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Sample records for abiotic feii oxidation

  1. Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate.

    PubMed

    Song, Jia; Jia, Shao-Yi; Yu, Bo; Wu, Song-Hai; Han, Xu

    2015-08-30

    Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust.

  2. Schwertmannite and Fe oxides formed by biological low-pH Fe(II) oxidation versus abiotic neutralization: Impact on trace metal sequestration

    NASA Astrophysics Data System (ADS)

    Burgos, William D.; Borch, Thomas; Troyer, Lyndsay D.; Luan, Fubo; Larson, Lance N.; Brown, Juliana F.; Lambson, Janna; Shimizu, Masayuki

    2012-01-01

    Three low-pH coal mine drainage (CMD) sites in central Pennsylvania were studied to determine similarities in sediment composition, mineralogy, and morphology. Water from one site was used in discontinuous titration/neutralization experiments to produce Fe(III) minerals by abiotic oxidative hydrolysis for comparison with the field precipitates that were produced by biological low-pH Fe(II) oxidation. Even though the hydrology and concentration of dissolved metals of the CMD varied considerably between the three field sites, the mineralogy of the three iron mounds was very similar. Schwertmannite was the predominant mineral precipitated at low-pH (2.5-4.0) along with lesser amounts of goethite. Trace metals such as Zn, Ni and Co were only detected at μmol/g concentrations in the field sediments, and no metals (other than Fe) were removed from the CMD at any of the field sites. Metal cations were not lost from solution in the field because of unfavorable electrostatic attraction to the iron mound minerals. Ferrihydrite was the predominant mineral formed by abiotic neutralization (pH 4.4-8.4, 4 d aging) with lesser amounts of schwertmannite and goethite. In contrast to low-pH precipitation, substantial metal removal occurred in the neutralized CMD. Al was likely removed as hydrobasaluminite and Al(OH) 3, and as a co-precipitate into schwertmannite or ferrihydrite. Zn, Ni and Co were likely removed via adsorption onto and co-precipitation into the freshly formed Fe and Al solids. Mn was likely removed by co-precipitation and, at the highest final pH values, as a Mn oxide. Biological low-pH Fe(II) oxidation can be cost-effectively used to pre-treat CMD and remove Fe and acidity prior to conventional neutralization techniques. A further benefit is that solids formed under these conditions may be of industrial value because they do not contain trace metal or metalloid contaminants.

  3. Abiotic U(VI) Reduction by Sorbed Fe(II) on Natural Sediments

    SciTech Connect

    Fox, Patricia M.; Davis, James A.; Kukkadapu, Ravi K.; Singer, David M.; Bargar, John R.; Williams, Kenneth H.

    2013-09-15

    Laboratory experiments were performed as a function of aqueous Fe(II) concentration to determine the uptake and oxidation of Fe(II), and Fe(II)-mediated abiotic reduction of U(VI) by aquifer sediments from the Rifle IFRC field site in Colorado, USA. Mössbauer analysis of the sediments spiked with aqueous 57Fe(II) showed that 57Fe(II) was oxidized on the mineral surfaces to 57Fe(III) and most likely formed a nano-particulate Fe(III)-oxide or ferrihydrite-like phase. The extent of 57Fe oxidation decreased with increasing 57Fe(II) uptake, such that 100 % was oxidized at 7.3 μmol/g Fe and 52 % at 39.6 μmol/g Fe, indicating that the sediments had a finite capacity for oxidation of Fe(II). Abiotic U(VI) reduction was observed by XANES spectroscopy only when the Fe(II) uptake was greater than approximately 20 μmol/g and surface-bound Fe(II) was present. The level of U(VI) reduction increased with increasing Fe(II)- loading above this level to a maximum of 18 and 36 % U(IV) at pH 7.2 (40.7 μmol/g Fe) and 8.3 (56.1 μmol/g Fe), respectively in the presence of 400 ppm CO2. Greater U(VI) reduction was observed in CO2 free systems [up to 44 and 54 % at pH 7.2 (17.3 μmol/g Fe) and 8.3 (54.8 μmol/g Fe), respectively] compared to 400 ppm CO2 systems, presumably due to differences in aqueous U(VI) speciation. While pH affects the amount of Fe(II) uptake onto the solid phase, with greater Fe(II) uptake at higher pH, similar amounts of U(VI) reduction were observed at pH 7.2 and 8.3 for a similar Fe(II) uptake. Thus, it appears that abiotic U(VI) reduction is controlled primarily by Fe(II) concentration and aqueous U(VI) speciation. The range of Fe(II) loadings tested in this study are within the range observed in bioreduced sediments, suggesting that Fe(II)-mediated abiotic U(VI) reduction may indeed play a role in field settings.

  4. Nature and Reactivity of Sediment-Associated Spiked Fe(II) Toward Abiotic Uranium Reduction

    NASA Astrophysics Data System (ADS)

    Kukkadapu, R.; Fox, P. M.; Davis, J.

    2011-12-01

    Uranium (U) is a priority contaminant at U.S. Department of Energy Uranium Mill Tailings Remedial Action (UMTRA) sites. Mobility of U in contaminated aquifers is governed by a complex assortment of site-specific biogeochemical and hydrological properties, sediment Fe-mineralogy, and redox status. There is a particular interest in understanding factors governing U attenuation to Fe-mineralogy under natural conditions. Thus, the goal of this work is to investigate geochemical effects of Fe redox state on U mobility under conditions relevant to the Rifle aquifer, an UMTRA site. Particularly, the focus is to gain insights into the degree and mechanism of Fe(II) uptake by Rifle sediments that exhibit complex Fe-mineralogy composed of various Fe-oxides and Fe-containing clays and on the possibility of abiotic U(VI) reduction by adsorbed Fe(II) and secondary Fe(II) minerals. Earlier field studies where Fe(II)-amended groundwater was injected into the Rifle aquifer indicated: a) Fe(II) uptake by Rifle sediments is extensive and b) abiotic U(VI) reduction by Fe(II) may be important at pH 8.3. Batch reactions between Rifle sediment and 57Fe(II) (57Fe isotope is a Mossbauer sensitive nuclide with a natural abundance of 2%) under conditions relevant to the Rifle aquifer indicated that, depending on the solution conditions: a) a large fraction of the spiked 57Fe(II) (55-100%) is oxidized to 57Fe(III) on sediment surfaces and, at pH 7.2, the degree of oxidation decreased as Fe(II) loading increased; b) the 57Fe(II)-oxidation is coupled to the transformation of an intrinsic ferrihydrite-like mineral to a nanoparticulate, Fe(II)/57Fe(III)-like mineral phase, and c) increasing pH from 7.2 to 8.3 and including carbonate in the medium has little or no effect on percent oxidation or mineral transformation. Preliminary X-ray absorption near edge structure (XANES) spectroscopy studies suggested that 20-30% of abiotic U(VI) reduction occurred, both at pH 7.2 and 8.3, in the sediments

  5. Microbial Lithotrophic Oxidation of Structural Fe(II) in Biotite

    SciTech Connect

    Shelobolina, Evgenya S.; Xu, Huifang; Konishi, Hiromi; Kukkadapu, Ravi K.; Wu, Tao; Blothe, Marco; Roden, Eric E.

    2012-06-08

    Microorganisms are known to participate in the weathering of primary phyllosilicate minerals through production of organic ligands and acids, and through uptake of products of weathering. Here we show that a lithotrophic Fe(II)-oxidizing, nitrate-reducing enrichment culture (Straub, 6 1996) can grow via oxidation of structural Fe(II) in biotite, a Fe(II)-rich trioctahedral mica found in granitic rocks. Oxidation of silt/clay sized biotite particles was detected by a decrease in extractable Fe(II) content and simultaneous nitrate reduction. Moessbauer spectroscopy confirmed structural Fe(II) oxidation. Approximately 107 cells were produced per {micro}mol Fe(II) oxidized, in agreement with previous estimates of the growth yield of lithoautotrophic circumneutral-pH Fe(II)-oxidizing bacteria. Microbial oxidation of structural Fe(II) resulted in biotite alterations similar to those found in nature, including decrease in unit cell b-dimension toward dioctahedral levels and iron and potassium release. The demonstration of microbial oxidation of structural Fe(II) suggests that microorganisms may be directly responsible for the initial step in the weathering of biotite in granitic aquifers and the plant rhizosphere.

  6. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    SciTech Connect

    O'Day, Peggy A.; Asta, Maria P.; Kanematsu, Masakazu; Beller, Harry; Zhou, Peng; Steefel, Carl

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  7. Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

    SciTech Connect

    Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

    2009-07-01

    The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethite and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.

  8. The Diverse Microbiology of Anaerobic Fe(II) Oxidation

    NASA Astrophysics Data System (ADS)

    Coates, J. D.; Weber, K. A.; Scherer, M.; Achenbach, L. A.

    2007-12-01

    Although anaerobic microbial oxidation of Fe(II) has been know for over a decade there is still a paucity of information available on this important metabolic process or the organisms involved. Recent studies have indicated that the metabolism is ubiquitous and a broad diversity of organisms are capable of oxidizing Fe(II) in the absence of oxygen. Our previous studies demonstrated the existence of geochemical conditions conducive to supporting the activity of nitrate-dependent Fe(II) oxidizing bacteria (NFoB) in sedimentary environments. As part of these studies we isolated and characterized several novel NFoBs. Three of these organisms, Diaphorobacter sp. strain TPSY, Ferrutens nitratireducens strain 2002 and Azospira suillum strain PS are currently undergoing whole genome shotgun sequencing in an effort to gain insight into the biochemistry and molecular biology of this geochemically important metabolism. These organisms represent diverse genera capable of anaerobically oxidizing Fe(II) using nitrate as the electron acceptor. Two of these organisms, strain 2002 and strain TPSY, are also capable of the anaerobic nitrate-dependent oxidation of U(IV) to U(VI). Diaphorobacter sp. strain TPSY was isolated from uranium and nitrate contaminated groundwater and is a member of the Comamonadaceae family in the beta subclass of the Proteobacteria, closely related to Diaphorobacter nitroreducens. It represents the first example of an anaerobic Fe(II)-oxidizer from the Comamonadaceae family and grows mixotrophically requiring an organic carbon source when growing with Fe(II) and nitrate as the electron donor and acceptor respectively. F. nitratireducens strain 2002 was isolated from aquatic sediment and is the type strain of a new genus, Ferrutens, in the beta class of the Proteobacteria. Its closest relative is Chromobacterium violaceum, a common soil bacterium. In contrast to C. violaceum, F. nitratireducens is non-fermentative and does not produce free cyanide (CN-) or

  9. Immobilization of Radionuclides and Heavy Metals through Anaerobic Bio-Oxidation of Fe(II)

    PubMed Central

    Lack, Joseph G.; Chaudhuri, Swades K.; Kelly, Shelly D.; Kemner, Kenneth M.; O'Connor, Susan M.; Coates, John D.

    2002-01-01

    Adsorption of heavy metals and radionuclides (HMR) onto iron and manganese oxides has long been recognized as an important reaction for the immobilization of these compounds. However, in environments containing elevated concentrations of these HMR the adsorptive capacity of the iron and manganese oxides may well be exceeded, and the HMR can migrate as soluble compounds in aqueous systems. Here we demonstrate the potential of a bioremediative strategy for HMR stabilization in reducing environments based on the recently described anaerobic nitrate-dependent Fe(II) oxidation by Dechlorosoma species. Bio-oxidation of 10 mM Fe(II) and precipitation of Fe(III) oxides by these organisms resulted in rapid adsorption and removal of 55 μM uranium and 81 μM cobalt from solution. The adsorptive capacity of the biogenic Fe(III) oxides was lower than that of abiotically produced Fe(III) oxides (100 μM for both metals), which may have been a result of steric hindrance by the microbial cells on the iron oxide surfaces. The binding capacity of the biogenic oxides for different heavy metals was indirectly correlated to the atomic radius of the bound element. X-ray absorption spectroscopy indicated that the uranium was bound to the biogenically produced Fe(III) oxides as U(VI) and that the U(VI) formed bidentate and tridentate inner-sphere complexes with the Fe(III) oxide surfaces. Dechlorosoma suillum oxidation was specific for Fe(II), and the organism did not enzymatically oxidize U(IV) or Co(II). Small amounts (less than 2.5 μM) of Cr(III) were reoxidized by D. suillum; however, this appeared to be inversely dependent on the initial concentration of the Cr(III). The results of this study demonstrate the potential of this novel approach for stabilization and immobilization of HMR in the environment. PMID:12039723

  10. Uranium Immobilization through Fe(II) bio-oxidation: A Column study

    SciTech Connect

    Coates, John D.

    2009-09-14

    Current research on the bioremediation of heavy metals and radionuclides is focused on the ability of reducing organisms to use these metals as alternative electron acceptors in the absence of oxygen and thus precipitate them out of solution. However, many aspects of this proposed scheme need to be resolved, not the least of which is the time frame of the treatment process. Once treatment is complete and the electron donor addition is halted, the system will ultimately revert back to an oxic state and potentially result in the abiotic reoxidation and remobilization of the immobilized metals. In addition, the possibility exists that the presence of more electropositive electron acceptors such as nitrate or oxygen will also stimulate the biological oxidation and remobilization of these contaminants. The selective nitrate-dependent biooxidation of added Fe(II) may offer an effective means of “capping off” and completing the attenuation of these contaminants in a reducing environment making the contaminants less accessible to abiotic and biotic reactions and allowing the system to naturally revert to an oxic state. Our previous DOE-NABIR funded studies demonstrated that radionuclides such as uranium and cobalt are rapidly removed from solution during the biogenic formation of Fe(III)-oxides. In the case of uranium, X-ray spectroscopy analysis indicated that the uranium was in the hexavalent form (normally soluble) and was bound to the precipitated Fe(III)-oxides thus demonstrating the bioremediative potential of this process. We also demonstrated that nitrate-dependent Fe(II)- oxidizing bacteria are prevalent in the sediment and groundwater samples collected from sites 1 and 2 and the background site of the NABIR FRC in Oakridge, TN. However, all of these studies were performed in batch experiments in the laboratory with pure cultures and although a significant amount was learned about the microbiology of nitrate-dependent bio-oxidation of Fe(II), the effects of

  11. Constraining the role of iron in environmental nitrogen transformations: Dual stable isotope systematics of abiotic NO2- reduction by Fe(II) and its production of N2O

    NASA Astrophysics Data System (ADS)

    Buchwald, Carolyn; Grabb, Kalina; Hansel, Colleen M.; Wankel, Scott D.

    2016-08-01

    Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO2-) reduction by Fe(II) or 'chemodenitrification', and its relevance to the production of nitrous oxide (N2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmental conditions. We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (∼8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO2- reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO2- reduction by Fe(II) may represent an important abiotic source of environmental N2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO2- reduction and N2O formation, helping future studies constrain the relative roles of abiotic and biological N2O production pathways.

  12. Characterization of the physiology and cell-mineral interactions of the marine anoxygenic phototrophic Fe(II) oxidizer Rhodovulum iodosum--implications for Precambrian Fe(II) oxidation.

    PubMed

    Wu, Wenfang; Swanner, Elizabeth D; Hao, Likai; Zeitvogel, Fabian; Obst, Martin; Pan, Yongxin; Kappler, Andreas

    2014-06-01

    Anoxygenic phototrophic Fe(II)-oxidizing bacteria (photoferrotrophs) are suggested to have contributed to the deposition of banded iron formations (BIFs) from oxygen-poor seawater. However, most studies evaluating the contribution of photoferrotrophs to Precambrian Fe(II) oxidation have used freshwater and not marine strains. Therefore, we investigated the physiology and mineral products of Fe(II) oxidation by the marine photoferrotroph Rhodovulum iodosum. Poorly crystalline Fe(III) minerals formed initially and transformed to more crystalline goethite over time. During Fe(II) oxidation, cell surfaces were largely free of minerals. Instead, the minerals were co-localized with EPS suggesting that EPS plays a critical role in preventing cell encrustation, likely by binding Fe(III) and directing precipitation away from cell surfaces. Fe(II) oxidation rates increased with increasing initial Fe(II) concentration (0.43-4.07 mM) under a light intensity of 12 μmol quanta m(-2) s(-1). Rates also increased as light intensity increased (from 3 to 20 μmol quanta m(-2) s(-1)), while the addition of Si did not significantly change Fe(II) oxidation rates. These results elaborate on how the physical and chemical conditions present in the Precambrian ocean controlled the activity of marine photoferrotrophs and confirm the possibility that such microorganisms could have oxidized Fe(II), generating the primary Fe(III) minerals that were then deposited to some Precambrian BIFs.

  13. The oxidation kinetics of Fe(II) in seawater

    NASA Astrophysics Data System (ADS)

    Millero, Frank J.; Sotolongo, Sara; Izaguirre, Miguel

    1987-04-01

    The oxidation of Fe(II) has been studied as a function of pH (5 to 9), temperature (5 to 45°C), and salinity (0 to 35). The pseudo-first-order rate constant, k1, -d[Fe(II)]/dt = k 1[Fe(II)] in water and seawater was found to be a second degree function of pH over the pH range of 7.5 to 8.5 at 5°C and 6.0 to 8.0 at 25°C. The overall rate constant ( k) -d[Fe(II)]/dt = k[Fe(II)][O 2][OH -] 2 was determined from 5 to 45°C and S = 0 to 35. The results have been fit to an equation of the form ( T = 273.15 + t° C) log k = log k 0 - 3.29I 1/2 + 1.52I where logk0 = 21.56-1545/ T with a standard error = 0.09. The energy of activation for the overall rate constant in water and seawater was 29 ± 2 kJmol-1. The values of the rate constant for pure water ( k0) are in good agreement with literature data. The half times for seawater from some previous studies at a pH = 8.0 were slower than our results for Gulf Stream waters. Measurements on Biscayne Bay waters also yield slower half times apparently due to the presence of organic ligands that can complex Fe(II).

  14. As(III) removal and speciation of Fe (Oxyhydr)oxides during simultaneous oxidation of As(III) and Fe(II).

    PubMed

    Han, Xu; Song, Jia; Li, Yi-Liang; Jia, Shao-Yi; Wang, Wen-Hui; Huang, Fu-Gen; Wu, Song-Hai

    2016-03-01

    Abiotic oxidation of Fe(II) is an important pathway in the formation of Fe (oxyhydr)oxides. However, how can As(III) affect the oxidation rate of Fe(II) and the speciation of Fe (oxyhydr)oxides, and what's the extent of the newly formed Fe (oxyhydr)oxides on the removal of aqueous arsenic are still poorly understood. Oxidation of Fe(II) under neutral pH conditions was therefore investigated under different molar ratios of As:Fe. Our results suggest that co-existence of aqueous As(III) significantly slows down the oxidation rate of Fe(II). Speciation of Fe (oxyhydr)oxides is dependent on pH and As:Fe ratios. At pH 6.0, formation of lepidocrocite and goethite is apparently inhibited at low As:Fe ratios, and ferric arsenate is favored at high As:Fe ratios. At pH 7.0, lepidocrocite gradually degenerates with the increasing As:Fe ratios. At pH 8.0, arsenite significantly inhibits the development of magnetite and favors a formation of lepidocrocite. XPS analysis further reveals that more than half of As(III) is oxidized to As(V) at pH 6.0 and 7.0, whereas at pH 8.0, the rapid oxidation of Fe(II) as well as the rapid formation of Fe (oxyhydr)oxides facilitate a rapid removal of dissolved As(III) before its further oxidation to As(V).

  15. Oxidation kinetics of Fe(II) in sea water

    SciTech Connect

    Millero, F.J.; Sotolongo, S.; Izaguirre, M.

    1987-04-01

    The oxidation of Fe(II) has been studied as a function of pH (5 to 9), temperature (5 to 45/sup 0/C), and salinity (0 to 35). The pseudo-first-order rate constant, k/sub 1/, in water and sea water was found to be a second degree function of pH over the pH range of 7.5 to 8.5 at 5/sup 0/C and 6.0 to 8.0 at 25/sup 0/C. The overall rate constant (k) was determined from 5 to 45/sup 0/C and S = 0 to 35. The results have been fit to an equation of the form with a standard error = 0.09. The energy of activation for the overall rate constant in water and sea water was 29 +/- 2 kJ mol/sup -1/. The equations are provided with this paper. The values of the rate constant for pure water (k/sub 0/) are in good agreement with literature data. The half times for sea water from some previous studies at a pH = 8.0 were slower than the authors results for Gulf Stream waters. Measurements on Biscayne Bay waters also yield slower half times apparently due to the presence of organic ligands that can complex Fe(II).

  16. Thermodynamic controls on the kinetics of microbial low-pH Fe(II) oxidation.

    PubMed

    Larson, Lance N; Sánchez-España, Javier; Kaley, Bradley; Sheng, Yizhi; Bibby, Kyle; Burgos, William D

    2014-08-19

    Acid mine drainage (AMD) is a major worldwide environmental threat to surface and groundwater quality. Microbial low-pH Fe(II) oxidation could be exploited for cost-effective AMD treatment; however, its use is limited because of uncertainties associated with its rate and ability to remove Fe from solution. We developed a thermodynamic-based framework to evaluate the kinetics of low-pH Fe(II) oxidation. We measured the kinetics of low-pH Fe(II) oxidation at five sites in the Appalachian Coal Basin in the US and three sites in the Iberian Pyrite Belt in Spain and found that the fastest rates of Fe(II) oxidation occurred at the sites with the lowest pH values. Thermodynamic calculations showed that the Gibbs free energy of Fe(II) oxidation (ΔG(oxidation)) was also most negative at the sites with the lowest pH values. We then conducted two series of microbial Fe(II) oxidation experiments in laboratory-scale chemostatic bioreactors operated through a series of pH values (2.1-4.2) and found the same relationships between Fe(II) oxidation kinetics, ΔG(oxidation), and pH. Conditions that favored the fastest rates of Fe(II) oxidation coincided with higher Fe(III) solubility. The solubility of Fe(III) minerals, thus plays an important role on Fe(II) oxidation kinetics. Methods to incorporate microbial low-pH Fe(II) oxidation into active and passive AMD treatment systems are discussed in the context of these findings. This study presents a simplified model that describes the relationship between free energy and microbial kinetics and should be broadly applicable to many biogeochemical systems.

  17. Chemical reduction of U(VI) by Fe(II) at the solid-water interface using natural and synthetic Fe(III) oxides.

    PubMed

    Jeon, Byong-Hun; Dempsey, Brian A; Burgos, William D; Barnett, Mark O; Roden, Eric E

    2005-08-01

    Abiotic reduction of 0.1 mM U(VI) by Fe(II) in the presence of synthetic iron oxides (biogenic magnetite, goethite, and hematite) and natural Fe(III) oxide-containing solids was investigated in pH 6.8 artificial groundwater containing 10 mM NaHCO3. In most experiments, more than 95% of added U(VI) was sorbed to solids. U(VI) was rapidly and extensively (> or = 80%) reduced in the presence of synthetic Fe(III) oxides and highly Fe(II) oxide-enriched (18-35 wt % Fe) Atlantic coastal plain sediments. In contrast, long-term (20-60 d) U(VI) reduction was less than 30% in suspensions of six other natural solids with relatively low Fe(III) oxide content (1-5 wt % Fe). Fe(II) sorption site density was severalfold lower on these natural solids (0.2-1.1 Fe(II) nm(-2)) compared tothe synthetic Fe(lII) oxides (1.6-3.2 Fe(II) nm(-2)), which may explain the poor U(VI) reduction in the natural solid-containing systems. Addition of the reduced form of the electron shuttling compound anthrahydroquinone-2,6-disulfonate (AH2DS; final concentration 2.5 mM) to the natural solid suspensions enhanced the rate and extent of U(VI) reduction, suggesting that AH2DS reduced U(VI) at surface sites where reaction of U(VI) with sorbed Fe(II) was limited. This study demonstrates that abiotic, Fe(II)-driven U(VI) reduction is likely to be less efficient in natural soils and sediments than would be inferred from studies with synthetic Fe(III) oxides.

  18. Nanogoethite formation from oxidation of Fe(II) sorbed on aluminum oxide: implications for contaminant reduction.

    PubMed

    Larese-Casanova, Philip; Cwiertny, David M; Scherer, Michelle M

    2010-05-15

    Ferrous iron [Fe(II)] bound to mineral surfaces has been shown to reduce several important groundwater contaminants, but little is known of the nature of the newly formed, insoluble ferric iron [Fe(III)] and whether it influences the heterogeneous contaminant reduction process. To explore how the formation and evolution of the Fe oxidation products influences contaminant reduction, we measured the kinetics of nitrobenzene reduction by Fe(II) sorbed on alpha-Al(2)O(3) while simultaneously characterizing the Fe oxidation product with Mossbauer spectroscopy and electron microscopy. After a brief period of slow kinetics, the onset of nitrobenzene reduction coincided with a change in particle suspension color from white to yellow-ocher due to formation of nanogoethite rods (alpha-FeOOH) from oxidation of sorbed Fe(II). Formation of nanogoethite on the alpha-Al(2)O(3) particles appears to promote the rapid reduction of nitrobenzene. Our results show that nanogoethite crystals can form rapidly by heterogeneous Fe(II) oxidation, and formation of goethite can profoundly influence contaminant reduction rates by Fe(II).

  19. Evaluation of Fe(II) oxidation at an acid mine drainage site using laboratory-scale reactors

    NASA Astrophysics Data System (ADS)

    Brown, Juliana; Burgos, William

    2010-05-01

    decreased as residence time decreased and as water column depth increased. Control reactors with Co-60 irradiated sediments showed an increase in Fe concentration as a result of dissolution of the sediments; thus, it was concluded that Fe(II) oxidation in the reactors was a result of biological processes and not abiotic oxidation. It was also concluded that Fe(II) oxidation and removal rates were dependent upon geochemical gradients (pH, Fe(II) concentration) rather than depositional facies. Fluorescent in situ hybridization was also performed on field and reactor samples to determine which microbial communities were responsible for the highest Fe(II) oxidation rates.

  20. Effect of dissolved organic matter on Fe(II) oxidation in natural and engineered waters.

    PubMed

    Lee, Ying Ping; Fujii, Manabu; Terao, Koumei; Kikuchi, Tetsuro; Yoshimura, Chihiro

    2016-10-15

    Fe(II) oxidation was investigated in samples from the Sagami River basin (Japan) with particular emphasis on the effect of dissolved organic matter (DOM) in an urban river system. Collected samples consisted of main stream and tributary waters impacted to a moderate and minor extent by anthropogenic activities, respectively, and treated effluents from adjacent municipal wastewater treatment plants (MWWTPs: as representative anthropogenic point source). Nanomolar Fe(II) oxidation was measured in air-saturated waters using luminol chemiluminescence in the dark at 25 °C. Second-order rate constant for Fe(II) oxidation (with respect to Fe(II) and O2 concentrations) showed spatial and temporal variation. Annual average of the rate constant was highest for MWWTP effluents, followed by reservoir and river waters, with tributary waters showing the lowest oxidation rate. Manipulation experiments indicated that, in addition to pH (7.8-8.4), DOM characteristics are important explanatory variable for the Fe(II) oxidation. For example, the addition of MWWTP-derived humic-type DOM to anthropogenically less-influenced tributary water resulted in substantial increase in the oxidation rate. Significant negative correlation observed between the specific UV absorbance (SUVA254) and Fe(II) oxidation rate constant (pH 8.0) suggests a potential effect of humic-type DOM with low SUVA254 (high aliphatic content) on Fe(II) oxidation in natural and engineered waters.

  1. Iron-mediated microbial oxidation and abiotic reduction of organic contaminants under anoxic conditions.

    PubMed

    Tobler, Nicole B; Hofstetter, Thomas B; Straub, Kristina L; Fontana, Daniela; Schwarzenbach, René P

    2007-11-15

    In anoxic environments, the oxidation of organic compounds, such as BTEX fuel components, by dissimilatory Fe(III) reduction can generate reactive mineral-bound Fe(II) species, which in turn are able to reduce other classes of organic and inorganic groundwater contaminants. In this study, we designed and evaluated an anaerobic batch reactor that mimicks iron-reducing conditions to investigate the factors that favor the coupling of microbial toluene oxidation and abiotic reduction of nitroaromatic contaminants. We investigated the influence of different Fe(III)-bearing minerals and combinations thereof on the coupling of these two processes. Results from laboratory model systems show that complete oxidation of toluene to CO2 by Geobacter metallireducens in the presence of Fe(III)-bearing minerals leads to the formation of mineral-bound Fe(II) species capable of the reduction of 4-nitroacetophenone. Whereas significant microbial toluene oxidation was only observed in the presence of amorphous Fe(III) phases, reduction of nitroaromatic compounds only proceeded with Fe(II) species bound to crystalline Fe(III) oxides. Our results suggest that in anoxic soils and sediments containing amorphous and crystalline iron phases simultaneously, coupling of microbial oxidation and abiotic reduction of organic compounds may allow for concurrent natural attenuation of different contaminant classes.

  2. EPR and ENDOR studies of Fe(II) hemoproteins reduced and oxidized at 77 K.

    PubMed

    Davydov, Roman; Hoffman, Brian M

    2008-03-01

    gamma-irradiation of frozen solutions of Fe(II) hemoproteins at 77 K generates both electron paramagnetic resonance (EPR) active singly reduced and oxidized heme centers trapped in the conformation of the Fe(II) precursors. The reduction products of pentacoordinate (S = 2) Fe(II) globins, peroxidases and cytochrome P450cam show EPR and electron-nuclear double resonance (ENDOR) spectra characteristic of (3d 7) Fe(I) species. In addition, cryoreduced Fe(II) alpha-chains of hemoglobin and myoglobin exhibit an S = 3/2 spin state produced by antiferromagnetic coupling between a porphyrin anion radical and pentacoordinate (S = 2) Fe(II). The spectra of cryoreduced forms of Fe(II) hemoglobin alpha-chains and deoxymyoglobin reveal that the Fe(II) precursors adopt multiple conformational substates. Reduction of hexacoordinate Fe(II) cytochrome c and cytochrome b5 as well as carboxy complexes of deoxyglobins produces only Fe(II) porphyrin pi-anion radical species. The low-valent hemoprotein intermediates produced by cryoreduction convert to the Fe(II) states at T > 200 K. Cryogenerated Fe(III) cytochrome c and cytochrome b5 have spectra similar to these for the resting Fe(III) states, whereas the spectra of the products of cryooxidation of pentacoordinate Fe(II) globins and peroxidases are different. Cryooxidation of CO-Fe(II) globins generates Fe(III) hemes with quantum-mechanically admixed S = 3/2, 5/2 ground states. The trapped Fe(III) species relax to the equilibrium ferric states upon annealing at T > 190 K. Both cryooxidized and reduced centers provide very sensitive EPR/ENDOR structure probes of the EPR-silent Fe(II) state.

  3. Rhodobacter capsulatus Catalyzes Light-Dependent Fe(II) Oxidation under Anaerobic Conditions as a Potential Detoxification Mechanism▿

    PubMed Central

    Poulain, Alexandre J.; Newman, Dianne K.

    2009-01-01

    Diverse bacteria are known to oxidize millimolar concentrations of ferrous iron [Fe(II)] under anaerobic conditions, both phototrophically and chemotrophically. Yet whether they can do this under conditions that are relevant to natural systems is understood less well. In this study, we tested how light, Fe(II) speciation, pH, and salinity affected the rate of Fe(II) oxidation by Rhodobacter capsulatus SB1003. Although R. capsulatus cannot grow photoautotrophically on Fe(II), it oxidizes Fe(II) at rates comparable to those of bacteria that do grow photoautotrophically on Fe(II) as soon as it is exposed to light, provided it has a functional photosystem. Chelation of Fe(II) by diverse organic ligands promotes Fe(II) oxidation, and as the pH increases, so does the oxidation rate, except in the presence of nitrilotriacetate; nonchelated forms of Fe(II) are also more rapidly oxidized at higher pH. Salt concentrations typical of marine environments inhibit Fe(II) oxidation. When growing photoheterotrophically on humic substances, R. capsulatus is highly sensitive to low concentrations of Fe(II); it is inhibited in the presence of concentrations as low as 5 μM. The product of Fe(II) oxidation, ferric iron, does not hamper growth under these conditions. When other parameters, such as pH or the presence of chelators, are adjusted to promote Fe(II) oxidation, the growth inhibition effect of Fe(II) is alleviated. Together, these results suggest that Fe(II) is toxic to R. capsulatus growing under strictly anaerobic conditions and that Fe(II) oxidation alleviates this toxicity. PMID:19717624

  4. Constraining the role of iron in environmental nitrogen transformations. Dual stable isotope systematics of abiotic NO2- reduction by Fe(II) and its production of N2O

    SciTech Connect

    Johnston, David; Wankel, Scott David; Buchwald, Carolyn; Hansel, Colleen

    2015-09-16

    Redox reactions involving nitrogen and iron have been shown to have important implications for mobilization of priority contaminants. Thus, an understanding of the linkages between their biogeochemical cycling is critical for predicting subsurface mobilization of radionuclides such as uranium. Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO2-) reduction by Fe(II) or ‘chemodenitrification,’ and its relevance to the production of nitrous oxide (N2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmentally relevant conditions. We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (~8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO2- reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO2- reduction by Fe(II) may represent an important abiotic source of environmental N2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO2- reduction and N2O formation, helping future studies constrain the relative roles of abiotic and biological N2O production pathways.

  5. Phototrophic Fe(II) oxidation promotes organic carbon acquisition by Rhodobacter capsulatus SB1003.

    PubMed

    Caiazza, Nicky C; Lies, Douglas P; Newman, Dianne K

    2007-10-01

    Anoxygenic phototrophic Fe(II) oxidation is usually considered to be a lithoautotrophic metabolism that contributes to primary production in Fe-based ecosystems. In this study, we employed Rhodobacter capsulatus SB1003 as a model organism to test the hypothesis that phototrophic Fe(II) oxidation can be coupled to organic carbon acquisition. R. capsulatus SB1003 oxidized Fe(II) under anoxic conditions in a light-dependent manner, but it failed to grow lithoautotrophically on soluble Fe(II). When the strain was provided with Fe(II)-citrate, however, growth was observed that was dependent upon microbially catalyzed Fe(II) oxidation, resulting in the formation of Fe(III)-citrate. Subsequent photochemical breakdown of Fe(III)-citrate yielded acetoacetic acid that supported growth in the light but not the dark. The deletion of genes (RRC00247 and RRC00248) that encode homologs of atoA and atoD, required for acetoacetic acid utilization, severely impaired the ability of R. capsulatus SB1003 to grow on Fe(II)-citrate. The growth yield achieved by R. capsulatus SB1003 in the presence of citrate cannot be explained by lithoautotrophic growth on Fe(II) enabled by indirect effects of the ligand [such as altering the thermodynamics of Fe(II) oxidation or preventing cell encrustation]. Together, these results demonstrate that R. capsulatus SB1003 grows photoheterotrophically on Fe(II)-citrate. Nitrilotriacetic acid also supported light-dependent growth on Fe(II), suggesting that Fe(II) oxidation may be a general mechanism whereby some Fe(II)-oxidizing bacteria mine otherwise inaccessible organic carbon sources.

  6. Oxidation of Structural Fe(II) in Biotite by Lithotrophic Fe(II)-oxidizing microorganisms

    NASA Astrophysics Data System (ADS)

    Shelobolina, E.; Blöthe, M.; Xu, H.; Konishi, H.; Roden, E.

    2008-12-01

    The potential for microbial involvement in the oxidation of Fe(II)-bearing phyllosilicates is an understudied aspect of soil/sediment Fe biogeochemistry. An important property of structural Fe in Fe-bearing smectites is their ability to undergo multiple redox cycles without being mobilized. An obvious choice of mineral substrate for enumeration/isolation of Fe(II)-oxidizing microorganisms would be reduced smectite. But reduced smectite is readily oxidized by air. That is why biotite was chosen as a substrate for this study. In contrast to smectite, biotite is more stable in the presence of air, but incapable of redox cycling. Once Fe(II) is oxidized, biotite is weathered to expendable 2:1 phyllosilicates or kaolinite. First, we evaluated the ability of a neutral-pH lithoautotrophic nitrate-reducing enrichment culture (MPI culture), recovered by Straub et al (Appl. Environ. Microbiol., 1996, 62:1458-1460) from a freshwater ditch, to oxidize two different specimens of biotite. The culture was capable of multiple transfers in anaerobic nitrate-containing biotite suspensions. The growth of MPI culture resulted in decrease of 0.5 N HCl-extractable Fe(II) content and simultaneous nitrate reduction. Cell yields were comparable to those observed for other neutral-pH lithoautotrophic Fe(II)-oxidizing bacteria. High resolution TEM examination revealed structural and chemical changes at the edges of oxidized biotite and formation of reddish amorphous precipitates dominated by Si and Fe. To further evaluate efficiency of biotite for recovery of oxygen- and nitrate-dependent Fe(II) oxidizing cultures microbial enumeration study was performed using subsoil from a site near Madison, WI. The soil is rich in Fe-bearing smectite and shows evidence of redoximorphic features. The enumeration of Fe(II) oxidizing organisms from this sediment showed 10-fold higher efficiency of biotite over soluble Fe(II) for recovery of Fe(II)-oxidizers. Isolation and identification of both aerobic and

  7. Physiology and Mechanism of Phototrophic Fe(II) Oxidation by Rhodopseudomonas palustris TIE-1

    NASA Astrophysics Data System (ADS)

    Jiao, Y.; Newman, D.

    2007-12-01

    Phototrophic Fe(II)-oxidizing bacteria use electrons from ferrous iron [Fe(II)] and energy from light to drive reductive CO2 fixation. This metabolism is thought to be ancient in origin, and plays an important role in environmental iron cycling. It has been implicated in the deposition of Banded Iron Formations, a class of ancient sedimentary iron deposits. Consistent with this hypothesis, we discovered that hydrogen gas, a thermodynamically favorable electron donor to Fe(II), in an Archean atmosphere would not have inhibited phototrophic Fe(II) oxidation. To understand this physiology and the connection to BIF formation at the molecular level, the mechanisms of phototrophic Fe(II) oxidation were examined in a model organism Rhodopseudomonas palustris TIE-1. Increased expression of a putative decaheme c-type cytochrome, encoded by pioA, was observed when cells were grown under Fe(II)-oxidizing conditions. Two genes located immediately downstream of pioA in the same operon, pioB and pioC, encode a putative outer membrane beta-barrel protein and a putative high potential iron-sulfur protein, respectively. Deletion studies demonstrated that all three genes are involved in phototrophic Fe(II) oxidation. This study provides our first insight into the molecular mechanisms of this metabolism, which will be further characterized by in vitro biochemical studies.

  8. Fractionation of Fe isotopes during Fe(II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth D.; Wu, Wenfang; Schoenberg, Ronny; Byrne, James; Michel, F. Marc; Pan, Yongxin; Kappler, Andreas

    2015-09-01

    Much interest exists in finding mineralogical, organic, morphological, or isotopic biosignatures for Fe(II)-oxidizing bacteria (FeOB) that are retained in Fe-rich sediments, which could indicate the activity of these organisms in Fe-rich seawater, more common in the Precambrian Era. To date, the effort to establish a clear Fe isotopic signature in Fe minerals produced by Fe(II)-oxidizing metabolisms has been thwarted by the large kinetic fractionation incurred as freshly oxidized aqueous Fe(III) rapidly precipitates as Fe(III) (oxyhydr)oxide minerals at near neutral pH. The Fe(III) (oxyhydr)oxide minerals resulting from abiotic Fe(II) oxidation are isotopically heavy compared to the Fe(II) precursor and are not clearly distinguishable from minerals formed by FeOB isotopically. However, in marine hydrothermal systems and Fe(II)-rich springs the minerals formed are often isotopically lighter than expected considering the fraction of Fe(II) that has been oxidized and experimentally-determined fractionation factors. We measured the Fe isotopic composition of aqueous Fe (Feaq) and the final Fe mineral (Feppt) produced in batch experiment using the marine Fe(II)-oxidizing phototroph Rhodovulum iodosum. The δ56Feaq data are best described by a kinetic fractionation model, while the evolution of δ56Feppt appears to be controlled by a separate fractionation process. We propose that soluble Fe(III), and Fe(II) and Fe(III) extracted from the Feppt may act as intermediates between Fe(II) oxidation and Fe(III) precipitation. Based on 57Fe Mössbauer spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and X-ray total scattering, we suggests these Fe phases, collectively Fe(II/III)interm, may consist of organic-ligand bound, sorbed, and/or colloidal Fe(II) and Fe(III) mineral phases that are isotopically lighter than the final Fe(III) mineral product. Similar intermediate phases, formed in response to organic carbon produced by FeOB and inorganic

  9. Minerals Masquerading As Enzymes: Abiotic Oxidation Of Soil Organic Matter In An Iron-Rich Humid Tropical Forest Soil

    NASA Astrophysics Data System (ADS)

    Hall, S. J.; Silver, W. L.

    2010-12-01

    Oxidative reactions play an important role in decomposing soil organic matter fractions that resist hydrolytic degradation, and fundamentally affect the cycling of recalcitrant soil carbon across ecosystems. Microbial extracellular oxidative enzymes (e.g. lignin peroxidases and laccases) have been assumed to provide a dominant role in catalyzing soil organic matter oxidation, while other potential oxidative mechanisms remain poorly explored. Here, we show that abiotic reactions mediated by the oxidation of ferrous iron (Fe(II)) could explain high potential oxidation rates in humid tropical forest soils, which often contain high concentrations of Fe(II) and experience rapid redox fluctuations between anaerobic and aerobic conditions. These abiotic reactions could provide an additional mechanism to explain high rates of decomposition in these ecosystems, despite frequent oxygen deficits. We sampled humid tropical forest soils in Puerto Rico, USA from various topographic positions, ranging from well-drained ridges to riparian valleys that experience broad fluctuations in redox potential. We measured oxidative activity by adding the model humic compound L-DOPA to soil slurries, followed by colorimetric measurements of the supernatant solution over time. Dilute hydrogen peroxide was added to a subset of slurries to measure peroxidative activity. We found that oxidative and peroxidative activity correlated positively with soil Fe(II) concentrations, counter to prevailing theory that low redox potential should suppress oxidative enzymes. Boiling or autoclaving sub-samples of soil slurries to denature any enzymes present typically increased peroxidative activity and did not eliminate oxidative activity, further suggesting the importance of an abiotic mechanism. We found substantial differences in the oxidation products of the L-DOPA substrate generated by our soil slurries in comparison with oxidation products generated by a purified enzyme (mushroom tyrosinase

  10. Monitoring, field experiments, and geochemical modeling of Fe(II) oxidation kinetics in a stream dominated by net-alkaline coal-mine drainage, Pennsylvania, USA

    USGS Publications Warehouse

    Cravotta, Charles A.

    2015-01-01

    Watershed-scale monitoring, field aeration experiments, and geochemical equilibrium and kinetic modeling were conducted to evaluate interdependent changes in pH, dissolved CO2, O2, and Fe(II) concentrations that typically take place downstream of net-alkaline, circumneutral coal-mine drainage (CMD) outfalls and during aerobic treatment of such CMD. The kinetic modeling approach, using PHREEQC, accurately simulates observed variations in pH, Fe(II) oxidation, alkalinity consumption, and associated dissolved gas concentrations during transport downstream of the CMD outfalls (natural attenuation) and during 6-h batch aeration tests on the CMD using bubble diffusers (enhanced attenuation). The batch aeration experiments demonstrated that aeration promoted CO2 outgassing, thereby increasing pH and the rate of Fe(II) oxidation. The rate of Fe(II) oxidation was accurately estimated by the abiotic homogeneous oxidation rate law −d[Fe(II)]/dt = k1·[O2]·[H+]−2·[Fe(II)] that indicates an increase in pH by 1 unit at pH 5–8 and at constant dissolved O2 (DO) concentration results in a 100-fold increase in the rate of Fe(II) oxidation. Adjusting for sample temperature, a narrow range of values for the apparent homogeneous Fe(II) oxidation rate constant (k1′) of 0.5–1.7 times the reference value of k1 = 3 × 10−12 mol/L/min (for pH 5–8 and 20 °C), reported by Stumm and Morgan (1996), was indicated by the calibrated models for the 5-km stream reach below the CMD outfalls and the aerated CMD. The rates of CO2 outgassing and O2ingassing in the model were estimated with first-order asymptotic functions, whereby the driving force is the gradient of the dissolved gas concentration relative to equilibrium with the ambient atmosphere. Although the progressive increase in DO concentration to saturation could be accurately modeled as a kinetic function for the conditions evaluated, the simulation of DO as an instantaneous equilibrium process did not affect the

  11. Fe hydroxyphosphate precipitation and Fe(II) oxidation kinetics upon aeration of Fe(II) and phosphate-containing synthetic and natural solutions

    NASA Astrophysics Data System (ADS)

    van der Grift, B.; Behrends, T.; Osté, L. A.; Schot, P. P.; Wassen, M. J.; Griffioen, J.

    2016-08-01

    Exfiltration of anoxic Fe-rich groundwater into surface water and the concomitant oxidative precipitation of Fe are important processes controlling the transport of phosphate (PO4) from agricultural areas to aquatic systems. Here, we explored the relationship between solution composition, reaction kinetics, and the characteristics of the produced Fe hydroxyphosphate precipitates in a series of aeration experiments with anoxic synthetic water and natural groundwater. A pH stat device was used to maintain constant pH and to record the H+ production during Fe(II) oxidation in the aeration experiments in which the initial aqueous P/Fe ratios ((P/Fe)ini), oxygen concentration and pH were varied. In general, Fe(II) oxidation proceeded slower in the presence of PO4 but the decrease of the PO4 concentration during Fe(II) oxidation due to the formation of Fe hydroxyphosphates caused additional deceleration of the reaction rate. The progress of the reaction could be described using a pseudo-second-order rate law with first-order dependencies on PO4 and Fe(II) concentrations. After PO4 depletion, the Fe(II) oxidation rates increased again and the kinetics followed a pseudo-first-order rate law. The first-order rate constants after PO4 depletion, however, were lower compared to the Fe(II) oxidation in a PO4-free solution. Hence, the initially formed Fe hydroxyphosphates also affect the kinetics of continuing Fe(II) oxidation after PO4 depletion. Presence of aqueous PO4 during oxidation of Fe(II) led to the formation of Fe hydroxyphosphates. The P/Fe ratios of the precipitates ((P/Fe)ppt) and the recorded ratio of H+ production over decrease in dissolved Fe(II) did not change detectably throughout the reaction despite a changing P/Fe ratio in the solution. When (P/Fe)ini was 0.9, precipitates with a (P/Fe)ppt ratio of about 0.6 were formed. In experiments with (P/Fe)ini ratios below 0.6, the (P/Fe)ppt decreased with decreasing (P/Fe)ini and pH value. Aeration experiments with

  12. Rate law of Fe(II) oxidation under low O2 conditions

    NASA Astrophysics Data System (ADS)

    Kanzaki, Yoshiki; Murakami, Takashi

    2013-12-01

    Despite intensive studies on Fe(II) oxidation kinetics, the oxidation rate law has not been established under low O2 conditions. The importance of Fe(II) oxidation under low O2 conditions has been recently recognized; for instance, the Fe(II)/Fe(III) compositions of paleosols, ancient soils formed by weathering, can produce a quantitative pattern of the atmospheric oxygen increase during the Paleoproterozoic. The effects of partial pressure of atmospheric oxygen (PO2) on the Fe(II) oxidation rate were investigated to establish the Fe(II) oxidation rate - PO2 relationships under low O2 conditions. All oxidation experiments were carried out in a glove box by introducing Ar gas at ∼10-5-∼10-4 atm of PO2, pH 7.57-8.09 and 22 °C. Luminol chemiluminescence was adopted to measure low Fe(II) concentrations (down to ∼2 nM). Combining previous data under higher PO2 conditions (10-3-0.2 atm) with the present data, the rate law for Fe(II) oxidation over a wide range of PO2 (10-5-0.2 atm) was found to be written as: d[Fe(II)]/dt=-k[Fe(II)][[]2 where the exponent of [O2], x, and the rate constant, k, change from x = 0.98 (±0.04) and log k = 15.46 (±0.06) at ∼6 × 10-3-0.2 atm of PO2 to x = 0.58 (±0.02) and log k = 13.41 (±0.03) at 10-5-∼6 × 10-3 atm of PO2. The most plausible mechanism that explains the change in x under low O2 conditions is that, instead of O2, oxygen-derived oxidants, H2O2 and to some extent, O2rad -, dominate the oxidation reactions at <∼10-3 atm of PO2. The rate law found in the present study requires us to reconsider distributions of Fe redox species at low PO2 in natural environments, especially in paleoweathering profiles, and may provide a deeper understanding of the evolution of atmospheric oxygen in the Precambrian.

  13. Fe(II) oxidation during acid mine drainage neutralization in a pilot-scale Sequencing Batch Reactor.

    PubMed

    Zvimba, J N; Mathye, M; Vadapalli, V R K; Swanepoel, H; Bologo, L

    2013-01-01

    This study investigated Fe(II) oxidation during acid mine drainage (AMD) neutralization using CaCO3 in a pilot-scale Sequencing Batch Reactor (SBR) of hydraulic retention time (HRT) of 90 min and sludge retention time (SRT) of 360 min in the presence of air. The removal kinetics of Fe(II), of initial concentration 1,033 ± 0 mg/L, from AMD through oxidation to Fe(III) was observed to depend on both pH and suspended solids, resulting in Fe(II) levels of 679 ± 32, 242 ± 64, 46 ± 16 and 28 ± 0 mg/L recorded after cycles 1, 2, 3 and 4 respectively, with complete Fe(II) oxidation only achieved after complete neutralization of AMD. Generally, it takes 30 min to completely oxidize Fe(II) during cycle 4, suggesting that further optimization of SBR operation based on both pH and suspended solids manipulation can result in significant reduction of the number of cycles required to achieve acceptable Fe(II) oxidation for removal as ferric hydroxide. Overall, complete removal of Fe(II) during AMD neutralization is attractive as it promotes recovery of better quality waste gypsum, key to downstream gypsum beneficiation for recovery of valuables, thereby enabling some treatment-cost recovery and prevention of environmental pollution from dumping of sludge into landfills.

  14. Effect of Oxidation Rate and Fe(II) State on Microbial Nitrate-Dependent Fe(III) Mineral Formation

    PubMed Central

    Senko, John M.; Dewers, Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems. PMID:16269756

  15. Effect of the oxidation rate and Fe(II) state on microbial nitrate-dependent Fe(III) mineral formation

    USGS Publications Warehouse

    Senko, John M.; Dewers , Thomas A.; Krumholz, Lee R.

    2005-01-01

    A nitrate-dependent Fe(II)-oxidizing bacterium was isolated and used to evaluate whether Fe(II) chemical form or oxidation rate had an effect on the mineralogy of biogenic Fe(III) (hydr)oxides resulting from nitrate-dependent Fe(II) oxidation. The isolate (designated FW33AN) had 99% 16S rRNA sequence similarity to Klebsiella oxytoca. FW33AN produced Fe(III) (hydr)oxides by oxidation of soluble Fe(II) [Fe(II)sol] or FeS under nitrate-reducing conditions. Based on X-ray diffraction (XRD) analysis, Fe(III) (hydr)oxide produced by oxidation of FeS was shown to be amorphous, while oxidation of Fe(II)sol yielded goethite. The rate of Fe(II) oxidation was then manipulated by incubating various cell concentrations of FW33AN with Fe(II)sol and nitrate. Characterization of products revealed that as Fe(II) oxidation rates slowed, a stronger goethite signal was observed by XRD and a larger proportion of Fe(III) was in the crystalline fraction. Since the mineralogy of Fe(III) (hydr)oxides may control the extent of subsequent Fe(III) reduction, the variables we identify here may have an effect on the biogeochemical cycling of Fe in anoxic ecosystems.

  16. Formation of layered Fe(II)-Al(III)-hydroxides during reaction of Fe(II) with aluminum oxide.

    PubMed

    Elzinga, Evert J

    2012-05-01

    The reactivity of aqueous Fe(II) with aluminum oxide in anoxic solutions was investigated with batch kinetic experiments combined with Fe K edge X-ray absorption spectroscopy measurements to characterize Fe(II) sorption products. Formation of Fe(II)-Al(III)-layered double hydroxides with an octahedral sheet structure similar to nikischerite (NaFe(II)(6) Al(3)(SO(4))(2)(OH)(18) (H(2)O)(12)) was observed within a few hours during sorption at pH 7.5 and aqueous Fe(II) concentrations of 1-3 mM. These Fe(II) phases are composed of brucite-like Fe(II)(OH)(2) sheets with partial substitution of Al(III) for Fe(II), charge balanced by anions coordinated along the basal planes. Their fast rate of formation suggests that these previously unrecognized Fe(II) phases, which are structurally and compositionally similar to green rust, may be an important sink of Fe(II) in suboxic and anoxic geochemical environments, and impact the fate of structurally compatible trace metals, such as Co(II), Ni(II), and Zn(II), as well as redox-reactive species including Cr(VI) and U(VI). Further studies are required to assess the thermodynamics, formation kinetics, and stability of these Fe(II) minerals under field conditions.

  17. Fluctuation Analysis of Redox Potential to Distinguish Microbial Fe(II) Oxidation

    NASA Astrophysics Data System (ADS)

    Enright, A. M. L.; Ferris, F. G.

    2016-11-01

    We developed a novel method for distinguishing abiotic and biological iron oxidation in liquid media using oxidation-reduction (redox) potential time series data. The instrument and processing algorithm were tested by immersing the tip of a Pt electrode with an Ag-AgCl reference electrode into an active iron-oxidizing biofilm in a groundwater discharge zone, as well as in two abiotic systems: a killed sample and a chemical control from the same site. We used detrended fluctuation analysis to characterize average root mean square fluctuation behavior, which was distinct in the live system. The calculated α value scaling exponents determined by detrended fluctuation analysis were significantly different at p < 0.001. This indicates that time series of electrode response data may be used to distinguish live and abiotic chemical reaction pathways. Due to the simplicity, portability, and small size, it may be suitable for characterization of extraterrestrial environments where water has been observed, such as Mars and Europa.

  18. Biological Oxidation of Fe(II) in Reduced Nontronite Coupled with Nitrate Reduction by Pseudogulbenkiania sp. Strain 2002

    SciTech Connect

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Agrawal, A.; Liu, Deng; Zhang, Jing; Edelmann, Richard E.

    2013-10-15

    Nitrate contamination in soils, sediments, and water bodies is a significant issue. Although much is known about nitrate degradation in these environments, especially via microbial pathways, a complete understanding of all degradation processes, especially in clay mineral-rich soils, is still lacking. The objective of this study was to study the potential of removing nitrate contaminant using structural Fe(II) in clay mineral nontronite. Specifically, the coupled processes of microbial oxidation of Fe(II) in microbially reduced nontronite (NAu-2) and nitrate reduction by Pseudogulbenkiania species strain 2002 was investigated. Bio-oxidation experiments were conducted in bicarbonate-buffered medium under both growth and nongrowth conditions. The extents of Fe(II) oxidation and nitrate reduction were measured by wet chemical methods. X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and 57Fe-Mössbauer spectroscopy were used to observe mineralogical changes associated with Fe(III) reduction and Fe(II) oxidation in nontronite. The bio-oxidation extent under growth and nongrowth conditions reached 93% and 57%, respectively. Over the same time period, nitrate was completely reduced under both conditions to nitrogen gas (N2), via an intermediate product nitrite. Magnetite was a mineral product of nitrate-dependent Fe(II) oxidation, as evidenced by XRD data and TEM diffraction patterns. The results of this study highlight the importance of iron-bearing clay minerals in the global nitrogen cycle with potential applications in nitrate removal in soils.

  19. Biochemistry and Ecology of Novel Cytochromes Catalyzing Fe(II) Oxidation by an Acidophilic Microbial Community

    NASA Astrophysics Data System (ADS)

    Singer, S. W.; Jeans, C. J.; Thelen, M. P.; Verberkmoes, N. C.; Hettich, R. C.; Chan, C. S.; Banfield, J. F.

    2007-12-01

    An acidophilic microbial community found in the Richmond Mine at Iron Mountain, CA forms abundant biofilms in extremely acidic (pH<1) and toxic metal conditions. In this ecosystem, biological Fe(II) oxidation is critical to the metabolic functioning of the community, and in turn this process generates acid mine drainage, causing an environmental catastrophe. Two conspicuous novel proteins isolated from these biofilms were identified as gene products of Leptospirillum group II and were characterized as cytochromes with unique properties. Sulfuric acid extraction of biofilm samples liberated one of these proteins, a 16 kDa cytochrome with an unusual alpha-band absorption at 579 (Cyt579). Genomic sequencing of multiple biofilms indicated that several variants of Cyt579 were present in Leptospirillum strains. Intact protein MS analysis identified the dominant variants in each biofilm and documented multiple N-terminal cleavage sites for Cyt579. By combining biochemical, geochemical and microbiological data, we established that the sequence variation and N-terminal processing of Cyt579 are selected by ecological conditions. In addition to the soluble Cyt579, the second cytochrome appears as a much larger protein complex of ~210 kDa predominant in the biofilm membrane fraction, and has an alpha-band absorption at 572 nm. The 60 kDa cytochrome subunit, Cyt572, resides in the outer membrane of LeptoII, and readily oxidizes Fe(II) at low pH (0.95 - 3.0). Several genes encoding Cyt572 were localized within a recombination hotspot between two strains of LeptoII, causing a large range of variation in the sequences. Genomic sequencing and MS proteomic studies established that the variants were also selected by ecological conditions. A general mechanistic model for Fe(II) oxidation has been developed from these studies. Initial Fe(II) oxidation by Cyt572 occurs at the outer membrane. Cyt572 then transfers electrons to Cyt579, perhaps representing an initial step in energy flow

  20. Mariprofundus ferrooxydans PV-1 the First Genome of a Marine Fe(II) Oxidizing Zetaproteobacterium

    PubMed Central

    Singer, Esther; Emerson, David; Webb, Eric A.; Barco, Roman A.; Kuenen, J. Gijs; Nelson, William C.; Chan, Clara S.; Comolli, Luis R.; Ferriera, Steve; Johnson, Justin; Heidelberg, John F.; Edwards, Katrina J.

    2011-01-01

    Mariprofundus ferrooxydans PV-1 has provided the first genome of the recently discovered Zetaproteobacteria subdivision. Genome analysis reveals a complete TCA cycle, the ability to fix CO2, carbon-storage proteins and a sugar phosphotransferase system (PTS). The latter could facilitate the transport of carbohydrates across the cell membrane and possibly aid in stalk formation, a matrix composed of exopolymers and/or exopolysaccharides, which is used to store oxidized iron minerals outside the cell. Two-component signal transduction system genes, including histidine kinases, GGDEF domain genes, and response regulators containing CheY-like receivers, are abundant and widely distributed across the genome. Most of these are located in close proximity to genes required for cell division, phosphate uptake and transport, exopolymer and heavy metal secretion, flagellar biosynthesis and pilus assembly suggesting that these functions are highly regulated. Similar to many other motile, microaerophilic bacteria, genes encoding aerotaxis as well as antioxidant functionality (e.g., superoxide dismutases and peroxidases) are predicted to sense and respond to oxygen gradients, as would be required to maintain cellular redox balance in the specialized habitat where M. ferrooxydans resides. Comparative genomics with other Fe(II) oxidizing bacteria residing in freshwater and marine environments revealed similar content, synteny, and amino acid similarity of coding sequences potentially involved in Fe(II) oxidation, signal transduction and response regulation, oxygen sensation and detoxification, and heavy metal resistance. This study has provided novel insights into the molecular nature of Zetaproteobacteria. PMID:21966516

  1. Structure and oxidation state of hemitite surfaces reacted with aqueous Fe(II) at acidic and neutral pH.

    SciTech Connect

    Catalano, J. G.; Fenter, P.; Park, C.; Zhang, Z.; Rosso, K. M.; Washington Univ.; PNNL

    2010-01-01

    Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 {micro}mol/m{sup 2} on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom

  2. Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH

    SciTech Connect

    Catalano, Jeffrey G.; Fenter, Paul; Park, Changyong; Zhang, Zhan; Rosso, Kevin M.

    2010-03-01

    Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5–1 μmol/m2 on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Finally, given the general pH-independence and substantial mass transfer involved, this electron and

  3. Denitrification and Nitrate-Dependent Fe(II) Oxidation in Various Pseudogulbenkiania Strains

    PubMed Central

    Ishii, Satoshi; Joikai, Kazuki; Otsuka, Shigeto; Senoo, Keishi; Okabe, Satoshi

    2016-01-01

    Pseudogulbenkiania is a relatively recently characterized genus within the order Neisseriales, class Betaproteobacteria. This genus contains several strains that are capable of anaerobic, nitrate-dependent Fe(II) oxidation (NDFO), a geochemically important reaction for nitrogen and iron cycles. In the present study, we examined denitrification functional gene diversities within this genus, and clarified whether other Pseudogulbenkiania sp. strains perform denitrification and NDFO. Seventy strains were analyzed, including two type strains, a well-characterized NDFO strain, and 67 denitrifying strains isolated from various rice paddy fields and rice-soybean rotation fields in Japan. We also attempted to identify the genes responsible for NDFO by mutagenesis. Our comprehensive analysis showed that all Pseudogulbenkiania strains tested performed denitrification and NDFO; however, we were unable to obtain NDFO-deficient denitrifying mutants in our mutagenesis experiment. This result suggests that Fe(II) oxidation in these strains is not enzymatic, but is caused by reactive N-species that are formed during nitrate reduction. Based on the results of the comparative genome analysis among Pseudogulbenkiania sp. strains, we identified low sequence similarity within the nos gene as well as different gene arrangements within the nos gene cluster, suggesting that nos genes were horizontally transferred. Since Pseudogulbenkiania sp. strains have been isolated from various locations around the world, their denitrification and NDFO abilities may contribute significantly to nitrogen and iron biogeochemical cycles. PMID:27431373

  4. Stable Isotope Systematics of Abiotic Nitrite Reduction Coupled with Anaerobic Iron Oxidation: The Role of Reduced Clays and Fe-bearing Minerals

    NASA Astrophysics Data System (ADS)

    Grabb, K. C.; Buchwald, C.; Hansel, C. M.; Wankel, S. D.

    2014-12-01

    Under anaerobic conditions, it is widely assumed that nitrate (NO3-) and nitrite (NO2-) reduction is primarily the result of microbial respiration. However, it has also been shown that abiotic reduction of nitrate and nitrite by reduced iron (Fe(II)), whether mineral-bound or surface-associated, may also occur under certain environmentally relevant conditions. With a range of experimental conditions, we investigated the nitrogen and oxygen stable isotope systematics of abiotic nitrite reduction by Fe(II) in an effort to characterize biotic and abiotic processes in the environment. While homogenous reactions between NO2- and Fe(II) in artificial seawater showed little reduction, heterogeneous reactions involving Fe-containing minerals showed considerable nitrite loss. Specifically, rapid nitrite reduction was observed in experiments that included reduced clays (illite, Na-montmorillonite, and nontronite) and those that exhibited iron oxide formation (ferrihydrite, magnetite and/or green rust). While these iron oxides and clay minerals offer both a source of reduced iron in the mineral matrix as well as a surface for Fe(II) activation, control experiments with corundum as a non-Fe containing mineral surface showed little NO2- loss, implicating a more dominant role of structural Fe in the clays during nitrite reduction. The isotope effects for 15N and 18O (15ɛ and 18ɛ) ranged from 5 to 14‰ for 15ɛ and 5 to 17‰ for 18ɛ and were typically coupled such that 15ɛ ~ 18ɛ. Reactions below pH 7 were slower and the 18ɛ was affected by oxygen atom exchange with water. Although little data exist for comparison with the dual isotopes of microbial NO2- reduction, these data serve as a benchmark for evaluating the role of abiotic processes in N reduction, particularly in sediment systems low in organic carbon and high in iron.

  5. Fluctuation Analysis of Redox Potential to Distinguish Microbial Fe(II) Oxidation.

    PubMed

    Enright, A M L; Ferris, F G

    2016-11-01

    We developed a novel method for distinguishing abiotic and biological iron oxidation in liquid media using oxidation-reduction (redox) potential time series data. The instrument and processing algorithm were tested by immersing the tip of a Pt electrode with an Ag-AgCl reference electrode into an active iron-oxidizing biofilm in a groundwater discharge zone, as well as in two abiotic systems: a killed sample and a chemical control from the same site. We used detrended fluctuation analysis to characterize average root mean square fluctuation behavior, which was distinct in the live system. The calculated α value scaling exponents determined by detrended fluctuation analysis were significantly different at p < 0.001. This indicates that time series of electrode response data may be used to distinguish live and abiotic chemical reaction pathways. Due to the simplicity, portability, and small size, it may be suitable for characterization of extraterrestrial environments where water has been observed, such as Mars and Europa. Key Words: Oxidation-reduction potential-Detrended fluctuation analysis-Iron-oxidizing bacteria. Astrobiology 16, 846-852.

  6. Physiology, Fe(II) oxidation, and Fe mineral formation by a marine planktonic cyanobacterium grown under ferruginous conditions

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth; Wu, Wenfang; Hao, Likai; Wuestner, Marina; Obst, Martin; Moran, Dawn; McIlvin, Matthew; Saito, Mak; Kappler, Andreas

    2015-10-01

    Evidence for Fe(II) oxidation and deposition of Fe(III)-bearing minerals from anoxic or redox-stratified Precambrian oceans has received support from decades of sedimentological and geochemical investigation of Banded Iron Formations (BIF). While the exact mechanisms of Fe(II) oxidation remains equivocal, reaction with O2 in the marine water column, produced by cyanobacteria or early oxygenic phototrophs, was likely. In order to understand the role of cyanobacteria in the deposition of Fe(III) minerals to BIF, we must first know how planktonic marine cyanobacteria respond to ferruginous (anoxic and Fe(II)-rich) waters in terms of growth, Fe uptake and homeostasis, and Fe mineral formation. We therefore grew the common marine cyanobacterium Synechococcus PCC 7002 in closed bottles that began anoxic, and contained Fe(II) concentrations that span the range of possible concentrations in Precambrian seawater. These results, along with cell suspension experiments, indicate that Fe(II) is likely oxidized by this strain via chemical oxidation with oxygen produced during photosynthesis, and not via any direct enzymatic or photosynthetic pathway. Imaging of the cell-mineral aggregates with scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM) are consistent with extracellular precipitation of Fe(III) (oxyhydr)oxide minerals, but that >10% of Fe(III) sorbs to cell surfaces rather than precipitating. Proteomic experiments support the role of reactive oxygen species (ROS) in Fe(II) toxicity to Synechococcus PCC 7002. The proteome expressed under low Fe conditions included multiple siderophore biosynthesis and siderophore and Fe transporter proteins, but most siderophores are not expressed during growth with Fe(II). These results provide a mechanistic and quantitative framework for evaluating the geochemical consequences of perhaps life’s greatest metabolic innovation, i.e. the evolution and activity of oxygenic photosynthesis, in ferruginous

  7. Nitric oxide signaling in plant responses to abiotic stresses.

    PubMed

    Qiao, Weihua; Fan, Liu-Min

    2008-10-01

    Nitric oxide (NO) plays important roles in diverse physiological processes in plants. NO can provoke both beneficial and harmful effects, which depend on the concentration and location of NO in plant cells. This review is focused on NO synthesis and the functions of NO in plant responses to abiotic environmental stresses. Abiotic stresses mostly induce NO production in plants. NO alleviates the harmfulness of reactive oxygen species, and reacts with other target molecules, and regulates the expression of stress responsive genes under various stress conditions.

  8. Heterogeneous oxidation of Fe(II) on iron oxides in aqueous systems: Identification and controls of Fe(III) product formation

    NASA Astrophysics Data System (ADS)

    Larese-Casanova, Philip; Kappler, Andreas; Haderlein, Stefan B.

    2012-08-01

    The aqueous Fe(II)-oxide Fe(III) system is a reactant for many classes of redox sensitive compounds via an interfacial Fe(II) sorption and electron transfer process. The poorly soluble Fe(III) products formed as a result of contaminant reduction and Fe(II) oxidation on iron oxides may be capable of modifying iron oxide surfaces and affecting subsequent reduction rates of contaminants such as halogenated ethenes or nitroaromatic compounds. The scope of this study was to identify the secondary Fe(III) mineral phases formed after Fe(II) oxidation on common iron oxides during heterogeneous contaminant reduction by directly targeting the secondary minerals using Mössbauer-active isotopes. Fe(III) mineral characterization was performed using 57Fe-Mössbauer spectroscopy, μ-X-ray diffraction, and electron microscopy after oxidation of dissolved 57Fe(II) using nitrobenzenes as a model oxidant in pH-buffered suspensions of 56hematite, 56goethite, 56magnetite, and 56maghemite. Mössbauer spectra confirmed sorbed 57Fe(II) becomes oxidized by the parent 56Fe(III)-oxide sorbent and assimilated as the sorbent oxide prior to any nitrobenzene reduction, consistent with several reports in the literature. In addition to oxide sorbent growth, Fe(II) sorption and oxidation by nitrobenzene result also in the formation of secondary Fe(III) minerals. Goethite formed on three hematite morphologies (rhombohedra, needles, and hexagonal platelets), and acicular needle shapes typical of goethite appeared on the micron-sized hexagonal platelets, at times aligned in 60° orientations on (0 0 1) faces. The proportion of goethite formation on the three hematites was linked to number of surface sites. Only goethite was observed to form on a goethite sorbent. In contrast, lepidocrocite was observed to form on magnetite and maghemite sorbents (consistent with homogeneous Fe(II) oxidation by O2) and assumed spherulite morphologies. All secondary Fe(III) phases were confirmed within

  9. Anaerobic microbial Fe(II) oxidation and Fe(III) reduction in coastal marine sediments controlled by organic carbon content.

    PubMed

    Laufer, Katja; Byrne, James M; Glombitza, Clemens; Schmidt, Caroline; Jørgensen, Bo Barker; Kappler, Andreas

    2016-09-01

    Coastal marine sediments contain varying concentrations of iron, oxygen, nitrate and organic carbon. It is unknown how organic carbon content influences the activity of nitrate-reducing and phototrophic Fe(II)-oxidizers and microbial Fe-redox cycling in such sediments. Therefore, microcosms were prepared with two coastal marine sediments (Kalø Vig and Norsminde Fjord at Aarhus Bay, Denmark) varying in TOC from 0.4 to 3.0 wt%. The microcosms were incubated under light/dark conditions with/without addition of nitrate and/or Fe(II). Although most probable number (MPN) counts of phototrophic Fe(II)-oxidizers were five times lower in the low-TOC sediment, phototrophic Fe(II) oxidation rates were higher compared with the high-TOC sediment. Fe(III)-amended microcosms showed that this lower net Fe(II) oxidation in the high-TOC sediment is caused by concurrent bacterial Fe(III) reduction. In contrast, MPN counts of nitrate-reducing Fe(II)-oxidizers and net rates of nitrate-reducing Fe(II) oxidation were comparable in low- and high-TOC sediments. However, the ratio of nitratereduced :iron(II)oxidized was higher in the high-TOC sediment, suggesting that a part of the nitrate was reduced by mixotrophic nitrate-reducing Fe(II)-oxidizers and chemoorganoheterotrophic nitrate-reducers. Our results demonstrate that dynamic microbial Fe cycling occurs in these sediments and that the extent of Fe cycling is dependent on organic carbon content.

  10. Self-assembly Is Prerequisite for Catalysis of Fe(II) Oxidation by Catalytically Active Subunits of Ferritin*

    PubMed Central

    Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2015-01-01

    Fe(III) storage by ferritin is an essential process of the iron homeostasis machinery. It begins by translocation of Fe(II) from outside the hollow spherical shape structure of the protein, which is formed as the result of self-assembly of 24 subunits, to a di-iron binding site, the ferroxidase center, buried in the middle of each active subunit. The pathway of Fe(II) to the ferroxidase center has remained elusive, and the importance of self-assembly for the functioning of the ferroxidase center has not been investigated. Here we report spectroscopic and metal ion binding studies with a mutant of ferritin from Pyrococcus furiosus (PfFtn) in which self-assembly was abolished by a single amino acid substitution. We show that in this mutant metal ion binding to the ferroxidase center and Fe(II) oxidation at this site was obliterated. However, metal ion binding to a conserved third site (site C), which is located in the inner surface of each subunit in the vicinity of the ferroxidase center and is believed to be the path for Fe(II) to the ferroxidase center, was not disrupted. These results are the basis of a new model for Fe(II) translocation to the ferroxidase center: self-assembly creates channels that guide the Fe(II) ions toward the ferroxidase center directly through the protein shell and not via the internal cavity and site C. The results may be of significance for understanding the molecular basis of ferritin-related disorders such as neuroferritinopathy in which the 24-meric structure with 432 symmetry is distorted. PMID:26370076

  11. Coupling of Fe(II) oxidation in illite with nitrate reduction and its role in clay mineral transformation

    NASA Astrophysics Data System (ADS)

    Zhao, Linduo; Dong, Hailiang; Edelmann, Richard E.; Zeng, Qiang; Agrawal, Abinash

    2017-03-01

    In pedogenic and diagenetic processes, clay minerals transform from pre-existing phases to other clay minerals via intermediate interstratified clays. Temperature, pressure, chemical composition of fluids, and time are traditionally considered to be the important geological variables for clay mineral transformations. Nearly ten years ago, the role of microbes was recognized for the first time, where microbial reduction of structural Fe(III) in smectite resulted in formation of illite under ambient conditions within two weeks. However, the opposite process, the oxidation of structural Fe(II) in illite has not been studied and it remains unclear whether or not this process would result in the back reaction, e.g., from illite to smectite. The overall objective of this study was to investigate biological oxidation of structural Fe(II) in illite coupled with nitrate reduction and the effect of this process on clay mineral transformation. Laboratory incubations were set up, where structural Fe(II) in illite served as electron donor, nitrate as electron acceptor, and Pseudogulbenkiania sp. strain 2002 as mediator. Solution chemistry and gas composition were monitored over time. Mineralogical transformation resulting from bio-oxidation was characterized with X-ray diffraction and scanning and transmission electron microscopy. Our results demonstrated that strain 2002 was able to couple oxidation of structural Fe(II) in illite with reduction of nitrate to N2 with nitrite as a transient intermediate. This oxidation reaction resulted in transformation of illite to smectite and ultimately to kaolinite (illite → smectite → kaolinite transformations). This study illustrates the importance of Fe redox process in mediating the smectite-illite mineral cycle with important implications for Fe redox cycling and mineral evolution in surficial earth environments.

