Microbial oxidation of mixtures of methylmercaptan and hydrogen sulfide.

PubMed

Subramaniyan, A; Kolhatkar, R; Sublette, K L; Beitle, R

1998-01-01

Refinery spent-sulfidic caustic, containing only inorganic sulfides, has previously been shown to be amenable to biotreatment with Thiobacillus denitrificans strain F with complete oxidation of sulfides to sulfate. However, many spent caustics contain mercaptans that cannot be metabolized by this strict autotroph. An aerobic enrichment culture was developed from mixed Thiobacilli and activated sludge that was capable of simultaneous oxidation of inorganic sulfide and mercaptans using hydrogen sulfide (H2S) and methylmercaptan (MeSH) gas feeds used to simulate the inorganic and organic sulfur of a spent-sulfidic caustic. The enrichment culture was also capable of biotreatment of an actual mercaptan-containing, spent-sulfidic caustic but at lower rates than predicted by operation on MeSH and H2S fed to the culture in the gas phase, indicating that the caustic contained other inhibitory components.

Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

PubMed

Liu, Xue; Huang, Jia-Qi; Zhang, Qiang; Mai, Liqiang

2017-05-01

Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Summary of GPC/DV results for space exposed poly(arylene ether phosphine oxide)s

NASA Technical Reports Server (NTRS)

Siochi, Emilie

1995-01-01

Gel Permeation Chromatography (GPC) was used to analyze poly(arylene ether phosphine oxide)s whose backbones were identical except for the ketone content and placement. These samples were exposed to low Earth orbit environment (predominantly atomic oxygen) on space shuttle flights. The materials and their unexposed controls were then characterized by GPC to investigate the effect of atomic oxygen on the molecular weight distributions. Analysis of the soluble portion of the samples revealed that there was significant loss of high molecular weight species. The presence of insoluble material also suggested that crosslinking was induced by the atomic oxygen exposure and that this very likely occurred at the high molecular weight portion of the molecular weight distribution.

Vegetation successfully prevents oxidization of sulfide minerals in mine tailings.

PubMed

Li, Yang; Sun, Qingye; Zhan, Jing; Yang, Yang; Wang, Dan

2016-07-15

The oxidization of metal sulfide in tailings causes acid mine drainage. However, it remains unclear whether vegetation prevents the oxidization of metal sulfides. The oxidization characteristics and microbial indices of the tailings in the presence of various plant species were investigated to explore the effects of vegetation on the oxidization of sulfide minerals in tailings. The pH, reducing sulfur, free iron oxides (Fed), chemical oxygen consumption (COC) and biological oxygen consumption (BOC) were measured. Key iron- and sulfur-oxidizing bacteria (Acidithiobacillus spp., Leptospirillum spp. and Thiobacillus spp.) were quantified using real-time PCR. The results indicate that vegetation growing on tailings can effectively prevent the oxidization of sulfide minerals in tailings. A higher pH and reducing-sulfur content and lower Fed were observed in the 0-30 cm depth interval in the presence of vegetation compared to bare tailings (BT). The COC gradually decreased with depth in all of the soil profiles; specifically, the COC rapidly decreased in the 10-20 cm interval in the presence of vegetation but gradually decreased in the BT profiles. Imperata cylindrica (IC) and Chrysopogon zizanoides (CZ) profiles contained the highest BOC in the 10-20 cm interval. The abundance of key iron- and sulfur-oxidizing bacteria in the vegetated tailings were significantly lower than in the BT; in particular, IC was associated with the lowest iron- and sulfur-oxidizing bacterial abundance. In conclusion, vegetation successfully prevented the oxidization of sulfide minerals in the tailings, and Imperata cylindrica is the most effective in reducing the number of iron- and sulfur-oxidizing bacteria and helped to prevent the oxidization of sulfide minerals in the long term. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lithium cation enhances anion binding in a tripodal phosphine oxide-based ditopic receptor†

PubMed Central

Gavette, Jesse V.; Lara, Juven; Berryman, Orion B.; Zakharov, Lev N.; Haley, Michael M.; Johnson, Darren W.

2012-01-01

A tripodal ditopic receptor presents H-bond donors and a phosphine oxide to potential guests. In the idealized binding conformation, an endohedral P═O functionality provides enhanced halide binding in the presence of lithium with the greatest ΔΔG° observed for bromide, while minimal changes in Ka are observed in the presence of sodium. PMID:21655566

Synthesis and Mossbauer spectroscopic studies of chemically oxidized ferrocenyl(phenyl)phosphines.

PubMed

Durfey, D A; Kirss, R U; Frommen, C; Feighery, W

The electrochemical potentials of Fc3-xPPhx, (1-3, x = 0-2) and (FcPPh)n (4) indicate that iodine should oxidize ferrocenyl(phenyl)phosphines. The molar conductivity of solutions of 1-3 increases sharply when the solutions are titrated with iodine, leveling off after the addition of > 2 equiv of oxidant, consistent with formation of 1:1 electrolytes. Diamagnetic salts 6-9 are observed upon addition of a benzene solution of iodine to a benzene solution of 1-4 at ambient temperature in ratios of I2/metallocene ranging from 1:1 to 2:1. Well-resolved 1H and 31P NMR spectra are obtained for 6-8. Absorptions assigned to the I3- anion dominate the UV-vis spectrum of 6-8, whereas characteristic absorptions for [Fc][I3] are absent. Mossbauer spectra of 7-9 reveal isomer shifts consistent with low-spin iron(II) in ferrocene derivatives rather than those in ferricenium ions. Small amounts of low-spin FeIII appear to be present in 6. Taken together, the results suggest that 6-9 are iodophosphonium salts and not ferricenium salts. Diferrocenyl(phenyl)phosphine oxide (5) reacts with iodine to produce a diamagnetic, dark solid 10. Low-spin FeII is observed at 77 and 293 K in the Mossbauer spectra of 10 with no evidence for oxidation of FeII to FeIII. Compound 10 is proposed to be a neutral complex between 5 and I2. Reactions between 5 and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) yield [Fc2P(=O)][DDQ]2 (11). Mossbauer spectroscopy of 11 indicates the presence of a mixture of low-spin FeII and low-spin FeIII at 77 K, suggesting that some electron transfer occurs from 5 to DDQ. The fraction of low-spin FeIII increases at room temperature.

A physiologically based kinetic model for bacterial sulfide oxidation.

PubMed

Klok, Johannes B M; de Graaff, Marco; van den Bosch, Pim L F; Boelee, Nadine C; Keesman, Karel J; Janssen, Albert J H

2013-02-01

In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was concluded that the oxidation-reduction state of cytochrome c is a direct measure for the bacterial end-product formation. Given this physiological feature, incorporation of the oxidation state of cytochrome c in a mathematical model for the bacterial oxidation kinetics will yield a physiologically based model structure. This paper presents a physiologically based model, describing the dynamic formation of the various end-products in the biodesulfurization process. It consists of three elements: 1) Michaelis-Menten kinetics combined with 2) a cytochrome c driven mechanism describing 3) the rate determining enzymes of the respiratory system of haloalkaliphilic sulfide oxidizing bacteria. The proposed model is successfully validated against independent data obtained from biological respiration tests and bench scale gas-lift reactor experiments. The results demonstrate that the model is a powerful tool to describe product formation for haloalkaliphilic biomass under dynamic conditions. The model predicts a maximum S⁰ formation of about 98 mol%. A future challenge is the optimization of this bioprocess by improving the dissolved oxygen control strategy and reactor design. Copyright © 2012 Elsevier Ltd. All rights reserved.

Complete oxidation of solid phase sulfides by manganese and bacteria in anoxic marine sediments

NASA Astrophysics Data System (ADS)

Aller, Robert C.; Rude, Peter D.

1988-03-01

During the physical or biological reworking of surficial marine sediments, metal oxides are often brought into contact with both solid and dissolved sulfides. Experiments simulating these mixing processes demonstrate that in natural sediments Mn-oxides can completely oxidize solid phase sulfides to SO 4- under anoxic conditions. The major source of sulfur is probably acid volatile sulfide. Minerals containing Mn +4 are apparently more effective than Mn +3 in driving the oxidation. There is slight or no evidence for complete sulfide oxidation by Fe-oxides under similar conditions. The reaction is inhibited by DNP (dinitrophenol) and azide, implying biological mediation by a group of chemolithotrophic bacteria such as the thiobacilli, having a well-organized cytochrome system, oxidative phosphorylation coupled with sulfide oxidation, and possibly aulolrophic CO 2 fixation. Lack of sensitivity to chlorate suggests that a No 3- reductase complex is not involved. Because of metal reduction and the overall stoichiometry of reaction, this sulfide oxidation causes a rise in pH in contrast to oxidation by O 2. Alkalinity is also simultaneously depeleted by Mn, Ca carbonate precipitation. Both manganoan kutnahorite and manganoan calcite are observed to form rapidly (days) during Mn reduction. The oxidation of sulfides by Mn-oxides is likely to be important, but highly variable, in organic-rich shelf sediments and environments such as hydrothermal vents where sulfidic plumes contact oxidized metals. A substantial Proportion of sedimentary sulfide may be oxidized and Mn reduced by this pathway, particularly in bioturbated sediments. The relative roles of lithotrophic (S) and heterotrophic (C) Mn-reduction in marine sediments are presently unknown.

Biomolecule conjugation strategy using novel water-soluble phosphine-based chelating agents

DOEpatents

Katti, Kattesh V.; Gali, Hariprasad; Volkert, Wynn A.

2004-08-24

This invention describes a novel strategy to produce phosphine-functionalized biomolecules (e.g. peptides or proteins) for potential use in the design and development of site-specific radiopharmaceuticals for diagnosis or therapy of specific cancers. Hydrophilic alkyl phosphines, in general, tend to be oxidatively unstable. Therefore, incorporation of such phosphine functionalities on peptide (and other biomolecule) backbones, without oxidizing the P.sup.III centers, is difficult. In this context this discovery reports on a new technology by which phosphines, in the form of bifunctional chelating agents, can be directly incorporated on biomolecular backbones using manual synthetic or solid phase peptide synthesis methodologies. The superior ligating abilities of phosphine ligands, with various diagnostically (e.g. TC-99m) or therapeutically (e.g. Re186/188, Rh-105, Au-199) useful radiometals, coupled with the findings that the resulting complexes demonstrate high in vivo stability makes this approach useful in the development of radiolabeled biomolecules for applications in the design of tumor-specific radiopharmaceuticals.

Coenzyme Q deficiency causes impairment of the sulfide oxidation pathway.

PubMed

Ziosi, Marcello; Di Meo, Ivano; Kleiner, Giulio; Gao, Xing-Huang; Barca, Emanuele; Sanchez-Quintero, Maria J; Tadesse, Saba; Jiang, Hongfeng; Qiao, Changhong; Rodenburg, Richard J; Scalais, Emmanuel; Schuelke, Markus; Willard, Belinda; Hatzoglou, Maria; Tiranti, Valeria; Quinzii, Catarina M

2017-01-01

Coenzyme Q (CoQ) is an electron acceptor for sulfide-quinone reductase (SQR), the first enzyme of the hydrogen sulfide oxidation pathway. Here, we show that lack of CoQ in human skin fibroblasts causes impairment of hydrogen sulfide oxidation, proportional to the residual levels of CoQ. Biochemical and molecular abnormalities are rescued by CoQ supplementation in vitro and recapitulated by pharmacological inhibition of CoQ biosynthesis in skin fibroblasts and ADCK3 depletion in HeLa cells. Kidneys of Pdss2 kd/kd mice, which only have ~15% residual CoQ concentrations and are clinically affected, showed (i) reduced protein levels of SQR and downstream enzymes, (ii) accumulation of hydrogen sulfides, and (iii) glutathione depletion. These abnormalities were not present in brain, which maintains ~30% residual CoQ and is clinically unaffected. In Pdss2 kd/kd mice, we also observed low levels of plasma and urine thiosulfate and increased blood C4-C6 acylcarnitines. We propose that impairment of the sulfide oxidation pathway induced by decreased levels of CoQ causes accumulation of sulfides and consequent inhibition of short-chain acyl-CoA dehydrogenase and glutathione depletion, which contributes to increased oxidative stress and kidney failure. © 2016 The Authors. Published under the terms of the CC BY 4.0 license.

High conducting oxide--sulfide composite lithium superionic conductor

DOEpatents

Liang, Chengdu; Rangasamy, Ezhiylmurugan; Dudney, Nancy J.; Keum, Jong Kahk; Rondinone, Adam Justin

2017-01-17

A solid electrolyte for a lithium-sulfur battery includes particles of a lithium ion conducting oxide composition embedded within a lithium ion conducting sulfide composition. The lithium ion conducting oxide composition can be Li.sub.7La.sub.3Zr.sub.2O.sub.12 (LLZO). The lithium ion conducting sulfide composition can be .beta.-Li.sub.3PS.sub.4 (LPS). A lithium ion battery and a method of making a solid electrolyte for a lithium ion battery are also disclosed.

Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment

NASA Astrophysics Data System (ADS)

Lengke, Maggy F.; Tempel, Regina N.

2005-01-01

Arsenic sulfide (AsS (am), As 2S 3 (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH˜2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As 2S 3 (am), orpiment, AsS (am), and realgar, respectively. Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ˜1.14 to 13 times and that pH values decrease by ˜0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase. Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As 2S 3 (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH˜8 and temperature 25 to 40°C, and pyrite activation energies are ˜52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As 2S 3 (am). Low activation energies of As 2S 3 (am) indicate that diffusion may be rate controlling. Limestone is

Oxidative Weathering and Microbial Diversity of an Inactive Seafloor Hydrothermal Sulfide Chimney

PubMed Central

Li, Jiangtao; Cui, Jiamei; Yang, Qunhui; Cui, Guojie; Wei, Bingbing; Wu, Zijun; Wang, Yong; Zhou, Huaiyang

2017-01-01

When its hydrothermal supply ceases, hydrothermal sulfide chimneys become inactive and commonly experience oxidative weathering on the seafloor. However, little is known about the oxidative weathering of inactive sulfide chimneys, nor about associated microbial community structures and their succession during this weathering process. In this work, an inactive sulfide chimney and a young chimney in the early sulfate stage of formation were collected from the Main Endeavor Field of the Juan de Fuca Ridge. To assess oxidative weathering, the ultrastructures of secondary alteration products accumulating on the chimney surface were examined and the presence of possible Fe-oxidizing bacteria (FeOB) was investigated. The results of ultrastructure observation revealed that FeOB-associated ultrastructures with indicative morphologies were abundantly present. Iron oxidizers primarily consisted of members closely related to Gallionella spp. and Mariprofundus spp., indicating Fe-oxidizing species likely promote the oxidative weathering of inactive sulfide chimneys. Abiotic accumulation of Fe-rich substances further indicates that oxidative weathering is a complex, dynamic process, alternately controlled by FeOB and by abiotic oxidization. Although hydrothermal fluid flow had ceased, inactive chimneys still accommodate an abundant and diverse microbiome whose microbial composition and metabolic potential dramatically differ from their counterparts at active vents. Bacterial lineages within current inactive chimney are dominated by members of α-, δ-, and γ-Proteobacteria and they are deduced to be closely involved in a diverse set of geochemical processes including iron oxidation, nitrogen fixation, ammonia oxidation and denitrification. At last, by examining microbial communities within hydrothermal chimneys at different formation stages, a general microbial community succession can be deduced from early formation stages of a sulfate chimney to actively mature sulfide

Polysulfides as Intermediates in the Oxidation of Sulfide to Sulfate by Beggiatoa spp.

PubMed Central

Schwedt, Anne; Kreutzmann, Anne-Christin; Kuypers, Marcel M. M.; Milucka, Jana

2014-01-01

Zero-valent sulfur is a key intermediate in the microbial oxidation of sulfide to sulfate. Many sulfide-oxidizing bacteria produce and store large amounts of sulfur intra- or extracellularly. It is still not understood how the stored sulfur is metabolized, as the most stable form of S0 under standard biological conditions, orthorhombic α-sulfur, is most likely inaccessible to bacterial enzymes. Here we analyzed the speciation of sulfur in single cells of living sulfide-oxidizing bacteria via Raman spectroscopy. Our results showed that under various ecological and physiological conditions, all three investigated Beggiatoa strains stored sulfur as a combination of cyclooctasulfur (S8) and inorganic polysulfides (Sn2−). Linear sulfur chains were detected during both the oxidation and reduction of stored sulfur, suggesting that Sn2− species represent a universal pool of bioavailable sulfur. Formation of polysulfides due to the cleavage of sulfur rings could occur biologically by thiol-containing enzymes or chemically by the strong nucleophile HS− as Beggiatoa migrates vertically between oxic and sulfidic zones in the environment. Most Beggiatoa spp. thus far studied can oxidize sulfur further to sulfate. Our results suggest that the ratio of produced sulfur and sulfate varies depending on the sulfide flux. Almost all of the sulfide was oxidized directly to sulfate under low-sulfide-flux conditions, whereas only 50% was oxidized to sulfate under high-sulfide-flux conditions leading to S0 deposition. With Raman spectroscopy we could show that sulfate accumulated in Beggiatoa filaments, reaching intracellular concentrations of 0.72 to 1.73 M. PMID:24212585

Room temperature alkynylation of H-phosphi(na)tes and secondary phosphine oxides with ethynylbenziodoxolone (EBX) reagents.

PubMed

Chen, C Chun; Waser, Jerome

2014-11-04

Highly efficient protocols for the alkynylation of H-phosphi(na)tes and secondary phosphine oxides with silyl, aryl and alkyl ethynyl-benziodoxolone (EBX) reagents are reported. Alkynyl phosphorus compounds were obtained in 69-93% yield without the need for a transition metal catalyst at room temperature under open flask conditions.

Electric coupling between distant nitrate reduction and sulfide oxidation in marine sediment

PubMed Central

Marzocchi, Ugo; Trojan, Daniela; Larsen, Steffen; Louise Meyer, Rikke; Peter Revsbech, Niels; Schramm, Andreas; Peter Nielsen, Lars; Risgaard-Petersen, Nils

2014-01-01

Filamentous bacteria of the Desulfobulbaceae family can conduct electrons over centimeter-long distances thereby coupling oxygen reduction at the surface of marine sediment to sulfide oxidation in deeper anoxic layers. The ability of these cable bacteria to use alternative electron acceptors is currently unknown. Here we show that these organisms can use also nitrate or nitrite as an electron acceptor thereby coupling the reduction of nitrate to distant oxidation of sulfide. Sulfidic marine sediment was incubated with overlying nitrate-amended anoxic seawater. Within 2 months, electric coupling of spatially segregated nitrate reduction and sulfide oxidation was evident from: (1) the formation of a 4–6-mm-deep zone separating sulfide oxidation from the associated nitrate reduction, and (2) the presence of pH signatures consistent with proton consumption by cathodic nitrate reduction, and proton production by anodic sulfide oxidation. Filamentous Desulfobulbaceae with the longitudinal structures characteristic of cable bacteria were detected in anoxic, nitrate-amended incubations but not in anoxic, nitrate-free controls. Nitrate reduction by cable bacteria using long-distance electron transport to get privileged access to distant electron donors is a hitherto unknown mechanism in nitrogen and sulfur transformations, and the quantitative importance for elements cycling remains to be addressed. PMID:24577351

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

2001-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, Brian S.; Gupta, Raghubir P.

1999-01-01

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream.

Metal sulfide initiators for metal oxide sorbent regeneration

DOEpatents

Turk, B.S.; Gupta, R.P.

1999-06-22

A process of regenerating a sulfided sorbent is provided. According to the process of the invention, a substantial portion of the energy necessary to initiate the regeneration reaction is provided by the combustion of a particulate metal sulfide additive. In using the particulate metal sulfide additive, the oxygen-containing gas used to regenerate the sulfided sorbent can be fed to the regeneration zone without heating or at a lower temperature than used in conventional processes wherein the regeneration reaction is initiated only by heating the oxygen-containing gas. The particulate metal sulfide additive is preferably an inexpensive mineral ore such as iron pyrite which does not adversely affect the regeneration or corresponding desulfurization reactions. The invention further includes a sorbent composition comprising the particulate metal sulfide additive in admixture with an active metal oxide sorbent capable of removing one or more sulfur compounds from a sulfur-containing gas stream. 1 fig.

Kinetics of Indigenous Nitrate Reducing Sulfide Oxidizing Activity in Microaerophilic Wastewater Biofilms

PubMed Central

Villahermosa, Desirée; Corzo, Alfonso; Garcia-Robledo, Emilio; González, Juan M.; Papaspyrou, Sokratis

2016-01-01

Nitrate decreases sulfide release in wastewater treatment plants (WWTP), but little is known on how it affects the microzonation and kinetics of related microbial processes within the biofilm. The effect of nitrate addition on these properties for sulfate reduction, sulfide oxidation, and oxygen respiration were studied with the use of microelectrodes in microaerophilic wastewater biofilms. Mass balance calaculations and community composition analysis were also performed. At basal WWTP conditions, the biofilm presented a double-layer system. The upper microaerophilic layer (~300 μm) showed low sulfide production (0.31 μmol cm-3 h-1) and oxygen consumption rates (0.01 μmol cm-3 h-1). The anoxic lower layer showed high sulfide production (2.7 μmol cm-3 h-1). Nitrate addition decreased net sulfide production rates, caused by an increase in sulfide oxidation rates (SOR) in the upper layer, rather than an inhibition of sulfate reducing bacteria (SRB). This suggests that the indigenous nitrate reducing-sulfide oxidizing bacteria (NR-SOB) were immediately activated by nitrate. The functional vertical structure of the biofilm changed to a triple-layer system, where the previously upper sulfide-producing layer in the absence of nitrate split into two new layers: 1) an upper sulfide-consuming layer, whose thickness is probably determined by the nitrate penetration depth within the biofilm, and 2) a middle layer producing sulfide at an even higher rate than in the absence of nitrate in some cases. Below these layers, the lower net sulfide-producing layer remained unaffected. Net SOR varied from 0.05 to 0.72 μmol cm-3 h-1 depending on nitrate and sulfate availability. Addition of low nitrate concentrations likely increased sulfate availability within the biofilm and resulted in an increase of both net sulfate reduction and net sulfide oxidation by overcoming sulfate diffusional limitation from the water phase and the strong coupling between SRB and NR-SOB syntrophic

'Low-acid' sulfide oxidation using nitrate-enriched groundwater

NASA Astrophysics Data System (ADS)

Donn, Michael; Boxall, Naomi; Reid, Nathan; Meakin, Rebecca; Gray, David; Kaksonen, Anna; Robson, Thomas; Shiers, Denis

2016-04-01

Acid drainage (AMD/ARD) is undoubtedly one of the largest environmental, legislative and economic challenges facing the mining industry. In Australia alone, at least 60m is spent on AMD related issues annually, and the global cost is estimated to be in the order of tens of billions US. Furthermore, the challenge of safely and economically storing or treating sulfidic wastes will likely intensify because of the trend towards larger mines that process increasingly higher volumes of lower grade ores and the associated sulfidic wastes and lower profit margins. While the challenge of managing potentially acid forming (PAF) wastes will likely intensify, the industrial approaches to preventing acid production or ameliorating the effects has stagnated for decades. Conventionally, PAF waste is segregated and encapsulated in non-PAF tips to limit access to atmospheric oxygen. Two key limitations of the 'cap and cover' approach are: 1) the hazard (PAF) is not actually removed; only the pollutant linkage is severed; and, 2) these engineered structures are susceptible to physical failure in short-to-medium term, potentially re-establishing that pollutant linkage. In an effort to address these concerns, CSIRO is investigating a passive, 'low-acid' oxidation mechanism for sulfide treatment, which can potentially produce one quarter as much acidity compared with pyrite oxidation under atmospheric oxygen. This 'low-acid' mechanism relies on nitrate, rather than oxygen, as the primary electron accepter and the activity of specifically cultured chemolithoautotrophic bacteria and archaea communities. This research was prompted by the observation that, in deeply weathered terrains of Australia, shallow (oxic to sub-oxic) groundwater contacting weathering sulfides are commonly inconsistent with the geochemical conditions produced by ARD. One key characteristic of these aquifers is the natural abundance of nitrate on a regional scale, which becomes depleted around the sulfide bodies, and

Discovery of Brigatinib (AP26113), a Phosphine Oxide-Containing, Potent, Orally Active Inhibitor of Anaplastic Lymphoma Kinase.

PubMed

Huang, Wei-Sheng; Liu, Shuangying; Zou, Dong; Thomas, Mathew; Wang, Yihan; Zhou, Tianjun; Romero, Jan; Kohlmann, Anna; Li, Feng; Qi, Jiwei; Cai, Lisi; Dwight, Timothy A; Xu, Yongjin; Xu, Rongsong; Dodd, Rory; Toms, Angela; Parillon, Lois; Lu, Xiaohui; Anjum, Rana; Zhang, Sen; Wang, Frank; Keats, Jeffrey; Wardwell, Scott D; Ning, Yaoyu; Xu, Qihong; Moran, Lauren E; Mohemmad, Qurish K; Jang, Hyun Gyung; Clackson, Tim; Narasimhan, Narayana I; Rivera, Victor M; Zhu, Xiaotian; Dalgarno, David; Shakespeare, William C

2016-05-26

In the treatment of echinoderm microtubule-associated protein-like 4 (EML4)-anaplastic lymphoma kinase positive (ALK+) non-small-cell lung cancer (NSCLC), secondary mutations within the ALK kinase domain have emerged as a major resistance mechanism to both first- and second-generation ALK inhibitors. This report describes the design and synthesis of a series of 2,4-diarylaminopyrimidine-based potent and selective ALK inhibitors culminating in identification of the investigational clinical candidate brigatinib. A unique structural feature of brigatinib is a phosphine oxide, an overlooked but novel hydrogen-bond acceptor that drives potency and selectivity in addition to favorable ADME properties. Brigatinib displayed low nanomolar IC50s against native ALK and all tested clinically relevant ALK mutants in both enzyme-based biochemical and cell-based viability assays and demonstrated efficacy in multiple ALK+ xenografts in mice, including Karpas-299 (anaplastic large-cell lymphomas [ALCL]) and H3122 (NSCLC). Brigatinib represents the most clinically advanced phosphine oxide-containing drug candidate to date and is currently being evaluated in a global phase 2 registration trial.

Microbial oxidation of soluble sulfide in produced water from the Bakkeen Sands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gevertz, D.; Zimmerman, S.; Jenneman, G.E.

1995-12-31

The presence of soluble sulfide in produced water results in problems for the petroleum industry due to its toxicity, odor, corrosive nature, and potential for wellbore plugging. Sulfide oxidation by indigenous nitrate-reducing bacteria (NRB) present in brine collected from wells at the Coleville Unit (CVU) in Saskatchewan, Canada, was investigated. Sulfide oxidation took place readily when nitrate and phosphate were added to brine enrichment cultures, resulting in a decrease in sulfide levels of 99-165 ppm to nondetectable levels (< 3.3 ppm). Produced water collected from a number of producing wells was screened to determine the time required for complete sulfidemore » oxidation, in order to select candidate wells for treatment. Three wells were chosen, based on sulfide removal in 48 hours or less. These wells were treated down the backside of the annulus with a solution containing 10 mM KNO{sub 3} and 100 {mu}M NaH{sub 2}PO{sub 4}. Following a 24- to 72-hour shut-in, reductions in pretreatment sulfide levels of greater than 90% were observed for two of the wells, as well as sustained sulfide reductions of 50% for at least two days following startup. NRB populations in the produced brine were observed to increase significantly following treatment, but no significant increases in sulfate-reducing bacteria were observed. These results demonstrate the technical feasibility of stimulating indigenous populations of NRB to remediate and control sulfide in produced brine.« less

Kinetic studies of sulfide mineral oxidation and xanthate adsorption

NASA Astrophysics Data System (ADS)

Mendiratta, Neeraj K.

2000-10-01

Sulfide minerals are a major source of metals; however, certain sulfide minerals, such as pyrite and pyrrhotite, are less desirable. Froth flotation is a commonly used separation technique, which requires the use of several reagents to float and depress different sulfide minerals. Xanthate, a thiol collector, has gained immense usage in sulfide minerals flotation. However, some sulfides are naturally hydrophobic and may float without a collector. Iron sulfides, such as pyrite and pyrrhotite, are few of the most abundant minerals, yet economically insignificant. Their existence with other sulfide minerals leads to an inefficient separation process as well as environmental problems, such as acid mine drainage during mining and processing and SO 2 emissions during smelting process. A part of the present study is focused on understanding their behavior, which leads to undesired flotation and difficulties in separation. The major reasons for the undesired flotation are attributed to the collectorless hydrophobicity and the activation with heavy metal ions. To better understand the collectorless hydrophobicity of pyrite, Electrochemical Impedance Spectroscopy (EIS) of freshly fractured pyrite electrodes was used to study the oxidation and reduction of the mineral. The EIS results showed that the rate of reaction increases with oxidation and reduction. At moderate oxidizing potentials, the rate of reaction is too slow to replenish hydrophilic iron species leaving hydrophobic sulfur species on the surface. However, at higher potentials, iron species are replaced fast enough to depress its flotation. Effects of pH and polishing were also explored using EIS. Besides collectorless hydrophobicity, the activation of pyrrhotite with nickel ions and interaction with xanthate ions makes the separation more difficult. DETA and SO2 are commonly used as pyrrhotite depressants; however, the mechanism is not very well understood. Contact angle measurements, cyclic voltammetry and Tafel

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate.

PubMed

Thorup, Casper; Schramm, Andreas; Findlay, Alyssa J; Finster, Kai W; Schreiber, Lars

2017-07-18

This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. IMPORTANCE Sulfide oxidation and sulfate reduction, the two major branches of the sulfur cycle, are usually ascribed to distinct sets of microbes with distinct diagnostic genes. Here we show a more complex picture, as D. alkaliphilus , with the genomic setup of a sulfate reducer, grows by sulfide oxidation. The high expression of genes typically involved in the sulfate reduction pathway suggests that these genes, including the reductive-type dissimilatory bisulfite reductases, are also involved in as-yet-unresolved sulfide oxidation pathways. Finally, D. alkaliphilus is closely related to cable bacteria, which grow by electrogenic sulfide oxidation. Since there are no pure cultures of cable bacteria, D. alkaliphilus may represent an

Oxygen and sulfur isotope fractionation during sulfide oxidation by anoxygenic phototrophic bacteria

NASA Astrophysics Data System (ADS)

Brabec, Michelle Y.; Lyons, Timothy W.; Mandernack, Kevin W.

2012-04-01

Sulfide-mediated anoxygenic photosynthesis (SMAP) carried out by anaerobic phototrophic bacteria may have played an important role in sulfur cycling, formation of sulfate, and, perhaps, primary production in the Earth’s early oceans. Determination of ε34SSO4-Sulfide- and ε18OSO4-H2O values for bacterial sulfide oxidation will permit more refined interpretation of the δ34S and δ18OSO4 values measured in modern anoxic environments, such as meromictic lakes where sulfide commonly extends into the photic zone, and in the ancient rock record, particularly during periods of the Precambrian when anoxic and sulfidic (euxinic) conditions were believed to be more pervasive than today. Laboratory experiments with anaerobic purple and green sulfur phototrophs, Allochromatium vinosum and Chlorobaculum tepidum, respectively, were conducted to determine the sulfur and oxygen isotope fractionation during the oxidation of sulfide to sulfate. Replicate experiments were conducted at 25 °C for A. vinosum and 45 °C for C. tepidum, and in duplicate at three different starting oxygen isotope values for water to determine sulfate-water oxygen isotope fractionations accurately (ε18OSO4-H2O). ε18OSO4-H2O values of 5.6 ± 0.2‰ and 5.4 ± 0.1‰ were obtained for A. vinosum and C. tepidum, respectively. Temperature had no apparent effect on the ε18OSO4-H2O values. By combining all data from both cultures, an average ε18OSO4-H2O value of 5.6 ± 0.3‰ was obtained for SMAP. This value falls between those previously reported for bacterial oxidation of sphalerite and elemental sulfur (7-9‰) and abiotic and biotic oxidation of pyrite and chalcopyrite (2-4‰). Sulfur isotope fractionation between sulfide and sulfate formed by A.vinosum was negligible (0.1 ± 0.2‰) during all experiments. For C. tepidum an apparent fractionation of -2.3 ± 0.5‰ was observed during the earlier stages of oxidation based on bulk δ34S measurements of sulfate and sulfide and became smaller (-0.7 �

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy

Online oxygen control for sulfide oxidation in anaerobic treatment of high-sulfate wastewater.

PubMed

Khanal, Samir Kumar; Huang, Ju-Chang

2006-04-01

A new technique for sulfide control was investigated in an upflow-anaerobic filter (UAF) treating high-strength, sulfate-rich wastewater. The technique used periodic oxygen injection using oxidation-reduction potential (ORP) as a controlling parameter to regulate oxygen injection. The UAF was operated at a constant influent total-organic carbon of 6740 mg/L but with different influent sulfates of 1000, 3000, and 6000 mg/L. At 1000 and 3000 mg/L influent sulfates, the produced sulfide did not impose any inhibition to methane-producing bacteria (MPB). However, at 6000 mg/L influent sulfate, the produced dissolved sulfide of 804 mg S/L (free sulfide = 280 mg S/L) severely inhibited the methanogenesis, but not the sulfidogenesis. Upon oxygen injection at elevated ORP of -265 mV, sulfides were almost completely eliminated with a concomitant improvement in methane yield by 46%. If oxygenation was excessive because of an oversetting of ORP, the excess oxygen could be used rapidly by facultative heterotrophs, thereby protecting the MPB from oxygen stress. Regarding online sulfide oxidation, it was found that the biogas and injected oxygen needed to pass through an aqueous layer containing trace metals, which were found to have a significant catalytic effect on abiotic sulfide oxidation.

Potentials of biological oxidation processes for the treatment of spent sulfidic caustics containing thiols.

PubMed

Sipma, Jan; Svitelskaya, Anna; van der Mark, Bart; Pol, Look W Hulshoff; Lettinga, Gatze; Buisman, Cees J N; Janssen, Albert J H

2004-12-01

This research focused on the biological treatment of sulfidic spent caustics from refineries, which contain mainly hydrogen sulfide, methanethiol (MT) and ethanethiol (ET). Also various organic compounds can be present such as BTEX. Biological oxidation of 2.5 mM MT in batch experiments occurred after MT was first auto-oxidized into dimethyldisulfide (DMDS) whereafter oxidation into sulfate was completed in 350 h. DMDS as sole substrate was completely oxidized within 40 h. Therefore, DMDS formation seems to play an important role in detoxification of MT. Biological oxidation of ET and buthanethiol was not successful in batch experiments. Complete oxidation of MT and ET was observed in flow-through reactor experiments. Simultaneous oxidation of sulfide and MT was achieved when treating a synthetic spent caustic, containing 10 mM sulfide and 2.5 mM MT, in a bubble column reactor with carrier material at a hydraulic retention time of 6 h. Addition of 7.5 mM phenol, a common pollutant of spent caustics, did not adversely affect the biological oxidation process and phenol was completely removed from the effluent. Finally, three different spent caustics solutions from refineries were successfully treated.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-02-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1-xFexS). The oxidation of synthetic Zn1-xFexS is easier than marmatite in air.

