Radiocarbon ages of calcium oxalate that occurs naturally on rock surfaces have been used recently in archaeological and paleoenvironmental studies. Oxalate rock coatings are found globally, with most appearing to be residues from epilithic lichens. To explore the source(s) of carbon used by these organisms for the production of oxalate we measured the natural abundances of 14C and 13C in 5 oxalate-producing lichen species, 3 growing on limestone in southwestern Texas and 2 on sandstone in Arkansas. We also examined the distribution of the isotopes between the calcium oxalate and lichen tissues by separating these components and measuring the 13C/C independently. The results demonstrate that the limestone species were slightly enriched in 14C, by 1.7 per mil, relative to the sandstone species, which suggests that "dead" carbon from the limestone substrate does not constitute a significant source of carbon for the production of oxalate. The calcium oxalate produced by the lichens is also enriched in 13C by 6.5 per mil compared to the lichen tissues, demonstrating that there is a large carbon isotope discrimination during oxalate biosynthesis. These results support the reliability of 14C ages of calcium oxalate rock coatings used for archaeological and paleoclimate studies.The Radiocarbon archives are made available by Radiocarbon and the University of Arizona Libraries. Contact [email protected] for further information.Migrated from OJS platform February 202

The role of anaerobic respiration in the immobilization 1 of uranium through biomineralization of phosphate minerals

Although bioreduction of uranyl ions (U(VI)) and biomineralization of U(VI)-phosphate minerals are both able to immobilize uranium in contaminated sediments, the competition between these processes and the role of anaerobic respiration in the biomineralization of U(VI)-phosphate minerals has yet to be investigated. In this study, contaminated sediments incubated anaerobically in static microcosms at pH 5.5 and 7.0 were amended with the organophosphate glycerol-2-phosphate (G2P) as sole phosphorus and external carbon source and iron oxides, sulfate, or nitrate as terminal electron acceptors to determine the most favorable geochemical conditions to these two processes. While sulfate reduction was not observed even in the presence of G2P at both pHs, iron reduction was more significant at circumneutral pH irrespective of the addition of G2P. In turn, nitrate reduction was stimulated by G2P at both pH 5.5 and 7.0, suggesting nitrate-reducing bacteria provided the main source of inorganic phosphate in these sediments. U(VI) was rapidly removed from solution in all treatments but was not reduced as determined by X-ray absorption near edge structure (XANES) spectroscopy. Simultaneously, wet chemical extractions and extended X-ray absorption fine structure (EXAFS) spectroscopy of these sediments indicated the presence of U-P species in reactors amended with G2P at both pHs. The rapid removal of dissolved U(VI), the simultaneous production of inorganic phosphate, and the existence of U-P species in the solid phase indicate that uranium was precipitated as U(VI)-phosphate minerals in sediments amended with G2P. Thus, under reducing conditions and in the presence of G2P, bioreduction of U(VI) was outcompeted by the biomineralization of U(VI)-phosphate minerals and U(VI) sorption at both pHs

Microbial Community Responses to Organophosphate Substrate Additions in Contaminated Subsurface Sediments

<div><p>Background</p><p>Radionuclide- and heavy metal-contaminated subsurface sediments remain a legacy of Cold War nuclear weapons research and recent nuclear power plant failures. Within such contaminated sediments, remediation activities are necessary to mitigate groundwater contamination. A promising approach makes use of extant microbial communities capable of hydrolyzing organophosphate substrates to promote mineralization of soluble contaminants within deep subsurface environments.</p><p>Methodology/Principal Findings</p><p>Uranium-contaminated sediments from the U.S. Department of Energy Oak Ridge Field Research Center (ORFRC) Area 2 site were used in slurry experiments to identify microbial communities involved in hydrolysis of 10 mM organophosphate amendments [i.e., glycerol-2-phosphate (G2P) or glycerol-3-phosphate (G3P)] in synthetic groundwater at pH 5.5 and pH 6.8. Following 36 day (G2P) and 20 day (G3P) amended treatments, maximum phosphate (PO₄³⁻) concentrations of 4.8 mM and 8.9 mM were measured, respectively. Use of the PhyloChip 16S rRNA microarray identified 2,120 archaeal and bacterial taxa representing 46 phyla, 66 classes, 110 orders, and 186 families among all treatments. Measures of archaeal and bacterial richness were lowest under G2P (pH 5.5) treatments and greatest with G3P (pH 6.8) treatments. Members of the phyla <i>Crenarchaeota</i>, <i>Euryarchaeota</i>, <i>Bacteroidetes</i>, and <i>Proteobacteria</i> demonstrated the greatest enrichment in response to organophosphate amendments and the OTUs that increased in relative abundance by 2-fold or greater accounted for 9%–50% and 3%–17% of total detected <i>Archaea</i> and <i>Bacteria</i>, respectively.</p><p>Conclusions/Significance</p><p>This work provided a characterization of the distinct ORFRC subsurface microbial communities that contributed to increased concentrations of extracellular phosphate via hydrolysis of organophosphate substrate amendments. Within subsurface environments that are not ideal for reductive precipitation of uranium, strategies that harness microbial phosphate metabolism to promote uranium phosphate precipitation could offer an alternative approach for <i>in situ</i> sequestration.</p></div