  12. Coexistence of Microaerophilic, Nitrate-Reducing, and Phototrophic Fe(II) Oxidizers and Fe(III) Reducers in Coastal Marine Sediment

    PubMed Central

    Laufer, Katja; Nordhoff, Mark; Røy, Hans; Schmidt, Caroline; Behrens, Sebastian; Jørgensen, Bo Barker

    2015-01-01

    Iron is abundant in sediments, where it can be biogeochemically cycled between its divalent and trivalent redox states. The neutrophilic microbiological Fe cycle involves Fe(III)-reducing and three different physiological groups of Fe(II)-oxidizing microorganisms, i.e., microaerophilic, anoxygenic phototrophic, and nitrate-reducing Fe(II) oxidizers. However, it is unknown whether all three groups coexist in one habitat and how they are spatially distributed in relation to gradients of O2, light, nitrate, and Fe(II). We examined two coastal marine sediments in Aarhus Bay, Denmark, by cultivation and most probable number (MPN) studies for Fe(II) oxidizers and Fe(III) reducers and by quantitative-PCR (qPCR) assays for microaerophilic Fe(II) oxidizers. Our results demonstrate the coexistence of all three metabolic types of Fe(II) oxidizers and Fe(III) reducers. In qPCR, microaerophilic Fe(II) oxidizers (Zetaproteobacteria) were present with up to 3.2 × 106 cells g dry sediment−1. In MPNs, nitrate-reducing Fe(II) oxidizers, anoxygenic phototrophic Fe(II) oxidizers, and Fe(III) reducers reached cell numbers of up to 3.5 × 104, 3.1 × 102, and 4.4 × 104 g dry sediment−1, respectively. O2 and light penetrated only a few millimeters, but the depth distribution of the different iron metabolizers did not correlate with the profile of O2, Fe(II), or light. Instead, abundances were homogeneous within the upper 3 cm of the sediment, probably due to wave-induced sediment reworking and bioturbation. In microaerophilic Fe(II)-oxidizing enrichment cultures, strains belonging to the Zetaproteobacteria were identified. Photoferrotrophic enrichments contained strains related to Chlorobium and Rhodobacter; the nitrate-reducing Fe(II) enrichments contained strains related to Hoeflea and Denitromonas. This study shows the coexistence of all three types of Fe(II) oxidizers in two near-shore marine environments and the potential for competition and interrelationships between them

  13. Coexistence of Microaerophilic, Nitrate-Reducing, and Phototrophic Fe(II) Oxidizers and Fe(III) Reducers in Coastal Marine Sediment.

    PubMed

    Laufer, Katja; Nordhoff, Mark; Røy, Hans; Schmidt, Caroline; Behrens, Sebastian; Jørgensen, Bo Barker; Kappler, Andreas

    2015-12-18

    Iron is abundant in sediments, where it can be biogeochemically cycled between its divalent and trivalent redox states. The neutrophilic microbiological Fe cycle involves Fe(III)-reducing and three different physiological groups of Fe(II)-oxidizing microorganisms, i.e., microaerophilic, anoxygenic phototrophic, and nitrate-reducing Fe(II) oxidizers. However, it is unknown whether all three groups coexist in one habitat and how they are spatially distributed in relation to gradients of O2, light, nitrate, and Fe(II). We examined two coastal marine sediments in Aarhus Bay, Denmark, by cultivation and most probable number (MPN) studies for Fe(II) oxidizers and Fe(III) reducers and by quantitative-PCR (qPCR) assays for microaerophilic Fe(II) oxidizers. Our results demonstrate the coexistence of all three metabolic types of Fe(II) oxidizers and Fe(III) reducers. In qPCR, microaerophilic Fe(II) oxidizers (Zetaproteobacteria) were present with up to 3.2 × 10(6) cells g dry sediment(-1). In MPNs, nitrate-reducing Fe(II) oxidizers, anoxygenic phototrophic Fe(II) oxidizers, and Fe(III) reducers reached cell numbers of up to 3.5 × 10(4), 3.1 × 10(2), and 4.4 × 10(4) g dry sediment(-1), respectively. O2 and light penetrated only a few millimeters, but the depth distribution of the different iron metabolizers did not correlate with the profile of O2, Fe(II), or light. Instead, abundances were homogeneous within the upper 3 cm of the sediment, probably due to wave-induced sediment reworking and bioturbation. In microaerophilic Fe(II)-oxidizing enrichment cultures, strains belonging to the Zetaproteobacteria were identified. Photoferrotrophic enrichments contained strains related to Chlorobium and Rhodobacter; the nitrate-reducing Fe(II) enrichments contained strains related to Hoeflea and Denitromonas. This study shows the coexistence of all three types of Fe(II) oxidizers in two near-shore marine environments and the potential for competition and interrelationships between

  14. Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

    USGS Publications Warehouse

    Balci, N.; Bullen, T.D.; Witte-Lien, K.; Shanks, Wayne C.; Motelica, M.; Mandernack, K.W.

    2006-01-01

    Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments

  15. Ligand-Enhanced Abiotic Iron Oxidation and the Effects of Chemical versus Biological Iron Cycling in Anoxic Environments

    PubMed Central

    2013-01-01

    This study introduces a newly isolated, genetically tractable bacterium (Pseudogulbenkiania sp. strain MAI-1) and explores the extent to which its nitrate-dependent iron-oxidation activity is directly biologically catalyzed. Specifically, we focused on the role of iron chelating ligands in promoting chemical oxidation of Fe(II) by nitrite under anoxic conditions. Strong organic ligands such as nitrilotriacetate and citrate can substantially enhance chemical oxidation of Fe(II) by nitrite at circumneutral pH. We show that strain MAI-1 exhibits unambiguous biological Fe(II) oxidation despite a significant contribution (∼30–35%) from ligand-enhanced chemical oxidation. Our work with the model denitrifying strain Paracoccus denitrificans further shows that ligand-enhanced chemical oxidation of Fe(II) by microbially produced nitrite can be an important general side effect of biological denitrification. Our assessment of reaction rates derived from literature reports of anaerobic Fe(II) oxidation, both chemical and biological, highlights the potential competition and likely co-occurrence of chemical Fe(II) oxidation (mediated by microbial production of nitrite) and truly biological Fe(II) oxidation. PMID:23402562

  16. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths.

    PubMed

    Kunoh, Tatsuki; Hashimoto, Hideki; McFarlane, Ian R; Hayashi, Naoaki; Suzuki, Tomoko; Taketa, Eisuke; Tamura, Katsunori; Takano, Mikio; El-Naggar, Mohamed Y; Kunoh, Hitoshi; Takada, Jun

    2016-06-03

    Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II) to Fe(III) and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II) concentrations, Fe(III) precipitates visibly formed immediately after addition of Fe(II) to the medium, suggesting prompt abiotic oxidation of Fe(II) to Fe(III). Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III) was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II) medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter), while those in the Fe(III) medium were composed of large, aggregated particles (≥3 µm diameter) with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved) of Fe encrustation of the Leptothrix sheaths.

  17. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

    PubMed Central

    Kunoh, Tatsuki; Hashimoto, Hideki; McFarlane, Ian R.; Hayashi, Naoaki; Suzuki, Tomoko; Taketa, Eisuke; Tamura, Katsunori; Takano, Mikio; El-Naggar, Mohamed Y.; Kunoh, Hitoshi; Takada, Jun

    2016-01-01

    Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II) to Fe(III) and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II) concentrations, Fe(III) precipitates visibly formed immediately after addition of Fe(II) to the medium, suggesting prompt abiotic oxidation of Fe(II) to Fe(III). Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III) was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II) medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter), while those in the Fe(III) medium were composed of large, aggregated particles (≥3 µm diameter) with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved) of Fe encrustation of the Leptothrix sheaths. PMID:27271677

  18. In situ Cr(VI) reduction within coarse-textured, oxide-coated soil and aquifer systems using Fe(II) solutions

    SciTech Connect

    Seaman, J.C.; Bertsch, P.M.; Schwallie, L.

    1999-03-15

    Batch and column techniques were used to evaluate the in situ Cr(VI) reduction and immobilization using Fe(II) solutions within the sediments of the Atlantic Coastal Plain. Remediation treatments included Cr-free groundwater and buffered and unbuffered Fe(II) solutions as either FeCl{sub 2} and FeSO{sub 4}. The slow release of Cr(VI) from the Fe-oxide rich subsurface sediment following exposure to Cr-free solutions indicated that simple pump-and-treat procedures would require extended operation time to meet regulatory standards. In situ reduction was confirmed by the loss of Cr(VI) and Fe(II) from solution and a drop in pH compared to control systems. Batch and column-effluent Cr(VI) decreased with increasing Fe(II), generally failing below detection limits as the persistence of Fe(II) occurred. However, Cr{sub Dissolved}, presumably Cr(III), exceeded regulatory limits due to the low pH ({approx}3.0) induced by oxidation and hydrolysis of Fe(II). Acetate-buffered Fe(II) solutions maintained an elevated pH in the presence of Cr(VI) reduction, making the treatment effective at lowering Cr{sub Dissolved} in batch evaluations. Acetate increased Cr(VI) mobility in columns ahead of the reactive Fe(II) front, suggesting that in situ reduction using soluble chemical additives may be somewhat ineffective due to the enhanced migration of Cr, either Cr(III) or Cr(VI), induced by the treatment solution.

  19. A dual nitrite isotopic investigation of chemodenitrification by mineral-associated Fe(II) and its production of nitrous oxide

    NASA Astrophysics Data System (ADS)

    Grabb, Kalina C.; Buchwald, Carolyn; Hansel, Colleen M.; Wankel, Scott D.

    2017-01-01

    Under anaerobic conditions, the environmental reduction of nitrate (NO3-) and nitrite (NO2-) to more reduced forms is widely regarded as being microbially catalyzed. However, the chemical reduction of oxidized nitrogen species by reduced iron (Fe(II)), whether mineral-bound or surface-associated, may also occur under environmentally relevant conditions. Here we examine the nitrogen (N) and oxygen (O) stable isotope dynamics of the chemical reduction of NO2- by mineral associated Fe(II) (chemodenitrification) and its production of the potent greenhouse gas nitrous oxide (N2O). By shedding light on factors controlling kinetics of the reaction and its corresponding dual isotopic expression in the reactant NO2- and product N2O, this work contributes to a growing body of work aiming to improve our ability to identify chemodenitrification in the environment. Consistent with previous studies, we find that while homogenous reactions between aqueous NO2- and Fe(II) were kinetically slow, heterogeneous reactions involving Fe(II)-containing minerals often catalyzed considerable nitrite loss. In particular, rapid reduction of NO2- was catalyzed by the Fe-rich smectite clay mineral nontronite as well as the mixed Fe(II)-Fe(III) oxyhydroxide phase green rust. These minerals serve as both a source of reduced iron within the mineral structure as well as a surface for promoting the reactivity of Fe(II). However, even in the presence of aqueous Fe(II), experiments with low-Fe and non-Fe containing minerals showed little to no NO2- loss, perhaps suggesting a more dominant role for structural iron during chemodenitrification. When catalyzed by nontronite and green rust, N and O isotope effects for chemodenitrification (15εcDNF and 18εcDNF) ranged from 2 to 11‰ and 4 to 10‰, respectively, with lower values generally observed at higher reaction rates. Higher reaction rates were also linked to higher molar yields of N2O (up to 31%), highlighting a strong potential for

  20. Coexistence of Fe(II)- and Mn(II)-oxidizing bacteria govern the formation of deep sea umber deposits

    NASA Astrophysics Data System (ADS)

    Peng, Xiaotong; Ta, Kaiwen; Chen, Shun; Zhang, Lijuan; Xu, Hengchao

    2015-11-01

    The genesis of umber deposits has remained controversial for several decades. Recently, microbial Fe(II) oxidation associated with low-temperature diffuse venting has been identified as a key process for the formation of umber deposits, but the exact biogeochemical mechanisms involved to the precipitation of Mn oxides in umber deposits still remain unknown. Here, we used nano secondary ion mass spectrometer, synchrotron-based X-ray absorption spectroscopy, electron microscopy, and molecular techniques to demonstrate the coexistence of two types of metal-oxidizing bacteria within deep-sea hydrothermal umber deposits at the South Mid-Atlantic Ridge, where we found unique spheroids composed of biogenic Fe oxyhydroxides and Mn oxides in the deposits. Our data show that Fe oxyhydroxides and Mn oxides are metabolic by-products of lithotrophic Fe(II)-oxidizing bacteria and heterotrophic Mn(II)-oxidizing bacteria, respectively. The hydrothermal vents fuel lithotrophic microorganisms, which constitute a trophic base that might support the activities of heterogenic Mn(II)-oxidizing bacteria. The biological origin of umber deposits shed light on the importance of geomicrobiological interaction in triggering the formation of metalliferous deposits, with important implications for the generation of submarine Mn deposits and crusts.

  1. Similarity of the Surface Reactivity of Hydrous Ferric Oxide and Hematite: Sorption and Redox of U(VI) and Fe(II)

    SciTech Connect

    Je-Hun Jang; Dempsey, Brian A.; Burgos, William D.; Yeh, George; Roden, Eric

    2004-03-17

    Hydrous Ferric Oxide (HFO) vs. Hematite--Thermodynamically distinctive bulk phases, but the surfaces could be similar due to hydration of the interface. Hypothesis--The surface of HFO is energetically similar to the surface of hematite. Objective--Compare the reactions of HFO and hematite with U(VI) and Fe(II). Experimental--The reactions of interests were (1) preparation of sub-micron hematite, (2) sorption of U(VI), and (3) redox of U(VI) and Fe(II) with HFO or hematite.

  2. Hydroxyl radical production by H2O2-mediated oxidation of Fe(II) complexed by Suwannee River fulvic acid under circumneutral freshwater conditions.

    PubMed

    Miller, Christopher J; Rose, Andrew L; Waite, T David

    2013-01-15

    The Fenton reaction, the oxidation of ferrous iron by hydrogen peroxide (H(2)O(2)), is typically assumed to be a source of hydroxyl radical (HO(•)) in natural systems, however, formation of HO(•) in this process is strongly dependent upon solution pH and the ligand environment, with HO(•) only formed when Fe(II) is organically complexed. In this study we examine the formation of HO(•) when Fe(II)-NOM complexes are oxidized by H(2)O(2) using phthalhydrazide as a probe for HO(•). We demonstrate that HO(•) formation can be quantitatively described using a kinetic model that assumes HO(•) formation occurs solely from the reaction of Fe(II)-NOM complexes with H(2)O(2), even though this reaction is sufficiently slow to play only a negligible role in the overall oxidation rate of total Fe(II). As such, NOM is seen to play a dual role in circumneutral natural systems in stabilizing Fe(II) toward oxidation by H(2)O(2) while enabling the formation of HO(•) through this oxidation process.

  3. Role of heterogeneous precipitation in determining the nature of products formed on oxidation of Fe(II) in seawater containing natural organic matter.

    PubMed

    Bligh, Mark W; Waite, T David

    2010-09-01

    A detailed kinetic model has been developed to describe the formation of the oxidation products, organically complexed Fe(III) and amorphous ferric oxide (AFO), on oxidation of Fe(II) in seawater containing Suwannee River fulvic acid (SRFA). Experimental data were collected using spectrophotometric detection of the Fe(III)-SRFA complex for a range of initial concentrations of Fe(II) and SRFA. Initial sensitivity analysis identified rate constants to which the model was most sensitive including those for heterogeneous precipitation of AFO and Fe(II)-SRFA formation and dissociation which to date have only been determined with a high degree of uncertainty. Using these rate constants as fitting parameters, an accurate fit to the experimental data could be obtained using a kinetic model describing key processes. However, reasonable fits could only be achieved with the inclusion of the heterogeneous precipitation reaction suggesting the importance of this reaction in determining the outcome of oxidation in the presence of organic ligands. The rate constants for Fe(II)-SRFA formation and dissociation were highly correlated and could not be determined uniquely, however their ratio revealed a stability constant of approximately 10(5), 3 orders of magnitude higher than previously reported. The fitted model also suggested that a complex interaction between Fe(II) and SRFA in the initial stages of the oxidation process determines the pathway of Fe(III)-SRFA formation.

  4. Reduction of U(VI) by Fe(II) in the presence of hydrous ferric oxide and hematite: effects of solid transformation, surface coverage, and humic acid.

    PubMed

    Jang, Je-Hun; Dempsey, Brian A; Burgos, William D

    2008-04-01

    Fe(II) was added to U(VI)-spiked suspensions of hydrous ferric oxide (HFO) or hematite to compare the redox behaviors of uranium in the presence of two different Fe(III) (oxyhydr)oxides. Experiments were conducted with low or high initial sorption density of U(VI) and in the presence or absence of humic acid (HA). About 80% of U(VI) was reduced within 3 days for low sorbed U(VI) conditions, with either hematite or HFO. The {Fe(3+)} in the low U(VI) experiments at 3 days, based on measured Fe(II) and U(VI) and the assumed presence of amorphous UO(2(s)), was consistent with control by HFO for either initial Fe(III) (oxyhydr)oxide. After about 1 day, partial re-oxidation to U(VI) was observed in the low sorbed U(VI) experiments in the absence of HA, without equivalent increase of dissolved U(VI). No reduction of U(VI) was observed in the high sorbed U(VI) experiments; it was hypothesized that the reduction required sorption proximity of U(VI) and Fe(II). Addition of 5mg/L HA slowed the reduction with HFO and had less effect with hematite. Mössbauer spectroscopy (MBS) of (57)Fe(II)-enriched samples identified the formation of goethite, hematite, and non-stoichiometric magnetite from HFO, and the formation of HFO, hydrated hematite, and non-stoichiometric magnetite from hematite.

  5. Abiotic selenium redox transformations in the presence of Fe(II,III) oxides

    SciTech Connect

    Myneni, S.C.B.; Tokunaga, T.K.; Brown, G.E. Jr.

    1997-11-07

    Many suboxic sediments and soils contain an Fe(II,III) oxide called green rust. Spectroscopic evidence showed that selenium reduces from an oxidation state of +VI to 0 in the presence of green rust at rates comparable with those found in sediments. Selenium speciation was different in solid and aqueous phases. These redox reactions represent an abiotic pathway for selenium cycling in natural environments, which has previously been considered to be mediated principally by microorganisms. Similar green rust-mediated abiotic redox reactions are likely to be involved in the mobility of several other trace elements and contaminants in the environment. 27 refs., 3 figs., 2 tabs.

  6. Improvement of biological nitrogen removal with nitrate-dependent Fe(II) oxidation bacterium Aquabacterium parvum B6 in an up-flow bioreactor for wastewater treatment.

    PubMed

    Zhang, Xiaoxin; Li, Ang; Szewzyk, Ulrich; Ma, Fang

    2016-11-01

    Aquabacterium parvum strain B6 exhibited efficient nitrate-dependent Fe(II) oxidation ability using nitrate as an electron acceptor. A continuous up-flow bioreactor that included an aerobic and an anoxic section was constructed, and strain B6 was added to the bioreactor as inocula to explore the application of microbial nitrate-dependent Fe(II) oxidizing (NDFO) efficiency in wastewater treatment. The maximum NRE (anoxic section) and TNRE of 46.9% and 79.7%, respectively, could be obtained at a C/N ratio of 5.3:1 in the influent with HRT of 17. Meanwhile, the taxonomy composition of the reactor was assessed, as well. The NDFO metabolism of strain B6 could be expected because of its relatively dominant position in the anoxic section, whereas potential heterotrophic nitrification and aerobic denitrification developed into the prevailing status in the aerobic section after 50days of continuous operation.

  7. A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

    NASA Astrophysics Data System (ADS)

    Taylor, S. D.; Marcano, M. C.; Becker, U.

    2017-01-01

    ) to travel through the hematite surface and reach U(VI). The progression and extent of ET occurring on the semiconducting hematite (0 0 1) surface via the proximity effect depends on the electronic properties of the surface. ET between the spatially separated U(VI) and Fe(II) occurs most readily when orbitals between the Fe and U adsorbates overlap with those of neighboring O and Fe ions at the hematite surface, as shown by calculations without the Hubbard U correction. Analyses of the spins densities confirm that the U and Fe adsorbates were reduced and oxidized, respectively, (acquiring 0.33 μB and 0.11-0.20 μB, respectively), while Fe cations at the hematite surface were reduced (losing ⩽0.6 μB). If electrons are highly localized, the amount of orbital mixing and electronic coupling through the hematite surface decreases and in turn leads to a lower degree of spin transfer, as predicted by calculations with the Hubbard U correction. Thus, the proximity effect is a potential mechanism on semiconducting surfaces facilitating surface-mediated redox reactions, although its significance varies depending on the electronic properties and subsequent charge-carrying ability of the surface. These results provide insight into ET pathways and mechanisms on insulating Al- and semiconducting Fe oxide surfaces influencing the reduction U(VI) by Fe(II) that may subsequently limit uranium's transport in the subsurface.

  8. Hydrogen peroxide priming modulates abiotic oxidative stress tolerance: insights from ROS detoxification and scavenging

    PubMed Central

    Hossain, Mohammad A.; Bhattacharjee, Soumen; Armin, Saed-Moucheshi; Qian, Pingping; Xin, Wang; Li, Hong-Yu; Burritt, David J.; Fujita, Masayuki; Tran, Lam-Son P.

    2015-01-01

    Plants are constantly challenged by various abiotic stresses that negatively affect growth and productivity worldwide. During the course of their evolution, plants have developed sophisticated mechanisms to recognize external signals allowing them to respond appropriately to environmental conditions, although the degree of adjustability or tolerance to specific stresses differs from species to species. Overproduction of reactive oxygen species (ROS; hydrogen peroxide, H2O2; superoxide, O2⋅-; hydroxyl radical, OH⋅ and singlet oxygen, 1O2) is enhanced under abiotic and/or biotic stresses, which can cause oxidative damage to plant macromolecules and cell structures, leading to inhibition of plant growth and development, or to death. Among the various ROS, freely diffusible and relatively long-lived H2O2 acts as a central player in stress signal transduction pathways. These pathways can then activate multiple acclamatory responses that reinforce resistance to various abiotic and biotic stressors. To utilize H2O2 as a signaling molecule, non-toxic levels must be maintained in a delicate balancing act between H2O2 production and scavenging. Several recent studies have demonstrated that the H2O2-priming can enhance abiotic stress tolerance by modulating ROS detoxification and by regulating multiple stress-responsive pathways and gene expression. Despite the importance of the H2O2-priming, little is known about how this process improves the tolerance of plants to stress. Understanding the mechanisms of H2O2-priming-induced abiotic stress tolerance will be valuable for identifying biotechnological strategies to improve abiotic stress tolerance in crop plants. This review is an overview of our current knowledge of the possible mechanisms associated with H2O2-induced abiotic oxidative stress tolerance in plants, with special reference to antioxidant metabolism. PMID:26136756

  9. Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

    NASA Astrophysics Data System (ADS)

    Gonzalez, Julia; Peña, Jasquelin

    2016-04-01

    Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the

  10. Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

    USGS Publications Warehouse

    Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

    2007-01-01

    To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2

  11. In vivo role of nitric oxide in plant response to abiotic and biotic stress.

    PubMed

    Shi, Hai-Tao; Li, Rong-Jun; Cai, Wei; Liu, Wen; Fu, Zheng-Wei; Lu, Ying-Tang

    2012-03-01

    Over the past few years, nitric oxide (NO) has emerged as an important regulator in many physiological events, especially in response to abiotic and biotic stress. However, the roles of NO were mostly derived from pharmacological studies or the mutants impaired NO synthesis unspecifically. In our recent study, we highlighted a novel strategy by expressing the rat neuronal NO synthase (nNOS) in Arabidopsis to explore the in vivo role of NO. Our results suggested that plants were able to perform well in the constitutive presence of nNOS, and provided a new class of plant experimental system with specific in vivo NO release. Furthermore, our findings also confirmed that the in vivo NO is essential for most of environmental abiotic stresses and disease resistance against pathogen infection. Proper level of NO may be necessary and beneficial, not only in plant response to the environmental abiotic stress, but also to biotic stress.

  12. Applicability of anaerobic nitrate-dependent Fe(II) oxidation to microbial enhanced oil recovery (MEOR).

    PubMed

    Zhu, Hongbo; Carlson, Han K; Coates, John D

    2013-08-06

    Microbial processes that produce solid-phase minerals could be judiciously applied to modify rock porosity with subsequent alteration and improvement of floodwater sweep in petroleum reservoirs. However, there has been little investigation of the application of this to enhanced oil recovery (EOR). Here, we investigate a unique approach of altering reservoir petrology through the biogenesis of authigenic rock minerals. This process is mediated by anaerobic chemolithotrophic nitrate-dependent Fe(II)-oxidizing microorganisms that precipitate iron minerals from the metabolism of soluble ferrous iron (Fe(2+)) coupled to the reduction of nitrate. This mineral biogenesis can result in pore restriction and reduced pore throat diameter. Advantageously and unlike biomass plugs, these biominerals are not susceptible to pressure or thermal degradation. Furthermore, they do not require continual substrate addition for maintenance. Our studies demonstrate that the biogenesis of insoluble iron minerals in packed-bed columns results in effective hydrology alteration and homogenization of heterogeneous flowpaths upon stimulated microbial Fe(2+) biooxidation. We also demonstrate almost 100% improvement in oil recovery from hydrocarbon-saturated packed-bed columns as a result of this metabolism. These studies represent a novel departure from traditional microbial EOR approaches and indicate the potential for nitrate-dependent Fe(2+) biooxidation to improve volumetric sweep efficiency and enhance both the quality and quantity of oil recovered.

  13. Suboxic Deposition of Ferric Iron by Bacteria in Opposing Gradients of Fe(II) and Oxygen at Circumneutral pH

    PubMed Central

    Sobolev, Dmitri; Roden, Eric E.

    2001-01-01

    The influence of lithotrophic Fe(II)-oxidizing bacteria on patterns of ferric oxide deposition in opposing gradients of Fe(II) and O2 was examined at submillimeter resolution by use of an O2 microelectrode and diffusion microprobes for iron. In cultures inoculated with lithotrophic Fe(II)-oxidizing bacteria, the majority of Fe(III) deposition occurred below the depth of O2 penetration. In contrast, Fe(III) deposition in abiotic control cultures occurred entirely within the aerobic zone. The diffusion microprobes revealed the formation of soluble or colloidal Fe(III) compounds during biological Fe(II) oxidation. The presence of mobile Fe(III) in diffusion probes from live cultures was verified by washing the probes in anoxic water, which removed ca. 70% of the Fe(III) content of probes from live cultures but did not alter the Fe(III) content of probes from abiotic controls. Measurements of the amount of Fe(III) oxide deposited in the medium versus the probes indicated that ca. 90% of the Fe(III) deposited in live cultures was formed biologically. Our findings show that bacterial Fe(II) oxidation is likely to generate reactive Fe(III) compounds that can be immediately available for use as electron acceptors for anaerobic respiration and that biological Fe(II) oxidation may thereby promote rapid microscale Fe redox cycling at aerobic-anaerobic interfaces. PMID:11229928

  14. Chemiluminescent examination of abiotic oxidative stress of watercress.

    PubMed

    Beals, Christopher; Byl, Thomas

    2013-06-20

    Watercress (Nasturtium officinale) is an aquatic plant that readily bioaccumulates heavy metals that may be found in contaminated aquatic systems. Toxic effects of contaminants on the physiological processes cause changes in oxidase enzymatic activity in watercress, which can be measured using a luminometer. The luminometer uses the reaction produced when peroxidases break down hydrogen peroxide into water and an oxygen radical. The resulting oxyradical binds to and oxidizes phenolic groups producing a measureable luminescent reaction. N. officinale plants were exposed to three different concentrations of heavy metals including lead, nickel, copper, and manganese for 24, 48, and 72 hour exposures. Aquatic exposure to the four heavy metals caused a significant increase in oxidative enzyme production. Fluorometric and morphometric measurements were also conducted in order to compare plant stress to the oxidative enzyme analyses. Fluorometric measurements performed on plants stressed by exposure to heavy metals revealed no significant decreases in photosystem II efficiency. Morphometric measurements of root length showed decreased root growth resulting from exposures to nickel, copper, and manganese. Environ Toxicol Chem © 2013 SETAC.

  15. Chemiluminescent examination of abiotic oxidative stress of watercress.

    PubMed

    Beals, Christopher; Byl, Thomas

    2014-04-01

    Watercress (Nasturtium officinale) is an aquatic plant that readily bioaccumulates heavy metals that may be found in contaminated aquatic systems. Toxic effects of contaminants on the physiological processes cause changes in oxidase enzymatic activity in watercress, which can be measured with a luminometer. The luminometer uses the reaction produced when peroxidases break down hydrogen peroxide into water and an oxygen radical. The resulting oxyradical binds to and oxidizes phenolic groups, producing a measureable luminescent reaction. Nasturtium officinale plants were exposed to 3 different concentrations of heavy metals, including lead, nickel, copper, and manganese for 24 h, 48 h, and 72 h. Aquatic exposure to the 4 heavy metals caused a significant increase in oxidative enzyme production. Fluorometric and morphometric measurements were also conducted to compare plant stress with the oxidative enzyme analyses. Fluorometric measurements performed on plants stressed by exposure to heavy metals revealed no significant decreases in photosystem II efficiency. Morphometric measurements of root length showed decreased root growth resulting from exposures to Ni, Cu, and Mn.

  16. Influence of organics and silica on Fe(II) oxidation rates and cell-mineral aggregate formation by the green-sulfur Fe(II)-oxidizing bacterium Chlorobium ferrooxidans KoFox - Implications for Fe(II) oxidation in ancient oceans

    NASA Astrophysics Data System (ADS)

    Gauger, Tina; Byrne, James M.; Konhauser, Kurt O.; Obst, Martin; Crowe, Sean; Kappler, Andreas

    2016-06-01

    Most studies on microbial phototrophic Fe(II) oxidation (photoferrotrophy) have focused on purple bacteria, but recent evidence points to the importance of green-sulfur bacteria (GSB). Their recovery from modern ferruginous environments suggests that these photoferrotrophs can offer insights into how their ancient counterparts grew in Archean oceans at the time of banded iron formation (BIF) deposition. It is unknown, however, how Fe(II) oxidation rates, cell-mineral aggregate formation, and Fe-mineralogy vary under environmental conditions reminiscent of the geological past. To address this, we studied the Fe(II)-oxidizer Chlorobium ferrooxidans KoFox, a GSB living in co-culture with the heterotrophic Geospirillum strain KoFum. We investigated the mineralogy of Fe(III) metabolic products at low/high light intensity, and in the presence of dissolved silica and/or fumarate. Silica and fumarate influenced the crystallinity and particle size of the produced Fe(III) minerals. The presence of silica also enhanced Fe(II) oxidation rates, especially at high light intensities, potentially by lowering Fe(II)-toxicity to the cells. Electron microscopic imaging showed no encrustation of either KoFox or KoFum cells with Fe(III)-minerals, though weak associations were observed suggesting co-sedimentation of Fe(III) with at least some biomass via these aggregates, which could support diagenetic Fe(III)-reduction. Given that GSB are presumably one of the most ancient photosynthetic organisms, and pre-date cyanobacteria, our findings, on the one hand, strengthen arguments for photoferrotrophic activity as a likely mechanism for BIF deposition on a predominantly anoxic early Earth, but, on the other hand, also suggest that preservation of remnants of Fe(II)-oxidizing GSB as microfossils in the rock record is unlikely.

  17. Accumulation of Flavonols over Hydroxycinnamic Acids Favors Oxidative Damage Protection under Abiotic Stress

    PubMed Central

    Martinez, Vicente; Mestre, Teresa C.; Rubio, Francisco; Girones-Vilaplana, Amadeo; Moreno, Diego A.; Mittler, Ron; Rivero, Rosa M.

    2016-01-01

    Efficient detoxification of reactive oxygen species (ROS) is thought to play a key role in enhancing the tolerance of plants to abiotic stresses. Although multiple pathways, enzymes, and antioxidants are present in plants, their exact roles during different stress responses remain unclear. Here, we report on the characterization of the different antioxidant mechanisms of tomato plants subjected to heat stress, salinity stress, or a combination of both stresses. All the treatments applied induced an increase of oxidative stress, with the salinity treatment being the most aggressive, resulting in plants with the lowest biomass, and the highest levels of H2O2 accumulation, lipid peroxidation, and protein oxidation. However, the results obtained from the transcript expression study and enzymatic activities related to the ascorbate-glutathione pathway did not fully explain the differences in the oxidative damage observed between salinity and the combination of salinity and heat. An exhaustive metabolomics study revealed the differential accumulation of phenolic compounds depending on the type of abiotic stress applied. An analysis at gene and enzyme levels of the phenylpropanoid metabolism concluded that under conditions where flavonols accumulated to a greater degree as compared to hydroxycinnamic acids, the oxidative damage was lower, highlighting the importance of flavonols as powerful antioxidants, and their role in abiotic stress tolerance. PMID:27379130

  18. Accumulation of Flavonols over Hydroxycinnamic Acids Favors Oxidative Damage Protection under Abiotic Stress.

    PubMed

    Martinez, Vicente; Mestre, Teresa C; Rubio, Francisco; Girones-Vilaplana, Amadeo; Moreno, Diego A; Mittler, Ron; Rivero, Rosa M

    2016-01-01

    Efficient detoxification of reactive oxygen species (ROS) is thought to play a key role in enhancing the tolerance of plants to abiotic stresses. Although multiple pathways, enzymes, and antioxidants are present in plants, their exact roles during different stress responses remain unclear. Here, we report on the characterization of the different antioxidant mechanisms of tomato plants subjected to heat stress, salinity stress, or a combination of both stresses. All the treatments applied induced an increase of oxidative stress, with the salinity treatment being the most aggressive, resulting in plants with the lowest biomass, and the highest levels of H2O2 accumulation, lipid peroxidation, and protein oxidation. However, the results obtained from the transcript expression study and enzymatic activities related to the ascorbate-glutathione pathway did not fully explain the differences in the oxidative damage observed between salinity and the combination of salinity and heat. An exhaustive metabolomics study revealed the differential accumulation of phenolic compounds depending on the type of abiotic stress applied. An analysis at gene and enzyme levels of the phenylpropanoid metabolism concluded that under conditions where flavonols accumulated to a greater degree as compared to hydroxycinnamic acids, the oxidative damage was lower, highlighting the importance of flavonols as powerful antioxidants, and their role in abiotic stress tolerance.

  19. Abiotic nitrous oxide emission from the hypersaline Don Juan Pond in Antarctica

    NASA Astrophysics Data System (ADS)

    Samarkin, Vladimir A.; Madigan, Michael T.; Bowles, Marshall W.; Casciotti, Karen L.; Priscu, John C.; McKay, Christopher P.; Joye, Samantha B.

    2010-05-01

    Nitrous oxide is a potent atmospheric greenhouse gas that contributes to ozone destruction. Biological processes such as nitrification and denitrification are thought to drive nitrous oxide production in soils, which comprise the largest source of nitrous oxide to the atmosphere. Here we present measurements of the concentration and isotopic composition of nitrous oxide in soil pore spaces in samples taken near Don Juan Pond, a metabolically dormant hypersaline pond in Southern Victoria Land, Antarctica in 2006, 2007 and 2008, together with in situ fluxes of nitrous oxide from the soil to the atmosphere. We find fluxes of nitrous oxide that rival those measured in fertilized tropical soils. Laboratory experiments-in which nitrite-rich brine was reacted with a variety of minerals containing Fe(II)-reveal a new mechanism of abiotic water-rock reaction that could support nitrous oxide fluxes at Don Juan Pond. Our findings illustrate a dynamic and unexpected link between the geosphere and atmosphere.

  20. Coupled biotic-abiotic Mn(II) oxidation pathway mediates the formation and structural evolution of biogenic Mn oxides

    NASA Astrophysics Data System (ADS)

    Learman, D. R.; Wankel, S. D.; Webb, S. M.; Martinez, N.; Madden, A. S.; Hansel, C. M.

    2011-10-01

    Manganese (Mn) oxides are among the strongest oxidants and sorbents in the environment, impacting the transport and speciation of metals, cycling of carbon, and flow of electrons within soils and sediments. The oxidation of Mn(II) to Mn(III/IV) oxides has been primarily attributed to biological processes, due in part to the faster rates of bacterial Mn(II) oxidation compared to observed mineral-induced and other abiotic rates. Here we explore the reactivity of biogenic Mn oxides formed by a common marine bacterium ( Roseobacter sp. AzwK-3b), which has been previously shown to oxidize Mn(II) via the production of extracellular superoxide. Oxidation of Mn(II) by superoxide results in the formation of highly reactive colloidal birnessite with hexagonal symmetry. The colloidal oxides induce the rapid oxidation of Mn(II), with dramatically accelerated rates in the presence of organics, presumably due to mineral surface-catalyzed organic radical generation. Mn(II) oxidation by the colloids is further accelerated in presence of both organics and light, implicating reactive oxygen species in aiding abiotic oxidation. Indeed, the enhancement of Mn(II) oxidation is negated when the colloids are reacted with Mn(II) in the presence of superoxide dismutase, an enzyme that scavenges the reactive oxygen species (ROS) superoxide. The reactivity of the colloidal phase is short-lived due to the rapid evolution of the birnessite from hexagonal to pseudo-orthogonal symmetry. The secondary particulate triclinic birnessite phase exhibits a distinct lack of Mn(II) oxidation and subsequent Mn oxide formation. Thus, the evolution of initial reactive hexagonal birnessite to non-reactive triclinic birnessite imposes the need for continuous production of new colloidal hexagonal particles for Mn(II) oxidation to be sustained, illustrating an intimate dependency of enzymatic and mineral-based reactions in Mn(II) oxidation. Further, the coupled enzymatic and mineral-induced pathways are linked

  1. Abiotic and biotic factors responsible for antimonite oxidation in Agrobacterium tumefaciens GW4

    PubMed Central

    Li, Jingxin; Yang, Birong; Shi, Manman; Yuan, Kai; Guo, Wei; Wang, Qian; Wang, Gejiao

    2017-01-01

    Antimonite [Sb(III)]-oxidizing bacteria can transform the toxic Sb(III) into the less toxic antimonate [Sb(V)]. Recently, the cytoplasmic Sb(III)-oxidase AnoA and the periplasmic arsenite [As(III)] oxidase AioAB were shown to responsible for bacterial Sb(III) oxidation, however, disruption of each gene only partially decreased Sb(III) oxidation efficiency. This study showed that in Agrobacterium tumefaciens GW4, Sb(III) induced cellular H2O2 content and H2O2 degradation gene katA. Gene knock-out/complementation of katA, anoA, aioA and anoA/aioA and Sb(III) oxidation and growth experiments showed that katA, anoA and aioA were essential for Sb(III) oxidation and resistance and katA was also essential for H2O2 resistance. Furthermore, linear correlations were observed between cellular H2O2 and Sb(V) content in vivo and chemical H2O2 and Sb(V) content in vitro (R2 = 0.93 and 0.94, respectively). These results indicate that besides the biotic factors, the cellular H2O2 induced by Sb(III) also catalyzes bacterial Sb(III) oxidation as an abiotic oxidant. The data reveal a novel mechanism that bacterial Sb(III) oxidation is associated with abiotic (cellular H2O2) and biotic (AnoA and AioAB) factors and Sb(III) oxidation process consumes cellular H2O2 which contributes to microbial detoxification of both Sb(III) and cellular H2O2. PMID:28252030

  2. Abiotic and biotic factors responsible for antimonite oxidation in Agrobacterium tumefaciens GW4

    NASA Astrophysics Data System (ADS)

    Li, Jingxin; Yang, Birong; Shi, Manman; Yuan, Kai; Guo, Wei; Wang, Qian; Wang, Gejiao

    2017-03-01

    Antimonite [Sb(III)]-oxidizing bacteria can transform the toxic Sb(III) into the less toxic antimonate [Sb(V)]. Recently, the cytoplasmic Sb(III)-oxidase AnoA and the periplasmic arsenite [As(III)] oxidase AioAB were shown to responsible for bacterial Sb(III) oxidation, however, disruption of each gene only partially decreased Sb(III) oxidation efficiency. This study showed that in Agrobacterium tumefaciens GW4, Sb(III) induced cellular H2O2 content and H2O2 degradation gene katA. Gene knock-out/complementation of katA, anoA, aioA and anoA/aioA and Sb(III) oxidation and growth experiments showed that katA, anoA and aioA were essential for Sb(III) oxidation and resistance and katA was also essential for H2O2 resistance. Furthermore, linear correlations were observed between cellular H2O2 and Sb(V) content in vivo and chemical H2O2 and Sb(V) content in vitro (R2 = 0.93 and 0.94, respectively). These results indicate that besides the biotic factors, the cellular H2O2 induced by Sb(III) also catalyzes bacterial Sb(III) oxidation as an abiotic oxidant. The data reveal a novel mechanism that bacterial Sb(III) oxidation is associated with abiotic (cellular H2O2) and biotic (AnoA and AioAB) factors and Sb(III) oxidation process consumes cellular H2O2 which contributes to microbial detoxification of both Sb(III) and cellular H2O2.

  3. Role of nitric oxide in tolerance of plants to abiotic stress.

    PubMed

    Siddiqui, Manzer H; Al-Whaibi, Mohamed H; Basalah, Mohammed O

    2011-07-01

    Nitric oxide (NO) has now gained significant place in plant science, mainly due to its properties (free radical, small size, no charge, short-lived, and highly diffusible across biological membranes) and multifunctional roles in plant growth, development, and regulation of remarkable spectrum of plant cellular mechanisms. In the last few years, the role of NO in tolerance of plants to abiotic stress has established much consideration. As it is evident from the present review, recent progress on NO potentiality in tolerance of plants to environmental stresses has been impressive. These investigations suggest that NO, itself, possesses antioxidant properties and might act as a signal in activating ROS-scavenging enzyme activities under abiotic stress. NO plays an important role in resistance to salt, drought, temperature (high and low), UV-B, and heavy metal stress. Rapidly increasing evidences indicate that NO is essentially involve in several physiological processes; however, there has been much disagreement regarding the mechanism(s) by which NO reduces abiotic stress.

  4. Hydrogen Peroxide Signaling in Plant Development and Abiotic Responses: Crosstalk with Nitric Oxide and Calcium.

    PubMed

    Niu, Lijuan; Liao, Weibiao

    2016-01-01

    Hydrogen peroxide (H2O2), as a reactive oxygen species, is widely generated in many biological systems. It has been considered as an important signaling molecule that mediates various physiological and biochemical processes in plants. Normal metabolism in plant cells results in H2O2 generation, from a variety of sources. Also, it is now clear that nitric oxide (NO) and calcium (Ca(2+)) function as signaling molecules in plants. Both H2O2 and NO are involved in plant development and abiotic responses. A wide range of evidences suggest that NO could be generated under similar stress conditions and with similar kinetics as H2O2. The interplay between H2O2 and NO has important functional implications to modulate transduction processes in plants. Moreover, close interaction also exists between H2O2 and Ca(2+) in response to development and abiotic stresses in plants. Cellular responses to H2O2 and Ca(2+) signaling systems are complex. There is quite a bit of interaction between H2O2 and Ca(2+) signaling in responses to several stimuli. This review aims to introduce these evidences in our understanding of the crosstalk among H2O2, NO, and Ca(2+) signaling which regulates plant growth and development, and other cellular and physiological responses to abiotic stresses.

  5. Hydrogen Peroxide Signaling in Plant Development and Abiotic Responses: Crosstalk with Nitric Oxide and Calcium

    PubMed Central

    Niu, Lijuan; Liao, Weibiao

    2016-01-01

    Hydrogen peroxide (H2O2), as a reactive oxygen species, is widely generated in many biological systems. It has been considered as an important signaling molecule that mediates various physiological and biochemical processes in plants. Normal metabolism in plant cells results in H2O2 generation, from a variety of sources. Also, it is now clear that nitric oxide (NO) and calcium (Ca2+) function as signaling molecules in plants. Both H2O2 and NO are involved in plant development and abiotic responses. A wide range of evidences suggest that NO could be generated under similar stress conditions and with similar kinetics as H2O2. The interplay between H2O2 and NO has important functional implications to modulate transduction processes in plants. Moreover, close interaction also exists between H2O2 and Ca2+ in response to development and abiotic stresses in plants. Cellular responses to H2O2 and Ca2+ signaling systems are complex. There is quite a bit of interaction between H2O2 and Ca2+ signaling in responses to several stimuli. This review aims to introduce these evidences in our understanding of the crosstalk among H2O2, NO, and Ca2+ signaling which regulates plant growth and development, and other cellular and physiological responses to abiotic stresses. PMID:26973673

  6. Improving abiotic reducing ability of hydrothermal biochar by low temperature oxidation under air.

    PubMed

    Xu, Yunfeng; Lou, Zhenjun; Yi, Peng; Chen, Junyu; Ma, Xianlong; Wang, Yang; Li, Mi; Chen, Wen; Liu, Qiang; Zhou, Jizhi; Zhang, Jia; Qian, Guangren

    2014-11-01

    Oxidized hydrothermal biochar was prepared by hydrothermal carbonization of Spartina alterniflora biomass (240°C for 4h) and subsequent oxidization (240°C for 10min) under air. Oxidized hydrochar achieved a Fe(III) reducing capacity of 2.15mmol/g at pH 2.0 with 120h, which is 1.2 times higher than un-oxidized hydrochar. Low temperature oxidization increases the contents of carboxyl and carbonyl groups on hydrochar surface. It is supposed that carboxyl groups provide bonding sites for soluble Fe species and carbonyl groups are responsible for Fe(3+) reduction. A Fenton-like process was established with Fe(2+) replaced by oxidized hydrochar and tested for methylene blue (MB) decoloration. Oxidized hydrochar achieved a MB decolorization (200mg/L, pH 7.0) rate of 99.21% within 3h and demonstrates prominent prevail over H2O2 absent control test. This study reveals low temperature oxidization is an effective way to improve and restore abiotic reducing ability of hydrochar.

  7. Terminal oxidase diversity and function in "Metallosphaera yellowstonensis": gene expression and protein modeling suggest mechanisms of Fe(II) oxidation in the sulfolobales.

    PubMed

    Kozubal, M A; Dlakic, M; Macur, R E; Inskeep, W P

    2011-03-01

    "Metallosphaera yellowstonensis" is a thermoacidophilic archaeon isolated from Yellowstone National Park that is capable of autotrophic growth using Fe(II), elemental S, or pyrite as electron donors. Analysis of the draft genome sequence from M. yellowstonensis strain MK1 revealed seven different copies of heme copper oxidases (subunit I) in a total of five different terminal oxidase complexes, including doxBCEF, foxABCDEFGHIJ, soxABC, and the soxM supercomplex, as well as a novel hypothetical two-protein doxB-like polyferredoxin complex. Other genes found in M. yellowstonensis with possible roles in S and or Fe cycling include a thiosulfate oxidase (tqoAB), a sulfite oxidase (som), a cbsA cytochrome b(558/566), several small blue copper proteins, and a novel gene sequence coding for a putative multicopper oxidase (Mco). Results from gene expression studies, including reverse transcriptase (RT) quantitative PCR (qPCR) of cultures grown autotrophically on either Fe(II), pyrite, or elemental S showed that the fox gene cluster and mco are highly expressed under conditions where Fe(II) is an electron donor. Metagenome sequence and gene expression studies of Fe-oxide mats confirmed the importance of fox genes (e.g., foxA and foxC) and mco under Fe(II)-oxidizing conditions. Protein modeling of FoxC suggests a novel lysine-lysine or lysine-arginine heme B binding domain, indicating that it is likely the cytochrome component of a heterodimer complex with foxG as a ferredoxin subunit. Analysis of mco shows that it encodes a novel multicopper blue protein with two plastocyanin type I copper domains that may play a role in the transfer of electrons within the Fox protein complex. An understanding of metabolic pathways involved in aerobic iron and sulfur oxidation in Sulfolobales has broad implications for understanding the evolution and niche diversification of these thermophiles as well as practical applications in fields such as bioleaching of trace metals from pyritic ores.

  8. Constraints on biotic and abiotic role in the formation of Fe-Si oxides from the PACMANUS hydrothermal field

    NASA Astrophysics Data System (ADS)

    Yang, Baoju; Zeng, Zhigang; Qi, Haiyan; Wang, Xiaoyuan; Ma, Yao; Rong, Kunbo

    2015-12-01

    Fe-Si oxide deposits were recovered from the PACMANUS (Papua New Guinea-Australia-Canada-Manus) hydrothermal field in Eastern Manus basin. Samples were loose and fragile. Optical and scanning electron microscopy showed that the samples had abundant rod-like or twisted filamentous and granular structures. Electron probe microanalysis revealed that these filaments and grains were mainly composed of Fe and Si. The presence of spherical grains on the surface of the filaments suggests the intergrowth of biotic and abiotic reactions. Biotic and abiotic kinetics competition always exists in the redox gradient. Based on the physico-chemical conditions of PACMANUS hydrothermal fluids, we calculated a strict abiotic oxidation rate of Fe2+ to Fe3+, which is approximately 0.0123 g/min. If the fluids had been erupting consistently and the concentration of Fe2+ was constant, 3.232 kg per year of Fe would be deposited in this vent. The amount of Fe oxides around the studied vent was larger than the amount determined by strict abiotic kinetic calculation. Bacteria may also play an important role in Fe oxidation. A mesh-like microenvironment constructed by biogenic filaments ensured adequate Fe2+ and low oxygen content for the growth of bacteria. Moreover, this structure promoted the deposition of abiotic Fe-Si oxides.

  9. Effect of aging on the structure and phosphate retention of Fe(III)-precipitates formed by Fe(II) oxidation in water

    NASA Astrophysics Data System (ADS)

    Senn, Anna-Caterina; Kaegi, Ralf; Hug, Stephan J.; Hering, Janet G.; Mangold, Stefan; Voegelin, Andreas

    2017-04-01

    Iron(III)-precipitates formed by Fe(II) oxidation in aqueous solutions affect the cycling and impact of Fe and other co-precipitated elements in environmental systems. Fresh Fe(III)-precipitates are metastable and their transformation into more stable phases during aging may result in the release of initially co-precipitated ions. Phosphate, silicate, Mg and Ca play key roles in determining the structure and composition of fresh Fe(III)-precipitates. Here we examine how these ions affect the structure and phosphate retention of Fe(III)-precipitates formed by oxidation of 0.5 mM dissolved Fe(II) at pH 7.0 after aging for 30 days at 40 °C. Iron K-edge X-ray absorption spectroscopy (XAS) shows that aged precipitates consist of the same structural units as fresh precipitates: Amorphous Fe(III)- or Ca-Fe(III)-phosphate, ferrihydrite, and poorly crystalline lepidocrocite. Mg, Ca, and dissolved phosphate stabilize (Ca-)Fe(III)-phosphate against transformation into ferrihydrite. Silicate further attenuates (Ca-)Fe(III)-phosphate transformation. The crystallinity of lepidocrocite formed in phosphate- and silicate-free solutions slightly increases during aging. The transformation of Fe(III)- and Ca-Fe(III)-phosphate into ferrihydrite and ongoing ferrihydrite crystallization during aging result in the release of co-precipitated phosphate. Dissolved Ca on the other hand limits phosphate concentrations to values consistent with solubility control by octacalciumphosphate. Owing to the combined effects of Ca and silicate, phosphate is most effectively retained by Fe(III)-precipitates formed and aged in Ca- and silicate-containing solutions. The results from this study contribute to an improved understanding of the formation and transformation of Fe(III)-precipitates and emphasize that the complexity of Fe(III)-precipitate dynamics in the presence of multiple interfering solutes must be considered when addressing their impact on major and trace elements in environmental systems.

  10. Protective function of nitric oxide on marine phytoplankton under abiotic stresses.

    PubMed

    Li, Peifeng; Liu, Chun-Ying; Liu, Huanhuan; Zhang, Qiang; Wang, Lili

    2013-09-01

    As an important signaling molecule, nitric oxide (NO) plays diverse physiological functions in plants, which has gained particular attention in recent years. We investigated the roles of NO in the growth of marine phytoplankton Platymonas subcordiforms and Skeletonema costatum under abiotic stresses. The growth of these two microalgae was obviously inhibited under non-metal stress (sodium selenium, Na2SeO3), heavy metal stress (lead nitrate, Pb(NO3)2), pesticide stress (methomyl) and UV radiation stress. After the addition of different low concentrations of exogenous NO (10(-10)-10(-8) mol L(-1)) twice each day during cultivation, the growth of these two microalgae was obviously promoted. Results showed that NO could relieve the oxidative stresses to protect the growth of the two microalgae. For different environmental stress, there is a different optimum NO concentration for marine phytoplankton. It is speculated that the protective effect of NO is related to its antioxidant ability.

  11. An Artificial Enzyme Made by Covalent Grafting of an Fe(II) Complex into β-Lactoglobulin: Molecular Chemistry, Oxidation Catalysis, and Reaction-Intermediate Monitoring in a Protein.

    PubMed

    Buron, Charlotte; Sénéchal-David, Katell; Ricoux, Rémy; Le Caër, Jean-Pierre; Guérineau, Vincent; Méjanelle, Philippe; Guillot, Régis; Herrero, Christian; Mahy, Jean-Pierre; Banse, Frédéric

    2015-08-17

    An artificial metalloenzyme based on the covalent grafting of a nonheme Fe(II) polyazadentate complex into bovine β-lactoglobulin has been prepared and characterized by using various spectroscopic techniques. Attachment of the Fe(II) catalyst to the protein scaffold is shown to occur specifically at Cys121. In addition, spectrophotometric titration with cyanide ions based on the spin-state conversion of the initial high spin (S=2) Fe(II) complex into a low spin (S=0) one allows qualitative and quantitative characterization of the metal center's first coordination sphere. This biohybrid catalyst activates hydrogen peroxide to oxidize thioanisole into phenylmethylsulfoxide as the sole product with an enantiomeric excess of up to 20 %. Investigation of the reaction between the biohybrid system and H2 O2 reveals the generation of a high spin (S=5/2) Fe(III) (η(2) -O2 ) intermediate, which is proposed to be responsible for the catalytic sulfoxidation of the substrate.

  12. Iron Atom Exchange between Hematite and Aqueous Fe(II).

    PubMed

    Frierdich, Andrew J; Helgeson, Maria; Liu, Chengshuai; Wang, Chongmin; Rosso, Kevin M; Scherer, Michelle M

    2015-07-21

    Aqueous Fe(II) has been shown to exchange with structural Fe(III) in goethite without any significant phase transformation. It remains unclear, however, whether aqueous Fe(II) undergoes similar exchange reactions with structural Fe(III) in hematite, a ubiquitous iron oxide mineral. Here, we use an enriched (57)Fe tracer to show that aqueous Fe(II) exchanges with structural Fe(III) in hematite at room temperature, and that the amount of exchange is influenced by particle size, pH, and Fe(II) concentration. Reaction of 80 nm-hematite (27 m(2) g(-1)) with aqueous Fe(II) at pH 7.0 for 30 days results in ∼5% of its structural Fe(III) atoms exchanging with Fe(II) in solution, which equates to about one surface iron layer. Smaller, 50 nm-hematite particles (54 m(2) g(-1)) undergo about 25% exchange (∼3× surface iron) with aqueous Fe(II), demonstrating that structural Fe(III) in hematite is accessible to the fluid in the presence of Fe(II). The extent of exchange in hematite increases with pH up to 7.5 and then begins to decrease as the pH progresses to 8.0, likely due to surface site saturation by sorbed Fe(II). Similarly, when we vary the initial amount of added Fe(II), we observe decreasing amounts of exchange when aqueous Fe(II) is increased beyond surface saturation. This work shows that Fe(II) can catalyze iron atom exchange between bulk hematite and aqueous Fe(II), despite hematite being the most thermodynamically stable iron oxide.

  13. Evidence for the Existence of Autotrophic Nitrate-Reducing Fe(II)-Oxidizing Bacteria in Marine Coastal Sediment.

    PubMed

    Laufer, Katja; Røy, Hans; Jørgensen, Bo Barker; Kappler, Andreas

    2016-10-15

    Nitrate-reducing Fe(II)-oxidizing microorganisms were described for the first time ca. 20 years ago. Most pure cultures of nitrate-reducing Fe(II) oxidizers can oxidize Fe(II) only under mixotrophic conditions, i.e., when an organic cosubstrate is provided. A small number of nitrate-reducing Fe(II)-oxidizing cultures have been proposed to grow autotrophically, but unambiguous evidence for autotrophy has not always been provided. Thus, it is still unclear whether or to what extent Fe(II) oxidation coupled to nitrate reduction is an enzymatically catalyzed and energy-yielding autotrophic process or whether Fe(II) is abiotically oxidized by nitrite from heterotrophic nitrate reduction. The aim of the present study was to find evidence for the existence of autotrophic nitrate-reducing Fe(II) oxidizers in coastal marine sediments. Microcosm incubations showed that with increasing incubation times, the stoichiometric ratio of reduced nitrate/oxidized Fe(II) [NO3(-)reduced/Fe(II)oxidized] decreased, indicating a decreasing contribution of heterotrophic denitrification and/or an increasing contribution of autotrophic nitrate-reducing Fe(II) oxidation over time. After incubations of sediment slurries for >10 weeks, nitrate-reducing activity ceased, although nitrate was still present. This suggests that heterotrophic nitrate reduction had ceased due to the depletion of readily available organic carbon. However, after the addition of Fe(II) to these batch incubation mixtures, the nitrate-reducing activity resumed, and Fe(II) was oxidized, indicating the activity of autotrophic nitrate-reducing Fe(II) oxidizers. The concurrent reduction of (14)C-labeled bicarbonate concentrations unambiguously proved that autotrophic C fixation occurred during Fe(II) oxidation and nitrate reduction. Our results clearly demonstrated that autotrophic nitrate-reducing Fe(II)-oxidizing bacteria were present in the investigated coastal marine sediments.

  14. Combined effects of Fe(II) and oxidizing radiolysis products on UO2 and PuO2 dissolution in a system containing solid UO2 and PuO2

    NASA Astrophysics Data System (ADS)

    Amme, Marcus; Pehrman, Reijo; Deutsch, Rudolf; Roth, Olivia; Jonsson, Mats

    2012-11-01

    The stability of UO2 spent nuclear fuel in an oxygen-free geological repository depends on the absence of oxidizing reaction partners in the near field. This work investigates the reactions between the products of water radiolysis by alpha radiation and Fe(II) an the effect on UO2 dissolution. Solid 238PuO2 powder and UO2 pellet were allowed to react in Fe(II) solution in oxygen-free batch reactor tests and kinetics of the subsequent redox reactions were measured. Depending on the concentration of Fe(II) (tests with 10-5 and 10-4 mol L-1 were made), the induced redox reactions took place between 20 and 400 h. Dissolved uranium concentrations went first through a minimum caused by reduction, followed by a maximum caused by radiolytic oxidation, and eventually reached another minimum, probably due to sorption on precipitated Fe(III). Plutonium concentrations were decreasing steadily after going through a maximum about 70 h from the start of the experiments. The results show that in the presence of the strong alpha-radiolytic field induced by the presence of solid 238Pu, the behavior of the system is largely governed by Fe(II) as it controls the H2O2 concentration, reduces U(VI) in solution and drives the Fenton reaction leading to the oxidation of Pu(IV).

  15. Real-Time Manganese Phase Dynamics during Biological and Abiotic Manganese Oxide Reduction.

    PubMed

    Johnson, Jena E; Savalia, Pratixa; Davis, Ryan; Kocar, Benjamin D; Webb, Samuel M; Nealson, Kenneth H; Fischer, Woodward W

    2016-04-19

    Manganese oxides are often highly reactive and easily reduced, both abiotically, by a variety of inorganic chemical species, and biologically during anaerobic respiration by microbes. To evaluate the reaction mechanisms of these different reduction routes and their potential lasting products, we measured the sequence progression of microbial manganese(IV) oxide reduction mediated by chemical species (sulfide and ferrous iron) and the common metal-reducing microbe Shewanella oneidensis MR-1 under several endmember conditions, using synchrotron X-ray spectroscopic measurements complemented by X-ray diffraction and Raman spectroscopy on precipitates collected throughout the reaction. Crystalline or potentially long-lived phases produced in these experiments included manganese(II)-phosphate, manganese(II)-carbonate, and manganese(III)-oxyhydroxides. Major controls on the formation of these discrete phases were alkalinity production and solution conditions such as inorganic carbon and phosphate availability. The formation of a long-lived Mn(III) oxide appears to depend on aqueous Mn(2+) production and the relative proportion of electron donors and electron acceptors in the system. These real-time measurements identify mineralogical products during Mn(IV) oxide reduction, contribute to understanding the mechanism of various Mn(IV) oxide reduction pathways, and assist in interpreting the processes occurring actively in manganese-rich environments and recorded in the geologic record of manganese-rich strata.

  16. Mechanisms of hydroxyl radical production from abiotic oxidation of pyrite under acidic conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Peng; Yuan, Songhu; Liao, Peng

    2016-01-01

    Hydroxyl radicals (radOH) produced from pyrite oxidation by O2 have been recognized, but mechanisms regarding the production under anoxic and oxic conditions are not well understood. In this study, the mechanisms of radOH production from pyrite oxidation under anoxic and oxic conditions were explored using benzoic acid (BA) as an radOH probe. Batch experiments were conducted at pH 2.6 to explore radOH production under anoxic and oxic conditions. The cumulative radOH concentrations produced under anoxic and oxic conditions increased linearly to 7.5 and 52.2 μM, respectively within 10 h at 10 g/L pyrite. Under anoxic conditions, radOH was produced from the oxidation of H2O on the sulfur-deficient sites on pyrite surface, showing an increased production with the increase of pyrite surface exposure due to oxidation. Under oxic conditions, the formation of radOH proceeds predominantly via the two-electron reduction of O2 on pyrite surface along with a minor contribution from the oxidation of H2O on surface sulfur-defects and the reactions of Fe2+/sulfur intermediates with O2. For both O2 reduction and H2O oxidation on the surface sulfur-defects, H2O2 was the predominant intermediate, which subsequently transformed to radOH through Fenton mechanism. The radOH produced had a significant impact on the transformation of contaminants in the environment. Anoxic pyrite suspensions oxidized 13.9% As(III) (C0 = 6.67 μM) and 17.6% sulfanilamide (C0 = 2.91 μM) within 10 h at pH 2.6 and 10 g/L pyrite, while oxic pyrite suspensions improved the oxidation percentages to 55.4% for As(III) and 51.9% for sulfanilamide. The ratios of anoxic to oxic oxidation are consistent with the relative contribution of surface sulfur-defects to radOH production. However, Fe2+ produced from pyrite oxidation competed with the contaminants for radOH, which is of particular significance with the increase of time in a static environment. We conclude that radOH can be produced from abiotic oxidation of

  17. Significance of the Henri-Michaelis-Menten theory in abiotic catalysis: catechol oxidation by δ-MnO 2

    NASA Astrophysics Data System (ADS)

    Naidja, A.; Huang, P. M.

    2002-05-01

    The Henri-Michaelis-Menten theory, for more than eight decades, was only restricted to homogeneous enzymatic catalysis. A mimic of an enzymatic kinetics based on the Henri-Michaelis-Menten concept was experimentally observed in heterogeneous catalysis in the present study with δ-MnO 2 as an abiotic catalyst in the oxidation of catechol (1,2-dihydroxybenzene). Using the derived linear forms of Lineweaver-Burk or Hofstee, the data show that similar to the enzyme tyrosinase, the kinetics of the catechol oxidation catalyzed by δ-MnO 2 can be described by the Henri-Michaelis-Menten equation, V0= VmaxS/( Km+ S), where Vmax is the maximum velocity and Km the concentration of the substrate ( S) corresponding to an initial velocity ( V0) half of Vmax. By analogy to the enzymatic kinetics, the parameters Vmax and Km for an heterogeneous abiotic catalysis were derived for the first time. Further, based on the concentration of the active centers of the mineral oxide, the kinetic constants kcat and kcat/ Km, respectively, representing the turnover frequency and the efficiency of the mineral catalyst, were also determined from the derived general rate equation of Briggs and Haldane. As an abiotic catalyst, δ-MnO 2 has a paramount role in the oxidation of phenolic compounds in soil, sediment and water environments. Therefore, the present observation is of fundamental and practical significance in elucidating the affinity between an abiotic catalyst and a substrate based on the Henri-Michaelis-Menten theory.

  18. Adsorption and abiotic oxidation of arsenic by aged biofilter media: equilibrium and kinetics.

    PubMed

    Sahabi, Danladi Mahuta; Takeda, Minoru; Suzuki, Ichiro; Koizumi, Jun-ichi

    2009-09-15

    Removal of arsenic from groundwater by biological adsorptive filtration depends largely on its interaction with biogenic iron and manganese oxides surfaces. In the present study we investigated the arsenic adsorption and abiotic oxidation capacities of an aged biofilter medium (BM2) collected from a long time established groundwater treatment plant for removal of iron and manganese by biological filtration. Batch oxidation/adsorption kinetic experiments indicated that BM2 can easily oxidize As(III) to As(V) with the rate of oxidation less affected by pH-variations from 4 to 8.5. The adsorption capacity of the biofilter medium for the produced or added As(V), however, depends strongly on the pH of the solution. The kinetics results have shown that As(III) sorption followed pseudo-second order kinetics, whereas the sorption of As(V) was best described by the intra-particle diffusion model, indicating that adsorptions of As(III) and As(V) onto BM2 were governed by different mechanisms. Adsorption isotherms at 25 degrees C were measured for a range of arsenite and arsenate initial concentrations of 0.67-20 micromol/L and the pH range from 4 to 9. Adsorption maxima were highest at pH 4 and decrease steadily as the pH increases. The equilibrium data for both As(III) and As(V) fitted very well to the Freundlich and Sips isotherm equations and, in most cases, the two isotherms overlapped with the same correlation coefficients, indicating sorption to be multilayer on the heterogeneous surface of BM2. The implication of the data for arsenic removal from water by biological filtration has been discussed.

  19. Oxidation of Fe(II)-EDTA by nitrite and by two nitrate-reducing Fe(II)-oxidizing Acidovorax strains.

    PubMed

    Klueglein, N; Picardal, F; Zedda, M; Zwiener, C; Kappler, A

    2015-03-01

    The enzymatic oxidation of Fe(II) by nitrate-reducing bacteria was first suggested about two decades ago. It has since been found that most strains are mixotrophic and need an additional organic co-substrate for complete and prolonged Fe(II) oxidation. Research during the last few years has tried to determine to what extent the observed Fe(II) oxidation is driven enzymatically, or abiotically by nitrite produced during heterotrophic denitrification. A recent study reported that nitrite was not able to oxidize Fe(II)-EDTA abiotically, but the addition of the mixotrophic nitrate-reducing Fe(II)-oxidizer, Acidovorax sp. strain 2AN, led to Fe(II) oxidation (Chakraborty & Picardal, 2013). This, along with other results of that study, was used to argue that Fe(II) oxidation in strain 2AN was enzymatically catalyzed. However, the absence of abiotic Fe(II)-EDTA oxidation by nitrite reported in that study contrasts with previously published data. We have repeated the abiotic and biotic experiments and observed rapid abiotic oxidation of Fe(II)-EDTA by nitrite, resulting in the formation of Fe(III)-EDTA and the green Fe(II)-EDTA-NO complex. Additionally, we found that cultivating the Acidovorax strains BoFeN1 and 2AN with 10 mM nitrate, 5 mm acetate, and approximately 10 mM Fe(II)-EDTA resulted only in incomplete Fe(II)-EDTA oxidation of 47-71%. Cultures of strain BoFeN1 turned green (due to the presence of Fe(II)-EDTA-NO) and the green color persisted over the course of the experiments, whereas strain 2AN was able to further oxidize the Fe(II)-EDTA-NO complex. Our work shows that the two used Acidovorax strains behave very differently in their ability to deal with toxic effects of Fe-EDTA species and the further reduction of the Fe(II)-EDTA-NO nitrosyl complex. Although the enzymatic oxidation of Fe(II) cannot be ruled out, this study underlines the importance of nitrite in nitrate-reducing Fe(II)- and Fe(II)-EDTA-oxidizing cultures and demonstrates that Fe(II)-EDTA cannot

  20. Abiotic Protein Fragmentation by Manganese Oxide: Implications for a Mechanism to Supply Soil Biota with Oligopeptides.

    PubMed

    Reardon, Patrick N; Chacon, Stephany S; Walter, Eric D; Bowden, Mark E; Washton, Nancy M; Kleber, Markus

    2016-04-05

    The ability of plants and microorganisms to take up organic nitrogen in the form of free amino acids and oligopeptides has received increasing attention over the last two decades, yet the mechanisms for the formation of such compounds in soil environments remain poorly understood. We used Nuclear Magnetic Resonance (NMR) and Electron Paramagnetic Resonance (EPR) spectroscopies to distinguish the reaction of a model protein with a pedogenic oxide (Birnessite, MnO2) from its response to a phyllosilicate (Kaolinite). Our data demonstrate that birnessite fragments the model protein while kaolinite does not, resulting in soluble peptides that would be available to soil biota and confirming the existence of an abiotic pathway for the formation of organic nitrogen compounds for direct uptake by plants and microorganisms. The absence of reduced Mn(II) in the solution suggests that birnessite acts as a catalyst rather than an oxidant in this reaction. NMR and EPR spectroscopies are shown to be valuable tools to observe these reactions and capture the extent of protein transformation together with the extent of mineral response.

  1. Transcriptome Analysis of Sunflower Genotypes with Contrasting Oxidative Stress Tolerance Reveals Individual- and Combined- Biotic and Abiotic Stress Tolerance Mechanisms

    PubMed Central

    Ramu, Vemanna S.; Paramanantham, Anjugam; Ramegowda, Venkategowda; Mohan-Raju, Basavaiah; Udayakumar, Makarla

    2016-01-01

    In nature plants are often simultaneously challenged by different biotic and abiotic stresses. Although the mechanisms underlying plant responses against single stress have been studied considerably, plant tolerance mechanisms under combined stress is not understood. Also, the mechanism used to combat independently and sequentially occurring many number of biotic and abiotic stresses has also not systematically studied. From this context, in this study, we attempted to explore the shared response of sunflower plants to many independent stresses by using meta-analysis of publically available transcriptome data and transcript profiling by quantitative PCR. Further, we have also analyzed the possible role of the genes so identified in contributing to combined stress tolerance. Meta-analysis of transcriptomic data from many abiotic and biotic stresses indicated the common representation of oxidative stress responsive genes. Further, menadione-mediated oxidative stress in sunflower seedlings showed similar pattern of changes in the oxidative stress related genes. Based on this a large scale screening of 55 sunflower genotypes was performed under menadione stress and those contrasting in oxidative stress tolerance were identified. Further to confirm the role of genes identified in individual and combined stress tolerance the contrasting genotypes were individually and simultaneously challenged with few abiotic and biotic stresses. The tolerant hybrid showed reduced levels of stress damage both under combined stress and few independent stresses. Transcript profiling of the genes identified from meta-analysis in the tolerant hybrid also indicated that the selected genes were up-regulated under individual and combined stresses. Our results indicate that menadione-based screening can identify genotypes not only tolerant to multiple number of individual biotic and abiotic stresses, but also the combined stresses. PMID:27314499

  2. Interactions Between Fe(III)-Oxides and Fe(III)-Phyllosilicates During Microbial Reduction 1: Synthetic Sediments

    SciTech Connect

    Wu, Tao; Kukkadapu, Ravi K.; Griffin, Aron M.; Gorski, Christopher A.; Konishi, Hiromi; Xu, Huifang; Roden, Eric E.