Mechanism study on the sulfidation of ZnO with sulfur and iron oxide at high temperature

PubMed Central

Han, Junwei; Liu, Wei; Zhang, Tianfu; Xue, Kai; Li, Wenhua; Jiao, Fen; Qin, Wenqing

2017-01-01

The mechanism of ZnO sulfidation with sulfur and iron oxide at high temperatures was studied. The thermodynamic analysis, sulfidation behavior of zinc, phase transformations, morphology changes, and surface properties were investigated by HSC 5.0 combined with FactSage 7.0, ICP, XRD, optical microscopy coupled with SEM-EDS, and XPS. The results indicate that increasing temperature and adding iron oxide can not only improve the sulfidation of ZnO but also promote the formation and growth of ZnS crystals. Fe2O3 captured the sulfur in the initial sulfidation process as iron sulfides, which then acted as the sulfurizing agent in the late period, thus reducing sulfur escape at high temperatures. The addition of carbon can not only enhance the sulfidation but increase sulfur utilization rate and eliminate the generation of SO2. The surfaces of marmatite and synthetic zinc sulfides contain high oxygen due to oxidation and oxygen adsorption. Hydroxyl easily absorbs on the surface of iron-bearing zinc sulfide (Zn1−xFexS). The oxidation of synthetic Zn1−xFexS is easier than marmatite in air. PMID:28186156

Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

NASA Astrophysics Data System (ADS)

Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

2012-04-01

Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to

Survival of hydrogen sulfide oxidizing bacteria on corroded concrete surfaces of sewer systems.

PubMed

Jensen, H S; Nielsen, A H; Hvitved-Jacobsen, T; Vollertsen, J

2008-01-01

The activity of hydrogen sulfide oxidizing bacteria within corroded concrete from a sewer manhole was investigated. The bacteria were exposed to hydrogen sulfide starvation for up till 18 months, upon which their hydrogen sulfide oxidizing activity was measured. It was tested whether the observed reduction in biological activity was caused by a biological lag phase or by decay of the bacteria. The results showed that the bacterial activity declined with approximately 40% pr. month during the first two months of hydrogen sulfide starvation. After 2-3 months of starvation, the activity stabilized. Even after 6 months of starvation, exposure to hydrogen sulfide for 6 hours a day on three successive days could restore the bacteriological activity to about 80% of the initial activity. After 12 months of starvation, the activity could, however, not be restored, and after 18 months the biological activity approached zero. The long-term survival aspect of concrete corroding bacteria has implications for predicting hydrogen sulfide corrosion in sewer systems subject to irregular hydrogen sulfide loadings, e.g. as they occur in temperate climates where hydrogen sulfide often is a summer-problem only.

Oxidative Weathering of Archean Sulfides: Implications for the Great Oxidation Event

NASA Astrophysics Data System (ADS)

Johnson, A.; Romaniello, S. J.; Reinhard, C.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2015-12-01

The first widely accepted evidence for oxidation of Earth's atmosphere and oceans occurs ~2.45 Ga immediately prior to the Great Oxidation Event (GOE). A major line of evidence for this transition includes the abundances and isotopic variations of redox-sensitive transition metals in marine sediments (e.g., Fe, Mo, Re, Cr, and U). It is often assumed that oxidative weathering is required to liberate these redox-sensitive elements from sulfide minerals in the crust, and hence that their presence in early Archean marine sediments signifies that oxidative weathering was stimulated by small and/or transient "whiffs" of O2 in the environment.1 However, studies of crustal sulfide reactivity have not been conducted at O2 concentrations as low as those that would have prevailed when O2 began its rise during the late Archean (estimated at <10-5 present atmospheric O2).2 As a result, it is difficult to quantify O2 concentrations implied by observed trace metal variations. As a first step toward providing more quantitative constraints on late Archean pO2, we conducted laboratory studies of pyrite and molybdenite oxidation kinetics at the nanomolar O2 concentrations that are relevant to late Archean environments. These measurements were made using recently developed, highly sensitive optical O2 sensors to monitor the rates at which the powdered minerals consumed dissolved O2 in a range of pH-buffered solutions.3Our data extend the range of experimental pyrite oxidation rates in the literature by three orders of magnitude from ~10-3 present atmospheric O2 to ~10-6. We find that molybdenite and pyrite oxidation continues to <1 nM O2 (4 x 10-6 present atmospheric O2). This implies that oxidative weathering of sulfides could occur under conditions which preserve MIF S fractionation. Furthermore, our results indicate that the rate law and reaction order of pyrite oxidation kinetics change significantly at nanomolar concentrations of O2 when compared to previous compilations.2 Our

Disguised as a Sulfate Reducer: Growth of the Deltaproteobacterium Desulfurivibrio alkaliphilus by Sulfide Oxidation with Nitrate

PubMed Central

Thorup, Casper; Schramm, Andreas

2017-01-01

ABSTRACT This study demonstrates that the deltaproteobacterium Desulfurivibrio alkaliphilus can grow chemolithotrophically by coupling sulfide oxidation to the dissimilatory reduction of nitrate and nitrite to ammonium. Key genes of known sulfide oxidation pathways are absent from the genome of D. alkaliphilus. Instead, the genome contains all of the genes necessary for sulfate reduction, including a gene for a reductive-type dissimilatory bisulfite reductase (DSR). Despite this, growth by sulfate reduction was not observed. Transcriptomic analysis revealed a very high expression level of sulfate-reduction genes during growth by sulfide oxidation, while inhibition experiments with molybdate pointed to elemental sulfur/polysulfides as intermediates. Consequently, we propose that D. alkaliphilus initially oxidizes sulfide to elemental sulfur, which is then either disproportionated, or oxidized by a reversal of the sulfate reduction pathway. This is the first study providing evidence that a reductive-type DSR is involved in a sulfide oxidation pathway. Transcriptome sequencing further suggests that nitrate reduction to ammonium is performed by a novel type of periplasmic nitrate reductase and an unusual membrane-anchored nitrite reductase. PMID:28720728

Sulfur speciation and sulfide oxidation in the water column of the Black Sea

NASA Astrophysics Data System (ADS)

Luther, George W., III; Church, Thomas M.; Powell, David

We have applied sulfur speciation techniques to understand the chemistry and cycling of sulfur in Black Sea waters. The only reduced dissolved inorganic sulfur species detected (above the low minimum detection limits of the voltammetric methods employed) in the water column was hydrogen sulfide. The maximum concentration of sulfide (423 μM) is similar to previous reports. Using a cathodic stripping square wave voltammetry (CSSWV) method for nanomolar levels of sulfide, we determined the precise boundary between the "free" hydrogen sulfide (sulfidic) zone and the upper (oxic/suboxic) water column at the two stations studied. This boundary has apparently moved up by about 50 m in the past 20 years. Our results help demonstrate three chemically distinct zones of water in the central basin of the Black Sea: (1) the oxic [0-65 m], (2) the anoxic/nonsulfidic [65-100 m] and (3) the sulfidic [>100 m]. Sulfide bound to metals ("complexed" sulfide) is observed in both the oxic and anoxic/nonsulfidic zones of the water column. This supports previous studies on metal sulfide forms. From the electrochemical data, it is possible to estimate the strength of the complexation of sulfide to metals (log K = 10 to 11). Thiosulfate and sulfite were below our minimum detectable limit (MDL) of 50 nM using CSSWV. Elemental sulfur (MDL 5 nM) was detected below the onset of the hydrogen sulfide zone (90-100 m) with a maximum of 30-60 nM near 120 m. The sulfur speciation results for the Black Sea are lower by one order of magnitude or more than other marine systems such as the Cariaco Trench and salt marshes. New HPLC techniques were applied to detect thiols at submicromolar levels. The presence of thiols (2-mercaptoethylamine, 2-mercaptoethanol, N-acetylcysteine and glutathione) is correlated with the remineralization of organic matter at the oxic and anoxic/nonsulfidic interface. Water samples collected from the upper 50 m of the sulfidic zone showed significant sulfide oxidation on

Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

DOEpatents

Crabtree, Robert H.; Brown, Stephen H.

1989-01-01

The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

DOEpatents

Crabtree, R.H.; Brown, S.H.

1989-10-17

The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

Oxidative Remobilization of Technetium Sequestered by Sulfide-Transformed Nano Zerovalent Iron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fan, Dimin; Anitori, Roberto; Tebo, Bradley M.

2014-06-02

The dissolution of Tc(IV) sulfide and concurrent transformation of sulfidated ZVI during 2 oxidation were examined. Kinetic data obtained with 10 mL batch reactors showed that Tc(VII) 3 reduced by sulfidated nZVI has significantly slower reoxidation rates than Tc(VII) reduced by 4 nZVI only. In a 50 mL batch reactor, initial inhibition of Tc(IV) dissolution was apparent and 5 lasted until 120 hours at S/Fe = 0.112, presumably due to the redox buffer capacity of FeS. This 6 is evidenced by the parallel trends in oxidation-reduction potentials (ORP) and Tc dissolution 7 kinetics. Mӧssbauer spectra and micro X-ray diffraction ofmore » S/Fe = 0.112 suggested the 8 persistence of FeS after 24-h oxidation although X-ray photoelectron spectroscopy indicated 9 substantial surface oxidation. After 120-h oxidation, all characterizations showed complete 10 oxidation of FeS, which further indicates that FeS inhibits Tc oxidation. X-ray absorption 11 spectroscopy for S/Fe = 0.011 showed significantly increasing percentage of TcS2 in the solid 12 phase after 24-h oxidation, indicating TcS2 is more resistant to oxidation than TcO2. At S/Fe = 13 0.112, the XAS results revealed significant transformation of Tc speciation from TcS2 to TcO2 14 after 120-h oxidation at S/Fe = 0.112. Given that no apparent Tc dissolution occurred during this 15 period, the speciation transformation might play a secondary role in hindering Tc oxidation, 16 especially as redox buffer capacity approached depletion.« less

Enzyme-Inspired Chiral Secondary-Phosphine-Oxide Ligand with Dual Noncovalent Interactions for Asymmetric Hydrogenation.

PubMed

Chen, Caiyou; Zhang, Zhefan; Jin, Shicheng; Fan, Xiangru; Geng, Mingyu; Zhou, Yan; Wen, Songwei; Wang, Xinrui; Chung, Lung Wa; Dong, Xiu-Qin; Zhang, Xumu

2017-06-06

Inspired by the unique character of enzymes, we developed novel chiral SPO (secondary-phosphine-oxide) ligand (SPO-Wudaphos) which can enter into both ion pair and H-bond noncovalent interactions. The novel chiral SPO-Wudaphos exhibited excellent results in the asymmetric hydrogenation of α-methylene-γ-keto carboxylic acids, affording the chiral γ-keto acids with up to over 99 % ee. A series of control experiments and DFT calculations were conducted to illustrate the critical roles of both the ion pair and H-bond noncovalent interactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalysts for the selective oxidation of hydrogen sulfide to sulfur

DOEpatents

Srinivas, Girish; Bai, Chuansheng

2000-08-08

This invention provides catalysts for the oxidation of hydrogen sulfide. In particular, the invention provides catalysts for the partial oxidation of hydrogen sulfide to elemental sulfur and water. The catalytically active component of the catalyst comprises a mixture of metal oxides containing titanium oxide and one or more metal oxides which can be selected from the group of metal oxides or mixtures of metal oxides of transition metals or lanthanide metals. Preferred metal oxides for combination with TiO.sub.2 in the catalysts of this invention include oxides of V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Tc, Ru, Rh, Hf, Ta, W, Au, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. Catalysts which comprise a homogeneous mixture of titanium oxide and niobium (Nb) oxide are also provided. A preferred method for preparing the precursor homogenous mixture of metal hydroxides is by coprecipitation of titanium hydroxide with one or more other selected metal hydroxides. Catalysts of this invention have improved activity and/or selectivity for elemental sulfur production. Further improvements of activity and/or selectivity can be obtained by introducing relatively low amounts (up to about 5 mol %)of a promoter metal oxide (preferably of metals other than titanium and that of the selected second metal oxide) into the homogeneous metal/titanium oxide catalysts of this invention.

Thermodynamics and Kinetics of Sulfide Oxidation by Oxygen: A Look at Inorganically Controlled Reactions and Biologically Mediated Processes in the Environment

PubMed Central

Luther, George W.; Findlay, Alyssa J.; MacDonald, Daniel J.; Owings, Shannon M.; Hanson, Thomas E.; Beinart, Roxanne A.; Girguis, Peter R.

2011-01-01

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide oxidation kinetics improve when reduced iron and/or manganese are oxidized by oxygen to form oxidized metals which in turn oxidize sulfide. Biological sulfur oxidation relies on enzymes that have evolved to overcome these kinetic constraints to affect rapid sulfide oxidation. Here we review the available thermodynamic and kinetic data for H2S and HS• as well as O2, reactive oxygen species, nitrate, nitrite, and NOx species. We also present new kinetic data for abiotic sulfide oxidation with oxygen in trace metal clean solutions that constrain abiotic rates of sulfide oxidation in metal free solution and agree with the kinetic and thermodynamic calculations. Moreover, we present experimental data that give insight on rates of chemolithotrophic and photolithotrophic sulfide oxidation in the environment. We demonstrate that both anaerobic photolithotrophic and aerobic chemolithotrophic sulfide oxidation rates are three or more orders of magnitude higher than abiotic rates suggesting that in most environments biotic sulfide oxidation rates will far exceed abiotic rates due to the thermodynamic and kinetic constraints discussed in the first section of the paper. Such data reshape our thinking about the biotic and abiotic contributions to sulfide oxidation in the environment. PMID:21833317

Synthesis and characterization of transition metal oxide/sulfide nanostructures for electrochemical applications

NASA Astrophysics Data System (ADS)

Yilmaz, Gamze

This thesis is essentially oriented to develop low-cost nanostructured transition metal (nickel and vanadium) oxides and sulfides with high energy density, power density and electrochemical stability via strategies of structural design, hybridization, functionalization and surface engineering. Metal oxide and metal oxide/sulfide hybrid nanostructures in several designs, including hierarchical porous nanostructures, hollow polyhedrons, nanocubes, nanoframes, octopod nanoframes, and nanocages, were synthesized to study the contribution of structural design, compositional engineering, functionalization and surface engineering to the electrochemical properties of the materials. Modulated compositional and structural features disclosed the opportunities of large accessible active sites, facile ion transport, robustness and enhanced electrical conductivity. The best electrochemical performance with merits of highest energy density (38.9 Wh kg-1), power density (7.4 kW kg-1) and electrochemical stability (90.9% after 10000 cycles) was obtained for nickel cobalt layered double hydroxide/cobalt sulfide (NiCo-LDH/Co9S8) hybrid hollow polyhedron structure.

Synthesis of actinide nitrides, phosphides, sulfides and oxides

DOEpatents

Van Der Sluys, William G.; Burns, Carol J.; Smith, David C.

1992-01-01

A process of preparing an actinide compound of the formula An.sub.x Z.sub.y wherein An is an actinide metal atom selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, x is selected from the group consisting of one, two or three, Z is a main group element atom selected from the group consisting of nitrogen, phosphorus, oxygen and sulfur and y is selected from the group consisting of one, two, three or four, by admixing an actinide organometallic precursor wherein said actinide is selected from the group consisting of thorium, uranium, plutonium, neptunium, and americium, a suitable solvent and a protic Lewis base selected from the group consisting of ammonia, phosphine, hydrogen sulfide and water, at temperatures and for time sufficient to form an intermediate actinide complex, heating said intermediate actinide complex at temperatures and for time sufficient to form the actinide compound, and a process of depositing a thin film of such an actinide compound, e.g., uranium mononitride, by subliming an actinide organometallic precursor, e.g., a uranium amide precursor, in the presence of an effectgive amount of a protic Lewis base, e.g., ammonia, within a reactor at temperatures and for time sufficient to form a thin film of the actinide compound, are disclosed.

Inhibition of microbiological sulfide oxidation by methanethiol and dimethyl polysulfides at natron-alkaline conditions.

PubMed

van den Bosch, Pim L F; de Graaff, Marco; Fortuny-Picornell, Marc; van Leerdam, Robin C; Janssen, Albert J H

2009-06-01

To avoid problems related to the discharge of sulfidic spent caustics, a biotechnological process is developed for the treatment of gases containing both hydrogen sulfide and methanethiol. The process operates at natron-alkaline conditions (>1 mol L(-1) of sodium- and potassium carbonates and a pH of 8.5-10) to enable the treatment of gases with a high partial CO(2) pressure. In the process, methanethiol reacts with biologically produced sulfur particles to form a complex mixture predominantly consisting of inorganic polysulfides, dimethyl disulfide (DMDS), and dimethyl trisulfide (DMTS). The effect of these organic sulfur compounds on the biological oxidation of sulfide to elemental sulfur was studied with natron-alkaliphilic bacteria belonging to the genus Thioalkalivibrio. Biological oxidation rates were reduced by 50% at 0.05 mM methanethiol, while for DMDS and DMTS, this was estimated to occur at 1.5 and 1.0 mM, respectively. The inhibiting effect of methanethiol on biological sulfide oxidation diminished due to its reaction with biologically produced sulfur particles. This reaction increases the feasibility of biotechnological treatment of gases containing both hydrogen sulfide and methanethiol at natron-alkaline conditions.

Adjustable coordination of a hybrid phosphine-phosphine oxide ligand in luminescent Cu, Ag and Au complexes.

PubMed

Dau, Thuy Minh; Asamoah, Benjamin Darko; Belyaev, Andrey; Chakkaradhari, Gomathy; Hirva, Pipsa; Jänis, Janne; Grachova, Elena V; Tunik, Sergey P; Koshevoy, Igor O

2016-09-28

A potentially tridentate hemilabile ligand, PPh2-C6H4-PPh(O)-C6H4-PPh2 (P(3)O), has been used for the construction of a family of bimetallic complexes [MM'(P(3)O)2](2+) (M = M' = Cu (1), Ag (2), Au (3); M = Au, M' = Cu (4)) and their mononuclear halide congeners M(P(3)O)Hal (M = Cu (5-7), Ag (8-10)). Compounds 1-10 have been characterized in the solid state by single-crystal X-ray diffraction analysis to reveal a variable coordination mode of the phosphine-oxide group of the P(3)O ligand depending on the preferable number of coordination vacancies on the metal center. According to the theoretical studies, the interaction of the hard donor P[double bond, length as m-dash]O moiety with d(10) ions becomes less effective in the order Cu > Ag > Au. 1-10 exhibit room temperature luminescence in the solid state, and the intensity and energy of emission are mostly determined by the nature of metal atoms. The photophysical characteristics of the monometallic species were compared with those of the related compounds M(P(3))Hal (11-16) with the non-oxidized ligand P(3). It was found that in the case of the copper complexes 5-7 the P(3)O hybrid ligand introduces effective non-radiative pathways of the excited state relaxation leading to poor emission, while for the silver luminophores the P[double bond, length as m-dash]O group leads mainly to the modulation of luminescence wavelength.

Ferrate(VI) oxidation of polychlorinated diphenyl sulfides: Kinetics, degradation, and oxidized products.

PubMed

Chen, Jing; Xu, Xinxin; Zeng, Xiaolan; Feng, Mingbao; Qu, Ruijuan; Wang, Zunyao; Nesnas, Nasri; Sharma, Virender K

2018-06-13

This paper presents oxidation of polychlorinated diphenyl sulfides (PCDPSs), dioxin-like compounds, by ferrate(VI) (Fe VI O 4 2- , Fe(VI)). Kinetics of the reactions of Fe(VI) with seventeen PCDPSs, differ in number and positions of chlorine atoms (from 2 to 7), were investigated at pH 8.0. The second-order rate constants (k, M -1 s -1 ) of the reactions varied with the numbers and positions of chlorine atoms and appeared to be related with standard Gibbs free energy of formation (Δ f G 0 ) of PCDPSs. Degradation experiments in the presence of ions and humic acid demonstrated complete removal of PeCDPS by Fe(VI) in minutes. Pathways of the reaction were investigated by identifying oxidized products (OPs) of the reaction between Fe(VI) and 2,2',3',4,5-pentachlorodiphenyl sulfide (PeCDPS) at pH 8.0. Pathways of oxidation involved major pathway of attack on sulfur(II) by Fe(VI) in steps to yield sulfoxide type products, and subsequent breakage of C-S bond with the formation of sulfonic acid-containing trichloro compound. Minor pathways were hydroxylation of benzene ring and substitution of chlorine atom with hydroxyl group. Estimation of toxicity of OPs of the oxidation of PeCDPS by Fe(VI) suggested the decreased toxicity from the parent contaminant. Copyright © 2018. Published by Elsevier Ltd.

Synthesis of P,N-Heterocycles from ω-Amino-H-Phosphinates: Conformationally Restricted α-Amino Acid Analogs

PubMed Central

Queffelec, Clémence; Ribière, Patrice; Montchamp, Jean-Luc

2009-01-01

P,N-Heterocycles (3-hydroxy-1,3-azaphospholane and 3-hydroxy-1,3-azaphosphorinane-3-oxide) are synthesized in moderate yield from readily available ω-amino-H-phosphinates and aldehydes or ketones via an intramolecular Kabachnik-Fields reaction. The products are conformationally restricted phosphinic analogs of α-amino acids. The multi-gram scale syntheses of the H2N(CH2)nPO2H2 phosphinic precursors (n = 1, 2, 3) and some derivatives are also described. PMID:18855477

CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECTS OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

EPA Science Inventory

This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and activities of Cu, Mo, Cr and Mn oxides, and mixed metal oxides supported on -alumina, were tes...

Sulfidization Contemporaneous with Oxidation and Metamorphism in CK6 Chondrites

NASA Technical Reports Server (NTRS)

McCoy, T. J.; Corrigan, C. M.; Davidson, J.; Schrader, D. L.; Righter, K.

2018-01-01

As the most oxidized chondrites and a group of carbonaceous chondrites spanning the range of petrologic types, CK chondrites occupy an extreme in our understanding of the origin and evolution of chondritic parent bodies. With the proposed linkage of CV and CK chondrites and the suggestion that differentiation of a postulated CV-CK asteroid could have differentiated to form a core and established a magnetic dynamo, CK chondrites are receiving considerable attention. Most of this attention has focused on the similarities between CK3 and CV3 chondrites and the origin of each. We have previously argued that melting of an oxidized core could produce a magnetite-sulfide core, rather than the more conventional metal-sulfide core. In this work, we focus on CK6 chondrites to understand the origin of the most highly metamorphosed members of the group as representative of the material that might differentiate to form such an oxidized core.

Light-Dependent Sulfide Oxidation in the Anoxic Zone of the Chesapeake Bay Can Be Explained by Small Populations of Phototrophic Bacteria

PubMed Central

Bennett, Alexa J.; Hanson, Thomas E.; Luther, George W.

2015-01-01

Microbial sulfide oxidation in aquatic environments is an important ecosystem process, as sulfide is potently toxic to aerobic organisms. Sulfide oxidation in anoxic waters can prevent the efflux of sulfide to aerobic water masses, thus mitigating toxicity. The contribution of phototrophic sulfide-oxidizing bacteria to anaerobic sulfide oxidation in the Chesapeake Bay and the redox chemistry of the stratified water column were investigated in the summers of 2011 to 2014. In 2011 and 2013, phototrophic sulfide-oxidizing bacteria closely related to Prosthecochloris species of the phylum Chlorobi were cultivated from waters sampled at and below the oxic-anoxic interface, where measured light penetration was sufficient to support populations of low-light-adapted photosynthetic bacteria. In 2012, 2013, and 2014, light-dependent sulfide loss was observed in freshly collected water column samples. In these samples, extremely low light levels caused 2- to 10-fold increases in the sulfide uptake rate over the sulfide uptake rate under dark conditions. An enrichment, CB11, dominated by Prosthecochloris species, oxidized sulfide with a Ks value of 11 μM and a Vmax value of 51 μM min−1 (mg protein−1). Using these kinetic values with in situ sulfide concentrations and light fluxes, we calculated that a small population of Chlorobi similar to those in enrichment CB11 can account for the observed anaerobic light-dependent sulfide consumption activity in natural water samples. We conclude that Chlorobi play a far larger role in the Chesapeake Bay than currently appreciated. This result has potential implications for coastal anoxic waters and expanding oxygen-minimum zones as they begin to impinge on the photic zone. PMID:26296727

CATALYTIC OXIDATION OF DIMETHYL SULFIDE WITH OZONE: EFFECT OF PROMOTER AND PHYSICO-CHEMICAL PROPERTIES OF METAL OXIDE CATALYSTS

EPA Science Inventory

This study reports improved catalytic activities and stabilities for the oxidation of dimethyl sulfide (DMS), a major pollutant of pulp and paper mills. Ozone was used as an oxidant and Cu, Mo, V, Cr and Mn metal oxides, and mixed metal oxides support on y-alumina as catalysts ov...

An Experiment in Autotrophic Fermentation: Microbial Oxidation of Hydrogen Sulfide.

ERIC Educational Resources Information Center

Sublette, Kerry L.

1989-01-01

Described is an experiment which uses an autotrophic bacterium to anaerobically oxidize hydrogen sulfide to sulfate in a batch-stirred tank reactor. Discusses background information, experimental procedure, and sample results of this activity. (CW)

Electrochemistry of 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene ligands: free phosphines, metal complexes, and chalcogenides.

PubMed

Mandell, Chelsea L; Kleinbach, Shannon S; Dougherty, William G; Kassel, W Scott; Nataro, Chip

2010-10-18

The oxidative electrochemistries of a series of chiral bisphosphinoferrocene ligands, 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene (FerroTANE) and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene (FerroLANE), were examined. The reversibility of the oxidation is sensitive to the steric bulk of the alkyl groups. New transition metal compounds and phosphine chalcogenides of these ligands were prepared and characterized. X-ray crystal structures of 10 of these compounds are reported. The percent buried volume (%V(bur)) is a recently developed measurement based on crystallographic data that examines the steric bulk of N-heterocyclic carbene and phosphine ligands. The %V(bur) for the FerroTANE and FerroLANE structures with methyl or ethyl substituents suggests these ligands are similar in steric properties to 1,1'-bis(diphenylphosphino)ferrocene (dppf). In addition the %V(bur) has been found to correlate well with the Tolman cone angle for phosphine chalcogenides. The oxidative electrochemistries of the transition metal complexes occur at more positive potentials than the free ligands. While a similar positive shift is seen for the oxidative electrochemistries of the phosphine chalcogenides, the oxidation of the phosphine selenides does not occur at the iron center, but rather oxidation occurs at the selenium atoms.

Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

2018-01-01

Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

Enhanced Oxidative and Adsorptive Removal of Diclofenac in Heterogeneous Fenton-like Reaction with Sulfide Modified Nanoscale Zerovalent Iron.

PubMed

Su, Yiming; Jassby, David; Song, Shikun; Zhou, Xuefei; Zhao, Hongying; Filip, Jan; Petala, Eleni; Zhang, Yalei

2018-06-05

Sulfidation of nanoscale zerovalent iron (nZVI) has shown some fundamental improvements on reactivity and selectivity toward pollutants in dissolved-oxygen (DO)-stimulated Fenton-like reaction systems (DO/S-nZVI system). However, the pristine microstructure of sulfide-modified nanoscale zerovalent iron (S-nZVI) remains uncovered. In addition, the relationship between pollutant removal and the oxidation of the S-nZVI is largely unknown. The present study confirms that sulfidation not only imparts sulfide and sulfate groups onto the surface of the nanoparticle (both on the oxide shell and on flake-like structures) but also introduces sulfur into the Fe(0) core region. Sulfidation greatly inhibits the four-electron transfer pathway between Fe(0) and oxygen but facilitates the electron transfer from Fe(0) to surface-bound Fe(III) and consecutive single-electron transfer for the generation of H 2 O 2 and hydroxyl radical. In the DO/S-nZVI system, slight sulfidation (S/Fe molar ratio = 0.1) is able to nearly double the oxidative removal efficacy of diclofenac (DCF) (from 17.8 to 34.2%), whereas moderate degree of sulfidation (S/Fe molar ratio = 0.3) significantly enhances both oxidation and adsorption of DCF. Furthermore, on the basis of the oxidation model of S-nZVI, the DCF removal process can be divided into two steps, which are well modeled by parabolic and logarithmic law separately. This study bridges the knowledge gap between pollutant removal and the oxidation process of chemically modified iron-based nanomaterials.

Monochloro non-bridged half-metallocene-type zirconium complexes containing phosphine oxide-(thio)phenolate chelating ligands as efficient ethylene polymerization catalysts.

PubMed

Tang, Xiao-Yan; Wang, Yong-Xia; Liu, San-Rong; Liu, Jing-Yu; Li, Yue-Sheng

2013-01-14

A series of novel monochloro half-zirconocene complexes containing phosphine oxide-(thio)phenolate chelating ligands of the type, ClCp'Zr[X-2-R(1)-4-R(2)-6-(Ph(2)P=O)C(6)H(2)](2) (Cp' = C(5)H(5), 2a: X = O, R(1) = Ph, R(2) = H; 2b: X = O, R(1) = F, R(2) = H; 2c: X = O, R(1) = (t)Bu, R(2) = H; 2d: X = O, R(1) = R(2) = (t)Bu; 2e: X = O, R(1) = SiMe(3), R(2) = H; 2f: X = S, R(1) = SiMe(3), R(2) = H; Cp' = C(5)Me(5), 2g: X = O, R(1) = SiMe(3), R(2) = H), have been synthesized in high yields. These complexes were identified by (1)H {(13)C} NMR and elemental analyses. Structures for 2b, 2c and 2f were further confirmed by X-ray crystallography. Structural characterization of these complexes reveals crowded environments around the zirconium. Complexes 2b and 2c adopt six-coordinate, distorted octahedral geometry around the zirconium center, in which the equatorial positions are occupied by three oxygen atoms of two chelating phosphine oxide-bridged phenolate ligands and a chlorine atom. The cyclopentadienyl ring and one oxygen atom of the ligand are coordinated on the axial position. Complex 2f also folds a six-coordinate, distorted octahedral geometry around the Zr center, consisting of a Cp-Zr-O (in P=O) axis [177.16°] and a distorted plane of two sulfur atoms and one oxygen atom of two chelating phosphine oxide-bridged thiophenolate ligands as well as a chlorine atom. When activated by modified methylaluminoxane (MMAO), all the complexes exhibited high activities towards ethylene polymerization at high temperature (75 °C), giving high molecular weight polymers with unimodal molecular weight distribution. The formation of 14-electron, cationic metal alkyl species might come from the Zr-O (in phenol ring) bond cleavage based on the DFT calculations study.

Sulfide and ammonium oxidation, acetate mineralization by denitrification in a multipurpose UASB reactor.

PubMed

Beristain-Cardoso, Ricardo; Gómez, Jorge; Méndez-Pampín, Ramón

2011-02-01

The physiological and kinetic behavior of a denitrifying granular sludge exposed to different sulfide loading rates (55-295 mg/L d) were evaluated in a UASB reactor fed with acetate, ammonium and nitrate. At any sulfide loading rates, the consumption efficiencies of sulfide, acetate and ammonium were above 95%, while nitrate consumption efficiencies were around 62-72%. At the highest sulfide loading rate the ammonium was used as electron donor for N(2) production. The increase of sulfide loading rate also affected the fate of sulfide oxidation, since elemental sulfur was the main end product instead of sulfate. However, the lithotrophic denitrifying kinetic was not affected. FISH oligonucleotide probes for Thiobacillus denitrificans, Thiomiscropira denitrificans, genus Paracoccus and Pseudomonas spp. were used to follow the microbial ecology. The results of this work have shown that four pollutants could simultaneously be removed, namely, sulfide, ammonium, acetate and nitrate under well defined denitrifying conditions. Copyright © 2010 Elsevier Ltd. All rights reserved.

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: a field evaluation.

PubMed

Nason, Peter; Johnson, Raymond H; Neuschütz, Clara; Alakangas, Lena; Öhlander, Björn

2014-02-28

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation. Copyright © 2014 Elsevier B.V. All rights reserved.

Alternative waste residue materials for passive in situ prevention of sulfide-mine tailings oxidation: A field evaluation

USGS Publications Warehouse

Nason, Peter; Johnson, Raymond H.; Neuschutz, Clara; Alakangas, Lena; Ohlander, Bjorn

2014-01-01

Novel solutions for sulfide-mine tailings remediation were evaluated in field-scale experiments on a former tailings repository in northern Sweden. Uncovered sulfide-tailings were compared to sewage-sludge biosolid amended tailings over 2 years. An application of a 0.2 m single-layer sewage-sludge amendment was unsuccessful at preventing oxygen ingress to underlying tailings. It merely slowed the sulfide-oxidation rate by 20%. In addition, sludge-derived metals (Cu, Ni, Fe, and Zn) migrated and precipitated at the tailings-to-sludge interface. By using an additional 0.6 m thick fly-ash sealing layer underlying the sewage sludge layer, a solution to mitigate oxygen transport to the underlying tailings and minimize sulfide-oxidation was found. The fly-ash acted as a hardened physical barrier that prevented oxygen diffusion and provided a trap for sludge-borne metals. Nevertheless, the biosolid application hampered the application, despite the advances in the effectiveness of the fly-ash layer, as sludge-borne nitrate leached through the cover system into the underlying tailings, oxidizing pyrite. This created a 0.3 m deep oxidized zone in 6-years. This study highlights that using sewage sludge in unconventional cover systems is not always a practical solution for the remediation of sulfide-bearing mine tailings to mitigate against sulfide weathering and acid rock drainage formation.

Identification of Bacteria Potentially Responsible for Oxic and Anoxic Sulfide Oxidation in Biofilters of a Recirculating Mariculture System

PubMed Central

Cytryn, Eddie; van Rijn, Jaap; Schramm, Andreas; Gieseke, Armin; de Beer, Dirk; Minz, Dror

2005-01-01

Bacteria presumably involved in oxygen- or nitrate-dependent sulfide oxidation in the biofilters of a recirculating marine aquaculture system were identified using a new application of reverse transcription-PCR denaturing gradient gel electrophoresis (DGGE) analysis termed differential-transcription (DT)-DGGE. Biofilter samples were incubated in various concentrations of sulfide or thiosulfate (0 to 5 mM) with either oxygen or nitrate as the sole electron acceptor. Before and after short-term incubations (10 to 20 h), total DNA and RNA were extracted, and a 550-bp fragment of the 16S rRNA genes was PCR amplified either directly or after reverse transcription. DGGE analysis of DNA showed no significant change of the original microbial consortia upon incubation. In contrast, DGGE of cDNA revealed several phylotypes whose relative band intensities markedly increased or decreased in response to certain incubation conditions, indicating enhanced or suppressed rRNA transcription and thus implying metabolic activity under these conditions. Specifically, species of the gammaproteobacterial genus Thiomicrospira and phylotypes related to symbiotic sulfide oxidizers could be linked to oxygen-dependent sulfide oxidation, while members of the Rhodobacteraceae (genera Roseobacter, Rhodobacter, and Rhodobium) were putatively active in anoxic, nitrate-dependent sulfide oxidation. For all these organisms, the physiology of their closest cultured relatives matches their DT-DGGE-inferred function. In addition, higher band intensities following exposure to 5 mM sulfide and nitrate were observed for Thauera-, Hydrogenophaga-, and Dethiosulfovibrio-like phylotypes. For these genera, nitrate-dependent sulfide oxidation has not been documented previously and therefore DT-DGGE might indicate a higher relative tolerance to high sulfide concentrations than that of other community members. We anticipate that DT-DGGE will be of general use in tracing functionally equivalent yet

Synthesis of bacteria promoted reduced graphene oxide-nickel sulfide networks for advanced supercapacitors.