    2015-11-19

    Fe(III)-oxides and Fe(III)-bearing phyllosilicates are the two major iron sources utilized as electron acceptors by dissimilatory iron-reducing bacteria (DIRB) in anoxic soils and sediments. Although there have been many studies of microbial Fe(III)-oxide and Fe(III)-phyllosilicate reduction with both natural and specimen materials, no controlled experimental information is available on the interaction between these two phases when both are available for microbial reduction. In this study, the model DIRB Geobacter sulfurreducens was used to examine the pathways of Fe(III) reduction in Fe(III)-oxide stripped subsurface sediment that was coated with different amounts of synthetic high surface area goethite. Cryogenic (12K) 57Fe Mössbauer spectroscopy was used to determine changes in the relative abundances of Fe(III)-oxide, Fe(III)-phyllosilicate, and phyllosilicate-associated Fe(II) (Fe(II)-phyllosilicate) in bioreduced samples. Analogous Mössbauer analyses were performed on samples from abiotic Fe(II) sorption experiments in which sediments were exposed to a quantity of exogenous soluble Fe(II) (FeCl22H2O) comparable to the amount of Fe(II) produced during microbial reduction. A Fe partitioning model was developed to analyze the fate of Fe(II) and assess the potential for abiotic Fe(II)-catalyzed reduction of Fe(III)-phyllosilicatesilicates. The microbial reduction experiments indicated that although reduction of Fe(III)-oxide accounted for virtually all of the observed bulk Fe(III) reduction activity, there was no significant abiotic electron transfer between oxide-derived Fe(II) and Fe(III)-phyllosilicatesilicates, with 26-87% of biogenic Fe(II) appearing as sorbed Fe(II) in the Fe(II)-phyllosilicate pool. In contrast, the abiotic Fe(II) sorption experiments showed that 41 and 24% of the added Fe(II) engaged in electron transfer to Fe(III)-phyllosilicate surfaces in synthetic goethite-coated and uncoated sediment. Differences in the rate of Fe(II) addition and

  3. [Investigation of effect and process of nitric oxide removal in rotating drum biofilter coupled with absorption by Fe(II) (EDTA)].

    PubMed

    Chen, Jun; Yang, Xuan; Yu, Jian-Ming; Jiang, Yi-Feng; Chen, Jian-Meng

    2012-02-01

    In order to accelerate the NO removal efficiency, a novel and effective system was developed for the complete treatment of NO from flue gases. The system features NO absorption by Fe(II) (EDTA) and biological denitrification in a rotating drum biofilter (RDB) so as to promote biological reduction. The experimental results show that a moderate amount of Fe(II) (EDTA) was added to the nutrient solution to improve the mass transfer efficiency of NO from gas to liquid, with the concomitant formation of nitrosyl complex Fe(II) (EDTA)-NO. Under the experimental conditions of rotational speed was at 0.5 r x min(-1), EBRT of 57.7 s, temperature was at 30 degrees C, pH was 7-8, with the increasing concentration of Fe(II) (EDTA) was from 0 mg x L(-1) to 500 mg x L(-1), the NO removal efficiency was improved from 61.1% to 97.6%, and the elimination capacity was from 16.2 g (m3 x h)(-1) to 26.7 g (m3 x h)(-1). In order to simulate the denitrifying process of waste gas containing NO by using RDB coupled with Fe(II) (EDTA) absorption, a tie-in equation of NO removal and the Fe(II) (EDTA) concentration added in RDB was established. The experimental NO removal efficiency change tendency agrees fairly with that predicted by the proposed equation.

  4. Effect Of Inorganic, Synthetic And Naturally Occurring Chelating Agents On Fe(II) Mediated Advanced Oxidation Of Chlorophenols

    EPA Science Inventory

    This study examines the feasibility and application of Advanced Oxidation Technologies (AOTs) for the treatment of chlorophenols that are included in US EPA priority pollutant list. A novel class of sulfate/hydroxyl radical-based homogeneous AOTs (Fe(II)/PS, Fe(II)/PMS, Fe(II)/H...

  5. Evidence for the Existence of Autotrophic Nitrate-Reducing Fe(II)-Oxidizing Bacteria in Marine Coastal Sediment

    PubMed Central

    Laufer, Katja; Røy, Hans; Jørgensen, Bo Barker

    2016-01-01

    ABSTRACT Nitrate-reducing Fe(II)-oxidizing microorganisms were described for the first time ca. 20 years ago. Most pure cultures of nitrate-reducing Fe(II) oxidizers can oxidize Fe(II) only under mixotrophic conditions, i.e., when an organic cosubstrate is provided. A small number of nitrate-reducing Fe(II)-oxidizing cultures have been proposed to grow autotrophically, but unambiguous evidence for autotrophy has not always been provided. Thus, it is still unclear whether or to what extent Fe(II) oxidation coupled to nitrate reduction is an enzymatically catalyzed and energy-yielding autotrophic process or whether Fe(II) is abiotically oxidized by nitrite from heterotrophic nitrate reduction. The aim of the present study was to find evidence for the existence of autotrophic nitrate-reducing Fe(II) oxidizers in coastal marine sediments. Microcosm incubations showed that with increasing incubation times, the stoichiometric ratio of reduced nitrate/oxidized Fe(II) [NO3−reduced/Fe(II)oxidized] decreased, indicating a decreasing contribution of heterotrophic denitrification and/or an increasing contribution of autotrophic nitrate-reducing Fe(II) oxidation over time. After incubations of sediment slurries for >10 weeks, nitrate-reducing activity ceased, although nitrate was still present. This suggests that heterotrophic nitrate reduction had ceased due to the depletion of readily available organic carbon. However, after the addition of Fe(II) to these batch incubation mixtures, the nitrate-reducing activity resumed, and Fe(II) was oxidized, indicating the activity of autotrophic nitrate-reducing Fe(II) oxidizers. The concurrent reduction of 14C-labeled bicarbonate concentrations unambiguously proved that autotrophic C fixation occurred during Fe(II) oxidation and nitrate reduction. Our results clearly demonstrated that autotrophic nitrate-reducing Fe(II)-oxidizing bacteria were present in the investigated coastal marine sediments. IMPORTANCE Twenty years after the

  6. Evidence that oxidative dephosphorylation by the nonheme Fe(II), α-ketoglutarate:UMP oxygenase occurs by stereospecific hydroxylation.

    PubMed

    Goswami, Anwesha; Liu, Xiaodong; Cai, Wenlong; Wyche, Thomas P; Bugni, Tim S; Meurillon, Maïa; Peyrottes, Suzanne; Perigaud, Christian; Nonaka, Koichi; Rohr, Jürgen; Van Lanen, Steven G

    2017-02-01

    LipL and Cpr19 are nonheme, mononuclear Fe(II)-dependent, α-ketoglutarate (αKG):UMP oxygenases that catalyze the formation of CO2 , succinate, phosphate, and uridine-5'-aldehyde, the last of which is a biosynthetic precursor for several nucleoside antibiotics that inhibit bacterial translocase I (MraY). To better understand the chemistry underlying this unusual oxidative dephosphorylation and establish a mechanistic framework for LipL and Cpr19, we report herein the synthesis of two biochemical probes-[1',3',4',5',5'-(2) H]UMP and the phosphonate derivative of UMP-and their activity with both enzymes. The results are consistent with a reaction coordinate that proceeds through the loss of one (2) H atom of [1',3',4',5',5'-(2) H]UMP and stereospecific hydroxylation geminal to the phosphoester to form a cryptic intermediate, (5'R)-5'-hydroxy-UMP. Thus, these enzyme catalysts can additionally be assigned as UMP hydroxylase-phospholyases.

  7. Formation, reactivity, and aging of ferric oxide particles formed from Fe(II) and Fe(III) sources: Implications for iron bioavailability in the marine environment

    NASA Astrophysics Data System (ADS)

    Bligh, Mark W.; Waite, T. David

    2011-12-01

    Freshly formed amorphous ferric oxides (AFO) in the water column are potentially highly reactive, but with reactivity declining rapidly with age, and have the capacity to partake in reactions with dissolved species and to be a significant source of bioavailable iron. However, the controls on reactivity in aggregated oxides are not well understood. Additionally, the mechanism by which early rapid aging occurs is not clear. Aging is typically considered in terms of changes in crystallinity as the structure of an iron oxide becomes more stable and ordered with time thus leading to declining reactivity. However, there has been recognition of the role that aggregation can play in determining reactivity, although it has received limited attention. Here, we have formed AFO in seawater in the laboratory from either an Fe(II) or Fe(III) source to produce either AFO(II) or AFO(III). The changes in reactivity of these two oxides following formation was measured using both ligand-promoted dissolution (LPD) and reductive dissolution (RD). The structure of the two oxides was examined using light scattering and X-ray adsorption techniques. The dissolution rate of AFO(III) was greater than that of AFO(II), as measured by both dissolution techniques, and could be attributed to both the less ordered molecular structure and smaller primary particle size of AFO(III). From EXAFS analysis shortly (90 min) following formation, AFO(II) and AFO(III) were shown to have the same structure as aged lepidocrocite and ferrihydrite respectively. Both oxides displayed a rapid decrease in dissolution rate over the first hours following formation in a pattern that was very similar when normalised. The early establishment and little subsequent change of crystal structure for both oxides undermined the hypothesis that increasing crystallinity was responsible for early rapid aging. Also, an aging model describing this proposed process could only be fitted to the data with kinetic parameters that were

  8. Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

    USGS Publications Warehouse

    Balci, N.; Mayer, B.; Shanks, Wayne C.; Mandernack, K.W.

    2012-01-01

    Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88Fe 0.12S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant ?? 34S and ?? 18O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying ?? 18O values to determine the relative contributions of H 2O-derived and O 2-derived oxygen in the newly formed sulfate. Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans, and S o as the sole energy source were also conducted. The ??34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations (??34SSO4-ZnS) of up to -2.6???, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors (??34SSO4-ZnS) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ?? 18OSO 4-H 2O values of 8.2??0.2??? and 7.5??0.1???, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A. ferrooxidans, all of the sulfate oxygen was derived from water with similar measured ?? 18OSO 4-H 2O values of 8.1??0.1??? and 8.3??0.3???, respectively. During biological oxidation

  9. Plant Survival in a Changing Environment: The Role of Nitric Oxide in Plant Responses to Abiotic Stress

    PubMed Central

    Simontacchi, Marcela; Galatro, Andrea; Ramos-Artuso, Facundo; Santa-María, Guillermo E.

    2015-01-01

    Nitric oxide in plants may originate endogenously or come from surrounding atmosphere and soil. Interestingly, this gaseous free radical is far from having a constant level and varies greatly among tissues depending on a given plant’s ontogeny and environmental fluctuations. Proper plant growth, vegetative development, and reproduction require the integration of plant hormonal activity with the antioxidant network, as well as the maintenance of concentration of reactive oxygen and nitrogen species within a narrow range. Plants are frequently faced with abiotic stress conditions such as low nutrient availability, salinity, drought, high ultraviolet (UV) radiation and extreme temperatures, which can influence developmental processes and lead to growth restriction making adaptive responses the plant’s priority. The ability of plants to respond and survive under environmental-stress conditions involves sensing and signaling events where nitric oxide becomes a critical component mediating hormonal actions, interacting with reactive oxygen species, and modulating gene expression and protein activity. This review focuses on the current knowledge of the role of nitric oxide in adaptive plant responses to some specific abiotic stress conditions, particularly low mineral nutrient supply, drought, salinity and high UV-B radiation. PMID:26617619

  10. Plant Survival in a Changing Environment: The Role of Nitric Oxide in Plant Responses to Abiotic Stress.

    PubMed

    Simontacchi, Marcela; Galatro, Andrea; Ramos-Artuso, Facundo; Santa-María, Guillermo E

    2015-01-01

    Nitric oxide in plants may originate endogenously or come from surrounding atmosphere and soil. Interestingly, this gaseous free radical is far from having a constant level and varies greatly among tissues depending on a given plant's ontogeny and environmental fluctuations. Proper plant growth, vegetative development, and reproduction require the integration of plant hormonal activity with the antioxidant network, as well as the maintenance of concentration of reactive oxygen and nitrogen species within a narrow range. Plants are frequently faced with abiotic stress conditions such as low nutrient availability, salinity, drought, high ultraviolet (UV) radiation and extreme temperatures, which can influence developmental processes and lead to growth restriction making adaptive responses the plant's priority. The ability of plants to respond and survive under environmental-stress conditions involves sensing and signaling events where nitric oxide becomes a critical component mediating hormonal actions, interacting with reactive oxygen species, and modulating gene expression and protein activity. This review focuses on the current knowledge of the role of nitric oxide in adaptive plant responses to some specific abiotic stress conditions, particularly low mineral nutrient supply, drought, salinity and high UV-B radiation.

  11. Composition and structure of Fe(III)-precipitates formed by Fe(II) oxidation in water at near-neutral pH: Interdependent effects of phosphate, silicate and Ca

    NASA Astrophysics Data System (ADS)

    Senn, Anna-Caterina; Kaegi, Ralf; Hug, Stephan J.; Hering, Janet G.; Mangold, Stefan; Voegelin, Andreas

    2015-08-01

    We studied the interdependent effects of phosphate, silicate and Ca on the formation of Fe(III)-precipitates by oxidation of 0.5 mM Fe(II) in near-neutral bicarbonate-buffered aqueous solutions at concentrations relevant for natural water resources. Complementary results obtained by a suite of analytical techniques including X-ray absorption spectroscopy and transmission electron microscopy showed that the ratio of initially dissolved phosphate over Fe(II) ((P/Fe)init) had a major impact on precipitate formation. At (P/Fe)init above a critical ratio ((P/Fe)crit) of ∼0.5 in 8 mM NaHCO3 and ∼0.8 in 4 mM Ca(HCO3)2 electrolyte, Fe(II) oxidation led to exclusive formation of amorphous basic Fe(III)-phosphate or Ca-Fe(III)-phosphate ((Ca-)Fe(III)-phosphate) with maximum precipitate P/Fe ratios ((P/Fe)ppt) of ∼0.7 in Na and ∼1.1 in Ca electrolyte. Enhanced phosphate uptake in the presence of Ca was due to phosphate-Ca interactions coupled to Fe precipitation, mainly formation of mitridatite-like Ca-Fe(III)-phosphate polymers and Ca-phosphate polymers. At (P/Fe)init < (P/Fe)crit, in the absence of silicate, (Ca-)Fe(III)-phosphate precipitation was followed by the formation of poorly crystalline lepidocrocite and concomitant transformation of the (Ca-)Fe(III)-phosphate into a phosphate-rich ferrihydrite-type precipitate with a (P/Fe)ppt of ∼0.25. In the presence of 0.5 mM silicate, initially formed (Ca-)Fe(III)-phosphate nanoparticles became coated with silicate-rich ferrihydrite during continuing Fe(II) oxidation and only limited transformation of the (Ca-)Fe(III)-phosphate occurred. The results from this study indicate the complexity of Fe(III)-precipitate formation in the presence of interfering solutes and its consequences for precipitate structure and phosphate sequestration. The findings provide a solid basis for further studies of the reactivity of different Fe(III)-precipitate types and for the systematic assessment of their impact on Fe, phosphate and

  12. DNA Oxidative Cleavage Induced by the Novel Peptide Derivatives of 3-(quinoxalin-6-yl)alanine in Combination with Cu(II) or Fe(II) Ions

    PubMed Central

    Szczepanik, Wojciech; Kucharczyk-Klamińska, Marzena; Stefanowicz, Piotr; Staszewska, Anna; Szewczuk, Zbigniew; Skała, Jacek; Mysiak, Andrzej; Jeżowska-Bojczuk, Małgorzata

    2009-01-01

    Three model dipeptides containing 3-(2,3-di(pyridin-2-yl)quinoxalin-6-yl)alanine, 3-(dipyrido[3,2-a:2,3-c]phenazin-11-yl)alanine, and 3-(2,3-diphenylquinoxalin-6-yl)alanine were studied with respect to their ability to bind selected transition metal ions, such as Cu(II), Fe(II), Ni(II), Co(II), Mn(II), and Cr(III). It was found that only Cu(II) and Fe(II) ions could form stable complex species with the studied compounds. The ability to form the complexes correlated well with DNA damage experiments. Only the ferrous and cupric complexes are capable of generating both single- and double-strand scissions. However, double-strand breakages appear to be dominating lesions in the presence of hydrogen peroxide, especially for copper(II) containing systems. The quantity of breakage products in the presence of N-(3-(dipyrido[3,2-a:2,3-c]phenazine-11-yl)alanyl)glycine complexes was the highest as compared to the complexes of the remaining compounds. Moreover, this ligand was the only one that cleaved DNA in the absence of either Cu(II) or Fe(II) ions. PMID:20224817

  13. Insights into the Mechanism of Fe(II) Adsorption and Oxidation at Fe-Clay Mineral Surfaces from First-Principles Calculations

    SciTech Connect

    Alexandrov, Vitali Y.; Rosso, Kevin M.

    2013-10-02

    Interfacial reactivity of redox-active iron-bearing mineral surfaces plays a crucial role in many environmental processes including biogeochemical cycling of various elements and contaminants. Herein, we apply density-functional-theory (DFT) calculations to provide atomistic insights into the heterogeneous reaction between aqueous Fe(II) and the Fe-bearing clay mineral nontronite Fe2Si4O10(OH)2 by studying its adsorption mechanism and interfacial Fe(II)-Fe(III) electron transfer (ET) at edge and basal surfaces. We find that edge-bound Fe(II) adsorption complexes at different surface sites (ferrinol, silanol and mixed) may coexist on both (010) and (110) edge facets, with complexes at ferrinol FeO(H) sites being the most energetically favorable and coupled to proton transfer. Calculation of the ET activation energy suggests that interfacial ET into dioctahedral Fe(III) sheets is probable at the clay edges and occurs predominantly but not exclusively through the complexes adsorbed at ferrinol sites and might also involve mixed sites. No clear evidence is found for complexes on basal surface that are compatible with ET through the basal sheet despite this experimentally hypothesized ET interface. This study suggests a strong pH-dependence of Fe(II) surface complexation at basal versus edge facets and highlights the importance of the protonation state of bridging ligands and proton coupled electron transfer to facilitate ET into Fe-rich clay minerals.

  14. Formation of singlet oxygen and protection against its oxidative damage in Photosystem II under abiotic stress.

    PubMed

    Pospíšil, Pavel; Prasad, Ankush

    2014-08-01

    Photosystem II (PSII) is exposed to various abiotic stresses associated with adverse environmental conditions such as high light, heat, heavy metals or mechanical injury. Distinctive functional response to adverse environmental conditions is formation of singlet oxygen ((1)O2). In this review, recent progress on mechanistic principles on (1)O2 formation under abiotic stresses is summarized. Under high light, (1)O2 is formed by excitation energy transfer from triplet chlorophylls to molecular oxygen formed by the spin conversion via photosensitization Type II reaction in the PSII antenna complex or by the recombination of (1)[P680(+)Pheo(-)] radical pair in the PSII reaction center. Apart from well-described (1)O2 formation by excitation energy transfer, (1)O2 formation by decomposition of dioxetane and tetroxide is summarized as a potential source of (1)O2 in PSII under heat, heavy metals and mechanical stress. The description of mechanistic principles on (1)O2 formation under abiotic stress allows us to understand how plants respond to adverse environmental conditions in vivo.

  15. Influence factors for the oxidation of pyrite by oxygen and birnessite in aqueous systems.

    PubMed

    Qiu, Guohong; Luo, Yao; Chen, Cheng; Lv, Qiang; Tan, Wenfeng; Liu, Fan; Liu, Chengshuai

    2016-07-01

    The oxidation of exposed pyrite causes acid mine drainage, soil acidification, and the release of toxic metal ions. As the important abiotic oxidants in supergene environments, oxygen and manganese oxides participate in the oxidation of pyrite. In this work, the oxidation processes of natural pyrite by oxygen and birnessite were studied in simulated systems, and the influence of pH, Fe(II) and Cr(III) on the intermediates and redox rate was investigated. SO4(2-) and elemental S were formed as the major and minor products, respectively, during the oxidation processes. Ferric (hydr) oxides including Fe(OH)3 and goethite were formed with low degree of crystallinity. Low pH and long-term reaction facilitated the formation of goethite and ferric hydroxide, respectively. The rate of pyrite oxidation by birnessite was enhanced in the presence of air (oxygen), and Fe(II) ions played a key role in the redox process. The addition of Fe(II) ions to the reaction system significantly enhanced the oxidation rate of pyrite; however, the presence of Cr(III) ions remarkably decreased the pyrite oxidation rate in aqueous systems. The introduction of Fe(II) ions to form a Fe(III)/Fe(II) redox couple facilitated the electron transfer and accelerated the oxidation rate of pyrite. The present work suggests that isolation from air and decreasing the concentration of Fe(II) ions in aqueous solutions might be effective strategies to reduce the oxidation rate of pyrite in mining soils.

  16. Life on the energetic edge: Iron oxidation by circumneutral lithotrophic bacteria in the wetland plant rhizosphere

    NASA Astrophysics Data System (ADS)

    Neubauer, S. C.; Emerson, D.; Megonigal, J. P.; Weiss, J. V.

    2002-05-01

    We have discovered a phylogenetically and genotypically coherent group of obligately lithotrophic Fe-oxidizing bacteria that grow at neutral pH and are globally distributed in a range of habitats, from the rhizosphere of freshwater wetlands to deep-sea hydrothermal vents. We have initiated bioreactor studies using pure cultures of these organisms to determine the significance of microbial Fe(II) oxidation at circumneutral pH and identify the biotic and abiotic variables that affect the partitioning between microbial and chemical oxidation. These studies have focused on strain BrT, which was isolated from an iron oxide precipitate in rhizosphere of a wetland plant. In one set of experiments, Fe(II) oxidation rates were measured before and after cultures of strain BrT were poisoned with sodium azide. These experiments indicated that 18 to 53 % of total iron oxidation was due to microbial metabolism. In a second set of experiments, Fe(II) was constantly added to bioreactors inoculated with live cells, killed cells, or no cells. A statistical model fit to the experimental data demonstrated that metabolic Fe(II) oxidation accounted for up to 62 % of total oxidation. Total Fe(II) oxidation rates in these experiments were strongly limited by the rate of Fe(II) delivery to the system, and were also influenced by O2 and total iron concentrations. Additionally, the model suggested that the microbes inhibited rates of abiotic Fe(II) oxidation, perhaps by binding Fe(II) to bacterial exopolymers. The net effect of strain BrT was to accelerate total oxidation rates by up to 18 % versus cell-free treatments. Using two independent techniques, we demonstrated that strain BrT actively metabolizes Fe(II) and can account for up to 50 to 60 % of total Fe(II) oxidation in laboratory cultures. These results suggest that neutrophilic Fe(II)-oxidizing bacteria may compete for limited O2 in the rhizosphere and influence the biogeochemistry of other elements including carbon, phosphorus, and

  17. Oxycline formation induced by Fe(II) oxidation in a water reservoir affected by acid mine drainage modeled using a 2D hydrodynamic and water quality model - CE-QUAL-W2.

    PubMed

    Torres, Ester; Galván, Laura; Cánovas, Carlos Ruiz; Soria-Píriz, Sara; Arbat-Bofill, Marina; Nardi, Albert; Papaspyrou, Sokratis; Ayora, Carlos

    2016-08-15

    The Sancho reservoir is an acid mine drainage (AMD)-contaminated reservoir located in the Huelva province (SW Spain) with a pH close to 3.5. The water is only used for a refrigeration system of a paper mill. The Sancho reservoir is holomictic with one mixing period per year in the winter. During this mixing period, oxygenated water reaches the sediment, while under stratified conditions (the rest of the year) hypoxic conditions develop at the hypolimnion. A CE-QUAL-W2 model was calibrated for the Sancho Reservoir to predict the thermocline and oxycline formation, as well as the salinity, ammonium, nitrate, phosphorous, algal, chlorophyll-a, and iron concentrations. The version 3.7 of the model does not allow simulating the oxidation of Fe(II) in the water column, which limits the oxygen consumption of the organic matter oxidation. However, to evaluate the impact of Fe(II) oxidation on the oxycline formation, Fe(II) has been introduced into the model based on its relationship with labile dissolved organic matter (LDOM). The results show that Fe oxidation is the main factor responsible for the oxygen depletion in the hypolimnion of the Sancho Reservoir. The limiting factors for green algal growth have also been studied. The model predicted that ammonium, nitrate, and phosphate were not limiting factors for green algal growth. Light appeared to be one of the limiting factors for algal growth, while chlorophyll-a and dissolved oxygen concentrations could not be fully described. We hypothesize that dissolved CO2 is one of the limiting nutrients due to losses by the high acidity of the water column. The sensitivity tests carried out support this hypothesis. Two different remediation scenarios have been tested with the calibrated model: 1) an AMD passive treatment plant installed at the river, which removes completely Fe, and 2) different depth water extractions. If no Fe was introduced into the reservoir, water quality would significantly improve in only two years

  18. Anoxygenic growth of cyanobacteria on Fe(II) and their associated biosignatures: Implications for biotic contributions to Precambrian Banded Iron Formations

    NASA Astrophysics Data System (ADS)

    Parenteau, M.; Jahnke, L. L.; Cady, S. L.; Pierson, B.

    2011-12-01

    Banded Iron Formations (BIFs) are widespread Precambrian sedimentary deposits that accumulated in deep ocean basins or shallow platformal areas with inputs of reduced iron (Fe(II)) and silica from deep ocean hydrothermal activity. There is debate as to whether abiotic or biotic mechanisms were responsible for the oxidation of aqueous Fe(II) and the subsequent accumulation of ferric iron (Fe(III)) mineral assemblages in BIFs. Biotic Fe(II) oxidation could have occurred indirectly as a result of the photosynthetic production of oxygen by cyanobacteria, or could have been directly mediated by anoxygenic phototrophs or chemolithotrophs. The anoxygenic use of Fe(II) as an electron donor for photosynthesis has also been hypothesized in cyanobacteria, representing another biotic mechanism by which Fe(II) could be oxidized in BIFs. This type of photoferrotrophic metabolism may also represent a key step in the evolution of oxygenic photosynthesis. Members of our group have speculated that an intermediate reductant such as Fe(II) could have acted as a transitional electron donor before water. The widespread abundance of Fe(II) in Archean and Neoproterozoic ferruginous oceans would have made it particularly suitable as an electron donor for photosynthesis. We have been searching for modern descendants of such an ancestral "missing link" cyanobacterium in the phototrophic mats at Chocolate Pots, a hot spring in Yellowstone National Park with a constant outflow of anoxic Fe(II)-rich thermal water. Our physiological ecology study of the Synechococcus-Chloroflexi mat using C-14 bicarbonate uptake and autoradiography experiments revealed that the cyanobacteria grow anoxygenically using Fe(II) as an electron donor for photosynthesis in situ. An initial set of similar experiments substituting C-13 bicarbonate as the tracer was used to characterize labeling of the community lipid biomarker signature and confirm the C-14 results. Under light conditions with and without Fe(II), the C

  19. Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

    USGS Publications Warehouse

    Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

    2006-01-01

    The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the

  20. The transcriptional network of WRKY53 in cereals links oxidative responses to biotic and abiotic stress inputs.

    PubMed

    Van Eck, Leon; Davidson, Rebecca M; Wu, Shuchi; Zhao, Bingyu Y; Botha, Anna-Maria; Leach, Jan E; Lapitan, Nora L V

    2014-06-01

    The transcription factor WRKY53 is expressed during biotic and abiotic stress responses in cereals, but little is currently known about its regulation, structure and downstream targets. We sequenced the wheat ortholog TaWRKY53 and its promoter region, which revealed extensive similarity in gene architecture and cis-acting regulatory elements to the rice ortholog OsWRKY53, including the presence of stress-responsive abscisic acid-responsive elements (ABRE) motifs and GCC-boxes. Four proteins interacted with the WRKY53 promoter in yeast one-hybrid assays, suggesting that this gene can receive inputs from diverse stress-related pathways such as calcium signalling and senescence, and environmental cues such as drought and ultraviolet radiation. The Ser/Thr receptor kinase ORK10/LRK10 and the apoplastic peroxidase POC1 are two downstream targets for regulation by the WRKY53 transcription factor, predicted based on the presence of W-box motifs in their promoters and coregulation with WRKY53, and verified by electrophoretic mobility shift assay (EMSA). Both ORK10/LRK10 and POC1 are upregulated during cereal responses to pathogens and aphids and important components of the oxidative burst during the hypersensitive response. Taken with our yeast two-hybrid assay which identified a strong protein-protein interaction between microsomal glutathione S-transferase 3 and WRKY53, this implies that the WRKY53 transcriptional network regulates oxidative responses to a wide array of stresses.

  1. Ranking of phenols for abiotic oxidation in aqueous environment: a QSPR approach.

    PubMed

    Gramatica, Paola; Pilutti, Pamela; Papa, Ester

    2005-01-01

    The limited availability and variability of data related to the overall degradation of compounds in the environment is a very relevant issue in studies related to environmental fate and chemical behavior. The studied phenol data set consists of reaction rate constants of different oxidation reactions in surface waters, available either experimentally or, to fill the data gap, from our QSAR models reported herein. A PCA (Principal Component Analysis) model based on these oxidative degradations has been proposed to evaluate the degradability of chemicals. The score of the first Principal Component is modelled by theoretical molecular descriptors to obtain a multiple linear regression (MLR) model with high predictive power, both internally and externally validated. This modeling approach allows a fast and preliminary ranking of phenols according to their tendency to be degraded by oxidants in water, starting only from knowledge of their molecular structure.

  2. Effect of Aqueous Fe(II) on Arsenate Sorption on Goethite and Hematite

    SciTech Connect

    Catalano, Jeffrey G.; Luo, Yun; Otemuyiwa, Bamidele

    2011-11-17

    Biogeochemical iron cycling often generates systems where aqueous Fe(II) and solid Fe(III) oxides coexist. Reactions between these species result in iron oxide surface and phase transformations, iron isotope fractionation, and redox transformations of many contaminant species. Fe(II)-induced recrystallization of goethite and hematite has recently been shown to cause the repartitioning of Ni(II) at the mineral-water interface, with adsorbed Ni incorporating into the iron oxide structure and preincorporated Ni released back into aqueous solution. However, the effect of Fe(II) on the fate and speciation of redox inactive species incompatible with iron oxide structures is unclear. Arsenate sorption to hematite and goethite in the presence of aqueous Fe(II) was studied to determine whether Fe(II) causes substantial changes in the sorption mechanisms of such incompatible species. Sorption isotherms reveal that Fe(II) minimally alters macroscopic arsenate sorption behavior except at circumneutral pH in the presence of elevated concentrations (10{sup -3} M) of Fe(II) and at high arsenate loadings, where a clear signature of precipitation is observed. Powder X-ray diffraction demonstrates that the ferrous arsenate mineral symplesite precipitates under such conditions. Extended X-ray absorption fine structure spectroscopy shows that outside this precipitation regime arsenate surface complexation mechanisms are unaffected by Fe(II). In addition, arsenate was found to suppress Fe(II) sorption through competitive adsorption processes before the onset of symplesite precipitation. This study demonstrates that the sorption of species incompatible with iron oxide structure is not substantially affected by Fe(II) but that such species may potentially interfere with Fe(II)-iron oxide reactions via competitive adsorption.

  3. Nitric oxide imbalance provokes a nitrosative response in plants under abiotic stress.

    PubMed

    Corpas, Francisco J; Leterrier, Marina; Valderrama, Raquel; Airaki, Morad; Chaki, Mounira; Palma, José M; Barroso, Juan B

    2011-11-01

    Nitric oxide (NO), a free radical generated in plant cells, belongs to a family of related molecules designated as reactive nitrogen species (RNS). When an imbalance of RNS takes place for any adverse environmental circumstances, some of these molecules can cause direct or indirect damage at the cellular or molecular level, promoting a phenomenon of nitrosative stress. Thus, this review will emphasize the recent progress in understanding the function of NO and its production under adverse environmental conditions.

  4. Mechanisms of nitric oxide crosstalk with reactive oxygen species scavenging enzymes during abiotic stress tolerance in plants.

    PubMed

    Arora, Dhara; Jain, Prachi; Singh, Neha; Kaur, Harmeet; Bhatla, Satish C

    2016-01-01

    Nitric oxide (NO) acts in a concentration and redox-dependent manner to counteract oxidative stress either by directly acting as an antioxidant through scavenging reactive oxygen species (ROS), such as superoxide anions (O(2)(-)*), to form peroxynitrite (ONOO(-)) or by acting as a signaling molecule, thereby altering gene expression. NO can interact with different metal centres in proteins, such as heme-iron, zinc-sulfur clusters, iron-sulfur clusters, and copper, resulting in the formation of a stable metal-nitrosyl complex or production of varied biochemical signals, which ultimately leads to modification of protein structure/function. The thiols (ferrous iron-thiol complex and nitrosothiols) are also involved in the metabolism and mobilization of NO. Thiols bind to NO and transport it to the site of action whereas nitrosothiols release NO after intercellular diffusion and uptake into the target cells. S-nitrosoglutathione (GSNO) also has the ability to transnitrosylate proteins. It is an NO˙ reservoir and a long-distance signaling molecule. Tyrosine nitration of proteins has been suggested as a biomarker of nitrosative stress as it can lead to either activation or inhibition of target proteins. The exact molecular mechanism(s) by which exogenous and endogenously generated NO (or reactive nitrogen species) modulate the induction of various genes affecting redox homeostasis, are being extensively investigated currently by various research groups. Present review provides an in-depth analysis of the mechanisms by which NO interacts with and modulates the activity of various ROS scavenging enzymes, particularly accompanying ROS generation in plants in response to varied abiotic stress.

  5. Modulation of oxygen production in Archaean oceans by episodes of Fe(II) toxicity

    NASA Astrophysics Data System (ADS)

    Swanner, Elizabeth D.; Mloszewska, Aleksandra M.; Cirpka, Olaf A.; Schoenberg, Ronny; Konhauser, Kurt O.; Kappler, Andreas

    2015-02-01

    Oxygen accumulated in the surface waters of the Earth's oceans and atmosphere several hundred million years before the Great Oxidation Event between 2.4 and 2.3 billion years ago. Before the Great Oxidation Event, periods of enhanced submarine volcanism associated with mantle plume events supplied Fe(II) to sea water. These periods generally coincide with the disappearance of indicators of the presence of molecular oxygen in Archaean sedimentary records. The presence of Fe(II) in the water column can lead to oxidative stress in some organisms as a result of reactions between Fe(II) and oxygen that produce reactive oxygen species. Here we test the hypothesis that the upwelling of Fe(II)-rich, anoxic water into the photic zone during the late Archaean subjected oxygenic phototrophic bacteria to Fe(II) toxicity. In laboratory experiments, we found that supplying Fe(II) to the anoxic growth medium housing a common species of planktonic cyanobacteria decreased both the efficiency of oxygenic photosynthesis and their growth rates. We suggest that this occurs because of increasing intracellular concentrations of reactive oxygen species. We use geochemical modelling to show that Fe(II) toxicity in conditions found in the late Archaean photic zone could have substantially inhibited water column oxygen production, thus decreasing fluxes of oxygen to the atmosphere. We therefore propose that the timing of atmospheric oxygenation was controlled by the timing of submarine, plume-type volcanism, with Fe(II) toxicity as the modulating factor.

  6. Plant responses to abiotic stresses: heavy metal-induced oxidative stress and protection by mycorrhization.

    PubMed

    Schützendübel, Andres; Polle, Andrea

    2002-05-01

    The aim of this review is to assess the mode of action and role of antioxidants as protection from heavy metal stress in roots, mycorrhizal fungi and mycorrhizae. Based on their chemical and physical properties three different molecular mechanisms of heavy metal toxicity can be distinguished: (a) production of reactive oxygen species by autoxidation and Fenton reaction; this reaction is typical for transition metals such as iron or copper, (b) blocking of essential functional groups in biomolecules, this reaction has mainly been reported for non-redox-reactive heavy metals such as cadmium and mercury, (c) displacement of essential metal ions from biomolecules; the latter reaction occurs with different kinds of heavy metals. Transition metals cause oxidative injury in plant tissue, but a literature survey did not provide evidence that this stress could be alleviated by increased levels of antioxidative systems. The reason may be that transition metals initiate hydroxyl radical production, which can not be controlled by antioxidants. Exposure of plants to non-redox reactive metals also resulted in oxidative stress as indicated by lipid peroxidation, H(2)O(2) accumulation, and an oxidative burst. Cadmium and some other metals caused a transient depletion of GSH and an inhibition of antioxidative enzymes, especially of glutathione reductase. Assessment of antioxidative capacities by metabolic modelling suggested that the reported diminution of antioxidants was sufficient to cause H(2)O(2) accumulation. The depletion of GSH is apparently a critical step in cadmium sensitivity since plants with improved capacities for GSH synthesis displayed higher Cd tolerance. Available data suggest that cadmium, when not detoxified rapidly enough, may trigger, via the disturbance of the redox control of the cell, a sequence of reactions leading to growth inhibition, stimulation of secondary metabolism, lignification, and finally cell death. This view is in contrast to the idea that

  7. Expression of the tetrahydrofolate-dependent nitric oxide synthase from the green alga Ostreococcus tauri increases tolerance to abiotic stresses and influences stomatal development in Arabidopsis.

    PubMed

    Foresi, Noelia; Mayta, Martín L; Lodeyro, Anabella F; Scuffi, Denise; Correa-Aragunde, Natalia; García-Mata, Carlos; Casalongué, Claudia; Carrillo, Néstor; Lamattina, Lorenzo

    2015-06-01

    Nitric oxide (NO) is a signaling molecule with diverse biological functions in plants. NO plays a crucial role in growth and development, from germination to senescence, and is also involved in plant responses to biotic and abiotic stresses. In animals, NO is synthesized by well-described nitric oxide synthase (NOS) enzymes. NOS activity has also been detected in higher plants, but no gene encoding an NOS protein, or the enzymes required for synthesis of tetrahydrobiopterin, an essential cofactor of mammalian NOS activity, have been identified so far. Recently, an NOS gene from the unicellular marine alga Ostreococcus tauri (OtNOS) has been discovered and characterized. Arabidopsis thaliana plants were transformed with OtNOS under the control of the inducible short promoter fragment (SPF) of the sunflower (Helianthus annuus) Hahb-4 gene, which responds to abiotic stresses and abscisic acid. Transgenic plants expressing OtNOS accumulated higher NO concentrations compared with siblings transformed with the empty vector, and displayed enhanced salt, drought and oxidative stress tolerance. Moreover, transgenic OtNOS lines exhibited increased stomatal development compared with plants transformed with the empty vector. Both in vitro and in vivo experiments indicate that OtNOS, unlike mammalian NOS, efficiently uses tetrahydrofolate as a cofactor in Arabidopsis plants. The modulation of NO production to alleviate abiotic stress disturbances in higher plants highlights the potential of genetic manipulation to influence NO metabolism as a tool to improve plant fitness under adverse growth conditions.

  8. Some new nano-sized Fe(II), Cd(II) and Zn(II) Schiff base complexes as precursor for metal oxides: Sonochemical synthesis, characterization, DNA interaction, in vitro antimicrobial and anticancer activities.

    PubMed

    Abdel-Rahman, Laila H; Abu-Dief, Ahmed M; El-Khatib, Rafat M; Abdel-Fatah, Shimaa Mahdy

    2016-12-01

    The complexes of Fe(II), Cd(II) and Zn(II) with Schiff base derived from 2-amino-3-hydroxypyridine and 3-methoxysalicylaldehyde have been prepared. Melting points, decomposition temperatures, Elemental analyses, TGA, conductance measurements, infrared (IR) and UV-Visible spectrophotometric studies were utilized in characterizing the compounds. The UV-Visible spectrophotometric analysis revealed 1:1 (metal-ligand) stoichiometry for the three complexes. In addition to, the prepared complexes have been used as precursors for preparing their corresponding metal oxides nanoparticles via thermal decomposition. The structures of the nano-sized complexes and their metal oxides were characterized by X-ray powder diffraction and transmittance electron microscopy. Moreover, the prepared Schiff base ligand, its complexes and their corresponding nano-sized metal oxides have been screened in vitro for their antibacterial activity against three bacteria, gram-positive (Microccus luteus) and gram-negative (Escherichia coli, Serratia marcescence) and three strains of fungus. The metal chelates were shown to possess more antimicrobial activity than the free Schiff-base chelate and their nano-sized metal oxides have the highest activity. The binding behaviors of the complexes to calf thymus DNA have been investigated by absorption spectra, viscosity mensuration and gel electrophoresis. The DNA binding constants reveal that all these complexes interact with DNA through intercalative binding mode. Furthermore, the cytotoxic activity of the prepared Schiff base complexes on human colon carcinoma cells, (HCT-116 cell line) and hepatic cellular carcinoma cells, (HepG-2) showed potent cytotoxicity effect against growth of carcinoma cells compared to the clinically used Vinblastine standard.

  9. 3-D analysis of bacterial cell-(iron)mineral aggregates formed during Fe(II) oxidation by the nitrate-reducing Acidovorax sp. strain BoFeN1 using complementary microscopy tomography approaches.

    PubMed

    Schmid, G; Zeitvogel, F; Hao, L; Ingino, P; Floetenmeyer, M; Stierhof, Y-D; Schroeppel, B; Burkhardt, C J; Kappler, A; Obst, M

    2014-07-01

    The formation of cell-(iron)mineral aggregates as a consequence of bacterial iron oxidation is an environmentally widespread process with a number of implications for processes such as sorption and coprecipitation of contaminants and nutrients. Whereas the overall appearance of such aggregates is easily accessible using 2-D microscopy techniques, the 3-D and internal structure remain obscure. In this study, we examined the 3-D structure of cell-(iron)mineral aggregates formed during Fe(II) oxidation by the nitrate-reducing Acidovorax sp. strain BoFeN1 using a combination of advanced 3-D microscopy techniques. We obtained 3-D structural and chemical information on different cellular encrustation patterns at high spatial resolution (4-200 nm, depending on the method): more specifically, (1) cells free of iron minerals, (2) periplasm filled with iron minerals, (3) spike- or platelet-shaped iron mineral structures, (4) bulky structures on the cell surface, (5) extracellular iron mineral shell structures, (6) cells with iron mineral filled cytoplasm, and (7) agglomerations of extracellular globular structures. In addition to structural information, chemical nanotomography suggests a dominant role of extracellular polymeric substances (EPS) in controlling the formation of cell-(iron)mineral aggregates. Furthermore, samples in their hydrated state showed cell-(iron)mineral aggregates in pristine conditions free of preparation (i.e., drying/dehydration) artifacts. All these results were obtained using 3-D microscopy techniques such as focused ion beam (FIB)/scanning electron microscopy (SEM) tomography, transmission electron microscopy (TEM) tomography, scanning transmission (soft) X-ray microscopy (STXM) tomography, and confocal laser scanning microscopy (CLSM). It turned out that, due to the various different contrast mechanisms of the individual approaches, and due to the required sample preparation steps, only the combination of these techniques was able to provide a

  10. Effect of NaCl, myoglobin, Fe(II), and Fe(III) on lipid oxidation of raw and cooked chicken breast and beef loin.

    PubMed

    Min, Byungrok; Cordray, Joseph C; Ahn, Dong Uk

    2010-01-13

    Chicken breast and beef loin were ground, and no, NaCl, NaCl+myoglobin, NaCl+Fe(II), or NaCl+Fe(III) additions were made; patties were then prepared. Half of the patties were packaged in oxygen-permeable bags and stored at 4 degrees C for 10 days, and the other half were cooked in a 95 degrees C water bath to an internal temperature of 75 degrees C, packaged in oxygen-permeable zipper bags, and stored at 4 degrees C for 7 days. The oxidative stability of raw and cooked chicken breast and beef loin were determined during storage. Chicken breast was more resistant to various exogenous oxidative factors than beef loin: addition of NaCl did not increase TBARS values and nonheme content of raw chicken breast, but significantly increased those of raw beef loin patties during storage. Addition of NaCl+Mb did not affect lipid oxidation in raw chicken breast patties, but decreased the TBARS of beef loin during storage. Addition of NaCl+Fe(III) or NaCl+Fe(II) increased the TBARS values of both raw chicken breast and beef loin during storage, but the increase was greater in beef loin than in chicken breast. The TBARS values of all cooked chicken breast and beef loin increased during 7 days of storage, but the increases in cooked chicken patties were significantly smaller than those of cooked beef loin patties with the same treatments. Addition of NaCl and cooking caused severe degradation of myoglobin, leading to a significant increase in free ionic iron content in beef loin. It is suggested that free ionic iron is the major catalyst for lipid oxidation, and the low "storage-stable and heat-stable" ferric ion reducing capacity in chicken breast were responsible for the high oxidative stability for raw and cooked chicken breast compared with beef loin under prooxidants, cooking, and storage conditions.

  11. Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

    NASA Astrophysics Data System (ADS)

    Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

    2017-01-01

    The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic

  12. When Bad Guys Become Good Ones: The Key Role of Reactive Oxygen Species and Nitric Oxide in the Plant Responses to Abiotic Stress.

    PubMed

    Farnese, Fernanda S; Menezes-Silva, Paulo E; Gusman, Grasielle S; Oliveira, Juraci A

    2016-01-01

    The natural environment of plants is composed of a complex set of abiotic stresses and their ability to respond to these stresses is highly flexible and finely balanced through the interaction between signaling molecules. In this review, we highlight the integrated action between reactive oxygen species (ROS) and reactive nitrogen species (RNS), particularly nitric oxide (NO), involved in the acclimation to different abiotic stresses. Under stressful conditions, the biosynthesis transport and the metabolism of ROS and NO influence plant response mechanisms. The enzymes involved in ROS and NO synthesis and scavenging can be found in different cells compartments and their temporal and spatial locations are determinant for signaling mechanisms. Both ROS and NO are involved in long distances signaling (ROS wave and GSNO transport), promoting an acquired systemic acclimation to abiotic stresses. The mechanisms of abiotic stresses response triggered by ROS and NO involve some general steps, as the enhancement of antioxidant systems, but also stress-specific mechanisms, according to the stress type (drought, hypoxia, heavy metals, etc.), and demand the interaction with other signaling molecules, such as MAPK, plant hormones, and calcium. The transduction of ROS and NO bioactivity involves post-translational modifications of proteins, particularly S-glutathionylation for ROS, and S-nitrosylation for NO. These changes may alter the activity, stability, and interaction with other molecules or subcellular location of proteins, changing the entire cell dynamics and contributing to the maintenance of homeostasis. However, despite the recent advances about the roles of ROS and NO in signaling cascades, many challenges remain, and future studies focusing on the signaling of these molecules in planta are still necessary.

  13. When Bad Guys Become Good Ones: The Key Role of Reactive Oxygen Species and Nitric Oxide in the Plant Responses to Abiotic Stress

    PubMed Central

    Farnese, Fernanda S.; Menezes-Silva, Paulo E.; Gusman, Grasielle S.; Oliveira, Juraci A.

    2016-01-01

    The natural environment of plants is composed of a complex set of abiotic stresses and their ability to respond to these stresses is highly flexible and finely balanced through the interaction between signaling molecules. In this review, we highlight the integrated action between reactive oxygen species (ROS) and reactive nitrogen species (RNS), particularly nitric oxide (NO), involved in the acclimation to different abiotic stresses. Under stressful conditions, the biosynthesis transport and the metabolism of ROS and NO influence plant response mechanisms. The enzymes involved in ROS and NO synthesis and scavenging can be found in different cells compartments and their temporal and spatial locations are determinant for signaling mechanisms. Both ROS and NO are involved in long distances signaling (ROS wave and GSNO transport), promoting an acquired systemic acclimation to abiotic stresses. The mechanisms of abiotic stresses response triggered by ROS and NO involve some general steps, as the enhancement of antioxidant systems, but also stress-specific mechanisms, according to the stress type (drought, hypoxia, heavy metals, etc.), and demand the interaction with other signaling molecules, such as MAPK, plant hormones, and calcium. The transduction of ROS and NO bioactivity involves post-translational modifications of proteins, particularly S-glutathionylation for ROS, and S-nitrosylation for NO. These changes may alter the activity, stability, and interaction with other molecules or subcellular location of proteins, changing the entire cell dynamics and contributing to the maintenance of homeostasis. However, despite the recent advances about the roles of ROS and NO in signaling cascades, many challenges remain, and future studies focusing on the signaling of these molecules in planta are still necessary. PMID:27148300

  14. The interactive biotic and abiotic processes of DDT transformation under dissimilatory iron-reducing conditions.

    PubMed

    Jin, Xin; Wang, Fang; Gu, Chenggang; Yang, Xinglun; Kengara, Fredrick O; Bian, Yongrong; Song, Yang; Jiang, Xin

    2015-11-01

    The objective of the study was to elucidate the biotic and abiotic processes under dissimilatory iron reducing conditions involved in reductive dechlorination and iron reduction. DDT transformation was investigated in cultures of Shewanella putrefaciens 200 with/without α-FeOOH. A modified first-order kinetics model was developed and described DDT transformation well. Both the α-FeOOH reduction rate and the dechlorination rate of DDT were positively correlated to the biomass. Addition of α-FeOOH enhanced reductive dechlorination of DDT by favoring the cell survival and generating Fe(II) which was absorbed on the surface of bacteria and iron oxide. 92% of the absorbed Fe(II) was Na-acetate (1M) extractable. However, α-FeOOH also played a negative role of competing for electrons as reflected by the dechlorination rate of DDT was inhibited when increasing the α-FeOOH from 1 g L(-1) to 5 g L(-1). DDT was measured to be toxic to S. putrefaciens 200. The metabolites DDD, DDE and DDMU were recalcitrant to S. putrefaciens 200. The results suggested that iron oxide was not the key factor to promote the dissipation of DDX (DDT and the metabolites), whereas the one-electron reduction potential (E1) of certain organochlorines is the main factor and that the E1 higher than the threshold of the reductive driving forces of DIRB probably ensures the occur of reductive dechlorination.

  15. Biotic conversion of sulphate to sulphide and abiotic conversion of sulphide to sulphur in a microbial fuel cell using cobalt oxide octahedrons as cathode catalyst.

    PubMed

    Chatterjee, Pritha; Ghangrekar, M M; Rao, Surampalli; Kumar, Senthil

    2017-02-08

    Varying chemical oxygen demand (COD) and sulphate concentrations in substrate were used to determine reaction kinetics and mass balance of organic matter and sulphate transformation in a microbial fuel cell (MFC). MFC with anodic chamber volume of 1 L, fed with wastewater having COD of 500 mg/L and sulphate of 200 mg/L, could harvest power of 54.4 mW/m(2), at a Coulombic efficiency of 14%, with respective COD and sulphate removals of 90 and 95%. Sulphide concentration, even up to 1500 mg/L, did not inhibit anodic biochemical reactions, due to instantaneous abiotic oxidation to sulphur, at high inlet sulphate. Experiments on abiotic oxidation of sulphide to sulphur revealed maximum oxidation taking place at an anodic potential of -200 mV. More than 99% sulphate removal could be achieved in a MFC with inlet COD/sulphate of 0.75, giving around 1.33 kg/m(3) day COD removal. Bioelectrochemical conversion of sulphate facilitating sulphur recovery in a MFC makes it an interesting pollution abatement technique.

  16. Experimental Study on How Human Lung Surfactant Protein SP-B1-25 is Oxidized by Ozone in the Presence of Fe(II) and Ascorbic Acid

    NASA Astrophysics Data System (ADS)

    Colussi, A. J.; Enami, S.; Hoffmann, M. R.

    2014-12-01

    We will report the results of experiments on the chemical fate of the human lung surfactant protein SP-B1-25 upon exposure to gaseous ozone in realistic aqueous media simulating the conditions prevalent in epithelial lining fluids in polluted ambient air. Our experiments consist of exposing aqueous microjets containing SP-B1-25, the natural antioxidant ascorbic acid, and the Fe2+ carried by most atmospheric fine particulates, under mild acidic conditions, such as those created by the innate lung host defense response. Reactants and the products of such interactions are detected via online electrospray ionization mass spectrometry. We will show that ascorbic acid largely inhibits the ozonation of SP-B1-25 in the absence of Fe2+, leading to the formation of an ascorbic acid ozonide (Enami et al., PNAS 2008). In the presence of Fe2+, however, the ozonide decomposes into reactive intermediates that result in the partial oxidation of SP-B1-25, presumable affecting its function as surfactant. We infer that these experimental results establish a plausible causal link for the observed synergic adverse health effects of ambient ozone and fine particulates

  17. Iron mediates catalysis of nucleic acid processing enzymes: support for Fe(II) as a cofactor before the great oxidation event.

    PubMed

    Okafor, C Denise; Lanier, Kathryn A; Petrov, Anton S; Athavale, Shreyas S; Bowman, Jessica C; Hud, Nicholas V; Williams, Loren Dean

    2017-03-15

    Life originated in an anoxic, Fe2+-rich environment. We hypothesize that on early Earth, Fe2+ was a ubiquitous cofactor for nucleic acids, with roles in RNA folding and catalysis as well as in processing of nucleic acids by protein enzymes. In this model, Mg2+ replaced Fe2+ as the primary cofactor for nucleic acids in parallel with known metal substitutions of metalloproteins, driven by the Great Oxidation Event. To test predictions of this model, we assay the ability of nucleic acid processing enzymes, including a DNA polymerase, an RNA polymerase and a DNA ligase, to use Fe2+ in place of Mg2+ as a cofactor during catalysis. Results show that Fe2+ can indeed substitute for Mg2+ in catalytic function of these enzymes. Additionally, we use calculations to unravel differences in energetics, structures and reactivities of relevant Mg2+ and Fe2+ complexes. Computation explains why Fe2+ can be a more potent cofactor than Mg2+ in a variety of folding and catalytic functions. We propose that the rise of O2 on Earth drove a Fe2+ to Mg2+ substitution in proteins and nucleic acids, a hypothesis consistent with a general model in which some modern biochemical systems retain latent abilities to revert to primordial Fe2+-based states when exposed to pre-GOE conditions.

  18. Connecting observations of hematite (alpha-Fe2O3) growth catalyzed by Fe(II).

    PubMed

    Rosso, Kevin M; Yanina, Svetlana V; Gorski, Christopher A; Larese-Casanova, Philip; Scherer, Michelle M

    2010-01-01

    Electron exchange between aqueous Fe(II) and structural Fe(III) in iron oxides and oxyhydroxides is important for understanding degradation of environmental pollutants through its apparent constitutive role underlying highly reactive "sorbed Fe(II)" and by catalyzing phase interconversion among these minerals. Although a mechanistic understanding of relationships between interfacial Fe(II)(ads)-Fe(III)(oxide) electron transfer, bulk electron conduction, Fe(II) release, and phase transformation behavior is emerging, much remains unclear, in part due to poorly interconnected investigations. The focus of this study is on reconciling two mutually similar observations of Fe(II)-catalyzed hematite growth documented spectroscopically and microscopically under substantially different chemical conditions. Here, we employ iron isotopic labeling to demonstrate that hematite grown on the (001) surface in Fe(II)-oxalate solution at pH 2.10 and 348 K has magnetic properties that closely correspond to those of hematite grown in Fe(II) solution at pH 7.4 and room temperature. The temperature evolution and extent of the Morin transition displayed in these two materials strongly suggest a mechanistic link involving trace structural Fe(II) incorporation into the growing hematite. Our findings indicate that Fe(II) catalyzed growth of hematite on hematite can occur under environmentally relevant conditions and may be due to bulk electron conduction previously demonstrated for hematite single crystals.

  19. Trace element cycling through iron oxide minerals during redox-driven dynamic recrystallization

    SciTech Connect

    Frierdich, Andrew J.; Luo, Yun; Catalano, Jeffrey G.

    2011-11-17

    Microbially driven iron redox cycling in soil and sedimentary systems, including during diagenesis and fluid migration, may activate secondary abiotic reactions between aqueous Fe(II) and solid Fe(III) oxides. These reactions catalyze dynamic recrystallization of iron oxide minerals through localized and simultaneous oxidative adsorption of Fe(II) and reductive dissolution of Fe(III). Redox-active trace elements undergo speciation changes during this process, but the impact redox-driven recrystallization has on redox-inactive trace elements associated with iron oxides is uncertain. Here we demonstrate that Ni is cycled through the minerals goethite and hematite during redox-driven recrystallization. X-ray absorption spectroscopy demonstrates that during this process adsorbed Ni becomes progressively incorporated into the minerals. Kinetic studies using batch reactors containing aqueous Fe(II) and Ni preincorporated into iron oxides display substantial release of Ni to solution. We conclude that iron oxide recrystallization activated by aqueous Fe(II) induces cycling of Ni through the mineral structure, with adsorbed Ni overgrown in regions of Fe(II) oxidative adsorption and incorporated Ni released in regions of reductive dissolution of structural Fe(III). The redistribution of Ni among the mineral bulk, mineral surface, and aqueous solution appears to be thermodynamically controlled and catalyzed by Fe(II). Our work suggests that important proxies for ocean composition on the early Earth may be invalid, identifies new processes controlling micronutrient availability in soil, sedimentary, and aquatic ecosystems, and points toward a mechanism for trace element mobilization during diagenesis and enrichment in geologic fluids.

  20. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    NASA Astrophysics Data System (ADS)

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J. K.

    2017-01-01

    . Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation-reduction reaction.

  1. Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems

    USGS Publications Warehouse

    Wang, Hongmei; Gong, Linfeng; Cravotta, Charles A.; Yang, Xiaofen; Tuovinen, Olli H.; Dong, Hailiang; Fu, Xiang

    2013-01-01

    Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO3)2 was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0–24.2 mM Pb(II) added as Pb(NO3)2. Anglesite (PbSO4) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe3(SO4)2(OH)6) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9–17.6 μM regardless of the concentrations of Pb(NO3)2 added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO3)2 addition even when anglesite was removed before inoculation. Experiments with 0–48 mM KNO3 demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO3)2 addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans.

  2. Inhibition of bacterial oxidation of ferrous iron by lead nitrate in sulfate-rich systems.

    PubMed

    Wang, Hongmei; Gong, Linfeng; Cravotta, Charles A; Yang, Xiaofen; Tuovinen, Olli H; Dong, Hailiang; Fu, Xiang

    2013-01-15

    Inhibition of bacterial oxidation of ferrous iron (Fe(II)) by Pb(NO(3))(2) was investigated with a mixed culture of Acidithiobacillus ferrooxidans. The culture was incubated at 30 °C in ferrous-sulfate medium amended with 0-24.2 mM Pb(II) added as Pb(NO(3))(2). Anglesite (PbSO(4)) precipitated immediately upon Pb addition and was the only solid phase detected in the abiotic controls. Both anglesite and jarosite (KFe(3)(SO(4))(2)(OH)(6)) were detected in inoculated cultures. Precipitation of anglesite maintained dissolved Pb concentrations at 16.9-17.6 μM regardless of the concentrations of Pb(NO(3))(2) added. Fe(II) oxidation was suppressed by 24.2 mM Pb(NO(3))(2) addition even when anglesite was removed before inoculation. Experiments with 0-48 mM KNO(3) demonstrated that bacterial Fe(II) oxidation decreased as nitrate concentration increased. Therefore, inhibition of Fe(II) oxidation at 24.2 mM Pb(NO(3))(2) addition resulted from nitrate toxicity instead of Pb addition. Geochemical modeling that considered the initial precipitation of anglesite to equilibrium followed by progressive oxidation of Fe(II) and the precipitation of jarosite and an amorphous iron hydroxide phase, without allowing plumbojarosite to precipitate were consistent with the experimental time-series data on Fe(II) oxidation under biotic conditions. Anglesite precipitation in mine tailings and other sulfate-rich systems maintains dissolved Pb concentrations below the toxicity threshold of A. ferrooxidans.

  3. Anoxic nitrate reduction coupled with iron oxidation and attenuation of dissolved arsenic and phosphate in a sand and gravel aquifer

    USGS Publications Warehouse

    Smith, Richard L.; Kent, Douglas B.; Repert, Deborah A.; Böhlke, J.K.

    2017-01-01

    weeks. Additionally, Fe(II)-oxidizing, nitrate-reducing microbial enrichment cultures were obtained from aquifer sediments. Growth experiments with the cultures sequentially produced nitrite and nitrous oxide from nitrate while simultaneously oxidizing Fe(II). Field and culture results suggest that nitrogen oxide reduction and Fe(II) oxidation in the aquifer are a complex interaction of coupled biotic and abiotic reactions. Overall, the results of this study demonstrate that anoxic nitrate-dependent iron oxidation can occur in groundwater; that it could control iron speciation; and that the process can impact the mobility of other chemical species (e.g., phosphate and arsenic) not directly involved in the oxidation–reduction reaction.

  4. Fe(II) uptake on natural montmorillonites. I. Macroscopic and spectroscopic characterization.

    PubMed

    Soltermann, Daniela; Marques Fernandes, Maria; Baeyens, Bart; Dähn, Rainer; Joshi, Prachi A; Scheinost, Andreas C; Gorski, Christopher A

    2014-01-01

    Iron is an important redox-active element that is ubiquitous in both engineered and natural environments. In this study, the retention mechanism of Fe(II) on clay minerals was investigated using macroscopic sorption experiments combined with Mössbauer and extended X-ray absorption fine structure (EXAFS) spectroscopy. Sorption edges and isotherms were measured under anoxic conditions on natural Fe-bearing montmorillonites (STx, SWy, and SWa) having different structural Fe contents ranging from 0.5 to 15.4 wt % and different initial Fe redox states. Batch experiments indicated that, in the case of low Fe-bearing (STx) and dithionite-reduced clays, the Fe(II) uptake follows the sorption behavior of other divalent transition metals, whereas Fe(II) sorption increased by up to 2 orders of magnitude on the unreduced, Fe(III)-rich montmorillonites (SWy and SWa). Mössbauer spectroscopy analysis revealed that nearly all the sorbed Fe(II) was oxidized to surface-bound Fe(III) and secondary Fe(III) precipitates were formed on the Fe(III)-rich montmorillonite, while sorbed Fe is predominantly present as Fe(II) on Fe-low and dithionite-reduced clays. The results provide compelling evidence that Fe(II) uptake characteristics on clay minerals are strongly correlated to the redox properties of the structural Fe(III). The improved understanding of the interfacial redox interactions between sorbed Fe(II) and clay minerals gained in this study is essential for future studies developing Fe(II) sorption models on natural montmorillonites.

  5. Triple-oxygen-isotope determination of molecular oxygen incorporation in sulfate produced during abiotic pyrite oxidation (pH = 2-11)

    NASA Astrophysics Data System (ADS)

    Kohl, Issaku; Bao, Huiming

    2011-04-01

    Aqueous oxidation of sulfide minerals to sulfate is an integral part of the global sulfur and oxygen cycles. The current model for pyrite oxidation emphasizes the role of Fe 2+-Fe 3+ electron shuttling and repeated nucleophilic attack by water molecules on sulfur. Previous δ 18O-labeled experiments show that a variable fraction (0-60%) of the oxygen in product sulfate is derived from dissolved O 2, the other potential oxidant. This indicates that nucleophilic attack cannot continue all the way to sulfate and that a sulfoxyanion of intermediate oxidation state is released into solution. The observed variability in O 2% may be due to the presence of competing oxidation pathways, variable experimental conditions (e.g. abiotic, biotic, or changing pH value), or uncertainties related to the multiple experiments needed to effectively use the δ 18O label to differentiate sulfate-oxygen sources. To examine the role of O 2 and Fe 3+ in determining the final incorporation of O 2 oxygen in sulfate produced during pyrite oxidation, we designed a set of aerated, abiotic, pH-buffered (pH = 2, 7, 9, 10, and 11), and triple-oxygen-isotope labeled solutions with and without Fe 3+ addition. While abiotic and pH-buffered conditions help to eliminate variables, triple oxygen isotope labeling and Fe 3+ addition help to determine the oxygen sources in sulfate and examine the role of Fe 2+-Fe 3+ electron shuttling during sulfide oxidation, respectively. Our results show that sulfate concentration increased linearly with time and the maximum concentration was achieved at pH 11. At pH 2, 7, and 9, sulfate production was slow but increased by 4× with the addition of Fe 3+. Significant amounts of sulfite and thiosulfate were detected in pH ⩾ 9 reactors, while concentrations were low or undetectable at pH 2 and 7. The triple oxygen isotope data show that at pH ⩾ 9, product sulfate contained 21-24% air O 2 signal, similar to pH 2 with Fe 3+ addition. Sulfate from the pH 2 reactor

  6. Anaerobic Nitrate-Dependent Metal Bio-Oxidation

    NASA Astrophysics Data System (ADS)

    Weber, K.; Knox, T.; Achenbach, L. A.; Coates, J. D.

    2007-12-01

    Direct biological oxidation of reduced metals (Fe(II) and U(IV)) coupled to nitrate reduction at circumneutral pH under anaerobic conditions has been recognized in several environments as well as pure culture. Several phylogentically diverse mesophilic bacteria have been described as capable of anaerobic, nitrate-dependent Fe(II) oxidation (NFOx). Our recent identification of a freshwater mesophilic, lithoautotroph, Ferrutens nitratireducens strain 2002, capable of growth through NFOx presents an opportunity to further study metal bio- oxidation. Continuing physiological studies revealed that in addition to Fe(II) oxidation, strain 2002 is capable of oxidizing U(IV) (4 μM) in washed cell suspensions with nitrate serving as the electron acceptor. Pasteurized cultures exhibited abiotic oxidation of 2 μM U(IV). Under growth conditions, strain 2002 catalyzed the oxidation of 12 μM U(IV) within a two week period. Cultures amended with sodium azide, an electron transport inhibitor, demonstrated limited oxidation (7 μM) similar to pasteurized cultures, supporting the direct role of electron transport in U(IV) bio-oxidation. The oxidation of U(IV) coupled denitrification at circumneutral pH would yield enough energy to support anaerobic microbial growth (ΔG°'= -460.36 kJ/mole). It is currently unknown whether or not strain 2002 can couple this metabolism to growth. The growth of F. nitratireducens strain 2002 utilizing Fe(II) as the sole electron donor was previously demonstrated. The amount of U(IV) (~12 μM) that strain 2002 oxidized under similar autotrophic growth conditions yields 0.0019 kJ, enough energy for the generation of ATP (5.3 x 10-20 kJ ATP-1), but not enough energy for cell replication as calculated for nitrate-dependent Fe(II) oxidizing conditions (0.096 kJ) assuming a similar metabolism. In addition to F. nitratireducens strain 2002, a nitrate-dependent Fe(II) oxidizing bacterium isolated from U contaminated groundwater, Diaphorobacter sp. strain

  7. Determination of dissolved Fe(II) in seawater of the western North Pacific with luminol chemiluminescence method

    NASA Astrophysics Data System (ADS)

    Obata, H.; Mase, A.; Gamo, T.; Nishioka, J.; Takeda, S.

    2010-12-01

    Determination of dissolved Fe(II) in seawater of the western North Pacific with luminol chemiluminescence method Hajime Obata, Akira Mase, Toshitaka Gamo (Atmosphere and Ocean Research Institute, University of Tokyo, Japan), Jun Nishioka (Institute of Low Temperature Science, Hokkaido University, Japan), Shigenobu Takeda (Faculty of Fisheries, Nagasaki University, Japan) Speciation of iron in the ocean is now important topics because the bioavailability of iron depends on its chemical form in seawater. However, marine biogeochemical process of Fe(II) has not been fully investigated. In this study, we determined Fe(II) in seawaters using the luminol chemiluminescence method after acidifying the samples to pH 6(Hansard and Landing, 2009). The same samples collected in the western North Pacific were analyzed by the flow chemiluminescence methods with acidification to pH 6 and without acidification. The results with both methods were almost identical. Time variation of Fe(II) in seawater after acidifying the samples to pH 6 were examined in the western North Pacific and the Bering Sea. Within 10 minutes, variations of Fe(II) were small in the open ocean waters, whereas Fe(II) concentrations increased rapidly in surface waters collected in the Bering Sea. The acidification method is not always applicable for seawater samples, especially in the marginal sea. Surface distributions of Fe(II) in the western subarctic North Pacific were investigated by using a continuous clean sampling system for surface waters. The Fe(II) concentrations ranged from <9 to 42 pM, which were lower than those in previous studies (Roy et al., 2008). The variation of Fe(II) probably reflects the photoreduction process of Fe(III), slow oxidation of Fe(II) and differences of Fe(II) concentrations among water masses. In this study, we also examined the oxidation process of Fe(II) in seawater of the western North Pacific and the Bering Sea at some temperatures. The oxidation rates were slower in the

  8. Effect of Phosphate on Surface Properties of Ferrihydrite and its Reactivity towards Aqueous Fe(II)

    NASA Astrophysics Data System (ADS)

    Liao, D.; Schroeder, C.; Haderlein, S.

    2012-12-01

    The iron redox cycle plays a prominent role for the biogeochemical cycling of nutrients and metals as well as transformation of contaminants in soils, sediments and aquifers. The mineral surface acts as a sorption site for Fe(II), which becomes partially oxidized upon sorption [1]. According to Gorski and Scherer [2], the electron is transferred to the bulk mineral, where it may be stored in a conduction band leading to an increased reductive potential of the system. Iron (hydr)oxides also exhibit a high sorption capacity for phosphate which forms strong surface complexes with iron. Phosphate is a common constituent of pore waters as a result of agricultural fertilizers, and is frequently used by microbiologists as buffer in laboratory experiments. We investigated the effect of phosphate on the oxidation of Fe(II) in the presence of ferrihydrite minerals in batch reactors. We synthesized three different ferrihydrites: untreated ferrihydrite (Fh); phosphate-coated ferrihydrite (pc-Fh), where phosphate was added to suspensions of pure ferrihydrite and allowed to sorb to the mineral surface; and phosphate-doped ferrihydrite (pd-Fh), where phosphate co-precipitated with ferrihydrite and was included in the bulk mineral structure. Nitrobenzene was used as model oxidant to study ferrous iron oxidation in anoxic Fh-Fe(II) suspensions. Fe(II) oxidation was much slower in the presence of pc-Fh and pd-Fh compared to untreated Fh. Using Mössbauer spectroscopy, we added dissolved Fe(II) either as pure 57Fe (Mössbauer-active) to analyse for the iron fraction associated with the minerals surface, or as 56Fe (Mössbauer-inactive) to focus on the bulk mineral only. We took Mössbauer spectra for each system before and after Fe(II) oxidation by nitrobenzene. Surface bound Fe(II) was oxidized by two processes: e-transfer to structural Fe(III) in Fh and nitrobenzene reduction. The oxidation product was lepidocrocite which increased with nitrobenzene reduction. Phosphate-doped and

  9. Reduction of the carbamate pesticides oxamyl and methomyl by dissolved FeII and CuI.

    PubMed

    Strathmann, T J; Stone, A T

    2001-06-15

    The degradation of two oxime carbamate pesticides, oxamyl and methomyl, was investigated in anoxic solutions containing various metal ions and reducing agents. In reagent-free solutions, these carbamates degrade slowly via base-catalyzed elimination. Rates of carbamate degradation are accelerated by Fe(II), Cu(I), and Cu(II), but not by several other metal ions and reducing agents. In the presence of Fe(II), carbamates undergo a net two-electron reduction that is coupled to the sequential one-electron oxidation of two Fe(II) ions. The observed products are a substituted nitrile, methanethiol, and methylamine. A radical intermediate is inferred by polymerization of the radical scavenger acrylonitrile. Redox kinetics (i) vary with carbamate identity, (ii) exhibit first-order dependence on both Fe(II) and carbamate concentration, (iii) are relatively independent of pH, (iv) follow Arrhenius temperature dependence, and (v) are only indirectly influenced by the presence of O2. Coordinatively saturated Fe(II) complexes (Fe(II)EDTA2- and Fe(II)(CN)6(4-)) react with oxamyl at rates equal to and greater than hexaquo Fe(II), respectively, indicating that an inner-sphere Fe(II)-carbamate coordination complex is not required for electron transfer. Experimental results indicate that Cu(I) reduces the carbamates by the same mechanism as Fe(II) but at much higher rates. In contrast, Cu(II) acts as a catalyst for both elimination and reduction reactions.

  10. Reduction of TcO4- by sediment-associated biogenic Fe(II)

    SciTech Connect

    Fredrickson, Jim K.; Zachara, John M.; Kennedy, David W.; Kukkadapu, Ravi K.; McKinley, James P.; Heald, Steve M.; Liu, Chongxuan; Plymale, Andrew E.

    2004-08-01

    The potential for reduction of {sup 99}TcO{sub 4}{sup -}{sub aq} to poorly soluble {sup 99}TcO{sub 2} {center_dot} nH{sub 2}O{sub (s)} by biogenic sediment-associated Fe(II) was investigated with three Fe(III)-oxide containing subsurface materials and the dissimilatory metal-reducing subsurface bacterium Shewanella putrefaciens CN32. Two of the subsurface materials from the U.S. Department of Energy's Hanford and Oak Ridge sites contained significant amounts of Mn(III,IV) oxides and net bioreduction of Fe(III) to Fe(II) was not observed until essentially all of the hydroxylamine HCl-extractable Mn was reduced. In anoxic, unreduced sediment or where Mn oxide bioreduction was incomplete, exogenous biogenic TcO{sub 2} {center_dot} nH{sub 2}O{sub (s)} was slowly oxidized over a period of weeks. Subsurface materials that were bioreduced to varying degrees and then pasteurized to eliminate biological activity, reduced TcO{sub 4}{sup -}{sub (aq)} at rates that generally increased with increasing concentrations of 0.5 N HCl-extractable Fe(II). Two of the sediments showed a common relationship between extractable Fe(II) concentration (in mM) and the first-order reduction rate (in h{sup -1}), whereas the third demonstrated a markedly different trend. A combination of chemical extractions and {sup 57}Fe Moessbauer spectroscopy were used to characterize the Fe(III) and Fe(II) phases. There was little evidence of the formation of secondary Fe(II) biominerals as a result of bioreduction, suggesting that the reactive forms of Fe(II) were predominantly surface complexes of different forms. The reduction rates of Tc(VII)O{sub 4}{sup -} were slowest in the sediment that contained plentiful layer silicates (illite, vermiculite, and smectite), suggesting that Fe(II) sorption complexes on these phases were least reactive toward pertechnetate. These results suggest that the in situ microbial reduction of sediment-associated Fe(III), either naturally or via redox manipulation, may be

  11. Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

    USGS Publications Warehouse

    Asta, M.P.; Kirk, Nordstrom D.; Blaine, McCleskey R.

    2012-01-01

    Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)-H 2SO 4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl - concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15-78??mol/L/h whereas Sb(III) oxidized at 0.03-0.05??mol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01-0.03 and 0.01-0.02??mol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt. ?? 2011 Elsevier Ltd.

  12. The Impact of Fe(II) on NO2- Isotopic Composition During Denitrification by Natural Sediment

    NASA Astrophysics Data System (ADS)

    Diaz-Etchevehere, D.; Wankel, S. D.

    2015-12-01

    The role of Fe(II) on Nitrite (NO2-) isotopic composition during denitrification was investigated in anaerobic, closed-system batch incubations of tidal marsh sediments. Fe(II) is often found in similar redox conditions and can rapidly reduce NO2- to N2 and/or nitrous oxide (N2O), a potent greenhouse gas, through a process called chemodenitrification. Microbial communities can also reduce nitrate (NO3-) to NO2- and eventually to N2O through the anaerobic process of biological denitrification. This study compared the impact on NO2- accumulation when Fe(III)-containing minerals ferrihydrite and goethite were added to natural sediments. The presence of dissolved Fe(II), presumably produced by microbial iron reduction, significantly limited the amount of NO2- accumulation, suggesting that Fe(II) may have chemically reduced NO2-. Changes in the δ15N of the intermediate NO2- pool in each bottle was measured, but the apparent isotope effects of NO2- reduction were indistinguishable among treatments, suggesting that the reaction of Fe(II) and NO2- imparts an isotope effect on the NO2- pool of a similar magnitude to that of biological NO2- reduction. The isotopic composition of N2O and its 15N site preference will be measured to determine if chemodenitrification truly occurred, and if so, the relative contributions to N2O production from biological denitrification and chemodenitrification will be determined.

  13. Inhibited Cr(VI) reduction by aqueous Fe(II) under hyperalkaline conditions.

    PubMed

    He, Y Thomas; Chen, Chia-Chen; Traina, Samuel J

    2004-11-01

    This study investigated Cr(VI) reduction by dissolved Fe(II) in hyperalkaline pH conditions as found in fluid wastes associated with the U.S. nuclear weapons program. The results show that Cr(VI) reduction by Fe(II) at alkaline pH solutions proceeds very quickly. The amount of Cr(VI) removed from solution and the amount reduced increases with Fe(II):Cr(VI) ratio. However, the Cr(VI) reduction under alkaline pH condition is nonstoichiometric, probably due to Fe(II) precipitation and mixed iron(III)-chromium-(III) (oxy)hydroxides blocking Fe(II) surface sites, as well as removing Fe(II) from solution through O2 oxidation. After Cr(VI) was reduced to Cr(III), it precipitated out as mixed Fe(x)Cr1-xO3(solids) and various Fe(III) precipitates with an overall Cr:Fe ratio of 1:3; all Cr remaining in the solution phase was unreduced Cr(VI). EXAFS data showed that Cr-O and Cr-Cr distances in the precipitates equal to 1.98 and 3.01 A, respectively, consistent with the spinel-type structure as chromite.

  14. Dissolved Fe(II) in the Arabian Sea oxygen minimum zone and western tropical Indian Ocean during the inter-monsoon period

    NASA Astrophysics Data System (ADS)

    Kondo, Yoshiko; Moffett, James W.

    2013-03-01

    The concentration of iron(II) (Fe(II)) in seawater was investigated throughout the water column in the Arabian Sea and western tropical Indian Ocean including the oxygen minimum zone (OMZ) as part of the 2009 Japanese GEOTRACES cruise using a luminol-chemiluminescence detection based flow injection analysis technique. A novel modification was the adjustment of the sample pH to 7.2 with a 3-(N-morpholino) propanesulfonic acid (MOPS) buffer to minimize Fe(II) oxidation during sampling. At stations in the Arabian Sea OMZ, Fe(II) had subsurface maxima in the oxygen-deficient and high nitrite layers; fully 7-29% of total dissolved Fe existed as Fe(II) in these samples. Subsurface Fe(II) maxima were not observed in stations south of the oxygen minimum zone. Within the OMZ, the distribution of Fe(II) resembled previous data obtained during the 2004 southwest monsoon, indicating that the Fe(II) maxima are seasonally and interannually persistent feature. These results confirm the close relationship between Fe(II) and the secondary nitrite maxima and suggest that the rich microbial community within this feature is closely involved with Fe redox cycling. Fe(II) concentrations near the seafloor were elevated in locations underlying the OMZ but nowhere else, possibly reflecting inputs from reducing sediments. To the south, a clear maximum in dissolved Fe from the Rodriguez Triple Junction hydrothermal system showed no evidence of Fe(II). The center location of the Rodriguez Triple Junction is 25° 35'S, 70° 00'E (Gamo et al., 2001), more than 800 km southwest of station ER10 (the closest station), so hydrothermally-derived Fe(II) was probably oxidized.

  15. Phototrophic Fe(II)-oxidation in the chemocline of a ferruginous meromictic lake

    PubMed Central

    Walter, Xavier A.; Picazo, Antonio; Miracle, Maria R.; Vicente, Eduardo; Camacho, Antonio; Aragno, Michel; Zopfi, Jakob

    2014-01-01

    Precambrian Banded Iron Formation (BIF) deposition was conventionally attributed to the precipitation of iron-oxides resulting from the abiotic reaction of ferrous iron (Fe(II)) with photosynthetically produced oxygen. Earliest traces of oxygen date from 2.7 Ga, thus raising questions as to what may have caused BIF precipitation before oxygenic photosynthesis evolved. The discovery of anoxygenic phototrophic bacteria thriving through the oxidation of Fe(II) has provided support for a biological origin for some BIFs, but despite reports suggesting that anoxygenic phototrophs may oxidize Fe(II) in the environment, a model ecosystem of an ancient ocean where they are demonstrably active was lacking. Here we show that anoxygenic phototrophic bacteria contribute to Fe(II) oxidation in the water column of the ferruginous sulfate-poor, meromictic lake La Cruz (Spain). We observed in-situ photoferrotrophic activity through stimulation of phototrophic carbon uptake in the presence of Fe(II), and determined light-dependent Fe(II)-oxidation by the natural chemocline microbiota. Moreover, a photoferrotrophic bacterium most closely related to Chlorobium ferrooxidans was enriched from the ferruginous water column. Our study for the first time demonstrates a direct link between anoxygenic photoferrotrophy and the anoxic precipitation of Fe(III)-oxides in a ferruginous water column, providing a plausible mechanism for the bacterial origin of BIFs before the advent of free oxygen. However, photoferrotrophs represent only a minor fraction of the anoxygenic phototrophic community with the majority apparently thriving by sulfur cycling, despite the very low sulfur content in the ferruginous chemocline of Lake La Cruz. PMID:25538702

  16. Electrical Signatures Associated with Abiotic and In Vitro Dissimilatory Iron Reduction

    NASA Astrophysics Data System (ADS)

    Regberg, A. B.; Brantley, S. L.; Singha, K.; Tien, M.

    2007-05-01

    Several researchers have described anomalous electrical signatures associated with bacterial activity in anoxic zones in aquifers containing organic contaminants. It is thought that these signals can be attributed to (bio)geochemical changes caused by the oxidation of organic contaminants and the reduction of associated species like iron oxides. We report laboratory observations of changes in electrical conductivity (EC) that can be attributed to specific (bio)geochemical reactions involving reductive dissolution of iron oxides enzymatically and nonenzymatically. Abiotic reduction of ferrihydrite by ascorbic acid in batch experiments causes a cumulative 20- 40% increase in measured conductivity, (EC increases by ~300 μ S/cm). This change can be attributed to a decrease in conductivity (Δ EC) from increasing proton activity (Δ pH = 3.25 --> 5.07, Δ EC = -200 μ S/cm) and an increase in dissolved Fe(II) (Δ [Fe] = 2.2 - 3.3 mM, Δ EC = 400 -700 μ S/cm). Conductivity is presumably unaffected by Fe(II) sorbed to the ferrihydrite. Rates calculated from this method are comparable to literature rates for similar experiments. In a similar in vitro system, total membrane fractions from Shewanella oneidensis MR-1 were used to reduce ferrihydrite in the presence of formate and HEPES buffer. A 10 - 15% increase in conductivity was observed in the batch experiment (Δ EC = ~280 μ S/cm). This Δ EC is attributed to an increase in the concentration of de-protonated HEPES as well as carbonate ion as formate is oxidized. Fe(II) released in this system is quickly sorbed onto the ferrihydrite surface and is not thought to change conductivity. Despite the sorption of iron in these in vitro experiments, conductivity changes measurably and documents the rate of the reaction. Accessory changes like buffer de- protonation play an important role in interpreting the electrical signals caused by dissimilatory iron reduction. In order to accurately interpret field data it is necessary

  17. Simultaneous oxidation of arsenic and antimony at low and circumneutral pH, with and without microbial catalysis

    USGS Publications Warehouse

    Asta, Maria P.; Nordstrom, D. Kirk; McCleskey, R. Blaine

    2012-01-01

    Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H2SO4 solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl- concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbialoxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.

  18. Redox buffering by melanin and Fe(II) in Cryptococcus neoformans.

    PubMed Central

    Jacobson, E S; Hong, J D

    1997-01-01

    Melanin is a fungal extracellular redox buffer which, in principle, can neutralize antimicrobial oxidants generated by immunologic effector cells, but its source of reducing equivalents is not known. We wondered whether Fe(II) generated by the external ferric reductase of fungi might have the physiologic function of reducing fungal melanin and thereby promoting pathogenesis. We observed that exposure of a melanin film electrode to reductants decreased the open-circuit potential (OCP) and reduced the area of a cyclic voltammetric reduction wave whereas exposure to oxidants produced the opposite effects. Exposure to 10, 100, 1,000 or 10,000 microM Fe(II) decreased the OCP of melanin by 0.015, 0.038, 0.100, and 0.120 V, respectively, relative to a silver-silver chloride standard, and decreased the area of the cyclic voltammetric reduction wave by 27, 35, 50, and 83%, respectively. Moreover, exposure to Fe(II) increased the buffering capacity by 44%, while exposure to millimolar dithionite did not increase the buffering capacity. The ratio of the amount of bound iron to the amount of the incremental increase in the following oxidation wave was approximately 1.0, suggesting that bound iron participates in buffering. Light absorption by melanin suspensions was decreased 14% by treatment with Fe(II), consistent with reduction of melanin. Light absorption by suspensions of melanized Cryptococcus neoformans was decreased 1.3% by treatment with Fe(II) (P < 0.05). Cultures of C. neoformans generated between 2 and 160 microM Fe(II) in culture supernatant, depending upon the strain and the conditions [the higher values were achieved by a constitutive ferric reductase mutant in high concentrations of Fe(III)]. We infer that Fe(II) can reduce melanin under physiologic conditions; moreover, it binds to melanin and cooperatively increases redox buffering. The data support a model for physiologic redox cycling of fungal melanin, whereby electrons exported by the yeast to form

  19. Endogenous salicylic acid protects rice plants from oxidative damage caused by aging as well as biotic and abiotic stress.

    PubMed

    Yang, Yinong; Qi, Min; Mei, Chuansheng

    2004-12-01

    Salicylic acid (SA) is a key endogenous signal that mediates defense gene expression and disease resistance in many dicotyledonous species. In contrast to tobacco and Arabidopsis, which contain low basal levels of SA, rice has two orders of magnitude higher levels of SA and appears to be insensitive to exogenous SA treatment. To determine the role of SA in rice plants, we have generated SA-deficient transgenic rice by expressing the bacterial salicylate hydroxylase that degrades SA. Depletion of high levels of endogenous SA in transgenic rice does not measurably affect defense gene expression, but reduces the plant's capacity to detoxify reactive oxygen intermediates (ROI). SA-deficient transgenic rice contains elevated levels of superoxide and H2O2, and exhibits spontaneous lesion formation in an age- and light-dependent manner. Exogenous application of SA analog benzothiadiazole complements SA deficiency and suppresses ROI levels and lesion formation. Although an increase of conjugated catechol was detected in SA-deficient rice, catechol does not appear to significantly affect ROI levels based on the endogenous catechol data and exogenous catechol treatment. When infected with the blast fungus (Magnaporthe grisea), SA-deficient rice exhibits increased susceptibility to oxidative bursts elicited by avirulent isolates. Furthermore, SA-deficient rice is hyperresponsive to oxidative damage caused by paraquat treatment. Taken together, our results strongly suggest that SA plays an important role to modulate redox balance and protect rice plants from oxidative stress.

  20. Influence of iron sulfides on abiotic oxidation of UO2 by nitrite and dissolved oxygen in natural sediments.

    PubMed

    Carpenter, Julian; Bi, Yuqiang; Hayes, Kim F

    2015-01-20

    Iron sulfide precipitates formed under sulfate reducing conditions may buffer U(IV) insoluble solid phases from reoxidation after oxidants re-enter the reducing zone. In this study, sediment column experiments were performed to quantify the effect of biogenic mackinawite on U(IV) stability in the presence of nitrite or dissolved oxygen (DO). Two columns, packed with sediment from an abandoned U contaminated mill tailings site near Rifle, CO, were biostimulated for 62 days with an electron donor (3 mM acetate) in the presence (BRS+) and absence (BRS−) of 7 mM sulfate. The bioreduced sediment was supplemented with synthetic uraninite (UO2(s)), sterilized by gamma-irradiation, and then subjected to a sequential oxidation by nitrite and DO. Biogenic iron sulfides produced in the BRS+ column, mostly as mackinawite, inhibited U(IV) reoxidation and mobilization by both nitrite and oxygen. Most of the influent nitrite (0.53 mM) exited the columns without oxidizing UO2, while a small amount of nitrite was consumed by iron sulfides precipitates. An additional 10-day supply of 0.25 mM DO influent resulted in the release of about 10% and 49% of total U in BRS+ and BRS– columns, respectively. Influent DO was effectively consumed by biogenic iron sulfides in the BRS+ column, while DO and a large U spike were detected after only a brief period in the effluent in the BRS– column.

  1. Magnetic transitions and Fe(II) spin state in mackinawite

    NASA Astrophysics Data System (ADS)

    Schroeder, C.; Wan, M.; Peiffer, S.

    2012-12-01

    We used Mössbauer spectroscopy to investigate products during sulfidation of Fe (hydr)oxides and their subsequent transformation to pyrite (FeS2) [1,2]. The Fe(II) monosulfide mackinawite (FeSm) was identified in transmission electron microscopy images as one of the intermediate phases [3]. Mössbauer spectra obtained at a temperature of ~5 K showed a magnetically ordered phase, which at first instance seemed inconsistent with data reported for mackinawite in the literature. In fact, a literature review revealed large discrepancies between Mössbauer data reported for mackinawite: Morice et al. [4] measured a spectrum that consisted of overlapping magnetic hyperfine patterns already at room temperature; Vaughan and Ridout [5] observed a single line, i.e. no magnetic ordering down to a temperature of 1.7 K; Mullet et al. [6] observed the onset of magnetic splitting at ~11 K, with a single line still dominating the spectrum. In order to understand these discrepancies we synthesized several mackinawite samples from different protocols and investigated the products with Mössbauer spectroscopy. Freshly precipitated mackinawite filtered from Fe(II)/sulfide solutions showed single line spectra down to ~5 K, i.e. no magnetic ordering, as reported by [5]. Freeze-dried mackinawite showed onset of magnetic splitting in the ~5 K spectrum, analogous to [6]. Mackinawite derived from reacting Fe (hydr)oxides with sulfide at a molar Fe/S ratio of 0.5 showed complete magnetic ordering at ~5 K [2]. The splitting disappeared between 77 K and 140 K. The peak positions of the magnetically ordered phase at ~5 K match the peak positions of the magnetically ordered phase in our freeze-dried mackinawite, and the corresponding phase in our Fe (hydr)oxide sulfidation experiments. The isomer shifts as measured Mössbauer parameters for all mackinawites investigated here as well as values reported in the literature are consistent with Fe(II) either in a low spin (S=0) or an intermediate spin

  2. Hydrogen peroxide and nitric oxide mediated cold- and dehydration-induced myo-inositol phosphate synthase that confers multiple resistances to abiotic stresses.

    PubMed

    Tan, Jiali; Wang, Congying; Xiang, Bin; Han, Ruihong; Guo, Zhenfei

    2013-02-01

    myo-Inositol phosphate synthase (MIPS) is the key enzyme of myo-inositol synthesis, which is a central molecule required for cell metabolism and plant growth as a precursor to a large variety of compounds. A full-length fragment of MfMIPS1 cDNA was cloned from Medicago falcata that is more cold-tolerant than Medicago sativa. While MfMIPS1 transcript was induced in response to cold, dehydration and salt stress, MIPS transcript and myo-inositol were maintained longer and at a higher level in M. falcata than in M. sativa during cold acclimation at 5 °C. MfMIPS1 transcript was induced by hydrogen peroxide (H(2) O(2)) and nitric oxide (NO), but was not responsive to abscisic acid (ABA). Pharmacological experiments revealed that H(2) O(2) and NO are involved in the regulation of MfMIPS1 expression by cold and dehydration, but not by salt. Overexpression of MfMIPS1 in tobacco increased the MIPS activity and levels of myo-inositol, galactinol and raffinose, resulting in enhanced resistance to chilling, drought and salt stresses in transgenic tobacco plants. It is suggested that MfMIPS1 is induced by diverse environmental factors and confers resistance to various abiotic stresses.

  3. Priming of pathogenesis related-proteins and enzymes related to oxidative stress by plant growth promoting rhizobacteria on rice plants upon abiotic and biotic stress challenge.

    PubMed

    García-Cristobal, J; García-Villaraco, A; Ramos, B; Gutierrez-Mañero, J; Lucas, J A

    2015-09-01

    Two plant growth promoting rhizobacteria (PGPR) were tested to evaluate their capacity to prime rice seedlings against stress challenge (salt and Xanthomonas campestris infection). As is accepted that plants respond to biotic and abiotic stresses by generation of reactive oxygen species (ROS), enzyme activities related to oxidative stress (ascorbate peroxidase (APX, EC 1.11.1.11), guaiacol peroxidase (GPX, EC 1.11.1.7), glutathione reductase (GR, EC 1.6.4.2) and superoxide dismutase (SOD, EC 1.15.1.1)) as well as the pathogenesis-related proteins (PRs) ß-1,3-glucanase (PR2, EC 3.2.1.6) and chitinase (PR3, EC 3.2.1.14) were measured at 3 time points after stress challenge. In addition, photosynthetic parameters related with fluorescence emission of photosystem II (F0, Fv/Fm, ΦPSII and NPQ) were also measured although they were barely affected. Both strains were able to protect rice seedlings against salt stress. AMG272 reduced the salt symptoms over 47% with regard to control, and L81 over 90%. Upon pathogen challenge, 90% protection was achieved by both strains. All enzyme activities related to oxidative stress were modified by the two PGPR, especially APX and SOD upon salinity stress challenge, and APX and GR upon pathogen presence. Both bacteria induced chitinase activity 24 and 48 h after pathogen inoculation, and L81 induced ß-1,3-Glucanase activity 48 h after pathogen inoculation, evidencing the priming effect. These results indicate that these strains could be used as bio-fortifying agents in biotechnological inoculants in order to reduce the effects of different stresses, and indirectly reduce the use of agrochemicals.

  4. Spermidine exodus and oxidation in the apoplast induced by abiotic stress is responsible for H2O2 signatures that direct tolerance responses in tobacco.

    PubMed

    Moschou, Panagiotis N; Paschalidis, Konstantinos A; Delis, Ioannis D; Andriopoulou, Athina H; Lagiotis, George D; Yakoumakis, Dimitrios I; Roubelakis-Angelakis, Kalliopi A

    2008-06-01

    Polyamines (PAs) exert a protective effect against stress challenges, but their molecular role in this remains speculative. In order to detect the signaling role of apoplastic PA-derived hydrogen peroxide (H2O2) under abiotic stress, we developed a series of tobacco (Nicotiana tabacum cv Xanthi) transgenic plants overexpressing or downregulating apoplastic polyamine oxidase (PAO; S-pao and A-pao plants, respectively) or downregulating S-adenosyl-l-methionine decarboxylase (samdc plants). Upon salt stress, plants secreted spermidine (Spd) into the apoplast, where it was oxidized by the apoplastic PAO, generating H2O2. A-pao plants accumulated less H2O2 and exhibited less programmed cell death (PCD) than did wild-type plants, in contrast with S-pao and samdc downregulating plants. Induction of either stress-responsive genes or PCD was dependent on the level of Spd-derived apoplastic H2O2. Thus, in wild-type and A-pao plants, stress-responsive genes were efficiently induced, although in the latter at a lower rate, while S-pao plants, with higher H2O2 levels, failed to accumulate stress-responsive mRNAs, inducing PCD instead. Furthermore, decreasing intracellular PAs, while keeping normal apoplastic Spd oxidation, as in samdc downregulating transgenic plants, caused enhanced salinity-induced PCD. These results reveal that salinity induces the exodus of Spd into the apoplast, where it is catabolized by PAO, producing H2O2. The accumulated H2O2 results in the induction of either tolerance responses or PCD, depending also on the levels of intracellular PAs.

  5. Heterogeneous Reduction of Tc(VII) by Fe(II) at the Solid-Water Interface

    SciTech Connect

    Peretyazhko, Tetyana; Zachara, John M.; Heald, Steve M.; Jeon, Byong Hun; Kukkadapu, Ravi K.; Liu, Chongxuan; Moore, Dean A.; Resch, Charles T.

    2008-03-15

    Technetium-99 is a byproduct of uranium fission. It exists in two stable valence states (IV/VII) and exhibits a half-cell potential of intermediate value (Eo = 0.748 V). The oxidized form of 99Tc [pertechnetate, TcO4-] is an oxyanion that sorbs poorly to amphoteric surfaces and forms few solid phases with geochemically relevant cations. It is consequently highly mobile in oxic water-rock systems. The reduced valence state [Tc(IV)] is relatively insoluble (<10-8 mol L-1), and, hence immobile as an oxyhydroxide precipitate [TcO2•nH2O(s)]. In spite of favorable thermodynamics, Tc(VII) reacts slowly with Fe2+(aq) under anoxic conditions. Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) sorbed to hematite and goethite, and by structural Fe(II) in a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) sorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of Fe2+(aq) adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by structural Fe(II) in the DCB-reduced phyllollsilicates, were not sensitive to pH or the concentration of ion-exchangeable Fe(II), and were orders of magnitude slower than observed for the Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with 56Fe-goethite with adsorbed 57Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB

  6. Connecting Observations of Hematite (a Fe2O3) Growth Catalyzed by Fe(II)

    SciTech Connect

    Rosso, Kevin M.; Yanina, Svetlana; Gorski, Christopher A.; Larese-Casanova, Philip; Scherer, Michelle

    2010-01-14

    Electron exchange between aqueous Fe(II) and structural Fe(III) in iron oxides and oxyhydroxides is important for understanding degradation of environmental pollutants through its apparent constitutive role underlying highly reactive “sorbed Fe(II)” and by catalyzing phase interconversion among these minerals. Although a mechanistic understanding of relationships between interfacial Fe(II)ads-Fe(III)oxide electron transfer, bulk electron conduction, and phase transformation behavior is emerging, much remains unclear in part due to poorly interconnected investigations. The focus of this study is on reconciling two mutually similar observations of Fe(II)-catalyzed hematite growth documented spectroscopically and microscopically under substantially different chemical conditions. Here we employ iron isotopic labeling to demonstrate that hematite grown on the (001) surface in Fe(II)-oxalate solution at low pH and elevated temperature has temperature-dependent magnetic properties that closely correspond to those of hematite grown in Fe(II) solution at circumneutral pH at room temperature. The temperature evolution and extent of the Morin transition displayed in these two materials strongly suggest a mechanistic link between the two studies, and that this mechanism involves in part trace structural Fe(II) incorporation into the growing hematite. Our findings indicate that Fe(II) catalyzed growth of hematite on hematite can occur under environmentally relevant conditions and may be due to bulk electron conduction previously demonstrated for hematite single crystals.

  7. Interactions Between Fe(III)-oxides and Fe(III)-phyllosilicates During Microbial Reduction 2: Natural Subsurface Sediments

    SciTech Connect

    Wu, T.; Griffin, A. M.; Gorski, C. A.; Shelobolina, E. S.; Xu, H.; Kukkadapu, R. K.; Roden, E. E.

    2016-04-19

    Dissimilatory microbial reduction of solid-phase Fe(III)-oxides and Fe(III)-bearing phyllosilicates (Fe(III)-phyllosilicates) is an important process in anoxic soils, sediments, and subsurface materials. Although various studies have documented the relative extent of microbial reduction of single-phase Fe(III)-oxides and Fe(III)-phyllosilicates, detailed information is not available on interaction between these two processes in situations where both phases are available for microbial reduction. The goal of this research was to use the model dissimilatory iron-reducing bacterium (DIRB) Geobacter sulfurreducens to study Fe(III)-oxide vs. Fe(III)-phyllosilicate reduction in a range of subsurface materials and Fe(III)-oxide stripped versions of the materials. Low temperature (12K) Mossbauer spectroscopy was used to infer changes in the relative abundances of Fe(III)-oxide, Fe(III)-phyllosilicate, and phyllosilicate-associated Fe(II) (Fe(II)-phyllosilicate). A Fe partitioning model was employed to analyze the fate of Fe(II) and assess the potential for abiotic Fe(II)-catalyzed reduction of Fe(III)-phyllosilicates. The results showed that in most cases Fe(III)- oxide utilization dominated (70-100 %) bulk Fe(III) reduction activity, and that electron transfer from oxide-derived Fe(II) played only a minor role (ca. 10-20 %) in Fe partitioning. In addition, the extent of Fe(III)-oxide reduction was positively correlated to surface area-normalized cation exchange capacity and the phyllosilicate-Fe(III)/total Fe(III) ratio, which suggests that the phyllosilicates in the natural sediments promoted Fe(III)-oxide reduction by binding of oxide-derived Fe(II), thereby enhancing Fe(III)-oxide reduction by reducing or delaying the inhibitory effect that Fe(II) accumulation on oxide and DIRB cell surfaces has on Fe(III)-oxide reduction. In general our results suggest that although Fe(III)-oxide reduction is likely to dominate bulk Fe(III) reduction in most subsurface sediments, Fe(II

  8. Sequestration of chelated copper by structural Fe(II): Reductive decomplexation and transformation of Cu(II)-EDTA.

    PubMed

    He, Hongping; Wu, Deli; Zhao, Linghui; Luo, Cong; Dai, Chaomeng; Zhang, Yalei

    2016-05-15

    Chelated coppers, such as Cu(II)-EDTA, are characteristically refractory and difficult to break down because of their high stability and solubility. Cu(II)-EDTA sequestration by structural Fe(II) (Fe(II)) was investigated intensively in this study. Up to 101.21mgCu(II)/gFe(II) was obtained by Fe(II) in chelated copper sequestration under near neutral pH condition (pH 7.70). The mechanism of Cu(II)-EDTA sequestration by Fe(II) was concluded as follows: 3Cu(II)-EDTA+7Fe(II)+9H2O → Cu(0)↓+ Cu2O↓(the major product)+2Fe2O3·H2O↓+3Fe(II)-EDTA +14H(+) Novel results strongly indicate that Cu(II) reductive transformation induced by surface Fe(II) was mainly responsible for chelated copper sequestration. Cu(0) generation was initially facilitated, and subsequent reduction of Cu(II) into Cu(I) was closely combined with the gradual increase of ORP (Oxidation-Reduction Potential). Cu-containing products were inherently stable, but Cu2O would be reoxidized to Cu(II) with extra-aeration, resulting in the release of copper, which was beneficial to Cu reclamation. Concentration diminution of Cu(II)-EDTA within the electric double layer and competitive adsorption were responsible for the negative effects of Ca(2+), Mg(2+). By generating vivianite, PO4(3-) was found to decrease surface Fe(II) content. This study is among the first ones to identify the indispensible role of reductive decomplexation in chelated copper sequestration. Given the high feasibility and reactivity, Fe(II) may provide a potential alternative in chelated metals pollution controlling.

  9. The effect of biogenic Fe(II) on the stability and sorption of Co(II)EDTA 2- to goethite and a subsurface sediment

    NASA Astrophysics Data System (ADS)

    Zachara, John M.; Smith, Steven C.; Fredrickson, James K.

    2000-04-01

    Laboratory experiments were conducted with suspensions of goethite (α-FeOOH) and a subsurface sediment to assess the influence of bacterial iron reduction on the fate of Co(II)EDTA 2-, a representative metal-ligand complex of intermediate stability (log K Co(II)EDTA = 17.97). The goethite was synthetic (ca. 55 m 2/g) and the sediment was a Pleistocene age, Fe(III) oxide-containing material from the Atlantic coastal plain (Milford). Shewanella alga strain BrY, a dissimilatory iron reducing bacterium (DIRB), was used to promote Fe(III) oxide reduction. Sorption isotherms and pH adsorption edges were measured for Co 2+, Fe 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- on the two sorbents in 0.001 mol/L Ca(ClO 4) 2 to aid in experiment interpretation. Anoxic suspensions of the sorbents in PIPES buffer at pH 6.5-7.0 were spiked with Co(II)EDTA 2- (10 -5 mol/L, 60Co and 14EDTA labeled), inoculated with BrY (1-6 × 10 8 organisms/mL), and the headspace filled with a N 2/H 2 gas mix. The experiments were conducted under non-growth conditions. The medium did not contain PO 43- (with one exception), trace elements, or vitamins. The tubes were incubated under anoxic conditions at 25°C for time periods in excess of 100 d. Replicate tubes were sacrificed and analyzed at desired time periods for pH, Fe(II) TOT, Fe (aq)2+, 60Co, and 14EDTA. Abiotic analogue experiments were conducted where Fe (aq)2+ was added in increasing concentration to Co(II)EDTA 2-/mineral suspensions to simulate the influence of bacterial Fe(II) evolution. The DIRB generated Fe(II) from both goethite and the Milford sediment that was strongly sorbed by mineral surfaces. Aqueous Fe 2+ increased during the experiment as surfaces became saturated; Fe (aq)2+ induced the dissociation of Co(II)EDTA 2- into a mixture of Co 2+, Co(II)EDTA 2-, and Fe(II)EDTA 2- (log K Fe(II)EDTA = 15.98). The extent of dissociation of Co(II)EDTA 2- was greater in the subsurface sediment because it sorbed Fe(II) less strongly than did

  10. Abiotic Reductive Immobilization of U(VI) by Biogenic Mackinawite

    SciTech Connect

    Veeramani, Harish; Scheinost, Andreas; Monsegue, Niven; Qafoku, Nikolla; Kukkadapu, Ravi K.; Newville, Mathew; Lanzirotti, Anthony; Pruden, Amy; Murayama, Mitsuhiro; Hochella, Michael F.

    2013-03-01

    During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in-situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U6+ reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe1+xS, x = 0 to 0.11) to reduce U6+ abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U6+ indicate the formation of nanoparticulate UO2. This study suggests the relevance of Fe(II) and sulfide bearing biogenic minerals in mediating abiotic U6+ reduction, an alternative pathway in addition to direct enzymatic U6+ reduction.

  11. The Arabidopsis Transcription Factor ANAC032 Represses Anthocyanin Biosynthesis in Response to High Sucrose and Oxidative and Abiotic Stresses

    PubMed Central

    Mahmood, Kashif; Xu, Zhenhua; El-Kereamy, Ashraf; Casaretto, José A.; Rothstein, Steven J.

    2016-01-01

    Production of anthocyanins is one of the adaptive responses employed by plants during stress conditions. During stress, anthocyanin biosynthesis is mainly regulated at the transcriptional level via a complex interplay between activators and repressors of anthocyanin biosynthesis genes. In this study, we investigated the role of a NAC transcription factor, ANAC032, in the regulation of anthocyanin biosynthesis during stress conditions. ANAC032 expression was found to be induced by exogenous sucrose as well as high light (HL) stress. Using biochemical, molecular and transgenic approaches, we show that ANAC032 represses anthocyanin biosynthesis in response to sucrose treatment, HL and oxidative stress. ANAC032 was found to negatively affect anthocyanin accumulation and the expression of anthocyanin biosynthesis (DFR, ANS/LDOX) and positive regulatory (TT8) genes as demonstrated in overexpression line (35S:ANAC032) compared to wild-type under HL stress. The chimeric repressor line (35S:ANAC032-SRDX) exhibited the opposite expression patterns for these genes. The negative impact of ANAC032 on the expression of DFR, ANS/LDOX and TT8 was found to be correlated with the altered expression of negative regulators of anthocyanin biosynthesis, AtMYBL2 and SPL9. In addition to this, ANAC032 also repressed the MeJA- and ABA-induced anthocyanin biosynthesis. As a result, transgenic lines overexpressing ANAC032 (35S:ANAC032) produced drastically reduced levels of anthocyanin pigment compared to wild-type when challenged with salinity stress. However, transgenic chimeric repressor lines (35S:ANAC032-SRDX) exhibited the opposite phenotype. Our results suggest that ANAC032 functions as a negative regulator of anthocyanin biosynthesis in Arabidopsis thaliana during stress conditions. PMID:27790239

  12. As(III) oxidation by MnO2 during groundwater treatment.

    PubMed

    Gude, J C J; Rietveld, L C; van Halem, D

    2017-03-15

    The top layer of natural rapid sand filtration was found to effectively oxidise arsenite (As(III)) in groundwater treatment. However, the oxidation pathway has not yet been identified. The aim of this study was to investigate whether naturally formed manganese oxide (MnO2), present on filter grains, could abiotically be responsible for As(III) oxidation in the top of a rapid sand filter. For this purpose As(III) oxidation with two MnO2 containing powders was investigated in aerobic water containing manganese(II) (Mn(II)), iron(II) (Fe(II)) and/or iron(III) (Fe(III)). The first MnO2 powder was a very pure - commercially available - natural MnO2 powder. The second originated from a filter sand coating, produced over 22 years in a rapid filter during aeration and filtration. Jar test experiments showed that both powders oxidised As(III). However, when applying the MnO2 in aerated, raw groundwater, As(III) removal was not enhanced compared to aeration alone. It was found that the presence of Fe(II)) and Mn(II) inhibited As(III) oxidation, as Fe(II) and Mn(II) adsorption and oxidation were preferred over As(III) on the MnO2 surface (at pH 7). Therefore it is concluded that just because MnO2 is present in a filter bed, it does not necessarily mean that MnO2 will be available to oxidise As(III). However, unlike Fe(II), the addition of Fe(III) did not hinder As(III) oxidation on the MnO2 surface; resulting in subsequent effective As(V) removal by the flocculating hydrous ferric oxides.

  13. In-silico analysis and mRNA modulation of detoxification enzymes GST delta and kappa against various biotic and abiotic oxidative stressors.

    PubMed

    Chaurasia, Mukesh Kumar; Ravichandran, Gayathri; Nizam, Faizal; Arasu, Mariadhas Valan; Al-Dhabi, Naif Abdullah; Arshad, Aziz; Harikrishnan, Ramasamy; Arockiaraj, Jesu

    2016-07-01

    This study reports the comprehensive comparative information of two different detoxification enzymes such as glutathione S-transferases (GSTs) delta and kappa from freshwater giant prawn Macrobrachium rosenbergii (designated as MrGSTD and MrGSTK) by investigating their in-silico characters and mRNA modulation against various biotic and abiotic oxidative stressors. The physico-chemical properties of these cDNA and their polypeptide structure were analyzed using various bioinformatics program. The analysis indicated the variation in size of the polypeptides, presence or absence of domains and motifs and structure. Homology and phylogenetic analysis revealed that MrGSTD shared maximum identity (83%) with crustaceans GST delta, whereas MrGSTK fell in arthropods GST kappa. It is interesting to note that MrGSTD and MrGSTK shared only 21% identity; it indicated their structural difference. Structural analysis indicated that MrGSTD to be canonical dimer like shape and MrGSTK appeared to be butterfly dimer like shape, in spite of four β-sheets being conserved in both GSTs. Tissue specific gene expression analysis showed that both MrGSTD and MrGSTK are highly expressed in immune organs such as haemocyte and hepatopancreas, respectively. To understand the role of mRNA modulation of MrGSTD and MrGSTK, the prawns were inducted with oxidative stressors such as bacteria (Vibrio harveyi), virus [white spot syndrome virus (WSSV)] and heavy metal, cadmium (Cd). The analysis revealed an interesting fact that both MrGSTD and MrGSTK showed higher (P < 0.05) up-regulation at 48 h post-challenge, except MrGSTD stressed with bacteria, where it showed up-regulation at 24 h post-challenge. Overall, the results suggested that GSTs are diverse in their structure and possibly conferring their potential involvement in immune protection in crustaceans. However, further study is necessary to focus their functional differences at proteomic level.

  14. Efficient Low-pH Iron Removal by a Microbial Iron Oxide Mound Ecosystem at Scalp Level Run.

    PubMed

    Grettenberger, Christen L; Pearce, Alexandra R; Bibby, Kyle J; Jones, Daniel S; Burgos, William D; Macalady, Jennifer L

    2017-04-01

    Acid mine drainage (AMD) is a major environmental problem affecting tens of thousands of kilometers of waterways worldwide. Passive bioremediation of AMD relies on microbial communities to oxidize and remove iron from the system; however, iron oxidation rates in AMD environments are highly variable among sites. At Scalp Level Run (Cambria County, PA), first-order iron oxidation rates are 10 times greater than at other coal-associated iron mounds in the Appalachians. We examined the bacterial community at Scalp Level Run to determine whether a unique community is responsible for the rapid iron oxidation rate. Despite strong geochemical gradients, including a >10-fold change in the concentration of ferrous iron from 57.3 mg/liter at the emergence to 2.5 mg/liter at the base of the coal tailings pile, the bacterial community composition was nearly constant with distance from the spring outflow. Scalp Level Run contains many of the same taxa present in other AMD sites, but the community is dominated by two strains of Ferrovum myxofaciens, a species that is associated with high rates of Fe(II) oxidation in laboratory studies.IMPORTANCE Acid mine drainage pollutes more than 19,300 km of rivers and streams and 72,000 ha of lakes worldwide. Remediation is frequently ineffective and costly, upwards of $100 billion globally and nearly $5 billion in Pennsylvania alone. Microbial Fe(II) oxidation is more efficient than abiotic Fe(II) oxidation at low pH (P. C. Singer and W. Stumm, Science 167:1121-1123, 1970, https://doi.org/10.1126/science.167.3921.1121). Therefore, AMD bioremediation could harness microbial Fe(II) oxidation to fuel more-cost-effective treatments. Advances will require a deeper understanding of the ecology of Fe(II)-oxidizing microbial communities and the factors that control their distribution and rates of Fe(II) oxidation. We investigated bacterial communities that inhabit an AMD site with rapid Fe(II) oxidation and found that they were dominated by two

  15. Abiotic production of nitrous oxide by lightning. Implications for a false positive identification of life on Earth-Like Planets around quiescent M Dwarfs

    NASA Astrophysics Data System (ADS)

    Navarro, Karina F.; Navarro-Gonzalez, Rafael; McKay, Christopher P.

    Nitrous oxide (N _{2}O) is uniformly mixed in the troposphere with a concentration of about 310 ppb but disappears in the stratosphere (Prinn et al., 1990); N _{2}O is mostly emitted at a rate of 1x10 (13) g yr (-1) as a byproduct of microbial activity in soils and in the ocean by two processes: a) denitrification (reduction of nitrate and nitrite), and b) nitrification (oxidation of ammonia) (Maag and Vinther, 1996). The abiotic emission of N _{2}O in the contemporaneous Earth is small, mostly arising from lightning activity (2x10 (9) g yr (-1) , Hill et al., 1984) and by reduction of nitrite by Fe(II)-minerals in soils in Antarctica (Samarkin et al., 2010). Since N _{2}O has absorption bands in the mid-IR (7.8, 8.5, and 17 mumm) that makes it detectable by remote sensing (Topfer et al., 1997; Des Marais et al., 2002), it has been suggested as a potential biosignature in the search for life in extrasolar planets (Churchill and Kasting, 2000). However, the minimum required concentration for positive identification is 10,000 ppb with missions like Terrestrial Planet Finder and Darwin (Churchill and Kasting, 2000). Therefore, it is not a suitable biomarker for extrasolar Earth-like planets orbiting stars similar to the Sun. Because N _{2}O is protected in the troposphere from UV photolysis by the stratospheric ozone layer, its concentration would decrease with decreasing oxygen (O _{2}) concentrations, if the biological source strength remains constant (Kasting and Donahue, 1980). For a primitive Earth-like (Hadean) atmosphere dominated by CO _{2}, and no free O _{2}, the expected N _{2}O concentration would be about 3 ppb with the current microbial N _{2}O flux (Churchill and Kasting, 2000). The resulting N _{2}O spectral signature of this atmosphere would be undetectable unless the N _{2}O microbial flux would be 10 (4) greater than its present value (Churchill and Kasting, 2000). Since this flux is unlikely, it is impossible to use it as a biomarker in anoxic CO

  16. Abiotic pyrite formation produces a large Fe isotope fractionation.

    PubMed

    Guilbaud, Romain; Butler, Ian B; Ellam, Rob M

    2011-06-24

    The iron isotope composition of sedimentary pyrite has been proposed as a potential proxy to trace microbial metabolism and the redox evolution of the oceans. We demonstrate that Fe isotope fractionation accompanies abiotic pyrite formation in the absence of Fe(II) redox change. Combined fractionation factors between Fe(II)(aq), mackinawite, and pyrite permit the generation of pyrite with Fe isotope signatures that nearly encapsulate the full range of sedimentary δ(56)Fe(pyrite) recorded in Archean to modern sediments. We propose that Archean negative Fe isotope excursions reflect partial Fe(II)(aq) utilization during abiotic pyrite formation rather than microbial dissimilatory Fe(III) reduction. Late Proterozoic to modern sediments may reflect greater Fe(II)(aq) utilization and variations in source composition.

  17. Combined abiotic and biotic in-situ reduction of hexavalent chromium in groundwater using nZVI and whey: A remedial pilot test.

    PubMed

    Němeček, Jan; Pokorný, Petr; Lacinová, Lenka; Černík, Miroslav; Masopustová, Zuzana; Lhotský, Ondřej; Filipová, Alena; Cajthaml, Tomáš

    2015-12-30

    The paper describes a pilot remediation test combining two Cr(VI) geofixation methods - chemical reduction by nanoscale zero-valent iron (nZVI) and subsequent biotic reduction supported by whey. Combination of the methods exploited the advantages of both - a rapid decrease in Cr(VI) concentrations by nZVI, which prevented further spreading of the contamination and facilitated subsequent use of the cheaper biological method. Successive application of whey as an organic substrate to promote biotic reduction of Cr(VI) after application of nZVI resulted in a further and long-term decrease in the Cr(VI) contents in the groundwater. The effect of biotic reduction was observed even in a monitoring well located at a distance of 22 m from the substrate injection wells after 10 months. The results indicated a reciprocal effect of both the phases - nZVI oxidized to Fe(III) during the abiotic phase was microbially reduced back to Fe(II) and acted as a reducing agent for Cr(VI) even when the microbial density was already low due to the consumed substrate. Community analysis with pyrosequencing of the 16S rRNA genes further confirmed partial recycling of nZVI in the form of Fe(II), where the results showed that the Cr(VI) reducing process was mediated mainly by iron-reducing and sulfate-reducing bacteria.

  18. Abiotic tooth enamel

    NASA Astrophysics Data System (ADS)

    Yeom, Bongjun; Sain, Trisha; Lacevic, Naida; Bukharina, Daria; Cha, Sang-Ho; Waas, Anthony M.; Arruda, Ellen M.; Kotov, Nicholas A.

    2017-03-01

    Tooth enamel comprises parallel microscale and nanoscale ceramic columns or prisms interlaced with a soft protein matrix. This structural motif is unusually consistent across all species from all geological eras. Such invariability—especially when juxtaposed with the diversity of other tissues—suggests the existence of a functional basis. Here we performed ex vivo replication of enamel-inspired columnar nanocomposites by sequential growth of zinc oxide nanowire carpets followed by layer-by-layer deposition of a polymeric matrix around these. We show that the mechanical properties of these nanocomposites, including hardness, are comparable to those of enamel despite the nanocomposites having a smaller hard-phase content. Our abiotic enamels have viscoelastic figures of merit (VFOM) and weight-adjusted VFOM that are similar to, or higher than, those of natural tooth enamels—we achieve values that exceed the traditional materials limits of 0.6 and 0.8, respectively. VFOM values describe resistance to vibrational damage, and our columnar composites demonstrate that light-weight materials of unusually high resistance to structural damage from shocks, environmental vibrations and oscillatory stress can be made using biomimetic design. The previously inaccessible combinations of high stiffness, damping and light weight that we achieve in these layer-by-layer composites are attributed to efficient energy dissipation in the interfacial portion of the organic phase. The in vivo contribution of this interfacial portion to macroscale deformations along the tooth’s normal is maximized when the architecture is columnar, suggesting an evolutionary advantage of the columnar motif in the enamel of living species. We expect our findings to apply to all columnar composites and to lead to the development of high-performance load-bearing materials.

  19. Abiotic tooth enamel.

    PubMed

    Yeom, Bongjun; Sain, Trisha; Lacevic, Naida; Bukharina, Daria; Cha, Sang-Ho; Waas, Anthony M; Arruda, Ellen M; Kotov, Nicholas A

    2017-03-01

    Tooth enamel comprises parallel microscale and nanoscale ceramic columns or prisms interlaced with a soft protein matrix. This structural motif is unusually consistent across all species from all geological eras. Such invariability-especially when juxtaposed with the diversity of other tissues-suggests the existence of a functional basis. Here we performed ex vivo replication of enamel-inspired columnar nanocomposites by sequential growth of zinc oxide nanowire carpets followed by layer-by-layer deposition of a polymeric matrix around these. We show that the mechanical properties of these nanocomposites, including hardness, are comparable to those of enamel despite the nanocomposites having a smaller hard-phase content. Our abiotic enamels have viscoelastic figures of merit (VFOM) and weight-adjusted VFOM that are similar to, or higher than, those of natural tooth enamels-we achieve values that exceed the traditional materials limits of 0.6 and 0.8, respectively. VFOM values describe resistance to vibrational damage, and our columnar composites demonstrate that light-weight materials of unusually high resistance to structural damage from shocks, environmental vibrations and oscillatory stress can be made using biomimetic design. The previously inaccessible combinations of high stiffness, damping and light weight that we achieve in these layer-by-layer composites are attributed to efficient energy dissipation in the interfacial portion of the organic phase. The in vivo contribution of this interfacial portion to macroscale deformations along the tooth's normal is maximized when the architecture is columnar, suggesting an evolutionary advantage of the columnar motif in the enamel of living species. We expect our findings to apply to all columnar composites and to lead to the development of high-performance load-bearing materials.

  20. Isolated FeII on Silica As a Selective Propane Dehydrogenation Catalyst

    SciTech Connect

    Hu, Bo; Schweitzer, Neil M.; Zhang, Guanghui; Kraft, Steven J.; Childers, David J.; Lanci, Michael P.; Miller, Jeffrey T.; Hock, Adam S.

    2015-04-17

    ABSTRACT: We report a comparative study of isolated FeII, iron oxide particles, and metallic nanoparticles on silica for non-oxidative propane dehydrogenation. It was found that the most selective catalyst was an isolated FeII species on silica prepared by grafting the open cyclopentadienide iron complex, bis(2,4-dimethyl-1,3-pentadienide) iron(II) or Fe(oCp)2. The grafting and evolution of the surface species was elucidated by 1H NMR, diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption spectroscopies. The oxidation state and local structure of surface Fe were characterized by X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure. The initial grafting of iron proceeds by one surface hydroxyl Si-OH reacting with Fe(oCp)2 to release one diene ligand (oCpH), generating a SiO2-bound FeII(oCp) species, 1-FeoCp. Subsequent treatment with H2 at 400 °C leads to loss of the remaining diene ligand and formation of nanosized iron oxide clusters, 1-C. Dispersion of these Fe oxide clusters occurs at 650 °C, forming an isolated, ligand-free FeII on silica, 1-FeII, which is catalytically active and highly selective (~99%) for propane dehydrogenation to propene. Under reaction conditions, there is no evidence of metallic Fe by in situ XANES. For comparison, metallic Fe nanoparticles, 2-NP-Fe0, were independently prepared by grafting Fe[N(SiMe3)2]2 onto silica, 2-FeN*, and reducing it at 650 °C in H2. The Fe NPs were highly active for propane conversion but showed poor selectivity (~14%) to propene. Independently prepared Fe oxide clusters on silica display a low activity. The sum of these results suggests that selective propane dehydrogenation occurs at isolated FeII sites.

  1. Heterogeneous reduction of PuO₂ with Fe(II): importance of the Fe(III) reaction product.

    PubMed

    Felmy, Andrew R; Moore, Dean A; Rosso, Kevin M; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C; Ilton, Eugene S

    2011-05-01

    Heterogeneous reduction of actinides in higher, more soluble oxidation states to lower, more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied, even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO₂(am) by Fe(II). We present the first experimental evidence that reduction of PuO₂(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) {[Pu(III) + Pu(IV)] - Pu(IV)} by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

  2. Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

    PubMed

    Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

    2014-06-01

    Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments.

  3. Abiotic Bromination of Soil Organic Matter.

    PubMed

    Leri, Alessandra C; Ravel, Bruce

    2015-11-17

    Biogeochemical transformations of plant-derived soil organic matter (SOM) involve complex abiotic and microbially mediated reactions. One such reaction is halogenation, which occurs naturally in the soil environment and has been associated with enzymatic activity of decomposer organisms. Building on a recent finding that naturally produced organobromine is ubiquitous in SOM, we hypothesized that inorganic bromide could be subject to abiotic oxidations resulting in bromination of SOM. Through lab-based degradation treatments of plant material and soil humus, we have shown that abiotic bromination of particulate organic matter occurs in the presence of a range of inorganic oxidants, including hydrogen peroxide and assorted forms of ferric iron, producing both aliphatic and aromatic forms of organobromine. Bromination of oak and pine litter is limited primarily by bromide concentration. Fresh plant material is more susceptible to bromination than decayed litter and soil humus, due to a labile pool of mainly aliphatic compounds that break down during early stages of SOM formation. As the first evidence of abiotic bromination of particulate SOM, this study identifies a mechanistic source of the natural organobromine in humic substances and the soil organic horizon. Formation of organobromine through oxidative treatments of plant material also provides insights into the relative stability of aromatic and aliphatic components of SOM.

  4. Diagnosing Abiotic Degradation

    EPA Science Inventory

    The abiotic degradation of chlorinated solvents in ground water can be difficult to diagnose. Under current practice, most of the “evidence” is negative; specifically the apparent disappearance of chlorinated solvents with an accumulation of vinyl chloride, ethane, ethylene, or ...

  5. Model-based Analysis of Mixed Uranium(VI) Reduction by Biotic and Abiotic Pathways During in Situ Bioremediation

    SciTech Connect

    Zhao, Jiao; Scheibe, Timothy D.; Mahadevan, Radhakrishnan

    2013-10-24

    Uranium bioremediation has emerged as a potential strategy of cleanup of radionuclear contamination worldwide. An integrated geochemical & microbial community model is a promising approach to predict and provide insights into the bioremediation of a complicated natural subsurface. In this study, an integrated column-scale model of uranium bioremediation was developed, taking into account long-term interactions between biotic and abiotic processes. It is also combined with a comprehensive thermodynamic analysis to track the fate and cycling of biogenic species. As compared with other bioremediation models, the model increases the resolution of the connection of microbial community to geochemistry and establishes direct quantitative correlation between overall community evolution and geochemical variation, thereby accurately predicting the community dynamics under different sedimentary conditions. The thermodynamic analysis examined a recently identified homogeneous reduction of U(VI) by Fe(II) under dynamic sedimentary conditions across time and space. It shows that the biogenic Fe(II) from Geobacter metabolism can be removed rapidly by the biogenic sulphide from sulfate reducer metabolism, hence constituting one of the reasons that make the abiotic U(VI) reduction thermodynamically infeasible in the subsurface. Further analysis indicates that much higher influent concentrations of both Fe(II) and U(VI) than normal are required to for abiotic U(VI) reduction to be thermodynamically feasible, suggesting that the abiotic reduction cannot be an alternative to the biotic reduction in the remediation of uranium contaminated groundwater.

  6. Role of structural Fe in nontronite NAu-1 and dissolved Fe(II) in redox transformations of arsenic and antimony

    NASA Astrophysics Data System (ADS)

    Ilgen, Anastasia G.; Foster, Andrea L.; Trainor, Thomas P.

    2012-10-01

    Oxidation state is a major factor affecting the mobility of arsenic (As) and antimony (Sb) in soil and aquatic systems. Metal (hydr)oxides and clay minerals are effective sorbents, and may also promote redox reactions on their surfaces via direct or indirect facilitation of electron transfer. Iron substituted for Al in the octahedral sites of aluminosilicate clay minerals has the potential to be in variable oxidation states and is a key constituent of electron transfer reactions in clay minerals. This experimental work was conducted to determine whether structural Fe in clays can affect the oxidation state of As and Sb adsorbed at the clay surface. Another goal of our study was to compare the reactivity of clay structural Fe(II) with systems containing Fe(II) present in dissolved/adsorbed forms. The experimental systems included batch reactors with various concentrations of As(III), Sb(III), As(V), or Sb(V) equilibrated with oxidized (NAu-1) or partially reduced (NAu-1-Red) nontronite, hydrous aluminum oxide (HAO) and kaolinite (KGa-1b) suspensions under oxic and anoxic conditions. The reaction times ranged from 0.5 to 720 h, and pH was constrained at 5.5 (for As) and at 5.5 or 8.0 (for Sb). The oxidation state of As and Sb in the liquid phase was determined by liquid chromatography in line with an inductively coupled plasma mass spectrometer, and in the solid phase by X-ray absorption spectroscopy. Our findings show that structural Fe(II) in NAu-1-Red was not able to reduce As(V)/Sb(V) under the conditions examined, but reduction was seen when aqueous Fe(II) was present in the systems with kaolinite (KGa-1b) and nontronite (NAu-1). The ability of the structural Fe in nontronite clay NAu-1 to promote oxidation of As(III)/Sb(III) was greatly affected by its oxidation state: if all structural Fe was in the oxidized Fe(III) form, no oxidation was observed; however, when the clay was partially reduced (˜20% of structural Fe was reduced to Fe(II)), NAu-1-Red promoted

  7. Role of structural Fe in nontronite NAu-1 and dissolved Fe(II) in redox transformations of arsenic and antimony

    SciTech Connect

    Ilgen, Anastasia G.; Foster, Andrea L.; Trainor, Thomas P.

    2012-11-01

    Oxidation state is a major factor affecting the mobility of arsenic (As) and antimony (Sb) in soil and aquatic systems. Metal (hydr)oxides and clay minerals are effective sorbents, and may also promote redox reactions on their surfaces via direct or indirect facilitation of electron transfer. Iron substituted for Al in the octahedral sites of aluminosilicate clay minerals has the potential to be in variable oxidation states and is a key constituent of electron transfer reactions in clay minerals. This experimental work was conducted to determine whether structural Fe in clays can affect the oxidation state of As and Sb adsorbed at the clay surface. Another goal of our study was to compare the reactivity of clay structural Fe(II) with systems containing Fe(II) present in dissolved/adsorbed forms. The experimental systems included batch reactors with various concentrations of As(III), Sb(III), As(V), or Sb(V) equilibrated with oxidized (NAu-1) or partially reduced (NAu-1-Red) nontronite, hydrous aluminum oxide (HAO) and kaolinite (KGa-1b) suspensions under oxic and anoxic conditions. The reaction times ranged from 0.5 to 720 h, and pH was constrained at 5.5 (for As) and at 5.5 or 8.0 (for Sb). The oxidation state of As and Sb in the liquid phase was determined by liquid chromatography in line with an inductively coupled plasma mass spectrometer, and in the solid phase by X-ray absorption spectroscopy. Our findings show that structural Fe(II) in NAu-1-Red was not able to reduce As(V)/Sb(V) under the conditions examined, but reduction was seen when aqueous Fe(II) was present in the systems with kaolinite (KGa-1b) and nontronite (NAu-1). The ability of the structural Fe in nontronite clay NAu-1 to promote oxidation of As(III)/Sb(III) was greatly affected by its oxidation state: if all structural Fe was in the oxidized Fe(III) form, no oxidation was observed; however, when the clay was partially reduced ({approx}20% of structural Fe was reduced to Fe(II)), NAu-1-Red

  8. Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

    NASA Astrophysics Data System (ADS)

    Roden, Eric E.

    2004-08-01

    Data from studies of dissimilatory bacterial (10 8 cells mL -1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L -1) were analyzed in relation to a generalized rate law for mineral dissolution (J t/m 0 = k'(m/m 0) γ, where J t is the rate of dissolution and/or reduction at time t, m 0 is the initial mass of oxide, and m/m 0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to

  9. Second Harmonic Generation Studies of Fe(II) Interactions with Hematite (α-Fe2O3)

    SciTech Connect

    Jordan, David S.; Hull, Christopher J.; Troiano, Julianne M.; Riha, Shannon C.; Martinson, Alex B.; Rosso, Kevin M.; Geiger, Franz M.

    2013-02-28

    Iron oxides are a ubiquitous class of compounds that are involved in many biological, geological, and technological processes, and the Fe(III)/Fe(II) redox couple is a fundamental transformation pathway; however, the study of iron oxide surfaces in aqueous solution by powerful spectroscopic techniques has been limited due to "strong absorber problem". In this work, atomic layer deposition (ALD) thin films of polycrystalline alpha-Fe2O3 were analyzed using the Eisenthal chi((3)) technique, a variant of second harmonic generation that reports on interfacial potentials. By determining the surface charge densities at multiple pH values, the point of zero charge was found to be 5.5 +/- 0.3. The interaction of aqueous Fe(II) at pH 4 and in 1 mM NaCl with ALD-prepared hematite was found to be fully reversible and to lead to about 4 times more ferrous iron ions adsorbed per square centimeter than on fused-silica surfaces under the same conditions. The data are consistent with a recently proposed conceptual model for net Fe(II) uptake or release that is underlain by a dynamic equilibrium between Fe(II) adsorbed onto hematite, electron transfer into favorable surface sites with attendant Fe(III) deposition, and electron conduction to favorable remote sites that release and replenish aqueous Fe(II).

  10. Abiotic origin of biopolymers

    NASA Technical Reports Server (NTRS)

    Oro, J.; Stephen-Sherwood, E.

    1976-01-01

    A variety of methods have been investigated in different laboratories for the polymerization of amino acids and nucleotides under abiotic conditions. They include (1) thermal polymerization; (2) direct polymerization of certain amino acid nitriles, amides, or esters; (3) polymerization using polyphosphate esters; (4) polymerization under aqueous or drying conditions at moderate temperatures using a variety of simple catalysts or condensing agents like cyanamide, dicyandiamide, or imidazole; and (5) polymerization under similar mild conditions but employing activated monomers or abiotically synthesized high-energy compounds such as adenosine 5'-triphosphate (ATP). The role and significance of these methods for the synthesis of oligopeptides and oligonucleotides under possible primitive-earth conditions is evaluated. It is concluded that the more recent approach involving chemical processes similar to those used by contemporary living organisms appears to offer a reasonable solution to the prebiotic synthesis of these biopolymers.

  11. Photochemical Formation of Fe(II) and Peroxides in Coastal Seawater Collected around Okinawa Island, Japan - Impact of Red Soil Pollution

    NASA Astrophysics Data System (ADS)

    Okada, K.; Nakajima, H.; Higuchi, T.; Fujimura, H.; Arakaki, T.; Taira, H.

    2003-12-01

    In a study to elucidate the impacts of red soil pollution on the oxidizing power of seawater, photochemical formation of Fe(II) and peroxides was studied in seawaters collected around Okinawa Island, Japan. The northern part of Okinawa Island suffers from red soil pollution which is caused mainly by land development such as pineapple farming and the construction of recreational facilities. We studied photochemical formation of peroxides and Fe(II) in the same seawater samples because the reaction between HOOH and Fe(II) forms hydroxyl radical (OH radical), the most potent environmental oxidant. Photochemical formation of Fe(II) was fast and reached steady-state in 30 minutes of simulated sunlight illumination and the steady-state Fe(II) concentrations were about 80% of total iron concentrations. Photochemical formation of peroxides was relatively slow and formation kinetics varied, depending on the initial peroxide concentrations. Because photochemical formation of peroxides was faster and total iron concentrations in the red soil polluted seawater were higher, red soil polluted seawater is expected to have greater oxidizing power than seawater that is not polluted with red soil.

  12. Cultivation of an Obligate Fe(II)-Oxidizing Lithoautotrophic Bacterium Using Electrodes

    PubMed Central

    Summers, Zarath M.; Gralnick, Jeffrey A.; Bond, Daniel R.

    2013-01-01

    ABSTRACT Fe(II)-oxidizing aerobic bacteria are poorly understood, due in part to the difficulties involved in laboratory cultivation. Specific challenges include (i) providing a steady supply of electrons as Fe(II) while (ii) managing rapid formation of insoluble Fe(III) oxide precipitates and (iii) maintaining oxygen concentrations in the micromolar range to minimize abiotic Fe(II) oxidation. Electrochemical approaches offer an opportunity to study bacteria that require problematic electron donors or acceptors in their respiration. In the case of Fe(II)-oxidizing bacteria, if the electron transport machinery is able to oxidize metals at the outer cell surface, electrodes poised at potentials near those of natural substrates could serve as electron donors, eliminating concentration issues, side reactions, and mineral end products associated with metal oxidation. To test this hypothesis, the marine isolate Mariprofundus ferrooxydans PV-1, a neutrophilic obligate Fe(II)-oxidizing autotroph, was cultured using a poised electrode as the sole energy source. When cells grown in Fe(II)-containing medium were transferred into a three-electrode electrochemical cell, a cathodic (negative) current representing electron uptake by bacteria was detected, and it increased over a period of weeks. Cultures scraped from a portion of the electrode and transferred into sterile reactors consumed electrons at a similar rate. After three transfers in the absence of Fe(II), electrode-grown biofilms were studied to determine the relationship between donor redox potential and respiration rate. Electron microscopy revealed that under these conditions, M. ferrooxydans PV-1 attaches to electrodes and does not produce characteristic iron oxide stalks but still appears to exhibit bifurcate cell division. PMID:23362318

  13. Acid-tolerant microaerophilic Fe(II)-oxidizing bacteria promote Fe(III)-accumulation in a fen.

    PubMed

    Lüdecke, Claudia; Reiche, Marco; Eusterhues, Karin; Nietzsche, Sandor; Küsel, Kirsten

    2010-10-01

    The ecological importance of Fe(II)-oxidizing bacteria (FeOB) at circumneutral pH is often masked in the presence of O(2) where rapid chemical oxidation of Fe(II) predominates. This study addresses the abundance, diversity and activity of microaerophilic FeOB in an acidic fen (pH ∼ 5) located in northern Bavaria, Germany. Mean O(2) penetration depth reached 16 cm where the highest dissolved Fe(II) concentrations (up to 140 µM) were present in soil water. Acid-tolerant FeOB cultivated in gradient tubes were most abundant (10(6) cells g(-1) peat) at the 10-20 cm depth interval. A stable enrichment culture was active at up to 29% O(2) saturation and Fe(III) accumulated 1.6 times faster than in abiotic controls. An acid-tolerant, microaerophilic isolate (strain CL21) was obtained which was closely related to the neutrophilic, lithoautotrophic FeOB Sideroxydans lithotrophicus strain LD-1. CL21 oxidized Fe(II) between pH 4 and 6.0, and produced nanoscale-goethites with a clearly lower mean coherence length (7 nm) perpendicular to the (110) plane than those formed abiotically (10 nm). Our results suggest that an acid-tolerant population of FeOB is thriving at redox interfaces formed by diffusion-limited O(2) transport in acidic peatlands. Furthermore, this well-adapted population is successfully competing with chemical oxidation and thereby playing an important role in the microbial iron cycle.

  14. Abiotic reductive immobilization of U(VI) by biogenic mackinawite.

    PubMed

    Veeramani, Harish; Scheinost, Andreas C; Monsegue, Niven; Qafoku, Nikolla P; Kukkadapu, Ravi; Newville, Matt; Lanzirotti, Antonio; Pruden, Amy; Murayama, Mitsuhiro; Hochella, Michael F

    2013-03-05

    During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U(VI) reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe 1+x S, x = 0 to 0.11) to reduce U(VI) abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS, and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U(VI) indicate the formation of nanoparticulate UO2. This study suggests the relevance of sulfide-bearing biogenic minerals in mediating abiotic U(VI) reduction, an alternative pathway in addition to direct enzymatic U(VI) reduction.

  15. Selenate removal by zero-valent iron in oxic condition: the role of Fe(II) and selenate removal mechanism.

    PubMed

    Yoon, In-Ho; Bang, Sunbaek; Kim, Kyoung-Woong; Kim, Min Gyu; Park, Sang Yoon; Choi, Wang-Kyu

    2016-01-01

    In this study, batch experiments were conducted to investigate the effect of the concentration of ferrous [Fe(II)] ions on selenate [Se(VI)] removal using zero-valent iron (ZVI). The mechanism of removal was investigated using spectroscopic and image analyses of the ZVI-Fe(II)-Se(VI) system. The test to remove 50 mg/L of Se(VI) by 1 g/L of ZVI resulted in about 60% removal of Se(VI) in the case with absence of Fe(II), but other tests with the addition of 50 and 100 mg/L of the Fe(II) had increased the removal efficiencies about 93 and 100% of the Se(VI), respectively. In other batch tests with the absence of ZVI, there were little changes on the Se(VI) removal by the varied concentration of the Fe(II). From these results, we found that Fe(II) ion plays an accelerator for the reduction of Se(VI) by ZVI with the stoichiometric balance of 1.4 (=nFe(2+)/nSe(6+)). Under anoxic conditions, the batch test revealed about 10% removal of the Se(VI), indicating that the presence of dissolved oxygen increased the kinetics of Se(VI) removal due to the Fe(II)-containing oxides on the ZVI, as analyzed by scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS). The X-ray absorption near edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) spectra also showed that the reductive process of Se(VI) to Se(0)/Se(-II) occurred in the presence of the both ZVI and Fe(II). The final product of iron corrosion was lepidocrocite (γ-FeOOH), which acts as an electron transfer barrier from Fe(0) core to Se(VI). Therefore, the addition of Fe(II) enhanced the reactivity of ZVI through the formation of iron oxides (magnetite) favoring electron transfer during the removal of Se(VI), which was through the exhaustion of the Fe(0) core reacted with Se(VI).

  16. Heterogeneous Reduction of PuO2 with Fe(II): Importance of the Fe(III) Reaction Product

    SciTech Connect

    Felmy, Andrew R.; Moore, Dean A.; Rosso, Kevin M.; Qafoku, Odeta; Rai, Dhanpat; Buck, Edgar C.; Ilton, Eugene S.

    2011-05-01

    Abstract Heterogeneous reduction of actinides in higher and more soluble oxidation states to lower more insoluble oxidation states by reductants such as Fe(II) has been the subject of intensive study for more than two decades. However, Fe(II)-induced reduction of sparingly soluble Pu(IV) to the more soluble lower oxidation state Pu(III) has been much less studied even though such reactions can potentially increase the mobility of Pu in the subsurface. Thermodynamic calculations are presented that show how differences in the free energy of various possible solid-phase Fe(III) reaction products can greatly influence aqueous Pu(III) concentrations resulting from reduction of PuO2(am) by Fe(II). We present the first experimental evidence that reduction of PuO2(am) to Pu(III) by Fe(II) was enhanced when the Fe(III) mineral goethite was spiked into the reaction. The effect of goethite on reduction of Pu(IV) was demonstrated by measuring the time-dependence of total aqueous Pu concentration, its oxidation state, and system pe/pH. We also re-evaluated established protocols for determining Pu(III) [(Pu(III) + Pu(IV)) - Pu(IV)] by using thenoyltrifluoroacetone (TTA) in toluene extractions; the study showed that it is important to eliminate dissolved oxygen from the TTA solutions for accurate determinations. More broadly, this study highlights the importance of the Fe(III) reaction product in actinide reduction rate and extent by Fe(II).

  17. Mechanism for the abiotic synthesis of uracil via UV-induced oxidation of pyrimidine in pure H{sub 2}O ices under astrophysical conditions

    SciTech Connect

    Bera, Partha P.; Nuevo, Michel; Sandford, Scott A.; Lee, Timothy J.; Milam, Stefanie N.

    2010-09-14

    The UV photoirradiation of pyrimidine in pure H{sub 2}O ices has been explored using second-order Moeller-Plesset perturbation theory and density functional theory methods, and compared with experimental results. Mechanisms studied include those starting with neutral pyrimidine or cationic pyrimidine radicals, and reacting with OH radical. The ab initio calculations reveal that the formation of some key species, including the nucleobase uracil, is energetically favored over others. The presence of one or several water molecules is necessary in order to abstract a proton which leads to the final products. Formation of many of the photoproducts in UV-irradiated H{sub 2}O:pyrimidine=20:1 ice mixtures was established in a previous experimental study. Among all the products, uracil is predicted by quantum chemical calculations to be the most favored, and has been identified in experimental samples by two independent chromatography techniques. The results of the present study strongly support the scenario in which prebiotic molecules, such as the nucleobase uracil, can be formed under abiotic processes in astrophysically relevant environments, namely in condensed phase on the surface of icy, cold grains before being delivered to the telluric planets, like Earth.

  18. The mechanism of the reduction of [AnO2]2+ (An = U, Np, Pu) in aqueous solution, and by Fe(II) containing proteins and mineral surfaces, probed by DFT calculations.

    PubMed

    Sundararajan, Mahesh; Assary, Rajeev S; Hillier, Ian H; Vaughan, David J

    2011-11-14

    The fate of actinyl species in the environment is closely linked to oxidation state, since the reduction of An(VI) to An(IV) greatly decreases their mobility due to the precipitation of the relatively insoluble An(IV) species. Here we study the mechanism of the reduction of [AnO(2)](2+) (An = U, Np, Pu) both in aqueous solution and by Fe(II) containing proteins and mineral surfaces, using density functional theory calculations. We find a disproportionation mechanism involving a An(V)-An(V) cation-cation complex, and we have investigated how these complexes are formed in the different environments. We find that the behaviour of U and Pu complexes are similar, but the reduction of Np(V) to Np(IV) would seems to be more difficult, in line with the experimental finding that Np(V) is generally more stable than U(V) or Pu(V). Although the models we have used are somewhat idealised, our calculations suggest that there are strong similarities between the biotic and abiotic reduction pathways.

  19. Cultivation of an obligate Fe(II)-oxidizing lithoautotrophic bacterium using electrodes.

    PubMed

    Summers, Zarath M; Gralnick, Jeffrey A; Bond, Daniel R

    2013-01-29

    Fe(II)-oxidizing aerobic bacteria are poorly understood, due in part to the difficulties involved in laboratory cultivation. Specific challenges include (i) providing a steady supply of electrons as Fe(II) while (ii) managing rapid formation of insoluble Fe(III) oxide precipitates and (iii) maintaining oxygen concentrations in the micromolar range to minimize abiotic Fe(II) oxidation. Electrochemical approaches offer an opportunity to study bacteria that require problematic electron donors or acceptors in their respiration. In the case of Fe(II)-oxidizing bacteria, if the electron transport machinery is able to oxidize metals at the outer cell surface, electrodes poised at potentials near those of natural substrates could serve as electron donors, eliminating concentration issues, side reactions, and mineral end products associated with metal oxidation. To test this hypothesis, the marine isolate Mariprofundus ferrooxydans PV-1, a neutrophilic obligate Fe(II)-oxidizing autotroph, was cultured using a poised electrode as the sole energy source. When cells grown in Fe(II)-containing medium were transferred into a three-electrode electrochemical cell, a cathodic (negative) current representing electron uptake by bacteria was detected, and it increased over a period of weeks. Cultures scraped from a portion of the electrode and transferred into sterile reactors consumed electrons at a similar rate. After three transfers in the absence of Fe(II), electrode-grown biofilms were studied to determine the relationship between donor redox potential and respiration rate. Electron microscopy revealed that under these conditions, M. ferrooxydans PV-1 attaches to electrodes and does not produce characteristic iron oxide stalks but still appears to exhibit bifurcate cell division. IMPORTANCE Electrochemical cultivation, supporting growth of bacteria with a constant supply of electron donors or acceptors, is a promising tool for studying lithotrophic species in the laboratory

  20. Photochemical Formation of Hydroxyl Radical, Hydrogen Peroxide and Fe(II) in the Sea Surface Microlayer (SML) Collected in Okinawa, Japan

    NASA Astrophysics Data System (ADS)

    Higaonna, Y.; Tachibana, C.; Kasaba, T.; Ishikawa, R.; Arakaki, T.