PubMed

Zhang, Haiming; Yu, Xinzhi; Guo, Di; Qu, Baihua; Zhang, Ming; Li, Qiuhong; Wang, Taihong

2013-08-14

Supercapacitors with potential high power are useful and have attracted much attention recently. Graphene-based composites have been demonstrated to be promising electrode materials for supercapacitors with enhanced properties. To improve the performance of graphene-based composites further and realize their synthesis with large scale, we report a green approach to synthesize bacteria-reduced graphene oxide-nickel sulfide (BGNS) networks. By using Bacillus subtilis as spacers, we deposited reduced graphene oxide/Ni3S2 nanoparticle composites with submillimeter pores directly onto substrate by a binder-free electrostatic spray approach to form BGNS networks. Their electrochemical capacitor performance was evaluated. Compared with stacked reduced graphene oxide-nickel sulfide (GNS) prepared without the aid of bacteria, BGNS with unique nm-μm structure exhibited a higher specific capacitance of about 1424 F g(-1) at a current density of 0.75 A g(-1). About 67.5% of the capacitance was retained as the current density increased from 0.75 to 15 A g(-1). At a current density of 75 A g(-1), a specific capacitance of 406 F g(-1) could still remain. The results indicate that the reduced graphene oxide-nickel sulfide network promoted by bacteria is a promising electrode material for supercapacitors.

Effectiveness of various cover scenarios on the rate of sulfide oxidation of mine tailings

NASA Astrophysics Data System (ADS)

Romano, Connie G.; Ulrich Mayer, K.; Jones, David R.; Ellerbroek, David A.; Blowes, David W.

2003-02-01

Long term environmentally sound disposal of the millions of tons of mining residue is a serious challenge to the international mining industry. This paper evaluates, through a numerical investigation, the potential performance of desulfurized tailings as a cover material for the reduction of acidic drainage from sulfidic tailings. This evaluation is facilitated through a comparison of various cover types as decommissioning options. The cover types considered consist of a desulfurized tailings material cover exposed to ambient climate conditions, a water cover (flooded tailings), and a combination cover type. As part of the evaluation of cover performances, the effect of climatic variability on the potential rate of sulfide oxidation in tailings with an open ground surface, was also assessed. The numerical analysis was conducted using the model PYROX, which was modified to allow for variably-saturated conditions, time varying moisture contents, and to account for the temperature dependence of Henry's law and gas diffusion. In the case study presented here, the benign cover material consists of a low sulfide waste stream (cassiterite float tails, CFT), a by-product of the production of tin concentrate (cassiterite, SnO 2). Modelling results after a simulation period of 100 years indicate that a water cover alone or an exposed CFT cover alone are both less effective options than the combined cover type. A water cover alone leads to a reduction of approximately 99.1%, in the oxidation rate relative to uncovered tailings while the combined cover type results in the lowest potential extent of sulfide oxidation after mine closure-an approximately 99.8% reduction. Importantly, a CFT cover exposed to ambient environmental conditions can still substantially reduce the sulfide oxidation rate, by approximately 75-82% over a 100-year time period, relative to uncovered tailings. Variability in precipitation (and hence percent saturation of the surface layer) had less of an

Phosphine Functionalization GaAs(111)A Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Traub, M.; Biteen, J; Michalak, D

Phosphorus-functionalized GaAs surfaces have been prepared by exposure of Cl-terminated GaAs(111)A surfaces to triethylphosphine (PEt3) or trichlorophosphine (PCl3), or by the direct functionalization of the native-oxide terminated GaAs(111)A surface with PCl3. The presence of phosphorus on each functionalized surface was confirmed by X-ray photoelectron spectroscopy. High-resolution, soft X-ray photoelectron spectroscopy was used to evaluate the As and Ga 3d regions of such surfaces. On PEt3 treated surfaces, the Ga 3d spectra exhibited a bulk Ga peak as well as peaks that were shifted to 0.35, 0.92 and 1.86 eV higher binding energy. These peaks were assigned to residual Cl-terminated Gamore » surface sites, surficial Ga2O and surficial Ga2O3, respectively. For PCl3-treated surfaces, the Ga 3d spectra displayed peaks ascribable to bulk Ga(As), Ga2O, and Ga2O3, as well as a peak shifted 0.30 eV to higher binding energy relative to the bulk signal. A peak corresponding to Ga(OH)3, observed on the Cl-terminated surface, was absent from all of the phosphine-functionalized surfaces. After reaction of the Cl-terminated GaAs(111)A surface with PCl3 or PEt3, the As 3d spectral region was free of As oxides and As0. Although native oxide-terminated GaAs surfaces were free of As oxides after reaction with PCl3, such surfaces contained detectable amounts of As0. Photoluminescence measurements indicted that phosphine-functionalized surfaces prepared from Cl-terminated GaAs(111)A surfaces had better electrical properties than the native-oxide capped GaAs(111)A surface, while the native-oxide covered surface treated with PCl3 showed no enhancement in PL intensity.« less

Evaluation of biological hydrogen sulfide oxidation coupled with two-stage upflow filtration for groundwater treatment.

PubMed

Levine, Audrey D; Raymer, Blake J; Jahn, Johna

2004-01-01

Hydrogen sulfide in groundwater can be oxidized by aerobic bacteria to form elemental sulfur and biomass. While this treatment approach is effective for conversion of hydrogen sulfide, it is important to have adequate control of the biomass exiting the biological treatment system to prevent release of elemental sulfur into the distribution system. Pilot scale tests were conducted on a Florida groundwater to evaluate the use of two-stage upflow filtration downstream of biological sulfur oxidation. The combined biological and filtration process was capable of excellent removal of hydrogen sulfide and associated turbidity. Additional benefits of this treatment approach include elimination of odor generation, reduction of chlorine demand, and improved stability of the finished water.

Apparatus for purifying arsine, phosphine, ammonia, and inert gases to remove Lewis acid and oxidant impurities therefrom

DOEpatents

Tom, Glenn M.; Brown, Duncan W.

1991-01-08

An apparatus for purifying a gaseous mixture comprising arsine, phosphine, ammonia, and/or inert gases, to remove Lewis acid and/or oxidant impurities therefrom, comprising a vessel containing a bed of a scavenger, the scavenger including a support having associated therewith an anion which is effective to remove such impurities, such anion being selected from one or more members of the group consisting of: (i) carbanions whose corresponding protonated compounds have a pK.sub.a value of from about 22 to about 36; and (ii) anions formed by reaction of such carbanions with the primary component of the mixture.

Organic-inorganic hybrid polyionic liquid based polyoxometalate as nano porous material for selective oxidation of sulfides

NASA Astrophysics Data System (ADS)

Rafiee, Ezzat; Shahebrahimi, Shabnam

2017-07-01

Organic-inorganic hybrid nano porous materials based on poly(ionic liquid)-polyoxometalate (PIL-POM) were reported. These hybrid materials were synthesized by the reaction of 4-vinyl pyridine with 1,3-propanesultone, followed by the polymerization and also sulfonate-functionalized cross-linked poly(4-vinylpyridine) and combining these polymers with H5PMo10V2O40 (PMo10V2). Activity of prepared PIL-PMo10V2 hybrids were investigated as catalysts for oxidation of sulfides with H2O2 as oxidant. For understanding catalytic activities of the PIL-PMo10V2 hybrids in oxidation of sulfides, effect of catalyst composition, substrate, and reaction conditions were studied. The results show that the PIL-PMo10V2 hybrids are active as selective heterogeneous catalysts for oxidation of sulfides and can be recovered and reused. The catalyst was characterized by FT-IR, TGA-DSC, XRD, SEM/EDX, BET, CV and zeta potential measurement. Also, average molecular weight of prepared catalysts were measured.

Nitrate promotes biological oxidation of sulfide in wastewaters: experiment at plant-scale.

PubMed

García de Lomas, Juan; Corzo, Alfonso; Gonzalez, Juan M; Andrades, Jose A; Iglesias, Emilio; Montero, María José

2006-03-05

Biogenic production of sulfide in wastewater treatment plants involves odors, toxicity and corrosion problems. The production of sulfide is a consequence of bacterial activity, mainly sulfate-reducing bacteria (SRB). To prevent this production, the efficiency of nitrate addition to wastewater was tested at plant-scale by dosing concentrated calcium nitrate (Nutriox) in the works inlet. Nutriox dosing resulted in a sharp decrease of sulfide, both in the air and in the bulk water, reaching maximum decreases of 98.7% and 94.7%, respectively. Quantitative molecular microbiology techniques indicated that the involved mechanism is the development of the nitrate-reducing, sulfide-oxidizing bacterium Thiomicrospira denitrificans instead of the direct inhibition of the SRB community. Denitrification rate in primary sedimentation tanks was enhanced by nitrate, being this almost completely consumed. No significant increase of inorganic nitrogen was found in the discharged effluent, thus reducing potential environmental hazards to receiving waters. This study demonstrates the effectiveness of nitrate addition in controlling sulfide generation at plant-scale, provides the mechanism and supports the environmental adequacy of this strategy.

Persistency-field Eh-pH diagrams for sulfides and their application to supergene oxidation and enrichment of sulfide ore bodies

USGS Publications Warehouse

Sato, M.

1992-01-01

At temperatures prevailing near the Earth's surface, metastable co-existence of chemical substances is common because chemical reactions that would directly lead to the attainment of thermody-namically most stable equilibria are often blocked by high activation energy barriers. The persistency of a metastable assemblage is then governed by alternative reaction paths that provide lower activation energy barriers. Comparison of observed mineral assemblages in the supergene oxidized and enriched sulfide ores with corresponding stability Eh-pH diagrams reveals that the supergene assemblages are mostly metastable due primarily to the persistency of sulfide minerals beyond stability boundaries. A new set of diagrams called persistency-field Eh-pH diagrams has been constructed for binary metal sulfides on the basis of electrochemical and other experimental data. Each diagram delineates the persistency field, which is a combined field of thermodynamic stability and reaction path-controlled metastability, for a specific sulfide mineral. When applied to the supergene assemblages, these new diagrams show much better correspondence to the field observations. Although there may still be room for further refinement, the new diagrams appear to provide a strong visual aid to the understanding of the behavior of sulfide minerals in the supergene conditions. ?? 1992.

Glacial weathering, sulfide oxidation, and global carbon cycle feedbacks.

PubMed

Torres, Mark A; Moosdorf, Nils; Hartmann, Jens; Adkins, Jess F; West, A Joshua

2017-08-15

Connections between glaciation, chemical weathering, and the global carbon cycle could steer the evolution of global climate over geologic time, but even the directionality of feedbacks in this system remain to be resolved. Here, we assemble a compilation of hydrochemical data from glacierized catchments, use this data to evaluate the dominant chemical reactions associated with glacial weathering, and explore the implications for long-term geochemical cycles. Weathering yields from catchments in our compilation are higher than the global average, which results, in part, from higher runoff in glaciated catchments. Our analysis supports the theory that glacial weathering is characterized predominantly by weathering of trace sulfide and carbonate minerals. To evaluate the effects of glacial weathering on atmospheric pCO 2 , we use a solute mixing model to predict the ratio of alkalinity to dissolved inorganic carbon (DIC) generated by weathering reactions. Compared with nonglacial weathering, glacial weathering is more likely to yield alkalinity/DIC ratios less than 1, suggesting that enhanced sulfide oxidation as a result of glaciation may act as a source of CO 2 to the atmosphere. Back-of-the-envelope calculations indicate that oxidative fluxes could change ocean-atmosphere CO 2 equilibrium by 25 ppm or more over 10 ky. Over longer timescales, CO 2 release could act as a negative feedback, limiting progress of glaciation, dependent on lithology and the concentration of atmospheric O 2 Future work on glaciation-weathering-carbon cycle feedbacks should consider weathering of trace sulfide minerals in addition to silicate minerals.

Glacial weathering, sulfide oxidation, and global carbon cycle feedbacks

PubMed Central

Torres, Mark A.; Moosdorf, Nils; Hartmann, Jens; Adkins, Jess F.

2017-01-01

Connections between glaciation, chemical weathering, and the global carbon cycle could steer the evolution of global climate over geologic time, but even the directionality of feedbacks in this system remain to be resolved. Here, we assemble a compilation of hydrochemical data from glacierized catchments, use this data to evaluate the dominant chemical reactions associated with glacial weathering, and explore the implications for long-term geochemical cycles. Weathering yields from catchments in our compilation are higher than the global average, which results, in part, from higher runoff in glaciated catchments. Our analysis supports the theory that glacial weathering is characterized predominantly by weathering of trace sulfide and carbonate minerals. To evaluate the effects of glacial weathering on atmospheric pCO2, we use a solute mixing model to predict the ratio of alkalinity to dissolved inorganic carbon (DIC) generated by weathering reactions. Compared with nonglacial weathering, glacial weathering is more likely to yield alkalinity/DIC ratios less than 1, suggesting that enhanced sulfide oxidation as a result of glaciation may act as a source of CO2 to the atmosphere. Back-of-the-envelope calculations indicate that oxidative fluxes could change ocean–atmosphere CO2 equilibrium by 25 ppm or more over 10 ky. Over longer timescales, CO2 release could act as a negative feedback, limiting progress of glaciation, dependent on lithology and the concentration of atmospheric O2. Future work on glaciation–weathering–carbon cycle feedbacks should consider weathering of trace sulfide minerals in addition to silicate minerals. PMID:28760954

Mechanism of the sulfurisation of phosphines and phosphites using 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride).

PubMed

Hanusek, Jirí; Russell, Mark A; Laws, Andrew P; Jansa, Petr; Atherton, John H; Fettes, Kevin; Page, Michael I

2007-02-07

Contrary to a previous report, the sulfurisation of phosphorus(III) derivatives by 3-amino-1,2,4-dithiazole-5-thione (xanthane hydride) does not yield carbon disulfide and cyanamide as the additional reaction products. The reaction of xanthane hydride with triphenyl phosphine or trimethyl phosphite yields triphenyl phosphine sulfide or trimethyl thiophosphate, respectively, and thiocarbamoyl isothiocyanate which has been trapped with nucleophiles. The reaction pathway involves initial nucleophilic attack of the phosphorus at sulfur next to the thiocarbonyl group of xanthane hydride followed by decomposition of the phosphonium intermediate formed to products. The Hammett rho-values for the sulfurisation of substituted triphenyl phosphines and triphenyl phosphites in acetonitrile are approximately -1.0. The entropies of activation are very negative (-114+/-15 J mol-1 K-1) with little dependence on solvent which is consistent with a bimolecular association step leading to the transition state. The negative values of DeltaS(not equal) and rho values indicate that the rate limiting step of the sulfurisation reaction is formation of the phosphonium ion intermediate which has an early transition state with little covalent bond formation. The site of nucleophilic attack has been also confirmed using computational calculations.

Arsenic Bioremediation by Biogenic Iron Oxides and Sulfides

PubMed Central

Couture, Raoul-Marie; Van Cappellen, Philippe; Corkhill, Claire L.; Charnock, John M.; Polya, David A.; Vaughan, David; Vanbroekhoven, Karolien; Lloyd, Jonathan R.

2013-01-01

Microcosms containing sediment from an aquifer in Cambodia with naturally elevated levels of arsenic in the associated groundwater were used to evaluate the effectiveness of microbially mediated production of iron minerals for in situ As remediation. The microcosms were first incubated without amendments for 28 days, and the release of As and other geogenic chemicals from the sediments into the aqueous phase was monitored. Nitrate or a mixture of sulfate and lactate was then added to stimulate biological Fe(II) oxidation or sulfate reduction, respectively. Without treatment, soluble As concentrations reached 3.9 ± 0.9 μM at the end of the 143-day experiment. However, in the nitrate- and sulfate-plus-lactate-amended microcosms, soluble As levels decreased to 0.01 and 0.41 ± 0.13 μM, respectively, by the end of the experiment. Analyses using a range of biogeochemical and mineralogical tools indicated that sorption onto freshly formed hydrous ferric oxide (HFO) and iron sulfide mineral phases are the likely mechanisms for As removal in the respective treatments. Incorporation of the experimental results into a one-dimensional transport-reaction model suggests that, under conditions representative of the Cambodian aquifer, the in situ precipitation of HFO would be effective in bringing groundwater into compliance with the World Health Organization (WHO) provisional guideline value for As (10 ppb or 0.13 μM), although soluble Mn release accompanying microbial Fe(II) oxidation presents a potential health concern. In contrast, production of biogenic iron sulfide minerals would not remediate the groundwater As concentration below the recommended WHO limit. PMID:23666325

Phosphine

Integrated Risk Information System (IRIS)

Phosphine ; CASRN 7803 - 51 - 2 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

Release of dissolved cadmium and sulfur nanoparticles from oxidizing sulfide minerals

EPA Science Inventory

Cadmium enrichment (relative to Fe and Zn) in paddy rice grain occurs during the pre-harvest drainage of flooded soil, which causes oxidative dissolution of sulfide minerals present in reduced soil. We investigated this process over a range of environmentally realistic Cdcontain...

Influence of liquid surface area on hydrogen sulfide oxidation during micro-aeration in dairy manure digesters

USDA-ARS?s Scientific Manuscript database

The specific objectives of this study were to evaluate headspace aeration for reducing hydrogen sulfide levels in low cost plug flow digesters, and to characterize the relationship between the liquid surface area and hydrogen sulfide oxidation rates. Experiments with replicate field scale plug flow ...

Biological oxidation of hydrogen sulfide in mineral media using a biofilm airlift suspension reactor.

PubMed

Moghanloo, G M Mojarrad; Fatehifar, E; Saedy, S; Aghaeifar, Z; Abbasnezhad, H

2010-11-01

Hydrogen sulfide (H(2)S) removal in mineral media using Thiobacillus thioparus TK-1 in a biofilm airlift suspension reactor (BAS) was investigated to evaluate the relationship between biofilm formation and changes in inlet loading rates. Aqueous sodium sulfide was fed as the substrate into the continuous BAS-reactor. The reactor was operated at a constant temperature of 30 degrees C and a pH of 7, the optimal temperature and pH for biomass growth. The startup of the reactor was performed with basalt carrier material. Optimal treatment performance was obtained at a loading rate of 4.8 mol S(2-) m(-3) h(-1) at a conversion efficiency as high as 100%. The main product of H(2)S oxidation in the BAS-reactor was sulfate because of high oxygen concentrations in the airlift reactor. The maximum sulfide oxidation rate was 6.7 mol S(2-) m(-3) h(-1) at a hydraulic residence time of 3.3 h in the mineral medium. The data showed that the BAS-reactor with this microorganism can be used for sulfide removal from industrial effluent. Copyright 2010 Elsevier Ltd. All rights reserved.

Enriching distinctive microbial communities from marine sediments via an electrochemical-sulfide-oxidizing process on carbon electrodes

PubMed Central

Li, Shiue-Lin; Nealson, Kenneth H.

2015-01-01

Sulfide is a common product of marine anaerobic respiration, and a potent reactant biologically and geochemically. Here we demonstrate the impact on microbial communities with the removal of sulfide via electrochemical methods. The use of differential pulse voltammetry revealed that the oxidation of soluble sulfide was seen at +30 mV (vs. SHE) at all pH ranges tested (from pH = 4 to 8), while non-ionized sulfide, which dominated at pH = 4 was poorly oxidized via this process. Two mixed cultures (CAT and LA) were enriched from two different marine sediments (from Catalina Island, CAT; from the Port of Los Angeles, LA) in serum bottles using a seawater medium supplemented with lactate, sulfate, and yeast extract, to obtain abundant biomass. Both CAT and LA cultures were inoculated in electrochemical cells (using yeast-extract-free seawater medium as an electrolyte) equipped with carbon-felt electrodes. In both cases, when potentials of +630 or +130 mV (vs. SHE) were applied, currents were consistently higher at +630 then at +130 mV, indicating more sulfide being oxidized at the higher potential. In addition, higher organic-acid and sulfate conversion rates were found at +630 mV with CAT, while no significant differences were found with LA at different potentials. The results of microbial-community analyses revealed a decrease in diversity for both CAT and LA after electrochemical incubation. In addition, some bacteria (e.g., Clostridium and Arcobacter) not well-known to be capable of extracellular electron transfer, were found to be dominant in the electrochemical cells. Thus, even though the different mixed cultures have different tolerances for sulfide, electrochemical-sulfide removal can lead to major population changes. PMID:25741331

Origin and fate of sulfide liquids in hotspot volcanism (La Réunion): Pb isotope constraints from residual Fe-Cu oxides

NASA Astrophysics Data System (ADS)

Vlastélic, I.; Gannoun, A.; Di Muro, A.; Gurioli, L.; Bachèlery, P.; Henot, J. M.

2016-12-01

Immiscible sulfide liquids in basaltic magmas play an important role in trace metal transport and the sulfur budget of volcanic eruptions. However, sulfides are transient phases, whose origin and fate are poorly constrained. We address these issues by analyzing sulfide destabilization products preserved in lavas from La Réunion Island. Iron oxide globules and coatings, typically 20-80 μm in size, were found to occur in vesicles of differentiated lavas from Piton des Neiges, and recent pumice samples from Piton de la Fournaise. Field and mineralogical evidence indicates that the iron oxides are syn-eruptive phases not resulting from hydrothermal processes. Samples were first studied by Scanning Electron Microscopy. The globules were separated, whereas the smaller spherules and coatings were concentrated by magnetic sorting and acid leaching, and samples were processed through wet chemistry. The Fe oxide phases comprise 49-74 wt.% Fe, 26-40 wt.% O, and up to 6 wt.% Cu, 811 ppm Ni, 140 ppm Bi, and 8.5 ppm Pb. Compared to the host lava, Cu, Ni, and Bi are enriched by a factor of 101-103. Systematic Pb isotope disequilibrium (between 500 ppm and 2.9% for 206Pb/204Pb) exists between Fe oxides and host rocks, with Fe oxides generally displaying less radiogenic ratios. Unradiogenic Pb is a typical signature of sulfide, which tends to concentrate Pb, but not its parent elements U and Th. Thus, both the chemical and isotopic compositions of the vesicle-hosted Fe oxides suggest that they are more or less direct products of the destabilization of immiscible sulfide liquids. Although Pb dominantly partitions into the gas phase during sulfide breakdown, the original Pb isotope signature of sulfide is preserved in the residual oxide. The composition estimated for the parent sulfides (206Pb/204Pb = 18.20-18.77, 207Pb/204Pb = 15.575, and 208Pb/204Pb = 38.2-38.8) precludes a genetic link with the La Réunion plume, and suggests a lithospheric or crustal origin. It is estimated

Pt(ii) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes.

PubMed

Casado-Sánchez, Antonio; Gómez-Ballesteros, Rocío; Tato, Francisco; Soriano, Francisco J; Pascual-Coca, Gustavo; Cabrera, Silvia; Alemán, José

2016-07-12

A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed.

Zn isotopes in hydrothermal sulfides and their oxidation products along the south mid-Atlantic ridge: evidence of hydrothermal fluid deposition

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Lei, Jijiang; Wang, Hao; Li, Zhenggang

2018-04-01

Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13-15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from -0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ ( n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=-0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ ( n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

Computational studies of complexation of nitrous oxide by borane-phosphine frustrated Lewis pairs.

PubMed

Gilbert, Thomas M

2012-08-14

Computational studies of complexes Ar(3)B-ONN-PR(3) derived from reactions between borane-phosphine frustrated Lewis pairs and N(2)O reveal several interesting facets. Natural resonance theory calculations support a change in the preferred resonance structure as the Lewis acidity of the borane increases. Potential constitutional isomers where phosphorus binds to oxygen and boron to nitrogen are predicted to be unstable with respect to loss of phosphine oxide and free N(2). Other constitutional isomers represent stationary points on the potential energy surface; most are considerably less stable than the observed complexes, but one is predicted to be as stable. This arises because the dominant resonance form combines alternating charge with the presence of a stabilizing NO double bond. The relationship between Lewis acidity and complex formation for a variety of boranes was explored; the results are consistent with the idea that greater Lewis acidity stabilizes both classical and frustrated Lewis acid-base pairs, but to differing degrees such that both types can entrap N(2)O. Calculations addressing the mechanism of complex formation suggest that N(2)O binds first through the nitrogen to the phosphine phosphorus of the FLP, whereupon boron coordinates the oxygen atom. Studies of the mechanism of the degenerate exchange reaction between (4-F-H(4)C(6))(3)B-ONN-P(t-Bu)(3) and B(C(6)H(4)-4-F)(3), involves a "transition state", with relatively short B-O distances, and so resembles a classical I(a) process. The process involves two barriers, one associated with bringing the incoming borane into proximity with the oxygen, and the other associated with isomerising from a ladle-shaped cis-trans ct conformer to the observed trans-trans tt-type structure. The overall barrier for degenerate exchange was predicted to be between 65 and 110 kJ mol(-1), in fair agreement with experiment. Similar studies of the reaction between (4-F-H(4)C(6))(3)B-ONN-P(t-Bu)(3) and B(C(6)F(5

Effect of temperature and initial dibutyl sulfide concentration in chloroform on its oxidation rate by ozone.

PubMed

Popiel, Stanisław; Nalepa, Tomasz; Dzierzak, Dorota; Stankiewicz, Romuald; Witkiewicz, Zygfryd

2008-09-15

A scheme of dibutyl sulfide (DBS) oxidation with ozone and generation of transitional products was determined in this study. The main identified intermediate product was dibutyl sulfoxide (DBSO), and the main end product of DBS oxidation was dibutyl sulfone (DBSO2). It was determined that for three temperatures: 0, 10 and 20 degrees C there was certain initial DBS concentration for which half-times observed in experimental conditions were equal and independent from temperature. Generation of phosgene and water as by-products was confirmed for the reaction of DBS with ozone in chloroform. Results of the described study allowed to present generalized mechanism of sulfide oxidation with ozone.

Hydrogen sulfide oxidation by a microbial consortium in a recirculation reactor system: sulfur formation under oxygen limitation and removal of phenols.

PubMed

Alcantara, Sergio; Velasco, Antonio; Muñoz, Ana; Cid, Juan; Revah, Sergio; Razo-Flores, Elías

2004-02-01

Wastewater from petroleum refining may contain a number of undesirable contaminants including sulfides, phenolic compounds, and ammonia. The concentrations of these compounds must be reduced to acceptable levels before discharge. Sulfur formation and the effect of selected phenolic compounds on the sulfide oxidation were studied in autotrophic aerobic cultures. A recirculation reactor system was implemented to improve the elemental sulfur recovery. The relation between oxygen and sulfide was determined calculating the O2/S2- loading rates (Q(O2)/Q(S)2- = Rmt), which adequately defined the operation conditions to control the sulfide oxidation. Sulfur-producing steady states were achieved at Rmt ranging from 0.5 to 1.5. The maximum sulfur formation occurred at Rmt of 0.5 where 85% of the total sulfur added to the reactor as sulfide was transformed to elemental sulfur and 90% of it was recovered from the bottom of the reactor. Sulfide was completely oxidized to sulfate (Rmt of 2) in a stirred tank reactor, even when a mixture of phenolic compounds was present in the medium. Microcosm experiments showed that carbon dioxide production increased in the presence of the phenols, suggesting that these compounds were oxidized and that they may have been used as carbon and energy source by heterotrophic microorganisms present in the consortium.

Polystyrene bound oxidovanadium(IV) and dioxidovanadium(V) complexes of histamine derived ligand for the oxidation of methyl phenyl sulfide, diphenyl sulfide and benzoin.

PubMed

Maurya, Mannar R; Arya, Aarti; Kumar, Amit; Pessoa, João Costa

2009-03-28

Ligand Hsal-his (I) derived from salicylaldehyde and histamine has been covalently bound to chloromethylated polystyrene cross-linked with 5% divinylbenzene. Upon treatment with [VO(acac)(2)] in DMF, the polystyrene-bound ligand (abbreviated as PS-Hsal-his, II) gave the stable polystyrene-bound oxidovanadium(iv) complex PS-[V(IV)O(sal-his)(acac)] , which upon oxidation yielded the dioxidovanadium(v) PS-[V(V)O(2)(sal-his)] complex. The corresponding non polymer-bound complexes [V(IV)O(sal-his)(acac)] and [V(V)O(2)(sal-his)] have also been obtained. These complexes have been characterised by IR, electronic, (51)V NMR and EPR spectral studies, and thermal as well as scanning electron micrograph studies. Complexes and have been used as a catalyst for the oxidation of methyl phenyl sulfide, diphenyl sulfide and benzoin with 30% H(2)O(2) as oxidant. Under the optimised reaction conditions, a maximum of 93.8% conversion of methyl phenyl sulfide with 63.7% selectivity towards methyl phenyl sulfoxide and 36.3% towards methyl phenyl sulfone has been achieved in 2 h with 2 . Under similar conditions, diphenyl sulfide gave 83.4% conversion where selectivity of reaction products varied in the order: diphenyl sulfoxide (71.8%) > diphenyl sulfone (28.2%). A maximum of 91.2% conversion of benzoin has been achieved within 6 h, and the selectivities of reaction products are: methylbenzoate (37.0%) > benzil (30.5%) > benzaldehyde-dimethylacetal (22.5%) > benzoic acid (8.1%). The PS-bound complex, 1 exhibits very comparable catalytic potential. These polymer-anchored heterogeneous catalysts do not leach during catalytic action, are recyclable and show higher catalytic activity and turnover frequency than the corresponding non polymer-bound complexes. EPR and (51)V NMR spectroscopy was used to characterise methanolic solutions of 3 and 4 and to identify species formed upon addition of H(2)O(2) and/or acid and/or methyl phenyl sulfide.

Oxidation kinetics of molten copper sulfide

NASA Astrophysics Data System (ADS)

Alyaser, A. H.; Brimacombe, J. K.

1995-02-01

The oxidation kinetics of molten Cu2S baths, during top lancing with oxygen/nitrogen (argon) mixtures, have been investigated as a function of oxygen partial pressure (0.2 to 0.78), bath temperature (1200 °C to 1300 °C), gas flow rate (1 to 4 L/min), and bath mixing. Surface-tension-driven flows (the Marangoni effect) were observed both visually and photographically. Thus, the oxidation of molten Cu2S was found to progress in two distinct stages, the kinetics of which are limited by the mass transfer of oxygen in the gas phase to the melt surface. During the primary stage, the melt is partially desulfurized while oxygen dissolves in the liquid sulfide. Upon saturation of the melt with oxygen, the secondary stage commences in which surface and bath reactions proceed to generate copper and SO2 electrochemically. A mathematical model of the reaction kinetics has been formulated and tested against the measurements. The results of this study shed light on the process kinetics of the copper blow in a Peirce-Smith converter or Mitsubishi reactor.

Oxygen enhances phosphine toxicity for postharvest pest control.

PubMed

Liu, Yong-Biao

2011-10-01

Phosphine fumigations under superatmospheric oxygen levels (oxygenated phosphine fumigations) were significantly more effective than the fumigations under the normal 20.9% atmospheric oxygen level against western flower thrips [Frankliniella occidentalis (Pergande)] adults and larvae, leafminer Liriomyza langei Frick pupae, grape mealybug [Pseudococcus maritimus (Ehrhorn)] eggs, and Indianmeal moth [Plodia interpunctella (Hübner)] eggs and pupae. In 5-h fumigations with 1,000 ppm phosphine at 5 degrees C, mortalities of western flower thrips increased significantly from 79.5 to 97.7% when oxygen was increased from 20.9 to 40% and reached 99.3% under 80% O2. Survivorships of leafminer pupae decreased significantly from 71.2% under 20.9% O2 to 16.2% under 40% O2 and reached 1.1% under 80% O2 in 24-h fumigations with 500 ppm phosphine at 5 degrees C. Complete control of leafminer pupae was achieved in 24-h fumigations with 1,000 ppm phosphine at 5 degrees C under 60% O2 or higher. Survivorships of grape mealybug eggs also decreased significantly in 48-h fumigations with 1,000 ppm phosphine at 2 degrees C under 60% O2 compared with the fumigations under 20.9% O2. Indian meal moth egg survivorships decreased significantly from 17.4 to 0.5% in responses to an oxygen level increase from 20.9 to 40% in 48-h fumigations with 1,000 ppm phosphine at 10 degrees C and reached 0.2% in fumigations under 80% O2. When the oxygen level was reduced from 20.9 to 15 and 10% in fumigations, survivorships of Indianmeal moth eggs increased significantly from 17.4 to 32.9 and 39.9%, respectively. Increased O2 levels also resulted in significantly lower survival rates of Indianmeal moth pupae in response to 24-h fumigations with 500 and 1,000 ppm phosphine at 10 degrees C and a complete control was achieved in the 1,000 ppm phosphine fumigations under 60% O2. Oxygenated phosphine fumigations have marked potential to improve insecticidal efficacy. Advantages and limitations of oxygenated

Multielectron donors based on TTF-phosphine and ferrocene-phosphine hybrid complexes of a hexarhenium(III) octahedral cluster core.

PubMed

Perruchas, Sandrine; Avarvari, Narcis; Rondeau, David; Levillain, Eric; Batail, Patrick

2005-05-16

Electroactive molecular materials precursors are obtained through coordination chemistry of the hexarhenium cluster core [Re(6)Se(8)](2+) on the six available apical positions with redox-active phosphines bearing tetrathiafulvalene- or ferrocene-based moieties. Single-crystal X-ray diffraction study and electrospray mass spectrometry ascertain the synthesis of these hexasubstituted electroactive clusters, containing up to 12 redox active sites. Cyclic voltammetry experiments demonstrate that these compounds can be reversibly oxidized at rather low potentials, thus allowing an easy access to the corresponding radical species which should provide new conducting and/or magnetic molecular materials.

Characterization of a transient +2 sulfur oxidation state intermediate from the oxidation of aqueous sulfide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vairavmurthy, M.A.; Zhou, Weiqing

1995-04-01

The oxidation H{sub 2}S to sulfate involves a net transfer of eight electrons and occurs through the formation of several partially oxidized intermediates with oxidation states ranging from {minus}1 to +5. Known intermediates include elemental sulfur (oxidation state 0), polysulfides (outer sulfur: {minus}1, inner sulfur: 0), sulfite (+4) and thiosulfate (outer sulfur: {minus}1, inner sulfur: +5). A noticeable gap in this series of intermediates is that of a +2 sulfur oxidation state oxoacid/oxoanion species, which was never detected experimentally. Here, we present evidence of the transient existence of +2 oxidation state intermediate in the Ni(II)-catalyzed oxidation of aqueous sulfide. X-raymore » absorption near-edge structure (XANES) spectroscopy and Fourier-transform-infrared (FT-IR) spectroscopy were used to characterize this species; they suggest that it has a sulfoxylate ion (SO{sub 2}{sup 2{minus}}) structure.« less

Oxidation sulfidation resistance of Fe-Cr-Ni alloys

DOEpatents

Natesan, Ken; Baxter, David J.

1984-01-01

High temperature resistance of Fe-Cr-Ni alloy compositions to oxidative and/or sulfidative conditions is provided by the incorporation of about 1-8 wt. % of Zr or Nb and results in a two-phase composition having an alloy matrix as the first phase and a fine grained intermetallic composition as the second phase. The presence and location of the intermetallic composition between grains of the matrix provides mechanical strength, enhanced surface scale adhesion, and resistance to corrosive attack between grains of the alloy matrix at temperatures of 500.degree.-1000.degree. C.

Tracking photosynthetic sulfide oxidation in a meromictic lake using sulfate δ34S and δ18O

NASA Astrophysics Data System (ADS)

Gilhooly, W. P.; Reinhard, C.; Lyons, T. W.; Glass, J. B.