    2014-12-01

    The sea surface microlayer (SML) covers upper 1 to 1000 μm deep boundary layer of the ocean, where important biogeochemical processes take place. Photo-chemical reactions are activated by sunlight, so it is assumed that more photo-chemical reactions occur in SML than underlying bulk seawater (bulk). We initiated a study to understand chemical changes occurring in the SML by studying photochemical formation of oxidants such as hydrogen peroxide and hydroxyl radical (OH), both of which react with various organic substances and determine their lifetimes. Since OH can be formed by reaction between hydrogen peroxide and Fe(II), Fe(II) photoformation was also studied. We collected SML samples using a widely-used glass plate method and bulk samples by using a polyethylene bottles near the coast of Okinawa Island, Japan. Results showed that dissolved organic carbon (DOC) concentrations in the SML were about twice those of bulk seawater samples. Hydrogen peroxide formation in the SML samples was ca. 2.8 times faster than the bulk seawater samples. On the other hand, Fe(II) and OH photoformation kinetics was similar for both SML and bulk samples. Although it was predicted that more OH could be formed from reaction between hydrogen peroxide and Fe(II), OH formation kinetics was similar in both SML and bulk, suggesting that either Fe(II) did not react with hydrogen peroxide or reaction is very slow, possibly by forming a complex with organic compounds in the SML and bulk.

  1. Fe(II) Oxidation and Sources of Acidity on Mars

    NASA Technical Reports Server (NTRS)

    Niles, P. B.; Peretyazkho, T. S.; Sutter, B.

    2017-01-01

    There is an apparent paradox be-tween the evidence that aqueous environments on Mars were predominantly acidic, and the fact that Mars is predominantly a basaltic (and olivine-rich) planet. The problem being that basalt and olivine will act to neutralize acidic solutions they come into contact with, and that there is a lot more basaltic crust on Mars than water or acid. This is especially true if there is an appreciable amount of water available to bring the acid in contact with the basaltic crust. Several hypotheses for ancient mar-tian environments call on long lived groundwater and aqueous systems.

  2. Abiotic degradation of plastic films

    NASA Astrophysics Data System (ADS)

    Ángeles-López, Y. G.; Gutiérrez-Mayen, A. M.; Velasco-Pérez, M.; Beltrán-Villavicencio, M.; Vázquez-Morillas, A.; Cano-Blanco, M.

    2017-01-01

    Degradable plastics have been promoted as an option to mitigate the environmental impacts of plastic waste. However, there is no certainty about its degradability under different environmental conditions. The effect of accelerated weathering (AW), natural weathering (NW) and thermal oxidation (TO) on different plastics (high density polyethylene, HDPE; oxodegradable high density polyethylene, HDPE-oxo; compostable plastic, Ecovio ® metalized polypropylene, PP; and oxodegradable metalized polypropylene, PP-oxo) was studied. Plastics films were exposed to AW per 110 hours; to NW per 90 days; and to TO per 30 days. Plastic films exposed to AW and NW showed a general loss on mechanical properties. The highest reduction in elongation at break on AW occurred to HDPE-oxo (from 400.4% to 20.9%) and was higher than 90% for HDPE, HDPE-oxo, Ecovio ® and PP-oxo in NW. No substantial evidence of degradation was found on plastics exposed to TO. Oxo-plastics showed higher degradation rates than their conventional counterparts, and the compostable plastic was resistant to degradation in the studied abiotic conditions. This study shows that degradation of plastics in real life conditions will vary depending in both, their composition and the environment.

  3. Role of Fe(II), phosphate, silicate, sulfate, and carbonate in arsenic uptake by coprecipitation in synthetic and natural groundwater.

    PubMed

    Ciardelli, Mark C; Xu, Huifang; Sahai, Nita

    2008-02-01

    Competitive effects of phosphate, silicate, sulfate, and carbonate on As(III) and As(V) removal at pH approximately 7.2 have been investigated to test the feasibility of Fe(II)(aq) and hydroxylapatite crystals as inexpensive and potentially efficient agents for remediation of contaminated well-water, using Bangladesh as a type study. Arsenic(III) removal approximately 50-55% is achieved, when Fe(II)(aq) oxidizes to Fe(III) and precipitates as Fe(OH)3 at 25 degrees C and 3h reaction time, in the presence of all the oxyanion. Similar results were obtained for well-water samples from two sites in Bangladesh. Heating at 95 degrees C for 24h results in 70% As(III) uptake due to precipitation of magnesian calcite. A two-step process, Fe(II) oxidation and Fe(OH)3 precipitation at 25 degrees C for 2h, followed by magnesian calcite precipitation at 95 degrees C for 3h, yields approximately 65% arsenic removal while reducing the expensive heating period. In the absence of silicate, up to 70% As(III) uptake occurs at 25 degrees C. In all cases, As(III) was oxidized to As(V) in solution by dissolved oxygen and the reaction rate was probably promoted by intermediates formed during Fe(II) oxidation. Iron-catalyzed oxidation of As(III) by oxygen and hydrogen peroxide is pH-dependent with formation of oxidants in the Fenton reaction. Buffering pH at near-neutral values by dissolved carbonate and hydroxylapatite seeds is important for faster Fe(II) oxidation kinetics ensuring rapid coprecipitation of As as As(V) in the ferric phases.

  4. Abiotic transformation of carbon tetrachloride at mineral surfaces. Final report, September 1990-September 1993

    SciTech Connect

    Kriegman-King, M.; Reinhard, M.

    1994-02-01

    The report addresses the ability of natural mineral surfaces to abiotically transform halogenated organic compounds in subsurface environments. The research focuses on carbon tetrachloride (CC14) as the halogenated organic and biotite, vermiculite, and pyrite as the mineral surfaces. The CCl4 transformation rates and products were quantified under different environmental conditions. The disappearance of CCl4 was significantly faster in the presence of mineral surfaces than in homogeneous solution. In systems containing the sheet silicates and HS-, the rate of reaction was dependent on the temperature, hydrogen sulfide ion concentration, surface concentration, and Fe(II) content in the minerals.

  5. Dissolved Fe(II) in the Pacific Ocean: Measurements from the P16N CLIVAR/CO2 Repeat Hydrography Cruise

    NASA Astrophysics Data System (ADS)

    Hansard, S. P.; Landing, W. M.; Measures, C. I.

    2006-12-01

    Vertical profiles of seawater Fe(II) concentration were obtained for 37 stations sampled in early 2006, in conjunction with the CLIVAR Repeat Hydrography P16N transect (152° W, Tahiti to Alaska). At each station, seawater samples were collected from 12 target depths (0-1000 m) using trace-metal clean Go-Flo bottles. Upon recovery, Go-Flo bottles were immediately transferred to a Class 100 clean van and sub-sampled for Fe(II) by passing sample water through a 0.2 μm Supor (polyethersulfone) cartridge filter into 125 mL containers, pre-loaded with 25 μL of 6M quartz-distilled HCl (final pH ~~ 6) to slow oxidation. Samples were immediately analyzed for Fe(II) using a luminol-based chemiluminescence method. Total dissolved iron was also determined shipboard by spectrophotometric flow injection analysis. The data collected from this cruise will be presented, along with corroborating data from another North Pacific cruise (PO2). Concentrations of Fe(II) ranged from below detection (< 20 pM) to 83 pM. Highest concentrations were found in surface samples near the equator, and in surface samples adjacent to the Alaskan coast. Within a profile, surface values were relatively high, sometimes as much as 50% of the total dissolved iron, and typically diminishing to undetectable levels within the upper 150 meters. Photoreduction of Fe(III) has been cited as a source of Fe(II) in surface waters, and the pattern of attenuation with depth is consistent with this mechanism. Many samples collected at or near the bottom of the profile (500-1000 m) exhibited elevated Fe(II) relative to the mid-depths of the profile. Due to the higher total dissolved iron at depth, the percentage of Fe(II) was low in these samples. Recent studies support the presence of Fe(II) at depth, in association with low or suboxic conditions. In situ processes such as the remineralization of sinking biogenic particles may provide a source for this Fe(II).

  6. Control of sulfidogenesis through bio-oxidation of H2S coupled to (per)chlorate reduction.

    PubMed

    Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G; Metlagel, Zoltan; Csencsits, Roseann; Auer, Manfred; Conrad, Mark E; Thieme, Jürgen; Northrup, Paul; Coates, John D

    2014-12-01

    We investigated H2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H2S coupled to (per)chlorate reduction without sustaining growth. H2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. Based on our results, we propose a novel hybrid enzymatic-abiotic mechanism for H2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

  7. Reduction of ferrihydrite with adsorbed and coprecipitated organic matter: microbial reduction by Geobacter bremensis vs. abiotic reduction by Na-dithionite

    NASA Astrophysics Data System (ADS)

    Eusterhues, K.; Hädrich, A.; Neidhardt, J.; Küsel, K.; Keller, T. F.; Jandt, K. D.; Totsche, K. U.

    2014-04-01

    Ferrihydrite (Fh) is a widespread poorly crystalline Fe oxide which becomes easily coated by natural organic matter (OM) in the environment. This mineral-bound OM entirely changes the mineral surface properties and therefore the reactivity of the original mineral. Here, we investigated the reactivity of 2-line Fh, Fh with adsorbed OM and Fh coprecipitated with OM towards microbial and abiotic reduction of Fe(III). As a surrogate for dissolved soil OM we used a water extract of a Podzol forest floor. Fh-OM associations with different OM-loadings were reduced either by Geobacter bremensis or abiotically by Na-dithionite. Both types of experiments showed decreasing initial Fe reduction rates and decreasing degrees of reduction with increasing amounts of mineral-bound OM. At similar OM-loadings, coprecipitated Fhs were more reactive than Fhs with adsorbed OM. The difference can be explained by the smaller crystal size and poor crystallinity of such coprecipitates. At small OM loadings this led to even faster Fe reduction rates than found for pure Fh. The amount of mineral-bound OM also affected the formation of secondary minerals: goethite was only found after reduction of OM-free Fh and siderite was only detected when Fhs with relatively low amounts of mineral-bound OM were reduced. We conclude that direct contact of G. bremensis to the Fe oxide mineral surface was inhibited when blocked by OM. Consequently, mineral-bound OM shall be taken into account besides Fe(II) accumulation as a further widespread mechanism to slow down reductive dissolution.

  8. Competing retention pathways of uranium upon reaction with Fe(II)

    SciTech Connect

    Massey, Michael S.; Lezama Pacheco, Juan S.; Jones, Morris; Ilton, Eugene S.; Cerrato, Jose M.; Bargar, John R.; Fendorf, Scott

    2014-10-01

    Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3•nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway’s contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ~7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM) coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended x-ray absorption fine structure (EXAFS) spectroscopy, x-ray powder diffraction, x-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14 to 89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ≤ 50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64 to 89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within

  9. Competing retention pathways of uranium upon reaction with Fe(II)

    NASA Astrophysics Data System (ADS)

    Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

    2014-10-01

    Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway’s contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron

  10. Abiotic stresses and endophyte effects

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Abiotic stresses consist of nonorganismal, nonpathogenic factors that inhibit plant function. Tall fescue [Lolium arundinaceum (Schreb.) Darbysh.] is widely symbiotic with a naturally occurring endophytic fungus [Neotyphodium coenophialum (Morgan-Jones and Gams) Glenn, Bacon, and Hanlin], which con...

  11. Treatment of groundwater containing Mn(II), Fe(II), As(III) and Sb(III) by bioaugmented quartz-sand filters.

    PubMed

    Bai, Yaohui; Chang, Yangyang; Liang, Jinsong; Chen, Chen; Qu, Jiuhui

    2016-12-01

    High concentrations of iron (Fe(II)) and manganese (Mn(II)) often occur simultaneously in groundwater. Previously, we demonstrated that Fe(II) and Mn(II) could be oxidized to biogenic Fe-Mn oxides (BFMO) via aeration and microbial oxidation, and the formed BFMO could further oxidize and adsorb other pollutants (e.g., arsenic (As(III)) and antimony (Sb(III))). To apply this finding to groundwater remediation, we established four quartz-sand columns for treating groundwater containing Fe(II), Mn(II), As(III), and Sb(III). A Mn-oxidizing bacterium (Pseudomonas sp. QJX-1) was inoculated into two parallel bioaugmented columns. Long-term treatment (120 d) showed that bioaugmentation accelerated the formation of Fe-Mn oxides, resulting in an increase in As and Sb removal. The bioaugmented columns also exhibited higher overall treatment effect and anti-shock load capacity than that of the non-bioaugmented columns. To clarify the causal relationship between the microbial community and treatment effect, we compared the biomass of active bacteria (reverse-transcribed real-time PCR), bacterial community composition (Miseq 16S rRNA sequencing) and community function (metagenomic sequencing) between the bioaugmented and non-bioaugmented columns. Results indicated that the QJX1 strain grew steadily and attached onto the filter material surface in the bioaugmented columns. In general, the inoculated strain did not significantly alter the composition of the indigenous bacterial community, but did improve the relative abundances of xenobiotic metabolism genes and Mn oxidation gene. Thus, bioaugmentation intensified microbial degradation/utilization for the direct removal of pollutants and increased the formation of Fe-Mn oxides for the indirect removal of pollutants. Our study provides an alternative method for the treatment of groundwater containing high Fe(II), Mn(II) and As/Sb.

  12. Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching.

    PubMed

    Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

    2016-01-01

    We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution.

  13. Direct Detection of Fe(II) in Extracellular Polymeric Substances (EPS) at the Mineral-Microbe Interface in Bacterial Pyrite Leaching

    PubMed Central

    Mitsunobu, Satoshi; Zhu, Ming; Takeichi, Yasuo; Ohigashi, Takuji; Suga, Hiroki; Jinno, Muneaki; Makita, Hiroko; Sakata, Masahiro; Ono, Kanta; Mase, Kazuhiko; Takahashi, Yoshio

    2016-01-01

    We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution. PMID:26947441

  14. Polyamines and abiotic stress in plants: a complex relationship1

    PubMed Central

    Minocha, Rakesh; Majumdar, Rajtilak; Minocha, Subhash C.

    2014-01-01

    The physiological relationship between abiotic stress in plants and polyamines was reported more than 40 years ago. Ever since there has been a debate as to whether increased polyamines protect plants against abiotic stress (e.g., due to their ability to deal with oxidative radicals) or cause damage to them (perhaps due to hydrogen peroxide produced by their catabolism). The observation that cellular polyamines are typically elevated in plants under both short-term as well as long-term abiotic stress conditions is consistent with the possibility of their dual effects, i.e., being protectors from as well as perpetrators of stress damage to the cells. The observed increase in tolerance of plants to abiotic stress when their cellular contents are elevated by either exogenous treatment with polyamines or through genetic engineering with genes encoding polyamine biosynthetic enzymes is indicative of a protective role for them. However, through their catabolic production of hydrogen peroxide and acrolein, both strong oxidizers, they can potentially be the cause of cellular harm during stress. In fact, somewhat enigmatic but strong positive relationship between abiotic stress and foliar polyamines has been proposed as a potential biochemical marker of persistent environmental stress in forest trees in which phenotypic symptoms of stress are not yet visible. Such markers may help forewarn forest managers to undertake amelioration strategies before the appearance of visual symptoms of stress and damage at which stage it is often too late for implementing strategies for stress remediation and reversal of damage. This review provides a comprehensive and critical evaluation of the published literature on interactions between abiotic stress and polyamines in plants, and examines the experimental strategies used to understand the functional significance of this relationship with the aim of improving plant productivity, especially under conditions of abiotic stress. PMID:24847338

  15. Control of Sulfidogenesis Through Bio-oxidation of H2S Coupled to (per)chlorate Reduction

    SciTech Connect

    Gregoire, Patrick; Engelbrektson, Anna; Hubbard, Christopher G.; Metlagel, Zoltan; Csencsits, Roseann; Auer, Manfred; Conrad, Mark E.; Thieme, Jurgen; Northrup, Paul; Coates, John D.

    2014-04-04

    Here, we investigate H2S attenuation by dissimilatory perchlorate-reducing bacteria (DPRB). All DPRB tested oxidized H2S coupled to (per)chlorate reduction without sustaining growth. H2S was preferentially utilized over organic electron donors resulting in an enriched (34S)-elemental sulfur product. Electron microscopy revealed elemental sulfur production in the cytoplasm and on the cell surface of the DPRB Azospira suillum. We also propose a novel hybrid enzymatic-abiotic mechanism for H2S oxidation similar to that recently proposed for nitrate-dependent Fe(II) oxidation. The results of this study have implications for the control of biosouring and biocorrosion in a range of industrial environments.

  16. Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing phyllosilicates.

    PubMed

    Lee, Woojin; Batchelor, Bill

    2004-09-01

    Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and vinylchloride (VC)) by iron-bearing phyllosilicates (biotite, vermiculite, and montmorillonite) was characterized to obtain better understanding of the behavior of these contaminants in systems undergoing remediation by natural attenuation and redox manipulation. Batch experiments were conducted to evaluate dechlorination kinetics and some experiments were conducted with addition of Fe(II) to simulate impact of microbial iron reduction. A modified Langmuir-Hinshelwood kinetic model adequately described reductive dechlorination kinetics of target organics by the iron-bearing phyllosilicates. The rate constants stayed between 0.08 (+/-10.4%) and 0.401 (+/-8.1%) day(-1) and the specific initial reductive capacity of iron-bearing phyllosilicates for chlorinated ethylenes stayed between 0.177 (+/-6.1%) and 1.06 (+/-7.1%) microM g(-1). The rate constants for the reductive dechlorination of TCE at reactive biotite surface increased as pH (5.5-8.5) and concentration of sorbed Fe(II) (0-0.15 mM g(-1)) increased. The appropriateness of the model is supported by the fact that the rate constants were independent of solid concentration (0.0085-0.17 g g(-1)) and initial TCE concentration (0.15-0.60 mM). Biotite had the greatest rate constant among the phyllosilicates both with and without Fe(II) addition. The rate constants were increased by a factor of 1.4-2.5 by Fe(II) addition. Between 1.8% and 36% of chlorinated ethylenes removed were partitioned to the phyllosilicates. Chloride was produced as a product of degradation and no chlorinated intermediates were observed throughout the experiment.

  17. Oxylipins and plant abiotic stress resistance.

    PubMed

    Savchenko, T V; Zastrijnaja, O M; Klimov, V V

    2014-04-01

    Oxylipins are signaling molecules formed enzymatically or spontaneously from unsaturated fatty acids in all aerobic organisms. Oxylipins regulate growth, development, and responses to environmental stimuli of organisms. The oxylipin biosynthesis pathway in plants includes a few parallel branches named after first enzyme of the corresponding branch as allene oxide synthase, hydroperoxide lyase, divinyl ether synthase, peroxygenase, epoxy alcohol synthase, and others in which various biologically active metabolites are produced. Oxylipins can be formed non-enzymatically as a result of oxygenation of fatty acids by free radicals and reactive oxygen species. Spontaneously formed oxylipins are called phytoprostanes. The role of oxylipins in biotic stress responses has been described in many published works. The role of oxylipins in plant adaptation to abiotic stress conditions is less studied; there is also obvious lack of available data compilation and analysis in this area of research. In this work we analyze data on oxylipins functions in plant adaptation to abiotic stress conditions, such as wounding, suboptimal light and temperature, dehydration and osmotic stress, and effects of ozone and heavy metals. Modern research articles elucidating the molecular mechanisms of oxylipins action by the methods of biochemistry, molecular biology, and genetics are reviewed here. Data on the role of oxylipins in stress signal transduction, stress-inducible gene expression regulation, and interaction of these metabolites with other signal transduction pathways in cells are described. In this review the general oxylipin-mediated mechanisms that help plants to adjust to a broad spectrum of stress factors are considered, followed by analysis of more specific responses regulated by oxylipins only under certain stress conditions. New approaches to improvement of plant resistance to abiotic stresses based on the induction of oxylipin-mediated processes are discussed.

  18. Abiotic reduction of nitroaromatic contaminants by iron(II) complexes with organothiol ligands.

    PubMed

    Naka, Daisuke; Kim, Dongwook; Carbonaro, Richard F; Strathmann, Timothy J

    2008-06-01

    Complexation of Fe(II) by dissolved and surface-bound ligands can significantly modify the metal's redox reactivity, and recent work reveals that Fe(II) complexes with selected classes of organic ligands are potent reductants that may contribute to the natural attenuation of subsurface contaminants. In the present study, we investigated the reactivity of Fe(II)-organothiol ligand complexes with nitroaromatic contaminants (NACs; ArNO(2)). Experimental results show that NACs are unreactive in Fe(2+)-only and ligand-only solutions but are reduced to the corresponding aniline compounds (ArNH(2)) in solutions containing both Fe(II) and a number of organothiol ligands. Observed reaction rates are highly dependent on the structure of the Fe(II)-complexing ligand, solution composition, Fe(II) speciation, and NAC structure. For two model ligands, cysteine and thioglycolic acid, observed pseudo-first order rate constants for 4-chloronitrobenzene reduction (k(obs); 1/s) are linearly correlated with the concentration of the respective 1:2 Fe(II)- organothiol complexes (FeL(2)(2-)), and k(obs) measurements are accurately predicted by k(obs) = k(FeL(2-)(2))[FeL(2-)(2)], where k(FeL(2-)(2)) = 1.70 (+/-0.59) 1/M/s and 26.0 (+/-4.8) 1/M/s for cysteine and thioglycolic acid, respectively. The high reactivity of these Fe(II) complexes is attributed to a lowering of the standard one-electron reduction potential of the Fe(III)/Fe(II) redox couple on complexation by organothiol ligands. The relative reactivity of a series of substituted NACs with individual Fe(II) complexes can be described by linear free-energy relationships with the apparent one-electron reduction potentials of the NACs. Tests also show that organothiol ligands can further promote NAC reduction indirectly by re-reducing the Fe(III) that forms when Fe(II) complexes are oxidized by reactions with the NACs.

  19. ROS Regulation During Abiotic Stress Responses in Crop Plants.

    PubMed

    You, Jun; Chan, Zhulong

    2015-01-01

    Abiotic stresses such as drought, cold, salt and heat cause reduction of plant growth and loss of crop yield worldwide. Reactive oxygen species (ROS) including hydrogen peroxide (H2O2), superoxide anions (O2 (•-)), hydroxyl radical (OH•) and singlet oxygen ((1)O2) are by-products of physiological metabolisms, and are precisely controlled by enzymatic and non-enzymatic antioxidant defense systems. ROS are significantly accumulated under abiotic stress conditions, which cause oxidative damage and eventually resulting in cell death. Recently, ROS have been also recognized as key players in the complex signaling network of plants stress responses. The involvement of ROS in signal transduction implies that there must be coordinated function of regulation networks to maintain ROS at non-toxic levels in a delicate balancing act between ROS production, involving ROS generating enzymes and the unavoidable production of ROS during basic cellular metabolism, and ROS-scavenging pathways. Increasing evidence showed that ROS play crucial roles in abiotic stress responses of crop plants for the activation of stress-response and defense pathways. More importantly, manipulating ROS levels provides an opportunity to enhance stress tolerances of crop plants under a variety of unfavorable environmental conditions. This review presents an overview of current knowledge about homeostasis regulation of ROS in crop plants. In particular, we summarize the essential proteins that are involved in abiotic stress tolerance of crop plants through ROS regulation. Finally, the challenges toward the improvement of abiotic stress tolerance through ROS regulation in crops are discussed.

  20. ROS Regulation During Abiotic Stress Responses in Crop Plants

    PubMed Central

    You, Jun; Chan, Zhulong

    2015-01-01

    Abiotic stresses such as drought, cold, salt and heat cause reduction of plant growth and loss of crop yield worldwide. Reactive oxygen species (ROS) including hydrogen peroxide (H2O2), superoxide anions (O2•-), hydroxyl radical (OH•) and singlet oxygen (1O2) are by-products of physiological metabolisms, and are precisely controlled by enzymatic and non-enzymatic antioxidant defense systems. ROS are significantly accumulated under abiotic stress conditions, which cause oxidative damage and eventually resulting in cell death. Recently, ROS have been also recognized as key players in the complex signaling network of plants stress responses. The involvement of ROS in signal transduction implies that there must be coordinated function of regulation networks to maintain ROS at non-toxic levels in a delicate balancing act between ROS production, involving ROS generating enzymes and the unavoidable production of ROS during basic cellular metabolism, and ROS-scavenging pathways. Increasing evidence showed that ROS play crucial roles in abiotic stress responses of crop plants for the activation of stress-response and defense pathways. More importantly, manipulating ROS levels provides an opportunity to enhance stress tolerances of crop plants under a variety of unfavorable environmental conditions. This review presents an overview of current knowledge about homeostasis regulation of ROS in crop plants. In particular, we summarize the essential proteins that are involved in abiotic stress tolerance of crop plants through ROS regulation. Finally, the challenges toward the improvement of abiotic stress tolerance through ROS regulation in crops are discussed. PMID:26697045

  1. Manganese oxide shuttling in pre-GOE oceans - evidence from molybdenum and iron isotopes

    NASA Astrophysics Data System (ADS)

    Kurzweil, Florian; Wille, Martin; Gantert, Niklas; Beukes, Nicolas J.; Schoenberg, Ronny

    2016-10-01

    The local occurrence of oxygen-rich shallow marine water environments has been suggested to significantly predate atmospheric oxygenation, which occurred during the Great Oxidation Event (GOE) ca. 2.4 billion years ago. However, the potential influence of such 'oxygen oases' on the mobility, distribution and isotopic composition of redox sensitive elements remains poorly understood. Here, we provide new molybdenum and iron isotopic data from shallow marine carbonate and silicate iron formations of the Koegas Subgroup, South Africa, that confirm local ocean redox stratification prior to the GOE. Mn concentrations correlate negatively with both δ98 Mo and δ56 Fe values, which highlights the substantial role of particulate manganese for the cycling of Mo and Fe in the Paleoproterozoic oceans. Based on these trends we propose that pore water molybdate was recharged (1) by the diffusional transport of seawater molybdate with high δ98 Mo and (2) by the re-liberation of adsorbed molybdate with low δ98 Mo during Mn oxide dissolution within the sediment. The relative contribution of isotopically light Mo is highest close to a Mn chemocline, where the flux of Mn oxides is largest, causing the negative correlation of Mn concentrations and δ98 Mo values in the Koegas sediments. The negative correlation between δ56 Fe values and Mn concentrations is likely related to Fe isotope fractionation during Fe(II) oxidation by Mn oxides, resulting in lower δ56 Fe values in the uppermost water column close to a Mn chemocline. We argue that the preservation of these signals within Paleoproterozoic sediments implies the existence of vertically extended chemoclines with a smoother gradient, probably as a result of low atmospheric oxygen concentrations. Furthermore, we suggest that abiotic oxidation of Fe(II) by a Mn oxide particle shuttle might have promoted the deposition of the Koegas iron formations.

  2. Effects of dissolved organic matter on adsorbed Fe(II) reactivity for the reduction of 2-nitrophenol in TiO2 suspensions.

    PubMed

    Zhu, Zhenke; Tao, Liang; Li, Fangbai

    2013-09-01

    Dissolved organic matter (DOM) is widespread in aquatic and terrestrial environments. Iron is the most abundant transition metal in the Earth's crust. The biogeochemistry of iron and the strength of Fe(II) as a reducing agent while adsorbed on minerals are affected by DOM. This study investigated the effects of Fe(II)/DOM interactions on the reduction of 2-nitrophenol (2-NP) in TiO2 suspensions. Kinetic measurements demonstrated that rates (k) of 2-NP reduction by adsorbed Fe(II) species are affected by adding DOM (denoted O-DOM), and the obtained k values under the impact of the Fe(II)/DOM interaction with different molecular weight DOM fractions [including MW<3500Da (L-DOM), 350014000Da (H-DOM)] showed significant differences. The enhanced rates of 2-NP reduction contributed to increases in the amount of adsorbed Fe(II) species and negative shifts in peak oxidation potential values (EP) in CV tests. For different molecular weight DOM fractions, increases in k (O-DOMFe(II) to the higher level of adsorbed Fe(II) and the lower EP values. In addition, the ETC values were slightly higher in the TiO2 suspension containing the H-DOM fraction as compared the other two DOM fractions, which would further enhance the reduction rate of 2-NP. These findings promote a general understanding of Fe(II)/DOM interactions and their impact on the fate of contaminants in actual subsurface environments.

  3. Reactive oxygen species signaling in plants under abiotic stress.

    PubMed

    Choudhury, Shuvasish; Panda, Piyalee; Sahoo, Lingaraj; Panda, Sanjib Kumar

    2013-04-01

    Abiotic stresses like heavy metals, drought, salt, low temperature, etc. are the major factors that limit crop productivity and yield. These stresses are associated with production of certain deleterious chemical entities called reactive oxygen species (ROS), which include hydrogen peroxide (H₂O₂), superoxide radical (O₂(-)), hydroxyl radical (OH(-)), etc. ROS are capable of inducing cellular damage by degradation of proteins, inactivation of enzymes, alterations in the gene and interfere in various pathways of metabolic importance. Our understanding on ROS in response to abiotic stress is revolutionized with the advancements in plant molecular biology, where the basic understanding on chemical behavior of ROS is better understood. Understanding the molecular mechanisms involved in ROS generation and its potential role during abiotic stress is important to identify means by which plant growth and metabolism can be regulated under acute stress conditions. ROS mediated oxidative stress, which is the key to understand stress related toxicity have been widely studied in many plants and the results in those studies clearly revealed that oxidative stress is the main symptom of toxicity. Plants have their own antioxidant defense mechanisms to encounter ROS that is of enzymic and non-enzymic nature . Coordinated activities of these antioxidants regulate ROS detoxification and reduces oxidative load in plants. Though ROS are always regarded to impart negative impact on plants, some reports consider them to be important in regulating key cellular functions; however, such reports in plant are limited. Molecular approaches to understand ROS metabolism and signaling have opened new avenues to comprehend its critical role in abiotic stress. ROS also acts as secondary messenger that signals key cellular functions like cell proliferation, apoptosis and necrosis. In higher eukaryotes, ROS signaling is not fully understood. In this review we summarize our understanding on ROS

  4. Redox cycling of Fe(II) and Fe(III) in magnetite by Fe-metabolizing bacteria

    NASA Astrophysics Data System (ADS)

    Byrne, James M.; Klueglein, Nicole; Pearce, Carolyn; Rosso, Kevin M.; Appel, Erwin; Kappler, Andreas

    2015-03-01

    Microorganisms are a primary control on the redox-induced cycling of iron in the environment. Despite the ability of bacteria to grow using both Fe(II) and Fe(III) bound in solid-phase iron minerals, it is currently unknown whether changing environmental conditions enable the sharing of electrons in mixed-valent iron oxides between bacteria with different metabolisms. We show through magnetic and spectroscopic measurements that the phototrophic Fe(II)-oxidizing bacterium Rhodopseudomonas palustris TIE-1 oxidizes magnetite (Fe3O4) nanoparticles using light energy. This process is reversible in co-cultures by the anaerobic Fe(III)-reducing bacterium Geobacter sulfurreducens. These results demonstrate that Fe ions bound in the highly crystalline mineral magnetite are bioavailable as electron sinks and electron sources under varying environmental conditions, effectively rendering magnetite a naturally occurring battery.

  5. Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

    PubMed

    Fortney, N W; He, S; Converse, B J; Beard, B L; Johnson, C M; Boyd, E S; Roden, E E

    2016-05-01

    Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers

  6. Anti-inflammatory and antioxidative activity of anthocyanins from purple basil leaves induced by selected abiotic elicitors.

    PubMed

    Szymanowska, Urszula; Złotek, Urszula; Karaś, Monika; Baraniak, Barbara

    2015-04-01

    This paper investigates changes in the anti-inflammatory and antioxidative activity of anthocyanins from purple basil (Ocimum basilicum L.) leaves induced by arachidonic acid (AA), jasmonic acid (JA) and β-aminobutyric acid (BABA). The anthocyanins content was significantly increased by all elicitors used in this study; however, no increase was observed in the antioxidant activity of the analyzed extracts. Additionally, a significant decrease by about 50% in the ability to chelate Fe(II) was noted. Further, an increase in the potential anti-inflammatory activity of basil anthocyanins was observed after treatment with each the abiotic elicitor. The IC50 value for lipoxygenase inhibition was almost twice as low after elicitation as that of the control. Also, cyclooxygenase inhibition by anthocyanins was stimulated by abiotic elicitors, except for JA-sample. Additionally, HPLC-analysis indicated that elicitation with AA, JA and BABA caused increases in content most of all anthocyanin compounds.

  7. Fe(II) sorption on pyrophyllite: Effect of structural Fe(III) (impurity) in pyrophyllite on nature of layered double hydroxide (LDH) secondary mineral formation

    SciTech Connect

    Starcher, Autumn N.; Li, Wei; Kukkadapu, Ravi K.; Elzinga, Evert J.; Sparks, Donald L.

    2016-11-01

    Fe(II)-Al(III)-LDH (layered double hydroxide) phases have been shown to form from reactions of aqueous Fe(II) with Fe-free Al-bearing minerals (phyllosilicate/clays and Al-oxides). To our knowledge, the effect of small amounts of structural Fe(III) impurities in “neutral” clays on such reactions, however, were not studied. In this study to understand the role of structural Fe(III) impurity in clays, laboratory batch studies with pyrophyllite (10 g/L), an Al-bearing phyllosilicate, containing small amounts of structural Fe(III) impurities and 0.8 mM and 3 mM Fe(II) (both natural and enriched in 57Fe) were carried out at pH 7.5 under anaerobic conditions (4% H2 – 96% N2 atmosphere). Samples were taken up to 4 weeks for analysis by Fe-X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy. In addition to the precipitation of Fe(II)-Al(III)-LDH phases as observed in earlier studies with pure minerals (no Fe(III) impurities in the minerals), the analyses indicated formation of small amounts of Fe(III) containing solid(s), most probably hybrid a Fe(II)-Al(III)/Fe(III)-LDH phase. The mechanism of Fe(II) oxidation was not apparent but most likely was due to interfacial electron transfer from the sorbed Fe(II) to the structural Fe(III) and/or surface-sorption-induced electron-transfer from the sorbed Fe(II) to the clay lattice. Increase in the Fe(II)/Al ratio of the LDH with reaction time further indicated the complex nature of the samples. This research provides evidence for the formation of both Fe(II)-Al(III)-LDH and Fe(II)-Fe(III)/Al(III)-LDH-like phases during reactions of Fe(II) in systems that mimic the natural environments. Better understanding Fe phase formation in complex laboratory studies will improve models of natural redox systems.

  8. Chemical Reactivity Probes for Assessing Abiotic Natural Attenuation by Reducing Iron Minerals.

    PubMed

    Fan, Dimin; Bradley, Miranda J; Hinkle, Adrian W; Johnson, Richard L; Tratnyek, Paul G

    2016-02-16

    Increasing recognition that abiotic natural attenuation (NA) of chlorinated solvents can be important has created demand for improved methods to characterize the redox properties of the aquifer materials that are responsible for abiotic NA. This study explores one promising approach: using chemical reactivity probes (CRPs) to characterize the thermodynamic and kinetic aspects of contaminant reduction by reducing iron minerals. Assays of thermodynamic CRPs were developed to determine the reduction potentials (ECRP) of suspended minerals by spectrophotometric determination of equilibrium CRP speciation and calculations using the Nernst equation. ECRP varied as expected with mineral type, mineral loading, and Fe(II) concentration. Comparison of ECRP with reduction potentials measured potentiometrically using a Pt electrode (EPt) showed that ECRP was 100-150 mV more negative than EPt. When EPt was measured with small additions of CRPs, the systematic difference between EPt and ECRP was eliminated, suggesting that these CRPs are effective mediators of electron transfer between mineral and electrode surfaces. Model contaminants (4-chloronitrobenzene, 2-chloroacetophenone, and carbon tetrachloride) were used as kinetic CRPs. The reduction rate constants of kinetic CRPs correlated well with the ECRP for mineral suspensions. Using the rate constants compiled from literature for contaminants and relative mineral reduction potentials based on ECRP measurements, qualitatively consistent trends were obtained, suggesting that CRP-based assays may be useful for estimating abiotic NA rates of contaminants in groundwater.

  9. Abiotic Methane Synthesis: Caveats and New Results

    NASA Astrophysics Data System (ADS)

    Zou, R.; Sharma, A.

    2005-12-01

    The role of mineral interaction with geochemical fluids under hydrothermal conditions has invoked models of geochemical synthesis of organic molecules at deep crustal conditions. Since Thomas Gold's (1992) hypothesis of the possibility of an abiotic organic synthesis, there have been several reports of hydrocarbon formation under high pressure and temperature conditions. Several previous experimental studies have recognized that small amounts of methane (and other light HC compounds) can be synthesized via catalysis by transition metals: Fe, Ni (Horita and Berndt, 1999 Science) and Cr (Foustavous and Seyfried, 2004 Science). In light of these pioneering experiments, an investigation of the feasibility of abiotic methane synthesis at higher pressure conditions in deep geological setting and the possible role of catalysis warrants a closer look. We conducted three sets of experiments in hydrothermal diamond anvil cell using FeO nanopowder, CaCO 3 and water at 300° - 600° C and 0.5 - 5 GPa : (a) with stainless steel gasket, (b) gold-lined gasket, and (c) gold-lined gasket with added Fe and Ni nanopowder. The reactions were monitored in-situ using micro-Raman spectroscopy with 532nm and 632nm lasers. The solids phases were characterized in-situ using synchrotron X-ray diffraction at CHESS-Cornell and quenched products with an electron microprobe. Interestingly, a variable amount of hydrocarbon was observed only in runs with stainless steel gasket and with Fe, Ni nanoparticles. Experiments with gold-lined reactors did not show any hydrocarbon formation. Added high resolution microscopy of the products and their textural relationship within the diamond cell with Raman spectroscopy data show that the hydrocarbon (methane and other light fractions) synthesis is a direct result of transition metal catalysis, rather than wustite - calcium carbonate reaction as recently reported by Scott et al (2004, PNAS). The author will further present new results highlighting abiotic

  10. Syntrophic Effects in a Subsurface Clostridial Consortium on Fe(III)-(Oxyhydr)oxide Reduction and Secondary Mineralization

    SciTech Connect

    Shah, Madhavi; Lin, Chu-Ching; Kukkadapu, Ravi K.; Engelhard, Mark H.; Zhao, Xiuhong; Wang, Yangping; Barkay, Tamar; Yee, Nathan

    2013-07-09

    In this study, we cultivated from subsurface sediments an anaerobic Clostridia 25 consortium that was composed of a fermentative Fe-reducer Clostridium species (designated as 26 strain FGH) and a novel sulfate-reducing bacterium belonging to the Clostridia family 27 Vellionellaceae (designated as strain RU4). In pure culture, Clostridium sp. strain FGH mediated 28 the reductive dissolution/transformation of iron oxides during growth on peptone. When 29 Clostridium sp. FGH was grown with strain RU4 on peptone, the rates of iron oxide reduction 30 were significantly higher. Iron reduction by the consortium was mediated by multiple 31 mechanisms, including biotic reduction by Clostridium sp. FGH and biotic/abiotic reactions 32 involving biogenic sulfide by strain RU4. The Clostridium sp. FGH produced hydrogen during 33 fermentation, and the presence of hydrogen inhibited growth and iron reduction activity. The 34 sulfate-reducing partner strain RU4 was stimulated by the presence of H2 gas and generated 35 reactive sulfide which promoted the chemical reduction of the iron oxides. Characterization of 36 Fe(II) mineral products showed the formation of magnetite during ferrihydrite reduction, and 37 the precipitation of iron sulfides during goethite and hematite reduction. The results suggest an 38 important pathway for iron reduction and secondary mineralization by fermentative sulfate-39 reducing microbial consortia is through syntrophy-driven biotic/abiotic reactions with biogenic 40 sulfide.

  11. Versatility of biological non-heme Fe(II) centers in oxygen activation reactions

    PubMed Central

    Kovaleva, Elena G; Lipscomb, John D

    2009-01-01

    Oxidase and oxygenase enzymes allow the use of relatively unreactive O2 in biochemical reactions. Many of the mechanistic strategies employed in nature for this key reaction are represented within the 2-His-1-carboxylate facial triad family of non-heme Fe(II) containing enzymes. The open face of the metal coordination sphere opposite the three endogenous ligands participates directly in the reaction chemistry. Here, data from several studies are presented showing that reductive O2 activation within this family is initiated by substrate (and in some cases co-substrate or cofactor) binding, which then allows coordination of O2 to the metal. From this starting point, both the O2 activation process and the reactions with substrates diverge broadly. The reactive species formed in these reactions have been proposed to encompass four oxidation states of iron and all forms of reduced O2 as well as several of the reactive oxygen species that derive from O–O bond cleavage. PMID:18277980

  12. Formation of single domain magnetite by green rust oxidation promoted by microbial anaerobic nitrate-dependent iron oxidation

    NASA Astrophysics Data System (ADS)

    Miot, Jennyfer; Li, Jinhua; Benzerara, Karim; Sougrati, Moulay Tahar; Ona-Nguema, Georges; Bernard, Sylvain; Jumas, Jean-Claude; Guyot, François

    2014-08-01

    Biomineralization of magnetite is a central geomicrobiological process that might have played a primordial role over Earth’s history, possibly leaving traces of life in the geological record or controlling trace metal(loid)s and organic pollutants mobility in modern environments. Magnetite biomineralization has been attributed to two main microbial pathways to date (namely magnetotactic bacteria and dissimilatory iron-reducing bacteria). Here, we uncover a new route of magnetite biomineralization involving the anaerobic nitrate-reducing iron(II) oxidizing bacterium Acidovorax sp. strain BoFeN1. Using transmission electron microscopy, scanning transmission X-ray microscopy, transmission Mössbauer spectroscopy and rock magnetic analyses, this strain is shown to promote the transformation of hydroxychloride green rust in equilibrium with dissolved Fe(II) to (1) periplasmic lepidocrocite (γ-FeOOH) and (2) extracellular magnetite, thus leading to strong redox heterogeneities at the nanometer scale. On the one hand, lepidocrocite was associated with protein moieties and exhibited an anisotropic texture, with the elongated axis parallel to the cell wall. On the other hand, magnetite crystals exhibited grain sizes and magnetic properties consistent with stable single domain particles. By comparison, abiotic controls led to a very slow (4 months vs. 2 days in BoFeN1 cultures) and incomplete oxidation of hydroxychloride green rust towards magnetite. As this abiotic magnetite exhibited the same size and magnetic properties (stable single domain particles) as magnetite produced in BoFeN1 cultures, only the co-occurrence of textured Fe(III)-oxides and magnetite, associated with the persistence of organic carbon molecules, might constitute valuable biosignatures to be looked for in the geological record. Our results furthermore contribute to a more complex picture of Fe redox cycling in the environment, providing an additional process of Fe(II)-bearing phase

  13. Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

    USGS Publications Warehouse

    Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

    2003-01-01

    In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

  14. Physical properties of FeII emission in active galactic nuclei

    NASA Astrophysics Data System (ADS)

    Marinello, M. A. O.; Rodríguez-Ardila, A.; Garcia-Rissman, A.

    2014-10-01

    Among the spectral lines emitted by the broad line region (BLR) in active galactic nuclei (AGN) the FeII emission is the most prominent one and therefore constitutes one of the most important contributors to the cooling of that region. In the near infra-red (NIR) the FeII emission is intense but free of blending effects opening a window to a more consistent analysis of that emission. With the aim of studying the FeII in the range 0.8-1.2 μ m in a sample of 21 AGNs we utilize a semi-empirical template obtained from IZw1, which is considered the prototype of FeII active galaxy emitter. That particular template reproduces accurately the FeII in IZw1 and it is now applied, by the first time in other AGNs. In this work we made a analysis of the width and intensity of the FeII lines in order to derive the most probable location of the emitting region and to study the formation mechanisms of that ion, respectively. We compare the width of the individual FeII lines with that of other lines emitted in BLR. Our results show that the FWHM of iron systematically approaches to that of OI and CaII and is considerably smaller than that of Hydrogen, confirming previous assumptions that the gas responsible for the FeII emission is the outer portion of the BLR. We correlate the strength of the NIR and optical iron lines to derive the relative contribution of the different mechanisms that produces that emission. We found that in all cases the Lyα fluorescence plays an important role.

  15. Spectroscopic and magnetic studies of wild-type and mutant forms of the Fe(II)- and 2-oxoglutarate-dependent decarboxylase ALKBH4.

    PubMed

    Bjørnstad, Linn G; Zoppellaro, Giorgio; Tomter, Ane B; Falnes, Pål Ø; Andersson, K Kristoffer

    2011-03-15

    The Fe(II)/2OG (2-oxoglutarate)-dependent dioxygenase superfamily comprises proteins that couple substrate oxidation to decarboxylation of 2OG to succinate. A member of this class of mononuclear non-haem Fe proteins is the Escherichia coli DNA/RNA repair enzyme AlkB. In the present work, we describe the magnetic and optical properties of the yet uncharacterized human ALKBH4 (AlkB homologue). Through EPR and UV-visible spectroscopy studies, we address the Fe-binding environment of the proposed catalytic centre of wild-type ALKBH4 and an Fe(II)-binding mutant. We could observe a novel unusual Fe(III) high-spin EPR-active species in the presence of sulfide with a g(max) of 8.2. The Fe(II) site was probed with NO. An intact histidine-carboxylate site is necessary for productive Fe binding. We also report the presence of a unique cysteine-rich motif conserved in the N-terminus of ALKBH4 orthologues, and investigate its possible Fe-binding ability. Furthermore, we show that recombinant ALKBH4 mediates decarboxylation of 2OG in absence of primary substrate. This activity is dependent on Fe as well as on residues predicted to be involved in Fe(II) co-ordination. The present results demonstrate that ALKBH4 represents an active Fe(II)/2OG-dependent decarboxylase and suggest that the cysteine cluster is involved in processes other than Fe co-ordination.

  16. Review of recent transgenic studies on abiotic stress tolerance and future molecular breeding in potato

    PubMed Central

    Kikuchi, Akira; Huynh, Huu Duc; Endo, Tsukasa; Watanabe, Kazuo

    2015-01-01

    Global warming has become a major issue within the last decade. Traditional breeding programs for potato have focused on increasing productivity and quality and disease resistance, thus, modern cultivars have limited tolerance of abiotic stresses. The introgression of abiotic stress tolerance into modern cultivars is essential work for the future. Recently, many studies have investigated abiotic stress using transgenic techniques. This manuscript focuses on the study of abiotic stress, in particular drought, salinity and low temperature, during this century. Dividing studies into these three stress categories for this review was difficult. Thus, based on the study title and the transgene property, transgenic studies were classified into five categories in this review; oxidative scavengers, transcriptional factors, and above three abiotic categories. The review focuses on studies that investigate confer of stress tolerance and the identification of responsible factors, including wild relatives. From a practical application perspective, further evaluation of transgenic potato with abiotic stress tolerance is required. Although potato plants, including wild species, have a large potential for abiotic stress tolerance, exploration of the factors responsible for conferring this tolerance is still developing. Molecular breeding, including genetic engineering and conventional breeding using DNA markers, is expected to develop in the future. PMID:25931983

  17. Review of recent transgenic studies on abiotic stress tolerance and future molecular breeding in potato.

    PubMed

    Kikuchi, Akira; Huynh, Huu Duc; Endo, Tsukasa; Watanabe, Kazuo

    2015-03-01

    Global warming has become a major issue within the last decade. Traditional breeding programs for potato have focused on increasing productivity and quality and disease resistance, thus, modern cultivars have limited tolerance of abiotic stresses. The introgression of abiotic stress tolerance into modern cultivars is essential work for the future. Recently, many studies have investigated abiotic stress using transgenic techniques. This manuscript focuses on the study of abiotic stress, in particular drought, salinity and low temperature, during this century. Dividing studies into these three stress categories for this review was difficult. Thus, based on the study title and the transgene property, transgenic studies were classified into five categories in this review; oxidative scavengers, transcriptional factors, and above three abiotic categories. The review focuses on studies that investigate confer of stress tolerance and the identification of responsible factors, including wild relatives. From a practical application perspective, further evaluation of transgenic potato with abiotic stress tolerance is required. Although potato plants, including wild species, have a large potential for abiotic stress tolerance, exploration of the factors responsible for conferring this tolerance is still developing. Molecular breeding, including genetic engineering and conventional breeding using DNA markers, is expected to develop in the future.

  18. Polyamines and abiotic stress tolerance in plants

    PubMed Central

    Gill, Sarvajeet Singh

    2010-01-01

    Environmental stresses including climate change, especially global warming, are severely affecting plant growth and productivity worldwide. It has been estimated that two-thirds of the yield potential of major crops are routinely lost due to the unfavorable environmental factors. On the other hand, the world population is estimated to reach about 10 billion by 2050, which will witness serious food shortages. Therefore, crops with enhanced vigour and high tolerance to various environmental factors should be developed to feed the increasing world population. Maintaining crop yields under adverse environmental stresses is probably the major challenge facing modern agriculture where polyamines can play important role. Polyamines (PAs)(putrescine, spermidine and spermine) are group of phytohormone-like aliphatic amine natural compounds with aliphatic nitrogen structure and present in almost all living organisms including plants. Evidences showed that polyamines are involved in many physiological processes, such as cell growth and development and respond to stress tolerance to various environmental factors. In many cases the relationship of plant stress tolerance was noted with the production of conjugated and bound polyamines as well as stimulation of polyamine oxidation. Therefore, genetic manipulation of crop plants with genes encoding enzymes of polyamine biosynthetic pathways may provide better stress tolerance to crop plants. Furthermore, the exogenous application of PAs is also another option for increasing the stress tolerance potential in plants. Here, we have described the synthesis and role of various polyamines in abiotic stress tolerance in plants. PMID:20592804

  19. Improvement of plant abiotic stress tolerance through modulation of the polyamine pathway.

    PubMed

    Shi, Haitao; Chan, Zhulong

    2014-02-01

    Polyamines (mainly putrescine (Put), spermidine (Spd), and spermine (Spm)) have been widely found in a range of physiological processes and in almost all diverse environmental stresses. In various plant species, abiotic stresses modulated the accumulation of polyamines and related gene expression. Studies using loss-of-function mutants and transgenic overexpression plants modulating polyamine metabolic pathways confirmed protective roles of polyamines during plant abiotic stress responses, and indicated the possibility to improve plant tolerance through genetic manipulation of the polyamine pathway. Additionally, putative mechanisms of polyamines involved in plant abiotic stress tolerance were thoroughly discussed and crosstalks among polyamine, abscisic acid, and nitric oxide in plant responses to abiotic stress were emphasized. Special attention was paid to the interaction between polyamine and reactive oxygen species, ion channels, amino acid and carbon metabolism, and other adaptive responses. Further studies are needed to elucidate the polyamine signaling pathway, especially polyamine-regulated downstream targets and the connections between polyamines and other stress responsive molecules.

  20. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    NASA Astrophysics Data System (ADS)

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-12-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets.Reference:Narita N. et al.,Scientific Reports 5, Article number: 13977 (2015)http://www.nature.com/articles/srep13977

  1. Titania may produce abiotic oxygen atmospheres on habitable exoplanets.

    PubMed

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-09-10

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets.

  2. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    PubMed Central

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-01-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets. PMID:26354078

  3. Physiology of phototrophic iron(II)-oxidizing bacteria: implications for modern and ancient environments.

    PubMed

    Hegler, Florian; Posth, Nicole R; Jiang, Jie; Kappler, Andreas

    2008-11-01

    Phototrophic iron(II) [Fe(II)]-oxidizing bacteria are present in modern environments and evidence suggests that this metabolism was present already on early earth. We determined Fe(II) oxidation rates depending on pH, temperature, light intensity, and Fe(II) concentration for three phylogenetically different phototrophic Fe(II)-oxidizing strains (purple nonsulfur bacterium Rhodobacter ferrooxidans sp. strain SW2, purple sulfur bacterium Thiodictyon sp. strain F4, and green sulfur bacterium Chlorobium ferrooxidans strain KoFox). While we found the overall highest Fe(II) oxidation rates with strain F4 (4.5 mmol L(-1) day(-1), 800 lux, 20 degrees C), the lowest light saturation values [at which maximum Fe(II) oxidation occurred] were determined for strain KoFox with light saturation already below 50 lux. The oxidation rate per cell was determined for R. ferrooxidans strain SW2 to be 32 pmol Fe(II) h(-1) per cell. No significant toxic effect of Fe(II) was observed at Fe(II) concentrations of up to 30 mM. All three strains are mesophiles with upper temperature limits of c. 30 degrees C. The main pigments were identified to be spheroidene, spheroidenone, OH-spheroidenone (SW2), rhodopinal (F4), and chlorobactene (KoFox). This study will improve our ecophysiological understanding of iron cycling in modern environments and will help to evaluate whether phototrophic iron oxidizers may have contributed to the formation of Fe(III) on early earth.

  4. Ferrous iron oxidation by molecular oxygen under acidic conditions: The effect of citrate, EDTA and fulvic acid

    NASA Astrophysics Data System (ADS)

    Jones, Adele M.; Griffin, Philippa J.; Waite, T. David

    2015-07-01

    In this study, the rates of Fe(II) oxidation by molecular oxygen in the presence of citrate, ethylenediaminetetraacetic acid (EDTA) and Suwannee River fulvic acid (SRFA) were determined over the pH range 4.0-5.5 and, for all of the ligands investigated, found to be substantially faster than oxidation rates in the absence of any ligand. EDTA was found to be particularly effective in enhancing the rate of Fe(II) oxidation when sufficient EDTA was available to complex all Fe(II) present in solution, with a kinetic model of the process found to adequately describe all results obtained. When Fe(II) was only partially complexed by EDTA, reactions with reactive oxygen species (ROS) and heterogeneous Fe(II) oxidation were found to contribute significantly to the removal rate of iron from solution at different stages of oxidation. This was possible due to the rapid rate at which EDTA enhanced Fe(II) oxidation and formed ROS and Fe(III). The rapid rate of Fe(III) generation facilitated the formation of free ferric ion activities in excess of those required for ferric oxyhydroxide precipitation following Fe(III)-EDTA dissociation. In comparison, the rate of Fe(II) oxidation was slower in the presence of citrate, and therefore the concentrations of free Fe(III) able to form in the initial stages of Fe(II) oxidation were much lower than those formed in the presence of EDTA, despite the resultant Fe(III)-citrate complex being less stable than that of Fe(III)-EDTA. The slower rate of citrate enhanced oxidation also resulted in slower rates of ROS generation, and, as such, oxidation of the remaining inorganic Fe(II) species by ROS was negligible. Overall, this study demonstrates that organic ligands may substantially enhance the rate of Fe(II) oxidation. Even under circumstances where the ligand is not present at sufficient concentrations to complex all of the Fe(II) in solution, ensuing oxidative processes may sustain an enhanced rate of Fe(II) oxidation relative to that of

  5. Effects of waterborne Fe(II) on juvenile turbot Scophthalmus maximus: analysis of respiratory rate, hematology and gill histology

    NASA Astrophysics Data System (ADS)

    Wu, Zhihao; You, Feng; Liu, Hongjun; Liu, Mengxia; Li, Jun; Zhang, Peijun

    2012-03-01

    The concentration of Fe(II) is high in some groundwater supplies used in turbot culture, and the toxicity of waterborne Fe(II) is unknown. We investigated the stress responses of juvenile turbot, Scophthalmus maximus, exposed to Fe(II) of different concentrations (0.01, 0.05, 0.1, 0.5, 1, and 2 mg/L) for 1, 7, 14, and 28 d, under the same ambient conditions of other parameters. Changes in respiratory rate, hematological parameters, and gill structure were determined. The results show that waterborne Fe(II) did not cause severe hematological perturbation to turbot. A low-medium Fe(II) concentration (lower than 0.1 mg/L) could boost the respiratory rate, and caused no or very limited damage to fish. A high Fe(II) concentration (0.1 mg/L or higher), however, caused gill damage, such as vacuoles in branchial lamellae, epithelial necrosis, and hypertrophy of epithelial cells, and even death after extended exposure time. Therefore, excess waterborne Fe(II) and long-term exposure to Fe(II) could be responsible for poor growth and high mortality of turbot in culture. The concentration of waterborne Fe(II) in turbot culture should be kept below 0.1 mg/L.

  6. Photochemical Formation of Fe(II) in the Aqueous Solutions of Fe(III)- Dicarboxylates

    NASA Astrophysics Data System (ADS)

    Okada, K.; Arakaki, T.

    2007-12-01

    Although there have been many studies reporting the photochemical formation of Fe(II) in various aqueous-phase such as rain, cloud waters, seawater and aerosols, the detailed formation mechanisms are not well understood. To better understand the mechanisms of Fe(II) formation, we attempted to determine the molar absorptivity and the quantum yield of Fe(II) photoformation for individual Fe(III)-dicarboxylate species. The concentrations of Fe(II) and total dissolved Fe were measured by a Ferrozine-HPLC method. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of chemical species in the solutions of Fe(III)-dicarboxylate complexes. The molar absorptivity and the product of the quantum yield and the molar absorptivity of Fe(III)- dicarboxylate complex can be analysed by UV-VIS spectrophotometer and photochemical experiments, and these experimental data were combined with the calculated equilibrium Fe(III) speciation to determine individual molar absorptivity and quantum yield of Fe(II) photoformation for a specific Fe(III)-dicarboxylate complex. Preliminary results, using an oxalate whose quantum yield has been previously reported, indicate that this approach gives lower quantum yield values in air saturated solutions than previously reported.

  7. Microbial mediated iron redox cycling in Fe (hydr)oxides for nitrite removal.

    PubMed

    Lu, Yongsheng; Xu, Lu; Shu, Weikang; Zhou, Jizhi; Chen, Xueping; Xu, Yunfeng; Qian, Guangren

    2017-01-01

    Nitrite, at an environmentally relevant concentration, was significantly reduced with iron (hydr)oxides mediated by Shewanella oneidensis MR-1. The average nitrite removal rates of 1.28±0.08 and 0.65±0.02(mgL(-1))h(-1) were achieved with ferrihydrite and magnetite, respectively. The results showed that nitrite removal was able to undergo multiple redox cycles with iron (hydr)oxides mediated by Shewanella oneidensis MR-1. During the bioreduction of the following cycles, biogenic Fe(II) was subsequently chemically oxidized to Fe(III), which is associated with nitrite reduction. There was 11.18±1.26mgL(-1) of NH4(+)-N generated in the process of redox cycling of ferrihydrite. Additionally, results obtained by using X-ray diffraction showed that ferrihydrite and magnetite remained mainly stable in the system. This study indicated that redox cycling of Fe in iron (hydr)oxides was a potential process associated with NO2(-)-N removal from solution, and reduced most nitrite abiotically to gaseous nitrogen species.

  8. Abiotic synthesis of fatty acids

    NASA Technical Reports Server (NTRS)

    Leach, W. W.; Nooner, D. W.; Oro, J.

    1978-01-01

    The formation of fatty acids by Fischer-Tropsch-type synthesis was investigated with ferric oxide, ammonium carbonate, potassium carbonate, powdered Pueblito de Allende carbonaceous chondrite, and filings from the Canyon Diablo meteorite used as catalysts. Products were separated and identified by gas chromatography and mass spectrometry. Iron oxide, Pueblito de Allende chondrite, and Canyon Diablo filings in an oxidized catalyst form yielded no fatty acids. Canyon Diablo filings heated overnight at 500 C while undergoing slow purging by deuterium produced fatty acids only when potassium carbonate was admixed; potassium carbonate alone also produced these compounds. The active catalytic combinations gave relatively high yields of aliphatic and aromatic hydrocarbons; substantial amounts of n-alkenes were almost invariably observed when fatty acids were produced; the latter were in the range C6 to C18, with maximum yield in C9 or 10.

  9. ABIOTIC STRESS RESISTANCE IN YOUNG APPLE TREES IS ENHANCED BY OVEREXPRESSION OF A CYTOSOLIC SUPEROXIDE DISMUTASE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reactive oxygen species (ROS) are induced during both biotic and abiotic stress, either as signaling molecules or as a response to stress injury. ROS are highly destructive to cell components and the injury resulting from these compounds is referred to as oxidative stress. Antioxidant enzymes, suc...

  10. Fe-As sludge stability and effluent quality for a two-stage As-contaminated water treatment with Fe(II) and aeration.

    PubMed

    Zhuang, J Ming; Hobenshield, Evan; Walsh, Tony

    2009-02-01

    A two-stage (I and II) lab-scale treatment system has been studied for arsenic removal from water using Fe(II) and lignosulphonates with aeration. In stage I, using an Fe/As mole ratio of 1.5-2.5 at a pH of around 6.5-7.5, the dissolved arsenic can be reduced with Fe(II) oxidation-precipitation from an initial 72 mg L(-1) to < 2 mg L(-1). The generated sludge is entirely recycled to the second tank of stage II. In the first tank of stage II, the water is further treated with the same amount of Fe(II) as that used in stage I, in the presence of lignosulphonates and aeration. The air-oxidization of Fe(II) to Fe(III) is continued for about 30 minutes at a pH of around 7.0-8.0. The water output from the first tank is transferred to the second tank in which mixing under aeration occurs with the sludge recycled from stage I. Accordingly, the dissolved arsenic in the effluent is reduced to < 0.1 mg L(-1). The results show that this two-stage process can save more than 50% of total chemical costs, and reduce the amount of sludge by more than 50%, in comparison with the conventional Fe(III)/lime-treatment process. According to US EPA regulations, the final Fe-As sludge is classified as non-hazardous materials by the Toxicity Characteristic Leaching Procedure. But, the study shows that the instability of Fe-As sludge could be influenced by some factors, such as higher pH levels, a longer water-leaching time and larger water-leaching volume, leading to the liberation of more dissolvable As species. After being treated with Ligmet stabilizer, the Fe-As sludge showed an improved stability under varying pH conditions and large amounts of water leaching. The treated Fe-As sludge is suitable for landfill disposal.

  11. Reduction of the pesticides oxamyl and methomyl by FeII: effect of pH and inorganic ligands.

    PubMed

    Strathmann, Timothy J; Stone, Alan T

    2002-02-15

    This work examines the effect that pH and selected inorganic ligands have on the kinetics of reactions between FeII and two structurally related oxime carbamate pesticides, oxamyl and methomyl. In anoxic solutions containing FeII, these compounds degrade by parallel elimination and reduction pathways. Rates of FeII-independent carbamate elimination (EIcb mechanism) are proportional to [OH-], increasing 10-fold for each unit increase in pH. In homogeneous solution, rates of carbamate reduction by 0.5 mM FeII are relatively constant at pH <7, but increase dramatically between pH 7 and pH 8.3. At pH >8.3, Fe(OH)2(s) precipitation occurs, and carbamates react with both solution-phase and solid-phase FeII. Carbamate reduction by FeII is not significantly affected by the presence of chloride, bromide, nitrate, perchlorate, and sulfate. In contrast, increased rates of carbamate reduction are observed in solutions containing fluoride, carbonate, and phosphate. Kinetic measurements are interpreted in terms of changing FeII speciation according to the expression kred = [FeII]sigmaikialphai, where k(red) is the pseudo-first-order rate constant for carbamate reduction, [FeII] is the total FeII concentration, and ki and alphai are the second-order rate constant and fractional concentration of each FeII species, respectively. It follows that the overall kinetics of carbamate reduction is a function of the identity and concentration of individual FeII species present in solution as well as the inherent reactivity of each species with carbamates. The magnitude of ki is related to the standard one-electron reduction potential (E(H) degrees) of the corresponding FeIII/FeII redox couple.

  12. Preparation and reactivity of a tetranuclear Fe(II) core in the metallothionein α-domain.

    PubMed

    Sano, Yohei; Onoda, Akira; Sakurai, Rie; Kitagishi, Hiroaki; Hayashi, Takashi

    2011-05-01

    Metallothioneins (MTs) are small cysteine-rich proteins which exhibit high affinities for various metal ions and play roles in storage of essential metals and detoxification of toxic metals. Studies on the redox properties of MTs have been quite limited. Recently, we focused on the α-domain of MT (MTα) as a protein matrix and incorporated a tetranuclear metal cluster as a reductant. UV-visible, CD and MS data indicate the formation of the stable tetranuclear metal-cysteine cluster in the MTα matrix with Fe(II)(4)-MTα and Co(II)(4)-MTα species existing in water. Furthermore, the Fe(II)(4)-MTα species was found to promote the reduction of met-myoglobin and azobenzene derivatives under mild conditions. Particularly, the stoichiometric reduction of methyl red with Fe(II)(4)-MTα (1:1) was found to proceed with a conversion of 98% over a period of 6h at 25°C. This indicates that all of the four Fe(II) cores contribute to the reduction. In this paper, we describe the preparation and reactivity of the tetranuclear iron cluster in the protein matrix.

  13. Potential for microbial oxidation of ferrous iron in basaltic glass.

    PubMed

    Xiong, Mai Yia; Shelobolina, Evgenya S; Roden, Eric E

    2015-05-01

    Basaltic glass (BG) is an amorphous ferrous iron [Fe(II)]-containing material present in basaltic rocks, which are abundant on rocky planets such as Earth and Mars. Previous research has suggested that Fe(II) in BG can serve as an energy source for chemolithotrophic microbial metabolism, which has important ramifications for potential past and present microbial life on Mars. However, to date there has been no direct demonstration of microbially catalyzed oxidation of Fe(II) in BG. In this study, three different culture systems were used to investigate the potential for microbial oxidation of Fe(II) in BG, including (1) the chemolithoautotrophic Fe(II)-oxidizing, nitrate-reducing "Straub culture"; (2) the mixotrophic Fe(II)-oxidizing, nitrate-reducing organism Desulfitobacterium frappieri strain G2; and (3) indigenous microorganisms from a streambed Fe seep in Wisconsin. The BG employed consisted of clay and silt-sized particles of freshly quenched lava from the TEB flow in Kilauea, Hawaii. Soluble Fe(II) or chemically reduced NAu-2 smectite (RS) were employed as positive controls to verify Fe(II) oxidation activity in the culture systems. All three systems demonstrated oxidation of soluble Fe(II) and/or structural Fe(II) in RS, whereas no oxidation of Fe(II) in BG material was observed. The inability of the Straub culture to oxidize Fe(II) in BG was particularly surprising, as this culture can oxidize other insoluble Fe(II)-bearing minerals such as biotite, magnetite, and siderite. Although the reason for the resistance of the BG toward enzymatic oxidation remains unknown, it seems possible that the absence of distinct crystal faces or edge sites in the amorphous glass renders the material resistant to such attack. These findings have implications with regard to the idea that Fe(II)-Si-rich phases in basalt rocks could provide a basis for chemolithotrophic microbial life on Mars, specifically in neutral-pH environments where acid-promoted mineral dissolution and

  14. Ni(II) and Fe(II) complexes based on bis(imino)aryl pincer ligands: synthesis, structural characterization and catalytic activities.

    PubMed

    Zhang, Jingshun; Gao, Wei; Lang, Xiaomei; Wu, Qiaolin; Zhang, Lei; Mu, Ying

    2012-08-28

    Bis(imino)aryl NCN pincer Ni(II) complexes 2,6-(ArN=CH)(2)C(6)H(3)NiBr (1: Ar = 2,6-Me(2)C(6)H(3); 2: Ar = 2,6-Et(2)C(6)H(3); 3: Ar = 2,6-(i)Pr(2)C(6)H(3)) were prepared via the oxidative-addition of Ni(0)(Ph(3)P)(4) with bis(N-aryl)-2-bromoisophthalaldimine. These nickel complexes were characterized by NMR and elemental analyses. Their solid molecular structures were established by X-ray diffraction analyses. The nickel metal centers adopt distorted square planar geometries with the bromine atoms acting as one coordinate ligands. The NCN pincer Fe(II) complexes 2,6-(ArN=CH)(2)C(6)H(3)Fe(μ-Cl)(2)Li(THF)(2) (4: Ar = 2,6-Me(2)C(6)H(3); 5: Ar = 2,6-Et(2)C(6)H(3); 6: Ar = 2,6-(i)Pr(2)C(6)H(3)) were synthesized by lithium salt metathesis reactions of the ligand lithium salts with FeCl(2). X-ray structure analyses of 4 and 5 revealed that the Fe(II) complexes are hetero-dinuclear with the iron atoms in trigonal bipyramidal environments. When activated with MAO, the nickel complexes are active for norbornene vinyl polymerization but are inert for butadiene polymerization. The Fe(II) complexes show moderate activities in butadiene polymerization when activated with alkylaluminium, affording the cis-1,4 enriched polymer.

  15. Biochemical and Spectroscopic Characterization of the Non-Heme Fe(II)- and 2-Oxoglutarate-Dependent Ethylene-Forming Enzyme from Pseudomonas syringae pv. phaseolicola PK2.

    PubMed

    Martinez, Salette; Hausinger, Robert P

    2016-11-01

    The ethylene-forming enzyme (EFE) from Pseudomonas syringae pv. phaseolicola PK2 is a member of the mononuclear non-heme Fe(II)- and 2-oxoglutarate (2OG)-dependent oxygenase superfamily. This enzyme is reported to simultaneously catalyze the conversion of 2OG into ethylene and three CO2 molecules and the Cδ hydroxylation of l-arginine (l-Arg) while oxidatively decarboxylating 2OG to form succinate and carbon dioxide. A new plasmid construct for expression in recombinant Escherichia coli cells allowed for the purification of large amounts of EFE with activity greater than that previously recorded. A variety of assays were used to quantify and confirm the identity of the proposed products, including the first experimental demonstration of l-Δ(1)-pyrroline-5-carboxylate and guanidine derived from 5-hydroxyarginine. Selected l-Arg derivatives could induce ethylene formation without undergoing hydroxylation, demonstrating that ethylene production and l-Arg hydroxylation activities are not linked. Similarly, EFE utilizes the alternative α-keto acid 2-oxoadipate as a cosubstrate (forming glutaric acid) during the hydroxylation of l-Arg, with this reaction unlinked from ethylene formation. Kinetic constants were determined for both ethylene formation and l-Arg hydroxylation reactions. Anaerobic UV-visible difference spectra were used to monitor the binding of Fe(II) and substrates to the enzyme. On the basis of our results and what is generally known about EFE and Fe(II)- and 2OG-dependent oxygenases, an updated model for the reaction mechanism is presented.

  16. Simple flow injection method for simultaneous spectrophotometric determination of Fe(II) and Fe(III).

    PubMed

    Kozak, J; Jodłowska, N; Kozak, M; Kościelniak, P

    2011-09-30

    The method is based on spectrophotometric determination of Fe(II) and Fe(III) at a single wavelength (530 nm) with the use of a dedicated reversed-flow injection system. In the system, EDTA solution is injected into a carrier stream (HNO(3)) and then merged with a sample stream containing a mixture of sulfosalicylic acid and 1,10-phenanthroline as indicators. In an acid environment (pH≅3) the indicators form complexes with both Fe(III) and Fe(II), but EDTA replaces sulfosalicylic acid, forming a more stable colourless complex with Fe(III), whereas Fe(II) remains in a complex with 1,10-phenenthroline. As a result, the area and minimum of the characteristic peak can be exploited as measures corresponding to the Fe(III) and Fe(II) concentrations, respectively. The analytes were not found to affect each other's signals, hence two analytical curves were constructed with the use of a set of standard solutions, each containing Fe(II) and Fe(III). Both analytes were determined in synthetic samples within the concentration ranges of 0.05-4.0 and 0.09-6.0 mg L(-1), respectively, with precision less than 1.5 and 2.6% (RSD) and with accuracy less than 4.3 and 5.6% (RE). The method was applied to determination of the analytes in water samples collected from artesian wells and the results of the determination were consistent with those obtained using the ICP-OES technique.

  17. The effects of iron(II) on the kinetics of arsenic oxidation and sorption on manganese oxides.

    PubMed

    Wu, Yun; Li, Wei; Sparks, Donald L

    2015-11-01

    In this study, As(III) oxidation kinetics by a poorly-crystalline phyllomanganate (δ-MnO2) in the presence and absence of dissolved Fe(II) was investigated using stirred-flow and batch experiments. Chemically synthetic δ-MnO2 was reacted with four influent solutions, containing the same As(III) concentration but different Fe(II) concentrations, at pH 6. The results show an initial rapid As(III) oxidation by δ-MnO2, which is followed by an appreciably slow reaction after 8h. In the presence of Fe(II), As(III) oxidation is inhibited due to the competitive oxidation of Fe(II) as well as the formation of Fe(III)-(hydr)oxides on the δ-MnO2 surface. However, the sorption of As(III), As(V) and Mn(II) are increased, for the newly formed Fe(III)-(hydr)oxides provide additional sorption sites. This study suggests that the competitive oxidation of Fe(II) and consequently the precipitation of Fe(III) compounds on the δ-MnO2 surface play an important role in As(III) oxidation and As sequestration. Understanding these processes would be helpful in developing in situ strategies for remediation of As-contaminated waters and soils.

  18. Genome-enabled studies of anaerobic, nitrate-dependent iron oxidation in the chemolithoautotrophic bacterium Thiobacillus denitrificans

    PubMed Central

    Beller, Harry R.; Zhou, Peng; Legler, Tina C.; Chakicherla, Anu; Kane, Staci; Letain, Tracy E.; A. O’Day, Peggy

    2013-01-01

    Thiobacillus denitrificans is a chemolithoautotrophic bacterium capable of anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, both of which can strongly influence the long-term efficacy of in situ reductive immobilization of uranium in contaminated aquifers. We previously identified two c-type cytochromes involved in nitrate-dependent U(IV) oxidation in T. denitrificans and hypothesized that c-type cytochromes would also catalyze Fe(II) oxidation, as they have been found to play this role in anaerobic phototrophic Fe(II)-oxidizing bacteria. Here we report on efforts to identify genes associated with nitrate-dependent Fe(II) oxidation, namely (a) whole-genome transcriptional studies [using FeCO3, Fe2+, and U(IV) oxides as electron donors under denitrifying conditions], (b) Fe(II) oxidation assays performed with knockout mutants targeting primarily highly expressed or upregulated c-type cytochromes, and (c) random transposon-mutagenesis studies with screening for Fe(II) oxidation. Assays of mutants for 26 target genes, most of which were c-type cytochromes, indicated that none of the mutants tested were significantly defective in nitrate-dependent Fe(II) oxidation. The non-defective mutants included the c1-cytochrome subunit of the cytochrome bc1 complex (complex III), which has relevance to a previously proposed role for this complex in nitrate-dependent Fe(II) oxidation and to current concepts of reverse electron transfer. A transposon mutant with a disrupted gene associated with NADH:ubiquinone oxidoreductase (complex I) was ~35% defective relative to the wild-type strain; this strain was similarly defective in nitrate reduction with thiosulfate as the electron donor. Overall, our results indicate that nitrate-dependent Fe(II) oxidation in T. denitrificans is not catalyzed by the same c-type cytochromes involved in U(IV) oxidation, nor have other c-type cytochromes yet been implicated in the process. PMID:24065960

  19. Insight into the evolution of the iron oxidation pathways.

    PubMed

    Ilbert, Marianne; Bonnefoy, Violaine

    2013-02-01

    Iron is a ubiquitous element in the universe. Ferrous iron (Fe(II)) was abundant in the primordial ocean until the oxygenation of the Earth's atmosphere led to its widespread oxidation and precipitation. This change of iron bioavailability likely put selective pressure on the evolution of life. This element is essential to most extant life forms and is an important cofactor in many redox-active proteins involved in a number of vital pathways. In addition, iron plays a central role in many environments as an energy source for some microorganisms. This review is focused on Fe(II) oxidation. The fact that the ability to oxidize Fe(II) is widely distributed in Bacteria and Archaea and in a number of quite different biotopes suggests that the dissimilatory Fe(II) oxidation is an ancient energy metabolism. Based on what is known today about Fe(II) oxidation pathways, we propose that they arose independently more than once in evolution and evolved convergently. The iron paleochemistry, the phylogeny, the physiology of the iron oxidizers, and the nature of the cofactors of the redox proteins involved in these pathways suggest a possible scenario for the timescale in which each type of Fe(II) oxidation pathways evolved. The nitrate dependent anoxic iron oxidizers are likely the most ancient iron oxidizers. We suggest that the phototrophic anoxic iron oxidizers arose in surface waters after the Archaea/Bacteria-split but before the Great Oxidation Event. The neutrophilic oxic iron oxidizers possibly appeared in microaerobic marine environments prior to the Great Oxidation Event while the acidophilic ones emerged likely after the advent of atmospheric O(2). This article is part of a Special Issue entitled: The evolutionary aspects of bioenergetic systems.

  20. IRON-PEROXYMONOSULFATE: A NOVEL SULFATE RADICAL BASED ADVANCED OXIDATION TECHNOLOGY FOR DEGRADATION OF PCBS

    EPA Science Inventory

    This study investigates the degradation of recalcitrant polychlorinated biphenyl (PCBs) using sulfate radical-based advanced oxidation technologies. Sulfate radicals are generated through coupling of peroxymonosulfate (PMS) with iron (Fe(II), Fe(III)). Sulfate radicals have very ...

  1. Sedimentary reservoir oxidation during geologic CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Lammers, Laura N.; Brown, Gordon E.; Bird, Dennis K.; Thomas, Randal B.; Johnson, Natalie C.; Rosenbauer, Robert J.; Maher, Katharine

    2015-04-01

    Injection of carbon dioxide into subsurface geologic reservoirs during geologic carbon sequestration (GCS) introduces an oxidizing supercritical CO2 phase into a subsurface geologic environment that is typically reducing. The resulting redox disequilibrium provides the chemical potential for the reduction of CO2 to lower free energy organic species. However, redox reactions involving carbon typically require the presence of a catalyst. Iron oxide minerals, including magnetite, are known to catalyze oxidation and reduction reactions of C-bearing species. If the redox conditions in the reservoir are modified by redox transformations involving CO2, such changes could also affect mineral stability, leading to dissolution and precipitation reactions and alteration of the long-term fate of CO2 in GCS reservoirs. We present experimental evidence that reservoirs with reducing redox conditions are favorable environments for the relatively rapid abiotic reduction of CO2 to organic molecules. In these experiments, an aqueous suspension of magnetite nanoparticles was reacted with supercritical CO2 under pressure and temperature conditions relevant to GCS in sedimentary reservoirs (95-210 °C and ∼100 bars of CO2). Hydrogen production was observed in several experiments, likely caused by Fe(II) oxidation either at the surface of magnetite or in the aqueous phase. Heating of the Fe(II)-rich system resulted in elevated PH2 and conditions favorable for the reduction of CO2 to acetic acid. Implications of these results for the long-term fate of CO2 in field-scale systems were explored using reaction path modeling of CO2 injection into reservoirs containing Fe(II)-bearing primary silicate minerals, with kinetic parameters for CO2 reduction obtained experimentally. The results of these calculations suggest that the reaction of CO2 with reservoir constituents will occur in two primary stages (1) equilibration of CO2 with organic acids resulting in mineral-fluid disequilibrium, and

  2. RBM25 Mediates Abiotic Responses in Plants

    PubMed Central

    Cheng, Chunhong; Wang, Zhijuan; Yuan, Bingjian; Li, Xia

    2017-01-01

    Alternative splicing (AS) of pre-mRNAs is one of the most important post-transcriptional regulations that enable a single gene to code for multiple proteins resulting in the biodiversity of proteins in eukaryotes. Recently, we have shown that an Arabidopsis thaliana RNA recognition motif-containing protein RBM25 is a novel splicing factor to modulate plant response to ABA during seed germination and post-germination through regulating HAB1 pre-mRNA AS. Here, we show that RBM25 is preferentially expressed in stomata and vascular tissues in Arabidopsis and is induced by ABA and abiotic stresses. Loss-of-function mutant is highly tolerant to drought and sensitive to salt stress. Bioinformatic analysis and expression assays reveal that Arabidopsis RBM25 is induced by multiple abiotic stresses, suggesting a crucial role of RBM25 in Arabidopsis responses to adverse environmental conditions. Furthermore, we provide a comprehensive characterization of the homologous genes of Arabidopsis RBM25 based on the latest plant genome sequences and public microarray databases. Fourteen homologous genes are identified in different plant species which show similar structure in gene and protein. Notably, the promoter analysis reveals that RBM25 homologs are likely controlled by the regulators involved in multiple plant growth and abiotic stresses, such as drought and unfavorable temperature. The comparative analysis of general and unique cis regulatory elements of the RBM25 homologs highlights the conserved and unique molecular processes that modulate plant response to abiotic stresses through RBM25-mediated alternative splicing. PMID:28344583

  3. RBM25 Mediates Abiotic Responses in Plants.

    PubMed

    Cheng, Chunhong; Wang, Zhijuan; Yuan, Bingjian; Li, Xia

    2017-01-01

    Alternative splicing (AS) of pre-mRNAs is one of the most important post-transcriptional regulations that enable a single gene to code for multiple proteins resulting in the biodiversity of proteins in eukaryotes. Recently, we have shown that an Arabidopsis thaliana RNA recognition motif-containing protein RBM25 is a novel splicing factor to modulate plant response to ABA during seed germination and post-germination through regulating HAB1 pre-mRNA AS. Here, we show that RBM25 is preferentially expressed in stomata and vascular tissues in Arabidopsis and is induced by ABA and abiotic stresses. Loss-of-function mutant is highly tolerant to drought and sensitive to salt stress. Bioinformatic analysis and expression assays reveal that Arabidopsis RBM25 is induced by multiple abiotic stresses, suggesting a crucial role of RBM25 in Arabidopsis responses to adverse environmental conditions. Furthermore, we provide a comprehensive characterization of the homologous genes of Arabidopsis RBM25 based on the latest plant genome sequences and public microarray databases. Fourteen homologous genes are identified in different plant species which show similar structure in gene and protein. Notably, the promoter analysis reveals that RBM25 homologs are likely controlled by the regulators involved in multiple plant growth and abiotic stresses, such as drought and unfavorable temperature. The comparative analysis of general and unique cis regulatory elements of the RBM25 homologs highlights the conserved and unique molecular processes that modulate plant response to abiotic stresses through RBM25-mediated alternative splicing.

  4. Coupled Abiotic-Biotic Degradation of Bisphenol A

    NASA Astrophysics Data System (ADS)

    Im, J.; Prevatte, C.; Campagna, S. R.; Loeffler, F.

    2014-12-01

    Bisphenol A (BPA) is a ubiquitous environmental contaminant with weak estrogenic activity. BPA is readily biodegradable with oxygen available, but is recalcitrant to microbial degradation under anoxic conditions. However, BPA is susceptible to abiotic transformation under anoxic conditions. To better understand the fate of BPA in anoxic environments, the kinetics of BPA transformation by manganese oxide (d-MnO2) were investigated. BPA was rapidly transformed by MnO2 with a pseudo-first-order rate constant of 0.413 min-1. NMR and LC-MS analyses identified 4-hydroxycumyl alcohol (HCA) as a major intermediate. Up to 64% of the initial amount of BPA was recovered as HCA within 5 min, but the conversion efficiency decreased with time, suggesting that HCA was further degraded by MnO2. Further experiments confirmed that HCA was also susceptible to transformation by MnO2, albeit at 5-fold lower rates than BPA transformation. Mass balance approaches suggested that HCA was the major BPA transformation intermediate, but other compounds may also be formed. The abiotic transformation of BPA by MnO2 was affected by pH, and 10-fold higher transformation rates were observed at pH 4.5 than at pH 10. Compared to BPA, HCA has a lower octanol-water partitioning coefficient (Log Kow) of 0.76 vs 2.76 for BPA and a higher aqueous solubility of 2.65 g L-1 vs 0.31 g L-1 for BPA, suggesting higher mobility of HCA in the environment. Microcosms established with freshwater sediment materials collected from four geographically distinct locations and amended with HCA demonstrated rapid HCA biodegradation under oxic, but not under anoxic conditions. These findings suggest that BPA is not inert under anoxic conditions and abiotic reactions with MnO2 generate HCA, which has increased mobility and is susceptible to aerobic degradation. Therefore, coupled abiotic-biotic processes can affect the fate and longevity of BPA in terrestrial environments.

  5. Computational Molecular Simulation of the Oxidative Adsorption of Ferrous Iron at the Hematite (001)-Water Interface

    SciTech Connect

    Kerisit, Sebastien N.; Zarzycki, Piotr P.; Rosso, Kevin M.

    2015-04-30

    The interaction of Fe(II) with ferric oxide/oxyhydroxide phases is central to the biogeochemical redox chemistry of iron. Molecular simulation techniques were employed to determine the mechanisms and quantify the rates of Fe(II) oxidative adsorption at the hematite (001)-water interface. Molecular dynamics potential of mean force calculations of Fe(II) adsorbing on the hematite surface revealed the presence of three free energy minima corresponding to Fe(II) adsorbed in an outersphere complex, a monodentate innersphere complex, and a tridentate innersphere complex. The free energy barrier for adsorption from the outersphere position to the monodentate innersphere site was calculated to be similar to the activation enthalpy for water exchange around aqueous Fe(II). Adsorption at both innersphere sites was predicted to be unfavorable unless accompanied by release of protons. Molecular dynamics umbrella sampling simulations and ab initio cluster calculations were performed to determine the rates of electron transfer from Fe(II) adsorbed as an innersphere and outersphere complex. The electron transfer rates were calculated to range from 10^-4 to 10^2 s-1, depending on the adsorption site and the potential parameter set, and were generally slower than those obtained in the bulk hematite lattice. The most reliable estimate of the rate of electron transfer from Fe(II) adsorbed as an outersphere complex to lattice Fe(III) was commensurate with the rate of adsorption as an innersphere complex suggesting that adsorption does not necessarily need to precede oxidation.

  6. Method of removing oxidized contaminants from water

    DOEpatents

    Amonette, James E.; Fruchter, Jonathan S.; Gorby, Yuri A.; Cole, Charles R.; Cantrell, Kirk J.; Kaplan, Daniel I.

    1998-01-01

    The present invention is a method for removing oxidized contaminant(s) from water. More specifically, the invention has the steps of contacting water containing the oxidized contaminant(s) with a layered aluminosilicate having Fe(II). The aluminosilicate may contain naturally occurring Fe(II), or the Fe(II) may be produced by reducing Fe(III) that is initially present. Reduction may be either by exposure to a chemical or biological reductant. Contacting the water containing oxidized contaminant(s) may be by (1) injection of Fe(II)-containing layered aluminosilicate, via a well, into a saturated zone where it is likely to intercept the contaminated water; (2) injection of contaminated water into a vessel containing the Fe(II)-bearing layered aluminosilicate; and (3) first reducing Fe(III) in the layered aluminosilicate to Fe(II) by injection of a biological or chemical reductant, into an aquifer or vessel having sufficient Fe(III)-bearing aluminosilicate to produce the necessary Fe(II).

  7. Method of removing oxidized contaminants from water

    DOEpatents

    Amonette, J.E.; Fruchter, J.S.; Gorby, Y.A.; Cole, C.R.; Cantrell, K.J.; Kaplan, D.I.

    1998-07-21

    The present invention is a method for removing oxidized contaminant(s) from water. More specifically, the invention has the steps of contacting water containing the oxidized contaminant(s) with a layered aluminosilicate having Fe(II). The aluminosilicate may contain naturally occurring Fe(II), or the Fe(II) may be produced by reducing Fe(III) that is initially present. Reduction may be either by exposure to a chemical or biological reductant. Contacting the water containing oxidized contaminant(s) may be by (1) injection of Fe(II)-containing layered aluminosilicate, via a well, into a saturated zone where it is likely to intercept the contaminated water; (2) injection of contaminated water into a vessel containing the Fe(II)-bearing layered aluminosilicate; and (3) first reducing Fe(III) in the layered aluminosilicate to Fe(II) by injection of a biological or chemical reductant, into an aquifer or vessel having sufficient Fe(III)-bearing aluminosilicate to produce the necessary Fe(II). 8 figs.

  8. Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing soil minerals. 1. Pyrite and magnetite.

    PubMed

    Lee, Woojin; Batchelor, Bill

    2002-12-01

    Abiotic reductive dechlorination of chlorinated ethylenes (tetrachloroethylene (PCE), trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), and vinyl chloride (VC)) by pyrite and magnetite was characterized in a batch reactor system. Dechlorination kinetics was adequately described by a modified Langmuir-Hinshelwood model that includes the effect of a decreasing reductive capacity of soil mineral. The kinetic rate constant for the reductive dechlorination of target organics at reactive sites of soil minerals was in the range of 0.185 (+/- 0.023) to 1.71 (+/- 0.06) day(-1). The calculated specific reductive capacity of soil minerals for target organics was in the range of 0.33 (+/- 0.02) to 2.26 (+/- 0.06) microM/g and sorption coefficient was in the range of 0.181 (+/- 0.006) to 0.7 (+/- 0.022) mM(-1). Surface area-normalized pseudo-first-order initial rate constants for target organics by pyrite were found to be 23.5 to 40.3 times greater than those by magnetite. Target organics were mainly transformed to acetylene and small amount of chlorinated intermediates, which suggests that beta-elimination was the main dechlorination pathway. The dechlorination of VC followed a hydrogenolysis pathway to produce ethylene and ethane. The addition of Fe(II) increased the dechlorination rate of cis-DCE and VC in magnetite suspension by nearly a factor of 10. The results obtained in this research provide basic knowledge to better predict the fate of chlorinated ethylenes and to understand the potential of abiotic processes in natural attenuation.

  9. Iron-induced oxidation of (all-E)-β-carotene under model gastric conditions: kinetics, products, and mechanism.

    PubMed

    Sy, Charlotte; Dangles, Olivier; Borel, Patrick; Caris-Veyrat, Catherine

    2013-10-01

    The stability of (all-E)-β-carotene toward dietary iron was studied in a mildly acidic (pH 4) micellar solution as a simple model of the postprandial gastric conditions. The oxidation was initiated by free iron (Fe(II), Fe(III)) or by heme iron (metmyoglobin, MbFe(III)). Fe(II) and metmyoglobin were much more efficient than Fe(III) at initiating β-carotene oxidation. Whatever the initiator, hydrogen peroxide did not accumulate. Moreover, β-carotene markedly inhibited the conversion of Fe(II) into Fe(III). β-Carotene oxidation induced by Fe(II) or MbFe(III) was maximal with 5-10 eq Fe(II) or 0.05-0.1 eq MbFe(III) and was inhibited at higher iron concentrations, especially with Fe(II). UPLC/DAD/MS and GC/MS analyses revealed a complex distribution of β-carotene-derived products including Z-isomers, epoxides, and cleavage products of various chain lengths. Finally, the mechanism of iron-induced β-carotene oxidation is discussed. Altogether, our results suggest that dietary iron, especially free (loosely bound) Fe(II) and heme iron, may efficiently induce β-carotene autoxidation within the upper digestive tract, thereby limiting its supply to tissues (bioavailability) and consequently its biological activity.

  10. In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

    USGS Publications Warehouse

    Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

    2001-01-01

    The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

  11. Designed intramolecular blocking of the spin crossover of an Fe(ii) complex.

    PubMed

    Bartual-Murgui, C; Vela, S; Roubeau, O; Aromí, G

    2016-09-13

    A ligand derived from 1,3bpp (2-(pyrazol-1-yl)-6-(pyrazol-3-yl)-pyridine) has been prepared to prove that the spin crossover (SCO) of an Fe(ii) complex can be blocked by means of intramolecular interactions not related to the crystal field. Calculations show that the blocking is caused by the energy penalty incurred by the rotation of a phenyl ring, needed to avoid steric hindrance upon SCO.

  12. Bio-Inorganic Studies on the Fe(II) Sparfloxacin Complex

    PubMed Central

    Jain, Swati; Jain, N. K.; Pitre, K. S.

    2002-01-01

    The qualitative and quantitative analysis of an antibiotic drug, 5-amino-1 cyclopropyl-7 (cis-3, 5 dimethyl-1-piperazyl)-6,8- dihydro-1, 4 dihydro-4-oxo-3-quinoline carboxylic acid (Sparfloxacin, SFX) and its pharmaceutical formulation i.e.sparx-100 tablet, has been done using polarographic and amperometric methods. Complexation behavior of SFX with Fe(II), both in solid and liquid phases has been studied by elemental analysis, IR.-spectra and polarographic and amperometric methods. SFX produces a single cathodic reduction wave in 0.1 M ammonium tartrate (supporting electrolyte) at pH 6.0 ±0.1. The wave is diffusion controlled and wave height is proportional to the concentration of SFX. The complex is also reversibly reduced at the electrode surface with diffusion-controlled kinetics. The stoichiometry of the Fe(II)- SFX complex is 1:1. Antibacterial studies on the drug and its metal complex have been performed against different bacteria. The observed results revealed the complex to be more potent in its antibacterial activity as compared to the parent drug. On the basis of observed results it could be concluded that the prepared Fe(II)- SFX complex may be recommended to the therapeutic experts for its possible use as a more potent antibiotic drug. PMID:18475420

  13. Effect of aqueous Fe(II) on Sb(V) sorption on soil and goethite.

    PubMed

    Fan, Jian-Xin; Wang, Yu-Jun; Fan, Ting-Ting; Dang, Fei; Zhou, Dong-Mei

    2016-03-01

    The effects of Fe(II) on the sorption and precipitation of Sb(V) on soils and goethite were investigated using batch experiments and X-ray photoelectron spectroscopy (XPS) in this study. The sorption capacity of Sb(V) were much higher in anoxic soil than oxic soil. Typically, dissolved Fe(II) concentration in anoxic soils decreased significantly with increasing Sb(V), which may be suggestive of Fe-Sb precipitation. The elevated concentrations of Fe(II) (1 mM) enhanced the sorption capacity of Sb(V) on goethite significantly. However, synchrotron radiation X-ray diffraction showed no new characteristic peak, indicating that this Fe-Sb precipitate might be poor crystallinity or amorphous. Moreover, Sb(III) was detected in anoxic soil, and the reduction of Sb(V) to Sb (III) improved the sorption capacity of Sb in anoxic soil because of the low solubility and migration of Sb(III). Nevertheless, Fe-Sb co-precipitation and Sb(V) reduction to Sb(III) might contribute simultaneously to the increased sorption capacity of Sb(V) on anoxic soils. This research could improve our current understanding of soil Sb chemistry in paddy and wetland soils.

  14. Mimicking the Regulation Step of Fe-Monooxygenases: Allosteric Modulation of Fe(IV) -Oxo Formation by Guest Binding in a Dinuclear Zn(II) -Fe(II) Calix[6]arene-Based Funnel Complex.

    PubMed

    Ségaud, Nathalie; De Thomasson, Constance; Daverat, Caroline; Sénéchal-David, Katell; Dos Santos, Amandine; Steinmetz, Vincent; Maître, Philippe; Rebilly, Jean-Noël; Banse, Frédéric; Reinaud, Olivia

    2017-02-24

    A heteroditopic ligand associated with a calix[6]arene scaffold bearing a tris(imidazole) coordinating site at its small rim and an amine/pyridine ligand at its large rim has been prepared, and its regioselective coordination to Zn(II) at the small rim and Fe(II) in the amine/pyridine ligand has been achieved. The heterodinuclear complex obtained displays an overall cone conformation capped by the tris(imidazole)Zn(II) moiety and bears a non-heme Fe(II) complex at its base. Each of the metal centers exhibits one labile position, allowing the coordination inside the cavity of a guest alkylamine at Zn(II) and the generation of reaction intermediates (Fe(III) (OOH) and Fe(IV) O) at the large rim. A dependence between the chain length of the encapsulated alkylamine and the distribution of Fe(III) (OOH) intermediates and Fe(III) (OMe) is observed. In addition, it is shown that the generation of the Fe(IV) O intermediate is enhanced by addition of the alkylamine guest. Hence, this supramolecular system gathers the three levels of reactivity control encountered in oxidoreductases: i) control of the Fe(II) redox properties through its first coordination sphere, allowing us to generate high valent reactive species; ii) control of guest binding through a hydrophobic funnel that drives its alkyl chain next to the reactive iron complex, thus mimicking the binding pocket of natural systems; iii) guest-modulated reactivity of the Fe(II) center towards oxidants.

  15. Electrochemical evidences for promoted interfacial reactions: the role of Fe(II) adsorbed onto gamma-Al2O3 and TiO2 in reductive transformation of 2-nitrophenol.

    PubMed

    Li, Fang-Bai; Tao, Liang; Feng, Chun-hua; Li, Xiang-Zhong; Sun, Ke-Wen

    2009-05-15

    This study was aimed at elucidating the role of adsorbed Fe(II) on minerals in the reductive transformation of 2-nitrophenol (2-NP) by using electrochemical methods. The studies of Fe(ll) adsorption and 2-NP reduction kinetics showed that the identity of minerals such as gamma-Al2O3 and TiO and the solution pH were crucial factors to determine the Fe(ll) adsorption behavior and to influence the rate constant (k) of 2-NP reduction. Furthermore, two electrochemical methods, cyclic voltammetry (CV) and electrochemical impedance spectrometry (EIS), were applied to characterize the Fe(II) reactivity with both the mineral-coated and mineral-free electrodes. The electrochemical evidence confirmed that the peak oxidation potential (Ep) of complex Fe(II) can be significantly affected by the solution pH;the enhanced reductive transformation of 2-NP can be related to the reduced Ep of surface-complex Fe(II) and the reduced charge transfer resistance (R(CT)) of the Fe(III)/Fe(II) couple. All these relationships were studied quantitatively. At pH 6.7, the measured Ep and R(CT) decreased in the order TiO2/GC < gamma-Al2O3/ GC < GC (Ep, 0.140 < 0.190 < 0.242 V; R(CT), 0.30 < 0.41 < 0.78 komega), while the 2-NP reduction on different minerals were in the order TiO2 > gamma-Al2O3 > nonmineral (k x 10-2, 7.91 > 0.64 > 0.077 min(-l)).

  16. Substrate specificity and copper loading of the manganese-oxidizing multicopper oxidase Mnx from Bacillus sp. PL-12.

    PubMed

    Butterfield, Cristina N; Tebo, Bradley M

    2017-02-22

    Manganese(ii) oxidation in the environment is thought to be driven by bacteria because enzymatic catalysis is many orders of magnitude faster than the abiotic processes. The heterologously purified Mn oxidase (Mnx) from marine Bacillus sp. PL-12 is made up of the multicopper oxidase (MCO) MnxG and two small Cu and heme-binding proteins of unknown function, MnxE and MnxF. Mnx binds Cu and oxidizes both Mn(ii) and Mn(iii), generating Mn(iv) oxide minerals that resemble those found on the Bacillus spore surface. Spectroscopic techniques have illuminated details about the metallo-cofactors of Mnx, but very little is known about their requirement for catalytic activity, and even less is known about the substrate specificity of Mnx. Here we quantify the canonical MCO Cu and persistent peripheral Cu bound to Mnx, and test Mnx oxidizing ability toward different substrates at varying pH. Mn(ii) appears to be the best substrate in terms of kcat, but its oxidation does not follow Michaelis-Menten kinetics, instead showing a sigmoidal cooperative behavior. Mnx also oxidizes Fe(ii) substrate, but in a Michaelis-Menten manner and with a decreased activity, as well as organic substrates. The reduced metals are more rapidly consumed than the larger organic substrates, suggesting the hypothesis that the Mnx substrate site is small and tuned for metal oxidation. Of biological relevance is the result that Mnx has the highest catalytic efficiency for Mn(ii) at the pH of sea water, especially when the protein is loaded with greater than the requisite four MCO copper atoms, suggesting that the protein has evolved specifically for Mn oxidation.

  17. Online spectrophotometric determination of Fe(II) and Fe(III) by flow injection combined with low pressure ion chromatography

    NASA Astrophysics Data System (ADS)

    Chen, Shujuan; Li, Nan; Zhang, Xinshen; Yang, Dongjing; Jiang, Heimei

    2015-03-01

    A simple and new low pressure ion chromatography combined with flow injection spectrophotometric procedure for determining Fe(II) and Fe(III) was established. It is based on the selective adsorption of low pressure ion chromatography column to Fe(II) and Fe(III), the online reduction reaction of Fe(III) and the reaction of Fe(II) in sodium acetate with phenanthroline, resulting in an intense orange complex with a suitable absorption at 515 nm. Various chemical (such as the concentration of colour reagent, eluant and reductive agent) and instrumental parameters (reaction coil length, reductive coil length and wavelength) were studied and were optimized. Under the optimum conditions calibration graph of Fe(II)/Fe(III) was linear in the Fe(II)/Fe(III) range of 0.040-1.0 mg/L. The detection limit of Fe(III) and Fe(II) was respectively 3.09 and 1.55 μg/L, the relative standard deviation (n = 10) of Fe(II) and Fe(III) 1.89% and 1.90% for 0.5 mg/L of Fe(II) and Fe(III) respectively. About 2.5 samples in 1 h can be analyzed. The interfering effects of various chemical species were studied. The method was successfully applied in the determination of water samples.

  18. Regulatory roles of serotonin and melatonin in abiotic stress tolerance in plants

    PubMed Central

    Kaur, Harmeet; Mukherjee, Soumya; Baluska, Frantisek; Bhatla, Satish C

    2015-01-01

    Understanding the physiological and biochemical basis of abiotic stress tolerance in plants has always been one of the major aspects of research aiming to enhance plant productivity in arid and semi-arid cultivated lands all over the world. Growth of stress-tolerant transgenic crops and associated agricultural benefits through increased productivity, and related ethical issues, are also the major concerns of current research in various laboratories. Interesting data on the regulation of abiotic stress tolerance in plants by serotonin and melatonin has accumulated in the recent past. These two indoleamines possess antioxidative and growth-inducing properties, thus proving beneficial for stress acclimatization. Present review shall focus on the modes of serotonin and melatonin-induced regulation of abiotic stress tolerance in plants. Complex molecular interactions of serotonin and auxin-responsive genes have suggested their antagonistic nature. Data from genomic and metabolomic analyses of melatonin-induced abiotic stress signaling have lead to an understanding of the regulation of stress tolerance through the modulation of transcription factors, enzymes and various signaling molecules. Melatonin, nitric oxide (NO) and calmodulin interactions have provided new avenues for research on the molecular aspects of stress physiology in plants. Investigations on the characterization of receptors associated with serotonin and melatonin responses, are yet to be undertaken in plants. Patenting of biotechnological inventions pertaining to serotonin and melatonin formulations (through soil application or foliar spray) are expected to be some of the possible ways to regulate abiotic stress tolerance in plants. The present review, thus, summarizes the regulatory roles of serotonin and melatonin in modulating the signaling events accompanying abiotic stress in plants. PMID:26633566

  19. Regulatory roles of serotonin and melatonin in abiotic stress tolerance in plants.

    PubMed

    Kaur, Harmeet; Mukherjee, Soumya; Baluska, Frantisek; Bhatla, Satish C

    2015-01-01

    Understanding the physiological and biochemical basis of abiotic stress tolerance in plants has always been one of the major aspects of research aiming to enhance plant productivity in arid and semi-arid cultivated lands all over the world. Growth of stress-tolerant transgenic crops and associated agricultural benefits through increased productivity, and related ethical issues, are also the major concerns of current research in various laboratories. Interesting data on the regulation of abiotic stress tolerance in plants by serotonin and melatonin has accumulated in the recent past. These two indoleamines possess antioxidative and growth-inducing properties, thus proving beneficial for stress acclimatization. Present review shall focus on the modes of serotonin and melatonin-induced regulation of abiotic stress tolerance in plants. Complex molecular interactions of serotonin and auxin-responsive genes have suggested their antagonistic nature. Data from genomic and metabolomic analyses of melatonin-induced abiotic stress signaling have lead to an understanding of the regulation of stress tolerance through the modulation of transcription factors, enzymes and various signaling molecules. Melatonin, nitric oxide (NO) and calmodulin interactions have provided new avenues for research on the molecular aspects of stress physiology in plants. Investigations on the characterization of receptors associated with serotonin and melatonin responses, are yet to be undertaken in plants. Patenting of biotechnological inventions pertaining to serotonin and melatonin formulations (through soil application or foliar spray) are expected to be some of the possible ways to regulate abiotic stress tolerance in plants. The present review, thus, summarizes the regulatory roles of serotonin and melatonin in modulating the signaling events accompanying abiotic stress in plants.

  20. Abiotic production of iodine molecules in irradiated ice

    NASA Astrophysics Data System (ADS)

    Choi, Wonyong; Kim, Kitae; Yabushita, Akihiro

    2015-04-01

    Reactive halogen species play an important role in Earth's environmental systems. Iodine compounds are related to ozone depletion event (ODE) during Antarctic spring, formation of CCN (cloud condensation nuclei), and controlling the atmospheric oxidizing capacity. However, the processes and mechanisms for abiotic formation of iodine compounds in polar region are still unclear. Although the chemical reactions taking place in ice are greatly different from those in aquatic environment, reaction processes of halogens in frozen condition have rarely studied compared to those in water. In this study, we investigated iodide oxidation to form triiodide (I3-) in ice phase under UV irradiation ( λ > 300 nm) and dark condition. The production of I3- through iodide oxidation, which is negligible in aqueous solution, was significantly accelerated in ice phase even in the absence of UV irradiation. The following release of gaseous iodine molecule (I2) to the atmosphere was also monitored by cavity ring-down spectroscopy (CRDS). We speculate that the markedly enhanced iodide oxidation in polycrystalline ice is due to the freeze concentration of iodides, protons, and dissolved oxygen in the ice crystal grain boundaries. The experiments conducted under ambient solar radiation of the Antarctic region (King George Island, 62°13'S 58°47'W, sea level) also confirmed that the generation of I3- via iodide oxidation process is enhanced when iodide is trapped in ice. The observed intrinsic oxidative transformation of iodide to generate I3-(aq) and I2(g) in frozen environment suggests a previously unknown pathway for the substantial release of reactive iodine species to the atmosphere.

  1. Role of Natural Organic Matter in Regulating the Partitioning of Fe(II, III) in Seawater

    NASA Astrophysics Data System (ADS)

    Guo, L.; Chen, M.; Roberts, K.; Santschi, P. H.

    2008-12-01

    Iron (Fe) is an essential micronutrient and plays an important role in controlling ocean productivity and carbon cycling. Fe has been shown to be mostly complexed with dissolved organic matter in seawater. However, the interaction of Fe with natural organic matter and how the quality and quantity of organic matter affect the chemical speciation of Fe in seawater remain poorly understood. Controlled laboratory experiments have been conducted to examine the partitioning of Fe(II, III) between dissolved, colloidal and particulate phases using radiotracers, model organic compounds, and ultrafiltration. In natural seawater, Fe is mostly partitioned in the colloidal and particulate phases, resulting in a logKd value of 7.3 and a logKc of 6.1, respectively. On average, about 25% of dissolved Fe-55 was found in the <1 kDa fraction, 56% in the 1-10 kDa small colloidal fraction, 11% in the 10-100 kDa medium colloidal fraction, and 8% in the large colloidal fraction (100 kDa-0.4 μm). In experimental treatments with extracellular polysaccharides, the partitioning of Fe(II, III) changed from mostly in the colloidal fraction to mostly in the <1 kDa truly dissolved fraction, with on average 67% in the <1 kDa, 13% in the 1-10 kDa, 4% in the 10-100 kDa, and 6% in the 100 kDa-0.4 μm fraction. The increase in Fe(II, III) solubility in the presence of extracellular polysaccharides is hypothesized to be the result of Fe reduction from Fe(III), a more particle-reactive form, to Fe(II), a more soluble form, during its interactions with natural organic matter in seawater. This experimental result has important implications for the biogeochemical cycling of Fe(II, III) and other redox sensitive trace elements in the ocean. While the complexation of Fe with DOM could depress the bioavailability of Fe in seawater, the resultant Fe reduction may significantly enhance its solubility and bioavailability to marine organisms.

  2. A proposed abiotic reaction scheme for hydroxylamine and monochloramine under chloramination relevant drinking water conditions.

    PubMed

    Wahman, David G; Speitel, Gerald E; Machavaram, Madhav V

    2014-09-01

    Drinking water monochloramine (NH2Cl) use may promote ammonia-oxidizing bacteria (AOB). AOB use (i) ammonia monooxygenase for biological ammonia (NH3) oxidation to hydroxylamine (NH2OH) and (ii) hydroxylamine oxidoreductase for NH2OH oxidation to nitrite. NH2Cl and NH2OH may react, providing AOB potential benefits and detriments. The NH2Cl/NH2OH reaction would benefit AOB by removing the disinfectant (NH2Cl) and releasing their growth substrate (NH3), but the NH2Cl/NH2OH reaction would also provide a possible additional inactivation mechanism besides direct NH2Cl reaction with cells. Because biological NH2OH oxidation supplies the electrons required for biological NH3 oxidation, the NH2Cl/NH2OH reaction provides a direct mechanism for NH2Cl to inhibit NH3 oxidation, starving the cell of reductant by preventing biological NH2OH oxidation. To investigate possible NH2Cl/NH2OH reaction implications on AOB, an understanding of the underlying abiotic reaction is first required. The present study conducted a detailed literature review and proposed an abiotic NH2Cl/NH2OH reaction scheme (RS) for chloramination relevant drinking water conditions (μM concentrations, air saturation, and pH 7-9). Next, RS literature based kinetics and end-products were evaluated experimentally between pHs 7.7 and 8.3, representing (i) the pH range for future experiments with AOB and (ii) mid-range pHs typically found in chloraminated drinking water. In addition, a (15)N stable isotope experiment was conducted to verify nitrous oxide and nitrogen gas production and their nitrogen source. Finally, the RS was slightly refined using the experimental data and an AQUASIM implemented kinetic model. A chloraminated drinking water relevant RS is proposed and provides the abiotic reaction foundation for future AOB biotic experiments.

  3. Environmental Selenium Transformations: Distinguishing Abiotic and Biotic Factors Influencing Se Redox Transformations

    NASA Astrophysics Data System (ADS)

    Rosenfeld, C.; Kenyon, J.; James, B. R.; Santelli, C. M.

    2014-12-01

    Worldwide, selenium (Se) is proving to be a significant environmental concern, with many anthropogenic activities (e.g. coal mining and combustion, phosphate mining and agricultural irrigation) releasing potentially hazardous concentrations into surface and subsurface ecosystems. The US EPA is currently considering aquatic Se regulations, however no guidelines exist for excess soil Se, despite its ability to act as a persistent Se source. Various abiotic and biological processes mediate Se oxidation/reduction (redox) transformations in soils, thus influencing its solubility and bioavailability. In this research we assess (1) the ability of metal-transforming fungal species to aerobically reduce Se (Se (IV and/or VI) to Se(0)), and (2) the relative contribution of biotic and abiotic pathways for aerobic Se transformation. The primary objective of this research is to determine what abiotic and biotic factors enhance or restrict Se bioavailability. Results indicate that fungal-mediated Se reduction may be quite widespread, with at least 7 out of 10 species of known Mn(II)-oxidizing fungi isolated from metal impacted environments also identified as capable of aerobically reducing Se(IV) and/or Se(VI) to Se(0). Increasing concentrations of selenite (SeO32-; Se(IV)) and selenate (SeO42-; Se(VI)) generally reduced fungal growth rates, although selenate was more likely to inhibit fungal growth than selenite. To study oxidation, Se(0) was combined with Mn(III/IV) (hydr)oxides (henceforth referred to as Mn oxides), Se-transforming fungi (Alternaria alternata), and oxalic acid to mimic Se biogeochemistry at the plant-soil interface. Increased pH in the presence of fungi (7.2 with fungi, 6.8 without fungi after 24 days) was observed. Additionally, a slight decrease in redox potential was measured for incubations without Mn oxides (236 mV with Mn oxides, 205 mV without Mn oxides after 24 days), indicating that Mn oxides may enhance Se oxidation. Elemental Se oxidation rates to

  4. A Thiophene-Containing Conductive Metallopolymer Using an Fe(II) Bis(terpyridine) Core for Electrochromic Materials.

    PubMed

    Liang, Yawei; Strohecker, Daniel; Lynch, Vincent; Holliday, Bradley J; Jones, Richard A

    2016-12-21

    Three Fe(II) bis(terpyridine)-based complexes with thiophene (Fe(L1)2), bithiophene (Fe(L2)2), and 3,4-ethylenedioxythiophene (Fe(L3)2) side chains were designed and synthesized for the purpose of providing two terminal active sites for electrochemical polymerization. The corresponding metallopolymers (poly-Fe(Ln)2, n = 2 or 3) were synthesized on indium tin oxide (ITO)-coated glass substrates via oxidative electropolymerization of the thiophene-substituted monomers and characterized using electrochemistry, X-ray photoelectron spectroscopy, UV-vis spectroscopy, and atomic force microscopy. The film poly-Fe(L2)2 was further studied for electrochromic (EC) color-switching properties and fabricated into a solid-state EC device. Poly-Fe(L2)2 films exhibit an intense MLCT absorption band at 596 nm (ε = 4.7 × 10(4) M(-1) cm(-1)) in the UV-vis spectra without any applied voltage. Upon application of low potentials (between 1.1 and 0.4 V vs Fc(+)/Fc), the obtained electropolymerized film exhibited great contrast with a change of transmittance percentage (ΔT%) of 40% and a high coloration efficiency of 3823 cm(2) C(-1) with a switching time of 1 s. The film demonstrates commonplace stability and reversibility with a 10% loss in peak current intensity after 200 cyclic voltammetry cycles and almost no loss in change of transmittance (ΔT%) after 900 potential switches between 1.1 and 0.4 V (vs Fc(+)/Fc) with a time interval of 0.75 s. The electropolymerization of Fe(L2)2 provides convenient and controllable film fabrication. Electrochromic behavior was also achieved in a solid-state device composed of a poly-Fe(L2)2 film and a polymer-supported electrolyte sandwiched between two ITO-coated glass electrodes.

  5. Bioleaching of ilmenite and basalt in the presence of iron-oxidizing and iron-scavenging bacteria

    NASA Astrophysics Data System (ADS)

    Navarrete, Jesica U.; Cappelle, Ian J.; Schnittker, Kimberlin; Borrok, David M.

    2013-04-01

    Bioleaching has been suggested as an alternative to traditional mining techniques in extraterrestrial environments because it does not require extensive infrastructure and bulky hardware. In situ bioleaching of silicate minerals, such as those found on the moon or Mars, has been proposed as a feasible alternative to traditional extraction techniques that require either extreme heat and/or substantial chemical treatment. In this study, we investigated the biotic and abiotic leaching of basaltic rocks (analogues to those found on the moon and Mars) and the mineral ilmenite (FeTiO3) in aqueous environments under acidic (pH ˜ 2.5) and circumneutral pH conditions. The biological leaching experiments were conducted using Acidithiobacillus ferrooxidans, an iron (Fe)-oxidizing bacteria, and Pseudomonas mendocina, an Fe-scavenging bacteria. We found that both strains were able to grow using the Fe(II) derived from the tested basaltic rocks and ilmenite. Although silica leaching rates were the same or slightly less in the bacterial systems with A. ferrooxidans than in the abiotic control systems, the extent of Fe, Al and Ti released (and re-precipitated in new solid phases) was actually greater in the biotic systems. This is likely because the Fe(II) leached from the basalt was immediately oxidized by A. ferrooxidans, and precipitated into Fe(III) phases which causes a change in the equilibrium of the system, i.e. Le Chatelier's principle. Iron(II) in the abiotic experiment was allowed to build up in solution which led to a decrease in its overall release rate. For example, the percentage of Fe, Al and Ti leached (dissolved + reactive mineral precipitates) from the Mars simulant in the A. ferrooxidans experimental system was 34, 41 and 13% of the total Fe, Al and Ti in the basalt, respectively, while the abiotic experimental system released totals of only 11, 25 and 2%. There was, however, no measurable difference in the amounts of Fe and Ti released from ilmenite in the

  6. Reversing the relative 3MLCT-3MC order in Fe(ii) complexes using cyclometallating ligands: a computational study aiming at luminescent Fe(ii) complexes.

    PubMed

    Dixon, Isabelle M; Alary, Fabienne; Boggio-Pasqua, Martial; Heully, Jean-Louis

    2015-08-14

    Following a computational approach, the use of strongly electron-donating cyclometallating ligands has allowed us to increase the (3)MC-(3)MLCT gap dramatically in Fe(ii) bis(tridentate) polypyridine complexes, and eventually to reverse the ordering between these states, yielding a (3)MLCT state that is clearly more stable than the (3)MC state. Simultaneously, the quintet excited states ((5)MC and (5)MLCT) are displaced away from the region (in terms of geometry and energy) where classical photophysics occur, allowing us to avoid magnetism. The situation is thus similar to that of classical ruthenium polypyridine complexes. This opens the way towards luminescent iron(ii) complexes, in particular Fe(ii)bis(6-phenyl-2,2'-bipyridine) Fe(NNC)(2).

  7. Nitrate removal by nitrate-dependent Fe(II) oxidation in an upflow denitrifying biofilm reactor.

    PubMed

    Zhou, Jun; Wang, Hongyu; Yang, Kai; Sun, Yuchong; Tian, Jun

    2015-01-01

    A continuous upflow biofilm reactor packed with ceramsite was constructed for nitrate removal under an anaerobic atmosphere without an organic carbon source. Denitrifying bacteria, Pseudomonas sp. W1, Pseudomonas sp. W2 and Microbacterium sp. W5, were added to the bioreactor as inocula. Nitrate concentration, nitrite accumulation and nitrogen removal efficiency in the effluent were investigated under various conditions set by several parameters including pH, hydraulic retention time (HRT), ratios of carbon to nitrogen (C/N) and temperature. The results illustrated that the maximum removal efficiency of nitrogen was 85.39%, under optimum reaction parameters, approximately pH 6.5-7, HRT = 48 hours and C/N = 13.1:1 at temperature of 30 °C, which were determined by experiment.

  8. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    NASA Astrophysics Data System (ADS)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  9. Hydrous ferric oxide precipitation in the presence of nonmetabolizing bacteria: Constraints on the mechanism of a biotic effect

    NASA Astrophysics Data System (ADS)

    Rancourt, Denis G.; Thibault, Pierre-Jean; Mavrocordatos, Denis; Lamarche, Gilles

    2005-02-01

    We have used room temperature and cryogenic 57Fe Mössbauer spectroscopy, powder X-ray diffraction (pXRD), mineral magnetometry, and transmission electron microscopy (TEM), to study the synthetic precipitation of hydrous ferric oxides (HFOs) prepared either in the absence (abiotic, a-HFO) or presence (biotic, b-HFO) of nonmetabolizing bacterial cells ( Bacillus subtilis or Bacillus licheniformis, ˜10 8 cells/mL) and under otherwise identical chemical conditions, starting from Fe(II) (10 -2, 10 -3, or 10 -4 mol/L) under open oxic conditions and at different pH (6-9). We have also performed the first Mössbauer spectroscopy measurements of bacterial cell wall ( Bacillus subtilis) surface complexed Fe, where Fe(III) (10 -3.5-10 -4.5 mol/L) was added to a fixed concentration of cells (˜10 8 cells/mL) under open oxic conditions and at various pH (2.5-4.3). We find that non-metabolic bacterial cell wall surface complexation of Fe is not passive in that it affects Fe speciation in at least two ways: (1) it can reduce Fe(III) to sorbed-Fe 2+ by a proposed steric and charge transfer effect and (2) it stabilizes Fe(II) as sorbed-Fe 2+ against ambient oxidation. The cell wall sorption of Fe occurs in a manner that is not compatible with incorporation into the HFO structure (different coordination environment and stabilization of the ferrous state) and the cell wall-sorbed Fe is not chemically bonded to the HFO particle when they coexist (the sorbed Fe is not magnetically polarized by the HFO particle in its magnetically ordered state). This invalidates the concept that sorption is the first step in a heterogeneous nucleation of HFO onto bacterial cell walls. Both the a-HFOs and the b-HFOs are predominantly varieties of ferrihydrite (Fh), often containing admixtures of nanophase lepidocrocite (nLp), yet they show significant abiotic/biotic differences: Biotic Fh has less intraparticle (including surface region) atomic order (Mössbauer quadrupole splitting), smaller primary

  10. Natural abiotic formation of oxalic acid in soils: results from aromatic model compounds and soil samples.

    PubMed

    Studenroth, Sabine; Huber, Stefan G; Kotte, Karsten; Schöler, Heinz F

    2013-02-05

    Oxalic acid is the smallest dicarboxylic acid and plays an important role in soil processes (e.g., mineral weathering and metal detoxification in plants). We have first proven its abiotic formation in soils and investigated natural abiotic degradation processes based on the oxidation of soil organic matter, enhanced by Fe(3+) and H(2)O(2) as hydroxyl radical suppliers. Experiments with the model compound catechol and further hydroxylated benzenes were performed to examine a common degradation pathway and to presume a general formation mechanism of oxalic acid. Two soil samples were tested for the release of oxalic acid and the potential effects of various soil parameters on oxalic acid formation. Additionally, the soil samples were treated with different soil sterilization methods to prove the oxalic acid formation under abiotic soil conditions. Different series of model experiments were conducted to determine a range of factors including Fe(3+), H(2)O(2), reaction time, pH, and chloride concentration on oxalic acid formation. Under certain conditions, catechol is degraded up to 65.6% to oxalic acid referring to carbon. In serial experiments with two soil samples, oxalic acid was produced, and the obtained results are suggestive of an abiotic degradation process. In conclusion, Fenton-like conditions with low Fe(3+) concentrations and an excess of H(2)O(2) as well as acidic conditions were required for an optimal oxalic acid formation. The presence of chloride reduced oxalic acid formation.

  11. Unraveling the role of fungal symbionts in plant abiotic stress tolerance

    PubMed Central

    Singh, Lamabam Peter

    2011-01-01

    Fungal symbionts have been found to be associated with every plant studied in the natural ecosystem, where they colonize and reside entirely or partially in the internal tissues of their host plant. Fungal endophytes can express/form a range of different lifestyle/relationships with different host including symbiotic, mutualistic, commensalistic and parasitic in response to host genotype and environmental factors. In mutualistic association fungal endophyte can enhance growth, increase reproductive success and confer biotic and abiotic stress tolerance to its host plant. Since abiotic stress such as, drought, high soil salinity, heat, cold, oxidative stress and heavy metal toxicity is the common adverse environmental conditions that affect and limit crop productivity worldwide. It may be a promising alternative strategy to exploit fungal endophytes to overcome the limitations to crop production brought by abiotic stress. There is an increasing interest in developing the potential biotechnological applications of fungal endophytes for improving plant stress tolerance and sustainable production of food crops. Here we have described the fungal symbioses, fungal symbionts and their role in abiotic stress tolerance. A putative mechanism of stress tolerance by symbionts has also been covered. PMID:21512319

  12. Sequence-specific cleavage of single-stranded DNA: oligodeoxynucleotide-EDTA X Fe(II).

    PubMed Central

    Dreyer, G B; Dervan, P B

    1985-01-01

    The synthesis of a DNA hybridization probe 19 nucleotides in length, equipped with the metal chelator EDTA at C-5 of thymidine in position 10 (indicated by T*) is described. DNA-EDTA 1 has the sequence 5'-T-A-A-C-G-C-A-G-T*-C-A-G-G-C-A-C-C-G-T-3', which is complementary to a 19-nucleotide sequence in the plasmid pBR322. In the presence of Fe(II), O2, and dithiothreitol, DNA-EDTA 1 affords specific cleavage (25 degrees C, pH 7.4, 60 min) at its complementary sequence in a heat-denatured 167-base-pair restriction fragment. Cleavage occurs over a range of 16 nucleotides at the site of hybridization of 1, presumably due to a diffusible reactive species. No other cleavage sites are observed in the 167-base-pair restriction fragment. The procedure used to synthesize DNA-EDTA probes is based on the incorporation of a thymidine modified at C-5 with the triethyl ester of EDTA. By using routine phosphoramidite procedures, thymidine-EDTA can be incorporated into oligodeoxynucleotides of any desired length and sequence. Because the efficiency of the DNA cleavage reaction is dependent on the addition of both Fe(II) and reducing agent (dithiothreitol), the initiation of the cleavage reaction can be controlled. These DNA-EDTA X Fe(II) probes should be useful for the sequence-specific cleavage of single-stranded DNA (and most likely RNA) under mild conditions. Images PMID:3919391

  13. Comparative study of biogenic and abiotic iron-containing materials

    NASA Astrophysics Data System (ADS)

    Cherkezova-Zheleva, Z.; Shopska, M.; Paneva, D.; Kovacheva, D.; Kadinov, G.; Mitov, I.

    2016-12-01

    Series of iron-based biogenic materials prepared by cultivation of Leptothrix group of bacteria in different feeding media ( Sphaerotilus-Leptothrix group of bacteria isolation medium, Adler, Lieske and silicon-iron-glucose-peptone) were studied. Control samples were obtained in the same conditions and procedures but the nutrition media were not infected with bacteria, i.e. they were sterile. Room and low temperature Mössbauer spectroscopy, powder X-ray diffraction (XRD), and infrared spectroscopy (IRS) were used to reveal the composition and physicochemical properties of biomass and respective control samples. Comparative analysis showed differences in their composition and dispersity of present phases. Sample composition included different ratio of nanodimensional iron oxyhydroxide and oxide phases. Relaxation phenomena such as superparamagnetism or collective magnetic excitation behaviour were registered for some of them. The experimental data showed that the biogenic materials were enriched in oxyhydroxides of high dispersion. Catalytic behaviour of a selected biomass and abiotic material were studied in the reaction of CO oxidation. In situ diffuse-reflectance (DR) IRS was used to monitor the phase transformations in the biomass and CO conversion.

  14. Fe Isotope Fractionation During Fe(III) Reduction to Fe(II)

    NASA Astrophysics Data System (ADS)

    Baker, E. A.; Greene, S.; Hardin, E. E.; Hodierne, C. E.; Rosenberg, A.; John, S.

    2014-12-01

    The redox chemistry of Fe(III) and Fe(II) is tied to a variety of earth processes, including biological, chemical, or photochemical reduction of Fe(III) to Fe(II). Each process may fractionate Fe isotopes, but the magnitudes of the kinetic isotope effects have not been greatly explored in laboratory conditions. Here, we present the isotopic fractionation of Fe during reduction experiments under a variety of experimental conditions including photochemical reduction of Fe(III) bound to EDTA or glucaric acid, and chemical reduction of Fe-EDTA by sodium dithionite, hydroxylamine hydrochloride, Mn(II), and ascorbic acid. A variety of temperatures and pHs were tested. In all experiments, Fe(III) bound to an organic ligand was reduced in the presence of ferrozine. Ferrozine binds with Fe(II), forming a purple complex which allows us to measure the extent of reaction. The absorbance of the experimental solutions was measured over time to determine the Fe(II)-ferrozine concentration and thus the reduction rate. After about 5% of the Fe(III) was reduced, Fe(III)-EDTA and Fe(II)-ferrozine were separated using a C-18 column to which Fe(II)-ferrozine binds. The Fe(II) was eluted and purified through anion exchange chromatography for analysis of δ56Fe by MC-ICPMS. Preliminary results show that temperature and pH both affect reduction rate. All chemical reductants tested reduce Fe(III) at a greater rate as temperature increases. The photochemical reductant EDTA reduces Fe(III) at a greater rate under more acidic conditions. Comparison of the two photochemical reductants shows that glucaric acid reduces Fe(III) significantly faster than EDTA. For chemical reduction, the magnitude of isotopic fractionation depends on the reductant used. Temperature and pH also affect the isotopic fractionation of Fe. Experiments using chemical reductants show that an increase in temperature at low temperatures produces lighter 56Fe ratios, while at high temperatures some reductants produce heavier

  15. Pentagonal Bipyramid Fe(II) Complexes: Robust Ising-Spin Units towards Heteropolynuclear Nanomagnets.

    PubMed

    Bar, Arun Kumar; Gogoi, Nayanmoni; Pichon, Céline; Goli, V M L Durga Prasad; Thlijeni, Mehrez; Duhayon, Carine; Suaud, Nicolas; Guihéry, Nathalie; Barra, Anne-Laure; Ramasesha, S; Sutter, Jean-Pascal

    2017-01-24

    Pentagonal bipyramid Fe(II) complexes have been investigated to evaluate their potential as Ising-spin building units for the preparation of heteropolynuclear complexes that are likely to behave as single-molecule magnets (SMMs). The considered monometallic complexes were prepared from the association of a divalent metal ion with pentadentate ligands that have a 2,6-diacetylpyridine bis(hydrazone) core (H2 L(N3O2R) ). Their magnetic anisotropy was established by magnetometry to reveal their zero-field splitting (ZFS) parameter D, which ranged between -4 and -13 cm(-1) and was found to be modulated by the apical ligands (ROH versus Cl). The alteration of the D value by N-bound axial CN ligands, upon association with cyanometallates, was also assessed for heptacoordinated Fe(II) as well as for related Ni(II) and Co(II) derivatives. In all cases, N-coordinated cyanide ligands led to large magnetic anisotropy (i.e., -8 to -18 cm(-1) for Fe and Ni, +33 cm(-1) for Co). Ab initio calculations were performed on three Fe(II) complexes, which enabled one to rationalize the role of the ligand on the nature and magnitude of the magnetic anisotropy. Starting from the pre-existing heptacoordinated complexes, a series of pentanuclear compounds were obtained by reactions with paramagnetic [W(CN)8 ](3-) . Magnetic studies revealed the occurrence of ferromagnetic interactions between the spin carriers in all the heterometallic systems. Field-induced slow magnetic relaxation was observed for mononuclear Fe(II) complexes (Ueff /kB up to 53 K (37 cm(-1) ), τ0 =5×10(-9)  s), and SMM behavior was evidenced for a heteronuclear [Fe3 W2 ] derivative (Ueff /kB =35 K and τ0 =4.6 10(-10)  s), which confirmed that the parent complexes were robust Ising-type building units. High-field EPR spectroscopic investigation of the ZFS parameters for a Ni derivative is also reported.

  16. Substrate entasis and electronic coupling elements in electron transfer from FeII in a multicopper ferroxidase

    PubMed Central

    Kosman, Daniel J.

    2008-01-01

    Outersphere electron transfer in multicopper oxidases occurs at the type 1, blue CuII. One class of MCO proteins exhibits a specificity in this reaction towards FeII. In work carried out in collaboration with the Solomon lab over the past 7 years, we have delineated the structural motifs that support this ferroxidase specificity and have quantified the contributions that each makes to this outersphere electron transfer reaction from FeII to the type 1 CuII. Two features of this electron transfer catalysis stand out. First, the protein provides a binding site for FeII that actually favors FeIII; this coordination sphere places the bound FeII in a state of “entasis” that can be relieved by loss of an electron. In short, the EO of the bound FeII is lowered relative to that of aqueous ferrous iron making electron transfer thermodynamically favorable. Second, carboxylates within this coordination sphere provide an electronic coupling pathway for the electron transfer via their H-bond network with type 1 Cu histidine ligands thus making electron transfer kinetically efficient. This brief report breaks down these contributions to ferroxidase specificity in terms of the semi-classical Marcus equation describing outersphere electron transfer. PMID:18443651

  17. Mineralization of wastewater from the pharmaceutical industry containing chloride ions by UV photolysis of H2O2/Fe(II) and ultrasonic irradiation.

    PubMed

    Monteagudo, J M; Durán, A; San Martín, I

    2014-08-01

    The mineralization of pharmaceutical wastewater containing chloride ions using a UV/H2O2/Fe(II) process was studied. The addition of Fe(II) to the UV/H2O2 system did not improve the degradation efficiency due to inhibition of the photo-Fenton reaction, at acid pH, in the presence of chloride ions in these wastewaters. The increase of pH from 2 to 7 increased the degree of mineralization under UV photolysis of H2O2 because more HO radicals are available by HOCl dissociation reaction. Under the selected operation conditions ([H2O2]o = 11,500 ppm, [Fe(II)] = 0 ppm, [TOC]o = 125 ppm and pH = 7), 100% of TOC removal was attained in 120 min. A significant synergistic effect of combining photolysis (UV/H2O2) and sonolysis was observed. Sonophotolysis (UV/H2O2/ultrasound) technique significantly increased the degree of mineralization (100% TOC removal in 90 min using 6500 ppm H2O2) when compared with each individual process. Sonochemical reaction was favored by the presence of chloride ions since the concentration of contaminants at the gas-liquid interface increased. Free radicals reaction was the controlling mechanism in the UV/H2O2/ultrasound system. HO radicals were the main oxidative intermediate species in the process, although hydroperoxyl radicals (HO2) also played a role. The contribution of thermal-pyrolytic reaction (in gas-phase) to sonophotolysis process was negligible.

  18. Dynamics of Fe(II), sulphur and phosphate in pilot-scale constructed wetlands treating a sulphate-rich chlorinated hydrocarbon contaminated groundwater.

    PubMed

    Wu, Shubiao; Chen, Zhongbing; Braeckevelt, Mareike; Seeger, Eva M; Dong, Renjie; Kästner, Matthias; Paschke, Heidrun; Hahn, Anja; Kayser, Gernot; Kuschk, Peter

    2012-04-15

    Long-term investigations were carried out in two pilot-scale horizontal subsurface flow constructed wetlands (planted and unplanted) with an iron-rich soil matrix for treating sulphate-rich groundwater which was contaminated with low concentrations of chlorinated hydrocarbons. The temporal and spatial dynamics of pore-water sulphide, Fe(II) and phosphate concentrations in the wetland beds were characterized and the seasonal effects on sulphide production and nitrification inhibition were evaluated. The results demonstrated that the pore-water sulphide concentrations gradually increased from less than 0.2 mg/L in 2005 to annual average concentrations of 15 mg/L in 2010, while the pore-water Fe(II) concentrations decreased from 35.4 mg/L to 0.3 mg/L. From 2005 to 2010, the phosphate removal efficiency declined from 91% to 10% under a relatively constant inflow concentration of 5 mg/L. The pronounced effect of plants was accompanied by a higher sulphate reduction and ammonium oxidation in the planted bed, as compared to the unplanted control. A high tolerance of plants towards sulphide toxicity was observed, which might be due to the detoxification of sulphide by oxygen released by the roots. However, during the period of 2009-2010, the nitrification was negatively impacted by the sulphide production as the reduction in the removal of ammonium from 75% to 42% (with inflow concentration of 55 mg/L) correlated with the increasing mean annual sulphide concentrations. The effect of the detoxification of sulphide and the immobilization of phosphate by the application of the iron-rich soil matrix in the initial years was proven; however, the life-span of this effect should not only be taken into consideration in further design but also in scientific studies.

  19. Biotic and abiotic degradation behaviour of ethylene glycol monomethyl ether (EGME).

    PubMed

    Fischer, A; Hahn, C

    2005-05-01

    Glycol ethers are widely used in many processes in the chemical industry. Their high water solubility means they are used as solvents for different purposes (e.g. lacquers and varnishes). Since glycol ethers are known to produce toxic metabolites such as the teratogenic methoxyacetic acid during biodegradation, the biological treatment of glycol ethers can be hazardous. However, using oxidizing agents like hydrogen peroxide could be a feasible option for treating wastewater containing glycol ether. In this study, both-, biodegradation and abiotic oxidation experiments with ethylene glycol monomethyl ether (EGME) as contaminant were performed. The biodegradation experiments were conducted with a synthetic model wastewater containing 15 wt% NaCl and 5000 mgl(-1) of EGME. While experiments with the fungus Aspergillus versicolor resulted in the exhaustive biotic degradation of EGME, the toxic metabolite methoxyacetic acid (MAA) was produced as a 'dead end' product. Sodium hydroxide was added to adjust the decreasing pH caused by the production of MAA. In abiotic degradation experiments with EGME, other degradation products--organic acids and toxic aldehydes, e.g. methoxy acetaldehyde (MALD)--were detected. It must be taken into account that EGME and its biotic and abiotic degradation products are usually not analysed in routine wastewater measurements owing to their physical properties.

  20. Differential expression of ferritin genes in response to abiotic stresses and hormones in pear (Pyrus pyrifolia).

    PubMed

    Xi, Li; Xu, Kuanyong; Qiao, Yushan; Qu, Shenchun; Zhang, Zhen; Dai, Wenhao

    2011-10-01

    In this study, the expression patterns of four ferritin genes (PpFer1, PpFer2, PpFer3, and PpFer4) in pear were investigated using quantitative real-time PCR. Analysis of tissue-specific expression revealed higher expression level of these genes in leaves than in other tested tissues. These ferritin genes were differentially expressed in response to various abiotic stresses and hormones treatments. The expression of ferritin wasn't affected by Fe(III)-citrate treatment. Abscisic acid significantly enhanced the expression of all four ferritin genes, especially PpFer2, followed by N-benzylyminopurine, gibberellic acid, and indole-3-acetic acid. The expression peaks of PpFer1 and PpFer3 in leaves appeared at 6, 6, and 12 h, respectively, after pear plant was exposed to oxidative stress (5 mM H(2)O(2)), salt stress (200 mM NaCl), and heat stress (40°C). A significant increase in PpFer4 expression was detected at 6 h after salt stress or heat stress. The expression of ferritin genes was not altered by cold stress. These results suggested that ferritin genes might be functionally important in acclimation of pear to salt and oxidative stresses. Hormone treatments had no significant effect on expression of ferritin genes compared to abiotic stresses. This showed accumulation of ferritin genes could be operated by different transduction pathways under abiotic stresses and hormones treatments.

  1. Arsenic Uptake by Hydroxyapatite in the Presence of Fe(II)

    NASA Astrophysics Data System (ADS)

    Sahai, N.; Lee, Y. J.; Xu, H.; Ciardelli, M.

    2005-12-01

    We have examined As(III) and As(V) uptake by hydroxyapatite (HAP) in the absence and presence of the commonly occurring geochemical species, Fe(II), in a system open to the atmosphere and at near-neutral pH. The immediate goal of our project is to develop an inexpensive, efficient remediation method for the acute As contamination problem in well-waters of Bangladesh and Eastern India. Our study also provide a conceptual model system for understanding cation, neutral species and anion uptake by a class of minerals (apatites) capable of multiple substitutions, the effect of co-ions on metal(loid) uptake and the geochemically ubiquitous, but relatively poorly-understood, process of coprecipitation. Batch experiments on HAP suspensions, equilibrated for 24 hours, indicate that As(III) and As(V) uptake is slightly greater in the presence of HAP compared to the control experiment. The addition of Fe(II) significantly improves As(III) and As(V) uptake from solutions, both, without and with HAP suspensions. Analyses of equilibrated solutions and High Resolution Transmission Electron Microscopy of solids formed suggest that precipitation of amorphous FePO4.nH2O nanoparticles (10-20 nm) is mainly responsible for As removal with additional uptake by HAP. The efficiency of the process suggests the potential for an effective remediation strategy of As-contaminated drinking water after it has been withdrawn from the affected well.

  2. Reductive transformation of p-nitrophenol by Fe(II) species: the effect of anionic media.

    PubMed

    Wu, Yongjuan; Geng, Lina; Wang, Xiaorui; Chen, Rufen; Wei, Yu; Wu, Dong

    2013-12-15

    Electron exchange between aqueous Fe(II) and structural Fe(III) of iron minerals has been illustrated for understanding the reduction of nitroaromatic compounds (NAC). However, factors influencing Fe(II)-induced the reduction of NAC still remain elusive. In this paper, p-nitrophenol (1.5mM) was selected to explore the effects of pH, the stabilizing ligands (Cl(-), SO4(2-)) of ferrous ions and the extra addition of iron hydroxide on the reduction of NAC via Fe(II) species. The results indicate that the reduction degree of is much lower in SO4(2-) medium than that in Cl(-) medium at pH 7.6. p-Nitrophenol reduction increased in SO4(2-) medium and slightly decreased in Cl(-) medium when Fe hydroxide was extra added. Cl(-) strength (0.01-0.1 mol L(-1)) has no obvious effect on p-NP reduction. SO4(2-) species and its dosage have markedly inhibitory effect on p-NP reduction due to the selective adsorption of SO4(2-) and the formation of sulphated surface complexes on the fresh Fe hydroxide.

  3. Generation of RNA in abiotic conditions.

    NASA Astrophysics Data System (ADS)

    di Mauro, Ernesto

    Generation of RNA in abiotic conditions. Ernesto Di Mauro Dipartimento di Genetica Bi-ologia Molecolare, Universit` "Sapienza" Roma, Italy. a At least four conditions must be satisfied for the spontaneous generation of (pre)-genetic poly-mers: 1) availability of precursors that are activated enough to spontaneously polymerize. Preliminary studies showed that (a) nucleic bases and acyclonucleosides can be synthesized from formamide H2NCOH by simply heating with prebiotically available mineral catalysts [last reviewed in (1)], and that b) nucleic bases can be phosphorylated in every possible posi-tion [2'; 3'; 5'; cyclic 2',3'; cyclic 3',5' (2)]. The higher stability of the cyclic forms allows their accumulation. 2) A polymerization mechanism. A reaction showing the formation of RNA polymers starting from prebiotically plausible precursors (3',5' cyclic GMP and 3', 5'cyclic AMP) was recently reported (3). Polymerization in these conditions is thermodynamically up-hill and an equilibrium is attained that limits the maximum length of the polymer produced to about 40 nucleotides for polyG and 100 nucleotides for polyA. 3) Ligation of the synthesized oligomers. If this type of reaction could occur according to a terminal-joining mechanism and could generate canonical 3',5' phosphodiester bonds, exponential growth would be obtained of the generated oligomers. This type of reaction has been reported (4) , limited to homogeneous polyA sequences and leading to the production of polyA dimers and tetramers. What is still missing are: 4) mechanisms that provide the proof of principle for the generation of sequence complexity. We will show evidence for two mechanisms providing this proof of principle for simple complementary sequences. Namely: abiotic sequence complementary-driven terminal ligation and sequence-complementary terminal growth. In conclusion: all the steps leading to the generation of RNA in abiotic conditions are satisfied. (1) R Saladino, C Crestini, F

  4. Geochemical and Temporal Influences on the Enrichment of Acidophilic Iron-Oxidizing Bacterial Communities

    PubMed Central

    Sheng, Yizhi; Bibby, Kyle; Grettenberger, Christen; Kaley, Bradley; Macalady, Jennifer L.; Wang, Guangcai

    2016-01-01

    ABSTRACT Two acid mine drainage (AMD) sites in the Appalachian bituminous coal basin were selected to enrich for Fe(II)-oxidizing microbes and measure rates of low-pH Fe(II) oxidation in chemostatic bioreactors. Microbial communities were enriched for 74 to 128 days in fed-batch mode, then switched to flowthrough mode (additional 52 to 138 d) to measure rates of Fe(II) oxidation as a function of pH (2.1 to 4.2) and influent Fe(II) concentration (80 to 2,400 mg/liter). Biofilm samples were collected throughout these operations, and the microbial community structure was analyzed to evaluate impacts of geochemistry and incubation time. Alpha diversity decreased as the pH decreased and as the Fe(II) concentration increased, coincident with conditions that attained the highest rates of Fe(II) oxidation. The distribution of the seven most abundant bacterial genera could be explained by a combination of pH and Fe(II) concentration. Acidithiobacillus, Ferrovum, Gallionella, Leptospirillum, Ferrimicrobium, Acidiphilium, and Acidocella were all found to be restricted within specific bounds of pH and Fe(II) concentration. Temporal distance, defined as the cumulative number of pore volumes from the start of flowthrough mode, appeared to be as important as geochemical conditions in controlling microbial community structure. Both alpha and beta diversities of microbial communities were significantly correlated to temporal distance in the flowthrough experiments. Even after long-term operation under nearly identical geochemical conditions, microbial communities enriched from the different sites remained distinct. While these microbial communities were enriched from sites that displayed markedly different field rates of Fe(II) oxidation, rates of Fe(II) oxidation measured in laboratory bioreactors were essentially the same. These results suggest that the performance of suspended-growth bioreactors for AMD treatment may not be strongly dependent on the inoculum used for reactor

  5. The role of microaerophilic Fe-oxidizing micro-organisms in producing banded iron formations.

    PubMed

    Chan, C S; Emerson, D; Luther, G W

    2016-09-01

    Despite the historical and economic significance of banded iron formations (BIFs), we have yet to resolve the formation mechanisms. On modern Earth, neutrophilic microaerophilic Fe-oxidizing micro-organisms (FeOM) produce copious amounts of Fe oxyhydroxides, leading us to wonder whether similar organisms played a role in producing BIFs. To evaluate this, we review the current knowledge of modern microaerophilic FeOM in the context of BIF paleoenvironmental studies. In modern environments wherever Fe(II) and O2 co-exist, microaerophilic FeOM proliferate. These organisms grow in a variety of environments, including the marine water column redoxcline, which is where BIF precursor minerals likely formed. FeOM can grow across a range of O2 concentrations, measured as low as 2 μm to date, although lower concentrations have not been tested. While some extant FeOM can tolerate high O2 concentrations, many FeOM appear to prefer and thrive at low O2 concentrations (~3-25 μm). These are similar to the estimated dissolved O2 concentrations in the few hundred million years prior to the 'Great Oxidation Event' (GOE). We compare biotic and abiotic Fe oxidation kinetics in the presence of varying levels of O2 and show that microaerophilic FeOM contribute substantially to Fe oxidation, at rates fast enough to account for BIF deposition. Based on this synthesis, we propose that microaerophilic FeOM were capable of playing a significant role in depositing the largest, most well-known BIFs associated with the GOE, as well as afterward when global O2 levels increased.