2012-12-01

Phototrophic sulfur bacteria oxidize sulfide and fix carbon dioxide in the presence of sunlight without producing oxygen. Environmental conditions in the Paleo- and Mesoproterozoic, when atmospheric oxygen concentrations were at low levels and portions of the oceans were anoxic and sulfidic (euxinic), were conducive to widespread carbon fixation by anoxygenic photosynthesis. This pathway may have helped sustain euxinic conditions in the Proterozoic water column. With limited organic biomarker and geochemical evidence for widespread production of anoxygenic phototrophs, however, additional proxies are needed to fingerprint paleoecological and biogeochemical signals associated with photic zone euxinia. Paired δ34S and δ18O from ancient sulfates (gypsum, barite, or CAS) may offer an added constraint on the history and ecological dominance of photosynthetic S-oxidation. Sulfate-oxygen can fractionate during sulfate reduction, but the extent of isotopic enrichment is controlled either by kinetic isotope effects imparted during intracellular enzymatic steps or equilibrium oxygen exchange with ambient water. An improved understanding of these processes can be gained from modern natural environments. Mahoney Lake is a density-stratified lake located within the White Lake Basin of British Columbia. The euxinic water column supports a dense plate of purple sulfur bacteria (Amoebobacter purpureus) that thrives where free sulfide intercepts the photic zone at ~7 m water depth. We analyzed the isotopic composition of sulfate (δ34SSO4 and δ18OSO4), sulfide (δ34SH2S), and water (δ18OH2O) to track the potentially coupled processes of dissimilatory sulfate reduction and phototrophic sulfide oxidation within this meromictic lake. Large isotopic offsets observed between sulfate and sulfide within the monimolimnion (δ34SSO4-H2S = 51‰) and within pore waters along the oxic margin (δ34SSO4-H2S >50‰) are consistent with sulfate reduction in both the sediments and the anoxic

In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring

PubMed Central

Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

2016-01-01

We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ. PMID:27297893

In Situ Gene Expression Responsible for Sulfide Oxidation and CO2 Fixation of an Uncultured Large Sausage-Shaped Aquificae Bacterium in a Sulfidic Hot Spring.

PubMed

Tamazawa, Satoshi; Yamamoto, Kyosuke; Takasaki, Kazuto; Mitani, Yasuo; Hanada, Satoshi; Kamagata, Yoichi; Tamaki, Hideyuki

2016-06-25

We investigated the in situ gene expression profile of sulfur-turf microbial mats dominated by an uncultured large sausage-shaped Aquificae bacterium, a key metabolic player in sulfur-turfs in sulfidic hot springs. A reverse transcription-PCR analysis revealed that the genes responsible for sulfide, sulfite, and thiosulfate oxidation and carbon fixation via the reductive TCA cycle were continuously expressed in sulfur-turf mats taken at different sampling points, seasons, and years. These results suggest that the uncultured large sausage-shaped bacterium has the ability to grow chemolithoautotrophically and plays key roles as a primary producer in the sulfidic hot spring ecosystem in situ.

Chemical denudation and the role of sulfide oxidation at Werenskioldbreen, Svalbard

NASA Astrophysics Data System (ADS)

Stachnik, Łukasz; Majchrowska, Elżbieta; Yde, Jacob C.; Nawrot, Adam P.; Cichała-Kamrowska, Katarzyna; Ignatiuk, Dariusz; Piechota, Agnieszka

2016-07-01

This study aims to determine the rate of chemical denudation and the relationships between dominant geochemical reactions operating in the proglacial and subglacial environments of the polythermal glacier Werenskioldbreen (SW Svalbard) during an entire ablation season. Water sampling for major ion chemistry was performed at a proglacial hydrometric station and from subglacial outflows from May to September 2011. These data were combined with measurements of discharge and supraglacial ablation rates. The slopes and intercepts in best-fit regressions of [*Ca2+ + *Mg2+ vs. *SO42-] and [HCO3- vs. *SO42-] in meltwater from ice-marginal subglacial channels were close to the stoichiometric parameters of sulfide oxidation and simple hydrolysis coupled to carbonate dissolution (*concentrations corrected for input of sea-salt). This shows that these relationships predominates the meltwater chemistry. Our findings also show that sulfide oxidation is a better indicator of the configuration of subglacial drainage systems than, for instance, Na+ and K+. In the proglacial area and in sub-artesian outflows, the ion associations represent sulfide oxidation but other processes such as ion exchange and dissolution of Ca and Mg efflorescent salts may also contribute to the solute variations. These processes may cause enhanced fluxes of Ca2+ and HCO3- from glacierized basins during the early ablation and peak flow seasons as the proglacial salts re-dissolve. The overall chemical denudation rate in the basin for 2011 (ranging from 1601 to 1762 meq m-2 yr-1 (121.9 to 132.2 t km-2 yr-1)) was very high when compared to other Svalbard valley glaciers suggesting that the high rate of chemical denudation was mostly caused by the high rates of discharge and ablation. Chemical weathering intensities (876 and 964 meq m-3 yr-1) exceeded previously reported intensities in Svalbard.

Bioflotation of sulfide minerals with Acidithiobacillus ferrooxidans in relation to copper activation and surface oxidation.

PubMed

Pecina-Treviño, E T; Ramos-Escobedo, G T; Gallegos-Acevedo, P M; López-Saucedo, F J; Orrantia-Borunda, E

2012-09-01

Surface oxidation of sulfides and copper (Cu) activation are 2 of the main processes that determine the efficiency of flotation. The present study was developed with the intention to ascertain the role of the phenomena in the biomodification of sulfides by Acidithiobacillus ferrooxidans culture (cells and growth media) and their impact in bioflotation. Surface characteristics of chalcopyrite, sphalerite, and pyrrhotite, alone and in mixtures, after interaction with A. ferrooxidans were evaluated. Chalcopyrite floatability was increased substantially by biomodification, while bacteria depressed pyrrhotite floatability, favoring separation. The results showed that elemental sulfur concentration increased because of the oxidation generated by bacterial cells, the effect is intensified by the Fe(III) left in the culture and by galvanic contact. Acidithiobacillus ferrooxidans culture affects the Cu activation of sphalerite. The implications of elemental sulfur concentration and Cu activation of sphalerite are key factors that must be considered for the future development of sulfide bioflotation processes, since the depressive effect of cells could be counteracted by elemental sulfur generation.

Method for separating metal chelates from other materials based on solubilities in supercritical fluids

DOEpatents

Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

2001-01-01

A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

Hydrogen sulfide-powered solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Man

2004-12-01

The potential utilization of hydrogen sulfide as fuel in solid oxide fuel cells has been investigated using an oxide-ion conducting YSZ electrolyte and different kinds of anode catalysts at operating temperatures in the range of 700--900°C and at atmospheric pressure. This technology offers an economically attractive alternative to present methods for removing toxic and corrosive H2S gas from sour gas streams and a promising approach for cogenerating electrical energy and useful chemicals. The primary objective of the present research was to find active and stable anode materials. Fuel cell experimental results showed that platinum was a good electrocatalyst for the conversion of H2S, but the Pt/YSZ interface was physically unstable due to the reversible formation and decomposition of PtS in H 2S streams at elevated temperatures. Moreover, instability of the Pt/YSZ interface was accelerated significantly by electrochemical reactions, and ultimately led to the detachment of the Pt anode from the electrolyte. It has been shown that an interlayer of TiO2 stabilized the Pt anode on YSZ electrolyte, thereby prolonging cell lifetime. However, the current output for a fuel cell using Pt/TiO2 as anode was not improved compared to using Pt alone. It was therefore necessary to investigate novel anode systems for H 2S-air SOFCs. New anode catalysts comprising composite metal sulfides were developed. These catalysts exhibited good electrical conductivity and better catalytic activity than Pt. In contrast to MoS2 alone, composite catalysts (M-Mo-S, M = Fe, Co, Ni) were not volatile and had superior stability. However, when used for extended periods of time, detachment of Pt current collecting film from anodes comprising metal sulfides alone resulted in a large increase in contact resistance and reduction in cell performance. Consequently, a systematic investigation was conducted to identify alternative electronic conductors for use with M-Mo-S catalysts. Anode catalysts

Sensitivity of Interfibrillar and Subsarcolemmal Mitochondria to Cobalt Chloride-induced Oxidative Stress and Hydrogen Sulfide Treatment

PubMed Central

Ayswarya, A.; Kurian, G. A.

2016-01-01

Oxidative stress plays a significant role not only in cardiovascular disease but also in non-communicable diseases, where it plays a significant role the mortality rate. Hydrogen sulfide, the biological gaseous signaling molecule that preserves mitochondria in its mode of action, is an effective cardioprotective drug. However, cardiac mitochondria comprise of two distinct populations, namely interfibrillar and subsarcolemmal mitochondria, which respond distinctly in cardiovascular disease. This study was designed to determine the direct impact of cobalt chloride-induced oxidative stress in isolated mitochondrial subpopulations with an intention to examine the efficacy of hydrogen sulfide in preserving interfibrillar and subsarcolemmal mitochondria functional activities when they were incubated as pretreated, co-treated and post-treated agent. Mitochondrial subpopulations were isolated from the heart of male Wistar rats and subjected to cobalt chloride treatment (500 μM) for 20 min, followed by incubation with 10 μM sodium hydrosulfide in three different ways (Pre, Co, and Post-cobalt chloride treatment). Mitochondrial oxidative stress was measured by the concentration of thiobarbituric acid reactive species, reduced glutathione and the activities of enzymes like superoxide dismutase, catalase and glutathione peroxidase. Mitochondrial membrane potential, swelling behavior and enzyme activities were measured to assess its function. The increased level of lipid peroxidation and the decreased level of reduced glutathione in cobalt chloride-induced group confirm the induction of oxidative stress and were more predominant in the subsarcolemmal mitochondria. Hydrogen sulfide treatment to interfibrillar and subsarcolemmal mitochondria preserved their functional activities, but the effect was prominent only with co-treated group. In conclusion, the present study demonstrated that subsarcolemmal mitochondria are more prone to oxidative stress and the co-treatment of the

Coinage metal coordination chemistry of stable primary, secondary and tertiary ferrocenylethyl-based phosphines.

PubMed

Azizpoor Fard, M; Rabiee Kenaree, A; Boyle, P D; Ragogna, P J; Gilroy, J B; Corrigan, J F

2016-02-21

Ferrocene-based phosphines constitute an important auxiliary ligand in inorganic chemistry. Utilizing the (ferrocenylethyl)phosphines (FcCH2CH2)3-nHnP (Fc = ferrocenyl; n = 2, 1; n = 1, 2; n = 0, 3) the synthesis of a series of coordination complexes [(FcCH2CH2)3-nHnPCuCl]4 (n = 2, 1-CuCl; n = 0, 3-CuCl), [(FcCH2CH2)2HPCuCl] (2-CuCl), {[(FcCH2CH2)H2P]2AgCl}2 (1-AgCl), [(FcCH2CH2)2HPAgCl] (2-AgCl), [(FcCH2CH2)3PAgCl]4 (3-AgCl), [(FcCH2CH2)3PM(OAc)]4 (M = Cu, 3-CuOAc M = Ag, 3-AgOAc), [(FcCH2CH2)3-nHnPAuCl] (n = 1, 2-AuCl; n = 0, 3-AuCl), via the reaction between the free phosphine and MX (M = Cu, Ag and Au; X = Cl, OAc), is described. The reaction between the respective phosphine with a suspension of metal-chloride or -acetate in a 1 : 1 ratio in THF at ambient temperature affords coordinated phosphine-coinage metal complexes. Varying structural motifs are observed in the solid state, as determined via single crystal X-ray analysis of 1-CuCl, 3-CuCl, 1-AgCl, 3-AgCl, 3-CuOAc, 3-AgOAc, 2-AuCl and 3-AuCl. Complexes 1-CuCl and 3-CuCl are tetrameric Cu(i) cubane-like structures with a Cu4Cl4 core, whereas silver complexes with primary and tertiary phosphine reveal two different structural types. The structure of 1-AgCl, unlike the rest, displays the coordination of two phosphines to each silver atom and shows a quadrangle defined by two Ag and two Cl atoms. In contrast, 3-AgCl is distorted from a cubane structure via elongation of one of the ClAg distances. 3-CuOAc and 3-AgOAc are isostructural with step-like cores, while complexes 2-AuCl and 3-AuCl reveal a linear geometry of a phosphine gold(i) chloride devoid of any aurophilic interactions. All of the complexes were characterized in solution by multinuclear (1)H, (13)C{(1)H} and (31)P NMR spectroscopic techniques; the redox chemistry of the series of complexes was examined using cyclic voltammetry. This class of complexes has been found to exhibit one reversible Fe(ii)/Fe(iii) oxidation couple, suggesting the

Electrochemical oxidation of iron and alkalinity generation for efficient sulfide control in sewers.

PubMed

Lin, Hui-Wen; Kustermans, Caroline; Vaiopoulou, Eleni; Prévoteau, Antonin; Rabaey, Korneel; Yuan, Zhiguo; Pikaar, Ilje

2017-07-01

The addition of iron salts is one of the most commonly used dosing strategies for sulfide control in sewers. However, iron salts decrease the sewage pH which not only reduces the effectiveness of sulfide precipitation but also enhances the release of residual sulfide to the sewer atmosphere. Equally important, concentrated iron salt solutions are corrosive and their frequent transport, handling, and on-site storage often come with Occupational Health and Safety (OH&S) concerns. Here, we experimentally demonstrated a novel sulfide control approach using electrochemical systems with parallel placed iron electrodes. This enabled combining anodic dissolved iron species release with cathodic hydroxyl anion production, which alleviates all the aforementioned concerns. A long-term experiment was successfully carried out achieving an average sulfide removal efficiency of 95.4 ± 4.4% at low voltage input of 2.90 ± 0.54 V over the course of 8 weeks. This electrochemical method was demonstrated to successfully achieve efficient sulfide control. In addition, it increases the sewage pH, thereby overcoming the drawbacks associated with the pH decrease in the case of conventional iron salt dosing. Ferrous ions were produced at an overall coulombic efficiency (CE) of 98.2 ± 1.2%, whereas oxygen evolution and direct sulfide oxidation were not observed. Short-term experiments showed that increasing either inter-electrode gap or current density increased the cell voltage associated with the increase in the ohmic drop of the system. Overall, this study highlights the practical potential of in-situ generation of dissolved iron species and simultaneous hydroxyl anion generation for efficient sulfide control in sewers. Copyright © 2017 Elsevier Ltd. All rights reserved.

In Situ Determination of Sulfide Turnover Rates in a Meromictic Alpine Lake

PubMed Central

Lüthy, Lucas; Fritz, Markus; Bachofen, Reinhard

2000-01-01

A push-pull method, previously used in groundwater analyses, was successfully adapted for measuring sulfide turnover rates in situ at different depths in the meromictic Lake Cadagno. In the layer of phototrophic bacteria at about 12 m in depth net sulfide consumption was observed during the day, indicating active bacterial photosynthesis. During the night the sulfide turnover rates were positive, indicating a net sulfide production from the reduction of more-oxidized sulfur compounds. Because of lack of light, no photosynthesis takes place in the monimolimnion; thus, only sulfide formation is observed both during the day and the night. Sulfide turnover rates in the oxic mixolimnion were always positive as sulfide is spontaneously oxidized by oxygen and as the rates of sulfide oxidation depend on the oxygen concentrations present. Sulfide oxidation by chemolithotrophic bacteria may occur at the oxicline, but this cannot be distinguished from spontaneous chemical oxidation. PMID:10653740

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

PubMed Central

Binyamin, Iris; Meidan-Shani, Shoval

2015-01-01

Summary The synthesis of P-chirogenic (±)-phosphine oxides and phosphinates via selective nucleophilic ring opening of the corresponding oxaphospholanes is described. Two representative substrates: the phosphonate 2-ethoxy-1,2-oxaphospholane 2-oxide and the phosphinate 2-phenyl-1,2-oxaphospholane 2-oxide were reacted with various Grignard reagents to produce a single alkyl/aryl product. These products may possess further functionalities in addition to the phosphorus center such as the γ-hydroxypropyl group which results from the ring opening and π-donor moieties such as aryl, allyl, propargyl and allene which originates from the Grignard reagent. PMID:26425187

Improved oxidation sulfidation resistance of Fe-Cr-Ni alloys

DOEpatents

Natesan, K.; Baxter, D.J.

1983-07-26

High temperature resistance of Fe-Cr-Ni alloy compositions to oxidative and/or sulfidative conditions is provided by the incorporation of about 1 to 8 wt % of Zr or Nb and results in a two-phase composition having an alloy matrix as the first phase and a fine grained intermetallic composition as the second phase. The presence and location of the intermetallic composition between grains of the matrix provides mechanical strength, enhanced surface scale adhesion, and resistance to corrosive attack between grains of the alloy matrix at temperatures of 500 to 1000/sup 0/C.

A Military Guide to Terrorism in the Twenty-First Century. U.S. Army DCSINT Handbook No. 1 (Version 3.0)

DTIC Science & Technology

2005-08-15

or varnished brown Length: 102mm Width: 61mm Weight: 773g Filler: Amatol Characteristics Color: Black and unmarked Length: 131mm Width: 55mm...isocyanate Diborane Boron tribromide Nitrogen dioxide Ethylene oxide Carbon monoxide Phosphine Fluorine Carbonyl sulfide Phosphorus oxychloride

Sulfide-responsive transcriptional repressor SqrR functions as a master regulator of sulfide-dependent photosynthesis.

PubMed

Shimizu, Takayuki; Shen, Jiangchuan; Fang, Mingxu; Zhang, Yixiang; Hori, Koichi; Trinidad, Jonathan C; Bauer, Carl E; Giedroc, David P; Masuda, Shinji

2017-02-28

Sulfide was used as an electron donor early in the evolution of photosynthesis, with many extant photosynthetic bacteria still capable of using sulfur compounds such as hydrogen sulfide (H 2 S) as a photosynthetic electron donor. Although enzymes involved in H 2 S oxidation have been characterized, mechanisms of regulation of sulfide-dependent photosynthesis have not been elucidated. In this study, we have identified a sulfide-responsive transcriptional repressor, SqrR, that functions as a master regulator of sulfide-dependent gene expression in the purple photosynthetic bacterium Rhodobacter capsulatus SqrR has three cysteine residues, two of which, C41 and C107, are conserved in SqrR homologs from other bacteria. Analysis with liquid chromatography coupled with an electrospray-interface tandem-mass spectrometer reveals that SqrR forms an intramolecular tetrasulfide bond between C41 and C107 when incubated with the sulfur donor glutathione persulfide. SqrR is oxidized in sulfide-stressed cells, and tetrasulfide-cross-linked SqrR binds more weakly to a target promoter relative to unmodified SqrR. C41S and C107S R. capsulatus SqrRs lack the ability to respond to sulfide, and constitutively repress target gene expression in cells. These results establish that SqrR is a sensor of H 2 S-derived reactive sulfur species that maintain sulfide homeostasis in this photosynthetic bacterium and reveal the mechanism of sulfide-dependent transcriptional derepression of genes involved in sulfide metabolism.

Interaction of some extreme-pressure type lubricating compounds with an iron surface

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1973-01-01

An iron surface was exposed to the extreme-pressure type lubricant benzyl chloride, dichlorophenyl phosphine, dichlorophenyl phosphine sulfide, ophenyl phosphine oxide. Iron, in the sputter-cleaned state, was exposed to these materials statically and during dynamic friction experiments. With benzyl chloride only chlorine adsorbed to the surface, and with dichlorophenyl phosphine no adsorption occurred, while the addition of sulfur to that same molecular structure resulted in the promotion of carbon and chlorine adsorption. substitution of oxygen for sulfur in the dichlorobenzyl phosphine molecule resulted in carbon, chlorine, and oxygen adsorption. With none of the phosphorus containing molecules was phosphorus detected on the surface. Sliding in an atmosphere of benzyl chloride promoted adsorption of chlorine to the iron surface. Increases in load resulted in a decrease in the surface concentration of iron chloride.

Phosphine-alkene ligands as mechanistic probes in the Pauson-Khand reaction.

PubMed

Ferrer, Catalina; Benet-Buchholz, Jordi; Riera, Antoni; Verdaguer, Xavier

2010-07-26

An alkyne tetracarbonyl dicobalt complex with a chelated phosphine-alkene ligand, in which the phosphorus atom and the alkene from the ligand are attached to the same cobalt atom has been prepared, isolated, and characterized by X-ray crystallography. The complex serves as a mechanistic model for an intermediate of the Pauson-Khand (PK) reaction. Although the alkene fragment is located in an equatorial coordination site with an appropriate orientation, and, therefore, should undergo insertion, it failed to give the PK product upon either thermal or N-methylmorpholine N-oxide activation. However, a phosphine-alkene complex that contains a terminal alkene readily provided the corresponding PK product. We attribute this change in reactivity to the different ability of each olefin to undergo 1,2-insertion. These results provide further insights into the factors that govern a crucial step in the PK reaction, the olefin insertion.

Phosphine from rocks: mechanically driven phosphate reduction?

PubMed

Glindemann, Dietmar; Edwards, Marc; Morgenstern, Peter

2005-11-01

Natural rock and mineral samples released trace amounts of phosphine during dissolution in mineral acid. An order of magnitude more phosphine (average 1982 ng PH3 kg rock and maximum 6673 ng PH3/kg rock) is released from pulverized rock samples (basalt, gneiss, granite, clay, quartzitic pebbles, or marble). Phosphine was correlated to hardness and mechanical pulverization energy of the rocks. The yield of PH3 ranged from 0 to 0.01% of the total P content of the dissolved rock. Strong circumstantial evidence was gathered for reduction of phosphate in the rock via mechanochemical or "tribochemical" weathering at quartz and calcite/marble inclusions. Artificial reproduction of this mechanism by rubbing quartz rods coated with apatite-phosphate to the point of visible triboluminescence, led to detection of more than 70 000 ng/kg PH3 in the apatite. This reaction pathway may be considered a mechano-chemical analogue of phosphate reduction from lightning or electrical discharges and may contribute to phosphine production via tectonic forces and processing of rocks.

The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review

PubMed Central

Zhao, Shunzheng; Yi, Honghong; Tang, Xiaolong; Jiang, Shanxue; Gao, Fengyu; Zhang, Bowen; Zuo, Yanran; Wang, Zhixiang

2013-01-01

Catalytic hydrolysis technology of carbonyl sulfide (COS) at low temperature was reviewed, including the development of catalysts, reaction kinetics, and reaction mechanism of COS hydrolysis. It was indicated that the catalysts are mainly involved metal oxide and activated carbon. The active ingredients which can load on COS hydrolysis catalyst include alkali metal, alkaline earth metal, transition metal oxides, rare earth metal oxides, mixed metal oxides, and nanometal oxides. The catalytic hydrolysis of COS is a first-order reaction with respect to carbonyl sulfide, while the reaction order of water changes as the reaction conditions change. The controlling steps are also different because the reaction conditions such as concentration of carbonyl sulfide, reaction temperature, water-air ratio, and reaction atmosphere are different. The hydrolysis of carbonyl sulfide is base-catalyzed reaction, and the force of the base site has an important effect on the hydrolysis of carbonyl sulfide. PMID:23956697

Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruhn, Debby Fox; Thompson, David Neal; Noah, Karl Scott

1999-06-01

Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, “Leptospirillum”, “Ferromicrobium”, and Acidiphilium. Two temperatures (30°C and 45°C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. Aftermore » acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to low the pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.« less

Microbial Ecology Assessment of Mixed Copper Oxide/Sulfide Dump Leach Operation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruhn, D F; Thompson, D N; Noah, K S

1999-06-01

Microbial consortia composed of complex mixtures of autotrophic and heterotrophic bacteria are responsible for the dissolution of metals from sulfide minerals. Thus, an efficient copper bioleaching operation depends on the microbial ecology of the system. A microbial ecology study of a mixed oxide/sulfide copper leaching operation was conducted using an "overlay" plating technique to differentiate and identify various bacterial consortium members of the genera Thiobacillus, Leptospirillum, Ferromicrobium, and Acidiphilium. Two temperatures (30C and 45C) were used to select for mesophilic and moderately thermophilic bacteria. Cell numbers varied from 0-106 cells/g dry ore, depending on the sample location and depth. Aftermore » acid curing for oxide leaching, no viable bacteria were recovered, although inoculation of cells from raffinate re-established a microbial population after three months. Due to the low pH of the operation, very few non-iron-oxidizing acidophilic heterotrophs were recovered. Moderate thermophiles were isolated from the ore samples. Pregnant liquor solutions (PLS) and raffinate both contained a diversity of bacteria. In addition, an intermittently applied waste stream that contained high levels of arsenic and fluoride was tested for toxicity. Twenty vol% waste stream in PLS killed 100% of the cells in 48 hours, indicating substantial toxicity and/or growth inhibition. The data indicate that bacteria populations can recover after acid curing, and that application of the waste stream to the dump should be avoided. Monitoring the microbial ecology of the leaching operation provided significant information that improved copper recovery.« less

Theoretical study of adsorption of organic phosphines on transition metal surfaces

NASA Astrophysics Data System (ADS)

Lou, Shujie; Jiang, Hong

2018-04-01

The adsorption properties of organic phosphines on transition metal (TM) surfaces (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) have been studied to explore the possibility of building novel heterogeneous chiral catalytic systems based on organic phosphines. Preferred adsorption sites, adsorption energies and surface electronic structures of a selected set of typical organic phosphines adsorbed on TM surfaces are calculated with density-functional theory to obtain a systematic understanding on the nature of adsorption interactions. All organic phosphines considered are found to chemically adsorb on these TM surfaces with the atop site as the most preferred one, and the TM-P bond is formed via the lone-pair electrons of the P atom and the directly contacted TM atom. These findings imply that it is indeed possible to build heterogeneous chiral catalytic systems based on organic phosphines adsorbed on TM surfaces, which, however, requires a careful design of molecular structure of organic phosphines.

Polyphosphazine-based polymer materials

DOEpatents

Fox, Robert V.; Avci, Recep; Groenewold, Gary S.

2010-05-25

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Methods for removing contaminant matter from a porous material

DOEpatents

Fox, Robert V [Idaho Falls, ID; Avci, Recep [Bozeman, MT; Groenewold, Gary S [Idaho Falls, ID

2010-11-16

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Systems and strippable coatings for decontaminating structures that include porous material

DOEpatents

Fox, Robert V [Idaho Falls, ID; Avci, Recep [Bozeman, MT; Groenewold, Gary S [Idaho Falls, ID

2011-12-06

Methods of removing contaminant matter from porous materials include applying a polymer material to a contaminated surface, irradiating the contaminated surface to cause redistribution of contaminant matter, and removing at least a portion of the polymer material from the surface. Systems for decontaminating a contaminated structure comprising porous material include a radiation device configured to emit electromagnetic radiation toward a surface of a structure, and at least one spray device configured to apply a capture material onto the surface of the structure. Polymer materials that can be used in such methods and systems include polyphosphazine-based polymer materials having polyphosphazine backbone segments and side chain groups that include selected functional groups. The selected functional groups may include iminos, oximes, carboxylates, sulfonates, .beta.-diketones, phosphine sulfides, phosphates, phosphites, phosphonates, phosphinates, phosphine oxides, monothio phosphinic acids, and dithio phosphinic acids.

Convenient synthesis and diversification of dehydroalaninyl phosphinic peptide analogues.

PubMed

Matziari, M; Georgiadis, D; Dive, V; Yiotakis, A

2001-03-08

[structure: see text]. Dehydroalaninyl phosphinic dipeptide analogues were synthesized, via an efficient tandem Arbuzov addition/allylic rearrangement, in high yields. The susceptibility of the conjugate system to 1,4 nucleophilic additions was investigated. C-Elongation of the dipeptides was performed, and the efficiency of 1,4 addition to the resulting acrylamidic moiety was evaluated. Derivatization of such phosphinic templates is a powerful approach for rapid access to large number of phosphinic pseudopeptides bearing various side chains in the P1' position.

Acid volatile sulfides oxidation and metals (Mn, Zn) release upon sediment resuspension: laboratory experiment and model development.

PubMed

Hong, Yong Seok; Kinney, Kerry A; Reible, Danny D

2011-03-01

Sediment from the Anacostia River (Washington, DC, USA) was suspended in aerobic artificial river water for 14 d to investigate the dynamics of dissolved metals release and related parameters including pH, acid volatile sulfides (AVS), and dissolved/solid phase Fe(2+). To better understand and predict the underlying processes, a mathematical model is developed considering oxidation of reduced species, dissolution of minerals, pH changes, and pH-dependent metals' sorption to sediment. Oxidation rate constants of elemental sulfur and zinc sulfide, and a dissolution rate constant of carbonate minerals, were adjusted to fit observations. The proposed model and parameters were then applied, without further calibration, to literature-reported experimental observations of resuspension in an acid sulfate soil collected in a coastal flood plain. The model provided a good description of the dynamics of AVS, Fe(2+), S(0)((s)), pH, dissolved carbonates concentrations, and the release of Ca((aq)), Mg((aq)), and Zn((aq)) in both sediments. Accurate predictions of Mn((aq)) release required adjustment of sorption partitioning coefficient, presumably due to the presence of Mn scavenging by phases not accounted for in the model. The oxidation of AVS (and the resulting release of sulfide-bound metals) was consistent with a two-step process, a relatively rapid AVS oxidation to elemental sulfur (S(0)((s))) and a slow oxidation of S(0)((s)) to SO(4)(2-)((aq)), with an associated decrease in pH from neutral to acidic conditions. This acidification was the dominant factor for the release of metals into the aqueous phase. Copyright © 2010 SETAC.

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.

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

USGS Publications Warehouse

Koski, R.A.; Munk, L.; Foster, A.L.; Shanks, Wayne C.; Stillings, L.L.

2008-01-01

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4

Advances in Nucleophilic Phosphine Catalysis of Alkenes, Allenes, Alkynes, and MBHADs

PubMed Central

Fan, Yi Chiao

2014-01-01

In nucleophilic phosphine catalysis, tertiary phosphines undergo conjugate additions to activated carbon–carbon multiple bonds to form β-phosphonium enolates, β-phosphonium dienolates, β-phosphonium enoates, and vinyl phosphonium ylides as intermediates. When these reactive zwitterionic species react with nucleophiles and electrophiles, they may generate carbo- and heterocycles with multifarious molecular architectures. This Article describes the reactivities of these phosphonium zwitterions, the applications of phosphine catalysis in the syntheses of biologically active compounds and natural products, and recent developments in the enantioselective phosphine catalysis. PMID:24196409

Metal- and Additive-Free Oxidation of Sulfides into Sulfoxides by Fullerene-Modified Carbon Nitride with Visible-Light Illumination.

PubMed

Chen, Xi; Deng, Kejian; Zhou, Peng; Zhang, Zehui

2018-05-24

Photocatalytic selective oxidation has attracted considerable attention as an environmentally friendly strategy for organic transformations. Some methods have been reported for the photocatalytic oxidation of sulfides into sulfoxides in recent years. However, the practical application of these processes is undermined by several challenges, such as low selectivity, sluggish reaction rates, the requirement of UV-light irradiation, the use of additives, and the instability of the photocatalyst. Herein, a metal-free C 60 /graphitic carbon nitride (g-C 3 N 4 ) composite photocatalyst was fabricated by a facile method, and well characterized by TEM, SEM, FTIR spectroscopy, XRD, X-ray photoelectron spectroscopy, diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The C 60 /g-C 3 N 4 catalyst exhibited a high photocatalytic activity at room temperature for the selective oxidation of sulfides into the corresponding sulfoxides in the presence of other functional groups, due to the synergetic roles of C 60 and g-C 3 N 4 . Several important parameters have been screened, and this method afforded good to excellent yields of sulfoxides under optimal conditions. The superoxide radical ( . O 2 - ) and singlet oxygen ( 1 O 2 ) were identified as the oxidative species for the oxidation of sulfides into sulfoxides by exploring EPR experiments, and hence, a plausible mechanism for this oxidation was proposed. Moreover, the C 60 /g-C 3 N 4 catalyst can be easily recovered by filtration and then reused at least four times without loss in activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

First principles search for n-type oxide, nitride, and sulfide thermoelectrics

PubMed Central

Garrity, Kevin F.

2016-01-01

Oxides have many potentially desirable characteristics for thermoelectric applications, including low cost and stability at high temperatures, but thus far there are few known high zT n-type oxide thermoelectrics. In this work, we use high-throughput first principles calculations to screen transition metal oxides, nitrides, and sulfides for candidate materials with high power factors and low thermal conductivity. We find a variety of promising materials, and we investigate these materials in detail in order to understand the mechanisms that cause them to have high power factors. These materials all combine a high density of states near the Fermi level with dispersive bands, reducing the trade-off between the Seebeck coefficient and the electrical conductivity, but they do so for several different reasons. In addition, our calculations indicate that many of our candidate materials have low thermal conductivity. PMID:27885361

Rapid oxidation of sulfide mine tailings by reaction with potassium ferrate.

PubMed

Murshed, Mohamed; Rockstraw, David A; Hanson, Adrian T; Johnson, Michael

2003-01-01

The chemistry of sulfide mine tailings treated with potassium ferrate (K2FeO4) in aqueous slurry has been investigated. The reaction system is believed to parallel a geochemical oxidation in which ferrate ion replaces oxygen. This chemical system utilized in a pipeline (as a plug flow reactor) may have application eliminating the potential for tailings to leach acid while recovering the metal from the tailings. Elemental analyses were performed using an ICP spectrometer for the aqueous phase extract of the treated tailings; and an SEM-EDX for the tailing solids. Solids were analyzed before and after treatments were applied. ICP shows that as the mass ratio of ferrate ion to tailings increases, the concentration of metals in the extract solution increases; while EDX indicates a corresponding decrease in sulfur content of the tailing solids. The extraction of metal and reduction in sulfide content is significant. The kinetic timeframe is on the order of minutes.

Effect of temperature on anoxic sulfide oxidation and denitrification in the bulk wastewater phase of sewer networks.

PubMed

Mathioudakis, V L; Aivasidis, A

2009-01-01

Artificial dosage of nitrate in sewer networks is considered as one of the most effective methods for odor and corrosion control. However, there is limited knowledge on the effect of temperature on the transformations that takes place during anoxic conditions. Thus, two groups of batch experiments were conducted to gain insight in the involved processes in bulk phase of a septic municipal wastewater. It can be concluded that sewer denitrification, in bulk phase, can be simplified in three stages. According to the experimental results, nitrate or nitrite is utilized for autotrophic denitrification with sulfide, while heterotrophic utilization is initiated after the completion of anoxic sulfide oxidation. Moreover, temperature is proved to have a significant impact on sewer denitrification kinetic profile, as it determines the extent of temporal nitrite accumulation. The temperature coefficient of each anoxic process, including sulfide oxidation, nitrate utilization and denitrification/nitrite utilization is experimentally calculated and temperature dependent equations are developed, providing the rate of all anoxic processes in bulk phase of sewer wastewater, in any given temperature.

Complete genome sequence of Metallosphaera cuprina, a metal sulfide-oxidizing archaeon from a hot spring.

PubMed

Liu, Li-Jun; You, Xiao-Yan; Zheng, Huajun; Wang, Shengyue; Jiang, Cheng-Ying; Liu, Shuang-Jiang

2011-07-01

The genome of the metal sulfide-oxidizing, thermoacidophilic strain Metallosphaera cuprina Ar-4 has been completely sequenced and annotated. Originally isolated from a sulfuric hot spring, strain Ar-4 grows optimally at 65°C and a pH of 3.5. The M. cuprina genome has a 1,840,348-bp circular chromosome (2,029 open reading frames [ORFs]) and is 16% smaller than the previously sequenced Metallosphaera sedula genome. Compared to the M. sedula genome, there are no counterpart genes in the M. cuprina genome for about 480 ORFs in the M. sedula genome, of which 243 ORFs are annotated as hypothetical protein genes. Still, there are 233 ORFs uniquely occurring in M. cuprina. Genome annotation supports that M. cuprina lives a facultative life on CO(2) and organics and obtains energy from oxidation of sulfidic ores and reduced inorganic sulfuric compounds.

Redox-Controlled Olefin (Co)Polymerization Catalyzed by Ferrocene-Bridged Phosphine-Sulfonate Palladium Complexes.