  6. Cell wall remodeling under abiotic stress

    PubMed Central

    Tenhaken, Raimund

    2015-01-01

    Plants exposed to abiotic stress respond to unfavorable conditions on multiple levels. One challenge under drought stress is to reduce shoot growth while maintaining root growth, a process requiring differential cell wall synthesis and remodeling. Key players in this process are the formation of reactive oxygen species (ROS) and peroxidases, which initially cross-link phenolic compounds and glycoproteins of the cell walls causing stiffening. The function of ROS shifts after having converted all the peroxidase substrates in the cell wall. If ROS-levels remain high during prolonged stress, OH°-radicals are formed which lead to polymer cleavage. In concert with xyloglucan modifying enzymes and expansins, the resulting cell wall loosening allows further growth of stressed organs. PMID:25709610

  7. Abiotic formation of oligonucleotides on basalt surfaces

    NASA Astrophysics Data System (ADS)

    Otroshchenko, V. A.; Vasilyeva, N. V.; Kopilov, A. M.

    1985-06-01

    The complication and further evolution of abiotic syntheses products occurred under environmental influences at the prebiological stage. From this point of view, the influence of some types of irradiation on the organic molecules adsorbed on the surfaces of volcanic rocks, appeared to be of great importance. In this connection, the effect of gamma rays on the AMP molecules adsorbed on mineral surfaces such as cinders and ashes has been studied. It has been shown that they can polymerize with the formation of oligonucleotides. The treatment of oligomers obtained by venom phosphodiesterase has shown that a polymeric product has mainly 3' 5' and 2' 5' bonds between nucleotides. The results obtained have been discussed from the evolutionary aspect.

  8. Abiotic Organic Chemistry in Hydrothermal Systems.

    NASA Astrophysics Data System (ADS)

    Simoneit, B. R.; Rushdi, A. I.

    2004-12-01

    Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

  9. ABIOTIC IN SITU TECHNOLOGIES FOR GROUNDWATER REMEDIATION CONFERENCE: PROCEEDINGS

    EPA Science Inventory

    The USEPA conference on Abiotic In Situ Technologies for Groundwater Remediation was held in Dallas, TX, 8/31-9/2/99. The goal of the meeting was to disseminate current information on abiotic in situ groundwater treatment echnologies. Although much information is being provided a...

  10. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

    NASA Technical Reports Server (NTRS)

    Summers, David P.

    2003-01-01

    mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

  11. Coordinated Actions of Glyoxalase and Antioxidant Defense Systems in Conferring Abiotic Stress Tolerance in Plants

    PubMed Central

    Hasanuzzaman, Mirza; Nahar, Kamrun; Hossain, Md. Shahadat; Mahmud, Jubayer Al; Rahman, Anisur; Inafuku, Masashi; Oku, Hirosuke; Fujita, Masayuki

    2017-01-01

    Being sessile organisms, plants are frequently exposed to various environmental stresses that cause several physiological disorders and even death. Oxidative stress is one of the common consequences of abiotic stress in plants, which is caused by excess generation of reactive oxygen species (ROS). Sometimes ROS production exceeds the capacity of antioxidant defense systems, which leads to oxidative stress. In line with ROS, plants also produce a high amount of methylglyoxal (MG), which is an α-oxoaldehyde compound, highly reactive, cytotoxic, and produced via different enzymatic and non-enzymatic reactions. This MG can impair cells or cell components and can even destroy DNA or cause mutation. Under stress conditions, MG concentration in plants can be increased 2- to 6-fold compared with normal conditions depending on the plant species. However, plants have a system developed to detoxify this MG consisting of two major enzymes: glyoxalase I (Gly I) and glyoxalase II (Gly II), and hence known as the glyoxalase system. Recently, a novel glyoxalase enzyme, named glyoxalase III (Gly III), has been detected in plants, providing a shorter pathway for MG detoxification, which is also a signpost in the research of abiotic stress tolerance. Glutathione (GSH) acts as a co-factor for this system. Therefore, this system not only detoxifies MG but also plays a role in maintaining GSH homeostasis and subsequent ROS detoxification. Upregulation of both Gly I and Gly II as well as their overexpression in plant species showed enhanced tolerance to various abiotic stresses including salinity, drought, metal toxicity, and extreme temperature. In the past few decades, a considerable amount of reports have indicated that both antioxidant defense and glyoxalase systems have strong interactions in conferring abiotic stress tolerance in plants through the detoxification of ROS and MG. In this review, we will focus on the mechanisms of these interactions and the coordinated action of

  12. Improved abiotic stress tolerance of bermudagrass by exogenous small molecules.

    PubMed

    Chan, Zhulong; Shi, Haitao

    2015-01-01

    As a widely used warm-season turfgrass in landscapes and golf courses, bermudagrass encounters multiple abiotic stresses during the growth and development. Physiology analysis indicated that abiotic stresses induced the accumulation of ROS and decline of photosynthesis, resulting in increased cell damage and inhibited growth. Proteomic and metabolomic approaches showed that antioxidant enzymes and osmoprotectant contents (sugar, sucrose, dehydrin, proline) were extensively changed under abiotic stress conditions. Exogenous application of small molecules, such as ABA, NO, CaCl2, H2S, polyamine and melatonin, could effectively alleviate damages caused by multiple abiotic stresses, including drought, salt, heat and cold. Based on high through-put RNA seq analysis, genes involved in ROS, transcription factors, hormones, and carbohydrate metabolisms were largely enriched. The data indicated that small molecules induced the accumulation of osmoprotectants and antioxidants, kept cell membrane integrity, increased photosynthesis and kept ion homeostasis, which protected bermudagrass from damages caused by abiotic stresses.

  13. Abiotic stresses induce different localizations of anthocyanins in Arabidopsis

    PubMed Central

    Kovinich, Nik; Kayanja, Gilbert; Chanoca, Alexandra; Otegui, Marisa S; Grotewold, Erich

    2015-01-01

    Anthocyanins are induced in plants in response to abiotic stresses such as drought, high salinity, excess light, and cold, where they often correlate with enhanced stress tolerance. Numerous roles have been proposed for anthocyanins induced during abiotic stresses including functioning as ROS scavengers, photoprotectants, and stress signals. We have recently found different profiles of anthocyanins in Arabidopsis (Arabidopsis thaliana) plants exposed to different abiotic stresses, suggesting that not all anthocyanins have the same function. Here, we discuss these findings in the context of other studies and show that anthocyanins induced in Arabidopsis in response to various abiotic stresses have different localizations at the organ and tissue levels. These studies provide a basis to clarify the role of particular anthocyanin species during abiotic stress. PMID:26179363

  14. Structure and reactivity of As(III)- and As(V)-rich schwertmannites and amorphous ferric arsenate sulfate from the Carnoulès acid mine drainage, France: Comparison with biotic and abiotic model compounds and implications for As remediation

    NASA Astrophysics Data System (ADS)

    Maillot, Fabien; Morin, Guillaume; Juillot, Farid; Bruneel, Odile; Casiot, Corinne; Ona-Nguema, Georges; Wang, Yuheng; Lebrun, Sophie; Aubry, Emmanuel; Vlaic, Gilberto; Brown, Gordon E.

    2013-03-01

    Poorly ordered nanocrystalline hydroxysulfate minerals of microbial origin, such as schwertmannite, Fe8O8(OH)6SO4, are important arsenic scavengers in sulfate-rich acid mine drainage (AMD) environments. However, despite the fact that As(III) and As(V) have been shown to sorb on schwertmannite, little is known about the actual mechanism of arsenic scavenging processes after microbial Fe(II) oxidation in AMD environments. The major focus of the present study is to determine the molecular-level structure of poorly ordered As(III) and As(V) bearing Fe oxyhydroxysulfate minerals from the Carnoulès AMD, France, which exhibits exceptional As(III) concentrations. Powder X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to compare field samples with a large set of synthetic analogs prepared via biotic or abiotic pathways, with As/Fe ratios typical of minerals and mineraloids ranging from nanocrystalline schwertmannite to amorphous hydroxysulfate compounds. Our results yield further evidence for the poisoning effect of As(V) in limiting the nucleation of schwertmannite. For initial dissolved As(V)/Fe(III) molar ratios ⩾0.2, amorphous Fe(III)-As(V) hydroxysulfate forms, with a local structure consistent with that of amorphous ferric arsenate. EXAFS data for this amorphous material are consistent with corner-sharing FeO6 octahedra to which AsO4 tetrahedra attach via double-corner 2C linkages. For As(V)/Fe(III) molar ratios lower than 0.2, As(V) binds to schwertmannite via 2C surface complexes. In contrast with the As(V)-containing samples, As(III) has a lower affinity for schwertmannite following its nucleation, as this mineral phase persists up to an initial As(III)/Fe(III) molar ratio of 0.6. EXAFS data indicate that during the precipitation process, As(III) forms dominantly 2C surface complexes on schwertmannite surfaces, likely on the sides of double-chains of Fe(III)(O,OH)6 octahedra, with a smaller proportion of edge

  15. Genome-Enabled Studies of Anaerobic, Nitrate-Dependent Iron Oxidation in the Chemolithoautotrophic Bacterium Thiobacillus denitrificans

    NASA Astrophysics Data System (ADS)

    Beller, H. R.; Zhou, P.; Legler, T. C.; Chakicherla, A.; O'Day, P. A.

    2013-12-01

    Thiobacillus denitrificans is a chemolithoautotrophic bacterium capable of anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, both of which can strongly influence the long-term efficacy of in situ reductive immobilization of uranium in contaminated aquifers. We previously identified two c-type cytochromes involved in nitrate-dependent U(IV) oxidation in T. denitrificans and hypothesized that c-type cytochromes would also catalyze Fe(II) oxidation, as they have been found to play this role in anaerobic phototrophic Fe(II)-oxidizing bacteria. Here we report on efforts to identify genes associated with nitrate-dependent Fe(II) oxidation, namely (a) whole-genome transcriptional studies [using FeCO3, Fe2+, and U(IV) oxides as electron donors under denitrifying conditions], (b) Fe(II) oxidation assays performed with knockout mutants targeting primarily highly expressed or upregulated c-type cytochromes, and (c) random transposon-mutagenesis studies with screening for Fe(II) oxidation. Assays of mutants for 26 target genes, most of which were c-type cytochromes, indicated that none of the mutants tested were significantly defective in nitrate-dependent Fe(II) oxidation. The non-defective mutants included the c1-cytochrome subunit of the cytochrome bc1 complex (complex III), which has relevance to a previously proposed role for this complex in nitrate-dependent Fe(II) oxidation and to current concepts of reverse electron transfer. Of the transposon mutants defective in Fe(II) oxidation, one mutant with a disrupted gene associated with NADH:ubiquinone oxidoreductase (complex I) was ~35% defective relative to the wild-type strain; this strain was similarly defective in nitrate reduction with thiosulfate as the electron donor. Overall, our results indicate that nitrate-dependent Fe(II) oxidation in T. denitrificans is not catalyzed by the same c-type cytochromes involved in U(IV) oxidation, nor have other c-type cytochromes yet been implicated in the process.

  16. Breakthrough studies with mono-, binary- and ternary-ion systems comprised of Fe(II), F(-) and As(III) using river sand packed columns for groundwater treatment.

    PubMed

    Ahamad, Kamal Uddin; Jawed, Mohammad

    2013-06-01

    Groundwater in Assam, India, contains excessive amounts of arsenic (As(III)), fluoride (F(-)) and iron (Fe(II)). The rural and semi-urban population of Assam uses indigenous iron filters fabricated using processed sand (PS) as one of the chief constituents to reduce Fe(II) concentration; however, no efforts have been made to reduce As(III) or F(-) concentrations before use. The present work is directed towards assessing the potential of PS for removal of these ions from mono-, binary- and ternary-ion systems through continuous mode column studies. Synthetic water samples containing fixed concentration of ions were prepared using deionized water. The observed order of breakthrough of ions was: As(III) followed by Fe(II) and F(-) followed by Fe(II) in the case of the binary ion systems of Fe(II) + As(III) and Fe(II) + F(-). The throughput volume for As(III) in the (Fe(II) + As(III)) system and for F(-) in the (Fe(II) + F(-)) system is termed the critical breakthrough throughput volume. In the ternary ion system (Fe(II) + As(III) + F(-)), the order of breakthrough of ions observed was F(-), then As(III) and then Fe(II) and hence the throughput volume F(-) is termed the critical breakthrough throughput volume. Results of column studies also indicate the impact on the uptake of the selected ion by the presence of the other ion present in the binary- and ternary-ion systems.

  17. Dioxygen Reactivity of Biomimetic Fe(II) Complexes with Noninnocent Catecholate, o-Aminophenolate, and o-Phenylenediamine Ligands

    PubMed Central

    2015-01-01

    This study describes the O2 reactivity of a series of high-spin mononuclear Fe(II) complexes each containing the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (Ph2TIP) ligand and one of the following bidentate, redox-active ligands: 4-tert-butylcatecholate (tBuCatH–), 4,6-di-tert-butyl-2-aminophenolate (tBu2APH–), or 4-tert-butyl-1,2-phenylenediamine (tBuPDA). The preparation and X-ray structural characterization of [Fe2+(Ph2TIP)(tBuCatH)]OTf, [3]OTf and [Fe2+(Ph2TIP)(tBuPDA)](OTf)2, [4](OTf)2 are described here, whereas [Fe2+(Ph2TIP)(tBu2APH)]OTf, [2]OTf was reported in our previous paper [Bittner et al., Chem.—Eur. J.2013,19, 9686–9698]. These complexes mimic the substrate-bound active sites of nonheme iron dioxygenases, which catalyze the oxidative ring-cleavage of aromatic substrates like catechols and aminophenols. Each complex is oxidized in the presence of O2, and the geometric and electronic structures of the resulting complexes were examined with spectroscopic (absorption, EPR, Mössbauer, resonance Raman) and density functional theory (DFT) methods. Complex [3]OTf reacts rapidly with O2 to yield the ferric-catecholate species [Fe3+(Ph2TIP)(tBuCat)]+ (3ox), which undergoes further oxidation to generate an extradiol cleavage product. In contrast, complex [4]2+ experiences a two-electron (2e–), ligand-based oxidation to give [Fe2+(Ph2TIP)(tBuDIBQ)]2+ (4ox), where DIBQ is o-diiminobenzoquinone. The reaction of [2]+ with O2 is also a 2e– process, yet in this case both the Fe center and tBu2AP ligand are oxidized; the resulting complex (2ox) is best described as [Fe3+(Ph2TIP)(tBu2ISQ)]+, where ISQ is o-iminobenzosemiquinone. Thus, the oxidized complexes display a remarkable continuum of electronic structures ranging from [Fe3+(L2–)]+ (3ox) to [Fe3+(L•–)]2+ (2ox) to [Fe2+(L0)]2+ (4ox). Notably, the O2 reaction rates vary by a factor of 105 across the series, following the order [3]+ > [2]+ > [4]2+, even though the

  18. Biosorption of Fe(II) and Mn(II) Ions from Aqueous Solution by Rice Husk Ash

    PubMed Central

    Zhao, Jiaying; Jiang, Zhao; Shan, Dexin; Lu, Yan

    2014-01-01

    Rice husk ash (RHA), an agricultural waste, was used as biosorbent for the removal of Iron(II) and Manganese(II) ions from aqueous solutions. The structural and morphological characteristics of RHA and its elemental compositions before and after adsorption of Fe(II) and Mn(II) were determined by scanning electron microscopic (SEM) and X-ray fluorescence (XRF) analyses. Batch experiments were carried out to determine the influence of initial pH, contact time, adsorbent dosage, and initial concentration on the removal of Fe(II) and Mn(II) ions. Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models were applied to describe the biosorption isotherm of the metal ions by RHA. The correlation coefficient (R2) of Langmuir and Freundlich isotherm models equals 0.995 and 0.901 for Fe(II), 0.9862 and 0.8924 for Mn(II), respectively, so the Langmuir model fitted the equilibrium data better than the Freundlich isotherm model. The mean free energy values evaluated from the D-R model indicated that the biosorption of Fe(II) and Mn(II) onto RHA was physical in nature. Experimental data also showed that the biosorption processes of both metal ions complied with the pseudo-second-order kinetics. PMID:24982918

  19. Coupling microbial catabolic actions with abiotic redox processes: a new recipe for persistent organic pollutant (POP) removal.

    PubMed

    Jeon, Jong-Rok; Murugesan, Kumarasamy; Nam, In-Hyun; Chang, Yoon-Seok

    2013-01-01

    The continuous release of toxic persistent organic pollutants (POPs) into the environment has raised a need for effective cleanup methods. The tremendous natural diversity of microbial catabolic mechanisms suggests that catabolic routes may be applied to the remediation of POP-contaminated fields. A large number of the recalcitrant xenobiotics have been shown to be removable via the natural catabolic mechanisms of microbes, and detailed biochemical studies of the catabolic methods, together with the development of sophisticated genetic engineering, have led to the use of synthetic microbes for the bioremediation of POPs. However, the steric effects of substituted halogen moieties, microbe toxicity, and the low bioavailability of POPs still deteriorate the efficiency of removal strategies based on natural and synthetic catabolic mechanisms. Recently, abiotic redox processes that induce rapid reductive dehalogenation, hydroxyl radical-based oxidation, or electron shuttling have been reasonably coupled with microbial catabolic actions, thereby compensating for the drawbacks of biotic processes in POP removal. In this review, we first compare the pros and cons of individual methodologies (i.e., the natural and synthetic catabolism of microbes and the abiotic processes involving zero-valent irons, advanced oxidation processes, and small organic stimulants) for POP removal. We then highlight recent trends in coupling the biotic-abiotic methodologies and discuss how the processes are both feasible and superior to individual methodologies for POP cleanup. Cost-effective and environmentally sustainable abiotic redox actions could enhance the microbial bioremediation potential for POPs.

  20. Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

    PubMed

    Neumann, Anke; Wu, Lingling; Li, Weiqiang; Beard, Brian L; Johnson, Clark M; Rosso, Kevin M; Frierdich, Andrew J; Scherer, Michelle M

    2015-03-03

    Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

  1. Analysis of dechlorination kinetics of chlorinated aliphatic hydrocarbons by Fe(II) in cement slurries.

    PubMed

    Jung, Bahngmi; Batchelor, Bill

    2008-03-21

    Degradative solidification/stabilization with ferrous iron (DS/S-Fe(II)) has been found to be effective in degrading a number of chlorinated aliphatic hydrocarbons including 1,1,1-trichloroethane (1,1,1-TCA), 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA), tetrachloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC), carbon tetrachloride (CT) and chloroform (CF). Previous studies have characterized degradation kinetics in DS/S-Fe(II) systems as affected by Fe(II) dose, pH and initial target organic concentration. The goal of this study is to investigate the importance of various chemical properties on degradation kinetics of DS/S-Fe(II). This was accomplished by first measuring rate constants for degradation of 1,1,1-TCA, 1,1,2,2-TeCA and 1,2-dichloroethane (1,2-DCA) in individual batch experiments. Rate constants developed in these experiments and those obtained from the literature were related to thermodynamic parameters including one-electron reduction potential, two-electron reduction potential, bond dissociation energy and lowest unoccupied molecular orbital energies. Degradation kinetics by Fe(II) in cement slurries were generally represented by a pseudo-first-order rate law. The results showed that the rate constants for chlorinated methanes (e.g. CT, CF) and chlorinated ethanes (e.g. 1,1,1-TCA) were higher than those for chlorinated ethylenes (e.g. PCE, TCE, 1,1-DCE and VC) under similar experimental conditions. The log of the pseudo-first-order rate constant (k) was found to correlate better with lowest unoccupied molecular orbital energies (E(LUMO)) (R2=0.874) than with other thermodynamic parameter descriptors.

  2. Effects of Zwitterionic buffers on sorption of ferrous iron at goethite and its oxidation by CCl4.

    PubMed

    Buchholz, Anke; Laskov, Christine; Haderlein, Stefan B

    2011-04-15

    A major factor which controls sorption and oxidation of Fe(II) at the mineral-water interface is pH, hence buffers are commonly used to control pH in experimental studies. Here, we examined the effects of widely used organic buffers (3-morpholinopropane-1-sulfonic acid (MOPS) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES)) on Fe(II) uptake and oxidation by CCl(4) in aqueous suspensions of goethite. Significant sorption of these zwitterionic buffers occurred only at Fe(II)-loaded goethite but not at native goethite. The addition of MOPS and HEPES caused substantial release of Fe(II) from goethite, retarded the oxidation of surface-bound Fe(II) by CCl(4) and changed the reaction pathway as indicated by lower yields of CHCl(3). To explore electrostatic and steric contributions of MOPS and HEPES to the observed phenomena we studied sorption and competitive effects of model sorbates (Ca(2+), sulfonates) which suggest the formation of a complex between surface-bound Fe(II) and MOPS or HEPES. Our study shows for the first time that these frequently used zwitterionic organic buffers may interfere significantly with the surface chemistry and thus with redox reactions of Fe(II) at goethite. Hence, kinetic or mechanistic information obtained in such systems requires careful interpretation.

  3. Single peak parameters technique for simultaneous measurements: Spectrophotometric sequential injection determination of Fe(II) and Fe(III).

    PubMed

    Kozak, J; Paluch, J; Węgrzecka, A; Kozak, M; Wieczorek, M; Kochana, J; Kościelniak, P

    2016-02-01

    Spectrophotometric sequential injection system (SI) is proposed to automate the method of simultaneous determination of Fe(II) and Fe(III) on the basis of parameters of a single peak. In the developed SI system, sample and mixture of reagents (1,10-phenanthroline and sulfosalicylic acid) are introduced into a vessel, where in an acid environment (pH≅3) appropriate compounds of Fe(II) and Fe(III) with 1,10-phenanthroline and sulfosalicylic acid are formed, respectively. Then, in turn, air, sample, EDTA and sample again, are introduced into a holding coil. After the flow reversal, a segment of air is removed from the system by an additional valve and as EDTA replaces sulfosalicylic acid forming a more stable colorless compound with Fe(III), a complex signal is registered. Measurements are performed at wavelength 530 nm. The absorbance measured at minimum of the negative peak and the area or the absorbance measured at maximum of the signal can be used as measures corresponding to Fe(II) and Fe(III) concentrations, respectively. The time of the peak registration is about 2 min. Two-component calibration has been applied to analysis. Fe(II) and Fe(III) can be determined within the concentration ranges of 0.04-4.00 and 0.1-5.00 mg L(-1), with precision less than 2.8% and 1.7% (RSD), respectively and accuracy better than 7% (RE). The detection limit is 0.04 and 0.09 mg L(-1) for Fe(II) and Fe(III), respectively. The method was applied to analysis of artesian water samples.

  4. Variations of the 2-His-1-carboxylate theme in mononuclear non-heme FeII oxygenases.

    PubMed

    Straganz, G D; Nidetzky, B

    2006-10-01

    A facial triad of two histidine side chains and one aspartate or glutamate side chain forms the canonical metal-coordinating motif in the catalytic centers of various mononuclear non-heme Fe(II) enzymes. Although these active sites are based on totally unrelated protein folds and bring about a wide range of chemical transformations, most of them share the ability to couple dioxygen reduction with the oxygenation of an organic substrate. With the increasing number of protein structures now solved, it has become clear that the 2-His-1-carboxylate signature is less of a paradigm for non-heme Fe(II) active sites than had long been thought and that it can be replaced by alternative metal centers in various oxygenases, the structure-function relationships and proposed catalytic mechanisms of which are reviewed here. Metal coordination through three histidines and one glutamate constitutes the classical motif described for enzyme members of the cupin protein superfamily, such as aci-reductone dioxygenase and quercetin dioxygenase, multiple metal forms of which (including the Fe(II) type) are found in nature. Cysteine dioxygenase and diketone dioxygenase, which are strictly Fe(II)-dependent oxygenases based on the cupin fold, bind the catalytic metal through the homologous triad of histidines, but lack the fourth glutamate ligand. An alpha-ketoglutarate-dependent Fe(II) halogenase shows metal coordination by two histidines as the only protein-derived ligands, whilst carotene oxygenase, from a different protein fold family, features an Fe(II) site consisting of four histidine side chains. These recently discovered metallocenters are discussed with respect to their metal-binding properties and the reaction coordinates of the O(2)-dependent conversions they catalyze.

  5. A Central Role for Thiols in Plant Tolerance to Abiotic Stress

    PubMed Central

    Zagorchev, Lyuben; Seal, Charlotte E.; Kranner, Ilse; Odjakova, Mariela

    2013-01-01

    Abiotic stress poses major problems to agriculture and increasing efforts are being made to understand plant stress response and tolerance mechanisms and to develop new tools that underpin successful agriculture. However, the molecular mechanisms of plant stress tolerance are not fully understood, and the data available is incomplete and sometimes contradictory. Here, we review the significance of protein and non-protein thiol compounds in relation to plant tolerance of abiotic stress. First, the roles of the amino acids cysteine and methionine, are discussed, followed by an extensive discussion of the low-molecular-weight tripeptide, thiol glutathione, which plays a central part in plant stress response and oxidative signalling and of glutathione-related enzymes, including those involved in the biosynthesis of non-protein thiol compounds. Special attention is given to the glutathione redox state, to phytochelatins and to the role of glutathione in the regulation of the cell cycle. The protein thiol section focuses on glutaredoxins and thioredoxins, proteins with oxidoreductase activity, which are involved in protein glutathionylation. The review concludes with a brief overview of and future perspectives for the involvement of plant thiols in abiotic stress tolerance. PMID:23549272

  6. The Ascorbate-glutathione-α-tocopherol Triad in Abiotic Stress Response

    PubMed Central

    Szarka, András; Tomasskovics, Bálint; Bánhegyi, Gábor

    2012-01-01

    The life of any living organism can be defined as a hurdle due to different kind of stresses. As with all living organisms, plants are exposed to various abiotic stresses, such as drought, salinity, extreme temperatures and chemical toxicity. These primary stresses are often interconnected, and lead to the overproduction of reactive oxygen species (ROS) in plants, which are highly reactive and toxic and cause damage to proteins, lipids, carbohydrates and DNA, which ultimately results in oxidative stress. Stress-induced ROS accumulation is counteracted by enzymatic antioxidant systems and non-enzymatic low molecular weight metabolites, such as ascorbate, glutathione and α-tocopherol. The above mentioned low molecular weight antioxidants are also capable of chelating metal ions, reducing thus their catalytic activity to form ROS and also scavenge them. Hence, in plant cells, this triad of low molecular weight antioxidants (ascorbate, glutathione and α-tocopherol) form an important part of abiotic stress response. In this work we are presenting a review of abiotic stress responses connected to these antioxidants. PMID:22605990

  7. The use of metabolomics to dissect plant responses to abiotic stresses.

    PubMed

    Obata, Toshihiro; Fernie, Alisdair R

    2012-10-01

    Plant metabolism is perturbed by various abiotic stresses. As such the metabolic network of plants must be reconfigured under stress conditions in order to allow both the maintenance of metabolic homeostasis and the production of compounds that ameliorate the stress. The recent development and adoption of metabolomics and systems biology approaches enable us not only to gain a comprehensive overview, but also a detailed analysis of crucial components of the plant metabolic response to abiotic stresses. In this review we introduce the analytical methods used for plant metabolomics and describe their use in studies related to the metabolic response to water, temperature, light, nutrient limitation, ion and oxidative stresses. Both similarity and specificity of the metabolic responses against diverse abiotic stress are evaluated using data available in the literature. Classically discussed stress compounds such as proline, γ-amino butyrate and polyamines are reviewed, and the widespread importance of branched chain amino acid metabolism under stress condition is discussed. Finally, where possible, mechanistic insights into metabolic regulatory processes are discussed.

  8. Recent Molecular Advances on Downstream Plant Responses to Abiotic Stress

    PubMed Central

    dos Reis, Sávio Pinho; Lima, Aline Medeiros; de Souza, Cláudia Regina Batista

    2012-01-01

    Abiotic stresses such as extremes of temperature and pH, high salinity and drought, comprise some of the major factors causing extensive losses to crop production worldwide. Understanding how plants respond and adapt at cellular and molecular levels to continuous environmental changes is a pre-requisite for the generation of resistant or tolerant plants to abiotic stresses. In this review we aimed to present the recent advances on mechanisms of downstream plant responses to abiotic stresses and the use of stress-related genes in the development of genetically engineered crops. PMID:22942725

  9. The Reduction of Aqueous Metal Species on the Surfaces of Fe(II)-Containing Oxides: The Role of Surface Passivation

    USGS Publications Warehouse

    White, A.F.; Peterson, M.L.

    1998-01-01

    The reduction of aqueous transition metal species at the surfaces of Fe(II)- containing oxides has important ramifications in predicting the transport behavior in ground water aquifers. Experimental studies using mineral suspensions and electrodes demonstrate that structural Fe(II) heterogeneously reduces aqueous ferric, cupric, vanadate and chromate ions on magnetite and ilmenite surfaces. The rates of metal reduction on natural oxides is strongly dependent on the extent of surface passivation and redox conditions in the weathering environment. Synchrotron studies show that surface oxidation of Fe(II)-containing oxide minerals decreases their capacity for Cr(VI) reduction at hazardous waste disposal sites.

  10. Abiotic stress and the plant circadian clock

    PubMed Central

    Sanchez, Alfredo; Shin, Jieun

    2011-01-01

    In this review, we focus on the interaction between the circadian clock of higher plants to that of metabolic and physiological processes that coordinate growth and performance under a predictable, albeit changing environment. In this, the phytochrome and cryptochrome photoreceptors have shown to be important, but not essential for oscillator control under diurnal cycles of light and dark. From this foundation, we will examine how emerging findings have firmly linked the circadian clock, as a central mediator in the coordination of metabolism, to maintain homeostasis. This occurs by oscillator synchronization of global transcription, which leads to a dynamic control of a host of physiological processes. These include the determination of the levels of primary and secondary metabolites, and the anticipation of future environmental stresses, such as mid-day drought and midnight coldness. Interestingly, metabolic and stress cues themselves appear to feedback on oscillator function. In such a way, the circadian clock of plants and abiotic-stress tolerance appear to be firmly interconnected processes. PMID:21325898

  11. S-Nitrosylated proteins in pea (Pisum sativum L.) leaf peroxisomes: changes under abiotic stress

    PubMed Central

    Ortega-Galisteo, Ana P.; Rodríguez-Serrano, María; Pazmiño, Diana M.; Gupta, Dharmendra K.; Sandalio, Luisa M.; Romero-Puertas, María C.

    2012-01-01

    Peroxisomes, single-membrane-bounded organelles with essentially oxidative metabolism, are key in plant responses to abiotic and biotic stresses. Recently, the presence of nitric oxide (NO) described in peroxisomes opened the possibility of new cellular functions, as NO regulates diverse biological processes by directly modifying proteins. However, this mechanism has not yet been analysed in peroxisomes. This study assessed the presence of S-nitrosylation in pea-leaf peroxisomes, purified S-nitrosylated peroxisome proteins by immunoprecipitation, and identified the purified proteins by two different mass-spectrometry techniques (matrix-assisted laser desorption/ionization tandem time-of-flight and two-dimensional nano-liquid chromatography coupled to ion-trap tandem mass spectrometry). Six peroxisomal proteins were identified as putative targets of S-nitrosylation involved in photorespiration, β-oxidation, and reactive oxygen species detoxification. The activity of three of these proteins (catalase, glycolate oxidase, and malate dehydrogenase) is inhibited by NO donors. NO metabolism/S-nitrosylation and peroxisomes were analysed under two different types of abiotic stress, i.e. cadmium and 2,4-dichlorophenoxy acetic acid (2,4-D). Both types of stress reduced NO production in pea plants, and an increase in S-nitrosylation was observed in pea extracts under 2,4-D treatment while no total changes were observed in peroxisomes. However, the S-nitrosylation levels of catalase and glycolate oxidase changed under cadmium and 2,4-D treatments, suggesting that this post-translational modification could be involved in the regulation of H2O2 level under abiotic stress. PMID:22213812

  12. Modulation of thiamine metabolism in Zea mays seedlings under conditions of abiotic stress.

    PubMed

    Rapala-Kozik, Maria; Kowalska, Ewa; Ostrowska, Katarzyna

    2008-01-01

    The responses of plants to abiotic stress involve the up-regulation of numerous metabolic pathways, including several major routes that engage thiamine diphosphate (TDP)-dependent enzymes. This suggests that the metabolism of thiamine (vitamin B1) and its phosphate esters in plants may be modulated under various stress conditions. In the present study, Zea mays seedlings were used as a model system to analyse for any relation between the plant response to abiotic stress and the properties of thiamine biosynthesis and activation. Conditions of drought, high salt, and oxidative stress were induced by polyethylene glycol, sodium chloride, and hydrogen peroxide, respectively. The expected increases in the abscisic acid levels and in the activities of antioxidant enzymes including catalase, ascorbate peroxidase, and glutathione reductase were found under each stress condition. The total thiamine compound content in the maize seedling leaves increased under each stress condition applied, with the strongest effects on these levels observed under the oxidative stress treatment. This increase was also found to be associated with changes in the relative distribution of free thiamine, thiamine monophosphate (TMP), and TDP. Surprisingly, the activity of the thiamine synthesizing enzyme, TMP synthase, responded poorly to abiotic stress, in contrast to the significant enhancement found for the activities of the TDP synthesizing enzyme, thiamine pyrophosphokinase, and a number of the TDP/TMP phosphatases. Finally, a moderate increase in the activity of transketolase, one of the major TDP-dependent enzymes, was detectable under conditions of salt and oxidative stress. These findings suggest a role of thiamine metabolism in the plant response to environmental stress.

  13. Role of "electron shuttles" in the bioreduction of Fe(III) oxides in humid forest tropical soils.

    NASA Astrophysics Data System (ADS)

    Peretyazhko, T.; Sposito, G.

    2004-12-01

    Dissimilatory iron-reducing bacteria (DIRB) can reduce Fe(III) oxides either by direct contact between the organisms and the oxide surface or by indirect mechanisms not involving contact. These latter mechanisms can include (i) "electron shuttling" or (ii) soluble Fe(III) complexation with subsequent reduction. In the presence of humic substances, indirect Fe(III) reduction occurs, particularly by mechanism (i). Important electron-accepting groups in humic substances include quinone moieties, complexed Fe(III) and conjugated aromatic moieties. A model compound frequently used to study mechanism (i) is anthraquinone-2,6-disulfonate (AQDS), which is believed to function as an "electron shuttle" in a manner similar to humic substances. We are currently investigating Fe(III) reduction in humid tropical forest soils as affected by "electron shuttles," using AQDS and humic substances in our experiments. The soil samples were collected at the bottom of a toposequence in the Luquillo Experimental Forest, Puerto Rico. Development of anaerobic conditions in these soils occurs due to high precipitation and runoff water inputs. Fourteen-day anoxic incubations of soil suspensions amended with AQDS showed enhanced production of both soluble and particulate forms of Fe(II) as compared to non-amended soil suspensions. Our data indicated clearly that DIRB in the soil could utilize added "electron shuttles" effectively to reduce Fe(III). To examine factors controlling Fe(III) reduction by humic acid (HA), three IHSS HA samples (soil, peat and Leonardite) were both abiotically reduced by H2 treatment and microbially reduced by incubation with a filtrate from a soil suspension, then titrated with three different oxidants (iodine, cyanoferrate, and ferric citrate) to provide chemical and biological estimates of electron-accepting capacity at pH 5 and 7. The results will be discussed in terms of the three oxidants used, the properties of the HA samples, pH, and the effects of chemical

  14. The Promoter of AtUSP Is Co-regulated by Phytohormones and Abiotic Stresses in Arabidopsis thaliana

    PubMed Central

    Bhuria, Monika; Goel, Parul; Kumar, Sanjay; Singh, Anil K.

    2016-01-01

    Universal stress proteins (USPs) are known to be expressed in response to various abiotic stresses in a wide variety of organisms, such as bacteria, archaebacteria, protists, algae, fungi, plants, and animals. However, in plants, biological function of most of the USPs still remains obscure. In the present study, Arabidopsis USP gene (AtUSP) showed induction in response to abscisic acid (ABA) and various abiotic stresses viz. heat, dehydration, salt, osmotic, and cold stresses. Additionally, in silico analysis of AtUSP promoter identified several cis-elements responsive to phytohormones and abiotic stresses such as ABRE, ERE, DRE, and HSE, etc. To functionally validate the AtUSP promoter, the 1115 bp region of promoter was characterized under phytohormone and abiotic stress treatments. Deletion analysis of promoter was carried out by cloning the full length promoter (D0) and its three 5′ deletion derivatives, D1 (964 bp), D2 (660 bp), and D3 (503 bp) upstream of the β-glucuronidase (GUS) reporter gene, which were then stably transformed in Arabidopsis plants. The AtUSP promoter (D0) showed minimal activity under non-stress conditions which was enhanced in response to phytohormone treatments (ABA and ACC) and abiotic stresses such as dehydration, heat, cold, salt, and osmotic stresses. The seedlings harboring D1 and D2 deletion fragments showed constitutive GUS expression even under control condition with increased activity almost under all the treatments. However, D3 seedlings exhibited complete loss of activity under control condition with induction under ACC treatment, dehydration, heat, oxidative, salt, and osmotic stresses. Thus, present study clearly showed that AtUSP promoter is highly inducible by phytohormones and multiple abiotic stresses and it can be exploited as stress inducible promoter to generate multi-stress tolerant crops with minimal effects on their other important traits. PMID:28083000

  15. Improved Tolerance to Various Abiotic Stresses in Transgenic Sweet Potato (Ipomoea batatas) Expressing Spinach Betaine Aldehyde Dehydrogenase

    PubMed Central

    Fan, Weijuan; Zhang, Min; Zhang, Hongxia; Zhang, Peng

    2012-01-01

    Abiotic stresses are critical delimiters for the increased productivity and cultivation expansion of sweet potato (Ipomoea batatas), a root crop with worldwide importance. The increased production of glycine betaine (GB) improves plant tolerance to various abiotic stresses without strong phenotypic changes, providing a feasible approach to improve stable yield production under unfavorable conditions. The gene encoding betaine aldehyde dehydrogenase (BADH) is involved in the biosynthesis of GB in plants, and the accumulation of GB by the heterologous overexpression of BADH improves abiotic stress tolerance in plants. This study is to improve sweet potato, a GB accumulator, resistant to multiple abiotic stresses by promoted GB biosynthesis. A chloroplastic BADH gene from Spinacia oleracea (SoBADH) was introduced into the sweet potato cultivar Sushu-2 via Agrobacterium-mediated transformation. The overexpression of SoBADH in the transgenic sweet potato improved tolerance to various abiotic stresses, including salt, oxidative stress, and low temperature. The increased BADH activity and GB accumulation in the transgenic plant lines under normal and multiple environmental stresses resulted in increased protection against cell damage through the maintenance of cell membrane integrity, stronger photosynthetic activity, reduced reactive oxygen species (ROS) production, and induction or activation of ROS scavenging by the increased activity of free radical-scavenging enzymes. The increased proline accumulation and systemic upregulation of many ROS-scavenging genes in stress-treated transgenic plants also indicated that GB accumulation might stimulate the ROS-scavenging system and proline biosynthesis via an integrative mechanism. This study demonstrates that the enhancement of GB biosynthesis in sweet potato is an effective and feasible approach to improve its tolerance to multiple abiotic stresses without causing phenotypic defects. This strategy for trait improvement in

  16. Transgenic Alfalfa Plants Expressing the Sweetpotato Orange Gene Exhibit Enhanced Abiotic Stress Tolerance

    PubMed Central

    Wang, Zhi; Ke, Qingbo; Kim, Myoung Duck; Kim, Sun Ha; Ji, Chang Yoon; Jeong, Jae Cheol; Lee, Haeng-Soon; Park, Woo Sung; Ahn, Mi-Jeong; Li, Hongbing; Xu, Bingcheng; Deng, Xiping; Lee, Sang-Hoon; Lim, Yong Pyo; Kwak, Sang-Soo

    2015-01-01

    Alfalfa (Medicago sativa L.), a perennial forage crop with high nutritional content, is widely distributed in various environments worldwide. We recently demonstrated that the sweetpotato Orange gene (IbOr) is involved in increasing carotenoid accumulation and enhancing resistance to multiple abiotic stresses. In this study, in an effort to improve the nutritional quality and environmental stress tolerance of alfalfa, we transferred the IbOr gene into alfalfa (cv. Xinjiang Daye) under the control of an oxidative stress-inducible peroxidase (SWPA2) promoter through Agrobacterium tumefaciens-mediated transformation. Among the 11 transgenic alfalfa lines (referred to as SOR plants), three lines (SOR2, SOR3, and SOR8) selected based on their IbOr transcript levels were examined for their tolerance to methyl viologen (MV)-induced oxidative stress in a leaf disc assay. The SOR plants exhibited less damage in response to MV-mediated oxidative stress and salt stress than non-transgenic plants. The SOR plants also exhibited enhanced tolerance to drought stress, along with higher total carotenoid levels. The results suggest that SOR alfalfa plants would be useful as forage crops with improved nutritional value and increased tolerance to multiple abiotic stresses, which would enhance the development of sustainable agriculture on marginal lands. PMID:25946429

  17. Abiotic degradation of methyl parathion by manganese dioxide: Kinetics and transformation pathway.

    PubMed

    Liao, Xiaoping; Zhang, Caixiang; Liu, Yuan; Luo, Yinwen; Wu, Sisi; Yuan, Songhu; Zhu, Zhenli

    2016-05-01

    Methyl parathion, a widely used insecticide around the world, has aroused gradually extensive concern of researchers due to its degradation product such as methyl paraoxon, with higher toxicity for mammals and more recalcitrant. Given the ubiquity of manganese dioxide (MnO2) in soils and aquatic sediments, the abiotic degradation of methyl parathion by α-MnO2 was investigated in batch experiments. It was found that methyl parathion was decomposed up to 90% by α-MnO2 in 30 h and the removal efficiency of methyl parathion depended strongly on the loading of α-MnO2 and pH value in the solution where the reactions followed pseudo-first-order model well. The coexisting metal ions (such as Ca(2+), Mg(2+) and Mn(2+)) weakened markedly the degradation of methyl parathion by α-MnO2. However, the effect of dissolved organic matter (HA-Na) on reaction rates presented two sides: to improve hydrolysis rate but deteriorate oxidation rate of methyl parathion. Based on the degradation products identified by gas chromatography-mass spectrometer (GC/MS) and liquid chromatography high-resolution mass spectrometer (LC/HRMS), both hydrolysis and oxidation processes were proposed to be two predominant reaction mechanisms contributing to methyl parathion degradation by α-MnO2. This study provided meaningful information to elucidate the abiotic dissipation of methyl parathion by manganese oxide minerals in the environment.

  18. Circadian regulation of abiotic stress tolerance in plants

    PubMed Central

    Grundy, Jack; Stoker, Claire; Carré, Isabelle A.

    2015-01-01

    Extremes of temperatures, drought and salinity cause widespread crop losses throughout the world and impose severe limitations on the amount of land that can be used for agricultural purposes. Hence, there is an urgent need to develop crops that perform better under such abiotic stress conditions. Here, we discuss intriguing, recent evidence that circadian clock contributes to plants’ ability to tolerate different types of environmental stress, and to acclimate to them. The clock controls expression of a large fraction of abiotic stress-responsive genes, as well as biosynthesis and signaling downstream of stress response hormones. Conversely, abiotic stress results in altered expression and differential splicing of the clock genes, leading to altered oscillations of downstream stress-response pathways. We propose a range of mechanisms by which this intimate coupling between the circadian clock and environmental stress-response pathways may contribute to plant growth and survival under abiotic stress. PMID:26379680

  19. Abiotic stress responses in plant roots: a proteomics perspective

    PubMed Central

    Ghosh, Dipanjana; Xu, Jian

    2014-01-01

    Abiotic stress conditions adversely affect plant growth, resulting in significant decline in crop productivity. To mitigate and recover from the damaging effects of such adverse environmental conditions, plants have evolved various adaptive strategies at cellular and metabolic levels. Most of these strategies involve dynamic changes in protein abundance that can be best explored through proteomics. This review summarizes comparative proteomic studies conducted with roots of various plant species subjected to different abiotic stresses especially drought, salinity, flood, and cold. The main purpose of this article is to highlight and classify the protein level changes in abiotic stress response pathways specifically in plant roots. Shared as well as stressor-specific proteome signatures and adaptive mechanism(s) are simultaneously described. Such a comprehensive account will facilitate the design of genetic engineering strategies that enable the development of broad-spectrum abiotic stress-tolerant crops. PMID:24478786

  20. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

    PubMed

    Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

    2017-02-03

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  1. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

    NASA Astrophysics Data System (ADS)

    Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

    2017-02-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  2. Oxidative dissolution of UO2 in a simulated groundwater containing synthetic nanocrystalline mackinawite

    NASA Astrophysics Data System (ADS)

    Bi, Yuqiang; Hyun, Sung Pil; Kukkadapu, Ravi K.; Hayes, Kim F.

    2013-02-01

    The long-term success of in situ reductive immobilization of uranium (U) depends on the stability of U(IV) precipitates (e.g., uraninite) in the presence of natural oxidants, such as oxygen, Fe(III) hydroxides, and nitrite. Field and laboratory studies have implicated iron sulfide minerals as redox buffers or oxidant scavengers that may slow oxidation of reduced U(IV) solid phases. Yet, the inhibition mechanism(s) and reaction rates of uraninite (UO2) oxidative dissolution by oxic species such as oxygen in FeS-bearing systems remain largely unresolved. To address this knowledge gap, abiotic batch experiments were conducted with synthetic UO2 in the presence and absence of synthetic mackinawite (FeS) under simulated groundwater conditions of pH = 7, P = 0.02 atm, and P = 0.05 atm. The kinetic profiles of dissolved uranium indicate that FeS inhibited UO2 dissolution for about 51 h by effectively scavenging oxygen and keeping dissolved oxygen (DO) low. During this time period, oxidation of structural Fe(II) and S(-II) of FeS were found to control the DO levels, leading to the formation of iron oxyhydroxides and elemental sulfur, respectively, as verified by X-ray diffraction (XRD), Mössbauer, and X-ray absorption spectroscopy (XAS). After FeS was depleted due to oxidation, DO levels increased and UO2 oxidative dissolution occurred at an initial rate of rm = 1.2 ± 0.4 × 10-8 mol g-1 s-1, higher than rm = 5.4 ± 0.3 × 10-9 mol g-1 s-1 in the control experiment where FeS was absent. XAS analysis confirmed that soluble U(VI)-carbonato complexes were adsorbed by iron oxyhydroxides (i.e., nanogoethite and lepidocrocite) formed from FeS oxidation, which provided a sink for U(VI) retention. This work reveals that both the oxygen scavenging by FeS and the adsorption of U(VI) to FeS oxidation products may be important in U reductive immobilization systems subject to redox cycling events.

  3. An omics approach to understand the plant abiotic stress.

    PubMed

    Debnath, Mousumi; Pandey, Mukeshwar; Bisen, P S

    2011-11-01

    Abiotic stress can lead to changes in development, productivity, and severe stress and may even threaten survival of plants. Several environmental stresses cause drastic changes in the growth, physiology, and metabolism of plants leading to the increased accumulation of secondary metabolites. As medicinal plants are important sources of drugs, steps are taken to understand the effect of stress on the physiology, biochemistry, genomic, proteomic, and metabolic levels. The molecular responses of plants to abiotic stress are often considered as a complex process. They are mainly based on the modulation of transcriptional activity of stress-related genes. Many genes have been induced under stress conditions. The products of stress-inducible genes protecting against these stresses includes the enzymes responsible for the synthesis of various osmoprotectants. Genetic engineering of tolerance to abiotic stresses help in molecular understanding of pathways induced in response to one or more of the abiotic stresses. Systems biology and virtual experiments allow visualizing and understanding how plants work to overcome abiotic stress. This review discusses the omic approach to understand the plant response to abiotic stress with special emphasis on medicinal plant.

  4. Production and Isomeric Distribution of Xanthylium Cation Pigments and Their Precursors in Wine-like Conditions: Impact of Cu(II), Fe(II), Fe(III), Mn(II), Zn(II), and Al(III).

    PubMed

    Guo, Anque; Kontoudakis, Nikolaos; Scollary, Geoffrey R; Clark, Andrew C

    2017-03-09

    This study establishes the influence of Cu(II), Fe(II), Fe(III), Zn(II), Al(III), and Mn(II) on the oxidative production of xanthylium cations from (+)-catechin and either tartaric acid or glyoxylic acid in model wine systems. The reaction was studied at 25 °C using UHPLC and LC-HRMS for the analysis of phenolic products and their isomeric distribution. In addition to the expected products, a colorless product, tentatively assigned as a lactone, was detected for the first time. The results show the importance of Fe ions and a synergistic influence of Mn(II) in degrading tartaric acid to glyoxylic acid, whereas the other metal ions had minimal activity in this mechanistic step. Fe(II) and Fe(III) were shown to mediate the (+)-catechin-glyoxylic acid addition reaction, a role previously attributed to only Cu(II). Importantly, the study demonstrates that C-8 addition products of (+)-catechin are promoted by Cu(II), whereas C-6 addition products are promoted by Fe ions.

  5. Synthesis of Zn–Fe layered double hydroxides via an oxidation process and structural analysis of products

    SciTech Connect

    Morimoto, Kazuya; Tamura, Kenji; Anraku, Sohtaro; Sato, Tsutomu; Suzuki, Masaya; Yamada, Hirohisa

    2015-08-15

    The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. The product derived from the synthesis employing Fe(II) was found to transition to a Zn–Fe(III) layered double hydroxides phase following oxidation process. In contrast, the product obtained with Fe(III) did not contain a layered double hydroxides phase, but rather consisted of simonkolleite and hydrous ferric oxide. It was determined that the valency of the Fe reagent used in the initial synthesis affected the generation of the layered double hydroxides phase. Fe(II) species have ionic radii and electronegativities similar to those of Zn, and therefore are more likely to form trioctahedral hydroxide layers with Zn species. - Graphical abstract: The synthesis of Zn–Fe(III) layered double hydroxides was attempted, employing different pathways using either Fe(II) or Fe(III) species together with Zn as the initial reagents. - Highlights: • Iron valency affected the generation of Zn–Fe layered double hydroxides. • Zn–Fe layered double hydroxides were successfully synthesized using Fe(II). • Fe(II) species were likely to form trioctahedral hydroxide layers with Zn species.

  6. Effects of tillage on the Fe oxides activation in soil

    NASA Astrophysics Data System (ADS)

    Chi, Guangyu; Chen, Xin; Shi, Yi; Wang, Jun; Zheng, Taihui

    2009-07-01

    Since mid-1950s, the wetland ecosystems in Sanjiang Plain of Northeast China have been experiencing greater changes in land use, which had negative effects on the soil environments. This study assessed the effects of soil tillage on the activation of soil Fe in the region. The test ecosystems included natural wetland, paddy field and upland field converted from wetland. Soil samples at the depths of 0-10 cm, 10-20 cm, 20-30 cm, 30-40 cm, 40-60 cm, 60-90 cm and 90-120 cm were collected from each of the ecosystems for the analysis of vertical distribution of soil pH, organic carbon, chelate Fe oxides and Fe(II). The results showed that the conversion of wetland into paddy field and upland field induced a decrease of organic carbon content in 0-10 cm soil layer by 61.8% (P <0.05) and 70.0% (P < 0.05), respectively. The correlations among iron forms and soil organic carbon showed that chelate Fe oxides and Fe(II) was correlated positively with soil organic carbon and chelate ratio had a more positive relationship with organic carbon than chelate Fe oxides and Fe(II). The results of chelate Fe oxides, Fe(II) and chelate ratio of Fe suggested that reclamation could prevent the Fe activation and organic matter is credited for having an important influence on the process of Fe activation.

  7. Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: divergent reactions in the presence of organic ligands.

    PubMed

    Wang, Zhaohui; Bush, Richard T; Liu, Jianshe

    2013-11-01

    Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H2O2, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA<1:1), contrasting with the rapid oxidation of Fe(II) by O2 and H2O2 at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.

  8. HyPRP1 Gene Suppressed by Multiple Stresses Plays a Negative Role in Abiotic Stress Tolerance in Tomato

    PubMed Central

    Li, Jinhua; Ouyang, Bo; Wang, Taotao; Luo, Zhidan; Yang, Changxian; Li, Hanxia; Sima, Wei; Zhang, Junhong; Ye, Zhibiao

    2016-01-01

    Many hybrid proline-rich protein (HyPRP) genes respond to biotic and abiotic stresses in plants, but little is known about their roles other than as putative cell-wall structural proteins. A HyPRP1 gene encodes a protein with proline-rich domain, and an eight-cysteine motif was identified from our previous microarray experiments on drought-tolerant tomato. In this study, the expression of the HyPRP1 gene in tomato was suppressed under various abiotic stresses, such as drought, high salinity, cold, heat, and oxidative stress. Transgenic functional analysis showed no obvious changes in phenotypes, but enhanced tolerance to various abiotic stresses (e.g., oxidative stress, dehydration, and salinity) was observed in RNAi transgenic plants. Interestingly, several SO2 detoxification-related enzymes, including sulfite oxidase, ferredoxins (Fds), and methionine sulfoxide reductase A (Msr A), were revealed in HyPRP1-interacting proteins identified by Yeast Two-Hybrid screening. More sulfates and transcripts of Msr A and Fds were accumulated in HyPRP1 knockdown lines when wild-type plants were exposed to SO2 gas. Our findings illustrate that the tomato HyPRP1 is a negative regulator of salt and oxidative stresses and is probably involved in sulfite metabolism. PMID:27446190

  9. Formation of pristane from α-tocopherol under simulated anoxic sedimentary conditions: A combination of biotic and abiotic degradative processes

    NASA Astrophysics Data System (ADS)

    Rontani, Jean-François; Nassiry, Mina; Michotey, Valérie; Guasco, Sophie; Bonin, Patricia

    2010-01-01

    Incubation of intact and oxidized α-tocopherol (vitamin E) in anaerobic sediment slurries allowed us to demonstrate that, as previously suggested by Goossens et al. (1984), the degradation of α-tocopherol in anoxic sediments results in the formation of pristane. The conversion of α-tocopherol to this isoprenoid alkane involves a combination of biotic and abiotic degradative processes, i.e. the anaerobic biodegradation (which seems to be mainly induced by denitrifying bacteria) of trimeric structures resulting from the abiotic oxidation of α-tocopherol. On the basis of the results obtained, it is proposed that in the marine environment most of the α-tocopherol present in phytoplanktonic cells should be quickly degraded within the water column and the oxic zone of sediments by way of aerobic biodegradation, photo- and autoxidation processes. Abiotic transformation of this compound mainly results in the production of trimeric oxidation products, sufficiently stable to be incorporated into anoxic sediments and whose subsequent anaerobic bacterial degradation affords pristane. These results confirm that the ratio pristane to phytane cannot be used as an indicator of the oxicity of the environment of deposition; in contrast, they support the use of PFI (Pristane Formation Index) as a proxy for the state of diagenesis of sedimentary organic matter.

  10. Oxidative Dissolution of UO2 in a Simulated Groundwater Containing Synthetic Nanocrystalline Mackinawite

    SciTech Connect

    Bi, Yuqiang; Hyun, Sung Pil; Kukkadapu, Ravi K.; Hayes, Kim F.

    2013-02-01

    The long-term success of in situ reductive immobilization of uranium (U) depends on the stability of U(IV) precipitates (e.g., uraninite) under oxic conditions. Field and laboratory studies have implicated iron sulfide minerals as redox buffers or oxidant scavengers that may slow oxidation of reduced U(VI) solid phases by oxygen and Fe(III). Yet, the inhibition mechanism(s) and reaction rates of uraninite (UO2) oxidative dissolution by oxic species such as oxygen in FeS-bearing systems remain largely unresolved. To address this knowledge gap, abiotic batch experiments were conducted with synthetic UO2 in the presence and absence of synthetic mackinawite (FeS) under simulated groundwater conditions of pH = 7, PO2 = 0.02 atm, and PCO2 = 0.05 atm (equivalent to total dissolved carbonate of 0.01 M). The kinetic profiles of dissolved uranium indicate that FeS inhibited UO2 dissolution for 51 hr by effectively scavenging oxygen and keeping dissolved oxygen (DO) low. During this time period, oxidation of structural Fe(II) and S(-II) of FeS were found to control the DO levels, leading to the formation of iron oxyhydroxides and elemental sulfur, respectively, as verified by X-ray diffraction (XRD), Mössbauer and X-ray absorption spectroscopy (XAS). After FeS was depleted due to oxidation, DO levels increased and UO2 oxidative dissolution occurred at an initial rate of rm = 1.2 ± 0.4 ×10-8 mol•g-1•s-1, higher than rm = 5.4 ± 0.3 ×10-9 mol•g-1•s-1 in the control experiment where FeS was absent. Soluble U(VI) products were adsorbed by iron oxyhydroxides (i.e. nanogoethite and ferrihydrite) formed from FeS oxidation, which facilitated the detachment of U(VI) surface complexes and more rapid dissolution of UO2. XAS analysis confirmed the adsorption of U(VI) species, and also showed that U(VI) was not significantly incorporated into iron oxyhydroxide structure. This work reveals that both the oxygen scavenging by FeS and the adsorption of U(VI) to FeS oxidation

  11. Fluorinated Dodecaphenylporphyrins: Synthetic and Electrochemical Studies Including the First Evidence of Intramolecular Electron Transfer Between an Fe(II) Porphyrin -Anion Radical and an Fe(I) Porphyrin

    SciTech Connect

    D'Souza, F.; Forsyth, T.P.; Fukuzumi, S.; Kadish, K.M.; Krattinger, B.; Lin, M.; Medforth, C.J.; Nakanishi, I.; Nurco, D.J.; Shelnutt, J.A.; Smith, K.M.; Van Caemelbecke, E.

    1998-10-19

    Dodecaphenylporphyrins with varying degrees of fluorination of the peripheral phenyl rings (FXDPPS) were synthesized as model compounds for studying electronic effects in nonplan~ porphyrins, and detailed electrochemical studies of the chloroiron(HI) complexes of these compounds were undertaken. The series of porphyrins, represented as FeDPPCl and as FeFXDPPCl where x = 4, 8 (two isomers), 12, 20,28 or 36, could be reversibly oxidized by two electrons in dichloromethane to give n-cation radicals and n-dications. All of the compounds investigated could also be reduced by three electrons in benzonitrile or pyridine. In benzonitrile, three reversible reductions were observed for the unfluorinated compound FeDPPC1, whereas the FeFXDPPCl complexes generally exhibited irreversible first and second reductions which were coupled to chemical reactions. The chemical reaction associated with the first reduction involved a loss of the chloride ion after generation of Fe FXDPPC1. The second chemical reaction involved a novel intramolecular electron transfer between the initially generated Fe(H) porphyrin n-anion radical and the final Fe(I) porphyrin reduction product. In pyridine, three reversible one electron reductions were observed with the second reduction affording stable Fe(II) porphyrin o - anion radicals for ail of the complexes investigated.

  12. Chiral Hydroxylation at the Mononuclear Nonheme Fe(II) Center of 4-(S) Hydroxymandelate Synthase – A Structure-Activity Relationship Analysis

    PubMed Central

    Di Giuro, Cristiana M. L.; Konstantinovics, Cornelia; Rinner, Uwe; Nowikow, Christina; Leitner, Erich; Straganz, Grit D.

    2013-01-01

    (S)-Hydroxymandelate synthase (Hms) is a nonheme Fe(II) dependent dioxygenase that catalyzes the oxidation of 4-hydroxyphenylpyruvate to (S)-4-hydroxymandelate by molecular oxygen. In this work, the substrate promiscuity of Hms is characterized in order to assess its potential for the biosynthesis of chiral α-hydroxy acids. Enzyme kinetic analyses, the characterization of product spectra, quantitative structure activity relationship (QSAR) analyses and in silico docking studies are used to characterize the impact of substrate properties on particular steps of catalysis. Hms is found to accept a range of α-oxo acids, whereby the presence of an aromatic substituent is crucial for efficient substrate turnover. A hydrophobic substrate binding pocket is identified as the likely determinant of substrate specificity. Upon introduction of a steric barrier, which is suspected to obstruct the accommodation of the aromatic ring in the hydrophobic pocket during the final hydroxylation step, the racemization of product is obtained. A steady state kinetic analysis reveals that the turnover number of Hms strongly correlates with substrate hydrophobicity. The analysis of product spectra demonstrates high regioselectivity of oxygenation and a strong coupling efficiency of C-C bond cleavage and subsequent hydroxylation for the tested substrates. Based on these findings the structural basis of enantioselectivity and enzymatic activity is discussed. PMID:23935907

  13. Ab Initio Modeling of Fe(II) Adsorption and Interfacial Electron Transfer at Goethite (α-FeOOH) Surfaces

    SciTech Connect

    Alexandrov, Vitali Y.; Rosso, Kevin M.

    2015-01-01

    Goethite (α-FeOOH) surfaces represent one of the most ubiquitous redox-active interfaces in the environment, playing an important role in biogeochemical metal cycling and contaminant residence in the subsurface. Fe(II)-catalyzed recrystallization of goethite is a fundamental process in this context, but the proposed Fe(II)aq-Fe(III)goethite electron and iron atom exchange mechanism of recrystallization remains poorly understood at the atomic level. We examine the adsorption of aqueous Fe(II) and subsequent interfacial electron transfer (ET) between adsorbed Fe(II) and structural Fe(III) at the (110) and (021) goethite surfaces using density functional theory calculations including Hubbard U corrections (DFT+U) aided by ab initio molecular dynamics simulations. We investigate various surface sites for the adsorption of Fe2+(H2O)6 in different coordination environments. Calculated energies for adsorbed complexes at both surfaces favor monodentate complexes with reduced 4- and 5-fold coordination over higher-dentate structures and 6- fold coordination. The hydrolysis of H2O ligands is observed for some pre-ET adsorbed Fe(II) configurations. ET from the adsorbed Fe(II) into the goethite lattice is calculated to be energetically uphill always, but simultaneous proton transfer from H2O ligands of the adsorbed complexes to the surface oxygen species stabilizes post-ET states. We find that surface defects such as oxygen vacancies near the adsorption site also can stabilize post-ET states, enabling the Fe(II)aq-Fe(III)goethite interfacial electron transfer reaction implied from experiments to proceed.

  14. A new family of diamagnetic macrocyclic Fe(II) compounds exhibiting the LIESST effect at high temperatures.

    PubMed

    Wang, Hongfeng; Desplanches, Cédric; Dagault, Philippe; Létard, Jean-François

    2014-11-07

    The photomagnetic properties of a new Fe(II) macrocyclic family [Fe(L(xyz)N5)(CN)2]·nH2O were investigated with respect to the T(LIESST) versus T(1/2) relationship. These compounds are diamagnetic below 400 K with T(LIESST) values above 100 K, which indicates that this family presents an unconventional LIESST effect that is much higher than the expected T0 = 180 K line for macrocyclic complexes.

  15. Chemical and biological reduction of Mn (III)-pyrophosphate complexes: Potential importance of dissolved Mn (III) as an environmental oxidant

    NASA Astrophysics Data System (ADS)

    Kostka, Joel E.; Luther, George W., III; Nealson, Kenneth H.

    1995-03-01

    Dissolved Mn (III) is a strong oxidant which could play an important role in the biogeochemistry of aquatic environments, but little is known about this form of Mn. Mn(III) was shown to form a stable complex with pyrophosphate which is easily measured by uv-vis spectrophotometry. The Mn(III)-pyrophosphate complex was produced at concentrations of 5 μM to 10 mM Mn at neutral pH. Inorganic electron donors, Fe(II) and sulfide, abiotically reduced Mn(III)-pyrophosphate in seconds with a stoichiometry of 1:1 and near 1:2 reductant:Mn (III), respectively. Shewanella putrefaciens strain MR-1 catalyzed the reduction of Mn(III)-pyrophosphate with formate or lactate as electron donors. Reduction of Mn(III) catalyzed by MR-1 was inhibited under aerobic conditions but only slightly under anaerobic conditions upon addition of the alternate electron acceptor, nitrate. MR-1 catalyzed reduction was also inhibited by metabolic inhibitors including formaldehyde, tetrachlorosalicylanilide (TCS), carbonyl cyanide m-chlorophenylhydrazone (CCCP), 2- n-heptyl-4-hydroxyquinoline N-oxide (HQNO), but not antimycin A. When formate or lactate served as electron donor for Mn(III) reduction, carbon oxidation to CO 2 was coupled to the respiration of Mn (III). Using the incorporation of 3H-leucine into the TCA-insoluble fraction of culture extracts, it was shown that Mn (III) reduction was coupled to protein synthesis in MR-1. These data indicate that Mn (III) complexes may be produced under conditions found in aquatic environments and that the reduction of Mn(III) can be coupled to the cycling of Fe, S, and C.

  16. Sorption of As(V) on aluminosilicates treated with Fe(II) nanoparticles.

    PubMed

    Dousová, Barbora; Grygar, Tomás; Martaus, Alexandr; Fuitová, Lucie; Kolousek, David; Machovic, Vladimír

    2006-10-15

    Adsorption of arsenic on clay surfaces is important for the natural and simulated removal of arsenic species from aqueous environments. In this investigation, three samples of clay minerals (natural metakaoline, natural clinoptilolite-rich tuff, and synthetic zeolite) in both untreated and Fe-treated forms were used for the sorption of arsenate from model aqueous solution. The treatment of minerals consisted of exposing them to concentrated solution of Fe(II). Within this process the mineral surface has been laden with Fe(III) oxi(hydroxides) whose high affinity for the As(V) adsorption is well known. In all investigated systems the sorption capacity of Fe(II)-treated sorbents increased significantly in comparison to the untreated material (from about 0.5 to >20.0 mg/g, which represented more than 95% of the total As removal). The changes of Fe-bearing particles in the course of treating process and subsequent As sorption were investigated by the diffuse reflectance spectroscopy and the voltammetry of microparticles. IR spectra of treated and As(V)-saturated solids showed characteristic bands caused by Fe(III)SO(4), Fe(III)O, and AsO vibrations. In untreated As(V)-saturated solids no significant AsO vibrations were observed due to the negligible content of sorbed arsenate.

  17. New technique for online measurement of water-soluble Fe(II) in atmospheric aerosols.

    PubMed

    Rastogi, Neeraj; Oakes, Michelle M; Schauer, James J; Shafer, Martin M; Majestic, Brian J; Weber, Rodney J

    2009-04-01

    A prototype instrument has been developed for online analysis of water-soluble Fe(II) (WS_Fe(II)) in atmospheric aerosols using a particle-into-liquid-sampler (PILS), which concentrates particles into a small flow of purified water, coupled with a liquid waveguide capillary cell (LWCC) and absorbance spectrophotometryto detect iron-ferrozine colored complexes. The analytical method is highly precise (<3% RSD), and the overall measurement uncertainty and limit of detection for the complete PILS-LWCC system are estimated at 12% and 4.6 ng m(-3), respectively. The online measurements compared well with those of 24 h integrated filter samples collected at two different sampling sites (n=27, R2 = 0.82, slope 0.90 +/- 0.08, and intercept 3.08 +/- 1.99 ng m(-3)). In urban Atlanta, fine particle WS_Fe(II) concentrations measured every 12 min exhibited large variability, ranging from below the detection limit (4.6) to 370 ng m(-3) during a 24 day period in June 2008. This instrument provides new capabilities for investigating the sources and atmospheric processing of fine particle WS_Fe(II) and may prove useful in studies ranging from effects of particle WS_Fe(II) on human health to effects of particle WS_Fe(II) on atmospheric chemistry and ocean biogeochemistry.

  18. Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands.

    PubMed

    Barrios, Leoní A; Bartual-Murgui, Carlos; Peyrecave-Lleixà, Eugènia; Le Guennic, Boris; Teat, Simon J; Roubeau, Olivier; Aromí, Guillem

    2016-05-02

    We show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L')](ClO4)2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H4L1)(Cl-tpy)](ClO4)2·C3H6O (1), [Fe(H2L3)(Me3bpp)](ClO4)2·C3H6O (2), [Fe(H4L1)(2bbp)](ClO4)2·3C3H6O (3). Structural studies demonstrate that 1 is in the low-spin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) state down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H4L1)(2bbp)](ClO4)2 (3a), through a single-crystal-to-single-crystal transformation. This guest extrusion process is accompanied by a spin switch, from HS to LS.

  19. The role of biogenic Fe-Mn oxides formed in situ for arsenic oxidation and adsorption in aquatic ecosystems.

    PubMed

    Bai, Yaohui; Yang, Tingting; Liang, Jinsong; Qu, Jiuhui

    2016-07-01

    As(III&V), Mn(II), and Fe(II) may occur simultaneously in some groundwater and surface water. Studying their redox reactions and interactions is essential to unravel the biogeochemical cycles of these metal ions in aquatic ecosystems and to find effective methods to remove them simultaneously in drinking water treatment. Here, the formation of biogenic Fe-Mn oxides (BFMO, defined as a mixture of biogenic Mn oxide (BMO) and Fe oxide) as well as its oxidation and adsorption of As in a Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe (Pseudomonas sp. QJX-1) system were investigated. Batch experiments and structure characterization revealed that the BFMO was formed via a sequential precipitation of Fe oxide and BMO. The first formed Fe oxide was identified as FeOOH (lepidocrocite) and the latter formed BMO was identified as MnO2 (similar to hexagonal birnessite). In the BFMO mixture, the BMO part was mainly responsible for As(III) oxidation, and the Fe oxide part dominated As adsorption. Remarkably, the BMO could oxidize Fe(II) to form FeOOH, which may improve As adsorption. The optimum Mn(II)/Fe(II) ratio for As removal was approximately 1:3 (mol/mol). Taken together, in Fe(II)-Mn(II)-As(III&V)-Mn-oxidizing microbe ecosystems, the in situ formation of BFMO could eliminate or decrease Fe(II), Mn(II), and As(III&V) species simultaneously. Therefore, based on this study, new approaches may be developed for As removal from water containing high concentrations of Fe(II) and Mn(II).

  20. Chelation of Cu(II), Zn(II), and Fe(II) by tannin constituents of selected edible nuts.

    PubMed

    Karamać, Magdalena

    2009-12-22

    The tannin fractions isolated from hazelnuts, walnuts and almonds were characterised by colorimetric assays and by an SE-HPLC technique. The complexation of Cu(II) and Zn(II) was determined by the reaction with tetramethylmurexide, whereas for Fe(II), ferrozine was employed. The walnut tannins exhibited a significantly weaker reaction with the vanillin/HCl reagent than hazelnut and almond tannins, but the protein precipitation capacity of the walnut fraction was high. The SE-HPLC chromatogram of the tannin fraction from hazelnuts revealed the presence of oligomers with higher molecular weights compared to that of almonds. Copper ions were most effectively chelated by the constituents of the tannin fractions of hazelnuts, walnuts and almonds. At a 0.2 mg/assay addition level, the walnut tannins complexed almost 100% Cu(II). The Fe(II) complexation capacities of the tannin fractions of walnuts and hazelnuts were weaker in comparison to that of the almond tannin fraction, which at a 2.5 mg/assay addition level, bound Fe(II) by approximately 90%. The capacity to chelate Zn(II) was quite varied for the different nut tannin fractions: almond tannins bound as much as 84% Zn(II), whereas the value for walnut tannins was only 8.7%; and for hazelnut tannins, no Zn(II) chelation took place at the levels tested.

  1. Ethanolic extract of Nigella sativa protects Fe(II) induced lipid peroxidation in rat's brain, kidney and liver homogenates.

    PubMed

    Hassan, Waseem; Noreen, Hamsa; Khalil, ShafqatUllah; Hussain, Arshad; Rehman, Shakilla; Sajjad, Shagufta; Rahman, Ataur; da Rocha, Joao B T

    2016-01-01

    The study describes the effect of ethanolic extract of Nigella sativa against Fe(II) induced lipid peroxidation. Basal and Fe(II) induced thiobarbituric acid reactive species (TBARS) production was significantly inhibited by the ethanolic extract of Nigella sativa at 25-200 μg/ml. Our data revealed that the extract has high DPPH radical scavenging activity at highest tested concentrations. The extract significantly chelated Fe(II) and scavenged hydroxyl (OH) radical at 25-200μg/ml concentration. The nutritional analysis was performed and carbohydrate, fats, fiber, protein, moisture and ash content were measured in the studied extract. The phytochemical analysis confirmed the presence of alkaloid, carbohydrate & sugar, glycosides, phenolic compounds, flavonoids, protein and amino acid, phytosterols, tannins, gum and mucilage. The extract also showed significant antimicrobial activities against 10 bacterial strains i.e. Salmonella typhi, Bacillus subtilis, Bacillus cereus, Klebsiella pneumonia, Escheria coli, Xanthomonas, Salmonella heidelberg, Staphylococcus aureus, Clostridium and Escheria coli (human) and 5 fungal strains i.e. Aspergillus niger, Entomola, Aspergillus flavus, Alternaria alternata and Penicillium. This study confirms the potential antioxidant and antimicrobial activities of ethanolic extract of Nigella sativa which can be considered not only as a diet supplement but can be used against a variety of free radical induced damage diseases.