PubMed

Chen, Min; Yang, Bangpei; Chen, Changle

2015-12-14

The facile and reversible interconversion between neutral and oxidized forms of palladium complexes containing ferrocene-bridged phosphine sulfonate ligands was demonstrated. The activity of these palladium complexes could be controlled using redox reagents during ethylene homopolymerization, ethylene/methyl acrylate copolymerization, and norbornene oligomerization. Specifically in norbornene oligomerization, the neutral complexes were not active at all whereas the oxidized counterparts showed appreciable activity. In situ switching between the neutral and oxidized forms resulted in an interesting "off" and "on" behavior in norbornene oligomerization. This work provides a new strategy to control the olefin polymerization process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liver histopathology of fatal phosphine poisoning.

PubMed

Saleki, Sepideh; Ardalan, Farid Azmoudeh; Javidan-Nejad, Abdullah

2007-03-02

Two commonly used pesticides in agriculture are phosphides of aluminium and zinc. Both of these metal phosphides act through elaboration of toxic phosphine gas. The poisoning in Iran is mostly oral and suicidal. Phosphine is rapidly absorbed throughout the gastrointestinal tract after ingestion and it is partly carried to the liver by the portal vein. In this study the liver histopathology of fatal poisoning is scrutinized. A descriptive, retrospective study was performed on 38 fatal phosphine poisonings. The slides of liver specimens of the cases were retrieved and studied separately by two pathologists. The poisoning was suicidal in 33 (86.5%) of cases. Portal inflammation was negligible in 37 cases and only in one of the cases, a moderate degree of chronic inflammation accompanied by granuloma formation was observed. Major histopathologic findings were as follows: mild sinusoidal congestion; 12 cases (31.6%), severe sinusoidal congestion; 25 cases (45.8%), central vein congestion; 23 cases (60.5%), centrilobular necrosis; 3 cases (7.9%), hepatocytes nuclear fragmentation; 6 cases (15.8%), sinusoidal clusters of polymorphonuclear leukocytes; 12 cases (31.6%), and mild macrovesicular steatosis; 5 cases (13.2%). Fine isomorphic cytoplasmic vacuoles were observed in 36 cases (94.7%). These vacuoles were distributed uniformly in all hepatic zones in the majority (75%) of cases. This study reveals that the main histopathologic findings of fatal phosphine poisoning in the liver are fine cytoplasmic vacuolization of hepatocytes and sinusoidal congestion.

Preparation of phosphines through C–P bond formation

PubMed Central

Wauters, Iris; Debrouwer, Wouter

2014-01-01

Summary Phosphines are an important class of ligands in the field of metal-catalysis. This has spurred the development of new routes toward functionalized phosphines. Some of the most important C–P bond formation strategies were reviewed and organized according to the hybridization of carbon in the newly formed C–P bond. PMID:24991257

Sulfide oxidation and acid mine drainage formation within two active tailings impoundments in the Golden Quadrangle of the Apuseni Mountains, Romania.

PubMed

Sima, Mihaela; Dold, Bernhard; Frei, Linda; Senila, Marin; Balteanu, Dan; Zobrist, Jurg

2011-05-30

Sulfidic mine tailings have to be classified as one of the major source of hazardous materials leading to water contamination. This study highlights the processes leading to sulfide oxidation and acid mine drainage (AMD) formation in the active stage of two tailings impoundments located in the southern part of the Apuseni Mountains, in Romania, a well-known region for its long-term gold-silver and metal mining activity. Sampling was undertaken when both impoundments were still in operation in order to assess their actual stage of oxidation and long-term behavior in terms of the potential for acid mine drainage generation. Both tailings have high potential for AMD formation (2.5 and 3.7 wt.% of pyrite equivalent, respectively) with lesser amount of carbonates (5.6 and 3.6 wt.% of calcite equivalent) as neutralization potential (ABA=-55.6 and -85.1 tCaCO(3)/1000 t ) and showed clear signs of sulfide oxidation yet during operation. Sequential extraction results indicate a stronger enrichment and mobility of elements in the oxidized tailings: Fe as Fe(III) oxy-hydroxides and oxides (transformation from sulfide minerals, leaching in oxidation zone), Ca mainly in water soluble and exchangeable form where gypsum and calcite are dissolved and higher mobility of Cu for Ribita and Pb for Mialu. Two processes leading to the formation of mine drainage at this stage could be highlighted (1) a neutral Fe(II) plume forming in the impoundment with ferrihydrite precipitation at its outcrop and (2) acid mine drainage seeping in the unsaturated zone of the active dam, leading to the formation of schwertmannite at its outcrop. Copyright © 2011 Elsevier B.V. All rights reserved.

Process for thin film deposition of cadmium sulfide

DOEpatents

Muruska, H. Paul; Sansregret, Joseph L.; Young, Archie R.

1982-01-01

The present invention teaches a process for depositing layers of cadmium sulfide. The process includes depositing a layer of cadmium oxide by spray pyrolysis of a cadmium salt in an aqueous or organic solvent. The oxide film is then converted into cadmium sulfide by thermal ion exchange of the O.sup.-2 for S.sup.-2 by annealing the oxide layer in gaseous sulfur at elevated temperatures.

Simulation of sulfide buildup in wastewater and atmosphere of sewer networks.

PubMed

Nielsen, A H; Yongsiri, C; Hvitved-Jacobsen, T; Vollertsen, J

2005-01-01

A model concept for prediction of sulfide buildup in sewer networks is presented. The model concept is an extension to--and a further development of--the WATS model (Wastewater Aerobic-anaerobic Transformations in Sewers), which has been developed by Hvitved-Jacobsen and co-workers at Aalborg University. In addition to the sulfur cycle, the WATS model simulates changes in dissolved oxygen and carbon fractions of different biodegradability. The sulfur cycle was introduced via six processes: 1. sulfide production taking place in the biofilm covering the permanently wetted sewer walls; 2. biological sulfide oxidation in the permanently wetted biofilm; 3. chemical and biological sulfide oxidation in the water phase; 4. sulfide precipitation with metals present in the wastewater; 5. emission of hydrogen sulfide to the sewer atmosphere and 6. adsorption and oxidation of hydrogen sulfide on the moist sewer walls where concrete corrosion may take place.

Stress pre-conditioning with temperature, UV and gamma radiation induces tolerance against phosphine toxicity.

PubMed

Alzahrani, Saad M; Ebert, Paul R

2018-01-01

Phosphine is the only general use fumigant for the protection of stored grain, though its long-term utility is threatened by the emergence of highly phosphine-resistant pests. Given this precarious situation, it is essential to identify factors, such as stress preconditioning, that interfere with the efficacy of phosphine fumigation. We used Caenorhabditis elegans as a model organism to test the effect of pre-exposure to heat and cold shock, UV and gamma irradiation on phosphine potency. Heat shock significantly increased tolerance to phosphine by 3-fold in wild-type nematodes, a process that was dependent on the master regulator of the heat shock response, HSF-1. Heat shock did not, however, increase the resistance of a strain carrying the phosphine resistance mutation, dld-1(wr4), and cold shock did not alter the response to phosphine of either strain. Pretreatment with the LD50 of UV (18 J cm-2) did not alter phosphine tolerance in wild-type nematodes, but the LD50 (33 J cm-2) of the phosphine resistant strain (dld-1(wr4)) doubled the level of resistance. In addition, exposure to a mild dose of gamma radiation (200 Gy) elevated the phosphine tolerance by ~2-fold in both strains.

Synthesis and biological applications of phosphinates and derivatives.

PubMed

Virieux, David; Volle, Jean-Noël; Bakalara, Norbert; Pirat, Jean-Luc

2015-01-01

This review first outlines general considerations on phosphinic acids and derivatives as bioisosteric groups. The next sections present key aspects of phosphinic acid-based molecules and include a brief description of the biological pathways involved for their activities. The synthetic aspects and the biological activities of such compounds reported in the literature between 2008 and 2013 are also described.

Polymer producing palladium complexes of unidentate phosphines in the methoxycarbonylation of ethene.

PubMed

Smith, Graeme; Vautravers, Nicolas R; Cole-Hamilton, David J

2009-02-07

A wide range of unidentate phosphines have been studied as ligands for the palladium-catalysed methoxycarbonylation of ethene in the presence of methanesulfonic acid using methanol as the solvent. At high phosphine to Pd ratios, methyl propanoate is formed at a low rate. However, at P-Pd ratios of 4 : 1, some unidentate phosphines promote the formation of polyketone with moderate rates. Analysis of all the phosphines shows that good electron donating power, combined with small size, favours polyketone formation.

Low-Temperature Fumigation of Harvested Lettuce Using a Phosphine Generator.

PubMed

Liu, Yong-Biao

2018-02-28

A research-scale phosphine generator, QuickPHlo-R, from United Phosphorus Ltd. (Mumbai, India) was tested to determine whether it was suitable for low-temperature fumigation and oxygenated phosphine fumigation of harvested lettuce. Vacuum cooled Iceberg and Romaine lettuce (Lactuca sativa) were fumigated in 442-liter chambers at 2°C for 24 and 72 h for control of western flower thrips [Frankliniella occidentalis (Pergande) (Thysanoptera: Thripidae)] and lettuce aphid [Nasonovia ribisnigri (Mosely) (Homoptera: Aphididae)]. Oxygenated phosphine fumigation for 48 h under 60% O2 was also conducted at 2°C with Iceberg and Romaine lettuce for control of lettuce aphid. The generator completed phosphine generation in 60-90 min. Complete control of western flower thrips was achieved in 24-h treatment, and the 48-h oxygenated fumigation, and 72-h regular fumigation treatments completely controlled lettuce aphid. Lettuce quality was evaluated 14 d after fumigation. There was increased incidence of brown stains on fumigated Iceberg lettuce, and the increases were more obvious in longer (≥48 h) treatments. Both Iceberg and Romaine lettuce from all treatments and controls had good visual quality even though there was significantly higher brown stain incidence on fumigated Iceberg lettuce in ≥48-h treatment and significant differences in quality score for both Iceberg and Romaine lettuce in the 72-h treatment. The brown stains were likely due to the high sensitivity of lettuce to carbon dioxide. The study indicated that QuiPHlo-R phosphine generator has potential in low-temperature phosphine fumigation due to the quick establishment of desired phosphine levels, efficacy in pest control, and reasonable safety to product quality.

Continuous sulfidogenic wastewater treatment with iron sulfide sludge oxidation and recycle.

PubMed

Deng, Dongyang; Lin, Lian-Shin

2017-05-01

This study evaluated the technical feasibility of packed-bed sulfidogenic bioreactors dosed with ferrous chloride for continuous wastewater treatment over a 450-day period. In phase I, the bioreactors were operated under different combinations of carbon, iron, and sulfate mass loads without sludge recycling to identify optimal treatment conditions. A COD/sulfate mass ratio of 2 and a Fe/S molar ratio of 1 yielded the best treatment performance with COD oxidation rate of 786 ± 82 mg/(L⋅d), which resulted in 84 ± 9% COD removal, 94 ± 6% sulfate reduction, and good iron retention (99 ± 1%) under favorable pH conditions (6.2-7.0). In phase II, the bioreactors were operated under this chemical load combination over a 62-day period, during which 7 events of sludge collection, oxidation, and recycling were performed. The collected sludge materials contained both inorganic and organic matter with FeS and FeS 2 as the main inorganic constituents. In each event, the sludge materials were oxidized in an oxidizing basin before recycling to mix with the wastewater influent. Sludge recycling yielded enhanced COD removal (90 ± 6% vs. 75 ± 7%), and better effluent quality in terms of pH (6.8 ± 0.1 vs. 6.5 ± 0.2), iron (0.7 ± 0.5 vs. 1.9 ± 1.7 mg/L), and sulfide-S (0.3 ± 0.1 vs. 0.4 ± 0.1 mg/L) removal compared to the baseline operation without sludge recycling during phase II. This process exhibited treatment stability with reasonable variations, and fairly consistent sludge content over long periods of operation under a range of COD/sulfate and Fe/S ratios without sludge recycling. The bioreactors were found to absorb recycling-induced changes efficiently without causing elevated suspended solids in the effluents. Copyright © 2017 Elsevier Ltd. All rights reserved.

Product distribution study of the Cl-atom initiated oxidation of ethyl methyl sulfide and diethyl sulfide

NASA Astrophysics Data System (ADS)

Oksdath-Mansilla, Gabriela; Peñéñory, Alicia B.; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

2014-03-01

The products formed in the gas-phase reactions of Cl atoms with (CH3CH2)2S and CH3CH2SCH3 have been investigated in a large volume reactor in NOx-free air at atmospheric pressure and (298 ± 2) K using long path “in situ” FTIR spectroscopy for the analysis. HCl, SO2 and CH3CHO were identified as the major products for both reactions. For the Cl + CH3CH2SCH3 reaction HCHO was also identified as a major product. The yields of the products obtained for the reaction of Cl with (CH3CH2)2S were (59 ± 2) %, (52 ± 5) % and (103 ± 4) % for HCl, SO2 and CH3CHO, respectively. For the reaction of Cl with CH3CH2SCH3 yields of (43 ± 5) %, (55 ± 3) %, (58 ± 3) % and (53 ± 5) % were obtained for HCl, SO2, CH3CHO and HCHO, respectively. This is the first products and mechanistic study for the gas-phase Cl-initiated oxidation of non-CH3SCH3 alkyl sulfides. Comparison with previous results for the reaction of Cl with dimethyl sulfide is made and simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

In situ Van der Pauw measurements of the Ni/YSZ anode during exposure to syngas with phosphine contaminant

NASA Astrophysics Data System (ADS)

Demircan, Oktay; Xu, Chunchuan; Zondlo, John; Finklea, Harry O.

Solid oxide fuel cells (SOFCs) represent an option to provide a bridging technology for energy conversion (coal syngas) as well as a long-term technology (hydrogen from biomass). Whether the fuel is coal syngas or hydrogen from biomass, the effect of impurities on the performance of the anode is a vital question. The anode resistivity during SOFC operation with phosphine-contaminated syngas was studied using the in situ Van der Pauw method. Commercial anode-supported solid oxide fuel cells (Ni/YSZ composite anodes, YSZ electrolytes) were exposed to a synthetic coal syngas mixture (H 2, H 2O, CO, and CO 2) at a constant current and their performance evaluated periodically with electrochemical methods (cyclic voltammetry, impedance spectroscopy, and polarization curves). In one test, after 170 h of phosphine exposure, a significant degradation of cell performance (loss of cell voltage, increase of series resistance and increase of polarization resistance) was evident. The rate of voltage loss was 1.4 mV h -1. The resistivity measurements on Ni/YSZ anode by the in situ Van der Pauw method showed that there were no significant changes in anode resistivity both under clean syngas and syngas with 10 ppm PH 3. XRD analysis suggested that Ni 5P 2 and P 2O 5 are two compounds accumulated on the anode. XPS studies provided support for the presence of two phosphorus phases with different oxidation states on the external anode surface. Phosphorus, in a positive oxidation state, was observed in the anode active layer. Based on these observations, the effect of 10 ppm phosphine impurity (or its reaction products with coal syngas) is assigned to the loss of performance of the Ni/YSZ active layer next to the electrolyte, and not to any changes in the thick Ni/YSZ support layer.

Redox reactions of [FeFe]-hydrogenase models containing an internal amine and a pendant phosphine.

PubMed

Zheng, Dehua; Wang, Mei; Chen, Lin; Wang, Ning; Sun, Licheng

2014-02-03

A diiron dithiolate complex with a pendant phosphine coordinated to one of the iron centers, [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe2(CO)5}] (1), was prepared and structurally characterized. The pendant phosphine is dissociated together with a CO ligand in the presence of excess PMe3, to afford [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe(CO)2(PMe3)}2] (2). Redox reactions of 2 and related complexes were studied in detail by in situ IR spectroscopy. A series of new Fe(II)Fe(I) ([3](+) and [6](+)), Fe(II)Fe(II) ([4](2+)), and Fe(I)Fe(I) (5) complexes relevant to Hox, Hox(CO), and Hred states of the [FeFe]-hydrogenase active site were detected. Among these complexes, the molecular structures of the diferrous complex [4](2+) with the internal amine and the pendant phosphine co-coordinated to the same iron center and the triphosphine diiron complex 5 were determined by X-ray crystallography. To make a comparison, the redox reactions of an analogous complex, [(μ-SCH2)2N(CH2C6H5){Fe(CO)2(PMe3)}2] (7), were also investigated by in situ IR spectroscopy in the absence or presence of extrinsic PPh3, which has no influence on the oxidation reaction of 7. The pendant phosphine in the second coordination sphere makes the redox reaction of 2 different from that of its analogue 7.

Method of removing hydrogen sulfide from gases utilizing a zinc oxide sorbent and regenerating the sorbent

DOEpatents

Jalan, Vinod M.; Frost, David G.

1984-01-01

A spent solid sorbent resulting from the removal of hydrogen sulfide from a fuel gas flow is regenerated with a steam-air mixture. The mixture of steam and air may also include additional nitrogen or carbon dioxide. The gas mixture contacts the spent sorbent containing metal sulfide at a temperature above 500.degree. C. to regenerate the sulfide to metal oxide or carbonate. Various metal species including the period four transition metals and the lanthanides are suitable sorbents that may be regenerated by this method. In addition, the introduction of carbon dioxide gas permits carbonates such as those of strontium, barium and calcium to be regenerated. The steam permits regeneration of spent sorbent without formation of metal sulfate. Moreover, the regeneration will proceed with low oxygen concentrations and will occur without the increase in temperature to minimize the risk of sintering and densification of the sorbent.

Henry's law constant for phosphine in seawater: determination and assessment of influencing factors

NASA Astrophysics Data System (ADS)

Fu, Mei; Yu, Zhiming; Lu, Guangyuan; Song, Xiuxian

2013-07-01

The Henry's Law constant ( k) for phosphine in seawater was determined by multiple phase equilibration combined with headspace gas chromatography. The effects of pH, temperature, and salinity on k were studied. The k value for phosphine in natural seawater was 6.415 at room temperature (approximately 23°C). This value increases with increases in temperature and salinity, but no obvious change was observed at different pH levels. At the same temperature, there was no significant difference between the k for phosphine in natural seawater and that in artificial seawater. This implies that temperature and salinity are major determining factors for k in marine environment. Double linear regression with Henry's Law constants for phosphine as a function of temperature and salinity confirmed our observations. These results provide a basis for the measurement of trace phosphine concentrations in seawater, and will be helpful for future research on the status of phosphine in the oceanic biogeochemical cycle of phosphorus.

Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

PubMed

Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

2012-06-27

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

The Role of Sulfide Oxidation Impairment in the Pathogenesis of Primary CoQ Deficiency.

PubMed

Quinzii, Catarina M; Luna-Sanchez, Marta; Ziosi, Marcello; Hidalgo-Gutierrez, Agustin; Kleiner, Giulio; Lopez, Luis C

2017-01-01

Coenzyme Q (CoQ) is a lipid present in all cell membranes. One of the multiple metabolic functions of CoQ is to transport electrons in the reaction catalyzed by sulfide:quinone oxidoreductase (SQOR), the first enzyme of the oxidation pathway of sulfides (hydrogen sulfide, H 2 S). Early evidence of a defect in the metabolism of H 2 S in primary CoQ deficiency came from yeast studies in Schizosaccharomyces pombe strains defective for dps1 and ppt1 (homologs of PDSS1 and COQ2 , respectively), which have H 2 S accumulation. Our recent studies in human skin fibroblasts and in murine models of primary CoQ deficiency show that, also in mammals, decreased CoQ levels cause impairment of H 2 S oxidation. Patient fibroblasts carrying different mutations in genes encoding proteins involved in CoQ biosynthesis show reduced SQOR activity and protein levels proportional to the levels of CoQ. In Pdss2 kd / kd mice, kidney, the only organ clinically affected, shows reduced SQOR levels and downstream enzymes, accumulation of H 2 S, and glutathione depletion. Pdss2 kd / kd mice have also low levels of thiosulfate in plasma and urine, and increased C4-C6 acylcarnitines in blood, due to inhibition of short-chain acyl-CoA dehydrogenase. Also in Coq9 R 239 X mice, the symptomatic organ, cerebrum, shows accumulation of H 2 S, reduced SQOR, increase in thiosulfate sulfurtransferase and sulfite oxidase, and reduction in the levels of glutathione and glutathione enzymes, leading to alteration of the biosynthetic pathways of glutamate, serotonin, and catecholamines. Coq9 R 239 X mice have also reduced blood pressure, possible consequence of H 2 S-induced vasorelaxation. Since liver is not clinically affected in Pdss2 and Coq9 mutant mice, the effects of the impairment of H 2 S oxidation in this organ were not investigated, despite its critical role in metabolism. In conclusion, in vitro and in vivo studies of CoQ deficient models provide evidence of tissue-specific H 2 S oxidation impairment

The Role of Sulfide Oxidation Impairment in the Pathogenesis of Primary CoQ Deficiency

PubMed Central

Quinzii, Catarina M.; Luna-Sanchez, Marta; Ziosi, Marcello; Hidalgo-Gutierrez, Agustin; Kleiner, Giulio; Lopez, Luis C.

2017-01-01

Coenzyme Q (CoQ) is a lipid present in all cell membranes. One of the multiple metabolic functions of CoQ is to transport electrons in the reaction catalyzed by sulfide:quinone oxidoreductase (SQOR), the first enzyme of the oxidation pathway of sulfides (hydrogen sulfide, H2S). Early evidence of a defect in the metabolism of H2S in primary CoQ deficiency came from yeast studies in Schizosaccharomyces pombe strains defective for dps1 and ppt1 (homologs of PDSS1 and COQ2, respectively), which have H2S accumulation. Our recent studies in human skin fibroblasts and in murine models of primary CoQ deficiency show that, also in mammals, decreased CoQ levels cause impairment of H2S oxidation. Patient fibroblasts carrying different mutations in genes encoding proteins involved in CoQ biosynthesis show reduced SQOR activity and protein levels proportional to the levels of CoQ. In Pdss2kd/kd mice, kidney, the only organ clinically affected, shows reduced SQOR levels and downstream enzymes, accumulation of H2S, and glutathione depletion. Pdss2kd/kd mice have also low levels of thiosulfate in plasma and urine, and increased C4–C6 acylcarnitines in blood, due to inhibition of short-chain acyl-CoA dehydrogenase. Also in Coq9R239X mice, the symptomatic organ, cerebrum, shows accumulation of H2S, reduced SQOR, increase in thiosulfate sulfurtransferase and sulfite oxidase, and reduction in the levels of glutathione and glutathione enzymes, leading to alteration of the biosynthetic pathways of glutamate, serotonin, and catecholamines. Coq9R239X mice have also reduced blood pressure, possible consequence of H2S-induced vasorelaxation. Since liver is not clinically affected in Pdss2 and Coq9 mutant mice, the effects of the impairment of H2S oxidation in this organ were not investigated, despite its critical role in metabolism. In conclusion, in vitro and in vivo studies of CoQ deficient models provide evidence of tissue-specific H2S oxidation impairment, an additional pathomechanism

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

USGS Publications Warehouse

Zhu, W.; Young, L.Y.; Yee, N.; Serfes, M.; Rhine, E.D.; Reinfelder, J.R.

2008-01-01

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As-1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O2), hypoxic (2% O2, 98% N2), and anoxic (5% H2, 95% N2) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (-1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 1: Copper-Catalyzed Oxidation.

PubMed

Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

2016-05-25

Sulfidic off-odors as a result of hydrogen sulfide (H2S) and low-molecular-weight thiols are commonly encountered in wine production. These odors are usually removed by the process of Cu(II) fining, a process that remains poorly understood. The present study aims to elucidate the underlying mechanisms by which Cu(II) interacts with H2S and thiol compounds (RSH) under wine-like conditions. Copper complex formation was monitored along with H2S, thiol, oxygen, and acetaldehyde concentrations after the addition of Cu(II) (50 or 100 μM) to air-saturated model wine solutions containing H2S, cysteine, 6-sulfanylhexan-1-ol, or 3-sulfanylhexan-1-ol (300 μM each). The presence of H2S and thiols in excess to Cu(II) led to the rapid formation of ∼1.4:1 H2S/Cu and ∼2:1 thiol/Cu complexes, resulting in the oxidation of H2S and thiols and reduction of Cu(II) to Cu(I), which reacted with oxygen. H2S was observed to initially oxidize rather than form insoluble copper sulfide. The proposed reaction mechanisms provide insight into the extent to which H2S can be selectively removed in the presence of thiols in wine.

Effect of inoculum and sulfide type on simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry and microbial mechanism.

PubMed

Wang, Lan; Wei, Benping; Chen, Ziai; Deng, Liangwei; Song, Li; Wang, Shuang; Zheng, Dan; Liu, Yi; Pu, Xiaodong; Zhang, Yunhong

2015-12-01

Four reactors were initiated to study the effect of inoculum and sulfide type on the simultaneous hydrogen sulfide removal from biogas and nitrogen removal from swine slurry (Ssu-Nir) process. Anaerobic sludge, aerobic sludge, and water were used as inocula, and Na2S and biogas were used as a sulfide substrate, respectively. Additionally, 454 pyrosequencing of the 16S rRNA gene was used to explore the bacterial diversity. The results showed that sulfur-oxidizing bacteria (Thiobacillus, 42.2-84.4 %) were dominant in Ssu-Nir process and led to the excellent performance. Aerobic sludge was more suitable for inoculation of the Ssu-Nir process because it is better for rapidly enriching dominant sulfur-oxidizing bacteria (Thiobacillus, 54.4 %), denitrifying sulfur-oxidizing bacteria (40.0 %) and denitrifiers (23.9 %). Lower S(2-) removal efficiency (72.6 %) and NO3 (-) removal efficiency (<90 %) of the Ssu-Nir process were obtained using biogas as a sulfide substrate than when Na2S was used. For the Ssu-Nir process with biogas as the sulfide substrate, limiting H2S absorption caused a high relative abundance of sulfur-oxidizing bacteria, Thiobacillus (84.8 %) and Thiobacillus sayanicus (39.6 %), which in turn led to low relative abundance of denitrifiers (1.6 %) and denitrifying sulfur-oxidizing bacteria (24.4 %), low NO3 (-) removal efficiency, and eventually poor performance.

Metal Sulfides as Sensing Materials for Chemoresistive Gas Sensors

PubMed Central

Gaiardo, Andrea; Fabbri, Barbara; Guidi, Vincenzo; Bellutti, Pierluigi; Giberti, Alessio; Gherardi, Sandro; Vanzetti, Lia; Malagù, Cesare; Zonta, Giulia

2016-01-01

This work aims at a broad overview of the results obtained with metal-sulfide materials in the field of chemoresistive gas sensing. Indeed, despite the well-known electrical, optical, structural and morphological features previously described in the literature, metal sulfides present lack of investigation for gas sensing applications, a field in which the metal oxides still maintain a leading role owing to their high sensitivity, low cost, small dimensions and simple integration, in spite of the wide assortment of sensing materials. However, despite their great advantages, metal oxides have shown significant drawbacks, which have led to the search for new materials for gas sensing devices. In this work, Cadmium Sulfide and Tin (IV) Sulfide were investigated as functional materials for thick-film chemoresistive gas-sensors fabrication and they were tested both in thermo- and in photo-activation modes. Furthermore, electrical characterization was carried out in order to verify their gas sensing properties and material stability, by comparing the results obtained with metal sulfides to those obtained by using their metal-oxides counterparts. The results highlighted the possibility to use metal sulfides as a novel class of sensing materials, owing to their selectivity to specific compounds, stability, and the possibility to operate at room temperature. PMID:26927120

The rate of sulfide oxidation by δMnO 2 in seawater

NASA Astrophysics Data System (ADS)

Yao, Wensheng; Millero, Frank J.

1993-07-01

The rate of oxidation of hydrogen sulfide by manganese dioxide in seawater was determined as a function of pH (2.0-9.0), temperature (5-45°C), and ionic strength (0-4 M). The overall rate constant, k, in seawater at pH = 8.17 was found to be first order with respect to both sulfide and manganese dioxide: - d[H 2S] T/dt = k[H 2S] τ[MnO 2] . The rate constant, k, for seawater (S = 35.8, pH = 8.17) at 25°C was found to be 436 M -1 min -1, or 0.0244 m -2 1 min -1 when [MnO 2] is expressed in surface area (m 2/L). The energies of activation were found to be 14 ± 1 KJ mol -1 and 10 ± 1 KJ mol -1, respectively, for pH = 8.2 and pH = 5.0 in seawater (S = 35). The rate increased from pH 2.0 to a maximum at a pH of about 5.0 and decreased at higher pH. This pH dependence was attributed to formation of a surface complex between >MnO - and H 2S. As the concentration of HS - increases above pH = 5 the rate of the reaction decreases. The rate of sulfide oxidation by MnO 2 is not strongly dependent on ionic strength. The rates in 0.57 M NaCl were found to be slightly higher than the rates in seawater. Measurements made in solutions of the major sea salts indicated that Ca 2+ and Mg 2+ caused the rates to decrease, apparently by absorbing on the surface of manganese dioxide. Measurements made in artificial seawater (Na +, Mg 2+, Ca 2+, Cl -, and SO 2-4) were found to be in good agreement with the measurements in actual seawater. Phosphate was found to inhibit the reaction significantly.

Enantioselective copper catalysed intramolecular C-H insertion reactions of α-diazo-β-keto sulfones, α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones; the influence of the carbene substituent.

PubMed

Shiely, Amy E; Slattery, Catherine N; Ford, Alan; Eccles, Kevin S; Lawrence, Simon E; Maguire, Anita R

2017-03-22

Enantioselectivities in C-H insertion reactions, employing the copper-bis(oxazoline)-NaBARF catalyst system, leading to cyclopentanones are highest with sulfonyl substituents on the carbene carbon, and furthermore, the impact is enhanced by increased steric demand on the sulfonyl substituent (up to 91%ee). Enantioselective intramolecular C-H insertion reactions of α-diazo-β-keto phosphine oxides and 2-diazo-1,3-diketones are reported for the first time.

Two New Sandwich-Type Polyoxomolybdates Functionalized with Diphosphonates: Efficient and Selective Oxidation of Sulfides to Sulfones

PubMed Central

Sun, Xiaopeng; Hu, Feng; Wan, Rong; Singh, Vikram; Ma, Pengtao; Wang, Jingping

2017-01-01

Two sandwich-type polyoxomolybdates Na8[MO2{Mo2O5(O3PCH3C(O)PO3)}2] (M = Ni2+ (1); Co2+ (2)) were synthesized by one-pot reaction of Na2HPMo12O40·14H2O, 1-hydroxy ethidene diphosphonic acid (HEDP=HOC(CH3)(PO3H2)2), and (1) NiCl2/CoCl2 (2). Compounds 1 and 2 were characterized by single crystal X-ray analysis, X-ray powder diffraction (XRPD), IR spectroscopy, 31P NMR spectra, UV-vis spectroscopy, and thermogravimetric analyses (TGA). Structural analysis reveals that 1 and 2 exhibit similar centrosymmetric structure, which consists of one transition metal (TM) ion sandwiched by two same subunits {Mo2O5(O3PCH3C(O)PO3)}. The clusters 1 and 2 show efficient catalytic activities for oxidation of thioanisole. Moreover, they are catalytically selective for oxidizing thioanisole. Both resuable polyoxomolybdates 1 and 2 catalysts show good thermo- and hydrolytic stability. It is noted that compound 1 shows outstanding catalytic activity for oxidation of various sulfides to corresponding sulfones with 93–100% selectivity at 97–100% conversion in one hour under mild conditions, which is potentially valuable to the removal of organic sulfides. PMID:29027947

Effects of Chlorine Promoted Oxidation on Arsenic Release from Sulfide Minerals

NASA Astrophysics Data System (ADS)

West, N.; Schreiber, M.; Gotkowitz, M.

2007-12-01

High arsenic concentrations (>100 ppb) have been measured in wells completed in the Ordovician St. Peter sandstone aquifer of eastern Wisconsin. The primary source of arsenic is As-bearing sulfide minerals within the aquifer. Periodic disinfection of wells by chlorination may facilitate arsenic release to groundwater by increasing the rate of sulfide mineral oxidation. During typical well disinfection procedures, aquifer solids exposed along uncased portions of wells remain in direct contact with chlorine disinfection solutions for up to twenty-four hours. Due to the redox sensitivity of arsenic mobility in groundwater, it is important to evaluate the effect of repeatedly adding oxidizers to an arsenic impacted aquifer system. This study focuses on abiotic processes that mobilize arsenic from the solid phase during controlled exposure to chlorinated solutions. Two St. Peter samples with As concentrations of 21 and 674 ppm were selected for the experiments. Before reaction, the aquifer mineralogy is characterized using scanning electron microscopy (SEM) and electron microprobe analysis (EMPA). The samples are then reacted with solutions of 60 mg/L free chlorine, 1200 mg/L free chlorine, or nanopure water (control) at pH 7.0 and pH 8.5. These parameters represent typical solution chemistries present within the wells after disinfection. Solutions are sampled periodically during the experiments and analyzed for As, Fe, other trace metals such as Co, Mo, Cr, and Ni, and sulfate. Analysis of the post-reaction solids using SEM, EMPA, laser ablation ICP-MS and Raman techniques are used to document the changes in mineralogy due to chlorination and to document which solid phases contain As.

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives.

PubMed

Viveros-Ceballos, José Luis; Ordóñez, Mario; Sayago, Francisco J; Cativiela, Carlos

2016-08-29

α-Amino-C-phosphinic acids and derivatives are an important group of compounds of synthetic and medicinal interest and particular attention has been dedicated to their stereoselective synthesis in recent years. Among these, phosphinic pseudopeptides have acquired pharmacological importance in influencing physiologic and pathologic processes, primarily acting as inhibitors for proteolytic enzymes where molecular stereochemistry has proven to be critical. This review summarizes the latest developments in the asymmetric synthesis of acyclic and phosphacyclic α-amino-C-phosphinic acids and derivatives, following in the first case an order according to the strategy used, whereas for cyclic compounds the nitrogen embedding in the heterocyclic core is considered. In addition selected examples of pharmacological implications of title compounds are also disclosed.

A preliminary cost analysis of the biotreatment of refinery spent-sulfidic caustic.

PubMed

Sublette, K L

1997-01-01

Caustics are used in petroleum refining to remove hydrogen sulfide from various hydrocarbon streams. Spent-sulfidic caustics from three refineries have been successfully biotreated on the bench and pilot scale, resulting in neutralization and removal of active Sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans strain F. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic. A commercial-scale treatment system has been designed that features a bioreactor with a suspended culture of flocculated T. denitrificans, a settler and acid and nutrient storage and delivery systems. A cost analysis has been performed for nine cases representing a range of spent caustic sulfide and hydroxide concentrations at a base treatment rate of 10 gpm. This analysis shows that refinery spent-sulfidic caustic can be biotreated for 4-8.3 cent/gal.

Coupling between anammox and autotrophic denitrification for simultaneous removal of ammonium and sulfide by enriched marine sediments.

PubMed

Rios-Del Toro, E Emilia; Cervantes, Francisco J

2016-06-01

In the present study, the capacity of enrichments derived from marine sediments collected from different sites of the Mexican littoral to perform anaerobic ammonium oxidation (anammox) coupled to sulfide-dependent denitrification for simultaneous removal of ammonium and sulfide linked to nitrite reduction was evaluated. Sulfide-dependent denitrification out-competed anammox during the simultaneous oxidation of sulfide and ammonium. Significant accumulation of elemental sulfur (ca. 14-30 % of added sulfide) occurred during the coupling between the two respiratory processes, while ammonium was partly oxidized (31-47 %) due to nitrite limitation imposed in sediment incubations. Nevertheless, mass balances revealed up to 38 % more oxidation of the electron donors available (ammonium and sulfide) than that expected from stoichiometry. Recycling of nitrite, from nitrate produced through anammox, is proposed to contribute to extra oxidation of sulfide, while additional ammonium oxidation is suggested by sulfate-reducing anammox (SR-anammox). The complex interaction between nitrogenous and sulfurous compounds occurring through the concomitant presence of autotrophic denitrification, conventional anammox and SR-anammox may significantly drive the nitrogen and sulfur fluxes in marine environments.

Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodrigues, A.; Duchesne, J., E-mail: josee.duchesne@ggl.ulaval.ca; Fournier, B.

Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivieres area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damagedmore » concrete include 'rust' mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH{sub 2}O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.« less

Phosphine and methylphosphine production by simulated lightning—a study for the volatile phosphorus cycle and cloud formation in the earth atmosphere

NASA Astrophysics Data System (ADS)

Glindemann, Dietmar; Edwards, Marc; Schrems, Otto

Phosphine (PH 3), was recently found worldwide even in the remote atmosphere (Naturwissenschaften83(1996a)131; Atmos. Environ. 37(2003)24 29). It is of interest to find natural mechanisms which could produce phosphine gas and drive a volatile link of the atmospheric phosphorus cycle and the formation of phosphoric acid as possible condensation nuclei for clouds. Here, we report on simulated lightning exposing sodium phosphate in a reducing medium (methane model atmosphere or organic matter) for 5 s to a spark induced by microwave. The gas product analyzed by gas chromatography contained phosphine (yield up to 0.6 g kg -1 phosphate P) and methylphosphine (CH 3)PH 2 (yield up to 0.02 g kg -1 phosphate P). We suggest a plasma-chemical formation mechanism where organic compounds or methane or secondary hydrogen thereof reduce phosphate to phosphine of which a small fraction can subsequently react with methyl radicals to form methylphosphine. A small yield of 6 mg phosphine per kg phosphate P was even obtained in methane free medium, by simple plasmatic recombination of inorganic phosphorus. We believe that methane and hydrogen are useful model substances of pyrolytic gases with high reducing power which may form if lightning strikes biomass, soil and aerosol. These results suggest evidence that phosphine and methylphosphine (detectable in the field by intense garlic odor) are produced when atmospheric lightning strikes the ground or aerosol which is containing oxidized forms of phosphorus and chemical reductants. Additional reviewed data show that laboratory lightning was able to reduce a much more significant portion of phosphate to phosphite (up to 25% yield), methylphosphonic acid (up to 8.5% yield) and traces of hypophosphite in a matter of seconds.

Uranium accumulation in modern and ancient Fe-oxide sediments: Examples from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and Yubileynoe massive sulfide deposit (South Urals, Russia)

NASA Astrophysics Data System (ADS)

Ayupova, N. R.; Melekestseva, I. Yu.; Maslennikov, V. V.; Tseluyko, A. S.; Blinov, I. A.; Beltenev, V. E.

2018-05-01

Fe-oxyhydroxide sediments (gossans) from the Ashadze-2 hydrothermal sulfide field (Mid-Atlantic Ridge) and hematite-carbonate-quartz rocks (gossanites) from the Yubileynoe Cu-Zn VHMS deposit (South Urals) are characterized by anomalously high U contents (up to 352 ppm and 73 ppm, respectively). In gossans from the Ashadze-2 hydrothermal sulfide field, rare isometric anhedral uraninite grains (up to 2 μm) with outer P- and Ca-rich rims, and numerous smaller (<1 μm) grains, occur in Fe-oxyhydroxides and sepiolite, associated with pyrite, isocubanite, chalcopyrite, galena, atacamite and halite. In gossanites from the Yubileynoe deposit, numerous uraninite particles (<3 μm) are associated with apatite, V-rich Mg-chlorite, micro-nodules of pyrite, Se-bearing galena, hessite and acanthite in a hematite-carbonate-quartz matrix. Small (1-3 μm) round grains of uraninite, which locally coalesce to large grains up to 10 μm in size, are associated with authigenic chalcopyrite. The similar diagenetic processes of U accumulation in modern and ancient Fe-oxyhydroxide sediments were the result of U fixation from seawater during the oxidation of sulfide minerals. Uraninite in gossanites was mainly deposited from diagenetic pore fluids, which circulated in the sulfide-hyaloclast-carbonate sediments.

Synthesis and Reactivity of a New (Methylene)Phosphine.

DTIC Science & Technology

1981-01-27

the synthesis of a variety of alkyl(silylamino)- 8phosphines Similarly, if two equivalents of the silylmethyl Grignard reagent were used (eq 3), the...n-BuLi (hexane solution), and t-BuLi (pentane solution). The Grignard reagent Me 3SiCH2 MgCl was prepared in Et 0 2 2 solution from Me3SiCH 2C and Mg...trimethylsilyl)amino] (chloro)- (trimethylsilylmethyl)phosphine (1) was prepared by the "one-pot" Grignard method (eqs 1 and 2) which we have used previously for

Removal of antimony (Sb(V)) from Sb mine drainage: biological sulfate reduction and sulfide oxidation-precipitation.

PubMed

Wang, Huawei; Chen, Fulong; Mu, Shuyong; Zhang, Daoyong; Pan, Xiangliang; Lee, Duu-Jong; Chang, Jo-Shu

2013-10-01

Antimony (Sb(V)) in Sb mine drainage has adverse effects on the receiving water environments. This study for the first time demonstrated the feasibility of using sulfate-reducing bacteria (SRB) to convert sulfate ions in SMD into sulfides that reduce Sb(V) to Sb(III) and to form complex with Sb(III) as precipitate. The principal compound in the precipitate was stibnite (Sb2S3) at pH 7 and pH 9. The Sb(V) removal mechanism is sulfate-reduction and sulfide oxidization-precipitation, different from the conventional SRB-precipitation processes for heavy metals. The Sb(V)/sulfate ratio is noted an essential parameter affecting the Sb removal efficiency from SMD. Copyright © 2013 Elsevier Ltd. All rights reserved.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances.

PubMed

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-25

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co 9 S 8 aerogel with a high surface area (274.2 m 2 g -1 ) and large pore volume (0.87 cm 3 g -1 ) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co 9 S 8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g -1 at 1 A g -1 ), good rate capability (74.3% capacitance retention from 1 to 20 A g -1 ) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

NASA Astrophysics Data System (ADS)

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-01

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

High-temperature experimental analogs of primitive meteoritic metal-sulfide-oxide assemblages

NASA Astrophysics Data System (ADS)

Schrader, Devin L.; Lauretta, Dante S.

2010-03-01

We studied the oxidation-sulfidation behavior of an Fe-based alloy containing 4.75 wt.% Ni, 0.99 wt.% Co, 0.89 wt.% Cr, and 0.66 wt.% P in H 2-H 2O-CO-CO 2-H 2S gas mixtures at 1000 °C. The samples were cooled at rates of ˜3000 °C/h, comparable to estimates of the conditions after a chondrule-formation event in the early Solar System. Gas compositions were monitored in real time by a quadrupole mass spectrometer residual gas analyzer. Linear rate constants associated with gas-phase adsorption were determined. Reaction products were analyzed by optical microscopy, wavelength-dispersive-spectroscopy X-ray elemental mapping, and electron probe microanalysis. Based on analysis of the Fe-Ni-S ternary phase diagram and the reaction products, the primary corrosion product is a liquid of composition 66.6 wt.% Fe, 3.5 wt.% Ni, 29.9 wt.% S, and minor amounts of P, Cr, and Co. Chromite (FeCr 2O 4) inclusions formed by oxidation and are present in the metal foil and at the outer boundary between the sulfide and experimental atmosphere. During cooling the liquid initially crystallizes into taenite (average composition ˜15 wt.% Ni), monosulfide solid solution [mss, (Fe,Ni,Co,Cr) 1-xS], and Fe-phosphates. Upon further cooling, kamacite exsolves from this metal, enriching the taenite in Ni. The remnant metal core is enriched in P and Co and depleted in Cr at the reaction interface, relative to the starting composition. The unreacted metal core composition remains unchanged, suggesting the reactions did not reach equilibrium. We present a detailed model of reaction mechanisms based on the observed kinetics and sample morphologies, and discuss meteoritic analogs in the CR chondrite MacAlpine Hills 87320.

Electrochemical sulfide removal and caustic recovery from spent caustic streams.

PubMed

Vaiopoulou, Eleni; Provijn, Thomas; Prévoteau, Antonin; Pikaar, Ilje; Rabaey, Korneel

2016-04-01

Spent caustic streams (SCS) are produced during alkaline scrubbing of sulfide containing sour gases. Conventional methods mainly involve considerable chemical dosing or energy expenditures entailing high cost but limited benefits. Here we propose an electrochemical treatment approach involving anodic sulfide oxidation preferentially to sulfur coupled to cathodic caustic recovery using a two-compartment electrochemical system. Batch experiments showed sulfide removal efficiencies of 84 ± 4% with concomitant 57 ± 4% efficient caustic production in the catholyte at a final concentration of 6.4 ± 0.1 wt% NaOH (1.6 M) at an applied current density of 100 A m(-2). Subsequent long-term continuous experiments showed that stable cell voltages (i.e. 2.7 ± 0.1 V) as well as constant sulfide removal efficiencies of 67 ± 5% at a loading rate of 47 g(S) L(-1) h(-1) were achieved over a period of 77 days. Caustic was produced at industrially relevant strengths for scrubbing (i.e. 5.1 ± 0.9 wt% NaOH) at current efficiencies of 96 ± 2%. Current density between 0 and 200 A m(-2) and sulfide loading rates of 50-200 g(S) L(-1) d(-1) were tested. The higher the current density the more oxidized the sulfur species produced and the higher the sulfide oxidation. On the contrary, high loading rate resulted in a reduction of sulfide oxidation efficiency. The results obtained in this study together with engineering calculations show that the proposed process could represent a cost-effective approach for sodium and sulfur recovery from SCS. Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of insoluble heavy metal sulfides from water.

PubMed

Banfalvi, Gaspar

2006-05-01

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.

Reconciling "Whiffs" of O2 with the Archean MIF S Record: Insights from Sulfide Oxidation Experiments

NASA Astrophysics Data System (ADS)

Johnson, A.; Reinhard, C. T.; Romaniello, S. J.; Greaney, A. T.; Garcia-Robledo, E.; Revsbech, N. P.; Canfield, D. E.; Lyons, T. W.; Anbar, A. D.

2016-12-01

The Archean-Proterozoic transition is marked by the first appreciable accumulation of O2 in Earth's oceans and atmosphere at 2.4 billion years ago (Ga). However, this Great Oxidation Event (GOE) is not the first evidence for O2 in Earth's surface environment. Paleoredox proxies preserved in ancient marine shales (Mo, Cr, Re, U) suggest transient episodes of oxidative weathering before the GOE, perhaps as early as 3.0 Ga. One marine shale in particular, the 2.5 Ga Mount McRae Shale of Western Australia, contains a euxinic interval with Mo enrichments up to 50 ppm. This enrichment is classically interpreted as the result of oxidative weathering of sulfides on the continental surface. However, prior weathering models based on experiments suggested that sulfides require large amounts of O2 [>10-4 present atmospheric level (PAL) pO2] to produce this weathering signature, in conflict with estimates of Archean pO2 from non-mass-dependent (NMD) sulfur isotope anomalies (<10-5 PAL pO2). To reconcile these datasets, we conducted aqueous oxidation experiments of pyrite and molybdenite from 3 - 700 nM O2 (equivalent at equilibrium to 10-5 - 10-3 PAL) to measure oxidation kinetics as a function of the concentration of dissolved O2. We measured rates by injecting oxygenated water at a steady flow rate and monitoring dissolved O2 concentrations with LUMOS sensors. Our data extend the O2 range explored in pyrite oxidation experiments by three orders of magnitude and provide the first rates for molybdenite oxidation at O2 concentrations potentially analogous to those characteristic of the Archean atmosphere. Our results show that pyrite and molybdenite oxidize significantly more rapidly at lower O2 levels than previously thought. As a result, our revised weathering model demonstrates that the Mo enrichments observed in late Archean marine shales are potentially attainable at extremely low atmospheric pO2 values (e.g., <10-5 PAL), reconciling large sedimentary Mo enrichments with co

Effect of pH on phosphine production and the fate of phosphorus during anaerobic process with granular sludge.

PubMed

Ding, Lili; Wang, Xiaorong; Zhu, Yixin; Edwards, Marc; Glindemann, Dietmar; Ren, Hongqiang

2005-03-01

The effect of pH on phosphine formation during anaerobic cultivation of granular sludge was investigated. The sludge was taken from full-scale anaerobic reactors treating brewery wastewater. Acetate and phosphate were used as the carbon source and phosphorus source respectively. After 10 days cultivation in the dark, results showed that acidic conditions were more favorable for free phosphine production. At pH 5, the optimum concentration 86.42 ng PH3 m-3 of free phosphine was obtained. The level at pH 7 was reduced to 18.53 ng PH3 m-3, about 1/5 of the maximum. The maximum concentration of matrix-bound phosphine of 3.30 ng PH3 kg-1 wet sludge was achieved at pH 6. More than 83% of the total phosphine was matrix-bound phosphine, which accounted for 0.003-0.009 per thousand of the phosphate removal, while free phosphine comprised 0.00002-0.001 per thousand of the phosphate removal. Most of the phosphorus removal from solution was turned into chemical precipitation or was adsorbed by sludge. The mechanism of the phosphate reduction-step in the formation of phosphine production is still unknown. The promotion of phosphine formation by low pH is compatible with an acidic bio-corrosion mechanism of metal particles in the sludge or of metal phosphides which form phosphine at low pH.

Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.

PubMed

Matthies, R; Krahé, L; Blowes, D W

2014-07-15

Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

Visible-light-enhanced interactions of hydrogen sulfide with composites of zinc (oxy)hydroxide with graphite oxide and graphene.

PubMed

Seredych, Mykola; Mabayoje, Oluwaniyi; Bandosz, Teresa J

2012-01-17

Composites of zinc(oxy)hydroxide-graphite oxide and of zinc(oxy)hydroxide-graphene were used as adsorbents of hydrogen sulfide under ambient conditions. The initial and exhausted samples were characterized by XRD, FTIR, potentiometric titration, EDX, thermal analysis, and nitrogen adsorption. An increase in the amount of H(2)S adsorbed/oxidized on their surfaces in comparison with that of pure Zn(OH)(2) is linked to the structure of the composite, the relative number of terminal hydroxyls, and the kind of graphene-based phase used. Although terminal groups are activated by a photochemical process, the graphite oxide component owing to the chemical bonds with the zinc(oxy)hydroxide phase and conductive properties helps in electron transfer, leading to more efficient oxygen activation via the formation of superoxide ions. Elemental sulfur, zinc sulfide, sulfite, and sulfate are formed on the surface. The formation of sulfur compounds on the surface of zinc(oxy)hydroxide during the course of the breakthrough experiments and thus Zn(OH)(2)-ZnS heterojunctions can also contribute to the increased surface activity of our materials. The results show the superiority of graphite oxide in the formation of composites owing to its active surface chemistry and the possibility of interface bond formation, leading to an increase in the number of electron-transfer reactions. © 2011 American Chemical Society

CoQ deficiency causes disruption of mitochondrial sulfide oxidation, a new pathomechanism associated with this syndrome.

PubMed

Luna-Sánchez, Marta; Hidalgo-Gutiérrez, Agustín; Hildebrandt, Tatjana M; Chaves-Serrano, Julio; Barriocanal-Casado, Eliana; Santos-Fandila, Ángela; Romero, Miguel; Sayed, Ramy Ka; Duarte, Juan; Prokisch, Holger; Schuelke, Markus; Distelmaier, Felix; Escames, Germaine; Acuña-Castroviejo, Darío; López, Luis C

2017-01-01

Coenzyme Q (CoQ) is a key component of the mitochondrial respiratory chain, but it also has several other functions in the cellular metabolism. One of them is to function as an electron carrier in the reaction catalyzed by sulfide:quinone oxidoreductase (SQR), which catalyzes the first reaction in the hydrogen sulfide oxidation pathway. Therefore, SQR may be affected by CoQ deficiency. Using human skin fibroblasts and two mouse models with primary CoQ deficiency, we demonstrate that severe CoQ deficiency causes a reduction in SQR levels and activity, which leads to an alteration of mitochondrial sulfide metabolism. In cerebrum of Coq9 R239X mice, the deficit in SQR induces an increase in thiosulfate sulfurtransferase and sulfite oxidase, as well as modifications in the levels of thiols. As a result, biosynthetic pathways of glutamate, serotonin, and catecholamines were altered in the cerebrum, and the blood pressure was reduced. Therefore, this study reveals the reduction in SQR activity as one of the pathomechanisms associated with CoQ deficiency syndrome. © 2016 The Authors. Published under the terms of the CC BY 4.0 license.

Early diagenetic partial oxidation of organic matter and sulfides in the Middle Pennsylvanian (Desmoinesian) Excello Shale Member of the Fort Scott Limestone and equivalents, northern Midcontinent region, USA

USGS Publications Warehouse

Hatch, J.R.; Leventhal, M.S.

1997-01-01

A process of early diagenetic partial oxidation of organic matter and sulfides has altered the chemical composition of the Middle Pennsylvanian Excello Shale Member of the Fort Scott Limestone and equivalents in the northern Midcontinent region. This process was identified by comparison of organic carbon contents, Rock-Eval hydrogen indices, organic carbon ??13C and element compositions of core and surface mine samples of the Excello Shale Member with analyses of three other underlying and overlying organic-matter-rich marine shales (offshore shale lithofacies) from southern Iowa, northern Missouri, eastern Kansas and northeastern Oklahoma. The end product of the partial oxidation process is shale with relatively low contents of hydrogen-poor, C13-enriched organic matter, lower contents of sulfur and sulfide-forming elements, and relatively unchanged contents of phosphorus and many trace elements (e.g. Cr, Ni, and V). However, because of lower organic carbon contents, element/organic carbon ratios are greatly increased. The partial oxidation process apparently took place during subaerial exposure of the overlying marine carbonate member (Blackjack Creek Member of the Fort Scott Limestone) following a marine regression when meteoric waters percolated down to the level of the Excello muds allowing oxidation of organic matter and sulfides. This hypothesis is supported by earlier workers, who have identified meteoric carbonate cements within, and soil horizons at the top of the Blackjack Creek Member. The period of oxidation is constrained in that organic matter and sulfides in the Little Osage Shale Member of the Fort Scott Limestone and equivalents (immediately overlying the Blackjack Creek Member) appear unaltered. Similar alteration of other shales in the Middle and Upper Pennsylvanian sections may be local to regional in extent and would depend on the extent and duration of the marine regression and be influenced by local variations in permeability and topography

Selective Sulfidation of Lead Smelter Slag with Sulfur

NASA Astrophysics Data System (ADS)

Han, Junwei; Liu, Wei; Wang, Dawei; Jiao, Fen; Qin, Wenqing

2016-02-01

The selective sulfidation of lead smelter slag with sulfur was studied. The effects of temperature, sulfur dosage, carbon, and Na salts additions were investigated based on thermodynamic calculation. The results indicated that more than 96 pct of zinc in the slag could be converted into sulfides. Increasing temperature, sulfur dosage, or Na salts dosage was conducive to the sulfidation of the zinc oxides in the slag. High temperature and excess Na salts would result in the more consumption of carbon and sulfur. Carbon addition not only promoted the selective sulfidation but reduced the sulfur dosage and eliminated the generation of SO2. Iron oxides had a buffering role on the sulfur efficient utilization. The transformation of sphalerite to wurtzite was feasible under reducing condition at high temperature, especially above 1273 K (1000 °C). The growth of ZnS particles largely depended upon the roasting temperature. They were significantly increased when the temperature was above 1273 K (1000 °C), which was attributed to the formation of a liquid phase.

Chiral phosphines in nucleophilic organocatalysis

PubMed Central

Xiao, Yumei; Sun, Zhanhu

2014-01-01

Summary This review discusses the tertiary phosphines possessing various chiral skeletons that have been used in asymmetric nucleophilic organocatalytic reactions, including annulations of allenes, alkynes, and Morita–Baylis–Hillman (MBH) acetates, carbonates, and ketenes with activated alkenes and imines, allylic substitutions of MBH acetates and carbonates, Michael additions, γ-umpolung additions, and acylations of alcohols. PMID:25246969

Action of phosphine on production of aflatoxins by various Aspergillus strains isolated from foodstuffs.

PubMed Central

Leitao, J; de Saint-Blanquat, G; Bailly, J R

1987-01-01

Phosphine is a food fumigant, used until now as an insecticide and rodenticide. The present work researches the action of phosphine treatment on growth and aflatoxin production of 23 Aspergillus strains. Production of aflatoxins B1, B2, G1, and G2 decreased in almost all cases by a ratio of 10 to 100. Phosphine treatment therefore seems favorable to prevent growth of various Aspergillus strains, in the context of keeping food safe. PMID:3426212

Characterization of 16S rRNA genes from oil field microbial communities indicates the presence of a variety of sulfate-reducing, fermentative, and sulfide-oxidizing bacteria.

PubMed

Voordouw, G; Armstrong, S M; Reimer, M F; Fouts, B; Telang, A J; Shen, Y; Gevertz, D

1996-05-01

Oil field bacteria were characterized by cloning and sequencing of PCR-amplified 16S rRNA genes. A variety of gram-negative, sulfate-reducing bacteria was detected (16 members of the family Desulfovibrionaceae and 8 members of the family Desulfobacteriaceae). In contrast, a much more limited number of anaerobic, fermentative, or acetogenic bacteria was found (one Clostridium sp., one Eubacterium sp., and one Synergistes sp.). Potential sulfide oxidizers and/or microaerophiles (Thiomicrospira, Arcobacter, Campylobacter, and Oceanospirillum spp.) were also detected. The first two were prominently amplified from uncultured production water DNA and represented 28 and 47% of all clones, respectively. Growth on media containing sulfide as the electron donor and nitrate as the electron acceptor and designed for the isolation of Thiomicrospira spp. gave only significant enrichment of the Campylobacter sp., which was shown to be present in different western Canadian oil fields. This newly discovered sulfide oxidizer may provide a vital link in the oil field sulfur cycle by reoxidizing sulfide formed by microbial sulfate or sulfur reduction.

Characterization of 16S rRNA genes from oil field microbial communities indicates the presence of a variety of sulfate-reducing, fermentative, and sulfide-oxidizing bacteria.

PubMed Central

Voordouw, G; Armstrong, S M; Reimer, M F; Fouts, B; Telang, A J; Shen, Y; Gevertz, D

1996-01-01

Oil field bacteria were characterized by cloning and sequencing of PCR-amplified 16S rRNA genes. A variety of gram-negative, sulfate-reducing bacteria was detected (16 members of the family Desulfovibrionaceae and 8 members of the family Desulfobacteriaceae). In contrast, a much more limited number of anaerobic, fermentative, or acetogenic bacteria was found (one Clostridium sp., one Eubacterium sp., and one Synergistes sp.). Potential sulfide oxidizers and/or microaerophiles (Thiomicrospira, Arcobacter, Campylobacter, and Oceanospirillum spp.) were also detected. The first two were prominently amplified from uncultured production water DNA and represented 28 and 47% of all clones, respectively. Growth on media containing sulfide as the electron donor and nitrate as the electron acceptor and designed for the isolation of Thiomicrospira spp. gave only significant enrichment of the Campylobacter sp., which was shown to be present in different western Canadian oil fields. This newly discovered sulfide oxidizer may provide a vital link in the oil field sulfur cycle by reoxidizing sulfide formed by microbial sulfate or sulfur reduction. PMID:8633860

Comparative effects of gamma irradiation and phosphine fumigation on the quality of white ginseng

NASA Astrophysics Data System (ADS)

Kwon, J.-H. J.-H.; Byun, M.-W. M.-W.; Kim, K.-S. K.-S.; Kang, I.-J. I.-J.

2000-03-01

The hygienic, physicochemical, and organoleptic qualities of white ginseng were monitored during 6 months under accelerated conditions (40°C, 90% r.h.) by observing its microbial populations, disinfestation, and some quality attributes following either gamma irradiation at 2.5-10 kGy or commercial phosphine (PH 3) fumigation. In a comparative study, both treatments were found to be effective for disinfecting the stored samples. Phosphine showed no appreciable decontaminating effects on microorganisms contaminated including coliforms, while 5 kGy irradiation was sufficient to control all microorganisms related to the quality of the packed samples. Irradiation at 5 kGy caused negligible changes in physicochemical attributes of the samples, such as ginsenosides, amino acids, fatty acids, and organoleptic properties, whereas phosphine fumigation was found detrimental to sensory flavor ( P<0.01). Quality deterioration occurred in the commercially-packed samples was in the following order: the control, 10 kGy-, phosphine-, and 2.5-5 kGy-treated samples. Accordingly, irradiation at <5 kGy was found to be an effective alternative to phosphine fumigation for white ginseng.

Kinetics of the Bicarbonate-Assisted Oxidation of Diethyl Sulfide by Hydrogen Peroxide and Sodium Peroxoborate

NASA Astrophysics Data System (ADS)

Dyatlenko, L. M.; Lobachev, V. L.; Bezbozhnaya, T. V.

2018-07-01

The kinetics of oxidation of diethyl sulfide (Et2S) is studied in aqueous solutions of hydrogen peroxide and sodium peroxoborate (Na2[B2(O2)2(OH)4]) in the presence of bicarbonate ions by means of gas-liquid distribution. The kinetics is investigated in a broad range of pH. Data show that the oxidation of Et2S by sodium peroxoborate in the range of pH 6-12 is mediated by such reactive species as hydrogen peroxide, hydrogen peroxide anions, and mono (B(O2H)(OH)3^{ - }) and diperoxoborate (B(O2H)2(OH)2^{ - }) anions. The rate of Et2S oxidation increases in the presence of bicarbonate, due to the additional reaction pathways mediated by monoperoxocarbonate species.

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

NASA Astrophysics Data System (ADS)

Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

2010-02-01

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II) (aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III) (s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.

Biological removal of air loaded with a hydrogen sulfide and ammonia mixture.

PubMed

Chen, Ying-xu; Yin, Jun; Fang, Shi

2004-01-01

The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH2S/(m3 x d) and 230 gNH3/(m3 x d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of ammonia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.

Nanoporous gold-based microbial biosensor for direct determination of sulfide.

PubMed

Liu, Zhuang; Ma, Hanyue; Sun, Huihui; Gao, Rui; Liu, Honglei; Wang, Xia; Xu, Ping; Xun, Luying

2017-12-15

Environmental pollution caused by sulfide compounds has become a major problem for public health. Hence, there is an urgent need to explore a sensitive, selective, and simple sulfide detection method for environmental monitoring and protection. Here, a novel microbial biosensor was developed using recombinant Escherichia coli BL21 (E. coli BL21) expressing sulfide:quinone oxidoreductase (SQR) for sulfide detection. As an important enzyme involved in the initial step of sulfide metabolism, SQR oxidizes sulfides to polysulfides and transfers electrons to the electron transport chain. Nanoporous gold (NPG) with its unique properties was selected for recombinant E. coli BL21 cells immobilization, and then glassy carbon electrode (GCE) was modified by the resulting E. coli/NPG biocomposites to construct an E. coli/NPG/GCE bioelectrode. Due to the catalytic oxidation properties of NPG for sulfide, the electrochemical reaction of the E. coli/NPG/GCE bioelectrode is attributed to the co-catalysis of SQR and NPG. For sulfide detection, the E. coli/NPG/GCE bioelectrode showed a good linear response ranging from 50μM to 5mM, with a high sensitivity of 18.35μAmM -1 cm -2 and a low detection limit of 2.55μM. The anti-interference ability of the E. coli/NPG/GCE bioelectrode is better than that of enzyme-based inhibitive biosensors. Further, the E. coli/NPG/GCE bioelectrode was successfully applied to the detection of sulfide in wastewater. These unique properties potentially make the E. coli/NPG/GCE bioelectrode an excellent choice for reliable sulfide detection. Copyright © 2017 Elsevier B.V. All rights reserved.

Retrievals of Jovian Tropospheric Phosphine from Cassini/CIRS

NASA Technical Reports Server (NTRS)

Irwin, P. G. J.; Parrish, P.; Fouchet, T.; Calcutt, S. B.; Taylor, F. W.; Simon-Miller, A. A.; Nixon, C. A.

2004-01-01

On December 30th 2000, the Cassini-Huygens spacecraft reached the perijove milestone on its continuing journey to the Saturnian system. During an extended six-month encounter, the Composite Infrared Spectrometer (CIRS) returned spectra of the Jovian atmosphere, rings and satellites from 10-1400 cm(exp -1) (1000-7 microns) at a programmable spectral resolution of 0.5 to 15 cm(exp -1). The improved spectral resolution of CIRS over previous IR instrument-missions to Jupiter, the extended spectral range, and higher signal-to-noise performance provide significant advantages over previous data sets. CIRS global observations of the mid-infrared spectrum of Jupiter at medium resolution (2.5 cm(exp -1)) have been analysed both with a radiance differencing scheme and an optimal estimation retrieval model to retrieve the spatial variation of phosphine and ammonia fractional scale height in the troposphere between 60 deg S and 60 deg N at a spatial resolution of 6 deg. The ammonia fractional scale height appears to be high over the Equatorial Zone (EZ) but low over the North Equatorial Belt (NEB) and South Equatorial Belt (SEB) indicating rapid uplift or strong vertical mixing in the EZ. The abundance of phosphine shows a similar strong latitudinal variation which generally matches that of the ammonia fractional scale height. However while the ammonia fractional scale height distribution is to a first order symmetric in latitude, the phosphine distribution shows a North/South asymmetry at mid latitudes with higher amounts detected at 40 deg N than 40 deg S. In addition the data show that while the ammonia fractional scale height at this spatial resolution appears to be low over the Great Red Spot (GRS), indicating reduced vertical mixing above the approx. 500 mb level, the abundance of phosphine at deeper levels may be enhanced at the northern edge of the GRS indicating upwelling.

Selection and Application of Sulfide Oxidizing Microorganisms Able to Withstand Thiols in Gas Biodesulfurization Systems.

PubMed

Roman, Pawel; Klok, Johannes B M; Sousa, João A B; Broman, Elias; Dopson, Mark; Van Zessen, Erik; Bijmans, Martijn F M; Sorokin, Dimitry Y; Janssen, Albert J H

2016-12-06

After the first commercial applications of a new biological process for the removal of hydrogen sulfide (H 2 S) from low pressure biogas, the need arose to broaden the operating window to also enable the removal of organosulfur compounds from high pressure sour gases. In this study we have selected microorganisms from a full-scale biodesulfurization system that are capable of withstanding the presence of thiols. This full-scale unit has been in stable operation for more than 10 years. We investigated the microbial community by using high-throughput sequencing of 16S rRNA gene amplicons which showed that methanethiol gave a competitive advantage to bacteria belonging to the genera Thioalkalibacter (Halothiobacillaceae family) and Alkalilimnicola (Ectothiorhosdospiraceae family). The sulfide-oxidizing potential of the acclimatized population was investigated under elevated thiol loading rates (4.5-9.1 mM d -1 ), consisting of a mix of methanethiol, ethanethiol, and propanethiol. With this biomass, it was possible to achieve a stable bioreactor operation at which 80% of the supplied H 2 S (61 mM d -1 ) was biologically oxidized to elemental sulfur. The remainder was chemically produced thiosulfate. Moreover, we found that a conventionally applied method for controlling the oxygen supply to the bioreactor, that is, by maintaining a redox potential set-point value, appeared to be ineffective in the presence of thiols.

Study on the sulfidation behavior of smithsonite

NASA Astrophysics Data System (ADS)

Wu, Dandan; Wen, Shuming; Deng, Jiushuai; Liu, Jian; Mao, Yingbo

2015-02-01

Zinc extraction from low-grade mineral resources of oxidized zinc has recently become a focus of study. Sulfidation is an important process in oxidized ore flotation. In this study, the influence of sulfur ion adsorption on smithsonite surface was investigated with the use of zeta potential, inductively coupled plasma (ICP), scanning electron microscope (SEM), and X-ray photoelectron spectroscopic studies. Zeta potential measurements of sodium sulfide showed that sulfur ions were adsorbed onto the surface of pure smithsonite, as evidenced by the increased negative charge and the decrease in the pHIEP of smithsonite from 7.7 to 6 after sodium sulfide treatment. The ICP test revealed the gradual reduction in sulfur ion adsorption onto the surface of smithsonite in pulp sulfur. After 30 min of absorption, CS in the solution declined from 1000 × 10-6 mol/L to 1.4 × 10-6 mol/L. SEM results showed that the mineral surface was partially changed to ZnS film after sodium sulfide treatment, whereas EDS analysis results showed that 2% S is contained on the smithsonite surface. X-ray photoelectron spectroscopy results indicated the presence of a characteristic signal peak of sulfur ions after sulfidation. Sulfur concentration increased to 11.89%, whereas oxygen concentration decreased from 42.31% to 13.74%. Sulfur ions were not only present during chemical adsorption, but were also incorporated into the crystal lattices of minerals by the exchange reaction between S2- and CO32- ions.

Reduction of produced elementary sulfur in denitrifying sulfide removal process.

PubMed

Zhou, Xu; Liu, Lihong; Chen, Chuan; Ren, Nanqi; Wang, Aijie; Lee, Duu-Jong

2011-05-01

Denitrifying sulfide removal (DSR) processes simultaneously convert sulfide, nitrate, and chemical oxygen demand from industrial wastewater into elemental sulfur, dinitrogen gas, and carbon dioxide, respectively. The failure of a DSR process is signaled by high concentrations of sulfide in reactor effluent. Conventionally, DSR reactor failure is blamed for overcompetition for heterotroph to autotroph communities. This study indicates that the elementary sulfur produced by oxidizing sulfide that is a recoverable resource from sulfide-laden wastewaters can be reduced back to sulfide by sulfur-reducing Methanobacterium sp. The Methanobacterium sp. was stimulated with excess organic carbon (acetate) when nitrite was completely consumed by heterotrophic denitrifiers. Adjusting hydraulic retention time of a DSR reactor when nitrite is completely consumed provides an additional control variable for maximizing DSR performance.

Weathering of sulfides on Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.; Fisher, Duncan S.

1987-01-01

Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

Parameterization of phosphine ligands demonstrates enhancement of nickel catalysis via remote steric effects.

PubMed

Wu, Kevin; Doyle, Abigail G

2017-08-01

The field of Ni-catalysed cross-coupling has seen rapid recent growth because of the low cost of Ni, its earth abundance, and its ability to promote unique cross-coupling reactions. Whereas advances in the related field of Pd-catalysed cross-coupling have been driven by ligand design, the development of ligands specifically for Ni has received minimal attention. Here, we disclose a class of phosphines that enable the Ni-catalysed Csp 3 Suzuki coupling of acetals with boronic acids to generate benzylic ethers, a reaction that failed with known ligands for Ni and designer phosphines for Pd. Using parameters to quantify phosphine steric and electronic properties together with regression statistical analysis, we identify a model for ligand success. The study suggests that effective phosphines feature remote steric hindrance, a concept that could guide future ligand design tailored to Ni. Our analysis also reveals that two classic descriptors for ligand steric environment-cone angle and % buried volume-are not equivalent, despite their treatment in the literature.

Parameterization of phosphine ligands demonstrates enhancement of nickel catalysis via remote steric effects

NASA Astrophysics Data System (ADS)

Wu, Kevin; Doyle, Abigail G.

2017-08-01

The field of Ni-catalysed cross-coupling has seen rapid recent growth because of the low cost of Ni, its earth abundance, and its ability to promote unique cross-coupling reactions. Whereas advances in the related field of Pd-catalysed cross-coupling have been driven by ligand design, the development of ligands specifically for Ni has received minimal attention. Here, we disclose a class of phosphines that enable the Ni-catalysed Csp3 Suzuki coupling of acetals with boronic acids to generate benzylic ethers, a reaction that failed with known ligands for Ni and designer phosphines for Pd. Using parameters to quantify phosphine steric and electronic properties together with regression statistical analysis, we identify a model for ligand success. The study suggests that effective phosphines feature remote steric hindrance, a concept that could guide future ligand design tailored to Ni. Our analysis also reveals that two classic descriptors for ligand steric environment—cone angle and % buried volume—are not equivalent, despite their treatment in the literature.