  2. New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique.

    PubMed

    Kozak, J; Gutowski, J; Kozak, M; Wieczorek, M; Kościelniak, P

    2010-05-23

    The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength lambda=530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic "cut off" peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 2(2) factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L(-1) of both analytes, respectively.

  3. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    NASA Astrophysics Data System (ADS)

    van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

    2014-05-01

    Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone

  4. Molar Absorptivity and Concentration-Dependent Quantum Yield of Fe(II) Photo-Formation for the Aqueous Solutions of Fe(III)-Dicarboxylate Complexes

    NASA Astrophysics Data System (ADS)

    Hitomi, Y.; Arakaki, T.

    2009-12-01

    Redox cycles of iron in the aquatic environment affect formation of reactive oxygen species such as hydrogen peroxide and hydroxyl radicals, which in turn determines lifetimes of many organic compounds. Although aqueous Fe(III)-dicarboxylate complexes are considered to be important sources of photo-formed Fe(II), molar absorptivity and quantum yield of Fe(II) formation for individual species are not well understood. We initiated a study to characterize Fe(II) photo-formation from Fe(III)-dicarboxylates with the concentration ranges that are relevant to the natural aquatic environment. The Visual MINTEQ computer program was used to calculate the equilibrium concentrations of individual Fe(III)-dicarboxylate species. The molar absorptivity of Fe(III)-dicarboxylate species was obtained by UV-VIS spectrophotometer, and the product of the quantum yield and the molar absorptivity of Fe(III)-dicarboxylate species were obtained from photochemical experiments. These experimental data were combined with the calculated equilibrium Fe(III)-dicarboxylate concentrations to determine individual molar absorptivity and quantum yield of Fe(II) photo-formation for a specific Fe(III)-dicarboxylate species. We used initial concentrations of less than 10 micromolar Fe(III) to study the photochemical formation of Fe(II). Dicarboxylate compounds studied include oxalate, malonate, succinate, malate, and phthalate. We report molar absorptivity and concentration-dependent quantum yields of Fe(II) photo-formation of individual Fe(III)-dicarboxylates.

  5. Plant cell organelle proteomics in response to abiotic stress.

    PubMed

    Hossain, Zahed; Nouri, Mohammad-Zaman; Komatsu, Setsuko

    2012-01-01

    Proteomics is one of the finest molecular techniques extensively being used for the study of protein profiling of a given plant species experiencing stressed conditions. Plants respond to a stress by alteration in the pattern of protein expression, either by up-regulating of the existing protein pool or by the synthesizing novel proteins primarily associated with plants antioxidative defense mechanism. Improved protein extraction protocols and advance techniques for identification of novel proteins have been standardized in different plant species at both cellular and whole plant level for better understanding of abiotic stress sensing and intracellular stress signal transduction mechanisms. In contrast, an in-depth proteome study of subcellular organelles could generate much detail information about the intrinsic mechanism of stress response as it correlates the possible relationship between the protein abundance and plant stress tolerance. Although a wealth of reviews devoted to plant proteomics are available, review articles dedicated to plant cell organelle proteins response under abiotic stress are very scanty. In the present review, an attempt has been made to summarize all significant contributions related to abiotic stresses and their impacts on organelle proteomes for better understanding of plants abiotic stress tolerance mechanism at protein level. This review will not only provide new insights into the plants stress response mechanisms, which are necessary for future development of genetically engineered stress tolerant crop plants for the benefit of humankind, but will also highlight the importance of studying changes in protein abundance within the cell organelles in response to abiotic stress.

  6. The impact of abiotic factors on cellulose synthesis.

    PubMed

    Wang, Ting; McFarlane, Heather E; Persson, Staffan

    2016-01-01

    As sessile organisms, plants require mechanisms to sense and respond to changes in their environment, including both biotic and abiotic factors. One of the most common plant adaptations to environmental changes is differential regulation of growth, which results in growth either away from adverse conditions or towards more favorable conditions. As cell walls shape plant growth, this differential growth response must be accompanied by alterations to the plant cell wall. Here, we review the impact of four abiotic factors (osmotic conditions, ionic stress, light, and temperature) on the synthesis of cellulose, an important component of the plant cell wall. Understanding how different abiotic factors influence cellulose production and addressing key questions that remain in this field can provide crucial information to cope with the need for increased crop production under the mounting pressures of a growing world population and global climate change.

  7. Integrated metabolomics for abiotic stress responses in plants.

    PubMed

    Nakabayashi, Ryo; Saito, Kazuki

    2015-04-01

    Plants are considered to biosynthesize specialized (traditionally called secondary) metabolites to adapt to environmental stresses such as biotic and abiotic stresses. The majority of specialized metabolites induced by abiotic stress characteristically exhibit antioxidative activity in vitro, but their function in vivo is largely yet to be experimentally confirmed. In this review, we highlight recent advances in the identification of the role of abiotic stress-responsive specialized metabolites with an emphasis on flavonoids. Integrated 'omics' analysis, centered on metabolomics with a series of plant resources differing in their flavonoid accumulation, showed experimentally that flavonoids play a major role in antioxidation in vivo. In addition, the results also suggest the role of flavonoids in the vacuole. To obtain more in-depth insights, chemical and biological challenges need to be addressed for the identification of unknown specialized metabolites and their in vivo functions.

  8. Abiotic methane formation during experimental serpentinization of olivine.

    PubMed

    McCollom, Thomas M

    2016-12-06

    Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH4). In many cases, the CH4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH4 synthesis have been observed. Here, the potential for abiotic formation of CH4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A (13)C-labeled inorganic carbon source was used to unambiguously determine the origin of CH4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH4 was observed in one experiment performed under conditions that allowed an H2-rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH4.

  9. Strategies to ameliorate abiotic stress-induced plant senescence.

    PubMed

    Gepstein, Shimon; Glick, Bernard R

    2013-08-01

    The plant senescence syndrome resembles, in many molecular and phenotypic aspects, plant responses to abiotic stresses. Both processes have an enormous negative global agro-economic impact and endanger food security worldwide. Premature plant senescence is the main cause of losses in grain filling and biomass yield due to leaf yellowing and deteriorated photosynthesis, and is also responsible for the losses resulting from the short shelf life of many vegetables and fruits. Under abiotic stress conditions the yield losses are often even greater. The primary challenge in agricultural sciences today is to develop technologies that will increase food production and sustainability of agriculture especially under environmentally limiting conditions. In this chapter, some of the mechanisms involved in abiotic stress-induced plant senescence are discussed. Recent studies have shown that crop yield and nutritional values can be altered as well as plant stress tolerance through manipulating the timing of senescence. It is often difficult to separate the effects of age-dependent senescence from stress-induced senescence since both share many biochemical processes and ultimately result in plant death. The focus of this review is on abiotic stress-induced senescence. Here, a number of the major approaches that have been developed to ameliorate some of the effects of abiotic stress-induced plant senescence are considered and discussed. Some approaches mimic the mechanisms already used by some plants and soil bacteria whereas others are based on development of new improved transgenic plants. While there may not be one simple strategy that can effectively decrease all losses of crop yield that accrue as a consequence of abiotic stress-induced plant senescence, some of the strategies that are discussed already show great promise.

  10. Abiotic methane formation during experimental serpentinization of olivine

    NASA Astrophysics Data System (ADS)

    McCollom, Thomas M.

    2016-12-01

    Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH4). In many cases, the CH4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH4 synthesis have been observed. Here, the potential for abiotic formation of CH4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13C-labeled inorganic carbon source was used to unambiguously determine the origin of CH4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH4 was observed in one experiment performed under conditions that allowed an H2-rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH4.

  11. Starch as a determinant of plant fitness under abiotic stress.

    PubMed

    Thalmann, Matthias; Santelia, Diana

    2017-03-09

    I. II. III. IV. V. VI. References SUMMARY: Abiotic stresses, such as drought, high salinity and extreme temperatures, pose one of the most important constraints to plant growth and productivity in many regions of the world. A number of investigations have shown that plants, including several important crops, remobilize their starch reserve to release energy, sugars and derived metabolites to help mitigate the stress. This is an essential process for plant fitness with important implications for plant productivity under challenging environmental conditions. In this Tansley insight, we evaluate the current literature on starch metabolism in response to abiotic stresses, and discuss the key enzymes involved and how they are regulated.

  12. Effects of chloride and sulfate on the rate of oxidation of ferrous ion by H2O2.

    PubMed

    Truong, Giang Le; De Laat, Joseph; Legube, Bernard

    2004-05-01

    The rates of oxidation of Fe(II) by H(2)O(2) in the presence of sodium perchlorate, sodium nitrate, sodium chloride and sodium sulfate salts (0-1M) have been compared in the study. Experiments were carried out in a batch reactor, in the dark, at pH <3, 25+/-0.5 degrees C and at controlled ionic strength (< or =1M). The experimental results showed that the rates of oxidation of Fe(II) in the presence of chloride, nitrate and perchlorate were identical. In the presence of sulfate, the rate of oxidation of Fe(II) was faster and depended on the pH and the concentration of sulfate. The pseudo second-order rate constants for the reaction of H(2)O(2) with Fe(2+), FeCl(+) and FeSO(4) were determined as 55+/-1, 55+/-1 and 78+/-3 M(-1) s(-1), respectively.

  13. Methemoglobinemia caused by 8-aminoquinoline drugs: DFT calculations suggest an analogy to H4B's role in nitric oxide synthase

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We suggest a possible mechanism of how 8-aminoquinolines (8-AQ's) cause hemotoxicity by oxidizing hemoglobin to methemoglobin. In our DFT calculations, we found that 5-hydroxyprimaquine is able to donate an electron to O2 to facilitate its conversion to H2O2. Meanwhile, Fe(II) is oxidized to Fe(III)...

  14. Mechanisms and Dynamics of Abiotic and Biotic Interactions at Environmental Interfaces

    SciTech Connect

    Roso, Kevin M.

    2006-06-01

    The Stanford EMSI (SEMSI) was established in 2004 through joint funding by the National Science Foundation and the OBER-ERSD. It encompasses a number of universities and national laboratories. The PNNL component of the SEMSI is funded by ERSD and is the focus of this report. This component has the objective of providing theory support to the SEMSI by bringing computational capabilities and expertise to bear on important electron transfer problems at mineral/water and mineral/microbe interfaces. PNNL staff member Dr. Kevin Rosso, who is also ''matrixed'' into the Environmental Molecular Sciences Laboratory (EMSL) at PNNL, is a co-PI on the SEMSI project and the PNNL lead. The EMSL computational facilities being applied to the SEMSI project include the 11.8 teraflop massively-parallel supercomputer. Science goals of this EMSL/SEMSI partnership include advancing our understanding of: (1) The kinetics of U(VI) and Cr(VI) reduction by aqueous and solid-phase Fe(II), (2) The structure of mineral surfaces in equilibrium with solution, and (3) Mechanisms of bacterial electron transfer to iron oxide surfaces via outer-membrane cytochromes.

  15. Guest-, Light- and Thermally-Modulated Spin Crossover in [Fe(II) 2 ] Supramolecular Helicates.

    PubMed

    Darawsheh, Mohanad; Barrios, Leoni A; Roubeau, Olivier; Teat, Simon J; Aromí, Guillem

    2016-06-13

    A new bis(pyrazolylpyridine) ligand (H2 L) has been prepared to form functional [Fe2 (H2 L)3 ](4+) metallohelicates. Changes to the synthesis yield six derivatives, X@[Fe2 (H2 L)3 ]X(PF6 )2 ⋅xCH3 OH (1, x=5.7 and X=Cl; 2, x=4 and X=Br), X@[Fe2 (H2 L)3 ]X(PF6 )2 ⋅yCH3 OH⋅H2 O (1 a, y=3 and X=Cl; 2 a, y=1 and X=Br) and X@[Fe2 (H2 L)3 ](I3 )2 ⋅3 Et2 O (1 b, X=Cl; 2 b, X=Br). Their structure and functional properties are described in detail by single-crystal X-ray diffraction experiments at several temperatures. Helicates 1 a and 2 a are obtained from 1 and 2, respectively, by a single-crystal-to-single-crystal mechanism. The three possible magnetic states, [LS-LS], [LS-HS], and [HS-HS] can be accessed over large temperature ranges as a result of the structural nonequivalence of the Fe(II) centers. The nature of the guest (Cl(-) vs. Br(-) ) shifts the spin crossover (SCO) temperature by roughly 40 K. Also, metastable [LS-HS] or [HS-HS] states are generated through irradiation. All helicates (X@[Fe2 (H2 L)3 ])(3+) persist in solution.

  16. Spin Crossover in Fe(II) Complexes with N4S2 Coordination.

    PubMed

    Arroyave, Alejandra; Lennartson, Anders; Dragulescu-Andrasi, Alina; Pedersen, Kasper S; Piligkos, Stergios; Stoian, Sebastian A; Greer, Samuel M; Pak, Chongin; Hietsoi, Oleksandr; Phan, Hoa; Hill, Stephen; McKenzie, Christine J; Shatruk, Michael

    2016-06-20

    Reactions of Fe(II) precursors with the tetradentate ligand S,S'-bis(2-pyridylmethyl)-1,2-thioethane (bpte) and monodentate NCE(-) coligands afforded mononuclear complexes [Fe(bpte)(NCE)2] (1, E = S; 2, E = Se; 3, E = BH3) that exhibit temperature-induced spin crossover (SCO). As the ligand field strength increases from NCS(-) to NCSe(-) to NCBH3(-), the SCO shifts to higher temperatures. Complex 1 exhibits only a partial (15%) conversion from the high-spin (HS) to the low-spin (LS) state, with an onset around 100 K. Complex 3 exhibits a complete SCO with T1/2 = 243 K. While the γ-2 polymorph also shows the complete SCO with T1/2 = 192 K, the α-2 polymorph exhibits a two-step SCO with the first step leading to a 50% HS → LS conversion with T1/2 = 120 K and the second step proceeding incompletely in the 80-50 K range. The amount of residual HS fraction of α-2 that remains below 60 K depends on the cooling rate. Fast flash-cooling allows trapping of as much as 45% of the HS fraction, while slow cooling leads to a 14% residual HS fraction. The slowly cooled sample of α-2 was subjected to irradiation in the magnetometer cavity resulting in a light-induced excited spin state trapping (LIESST) effect. As demonstrated by Mössbauer spectroscopy, an HS fraction of up to 85% could be achieved by irradiation at 4.2 K.

  17. Trehalose accumulation in rice plants confers high tolerance levels to different abiotic stresses

    PubMed Central

    Garg, Ajay K.; Kim, Ju-Kon; Owens, Thomas G.; Ranwala, Anil P.; Choi, Yang Do; Kochian, Leon V.; Wu, Ray J.

    2002-01-01

    Trehalose is a nonreducing disaccharide of glucose that functions as a compatible solute in the stabilization of biological structures under abiotic stress in bacteria, fungi, and invertebrates. With the notable exception of the desiccation-tolerant “resurrection plants,” trehalose is not thought to accumulate to detectable levels in most plants. We report here the regulated overexpression of Escherichia coli trehalose biosynthetic genes (otsA and otsB) as a fusion gene for manipulating abiotic stress tolerance in rice. The fusion gene has the advantages of necessitating only a single transformation event and a higher net catalytic efficiency for trehalose formation. The expression of the transgene was under the control of either tissue-specific or stress-dependent promoters. Compared with nontransgenic rice, several independent transgenic lines exhibited sustained plant growth, less photo-oxidative damage, and more favorable mineral balance under salt, drought, and low-temperature stress conditions. Depending on growth conditions, the transgenic rice plants accumulate trehalose at levels 3–10 times that of the nontransgenic controls. The observation that peak trehalose levels remain well below 1 mg/g fresh weight indicates that the primary effect of trehalose is not as a compatible solute. Rather, increased trehalose accumulation correlates with higher soluble carbohydrate levels and an elevated capacity for photosynthesis under both stress and nonstress conditions, consistent with a suggested role in modulating sugar sensing and carbohydrate metabolism. These findings demonstrate the feasibility of engineering rice for increased tolerance of abiotic stress and enhanced productivity through tissue-specific or stress-dependent overproduction of trehalose. PMID:12456878

  18. Seed treatment with Trichoderma harzianum alleviates biotic, abiotic, and physiological stresses in germinating seeds and seedlings.

    PubMed

    Mastouri, Fatemeh; Björkman, Thomas; Harman, Gary E

    2010-11-01

    Trichoderma spp. are endophytic plant symbionts that are widely used as seed treatments to control diseases and to enhance plant growth and yield. Although some recent work has been published on their abilities to alleviate abiotic stresses, specific knowledge of mechanisms, abilities to control multiple plant stress factors, their effects on seed and seedlings is lacking. We examined the effects of seed treatment with T. harzianum strain T22 on germination of seed exposed to biotic stress (seed and seedling disease caused by Pythium ultimum) and abiotic stresses (osmotic, salinity, chilling, or heat stress). We also evaluated the ability of the beneficial fungus to overcome physiological stress (poor seed quality induced by seed aging). If seed were not under any of the stresses noted above, T22 generally had little effect upon seedling performance. However, under stress, treated seed germinated consistently faster and more uniformly than untreated seeds whether the stress was osmotic, salt, or suboptimal temperatures. The consistent response to varying stresses suggests a common mechanism through which the plant-fungus association enhances tolerance to a wide range of abiotic stresses as well as biotic stress. A common factor that negatively affects plants under these stress conditions is accumulation of toxic reactive oxygen species (ROS), and we tested the hypothesis that T22 reduced damages resulting from accumulation of ROS in stressed plants. Treatment of seeds reduced accumulation of lipid peroxides in seedlings under osmotic stress or in aged seeds. In addition, we showed that the effect of exogenous application of an antioxidant, glutathione, or application of T22, resulted in a similar positive effect on seed germination under osmotic stress or in aged seed. This evidence supports the model that T. harzianum strain T22 increases seedling vigor and ameliorates stress by inducing physiological protection in plants against oxidative damage.

  19. Comparison on the Surface Structure Properties along with Fe(II) and Mn(II) Removal Characteristics of Rice Husk Ash, Inactive Saccharomyces cerevisiae Powder, and Rice Husk.

    PubMed

    Jiang, Zhao; Cao, Bo; Su, Guangxia; Lu, Yan; Zhao, Jiaying; Shan, Dexin; Zhang, Xiuyuan; Wang, Ziyi; Zhang, Ying

    2016-01-01

    This study selected solid wastes, such as rice husk ash (RHA), inactive Saccharomyces cerevisiae powder (ISP), and rice husk (RH), as the potential adsorbents for the removal of Fe(II) and Mn(II) in aqueous solution. The structural characteristics, functional groups, and elemental compositions were determined by scanning electron microscope (SEM) and Fourier translation infrared spectrum (FT-IR) analyses, respectively. Then the influence on the Fe(II) and Mn(II) removing efficiency by the factors, such as pH, adsorbent dosage, initial Fe(II) and Mn(II) concentration, and contact time, was investigated by the static batch test. The adsorption isotherm study results show that Langmuir equation can better fit the Fe(II) and Mn(II) adsorption process by the three adsorbents. The maximum adsorption amounts for Fe(II) were 6.211 mg/g, 4.464 mg/g, and 4.049 mg/g by RHA, ISP, and RH and for Mn(II) were 3.016 mg/g, 2.229 mg/g, and 1.889 mg/g, respectively. The adsorption kinetics results show that the pseudo-second-order kinetic model can better fit the Fe(II) and Mn(II) adsorption process. D-R model and thermodynamic parameters hint that the adsorption processes of Fe(II) and Mn(II) on the three adsorbents took place physically and the processes were feasible, spontaneous, and exothermic.

  20. Comparison on the Surface Structure Properties along with Fe(II) and Mn(II) Removal Characteristics of Rice Husk Ash, Inactive Saccharomyces cerevisiae Powder, and Rice Husk

    PubMed Central

    Jiang, Zhao; Cao, Bo; Su, Guangxia; Lu, Yan; Zhao, Jiaying; Shan, Dexin; Zhang, Xiuyuan; Wang, Ziyi

    2016-01-01

    This study selected solid wastes, such as rice husk ash (RHA), inactive Saccharomyces cerevisiae powder (ISP), and rice husk (RH), as the potential adsorbents for the removal of Fe(II) and Mn(II) in aqueous solution. The structural characteristics, functional groups, and elemental compositions were determined by scanning electron microscope (SEM) and Fourier translation infrared spectrum (FT-IR) analyses, respectively. Then the influence on the Fe(II) and Mn(II) removing efficiency by the factors, such as pH, adsorbent dosage, initial Fe(II) and Mn(II) concentration, and contact time, was investigated by the static batch test. The adsorption isotherm study results show that Langmuir equation can better fit the Fe(II) and Mn(II) adsorption process by the three adsorbents. The maximum adsorption amounts for Fe(II) were 6.211 mg/g, 4.464 mg/g, and 4.049 mg/g by RHA, ISP, and RH and for Mn(II) were 3.016 mg/g, 2.229 mg/g, and 1.889 mg/g, respectively. The adsorption kinetics results show that the pseudo-second-order kinetic model can better fit the Fe(II) and Mn(II) adsorption process. D-R model and thermodynamic parameters hint that the adsorption processes of Fe(II) and Mn(II) on the three adsorbents took place physically and the processes were feasible, spontaneous, and exothermic. PMID:28042571

  1. Biomineralization Associated with Microbial Reduction of Fe3+ and Oxidation of Fe2+ in Solid Minerals

    SciTech Connect

    Zhang, Gengxin; Dong, Hailiang; Jiang, Hongchen; Kukkadapu, Ravi K.; Kim, Jinwook; Eberl, Dennis D.; Xu, Zhiqin

    2009-07-01

    Iron- reducing and oxidizing microorganisms gain energy through reduction or oxidation of iron, and by doing so they play an important role in geochemical cycling of iron in a wide range of environments. This study was undertaken to investigate iron redox cycling in the deep subsurface by taking an advantage of the Chinese Continental Scientific Deep Drilling project. A fluid sample from 2450 m was collected and Fe(III)-reducing microorganisms were enriched using specific media (pH 6.2). Nontronite, an Fe(III)-rich clay mineral, was used in initial enrichments with lactate and acetate as electron donors under strictly anaerobic condition at the in-situ temperature of the fluid sample (65oC). Instead of a monotonic increase in Fe(II) concentration with time as would have been expected if Fe(III) bioreduction was the sole process, Fe(II) concentration initially increased, reached a peak, but then decreased to a minimum level. Continued incubation revealed an iron cycling with a cycling period of five to ten days. These initial results suggested that there might be Fe(III) reducers and Fe(II) oxidizers in the enrichment culture. Subsequently, multiple transfers were made with an attempt to isolate individual Fe(III) reducers and Fe(II) oxidizers. However, iron cycling persisted after multiple transfers. Additional experiments were conducted to ensure that iron reduction and oxidation was indeed biological. Biological Fe(II) oxidation was further confirmed in a series of roll tubes (with a pH gradient) where FeS and siderite were used as the sole electron donor. The oxidation of FeS occurred only at pH 10, and goethite, lepidocrocite, and ferrihydrite formed as oxidation products. Although molecular evidence (16S rRNA gene analysis) collectively suggested that only a single organism (a strain of Thermoanaerobacter ethanolicus) might be responsible for both Fe(III) reduction and Fe(II) oxidation, we could not rule out the possibility that Fe(III) reduction and Fe(II

  2. Genetic mapping of abiotic stress responses in sorghum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Due to rich genetic diversity for tolerance to various abiotic stress conditions, sorghum is an ideal system for genetic mapping and elucidation of genome regions that confer such response among cereal crops. Coupled with the development of DNA marker technologies and most recently the sequencing o...

  3. ABIOTIC DEGRADATION OF TRICHLOROETHYLENE UNDER THERMAL REMEDIATION CONDITIONS

    EPA Science Inventory

    The degradation of TCE (C2HCl3) to carbon dioxide (CO2) and chloride (Cl-) has been reported to occur during thermal remediation of subsurface environments. The overall goal of this study was to evaluate abiotic degradation of TCE at el...

  4. Abiotic reductive dechlorination of chlorinated ethylenes by iron-bearing soil minerals. 2. Green rust.

    PubMed

    Lee, Woojin; Batchelor, Bill

    2002-12-15

    Abiotic reductive dechlorination of chlorinated ethylenes by the sulfate form of green rust (GR(SO4)) was examined in batch reactors. Dechlorination kinetics were described by a modified Langmuir-Hinshelwood model. The rate constant for reductive dechlorination of chlorinated ethylenes at reactive GR(SO4) surfaces was in the range of 0.592 (+/-4.4%) to 1.59 (+/-6.3%) day(-1). The specific reductive capacity of GR(SO4) for target organics was in the range of 9.86 (+/-10.1%) to 18.0 (+/-4.3%) microM/g and sorption coefficient was in the range of 0.53 (+/-2.4%) to 1.22 (+/-4.3%) mM(-1). Surface area-normalized pseudo-first-order initial rate constants for chlorinated ethylenes by GR(SO4) were 3.4 to 8.2 times greater than those by pyrite. Chlorinated ethylenes were mainly transformed to acetylene, and no detectable amounts of chlorinated intermediates were observed. The rate constants for the reductive dechlorination of trichloroethylene (TCE) increased as pH increased (6.8 to 10.1) but were independent of solid concentration and initial TCE concentration. Magnetite and/or maghemite were produced by the oxidation of GR(SO4) by TCE. These findings are relevant to the understanding of the role of abiotic reductive dechlorination during natural attenuation in environments that contain GR(SO4).

  5. Protein Tyrosine Nitration during Development and Abiotic Stress Response in Plants

    PubMed Central

    Mata-Pérez, Capilla; Begara-Morales, Juan C.; Chaki, Mounira; Sánchez-Calvo, Beatriz; Valderrama, Raquel; Padilla, María N.; Corpas, Francisco J.; Barroso, Juan B.

    2016-01-01

    In recent years, the study of nitric oxide (NO) in plant systems has attracted the attention of many researchers. A growing number of investigations have shown the significance of NO as a signal molecule or as a molecule involved in the response against (a)biotic processes. NO can be responsible of the post-translational modifications (NO-PTM) of target proteins by mechanisms such as the nitration of tyrosine residues. The study of protein tyrosine nitration during development and under biotic and adverse environmental conditions has increased in the last decade; nevertheless, there is also an endogenous nitration which seems to have regulatory functions. Moreover, the advance in proteome techniques has enabled the identification of new nitrated proteins, showing the high variability among plant organs, development stage and species. Finally, it may be important to discern between a widespread protein nitration because of greater RNS content, and the specific nitration of key targets which could affect cell-signaling processes. In view of the above point, we present a mini-review that offers an update about the endogenous protein tyrosine nitration, during plant development and under several abiotic stress conditions. PMID:27895655

  6. Overexpression of a Pathogenesis-Related Protein 10 Enhances Biotic and Abiotic Stress Tolerance in Rice

    PubMed Central

    Wu, Jingni; Kim, Sang Gon; Kang, Kyu Young; Kim, Ju-Gon; Park, Sang-Ryeol; Gupta, Ravi; Kim, Yong Hwan; Wang, Yiming; Kim, Sun Tae

    2016-01-01

    Pathogenesis-related proteins play multiple roles in plant development and biotic and abiotic stress tolerance. Here, we characterize a rice defense related gene named “jasmonic acid inducible pathogenesis-related class 10” (JIOsPR10) to gain an insight into its functional properties. Semi-quantitative RT-PCR analysis showed up-regulation of JIOsPR10 under salt and drought stress conditions. Constitutive over-expression JIOsPR10 in rice promoted shoot and root development in transgenic plants, however, their productivity was unaltered. Further experiments exhibited that the transgenic plants showed reduced susceptibility to rice blast fungus, and enhanced salt and drought stress tolerance as compared to the wild type. A comparative proteomic profiling of wild type and transgenic plants showed that overexpression of JIOsPR10 led to the differential modulation of several proteins mainly related with oxidative stresses, carbohydrate metabolism, and plant defense. Taken together, our findings suggest that JIOsPR10 plays important roles in biotic and abiotic stresses tolerance probably by activation of stress related proteins. PMID:27904462

  7. Life without water: cross-resistance of anhydrobiotic cell line to abiotic stresses

    NASA Astrophysics Data System (ADS)

    Gusev, Oleg

    2016-07-01

    Anhydrobiosis is an intriguing phenomenon of natural ability of some organisms to resist water loss. The larvae of Polypedilum vanderplanki, the sleeping chironomid is the largest and most complex anhydrobionts known to date. The larvae showed ability to survive variety of abiotic stresses, including outer space environment. Recently cell line (Pv11) derived from the embryonic mass of the chironomid was established. Initially sensitive to desiccation cells, are capable to "induced" anhydrobiosis, when the resistance to desiccation can be developed by pre-treatment of the cells with trehalose followed by quick desiccation. We have further conducted complex analysis of the whole genome transcription response of Pv11 cells to different abiotic stresses, including oxidative stress and irradiation. Comparative analysis showed that the gene set, responsible for formation of desiccation resistance (ARID regions in the genome) is also activated in response to other types of stresses and likely to contribute to general enhancing of the resistance of the cells to harsh environment. We have further demonstrated that the cells are able to protect recombinant proteins from harmful effect of desiccation

  8. Connecting RNA Processing to Abiotic Environmental Response in Arabidopsis: the role of a polyadenylation factor

    NASA Astrophysics Data System (ADS)

    Li, Q. Q.; Xu, R.; Hunt, A. G.; Falcone, D. L.

    Plants are constantly challenged by numerous environmental stresses both biotic and abiotic It is clear that plants have evolved to counter these stresses using all but limited means We recently discovered the potential role of a messenger RNA processing factor namely the Arabidopsis cleavage and polyadenylation specificity factor 30 kDa subunit AtCPSF30 when a mutant deficient in this factor displayed altered responses to an array of abiotic stresses This AtCPSF30 mutant named oxt6 exhibited an elevated tolerance to oxidative stress Microarray experiments of oxt6 and its complemented lines revealed an altered gene expression profile among which were antioxidative defense genes Interestingly the same gene encoding AtCPSF30 can also be transcribed into a large transcript that codes for a potential splicing factor Both protein products have a domain for RNA binding and a calmodulin binding domain activities of which have been confirmed by biochemical assays Surprisingly binding of AtCPSF30 to calmodulin inhibits the RNA-binding activity of the protein Mutational analysis shows that a small part of the protein is responsible for calmodulin binding and point mutations in this region abolished both RNA binding activity and the inhibition of this activity by calmodulin Analyses of the potential splicing factor are on going and the results will be presented The interesting possibilities for both the interplay between splicing and polyadenylation and the regulation of these processes by stimuli that act through

  9. Abiotic nitrogen fixation on terrestrial planets: reduction of NO to ammonia by FeS.

    PubMed

    Summers, David P; Basa, Ranor C B; Khare, Bishun; Rodoni, David

    2012-02-01

    Understanding the abiotic fixation of nitrogen and how such fixation can be a supply of prebiotic nitrogen is critical for understanding both the planetary evolution of, and the potential origin of life on, terrestrial planets. As nitrogen is a biochemically essential element, sources of biochemically accessible nitrogen, especially reduced nitrogen, are critical to prebiotic chemistry and the origin of life. Loss of atmospheric nitrogen can result in loss of the ability to sustain liquid water on a planetary surface, which would impact planetary habitability and hydrological processes that shape the surface. It is known that NO can be photochemically converted through a chain of reactions to form nitrate and nitrite, which can be subsequently reduced to ammonia. Here, we show that NO can also be directly reduced, by FeS, to ammonia. In addition to removing nitrogen from the atmosphere, this reaction is particularly important as a source of reduced nitrogen on an early terrestrial planet. By converting NO directly to ammonia in a single step, ammonia is formed with a higher product yield (~50%) than would be possible through the formation of nitrate/nitrite and subsequent conversion to ammonia. In conjunction with the reduction of NO, there is also a catalytic disproportionation at the mineral surface that converts NO to NO₂ and N₂O. The NO₂ is then converted to ammonia, while the N₂O is released back in the gas phase, which provides an abiotic source of nitrous oxide.

  10. Integrating omic approaches for abiotic stress tolerance in soybean

    PubMed Central

    Deshmukh, Rupesh; Sonah, Humira; Patil, Gunvant; Chen, Wei; Prince, Silvas; Mutava, Raymond; Vuong, Tri; Valliyodan, Babu; Nguyen, Henry T.

    2014-01-01

    Soybean production is greatly influenced by abiotic stresses imposed by environmental factors such as drought, water submergence, salt, and heavy metals. A thorough understanding of plant response to abiotic stress at the molecular level is a prerequisite for its effective management. The molecular mechanism of stress tolerance is complex and requires information at the omic level to understand it effectively. In this regard, enormous progress has been made in the omics field in the areas of genomics, transcriptomics, and proteomics. The emerging field of ionomics is also being employed for investigating abiotic stress tolerance in soybean. Omic approaches generate a huge amount of data, and adequate advancements in computational tools have been achieved for effective analysis. However, the integration of omic-scale information to address complex genetics and physiological questions is still a challenge. In this review, we have described advances in omic tools in the view of conventional and modern approaches being used to dissect abiotic stress tolerance in soybean. Emphasis was given to approaches such as quantitative trait loci (QTL) mapping, genome-wide association studies (GWAS), and genomic selection (GS). Comparative genomics and candidate gene approaches are also discussed considering identification of potential genomic loci, genes, and biochemical pathways involved in stress tolerance mechanism in soybean. This review also provides a comprehensive catalog of available online omic resources for soybean and its effective utilization. We have also addressed the significance of phenomics in the integrated approaches and recognized high-throughput multi-dimensional phenotyping as a major limiting factor for the improvement of abiotic stress tolerance in soybean. PMID:24917870

  11. Abiotic ozone and oxygen in atmospheres similar to prebiotic Earth

    SciTech Connect

    Domagal-Goldman, Shawn D.; Segura, Antígona; Claire, Mark W.; Robinson, Tyler D.; Meadows, Victoria S.

    2014-09-10

    The search for life on planets outside our solar system will use spectroscopic identification of atmospheric biosignatures. The most robust remotely detectable potential biosignature is considered to be the detection of oxygen (O{sub 2}) or ozone (O{sub 3}) simultaneous to methane (CH{sub 4}) at levels indicating fluxes from the planetary surface in excess of those that could be produced abiotically. Here we use an altitude-dependent photochemical model with the enhanced lower boundary conditions necessary to carefully explore abiotic O{sub 2} and O{sub 3} production on lifeless planets with a wide variety of volcanic gas fluxes and stellar energy distributions. On some of these worlds, we predict limited O{sub 2} and O{sub 3} buildup, caused by fast chemical production of these gases. This results in detectable abiotic O{sub 3} and CH{sub 4} features in the UV-visible, but no detectable abiotic O{sub 2} features. Thus, simultaneous detection of O{sub 3} and CH{sub 4} by a UV-visible mission is not a strong biosignature without proper contextual information. Discrimination between biological and abiotic sources of O{sub 2} and O{sub 3} is possible through analysis of the stellar and atmospheric context—particularly redox state and O atom inventory—of the planet in question. Specifically, understanding the spectral characteristics of the star and obtaining a broad wavelength range for planetary spectra should allow more robust identification of false positives for life. This highlights the importance of wide spectral coverage for future exoplanet characterization missions. Specifically, discrimination between true and false positives may require spectral observations that extend into infrared wavelengths and provide contextual information on the planet's atmospheric chemistry.

  12. Abiotic, Graphitic Microstructures in Micaceous Metaquartzite about 3760 Million Years Old from Southwestern Greenland: Implications for Early Precambrian Microfossils

    PubMed Central

    Nagy, Bartholomew; Zumberge, John E.; Nagy, Lois Anne

    1975-01-01

    An Early Precambrian micaceous metaquartzite subjected to low to moderate metamorphism in the Isua area of Southwestern Greenland was derived from the erosion of preexisting rocks which were probably sialic in composition. This metaquartzite may have been formed before the emergence of life. It contains globular particles of graphite arranged in narrow veins or along foliation or bedding planes. This rock contains no organic compounds besides traces of methane and no biologically significant elements associated with the graphite microstructures. Reaction of primitive methane with ferric oxides appears to have oxidized the methane to the vein graphite and reduced the ferric oxides to ferrous-ferric oxide (magnetite). The graphitic microstructures are likely to be abiotic in origin, although a biological origin is not impossible. Somewhat younger microstructures found in other locations on earth have often been described as microfossils; this origin should be reexamined on the basis of the above mentioned conclusions. Images PMID:16592229

  13. Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

    SciTech Connect

    Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

    2014-12-01

    The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.

  14. Light harvesting and directional energy transfer in long-lived homo- and heterotrimetallic complexes of Fe(II), Ru(II), and Os(II).

    PubMed

    Maity, Dinesh; Bhaumik, Chanchal; Mardanya, Sourav; Karmakar, Srikanta; Baitalik, Sujoy

    2014-10-06

    A new family of trimetallic complexes of the form [(bpy)2 M(phen-Hbzim-tpy)M'(tpy-Hbzim-phen)M(bpy)2](6+) (M=Ru(II), Os; M'=Fe(II), Ru(II), Os; bpy=2,2'-bipyridine) derived from heteroditopic phenanthroline-terpyridine bridge 2-{4-[2,6-di(pyridin-2-yl) pyridine-4-yl]phenyl}-1H-imidazole[4,5-f][1,10]phenanthroline (phen-Hbzim-tpy) were prepared and fully characterized. Zn(2+) was used to prepare mixed-metal trimetallic complexes in situ by coordinating with the free tpy site of the monometallic precursors. The complexes show intense absorptions throughout the UV/Vis region and also exhibit luminescence at room temperature. The redox behavior of the compounds is characterized by several metal-centered reversible oxidation and ligand-centered reduction processes. Steady-state and time-resolved luminescence data show that the potentially luminescent Ru(II)- and Os(II)-based triplet metal-to-ligand charge-transfer ((3)MLCT) excited states in the triads are quantitatively quenched, most likely by intercomponent energy transfer to the lower lying (3)MLCT (for Ru and Os) or triplet metal-centered ((3)MC) excited states of the Fe(II) subunit (nonluminescent). Interestingly, iron did not adversely affect the photophysics of the respective systems. This suggests that the multicomponent molecular-wire-like complexes investigated here can behave as efficient light-harvesting antennas, because all the light absorbed by the various subunits is efficiently channeled to the subunit(s) in which the lowest-energy excited states are located.

  15. The metallomics approach: use of Fe(II) and Cu(II) footprinting to examine metal binding sites on serum albumins.

    PubMed

    Duff, Michael R; Kumar, Challa V

    2009-11-01

    Metal binding to serum albumins is examined by oxidative protein-cleavage chemistry, and relative affinities of multiple metal ions to particular sites on these proteins were identified using a fast and reliable chemical footprinting approach. Fe(ii) and Cu(ii), for example, mediate protein cleavage at their respective binding sites on serum albumins, in the presence of hydrogen peroxide and ascorbate. This metal-mediated protein-cleavge reaction is used to evaluate the binding of metal ions, Na(+), Mg(2+), Ca(2+), Al(3+), Cr(3+), Mn(2+), Co(2+), Ni(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ce(3+) to albumins, and the relative affinities (selectivities) of the metal ions are rapidly evaluated by examining the extent of inhibition of protein cleavage. Four distinct systems Fe(II)/BSA, Cu(II)/BSA, Fe(II)/HSA and Cu(II)/HSA are examined using the above strategy. This metallomics approach is novel, even though the cleavage of serum albumins by Fe(II)/Cu(II) has been reported previously by this laboratory and many others. The protein cleavage products were analyzed by SDS PAGE, and the intensities of the product bands quantified to evaluate the extent of inhibition of the cleavage and thereby evaluate the relative binding affinities of specific metal ions to particular sites on albumins. The data show that Co(II) and Cr(III) showed the highest degree of inhibition, across the table, followed by Mn(II) and Ce(III). Alakali metal ions and alkaline earth metal ions showed very poor affinity for these metal sites on albumins. Thus, metal binding profiles for particular sites on proteins can be obtained quickly and accurately, using the metallomics approach.

  16. Competitive Reduction of Pertechnetate (99TcO4- ) by Dissimilatory Metal Reducing Bacteria and Biogenic Fe(II)

    SciTech Connect

    Plymale, Andrew E.; Fredrickson, James K.; Zachara, John M.; Dohnalkova, Alice C.; Heald, Steve M.; Moore, Dean A.; Kennedy, David W.; Marshall, Matthew J.; Wang, Chongmin; Resch, Charles T.; Nachimuthu, Ponnusamy

    2011-01-06

    The fate of pertechnetate (99Tc(VII)O4-) during bioreduction was investigated in the presence of 2-line ferrihydrite (Fh) and various dissimilatory metal reducing bacteria (DMRB) (Geobacter, Anaeromyxobacter, Shewanella) in comparison with TcO4- bioreduction in the absence of Fh. In the presence of Fh, Tc was present primarily as a fine-grained Tc(IV)/Fe precipitate that was distinct from the Tc(IV)O2·nH2O solids produced by direct biological Tc(VII) reduction. Aqueous Tc concentrations (<0.2 μm) in the bioreduced Fh suspensions (1.7 to 3.2 × 10-9 mol L-1) were over 1 order of magnitude lower than when TcO4- was biologically reduced in the absence of Fh (4.0 × 10-8 to 1.0 × 10-7 mol L-1). EXAFS analyses of the bioreduced Fh-Tc products were consistent with variable chain length Tc-O octahedra bonded to Fe-O octahedra associated with the surface of the residual or secondary Fe(III) oxide. In contrast, biogenic TcO2·nH2O had significantly more Tc-Tc second neighbors and a distinct long-range order consistent with small particle polymers of TcO2. In Fe-rich subsurface sediments, the reduction of Tc(VII) by Fe(II) may predominate over direct microbial pathways, potentially leading to lower concentrations of aqueous 99Tc(IV).

  17. Arsenic Incorporation in Pyrite at Ambient Temperature at Both Tetrahedral S(-I) and Octahedral Fe(II) Sites: Evidence from EXAFS-DFT Analysis.

    PubMed

    Le Pape, Pierre; Blanchard, Marc; Brest, Jessica; Boulliard, Jean-Claude; Ikogou, Maya; Stetten, Lucie; Wang, Shuaitao; Landrot, Gautier; Morin, Guillaume

    2017-01-03

    Pyrite is a ubiquitous mineral in reducing environments and is well-known to incorporate trace elements such as Co, Ni, Se, Au, and commonly As. Indeed, As-bearing pyrite is observed in a wide variety of sedimentary environments, making it a major sink for this toxic metalloid. Based on the observation of natural hydrothermal pyrites, As(-I) is usually assigned to the occupation of tetrahedral S(-I) sites, with the same oxidation state as in arsenopyrite (FeAsS), although rare occurrences of As(III) and As(II) have been reported. However, the modes of As incorporation into pyrite during its crystallization under low-temperature diagenetic conditions have not yet been elucidated because arsenic acts as an inhibitor for pyrite nucleation at ambient temperature. Here, we provide evidence from X-ray absorption spectroscopy for As(II,III) incorporation into pyrite at octahedral Fe(II) sites and for As(-I) at tetrahedral S(-I) sites during crystallization at ambient temperature. Extended X-ray absorption fine structure (EXAFS) spectra of these As-bearing pyrites are explained by local structure models obtained using density functional theory (DFT), assuming incorporation of As at the Fe and S sites, as well as local clustering of arsenic. Such observations of As(-I) incorporation at ambient temperature can aid in the understanding of the early formation of authigenic arsenian pyrite in subsurface sediments. Moreover, evidence for substitution of As(II,III) for Fe in our synthetic samples raises questions about both the possible occurrence and the geochemical reactivity of such As-bearing pyrites in low-temperature subsurface environments.

  18. Peptide-based FeS4 complexes: the zinc ribbon fold is unsurpassed to stabilize both the FeII and FeIII states.

    PubMed

    Jacques, Aurélie; Latour, Jean-Marc; Sénèque, Olivier

    2014-03-14

    Whereas Zn(Cys)4 zinc fingers exist with different protein folds, only the zinc ribbon fold is found in rubredoxin Fe(Cys)4 sites. To assess the significance of this observation, we have investigated the binding and stability of Fe(2+) and Fe(3+) ions by a set of four peptides designed to model Zn(Cys)4 zinc fingers with various folds, i.e. zinc ribbon, treble clef and a loosened zinc ribbon fold. All peptides were shown by means of UV-Vis and CD spectroscopies to form stable 1 : 1 Fe(II)/peptide complexes with binding constants higher than 10(7) M(-1) at pH 7. Their oxidation into Fe(III) complexes and the stability of the latter were compared. The UV-Vis absorption and CD spectroscopic properties of the Fe(II) and Fe(III) complexes were analysed with respect to the structures of the zinc analogues in order to get insight into the local arrangement of the Fe(Cys)4 core around the metal ion. The chemical stability of these complexes was rationalized according to the shielding from the solvent provided by the various peptide folds to the FeS4 core. In addition, we showed that whereas UV-visible spectra inform only on the FeS4, the information derived from the corresponding CD spectra extend to the Cβ orientation and the peptide fold. The results presented here demonstrate that while the zinc ribbon fold is not strictly required to obtain a Fe(Cys)4 site, it affords a drastically superior protection of the site toward external redox agents. This finding brings new clues to engineer stable and redox-active Fe(Cys)4 sites in de novo proteins.

  19. A comparison between acoustic properties and heat effects in biogenic (magnetosomes) and abiotic magnetite nanoparticle suspensions

    NASA Astrophysics Data System (ADS)

    Józefczak, A.; Leszczyński, B.; Skumiel, A.; Hornowski, T.

    2016-06-01

    Magnetic nanoparticles show unique properties and find many applications because of the possibility to control their properties using magnetic field. Magnetic nanoparticles are usually synthesized chemically and modification of the particle surface is necessary. Another source of magnetic nanoparticles are various magnetotactic bacteria. These biogenic nanoparticles (magnetosomes) represent an attractive alternative to chemically synthesized iron oxide particles because of their unique characteristics and a high potential for biotechnological and biomedical applications. This work presents a comparison between acoustic properties of biogenic and abiotic magnetite nanoparticle suspensions. Experimental studies have shown the influence of a biological membrane on the ultrasound properties of magnetosomes suspension. Finally the heat effect in synthetic and biogenic magnetite nanoparticles is also discussed. The experimental study shows that magnetosomes present good heating efficiency.

  20. Ultraweak photon emission and proteomics analyses in soybean under abiotic stress.

    PubMed

    Komatsu, Setsuko; Kamal, Abu Hena Mostafa; Makino, Takahiro; Hossain, Zahed

    2014-07-01

    Biophotons are ultraweak photon emissions that are closely related to various biological activities and processes. In mammals, biophoton emissions originate from oxidative bursts in immunocytes during immunological responses. Biophotons emitted from plant organs provide novel information about the physiological state of plant under in vivo condition. In this review, the principles and recent advances in the measurement of biophoton emissions in plants are described. Furthermore, examples of biophoton emission and proteomics in soybean under abiotic stress are reviewed and discussed. Finally, this review suggests that the application of proteomics should provide a better interpretation of plant response to biophoton emission and allow the identification of genes that will allow the screening of crops able to produce maximal yields, even in stressful environments.

  1. Biotic and abiotic controls on co-occurring nitrogen cycling processes in shallow Arctic shelf sediments

    NASA Astrophysics Data System (ADS)

    McTigue, N. D.; Gardner, W. S.; Dunton, K. H.; Hardison, A. K.

    2016-10-01

    The processes that convert bioavailable inorganic nitrogen to inert nitrogen gas are prominent in continental shelf sediments and represent a critical global sink, yet little is known of these pathways in the Arctic where 18% of the world's continental shelves are located. Moreover, few data from the Arctic exist that separate loss processes like denitrification and anaerobic ammonium oxidation (anammox) from recycling pathways like dissimilatory nitrate reduction to ammonium (DNRA) or source pathways like nitrogen fixation. Here we present measurements of these co-occurring processes using 15N tracers. Denitrification was heterogeneous among stations and an order of magnitude greater than anammox and DNRA, while nitrogen fixation was undetectable. No abiotic factors correlated with interstation variability in biogeochemical rates; however, bioturbation potential explained most of the variation. Fauna-enhanced denitrification is a potentially important but overlooked process on Arctic shelves and highlights the role of the Arctic as a significant global nitrogen sink.

  2. Biotic and abiotic controls on co-occurring nitrogen cycling processes in shallow Arctic shelf sediments

    PubMed Central

    McTigue, N. D.; Gardner, W. S.; Dunton, K. H.; Hardison, A. K.

    2016-01-01

    The processes that convert bioavailable inorganic nitrogen to inert nitrogen gas are prominent in continental shelf sediments and represent a critical global sink, yet little is known of these pathways in the Arctic where 18% of the world's continental shelves are located. Moreover, few data from the Arctic exist that separate loss processes like denitrification and anaerobic ammonium oxidation (anammox) from recycling pathways like dissimilatory nitrate reduction to ammonium (DNRA) or source pathways like nitrogen fixation. Here we present measurements of these co-occurring processes using 15N tracers. Denitrification was heterogeneous among stations and an order of magnitude greater than anammox and DNRA, while nitrogen fixation was undetectable. No abiotic factors correlated with interstation variability in biogeochemical rates; however, bioturbation potential explained most of the variation. Fauna-enhanced denitrification is a potentially important but overlooked process on Arctic shelves and highlights the role of the Arctic as a significant global nitrogen sink. PMID:27782213

  3. Archaeal (Per)Chlorate Reduction at High Temperature: An Interplay of Biotic and Abiotic Reactions

    NASA Astrophysics Data System (ADS)

    Liebensteiner, Martin G.; Pinkse, Martijn W. H.; Schaap, Peter J.; Stams, Alfons J. M.; Lomans, Bart P.

    2013-04-01

    Perchlorate and chlorate anions [(per)chlorate] exist in the environment from natural and anthropogenic sources, where they can serve as electron acceptors for bacteria. We performed growth experiments combined with genomic and proteomic analyses of the hyperthermophile Archaeoglobus fulgidus that show (per)chlorate reduction also extends into the archaeal domain of life. The (per)chlorate reduction pathway in A. fulgidus relies on molybdo-enzymes that have similarity with bacterial enzymes; however, chlorite is not enzymatically split into chloride and oxygen. Evidence suggests that it is eliminated by an interplay of abiotic and biotic redox reactions involving sulfur compounds. Biological (per)chlorate reduction by ancient archaea at high temperature may have prevented accumulation of perchlorate in early terrestrial environments and consequently given rise to oxidizing conditions on Earth before the rise of oxygenic photosynthesis.

  4. Transformation of ferrihydrite in the presence or absence of trace Fe(II): The effect of preparation procedures of ferrihydrite

    SciTech Connect

    Liu Hui; Li Ping; Lu Bin; Wei Yu; Sun Yuhan

    2009-07-15

    Two-line ferrihydrite was prepared by two different procedures. In procedure 1, which is widely used, ferrihydrite (named as ferrihydrite-1) was prepared by droping NaOH solution into Fe(III) solution. In procedure 2, which is rarely reported, ferrihydrite (named as ferrihydrite-2) was prepared by adding Fe(III) and NaOH solutions into a certain volume of water simultaneously. The results showed that mixing procedures of Fe(III) and alkaline were critical in the sub-microstructures and the conversion mechanisms of ferrihydrites in the presence or absence of trace Fe(II). The sub-microstructure of ferrihydrite-1 favored the mechanism of its dissolution re-crystallization and hematite nanoparticles with rough surface were obtained. The sub-microstructure of ferrihydrite-2 favored the solid state transformation from ferrihydrite to hematite and hematite nanoparticles with smooth surface were formed. These research results will be helpful for us to control the synthesis of hematite nanoparticles with different surface state. - Graphical abstract: Ferrihydrites prepared by mixing Fe{sup 3+} and NaOH solutions according to different procedures can rapidly transform into hematite particles with different surface structures in the presence of trace Fe(II).

  5. Structure prediction of Fe(II) 2-oxoglutarate dioxygenase from a psychrophilic yeast Glaciozyma antarctica PI12

    NASA Astrophysics Data System (ADS)

    Yusof, Nik Yusnoraini; Bakar, Farah Diba Abu; Mahadi, Nor Muhammad; Raih, Mohd Firdaus; Murad, Abdul Munir Abdul

    2015-09-01

    A cDNA encoding Fe(II) 2-oxoglutarate (2OG) dependent dioxygenases was isolated from psychrophilic yeast, Glaciozyma antarctica PI12. We have successfully amplified 1,029 bp cDNA sequence that encodes 342 amino acid with predicted molecular weight 38 kDa. The prediction protein was analysed using various bioinformatics tools to explore the properties of the protein. Based on a BLAST search analysis, the Fe2OX amino acid sequence showed 61% identity to the sequence of oxoglutarate/iron-dependent oxygenase from Rhodosporidium toruloides NP11. SignalP prediction showed that the Fe2OX protein contains no putative signal peptide, which suggests that this enzyme most probably localised intracellularly.The structure of Fe2OX was predicted by homology modelling using MODELLER9v11. The model with the lowest objective function was selected from hundred models generated using MODELLER9v11. Analysis of the structure revealed the longer loop at Fe2OX from G.antarctica that might be responsible for the flexibility of the structure, which contributes to its adaptation to low temperatures. Fe2OX hold a highly conserved Fe(II) binding HXD/E…H triad motif. The binding site for 2-oxoglutarate was found conserved for Arg280 among reported studies, however the Phe268 was found to be different in Fe2OX.

  6. Does As(III) interact with Fe(II), Fe(III) and organic matter through ternary complexes?

    PubMed

    Catrouillet, Charlotte; Davranche, Mélanie; Dia, Aline; Bouhnik-Le Coz, Martine; Demangeat, Edwige; Gruau, Gérard

    2016-05-15

    Up until now, only a small number of studies have been dedicated to the binding processes of As(III) with organic matter (OM) via ionic Fe(III) bridges; none was interested in Fe (II). Complexation isotherms were carried out with As(III), Fe(II) or Fe(III) and Leonardite humic acid (HA). Although PHREEQC/Model VI, implemented with OM thiol groups, reproduced the experimental datasets with Fe(III), the poor fit between the experimental and modeled Fe(II) data suggested another binding mechanism for As(III) to OM. PHREEQC/Model VI was modified to take various possible As(III)-Fe(II)-OM ternary complex conformations into account. The complexation of As(III) as a mononuclear bidentate complex to a bidentate Fe(II)-HA complex was evidenced. However, the model needed to be improved since the distribution of the bidentate sites appeared to be unrealistic with regards to the published XAS data. In the presence of Fe(III), As(III) was bound to thiol groups which are more competitive with regards to the low density of formed Fe(III)-HA complexes. Based on the new data and previously published results, we propose a general scheme describing the various As(III)-Fe-MO complexes that are able to form in Fe and OM-rich waters.

  7. Confinement of a bioinspired nonheme Fe(II) complex in 2D hexagonal mesoporous silica with metal site isolation.

    PubMed

    Jollet, Véronique; Albela, Belén; Sénéchal-David, Katell; Jégou, Pascale; Kolodziej, Emilie; Sainton, Joëlle; Bonneviot, Laurent; Banse, Frédéric

    2013-08-28

    A mixed amine pyridine polydentate Fe(II) complex was covalently tethered in hexagonal mesoporous silica of the MCM-41 type. Metal site isolation was generated using adsorbed tetramethylammonium cations acting as a patterned silanol protecting mask and trimethylsilylazane as a capping agent. Then, the amine/pyridine ligand bearing a tethering triethoxysilane group was either grafted to such a pretreated silica surface prior to or after complexation to Fe(II). These two synthetic routes, denoted as two-step and one-step, respectively, were also applied to fumed silica for comparison, except that the silanol groups were capped after tethering the metal unit. The coordination of the targeted complex was monitored using UV-visible spectrophotometry and, according to XPS, the best control was achieved inside the channels of the mesoporous silica for the two-step route. For the solid prepared according to the one-step route, tethering of the complex occurred mainly at the entrance of the channel.

  8. Stability of uranium incorporated into Fe (hydr)oxides under fluctuating redox conditions.

    PubMed

    Stewart, Brandy D; Nico, Peter S; Fendorf, Scott

    2009-07-01

    Reaction pathways resulting in uranium-bearing solids that are stable (i.e., having limited solubility) under aerobic and anaerobic conditions will limit dissolved concentrations and migration of this toxin. Here, we examine the sorption mechanism and propensity for release of uranium reacted with Fe (hydr)oxides under cyclic oxidizing and reducing conditions. Upon reaction of ferrihydrite with Fe(II) under conditions where aqueous Ca-UO2-CO3 species predominate (3 mM Ca and 3.8 mM total CO3), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5-15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (14 d of reduction, followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM total CO3, dissolved uranium concentrations varied depending on the Fe(II) concentration during the initial and subsequent reduction phases. U concentrations resulting during the oxic "rebound" varied inversely with the Fe(II) concentration during the reduction cycle. Uranium removed from solution remains in the oxidized form and is found adsorbed onto and incorporated into the structure of newly formed goethite and magnetite. Our results reveal that the fate of uranium is dependent on anaerobic/ aerobic conditions, aqueous uranium speciation, and the fate of iron.

  9. Stability of uranium incorporated into Fe(hydr)oxides under fluctuating redox conditions

    SciTech Connect

    Stewart, B.D.; Nico, P.S.; Fendorf, S.

    2009-04-01

    Reaction pathways resulting in uranium bearing solids that are stable (i.e., having limited solubility) under both aerobic and anaerobic conditions will limit dissolved concentrations and migration of this toxin. Here we examine the sorption mechanism and propensity for release of uranium reacted with Fe (hydr)oxides under cyclic oxidizing and reducing conditions. Upon reaction of ferrihydrite with Fe(II) under conditions where aqueous Ca-UO{sub 2}-CO{sub 3} species predominate (3 mM Ca and 3.8 mM CO{sub 3}-total), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5 to 15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (15 d of reduction followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM CO{sub 3}-total, dissolved uranium concentrations varied depending on the Fe(II) concentration during the initial and subsequent reduction phases - U concentrations resulting during the oxic 'rebound' varied inversely with the Fe(II) concentration during the reduction cycle. Uranium removed from solution remains in the oxidized form and is found both adsorbed on and incorporated into the structure of newly formed goethite and magnetite. Our 15 results reveal that the fate of uranium is dependent on anaerobic/aerobic conditions, aqueous uranium speciation, and the fate of iron.

  10. Glutathione peroxidase genes in Arabidopsis are ubiquitous and regulated by abiotic stresses through diverse signaling pathways.

    PubMed

    Rodriguez Milla, Miguel A; Maurer, Alberto; Rodriguez Huete, Alicia; Gustafson, J Perry

    2003-12-01

    Glutathione peroxidases (GPXs) are a group of enzymes that protect cells against oxidative damage generated by reactive oxygen species (ROS). The presence of GPXs in plants has been reported by several groups, but the roles of individual members of this family in a single plant species have not been studied. A family of seven related proteins named AtGPX1- AtGPX7 in Arabidopsis was identified, and the genomic organization of this family was reported. The putative subcellular localizations of the encoded proteins are the cytosol, chloroplast, mitochondria, and endoplasmic reticulum. Expressed sequence tags (ESTs) for all the genes except AtGPX7 were identified. Expression analysis of AtGPX genes in Arabidopsis tissues was performed, and different patterns were detected. Interestingly, several genes were up-regulated coordinately in response to abiotic stresses. AtGPX6, like human phospholipid hydroperoxide GPX (PHGPX), possibly encodes mitochondrial and cytosolic isoforms by alternative initiation. In addition, this gene showed the strongest responses under most abiotic stresses tested. AtGPX6::GUS analysis in transgenic Arabidopsis showed that AtGPX6 is highly expressed throughout development in most tissues, thus supporting an important role for this gene in protection against oxidative damage. The different effects of salicylic acid (SA), jasmonic acid (JA), abscisic acid (ABA), and auxin on the expression of the genes indicate that the AtGPX family is regulated by multiple signaling pathways. Analysis of the upstream region of the AtGPX genes revealed the presence of multiple conserved motifs, and some of them resembled antioxidant-responsive elements found in plant and human promoters. The potential regulatory role of specific sequences is discussed.

  11. Hormone balance and abiotic stress tolerance in crop plants.

    PubMed

    Peleg, Zvi; Blumwald, Eduardo

    2011-06-01

    Plant hormones play central roles in the ability of plants to adapt to changing environments, by mediating growth, development, nutrient allocation, and source/sink transitions. Although ABA is the most studied stress-responsive hormone, the role of cytokinins, brassinosteroids, and auxins during environmental stress is emerging. Recent evidence indicated that plant hormones are involved in multiple processes. Cross-talk between the different plant hormones results in synergetic or antagonic interactions that play crucial roles in response of plants to abiotic stress. The characterization of the molecular mechanisms regulating hormone synthesis, signaling, and action are facilitating the modification of hormone biosynthetic pathways for the generation of transgenic crop plants with enhanced abiotic stress tolerance.

  12. An abiotic analogue of the nuclear pore complex hydrogel.

    PubMed

    Bird, Sean P; Baker, Lane A

    2011-09-12

    We describe an abiotic hydrogel that mimics selectivity of the nuclear pore complex. Copolymerization of peptide tetramers (phenylalanine-serine-phenylalanine-glycine, FSFG) with acrylamide results in hydrophobic interactions significant enough to allow the formation of freestanding hydrogel structures. Incorporation of FSFG motifs also renders the hydrogels selective. Selective binding of importins and nuclear transport receptor-cargo complexes is qualitatively demonstrated and compared with polyacrylamide, hydrogels prepared from a control peptide, and hydrogels prepared from the nuclear pore complex protein Nsp1. These abiotic hydrogels will enable further studies of the unique transport mechanisms of the nuclear pore complex and provide an interesting paradigm for the future development of synthetic platforms for separations and selective interfaces.

  13. Abiotic mediation of a mutualism drives herbivore abundance.

    PubMed

    Mooney, Emily H; Phillips, Joseph S; Tillberg, Chadwick V; Sandrow, Cheryl; Nelson, Annika S; Mooney, Kailen A

    2016-01-01

    Species abundance is typically determined by the abiotic environment, but the extent to which such effects occur through the mediation of biotic interactions, including mutualisms, is unknown. We explored how light environment (open meadow vs. shaded understory) mediates the abundance and ant tending of the aphid Aphis helianthi feeding on the herb Ligusticum porteri. Yearly surveys consistently found aphids to be more than 17-fold more abundant on open meadow plants than on shaded understory plants. Manipulations demonstrated that this abundance pattern was not due to the direct effects of light environment on aphid performance, or indirectly through host plant quality or the effects of predators. Instead, open meadows had higher ant abundance and per capita rates of aphid tending and, accordingly, ants increased aphid population growth in meadow but not understory environments. The abiotic environment thus drives the abundance of this herbivore exclusively through the mediation of a protection mutualism.

  14. Experiments on the abiotic amplification of optical activity

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Blair, N. E.; Dirbas, F. M.

    1981-01-01

    Experiments concerning the physical mechanisms for the abiotic generation and chemical mechanisms for the amplification of optical activity in biological compounds are reviewed. Attention is given to experiments involving the determination of the differential adsorption of racemic amino acids on d- and l-quartz, the asymmetric photolysis of racemic amino acids by circularly polarized light, and the asymmetric radiolysis of solid amino acids by longitudinally polarized electrons, and the enantiomeric enrichments thus obtained are noted. Further experiments on the amplification of the chirality in the polymerization of D, L-amino acid mixtures and the hydrolysis of D-, L-, and D, L-polypeptides are discussed. It is suggested that a repetitive cycle of partial polymerization-hydrolyses may account for the abiotic genesis of optically enriched polypeptides on the primitive earth.

  15. Transcriptional networks-crops, clocks, and abiotic stress.

    PubMed

    Gehan, Malia A; Greenham, Kathleen; Mockler, Todd C; McClung, C Robertson

    2015-04-01

    Several factors affect the yield potential and geographical range of crops including the circadian clock, water availability, and seasonal temperature changes. In order to sustain and increase plant productivity on marginal land in the face of both biotic and abiotic stresses, we need to more efficiently generate stress-resistant crops through marker-assisted breeding, genetic modification, and new genome-editing technologies. To leverage these strategies for producing the next generation of crops, future transcriptomic data acquisition should be pursued with an appropriate temporal design and analyzed with a network-centric approach. The following review focuses on recent developments in abiotic stress transcriptional networks in economically important crops and will highlight the utility of correlation-based network analysis and applications.

  16. SUMO, a heavyweight player in plant abiotic stress responses.

    PubMed

    Castro, Pedro Humberto; Tavares, Rui Manuel; Bejarano, Eduardo R; Azevedo, Herlânder

    2012-10-01

    Protein post-translational modifications diversify the proteome and install new regulatory levels that are crucial for the maintenance of cellular homeostasis. Over the last decade, the ubiquitin-like modifying peptide small ubiquitin-like modifier (SUMO) has been shown to regulate various nuclear processes, including transcriptional control. In plants, the sumoylation pathway has been significantly implicated in the response to environmental stimuli, including heat, cold, drought, and salt stresses, modulation of abscisic acid and other hormones, and nutrient homeostasis. This review focuses on the emerging importance of SUMO in the abiotic stress response, summarizing the molecular implications of sumoylation and emphasizing how high-throughput approaches aimed at identifying the full set of SUMO targets will greatly enhance our understanding of the SUMO-abiotic stress association.

  17. Arbuscular mycorrhizal fungal responses to abiotic stresses: A review.

    PubMed

    Lenoir, Ingrid; Fontaine, Joël; Lounès-Hadj Sahraoui, Anissa

    2016-03-01

    The majority of plants live in close collaboration with a diversity of soil organisms among which arbuscular mycorrhizal fungi (AMF) play an essential role. Mycorrhizal symbioses contribute to plant growth and plant protection against various environmental stresses. Whereas the resistance mechanisms induced in mycorrhizal plants after exposure to abiotic stresses, such as drought, salinity and pollution, are well documented, the knowledge about the stress tolerance mechanisms implemented by the AMF themselves is limited. This review provides an overview of the impacts of various abiotic stresses (pollution, salinity, drought, extreme temperatures, CO2, calcareous, acidity) on biodiversity, abundance and development of AMF and examines the morphological, biochemical and molecular mechanisms implemented by AMF to survive in the presence of these stresses.

  18. Sustainability of Long-Term Abiotic Attenuation of Chlorinated Ethenes

    DTIC Science & Technology

    2007-09-28

    that contribute to abiotic transformations is critical to assess the feasibility of natural attenuation and promote the rationale design of...anaerobic glovebox. The resulting slurry was mixed for three days and then decanted into polypropylene centrifuge bottles. These bottles were...tightly sealed and centrifuged at 8000 rpm for 10 minutes. The supernatant in the bottles was discarded, and fresh nitrogen-purged deionized water was

  19. Biotic-Abiotic Nanoscale Interactions in Biological Fuel Cells

    DTIC Science & Technology

    2014-03-28

    Force Office of Scientific Research 875 North Randolph Street 4027 Arlington VA 22203 email: Patrick.Bradshaw@afosr.af.mil phone : 703-588-8492...Science Center 215C Los Angeles, CA 90089-0484 email: mnaggar@usc.edu phone : 213-740-2394 2 Biotic-Abiotic Nanoscale Interactions in...aggregation – collaboration with Naval Research Lab. 2.4 As part of an international collaboration, we reported on filamentous bacteria mediating centimeter

  20. Changes in biotic and abiotic processes following mangrove clearing

    NASA Astrophysics Data System (ADS)

    Granek, Elise; Ruttenberg, Benjamin I.

    2008-12-01

    Mangrove forests, important tropical coastal habitats, are in decline worldwide primarily due to removal by humans. Changes to mangrove systems can alter ecosystem properties through direct effects on abiotic factors such as temperature, light and nutrient supply or through changes in biotic factors such as primary productivity or species composition. Despite the importance of mangroves as transitional habitats between land and sea, little research has examined changes that occur when they are cleared. We examined changes in a number of biotic and abiotic factors following the anthropogenic removal of red mangroves ( Rhizophora mangle) in the Panamanian Caribbean, including algal biomass, algal diversity, algal grazing rates, light penetration, temperature, sedimentation rates and sediment organic content. In this first study examining multiple ecosystem-level effects of mangrove disturbance, we found that areas cleared of mangroves had higher algal biomass and richness than intact mangrove areas. This increase in algal biomass and richness was likely due to changes in abiotic factors (e.g. light intensity, temperature), but not biotic factors (fish herbivory). Additionally the algal and cyanobacterial genera dominating mangrove-cleared areas were rare in intact mangroves and included a number of genera that compete with coral for space on reefs. Interestingly, sedimentation rates did not differ between intact and cleared areas, but the sediments that accumulated in intact mangroves had higher organic content. These findings are the first to demonstrate that anthropogenic clearing of mangroves changes multiple biotic and abiotic processes in mangrove forests and that some of these changes may influence adjacent habitats such as coral reefs and seagrass beds. Additional research is needed to further explore the community and ecosystem-level effects of mangrove clearing and their influence on adjacent habitats, but it is clear that mangrove conservation is an

  1. Wheat EST resources for functional genomics of abiotic stress

    PubMed Central

    Houde, Mario; Belcaid, Mahdi; Ouellet, François; Danyluk, Jean; Monroy, Antonio F; Dryanova, Ani; Gulick, Patrick; Bergeron, Anne; Laroche, André; Links, Matthew G; MacCarthy, Luke; Crosby, William L; Sarhan, Fathey

    2006-01-01

    Background Wheat is an excellent species to study freezing tolerance and other abiotic stresses. However, the sequence of the wheat genome has not been completely characterized due to its complexity and large size. To circumvent this obstacle and identify genes involved in cold acclimation and associated stresses, a large scale EST sequencing approach was undertaken by the Functional Genomics of Abiotic Stress (FGAS) project. Results We generated 73,521 quality-filtered ESTs from eleven cDNA libraries constructed from wheat plants exposed to various abiotic stresses and at different developmental stages. In addition, 196,041 ESTs for which tracefiles were available from the National Science Foundation wheat EST sequencing program and DuPont were also quality-filtered and used in the analysis. Clustering of the combined ESTs with d2_cluster and TGICL yielded a few large clusters containing several thousand ESTs that were refractory to routine clustering techniques. To resolve this problem, the sequence proximity and "bridges" were identified by an e-value distance graph to manually break clusters into smaller groups. Assembly of the resolved ESTs generated a 75,488 unique sequence set (31,580 contigs and 43,908 singletons/singlets). Digital expression analyses indicated that the FGAS dataset is enriched in stress-regulated genes compared to the other public datasets. Over 43% of the unique sequence set was annotated and classified into functional categories according to Gene Ontology. Conclusion We have annotated 29,556 different sequences, an almost 5-fold increase in annotated sequences compared to the available wheat public databases. Digital expression analysis combined with gene annotation helped in the identification of several pathways associated with abiotic stress. The genomic resources and knowledge developed by this project will contribute to a better understanding of the different mechanisms that govern stress tolerance in wheat and other cereals. PMID

  2. Bench-scale evaluation of ferrous iron oxidation kinetics in drinking water: effect of corrosion control and dissolved organic matter.

    PubMed

    Rahman, Safiur; Gagnon, Graham A

    2014-01-01

    Corrosion control strategies are important for many utilities in maintaining water quality from the water treatment plant to the customers' tap. In drinking water with low alkalinity, water quality can become significantly degraded in iron-based pipes if water utilities are not diligent in maintaining proper corrosion control. This article reports on experiments conducted in bicarbonate buffered (5 mg-C/L) synthetic water to determine the effects of corrosion control (pH and phosphate) and dissolved organic matter (DOM) on the rate constants of the Fe(II) oxidation process. A factorial design approach elucidated that pH (P = 0.007, contribution: 42.5%) and phosphate (P = 0.025, contribution: 22.7%) were the statistically significant factors in the Fe(II) oxidation process at a 95% confidence level. The comprehensive study revealed a significant dependency relationship between the Fe(II) oxidation rate constants (k) and phosphate-to- Fe(II) mole ratio. At pH 6.5, the optimum mole ratio was found to be 0.3 to reduce the k values. Conversely, the k values were observed to increase for the phosphate-to- Fe(II) mole ratio > 1. The factorial design approach revealed that chlorine and DOM for the designated dosages did not cause a statistically significant (α = 0.05, P > 0.05)change in rate constants. However, an increment of the chlorine to ferrous iron mole ratio by a factor of ∼ 2.5 resulted in an increase k values by a factor of ∼ 10. This study conclusively demonstrated that the lowest Fe(II) oxidation rate constant was obtained under low pH conditions (pH ≤ 6.5), with chlorine doses less than 2.2 mg/L and with a phosphate-to-Fe(II) mole ratio ≈ 0.3 in the iron water systems.

  3. New Insight into Microbial Iron Oxidation as Revealed by the Proteomic Profile of an Obligate Iron-Oxidizing Chemolithoautotroph.

    PubMed

    Barco, Roman A; Emerson, David; Sylvan, Jason B; Orcutt, Beth N; Jacobson Meyers, Myrna E; Ramírez, Gustavo A; Zhong, John D; Edwards, Katrina J

    2015-09-01

    Microaerophilic, neutrophilic, iron-