Geochemical, metagenomic and metaproteomic insights into trace metal utilization by methane-oxidizing microbial consortia in sulfidic marine sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glass, DR. Jennifer; Yu, DR. Hang; Steele, Joshua

Microbes have obligate requirements for trace metals in metalloenzymes that catalyze important biogeochemical reactions. In anoxic methane- and sulfide-rich environments, microbes may have unique adaptations for metal acquisition and utilization due to decreased bioavailability as a result of metal sulfide precipitation. However, micronutrient cycling is largely unexplored in cold ( 10 C) and sulfidic (>1 mM H2S) deep-sea methane seep ecosystems. We investigated trace metal geochemistry and microbial metal utilization in methane seeps offshore Oregon and California, USA, and report dissolved concentrations of nickel (0.5-270 nM), cobalt (0.5-6 nM), molybdenum (10-5,600 nM) and tungsten (0.3-8 nM) in Hydrate Ridge sedimentmore » porewaters. Despite low levels of cobalt and tungsten, metagenomic and metaproteomic data suggest that microbial consortia catalyzing anaerobic oxidation of methane utilize both scarce micronutrients in addition to nickel and molybdenum. Genetic machinery for cobalt-containing vitamin B12 biosynthesis was present in both anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). Proteins affiliated with the tungsten-containing form of formylmethanofuran dehydrogenase were expressed in ANME from two seep ecosystems, the first evidence for expression of a tungstoenzyme in psychrotolerant microorganisms. Finally, our data suggest that chemical speciation of metals in highly sulfidic porewaters may exert a stronger influence on microbial bioavailability than total concentration« less

Self-assembly of biomorphic carbon/sulfur microstructures in sulfidic environments

PubMed Central

Cosmidis, Julie; Templeton, Alexis S.

2016-01-01

In natural and laboratory-based environments experiencing sustained counter fluxes of sulfide and oxidants, elemental sulfur (S0)—a key intermediate in the sulfur cycle—can commonly accumulate. S0 is frequently invoked as a biomineralization product generated by enzymatic oxidation of hydrogen sulfide and polysulfides. Here we show the formation of S0 encapsulated in nanometre to micrometre-scale tubular and spherical organic structures that self-assemble in sulfide gradient environments in the absence of any direct biological activity. The morphology and composition of these carbon/sulfur microstructures so closely resemble microbial cellular and extracellular structures that new caution must be applied to the interpretation of putative microbial biosignatures in the fossil record. These reactions between sulfide and organic matter have important implications for our understanding of S0 mineralization processes and sulfur interactions with organic carbon in the environment. They furthermore provide a new pathway for the synthesis of carbon-sulfur nanocomposites for energy storage technologies. PMID:27628108

Self-assembly of biomorphic carbon/sulfur microstructures in sulfidic environments

NASA Astrophysics Data System (ADS)

Cosmidis, Julie; Templeton, Alexis S.

2016-09-01

In natural and laboratory-based environments experiencing sustained counter fluxes of sulfide and oxidants, elemental sulfur (S0)--a key intermediate in the sulfur cycle--can commonly accumulate. S0 is frequently invoked as a biomineralization product generated by enzymatic oxidation of hydrogen sulfide and polysulfides. Here we show the formation of S0 encapsulated in nanometre to micrometre-scale tubular and spherical organic structures that self-assemble in sulfide gradient environments in the absence of any direct biological activity. The morphology and composition of these carbon/sulfur microstructures so closely resemble microbial cellular and extracellular structures that new caution must be applied to the interpretation of putative microbial biosignatures in the fossil record. These reactions between sulfide and organic matter have important implications for our understanding of S0 mineralization processes and sulfur interactions with organic carbon in the environment. They furthermore provide a new pathway for the synthesis of carbon-sulfur nanocomposites for energy storage technologies.

Microbial control of hydrogen sulfide production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.

1995-12-31

A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of coresmore » and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.« less

Arsenic Repartitioning during Biogenic Sulfidization and Transformation of Ferrihydrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocar, B.; Borch, T; Fendorf, S

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within themore » zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II){sub (aq)} concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III){sub (s)} depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.« less

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocar, Benjamin D.; Borch, Thomas; Fendorf, Scott

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within themore » zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.« less

Perfluoroalkyl phosphonic and phosphinic acids as proton conductors for anhydrous proton-exchange membranes.

PubMed

Herath, Mahesha B; Creager, Stephen E; Kitaygorodskiy, Alex; DesMarteau, Darryl D

2010-09-10

A study of proton-transport rates and mechanisms under anhydrous conditions using a series of acid model compounds, analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, sulfonic, and carboxylic acid protogenic groups, is reported. Model compounds are characterized with respect to proton conductivity, viscosity, proton, and anion (conjugate base) self-diffusion coefficients, and Hammett acidity. The highest conductivities, and also the highest viscosities, are observed for the phosphonic and phosphinic acid model compounds. Arrhenius analysis of conductivity and viscosity for these two acids reveals much lower activation energies for ion transport than for viscous flow. Additionally, the proton self-diffusion coefficients are much higher than the conjugate-base self-diffusion coefficients for these two acids. Taken together, these data suggest that anhydrous proton transport in the phosphonic and phosphinic acid model compounds occurs primarily by a structure-diffusion, hopping-based mechanism rather than a vehicle mechanism. Further analysis of ionic conductivity and ion self-diffusion rates by using the Nernst-Einstein equation reveals that the phosphonic and phosphinic acid model compounds are relatively highly dissociated even under anhydrous conditions. In contrast, sulfonic and carboxylic acid-based systems exhibit relatively low degrees of dissociation under anhydrous conditions. These findings suggest that fluoroalkyl phosphonic and phosphinic acids are good candidates for further development as anhydrous, high-temperature proton conductors.

Surface Charge Development on Transition Metal Sulfides: An Electrokinetic Study

NASA Astrophysics Data System (ADS)

Bebie, Joakim; Schoonen, Martin A. A.; Fuhrmann, Mark; Strongin, Daniel R.

1998-02-01

The isoelectric points, pH i.e.p., of ZnS, PbS, CuFeS 2, FeS, FeS 2, NiS 2, CoS 2, and MnS 2 in NaCl supported electrolyte solutions are estimated to be between pH 3.3 and 0.6, with most of the isoelectric points below pH 2. The first electrokinetic measurements on NiS 2, CoS 2, and MnS 2 are reported here. Below pH i.e.p. the metal-sulfide surfaces are positively charged, above pH i.e.p. the surfaces are negatively charged. The addition of Me 2+ ions shifts the pH i.e.p. and changes the pH dependence considerably. The isoelectric points of the measured transition metal sulfides in the absence of metal ions or dissolved sulfide (H 2S or HS -) are in agreement with those found in earlier studies. The pH range of observed isoelectric points for metal sulfides (0.6-3.3) is compared to the considerably wider pH i.e.p. range (2-12) found for oxides. The correlation between pH i.e.p. and the electronegativities of the metal sulfides suggests that all metal sulfides will have an isoelectric point between pH 0.6 and 3.3. Compared to metal oxides, sulfides exhibit an isoelectric point that is largely independent of the nature of the metal cation in the solid.

Experiments in Thermodynamics and Kinetics of Phosphine Substitution in (p-Cymene)RuCl[subscript 2](PR[subscript 3])

ERIC Educational Resources Information Center

Ozerov, Oleg V.; Fafard, Claudia M.; Hoffman, Norris W.

2007-01-01

This manuscript describes a set of three experiments that investigates the thermodynamic and kinetic aspects of phosphine substitution at a Ru center. In the first experiment, the students synthesize a Ru organometallic complex containing a phosphine ligand. In the second, equilibria for phosphine substitution involving several different…

A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands.

PubMed

Chen, Weiping; Mbafor, William; Roberts, Stanley M; Whittall, John

2006-03-29

A very simple, highly stereoselective and modular synthesis of ferrocene-based P-chiral phosphine ligands has been developed. On the basis of this new methodology, several new families of ferrocene-based phosphine ligands have been prepared coupling chirality at phosphorus with other, more standard stereogenic features. The introduction of P-chirality into ferrocene-based phosphine ligands enhances the enantioselective discrimination produced by the corresponding Rh catalyst when a matching among the planar chirality, carbon chirality, and the chirality of phosphorus is achieved.

Atomic layer deposition of metal sulfide materials

DOE PAGES

Dasgupta, Neil P.; Meng, Xiangbo; Elam, Jeffrey W.; ...

2015-01-12

The field of nanoscience is delivering increasingly intricate yet elegant geometric structures incorporating an ever-expanding palette of materials. Atomic layer deposition (ALD) is a powerful driver of this field, providing exceptionally conformal coatings spanning the periodic table and atomic-scale precision independent of substrate geometry. This versatility is intrinsic to ALD and results from sequential and self-limiting surface reactions. This characteristic facilitates digital synthesis, in which the film grows linearly with the number of reaction cycles. While the majority of ALD processes identified to date produce metal oxides, novel applications in areas such as energy storage, catalysis, and nanophotonics are motivatingmore » interest in sulfide materials. Recent progress in ALD of sulfides has expanded the diversity of accessible materials as well as a more complete understanding of the unique chalcogenide surface chemistry. ALD of sulfide materials typically uses metalorganic precursors and hydrogen sulfide (H 2S). As in oxide ALD, the precursor chemistry is critical to controlling both the film growth and properties including roughness, crystallinity, and impurity levels. By modification of the precursor sequence, multicomponent sulfides have been deposited, although challenges remain because of the higher propensity for cation exchange reactions, greater diffusion rates, and unintentional annealing of this more labile class of materials. A deeper understanding of these surface chemical reactions has been achieved through a combination of in situ studies and quantum-chemical calculations. As this understanding matures, so does our ability to deterministically tailor film properties to new applications and more sophisticated devices. This Account highlights the attributes of ALD chemistry that are unique to metal sulfides and surveys recent applications of these materials in photovoltaics, energy storage, and photonics. Within each application

Fixed-charge phosphine ligands to explore gas-phase coinage metal-mediated decarboxylation reactions.

PubMed

Vikse, Krista; Khairallah, George N; McIndoe, J Scott; O'Hair, Richard A J

2013-05-14

A combination of multistage mass spectrometry experiments and density functional theory (DFT) calculations were used to examine the decarboxylation reactions of a series of metal carboxylate complexes bearing a fixed-charge phosphine ligand, [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph). Collision-induced dissociation (CID) of these complexes using an LTQ linear ion mass spectrometer results in three main classes of reactions being observed: (1) decarboxylation; (2) loss of the phosphine ligand; (3) loss of carboxylic acid. The gas-phase unimolecular chemistry of the resultant decarboxylated organometallic ions, [(O3SC6H4)(C6H5)2PM(I)R](-), were also explored using CID experiments, and fragment primarily via loss of the phosphine ligand. Energy-resolved CID experiments on [(O3SC6H4)(C6H5)2PM(I)O2CR](-) (M = Cu, Ag, Au; R = Me, Et, benzyl, Ph) using a Q-TOF mass spectrometer were performed to gain a more detailed understanding of the factors influencing coinage metal-catalyzed decarboxylation and DFT calculations on the major fragmentation pathways aided in interpretation of the experimental results. Key findings are that: (1) the energy required for loss of the phosphine ligand follows the order Ag < Cu < Au; (2) the ease of decarboxylation of the coordinated RCO2 groups follows the order of R: Ph < PhCH2 < Me < Et; (3) in general, copper is best at facilitating decarboxylation, followed by gold then silver. The one exception to this trend is when R = Ph and M = Au which has the highest overall propensity for decarboxylation. The influence of the phosphine ligand on decarboxylation is also considered in comparison with previous studies on metal carboxylates that do not contain a phosphine ligand.

Extracting metals directly from metal oxides

DOEpatents

Wai, Chien M.; Smart, Neil G.; Phelps, Cindy

1997-01-01

A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones, halogenated .beta.-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process.

Extracting metals directly from metal oxides

DOEpatents

Wai, C.M.; Smart, N.G.; Phelps, C.

1997-02-25

A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of {beta}-diketones, halogenated {beta}-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process. 4 figs.

Modeling of Sulfide Microenvironments on Mars

NASA Technical Reports Server (NTRS)

Schwenzer, S. P.; Bridges, J. C.; McAdam, A.; Steer, E. D.; Conrad, P. G.; Kelley, S. P.; Wiens, R. C.; Mangold, N.; Grotzinger, J.; Eigenbrode, J. L.;

Biological treatment process of air loaded with an ammonia and hydrogen sulfide mixture.

PubMed

Malhautier, Luc; Gracian, Catherine; Roux, Jean-Claude; Fanlo, Jean-Louis; Le Cloirec, Pierre

2003-01-01

The physico-chemical characteristics of granulated sludge lead us to develop its use as a packing material in air biofiltration. Then, the aim of this study is to investigate the potential of unit systems packed with this support in terms of ammonia and hydrogen sulfide emissions treatment. Two laboratory scale pilot biofilters were used. A volumetric load of 680 g H2S m(-3) empty bed day(-1) and 85 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to a unit called BGSn (column packed with granulated sludge and mainly supplied with hydrogen sulfide); a volumetric load of 170 g H2S m(-3) empty bed day(-1) and 340 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to the other called BGNs (column packed with granulated sludge and mainly supplied with ammonia). Ammonia and hydrogen sulfide elimination occur in the biofilters simultaneously. The hydrogen sulphide and ammonia removal efficiencies reached are very high: 100% and 80% for BGSn; 100% and 80% for BGNs respectively. Hydrogen sulfide is oxidized into sulphate and sulfur. The ammonia oxidation products are nitrite and nitrate. The nitrogen error mass balance is high for BGSn (60%) and BGNs (36%). This result could be explained by the denitrification process which would have occurred in anaerobic zones. High percentages of ammonia or hydrogen sulfide are oxidized on the first half of the column. The oxidation of high amounts of hydrogen sulfide would involve some environmental stress on nitrifying bacterial growth and activity.

A fuel-cell-assisted iron redox process for simultaneous sulfur recovery and electricity production from synthetic sulfide wastewater.

PubMed

Zhai, Lin-Feng; Song, Wei; Tong, Zhong-Hua; Sun, Min

2012-12-01

Sulfide present in wastewaters and waste gases should be removed due to its toxicity, corrosivity, and malodorous property. Development of effective, stable, and feasible methods for sulfur recovery from sulfide attains a double objective of waste minimization and resource recovery. Here we report a novel fuel-cell-assisted iron redox (FC-IR) process for simultaneously recovering sulfur and electricity from synthetic sulfide wastewater. The FC-IR system consists of an oxidizing reactor where sulfide is oxidized to elemental sulfur by Fe(III), and a fuel cell where Fe(III) is regenerated from Fe(II) concomitantly with electricity producing. The oxidation of sulfide by Fe(III) is significantly dependent on solution pH. Increasing the pH from 0.88 to 1.96 accelerates the oxidation of sulfide, however, lowers the purity of the produced elemental sulfur. The performance of fuel cell is also a strong function of solution pH. Fe(II) is completely oxidized to Fe(III) when the fuel cell is operated at a pH above 6.0, whereas only partially oxidized below pH 6.0. At pH 6.0, the highest columbic efficiency of 75.7% is achieved and electricity production maintains for the longest time of 106 h. Coupling operation of the FC-IR system obtains sulfide removal efficiency of 99.90%, sulfur recovery efficiency of 78.6 ± 8.3%, and columbic efficiency of 58.6 ± 1.6%, respectively. These results suggest that the FC-IR process is a promising tool to recover sulfur and energy from sulfide. Copyright © 2012 Elsevier B.V. All rights reserved.

One-step hydrothermal synthesis of three-dimensional porous Ni-Co sulfide/reduced graphene oxide composite with optimal incorporation of carbon nanotubes for high performance supercapacitors.

PubMed

Chiu, Cheng-Ting; Chen, Dong-Hwang

2018-04-27

Three-dimensional (3D) porous Ni-Co sulfide/reduced graphene oxide composite with the appropriate incorporation of carbon nanotubes (NCS/rGO/CNT) was fabricated as a promising material for supercapacitor electrodes. It combined the high pseudo-capacitance of Ni-Co sulfide as well as the large specific surface area and electrical double layer capacitance of reduced graphene oxide (rGO). Carbon nanotubes (CNTs) were incorporated to act as the spacer for hindering the restacking of rGO and to construct a conductive network for enhancing the electron transport. The 3D porous NCS/rGO/CNT composite was fabricated by a facile one-step hydrothermal process in which Ni-Co sulfide nanosheets were synthesized and graphene oxide was reduced simultaneously. It was shown that the capacitance and cyclic performance indeed could be effectively improved via the appropriate addition of CNTs. In addition, a flexible all-solid-state asymmetric supercapacitor based on the NCS/rGO/CNT electrode was fabricated and exhibited the same capacitive electrochemical performance under bending. Also, it could successfully turn on a light-emitting diode light, revealing its feasibility in practical application. All results demonstrated that the developed NCS/rGO/CNT composite has potential application in supercapacitors.

One-step hydrothermal synthesis of three-dimensional porous Ni-Co sulfide/reduced graphene oxide composite with optimal incorporation of carbon nanotubes for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Chiu, Cheng-Ting; Chen, Dong-Hwang

2018-04-01

Three-dimensional (3D) porous Ni-Co sulfide/reduced graphene oxide composite with the appropriate incorporation of carbon nanotubes (NCS/rGO/CNT) was fabricated as a promising material for supercapacitor electrodes. It combined the high pseudo-capacitance of Ni-Co sulfide as well as the large specific surface area and electrical double layer capacitance of reduced graphene oxide (rGO). Carbon nanotubes (CNTs) were incorporated to act as the spacer for hindering the restacking of rGO and to construct a conductive network for enhancing the electron transport. The 3D porous NCS/rGO/CNT composite was fabricated by a facile one-step hydrothermal process in which Ni-Co sulfide nanosheets were synthesized and graphene oxide was reduced simultaneously. It was shown that the capacitance and cyclic performance indeed could be effectively improved via the appropriate addition of CNTs. In addition, a flexible all-solid-state asymmetric supercapacitor based on the NCS/rGO/CNT electrode was fabricated and exhibited the same capacitive electrochemical performance under bending. Also, it could successfully turn on a light-emitting diode light, revealing its feasibility in practical application. All results demonstrated that the developed NCS/rGO/CNT composite has potential application in supercapacitors.

40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting under...

40 CFR 721.10135 - Phosphinic acid, P,P-diethyl-, zinc salt (2:1).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Phosphinic acid, P,P-diethyl-, zinc... Specific Chemical Substances § 721.10135 Phosphinic acid, P,P-diethyl-, zinc salt (2:1). (a) Chemical... acid, P,P-diethyl-, zinc salt (2:1) (PMN P-05-11; CAS No. 284685-45-6) is subject to reporting under...

Preparation of polyvinyl alcohol graphene oxide phosphonate film and research of thermal stability and mechanical properties.

PubMed

Li, Jihui; Song, Yunna; Ma, Zheng; Li, Ning; Niu, Shuai; Li, Yongshen

2018-05-01

In this article, flake graphite, nitric acid, peroxyacetic acid and phosphoric acid are used to prepare graphene oxide phosphonic and phosphinic acids (GOPAs), and GOPAs and polyvinyl alcohol (PVA) are used to synthesize polyvinyl alcohol graphene oxide phosphonate and phosphinate (PVAGOPs) in the case of faint acidity and ultrasound irradiation, and PVAGOPs are used to fabricate PVAGOPs film, and the structure and morphology of GOPAs, PVAGOPs and PVAGOPs film are characterized, and the thermal stability and mechanical properties of PVAGOPs film are investigated. Based on these, it has been proved that GOPAs consist of graphene oxide phosphonic acid and graphene oxide phosphinic acid, and there are CP covalent bonds between them, and PVAGOPs are composed of GOPAs and PVA, and there are six-member lactone rings between GOPAs and PVA, and the thermal stability and mechanical properties of PVAGOPs film are improved effectively. Copyright © 2018 Elsevier B.V. All rights reserved.

Small Molecule Activation by Intermolecular Zr(IV)-Phosphine Frustrated Lewis Pairs.

PubMed

Metters, Owen J; Forrest, Sebastian J K; Sparkes, Hazel A; Manners, Ian; Wass, Duncan F

2016-02-17

We report intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene aryloxide and phosphine moieties that exhibit a broad range of small molecule activation chemistry that has previously been the preserve of only intramolecular pairs. Reactions with D2, CO2, THF, and PhCCH are reported. By contrast with previous intramolecular examples, these systems allow facile access to a variety of steric and electronic characteristics at the Lewis acidic and Lewis basic components, with the three-step syntheses of 10 new intermolecular transition metal FLPs being reported. Systematic variation to the phosphine Lewis base is used to unravel steric considerations, with the surprising conclusion that phosphines with relatively small Tolman steric parameters not only give highly reactive FLPs but are often seen to have the highest selectivity for the desired product. DOSY NMR spectroscopic studies on these systems reveal for the first time the nature of the Lewis acid/Lewis base interactions in transition metal FLPs of this type.

Intumescent formulations based on lignin and phosphinates for the bio-based textiles

NASA Astrophysics Data System (ADS)

Mandlekar, N.; Cayla, A.; Rault, F.; Giraud, S.; Salaün, F.; Malucelli, G.; Guan, J.

2017-10-01

This study investigates new intumescent formulations based on lignin and phosphinates to improve the flame retardant properties of Polyamide 11, while preserving the bio-based characteristics of this latter. Lignin has the advantage of being a bio-based compound and can be effectively used as carbon source for the design of intumescent systems in combination with other flame retardant additives. Metal phosphinates belong to a novel class of phosphorus flame retardants. Despite their increasing use, there is lack of scientific understanding as far as their fire retardancy mechanism is considered, especially in char forming polymeric materials. In this context, Polyamide 11 was melt blended with lignin and metal phosphinates. The possibility of melt spinning the prepared blends were assessed through melt flow index (MFI) tests; thermogravimetric (TG) analyses and cone calorimetry tests were exploited for investigating the thermal stability and the combustion behaviour of the obtained products, respectively. MFI results indicate that some formulations are suitable for melt spinning processes to generate flame retardant multifilament. Furthermore, the combination of lignin and phosphinates provides charring properties to polyamide 11. Finally, cone calorimetry data confirmed that the designed intumescent formulations could remarkably reduce PHRR through formation of protective char layer, hence slowing down the combustion process.

Penguins significantly increased phosphine formation and phosphorus contribution in maritime Antarctic soils.

PubMed

Zhu, Renbin; Wang, Qing; Ding, Wei; Wang, Can; Hou, Lijun; Ma, Dawei

2014-11-14

Most studies on phosphorus cycle in the natural environment focused on phosphates, with limited data available for the reduced phosphine (PH3). In this paper, matrix-bound phosphine (MBP), gaseous phosphine fluxes and phosphorus fractions in the soils were investigated from a penguin colony, a seal colony and the adjacent animal-lacking tundra and background sites. The MBP levels (mean 200.3 ng kg(-1)) in penguin colony soils were much higher than those in seal colony soils, animal-lacking tundra soils and the background soils. Field PH3 flux observation and laboratory incubation experiments confirmed that penguin colony soils produced much higher PH3 emissions than seal colony soils and animal-lacking tundra soils. Overall high MBP levels and PH3 emissions were modulated by soil biogeochemical processes associated with penguin activities: sufficient supply of the nutrients phosphorus, nitrogen, and organic carbon from penguin guano, high soil bacterial abundance and phosphatase activity. It was proposed that organic or inorganic phosphorus compounds from penguin guano or seal excreta could be reduced to PH3 in the Antarctic soils through the bacterial activity. Our results indicated that penguin activity significantly increased soil phosphine formation and phosphorus contribution, thus played an important role in phosphorus cycle in terrestrial ecosystems of maritime Antarctica.

Penguins significantly increased phosphine formation and phosphorus contribution in maritime Antarctic soils

PubMed Central

Zhu, Renbin; Wang, Qing; Ding, Wei; Wang, Can; Hou, Lijun; Ma, Dawei

2014-01-01

Most studies on phosphorus cycle in the natural environment focused on phosphates, with limited data available for the reduced phosphine (PH3). In this paper, matrix-bound phosphine (MBP), gaseous phosphine fluxes and phosphorus fractions in the soils were investigated from a penguin colony, a seal colony and the adjacent animal-lacking tundra and background sites. The MBP levels (mean 200.3 ng kg−1) in penguin colony soils were much higher than those in seal colony soils, animal-lacking tundra soils and the background soils. Field PH3 flux observation and laboratory incubation experiments confirmed that penguin colony soils produced much higher PH3 emissions than seal colony soils and animal-lacking tundra soils. Overall high MBP levels and PH3 emissions were modulated by soil biogeochemical processes associated with penguin activities: sufficient supply of the nutrients phosphorus, nitrogen, and organic carbon from penguin guano, high soil bacterial abundance and phosphatase activity. It was proposed that organic or inorganic phosphorus compounds from penguin guano or seal excreta could be reduced to PH3 in the Antarctic soils through the bacterial activity. Our results indicated that penguin activity significantly increased soil phosphine formation and phosphorus contribution, thus played an important role in phosphorus cycle in terrestrial ecosystems of maritime Antarctica. PMID:25394572

ELECTROCHEMICAL DETERMINATION OF HYDROGEN SULFIDE AT CARBON NANOTUBE MODIFIED ELECTRODES. (R830900)

EPA Science Inventory

Carbon nanotube (CNT) modified glassy carbon electrodes exhibiting a strong and stable electrocatalytic response towards sulfide are described. A substantial (400 mV) decrease in the overvoltage of the sulfide oxidation reaction (compared to ordinary carbon electrodes) is...

Non-hydrolytic Sol-gel Synthesis of Tin Sulfides

NASA Astrophysics Data System (ADS)

Kaur, Rajvinder

The non-hydrolytic sol-gel (NHSG) process is an effective low temperature route well known for preparing homogeneous metal oxides. Thermodynamically as well as kinetically favored products, which cannot be prepared with the traditional solid-state routes, can be produced using NHSG. This project is focused on the exploration of NHSG synthesis of binary tin sulfides. In the past few years, metal sulfides have been the subject of significant interest. Much effort has been devoted to understand these materials because of their potential applications in electronic, optical, and superconductor devices.4 Among these materials, tin sulfides are materials of technological importance, which are being explored as semiconductors, anode materials for Li ion batteries, photoconductors, photocatalysts and absorber layer materials in photovoltaic solar cell devices. All of these applications depend upon features like homogeneity, oxidation state, high surface area and purity of the materials. These properties can be difficult to achieve by employing traditional synthetic routes, which require high temperatures due to slow diffusion, limiting the products to thermodynamically stable phases and prohibiting control over properties like particle size and surface area. A variety of low temperature methods are being explored due to the increased demand for such advanced materials. This project is focused on exploring the NHSG approach to synthesize binary tin sulfides, with the main goal of establishing conditions for the targeted synthesis of different tin sulfide polymorphs with controlled particle size. Being non-oxide materials, tin sulfides can be air sensitive, which requires special attention in handling. All reactions were carried out in absence of oxygen. This project explores the reaction of tin halides with thioethers in a dry solvent medium, leading to the formation of tin sulfides. There are a number of synthetic parameters that can be varied for the NHSG approach. A

Weathering of iron sulfides under Mars surface ambient conditions

NASA Technical Reports Server (NTRS)

Blackburn, T. R.

1981-01-01

The study of iron sulfide surface alternation reactions under Mars' surface ambient conditions begun during 1980 was extended through improved irradiation design and experimental protocols. A wider range of humidities and more intense irradiation were incorporated in the study. X-ray photoelectron spectra of irradiated chips suggest formation of FeSO4, FeCO3, and an iron oxide on the iron sulfide substrates studied.

Interaction of Hydrogen Sulfide with Nitric Oxide in the Cardiovascular System

PubMed Central

Nagpure, B. V.; Bian, Jin-Song

2016-01-01

Historically acknowledged as toxic gases, hydrogen sulfide (H2S) and nitric oxide (NO) are now recognized as the predominant members of a new family of signaling molecules, “gasotransmitters” in mammals. While H2S is biosynthesized by three constitutively expressed enzymes (CBS, CSE, and 3-MST) from L-cysteine and homocysteine, NO is generated endogenously from L-arginine by the action of various isoforms of NOS. Both gases have been transpired as the key and independent regulators of many physiological functions in mammalian cardiovascular, nervous, gastrointestinal, respiratory, and immune systems. The analogy between these two gasotransmitters is evident not only from their paracrine mode of signaling, but also from the identical and/or shared signaling transduction pathways. With the plethora of research in the pathophysiological role of gasotransmitters in various systems, the existence of interplay between these gases is being widely accepted. Chemical interaction between NO and H2S may generate nitroxyl (HNO), which plays a specific effective role within the cardiovascular system. In this review article, we have attempted to provide current understanding of the individual and interactive roles of H2S and NO signaling in mammalian cardiovascular system, focusing particularly on heart contractility, cardioprotection, vascular tone, angiogenesis, and oxidative stress. PMID:26640616

Interaction of tertiary phosphines with lignin-type, alpha,beta-unsaturated aldehydes in water.

PubMed

Moiseev, Dmitry V; Patrick, Brian O; James, Brian R; Hu, Thomas Q

2007-10-29

To learn more about the bleaching action of pulps by (hydroxymethyl)phosphines, lignin chromophores, such as the alpha,beta-unsaturated aromatic aldehydes, sinapaldehyde, coniferylaldehyde, and coumaraldehyde, were reacted with the tertiary phosphines R2R'P [R = R' = Me, Et, (CH2)3OH, iPr, cyclo-C6H11, (CH2)2CN; R = Me or Et, R' = Ph; R = Ph, R' = Me, m-NaSO3-C6H4] in water at room temperature under argon. In all cases, initial nucleophilic attack of the phosphine occurs at the activated C=C bond to form a zwitterionic monophosphonium species. With the phosphines PR3 [R = Me, Et, (CH2)3OH] and with R2R'P (R = Me or Et, R' = Ph), the zwitterion undergoes self-condensation to give a bisphosphonium zwitterion that can react with aqueous HCl to form the corresponding dichloride salts (as a mixture of R,R- and S,S-enantiomers); X-ray structures are presented for the bisphosphonium chlorides synthesized from the Et3P and Me3P reactions with sinapaldehyde. With the more bulky phosphines, iPr3P, MePPh2, (cyclo-C6H11)3P, and Na[Ph2P(m-SO3-C6H4)], only an equilibrium of the monophosphonium zwitterion with the reactant aldehyde is observed. The weakly nucleophilic [NC(CH2)2]3P does not react with sinapaldehyde. An analysis of some exceptional 1H NMR data within the prochiral phosphorus centers of the bisphosphonium chlorides is also presented.

Interactions among sulfide-oxidizing bacteria

NASA Technical Reports Server (NTRS)

Poplawski, R.

1985-01-01

The responses of different phototrophic bacteria in a competitive experimental system are studied, one in which primary factors such as H2S or light limited photometabolism. Two different types of bacteria shared one limited source of sulfide under specific conditions of light. The selection of a purple and a green sulfur bacteria and the cyanobacterium was based on their physiological similarity and also on the fact that they occur together in microbial mats. They all share anoxygenic photosynthesis, and are thus probably part of an evolutionary continuum of phototrophic organisms that runs from, strictly anaerobic physiology to the ability of some cyanobacteria to shift between anoxygenic bacterial style photosynthesis and the oxygenic kind typical of eukaryotes.

Corrosion Behavior of Cu40Zn in Sulfide-Polluted 3.5% NaCl Solution

NASA Astrophysics Data System (ADS)

Song, Q. N.; Xu, N.; Bao, Y. F.; Jiang, Y. F.; Gu, W.; Yang, Z.; Zheng, Y. G.; Qiao, Y. X.

2017-10-01

The corrosion behavior of a duplex-phase brass Cu40Zn in clean and sulfide-polluted 3.5% NaCl solutions was investigated by conducting electrochemical and gravimetric measurements. The corrosion product films were analyzed by scanning electron microscopy, energy-dispersive spectroscopy and x-ray diffraction. The presence of sulfide shifted the corrosion potential of Cu40Zn toward a more negative value by 100 mV and increased the mass loss rate by a factor of 1.257 compared with the result in the clean solution. The corrosion product film in the clean solution was thin and compact; it mainly consisted of oxides, such as ZnO and Cu2O. By contrast, the film in the sulfide-polluted solution was thick and porous. It mainly contained sulfides and zinc hydroxide chloride (i.e., Zn5(OH)8Cl2·H2O). The presence of sulfide ions accelerated the corrosion damage of Cu40Zn by hindering the formation of protective oxides and promoting the formation of a defective film which consisted of sulfides and hydroxide chlorides.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

1994-01-01

A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Phosphine and diphosphine complexes of silicon(IV) halides.

PubMed

Levason, William; Pugh, David; Reid, Gillian

2013-05-06

The reaction of SiX4 (X = Cl or Br) with PMe3 in anhydrous CH2Cl2 forms trans-[SiX4(PMe3)2], while the diphosphines, Me2P(CH2)2PMe2, Et2P(CH2)2PEt2, and o-C6H4(PMe2)2 form cis-[SiX4(diphosphine)], all containing six-coordinate silicon centers. With Me2PCH2PMe2 the product was trans-[SiCl4(κ(1)-Me2PCH2PMe2)2]. The complexes have been characterized by X-ray crystallography, microanalysis, IR, and multinuclear ((1)H, (13)C{(1)H}, and (31)P{(1)H}) NMR spectroscopies. The complexes are stable solids and not significantly dissociated in nondonor solvents, although they are very moisture and oxygen sensitive. This stability conflicts with the predictions of recent density functional theory (DFT) calculations (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) which suggested six-coordinate silicon phosphines would be unstable, and also contrasts with the failure to isolate complexes with SiF4 (George et al. Dalton Trans. 2011, 40, 1584-1593). No reaction occurred between phosphines and SiI4, or with SiX4 and arsine ligands including AsMe3 and o-C6H4(AsMe2)2. Attempts to make five-coordinate [SiX4(PR3)] using the sterically bulky phosphines, P(t)Bu3, P(i)Pr3, or PCy3 failed, with no apparent reaction occurring, consistent with predictions (Wilson et al. Inorg. Chem. 2012, 51, 7657-7668) that such compounds would be very endothermic, while the large cone angles of the phosphines presumably preclude formation of six-coordination at the small silicon center. The reaction of Si2Cl6 with PMe3 or the diphosphines in CH2Cl2 results in instant disproportionation to the SiCl4 adducts and polychlorosilanes, but from hexane solution very unstable white [Si2Cl6(PMe3)2] and [Si2Cl6(diphosphine)] (diphosphine = Me2P(CH2)2PMe2 or o-C6H4(PMe2)2) precipitate. The reactions of SiHCl3 with PMe3 and Me2P(CH2)2PMe2 also produce the SiCl4 adducts, but using Et2P(CH2)2PEt2, colorless [SiHCl3{Et2P(CH2)2PEt2}] was isolated, which was characterized by an X-ray structure which showed a pseudo

Enhanced performance of denitrifying sulfide removal process at high carbon to nitrogen ratios under micro-aerobic condition.

PubMed

Chen, Chuan; Zhang, Ruo-Chen; Xu, Xi-Jun; Fang, Ning; Wang, Ai-Jie; Ren, Nan-Qi; Lee, Duu-Jong

2017-05-01

The success of denitrifying sulfide removal (DSR) processes, which simultaneously degrade sulfide, nitrate and organic carbon in the same reactor, counts on synergetic growths of autotrophic and heterotrophic denitrifiers. Feeding wastewaters at high C/N ratio would stimulate overgrowth of heterotrophic bacteria in the DSR reactor so deteriorating the growth of autotrophic denitrifiers. The DSR tests at C/N=1.26:1, 2:1 or 3:1 and S/N =5:6 or 5:8 under anaerobic (control) or micro-aerobic conditions were conducted. Anaerobic DSR process has <50% sulfide removal with no elemental sulfur transformation. Under micro-aerobic condition to remove <5% sulfide by chemical oxidation pathway, 100% sulfide removal is achieved by the DSR consortia. Continuous-flow tests under micro-aerobic condition have 70% sulfide removal and 55% elemental sulfur recovery. Trace oxygen enhances activity of sulfide-oxidizing, nitrate-reducing bacteria to accommodate properly the wastewater with high C/N ratios. Copyright © 2017 Elsevier Ltd. All rights reserved.

Enhanced performance of denitrifying sulfide removal process under micro-aerobic condition.

PubMed

Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

2010-07-15

The denitrifying sulfide removal (DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate into di-nitrogen gas, elementary sulfur and carbon dioxide, respectively, at high loading rates. This study determines the reaction rate of sulfide oxidized into sulfur, as well as the reduction of nitrate to nitrite, would be enhanced under a micro-aerobic condition. The presence of limited oxygen mitigated the inhibition effects of sulfide on denitrifier activities, and enhanced the performance of DSR granules. The advantages and disadvantages of applying the micro-aerobic condition to the DSR process are discussed. 2010 Elsevier B.V. All rights reserved.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

1994-04-26

A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

High-rate synthesis of phosphine-stabilized undecagold nanoclusters using a multilayered micromixer.

PubMed

Jin, Hyung Dae; Garrison, Anna; Tseng, T; Paul, Brian K; Chang, Chih-Hung

2010-11-05

Growth in the potential applications of nanomaterials has led to a focus on the development of new manufacturing approaches for these materials. In particular, an increased demand due to the unique properties of nanomaterials requires a substantial yield of high-performance materials and a simultaneous reduction in the environmental impact of these processes. In this paper, a high-rate production of phosphine-stabilized undecagold nanoclusters was achieved using a layer-up strategy which involves the use of microlamination architectures; the patterning and bonding of thin layers of material (laminae) to create a multilayered micromixer in the range of 25-250 µm thick was used to step up the production of phosphine-stabilized undecagold nanoclusters. The continuous production of highly monodispersed phosphine-stabilized undecagold nanoclusters at a rate of about 11.8 (mg s(-1)) was achieved using a microreactor with a size of 1.687 cm(3). This result is about 500 times over conventional batch syntheses based on the production rate per reactor volume.

High-rate synthesis of phosphine-stabilized undecagold nanoclusters using a multilayered micromixer

NASA Astrophysics Data System (ADS)

Jin, Hyung Dae; Garrison, Anna; Tseng, T.; Paul, Brian K.; Chang, Chih-Hung

2010-11-01

Growth in the potential applications of nanomaterials has led to a focus on the development of new manufacturing approaches for these materials. In particular, an increased demand due to the unique properties of nanomaterials requires a substantial yield of high-performance materials and a simultaneous reduction in the environmental impact of these processes. In this paper, a high-rate production of phosphine-stabilized undecagold nanoclusters was achieved using a layer-up strategy which involves the use of microlamination architectures; the patterning and bonding of thin layers of material (laminae) to create a multilayered micromixer in the range of 25-250 µm thick was used to step up the production of phosphine-stabilized undecagold nanoclusters. The continuous production of highly monodispersed phosphine-stabilized undecagold nanoclusters at a rate of about 11.8 (mg s - 1) was achieved using a microreactor with a size of 1.687 cm3. This result is about 500 times over conventional batch syntheses based on the production rate per reactor volume.

Phosphine resistance does not confer cross-resistance to sulfuryl fluoride in four major stored grain insect pests.

PubMed

Jagadeesan, Rajeswaran; Nayak, Manoj K

2017-07-01

Susceptibility to phosphine (PH 3 ) and sulfuryl fluoride (SF) and cross-resistance to SF were evaluated in two life stages (eggs and adults) of key grain insect pests, Rhyzopertha dominca (F.), Sitophilus oryzae (L.), Cryptolestes ferrugineus (Stephens), and Tribolium castaneum (Herbst). This study was performed with an aim to integrate SF into phosphine resistance management programmes in Australia. Characterisation of susceptibility and resistance to phosphine in eggs and adults showed that C. ferrugineus was the most tolerant as well as resistant species. Mortality responses of eggs and adults to SF at 25 °C revealed T. castaneum to be the most tolerant species followed by S. oryzae, C. ferrugineus and R. dominica. A high dose range of SF, 50.8-62.2 mg L -1 over 48 h, representing c (concentration) × t (time) products of 2438-2985 gh m -3 , was required for complete control of eggs of T. castaneum, whereas eggs of the least tolerant R. dominca required only 630 gh m -3 for 48 h (13.13 mg L -1 ). Mortality response of eggs and adults of phosphine-resistant strains to SF in all four species confirmed the lack of cross-resistance to SF. Our research concludes that phosphine resistance does not confer cross-resistance to SF in grain insect pests irrespective of the variation in levels of tolerance to SF itself or resistance to phosphine in their egg and adult stages. While our study confirms that SF has potential as a 'phosphine resistance breaker', the observed higher tolerance in eggs stresses the importance of developing SF fumigation protocols with longer exposure periods. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

Improving the efficiency of cadmium sulfide-sensitized titanium dioxide/indium tin oxide glass photoelectrodes using silver sulfide as an energy barrier layer and a light absorber

PubMed Central

2014-01-01

Cadmium sulfide (CdS) and silver sulfide (Ag2S) nanocrystals are deposited on the titanium dioxide (TiO2) nanocrystalline film on indium tin oxide (ITO) substrate to prepare CdS/Ag2S/TiO2/ITO photoelectrodes through a new method known as the molecular precursor decomposition method. The Ag2S is interposed between the TiO2 nanocrystal film and CdS nanocrystals as an energy barrier layer and a light absorber. As a consequence, the energy conversion efficiency of the CdS/Ag2S/TiO2/ITO electrodes is significantly improved. Under AM 1.5 G sunlight irradiation, the maximum efficiency achieved for the CdS(4)/Ag2S/TiO2/ITO electrode is 3.46%, corresponding to an increase of about 150% as compared to the CdS(4)/TiO2/ITO electrode without the Ag2S layer. Our experimental results show that the improved efficiency is mainly due to the formation of Ag2S layer that may increase the light absorbance and reduce the recombination of photogenerated electrons with redox ions from the electrolyte. PMID:25411566

High temperature regenerable hydrogen sulfide removal agents

DOEpatents

Copeland, Robert J.

1993-01-01

A system for high temperature desulfurization of coal-derived gases using regenerable sorbents. One sorbent is stannic oxide (tin oxide, SnO.sub.2), the other sorbent is a metal oxide or mixed metal oxide such as zinc ferrite (ZnFe.sub.2 O.sub.4). Certain otherwise undesirable by-products, including hydrogen sulfide (H.sub.2 S) and sulfur dioxide (SO.sub.2) are reused by the system, and elemental sulfur is produced in the regeneration reaction. A system for refabricating the sorbent pellets is also described.

CYTOGENETIC EFFECTS OF PHOSPHINE INHALATION BY RODENTS

EPA Science Inventory

Phosphine (PH3) is a highly toxic grain fumigant that can be produced from the reaction of metal phosphides with water. o determine the in vivo cytogenetic effects of inhalation of PH3, male CD-1 mice were exposed to either 0, 5, 10, or 15 ppm target concentrations of PH3 for 6 h...

Phosphonate–Phosphinate Rearrangement

PubMed Central

2014-01-01

LiTMP metalated dimethyl N-Boc-phosphoramidates derived from 1-phenylethylamine and 1,2,3,4-tetrahydronaphthalen-1-ylamine highly selectively at the CH3O group to generate short-lived oxymethyllithiums. These isomerized to diastereomeric hydroxymethylphosphonamidates (phosphate–phosphonate rearrangement). However, s-BuLi converted the dimethyl N-Boc-phosphoramidate derived from 1-phenylethylamine to the N-Boc α-aminophosphonate preferentially. Only s-BuLi deprotonated dimethyl hydroxymethylphosphonamidates at the benzylic position and dimethyl N-Boc α-aminophosphonates at the CH3O group to induce phosphonate–phosphinate rearrangements. In the former case, the migration of the phosphorus substituent from the nitrogen to the carbon atom followed a retentive course with some racemization because of the involvement of a benzyllithium as an intermediate. PMID:25525945

Oxygenated Phosphine Fumigation for Control of Light Brown Apple Moth (Lepidoptera: Tortricidae) Eggs on Cut-Flowers.

PubMed

Liu, Samuel S; Liu, Yong-Biao; Simmons, Gregory S

2015-08-01

Light brown apple moth, Epiphyas postvittana (Walker), eggs were subjected to oxygenated phosphine fumigation treatments under 70% oxygen on cut flowers to determine efficacy and safety. Five cut flower species: roses, lilies, tulips, gerbera daisy, and pompon chrysanthemums, were fumigated in separate groups with 2,500 ppm phosphine for 72 h at 5°C. Egg mortality and postharvest quality of cut flowers were determined after fumigation. Egg mortalities of 99.7-100% were achieved among the cut flower species. The treatment was safe to all cut flowers except gerbera daisy. A 96-h fumigation treatment with 2,200 ppm phosphine of eggs on chrysanthemums cut flowers also did not achieve complete control of light brown apple moth eggs. A simulation of fumigation in hermetically sealed fumigation chambers with gerbera daisy showed significant accumulations of carbon dioxide and ethylene by the end of 72-h sealing. However, oxygenated phosphine fumigations with carbon dioxide and ethylene absorbents did not reduce the injury to gerbera daisy, indicating that it is likely that phosphine may directly cause the injury to gerbera daisy cut flowers. The study demonstrated that oxygenated phosphine fumigation is effective against light brown apple moth eggs. However, it may not be able to achieve the probit9 quarantine level of control and the treatment was safe to most of the cut flower species. Published by Oxford University Press on behalf of Entomological Society of America 2015. This work is written by US Government employees and is in the public domain in the US.

Selective sensing of two novel coordination polymers based on tris(4-carboxylphenyl)phosphine oxide for organic molecules and Fe3+ and Hg2+ ions

NASA Astrophysics Data System (ADS)

Huo, Liangqin; Zhang, Jie; Gao, Lingling; Wang, Xiaoqing; Fan, Liming; Fang, Kegong; Hu, Tuoping

2017-12-01

Two novel coordination polymers, formulated as {[Zn(HTPO)(bib)]·4H2O}n (1), {[Cu3(TPO)2 (bib)3]·2DMF·0.5EtOH·0.5H2O}n (2) (H3TPO = tris(4-carboxylphenyl)phosphine oxide; bib = 1,4-bis(1H-imidazol-4-yl) benzene), have been synthesized under solvothermal method and characterized by single-crystal X-ray diffraction, elemental analysis (EA), IR spectra, thermogravimetric (TG) analysis, powder X-ray diffraction (PXRD). Structural analysis reveals that complex 1 is a 2D 4-connected sheet with an intriguing 2D + 2D→2D network. Complex 2 displays a 3D 3,4-connected net with the point symbol of {103}2{106}3. Furthermore, the photoluminescence properties of 1 and 2 were investigated in the solid state and various solvent emulsions, the results show that 1 and 2 have better fluorescent recognition for organic molecules, Fe3+ and Hg2+ ions.

Effect of active zinc oxide dispersion on reduced graphite oxide for hydrogen sulfide adsorption at mid-temperature

NASA Astrophysics Data System (ADS)

Song, Hoon Sub; Park, Moon Gyu; Croiset, Eric; Chen, Zhongwei; Nam, Sung Chan; Ryu, Ho-Jung; Yi, Kwang Bok

2013-09-01

Composites of Zinc oxide (ZnO) with reduced graphite oxide (rGO) were synthesized and used as adsorbents for hydrogen sulfide (H2S) at 300 °C. Various characterization methods (TGA, XRD, FT-IR, TEM and XPS) were performed in order to link their H2S adsorption performance to the properties of the adsorbent's surface. Microwave-assisted reduction process of graphite oxide (GO) provided mild reduction environment, allowing oxygen-containing functional groups to remain on the rGO surface. It was confirmed that for the ZnO/rGO synthesize using the microwave-assisted reduction method, the ZnO particle size and the degree of ZnO dispersion remained stable over time at 300 °C, which was not the case for only the ZnO particles themselves. This stable highly dispersed feature allows for sustained high surface area over time. This was confirmed through breakthrough experiments for H2S adsorption where it was found that the ZnO/rGO composite showed almost four times higher ZnO utilization efficiency than ZnO itself. The effect of the H2 and CO2 on H2S adsorption was also investigated. The presence of hydrogen in the H2S stream had a positive effect on the removal of H2S since it allows a reducing environment for Znsbnd O and Znsbnd S bonds, leading to more active sites (Zn2+) to sulfur molecules. On the other hand, the presence of carbon dioxide (CO2) showed the opposite trend, likely due to the oxidation environment and also due to possible competitive adsorption between H2S and CO2.

Sulfidation treatment of copper-containing plating sludge towards copper resource recovery.

PubMed

Kuchar, D; Fukuta, T; Onyango, M S; Matsuda, H

2006-11-02

The present study is concerned with the sulfidation treatment of copper-containing plating sludge towards copper resource recovery by flotation of copper sulfide from treated sludge. The sulfidation treatment was carried out by contacting simulated or real copper plating sludge with Na(2)S solution for a period of 5 min to 24 h. The initial molar ratio of S(2-) to Cu(2+) (S(2-) to Me(2+) in the case of real sludge) was adjusted to 1.00, 1.25 or 1.50, while the solid to liquid ratio was set at 1:50. As a result, it was found that copper compounds were converted to various copper sulfides within the first 5 min. In the case of simulated copper sludge, CuS was identified as the main sulfidation product at the molar ratio of S(2-) to Cu(2+) of 1.00, while Cu(7)S(4) (Roxbyite) was mainly found at the molar ratios of S(2-) to Cu(2+) of 1.50 and 1.25. Based on the measurements of oxidation-reduction potential, the formation of either CuS or Cu(7)S(4) at different S(2-) to Cu(2+) molar ratios was attributed to the changes in the oxidation-reduction potential. By contrast, in the case of sulfidation treatment of real copper sludge, CuS was predominantly formed, irrespective of S(2-) to Me(2+) molar ratio.

Chemical dissolution of sulfide minerals

USGS Publications Warehouse

Chao, T.T.; Sanzolone, R.F.

1977-01-01

Chemical dissolution treatments involving the use of aqua regia, 4 N HNO3, H2O2-ascorbic acid, oxalic acid, KClO3+HCl, and KClO3+HCl followed by 4 N HNO3 were applied to specimens of nine common sulfide minerals (galena, chalcopyrite, cinnabar, molybdenite, orpiment, pyrite, stibnite, sphalerite, and tetrahedrite) mixed individually with a clay loam soil. The resultant decrease in the total sulfur content of the mixture, as determined by using the Leco induction furnace, was used to evaluate the effectiveness of each chemical treatment. A combination of KClO3+HCl followed by 4 N HNO3 boiling gently for 20 min has been shown to be very effective in dissolving all the sulfide minerals. This treatment is recommended to dissolve metals residing in sulfide minerals admixed with secondary weathering products, as one step in a fractionation scheme whereby metals in soluble and adsorbed forms, and those associated with organic materials and secondary oxides, are first removed by other chemical extractants.

Crystallinity of Fe-Ni Sulfides in Carbonaceous Chondrites

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.; Ohsumi, Kazumasa; Mikouchi, Takashi; Hagiya, Kenji; Le, Loan

2008-01-01

The main long-term goal of this research is to understand the physical conditions in the early solar nebula through the detailed characterization of a key class of mineral present in all primitive materials: Fe-Ni sulfides [1&2]. Fe-Ni sulfides can take dozens of structures, depending on the temperature of formation, as well as other physico-chemical factors which are imperfectly understood. Add to this the additional varying factor of Ni content, and we have a potentially sensitive cosmothermometer [3]. Unfortunately, this tool requires exact knowledge of the crystal structure of each grain being considered, and there have been few (none?) studies of the detailed structures of sulfides in chondritic materials. We report here on coordinated compositional and crystallographic investigation of Fe-Ni sulfides in diverse carbonaceous chondrites, initially Acfer 094 (the most primitive CM2 [4]) Tagish Lake (a unique type C2 [5]), a C1 lithology in Kaidun [6], Bali (oxidized CV3 [7]), and Efremovka (reduced CV3 [7]).

Controlled oxidation of organic sulfides to sulfoxides under ambient conditions by a series of titanium isopropoxide complexes using environmentally benign H2O2 as an oxidant.

PubMed

Panda, Manas K; Shaikh, Mobin M; Ghosh, Prasenjit

2010-03-07

Controlled oxidation of organic sulfides to sulfoxides under ambient conditions has been achieved by a series of titanium isopropoxide complexes that use environmentally benign H(2)O(2) as a primary oxidant. Specifically, the [N,N'-bis(2-oxo-3-R(1)-5-R(2)-phenylmethyl)-N,N'-bis(methylene-R(3))-ethylenediamine]Ti(O(i)Pr)(2) [R(1) = t-Bu, R(2) = Me, R(3) = C(7)H(5)O(2) (1b); R(1) = R(2) = t-Bu, R(3) = C(7)H(5)O(2) (2b); R(1) = R(2) = Cl, R(3) = C(7)H(5)O(2) (3b) and R(1) = R(2) = Cl, R(3) = C(6)H(5) (4b)] complexes efficiently catalyzed the sulfoxidation reactions of organic sulfides to sulfoxides at room temperature within 30 min of the reaction time using aqueous H(2)O(2) as an oxidant. A mechanistic pathway, modeled using density functional theory for a representative thioanisole substrate catalyzed by 4b, suggested that the reaction proceeds via a titanium peroxo intermediate 4c', which displays an activation barrier of 22.5 kcal mol(-1) (DeltaG(++)) for the overall catalytic cycle in undergoing an attack by the S atom of the thioanisole substrate at its sigma*-orbital of the peroxo moiety. The formation of the titanium peroxo intermediate was experimentally corroborated by a mild ionization atmospheric pressure chemical ionization (APCI) mass spectrometric technique.

An experimental study of Fe-Ni exchange between sulfide melt and olivine at upper mantle conditions: implications for mantle sulfide compositions and phase equilibria

NASA Astrophysics Data System (ADS)

Zhang, Zhou; von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

The behavior of nickel in the Earth's mantle is controlled by sulfide melt-olivine reaction. Prior to this study, experiments were carried out at low pressures with narrow range of Ni/Fe in sulfide melt. As the mantle becomes more reduced with depth, experiments at comparable conditions provide an assessment of the effect of pressure at low-oxygen fugacity conditions. In this study, we constrain the Fe-Ni composition of molten sulfide in the Earth's upper mantle via sulfide melt-olivine reaction experiments at 2 GPa, 1200 and 1400 °C, with sulfide melt X_{{{Ni}}}^{{{Sulfide}}}={{Ni}}/{{Ni+{Fe}}} (atomic ratio) ranging from 0 to 0.94. To verify the approach to equilibrium and to explore the effect of {f_{{{O}2}}} on Fe-Ni exchange between phases, four different suites of experiments were conducted, varying in their experimental geometry and initial composition. Effects of Ni secondary fluorescence on olivine analyses were corrected using the PENELOPE algorithm (Baró et al., Nucl Instrum Methods Phys Res B 100:31-46, 1995), "zero time" experiments, and measurements before and after dissolution of surrounding sulfides. Oxygen fugacities in the experiments, estimated from the measured O contents of sulfide melts and from the compositions of coexisting olivines, were 3.0 ± 1.0 log units more reduced than the fayalite-magnetite-quartz (FMQ) buffer (suite 1, 2 and 3), and FMQ - 1 or more oxidized (suite 4). For the reduced (suites 1-3) experiments, Fe-Ni distribution coefficients K_{{D}}{}={(X_{{{Ni}}}^{{{sulfide}}}/X_{{{Fe}}}^{{{sulfide}}})}/{(X_{{{Ni}}^{{{olivine}}}/X_{{{Fe}}}^{{{olivine}}})}} are small, averaging 10.0 ± 5.7, with little variation as a function of total Ni content. More oxidized experiments (suite 4) give larger values of K D (21.1-25.2). Compared to previous determinations at 100 kPa, values of K D from this study are chiefly lower, in large part owing to the more reduced conditions of the experiments. The observed difference does not seem

Sulfur and sulfides in chondrules

NASA Astrophysics Data System (ADS)

Marrocchi, Yves; Libourel, Guy

2013-10-01

The nature and distribution of sulfides within type I PO, POP and PP chondrules of the carbonaceous chondrite Vigarano (CV3) have been studied by secondary electron microscopy and electron microprobe. They occur predominantly as spheroidal blebs composed entirely of low-Ni iron sulfide (troilite, FeS) or troilite + magnetite but in less abundance in association with metallic Fe-Ni beads in opaque assemblages. Troilites are mainly located within the low-Ca pyroxene outer zone and their amounts increase with the abundance of low-Ca pyroxene within chondrules, suggesting co-crystallization of troilite and low-Ca pyroxene during high-temperature events. We show that sulfur concentration and sulfide occurrence in chondrules obey high temperature sulfur solubility and saturation laws. Depending on the fS2 and fO2 of the surrounding gas and on the melt composition, mainly the FeO content, sulfur dissolved in chondrule melts may eventually reach a concentration limit, the sulfur content at sulfide saturation (SCSS), at which an immiscible iron sulfide liquid separates from the silicate melt. The occurrence of both a silicate melt and an immiscible iron sulfide liquid is further supported by the non-wetting behavior of sulfides on silicate phases in chondrules due to the high interfacial tension between their precursor iron-sulfide liquid droplets and the surrounding silicate melt during the high temperature chondrule-forming event. The evolution of chondrule melts from PO to PP towards more silicic compositions, very likely due to high PSiO(g) of the surrounding nebular gas, induces saturation of FeS at much lower S content in PP than in PO chondrules, leading to the co-crystallization of iron sulfides and low-Ca pyroxenes. Conditions of co-saturation of low-Ca pyroxene and FeS are only achieved in non canonical environments characterized by high partial pressures of sulfur and SiO and redox conditions more oxidizing than IW-3. Fe and S mass balance calculations also

Nucleoside-O-Methyl-(H)-Phosphinates: Novel Monomers for the Synthesis of Methylphosphonate Oligonucleotides Using H-Phosphonate Chemistry.

PubMed

Kostov, Ondřej; Páv, Ondřej; Rosenberg, Ivan

2017-09-18

This unit comprises the straightforward synthesis of protected 2'-deoxyribonucleoside-O-methyl-(H)-phosphinates in both 3'- and 5'-series. These compounds represent a new class of monomers compatible with the solid-phase synthesis of oligonucleotides using H-phosphonate chemistry and are suitable for the preparation of both 3'- and 5'-O-methylphosphonate oligonucleotides. The synthesis of 4-toluenesulfonyloxymethyl-(H)-phosphinic acid as a new reagent for the preparation of O-methyl-(H)-phosphinic acid derivatives is described. © 2017 by John Wiley & Sons, Inc. Copyright © 2017 John Wiley & Sons, Inc.

Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

NASA Technical Reports Server (NTRS)

Caldwell, D.

1985-01-01

Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

Variation in trace element content of magnetite crystallized from a fractionating sulfide liquid, Sudbury, Canada: Implications for provenance discrimination

NASA Astrophysics Data System (ADS)

Dare, Sarah A. S.; Barnes, Sarah-Jane; Beaudoin, Georges

2012-07-01

Laser ablation ICP-MS analysis has been applied to many accessory minerals in order to understand better the process by which the rock formed and for provenance discrimination. We have determined trace element concentrations of Fe-oxides in massive sulfides that form Ni-Cu-PGE deposits at the base of the Sudbury Igneous Complex in Canada. The samples represent the crystallization products of fractionating sulfide liquids and consist of early-forming Fe-rich monosulfide solution (MSS) cumulates and residual Cu-rich intermediate solid solution (ISS). This study shows that Fe-oxide geochemistry is a sensitive petrogenetic indicator for the degree of fractionation of the sulfide liquid and provides an insight into the partitioning of elements between sulfide and Fe-oxide phases. In addition, it is useful in determining the provenance of detrital Fe-oxide. In a sulfide melt, all lithophile elements (Cr, Ti, V, Al, Mn, Sc, Nb, Ga, Ge, Ta, Hf, W and Zr) are compatible into Fe-oxide. The concentrations of these elements are highest in the early-forming Fe-oxide (titanomagnetite) which crystallized with Fe-rich MSS. Upon the continual crystallization of Fe-oxide from the sulfide liquid, the lithophile elements gradually decrease so that late-forming Fe-oxide (magnetite), which crystallized from the residual Cu-rich liquid, is depleted in these elements. This behavior is in contrast with Fe-oxides that crystallized from a fractionating silicate melt, whereby the concentration of incompatible elements, such as Ti, increases rather than decreases. The behavior of the chalcophile elements in magnetite is largely controlled by the crystallization of the sulfide minerals with only Ni, Co, Zn, Mo, Sn and Pb present above detection limit in magnetite. Nickel, Mo and Co are compatible in Fe-rich MSS and thus the co-crystallizing Fe-oxide is depleted in these elements. In contrast, magnetite that crystallized later from the fractionated liquid with Cu-rich ISS is enriched in Ni, Mo

Phosphine-catalyzed cycloadditions of allenic ketones: new substrates for nucleophilic catalysis.

PubMed

Wallace, Debra J; Sidda, Rachel L; Reamer, Robert A

2007-02-02

A range of phosphine-catalyzed cycloaddition reactions of allenic ketones have been studied, extending the scope of these processes from the more widely used 2,3-butadienoates to allow access to a number of synthetically useful products. Reaction of allenyl methyl ketone 4 with exo-enones afforded spirocyclic compounds in good regioselectivity and promising enantioselectivity via a [2 + 3] cycloaddtion. Aromatic allenyl ketones undergo a phosphine-promoted dimerization to afford functionalized pyrans, leading to a formal [2 + 4] Diels-Alder product, but did not react in the [2 + 3] cycloaddition. The results from other reactions that had found utility with 2,3-butadienoates are also reported.

Formation Mechanism of Oxide-Sulfide Complex Inclusions in High-Sulfur-Containing Steel Melts

NASA Astrophysics Data System (ADS)

Shin, Jae Hong; Park, Joo Hyun

2018-02-01

The [S] content in resulfurized steel is controlled in the range of 200 to 800 ppm to ensure good machinability and workability. It is well known that "MgAl2O4(spinel)+CaS" complex inclusions are formed in molten steel during the ladle refining process, and these cause nozzle clogging during continuous casting. Thus, in the present study, the "Refractory-Slag-Metal-Inclusions (ReSMI)" multiphase reaction model was employed in conjunction with experiments to investigate the influence of slag composition and [S] content in the steel on the formation of oxide-sulfide complex inclusions. The critical [S] and [Al] contents necessary for the precipitation of CaS in the CaO-Al2O3-MgO-SiO2 (CAMS) oxide inclusions were predicted from the composition of the liquid inclusions, as observed by scanning electron microscopy-electron dispersive spectrometry (SEM-EDS) and calculated using the ReSMI multiphase reaction model. The critical [S] content increases with increasing content of SiO2 in the slag at a given [Al] content. Formation mechanisms for spinel+CaS and spinel+MnS complex inclusions were also proposed.

Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts

NASA Astrophysics Data System (ADS)

Manoochehri, S.; Schmidt, M. W.; Guenther, D.

2013-12-01

both, the nucleation of newly formed sulfide droplets and the interconnectivity of separate droplets. The interfacial energies between sulfide melt and silicate or oxide crystals is even higher than for silicate melt, consequently in experiments with chromite, sulfide segregation is even more hindered. Partition coefficients of 50 elements between a sulfide and a silicate melt are determined as a function of differing temperature between 1250 - 1380 °C. As a proxy to investigate the bond strength of network modifier cations, the relation between the partition coefficients and ionic potentials of different groups of elements has been determined.

An experimental and theoretical method for determination of standard electrode potential for the redox couple diphenyl sulfone/diphenyl sulfide

NASA Astrophysics Data System (ADS)

Song, Y. Z.; Wei, K. X.; Lv, J. S.

2013-12-01

DFT calculations were performed for diphenyl sulfide and diphenyl sulfone. The electrochemistry of diphenyl sulfide on the gold electrode was investigated by cyclic voltammety and the results show that standard electrode potential for redox couple diphenyl sulfone/diphenyl sulfide is 1.058 V, which is consistent with that of 1.057 calculated at B3LYP/6-31++G( d, p)-IEFPCM level. The front orbit theory and Mulliken charges of molecular explain well on the oxidation of diphenyl sulfide in oxidative desulfurization. According to equilibrium theory the experimental equilibrium constant in the oxidative desulfurization of H2O2, is 1.17 × 1048, which is consistent with the theoretical equilibrium constant is 2.18 × 1048 at B3LYP/6-31++G( d, p)-IEFPCM level.

Red soil as a regenerable sorbent for high temperature removal of hydrogen sulfide from coal gas.

PubMed

Ko, Tzu-Hsing; Chu, Hsin; Lin, Hsiao-Ping; Peng, Ching-Yu

2006-08-25

In this study, hydrogen sulfide (H(2)S) was removed from coal gas by red soil under high temperature in a fixed-bed reactor. Red soil powders were collected from the northern, center and southern of Taiwan. They were characterized by XRPD, porosity analysis and DCB chemical analysis. Results show that the greater sulfur content of LP red soils is attributed to the higher free iron oxides and suitable sulfidation temperature is around 773K. High temperature has a negative effect for use red soil as a desulfurization sorbent due to thermodynamic limitation in a reduction atmosphere. During 10 cycles of regeneration, after the first cycle the red soil remained stable with a breakthrough time between 31 and 36 min. Hydrogen adversely affects sulfidation reaction, whereas CO exhibits a positive effect due to a water-shift reaction. COS was formed during the sulfidation stage and this was attributed to the reaction of H(2)S and CO. Results of XRPD indicated that, hematite is the dominant active species in fresh red soil and iron sulfide (FeS) is a product of the reaction between hematite and hydrogen sulfide in red soils. The spinel phase FeAl(2)O(4) was found during regeneration, moreover, the amount of free iron oxides decreased after regeneration indicating the some of the free iron oxide formed a spinel phase, further reducting the overall desulfurization efficiency.

Dimethyl Sulfide-Dimethyl Ether and Ethylene Oxide-Ethylene Sulfide Complexes Investigated by Fourier Transform Microwave Spectroscopy and AB Initio Calculation

NASA Astrophysics Data System (ADS)

Kawashima, Yoshiyuki; Tatamitani, Yoshio; Mase, Takayuki; Hirota, Eizi

2015-06-01

The ground-state rotational spectra of the dimethyl sulfide-dimethyl ether (DMS-DME) and the ethylene oxide and ethylene sulfide (EO-ES) complexes were observed by Fourier transform microwave spectroscopy, and a-type and c-type transitions were assigned for the normal, 34S, and three 13C species of the DMS-DME and a-type and b-type rotational transitions for the normal, 34S, and two 13C species of the EO-ES. The observed transitions were analyzed by using an S-reduced asymmetric-top rotational Hamiltonian. The rotational parameters thus derived for the DMS-DME were found consistent with a structure of Cs symmetry with the DMS bound to the DME by two C-H(DMS)---O and one S---H-C(DME) hydrogen bonds. The barrier height V3 to internal rotation of the "free" methyl group in the DME was determined to be 915.4 (23) wn, which is smaller than that of the DME monomer, 951.72 (70) wn, and larger than that of the DME dimer, 785.4 (52) wn. For the EO-ES complex the observed data were interpreted in the terms of an antiparallel Cs geometry with the EO bound to the ES by two C-H(ES)---O and two S---H-C(EO) hydrogen bonds. We have applied a natural bond orbital (NBO) analysis to the DMS-DME and EO-ES to calculate the stabilization energy CT (= ΔEσσ*), which were closely correlated with the binding energy EB, as found for other related complexes. Y. Niide and M. Hayashi, J. Mol. Spectrosc. 220, 65-79 (2003). Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati, and J. L. Alonso, J. Am. Chem. Soc. 124, 2739-2743 (2002).

Functional consortium for denitrifying sulfide removal process.

PubMed

Chen, Chuan; Ren, Nanqi; Wang, Aijie; Liu, Lihong; Lee, Duu-Jong

2010-03-01

Denitrifying sulfide removal (DSR) process simultaneously converts sulfide, nitrate, and chemical oxygen demand from industrial wastewaters to elemental sulfur, nitrogen gas, and carbon dioxide, respectively. This investigation utilizes a dilution-to-extinction approach at 10(-2) to 10(-6) dilutions to elucidate the correlation between the composition of the microbial community and the DSR performance. In the original suspension and in 10(-2) dilution, the strains Stenotrophomonas sp., Thauera sp., and Azoarcus sp. are the heterotrophic denitrifiers and the strains Paracoccus sp. and Pseudomonas sp. are the sulfide-oxidizing denitrifers. The 10(-4) dilution is identified as the functional consortium for the present DSR system, which comprises two functional strains, Stenotrophomonas sp. strain Paracoccus sp. At 10(-6) dilution, all DSR performance was lost. The functions of the constituent cells in the DSR granules were discussed based on data obtained using the dilution-to-extinction approach.

Empirical equations to predict the sulfur content of mafic magmas at sulfide saturation and applications to magmatic sulfide deposits

NASA Astrophysics Data System (ADS)

Li, Chusi; Ripley, Edward M.

2005-03-01

composition of the parent magma of the Sonju Lake Intrusion the presented equation indicates that sulfide saturation would have been reached at 60% crystallization, when iron oxide was a liquidus mineral; the prediction is in agreement with field evidence which indicates that PGE-enrichment occurs in the oxide-rich gabbro zone. Contamination and mixing processes that may be related to the attainment of sulfide saturation in mafic magmas can also be evaluated. Mixing of a siliceous melt and a liquid of olivine tholeiite composition, similar to that thought to be a reasonable parental composition for many Duluth Complex intrusions, can induce sulfide saturation at mixing ratios in excess of 0.1. If the contaminant contains low quantities of sulfur the mixing ratio required to promote saturation is reduced. Mixing of mafic magmas at various stages of fractionation is evaluated using magma compositions that are thought to be appropriate for the generation of the Merensky Reef in the Bushveld Complex. Magma mixing is shown to be an effective process for the attainment of sulfide saturation, depending strongly on the sulfur concentrations of the end-member magmas.

Giant Hydrogen Sulfide Plume in the Oxygen Minimum Zone off Peru Supports Chemolithoautotrophy

PubMed Central

Großkopf, Tobias; Kalvelage, Tim; Löscher, Carolin R.; Paulmier, Aurélien; Contreras, Sergio; Siegel, Herbert; Holtappels, Moritz; Rosenstiel, Philip; Schilhabel, Markus B.; Graco, Michelle; Schmitz, Ruth A.; Kuypers, Marcel M. M.; LaRoche, Julie

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km2, which contained ∼2.2×104 tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km3 the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel further

Giant hydrogen sulfide plume in the oxygen minimum zone off Peru supports chemolithoautotrophy.

PubMed

Schunck, Harald; Lavik, Gaute; Desai, Dhwani K; Großkopf, Tobias; Kalvelage, Tim; Löscher, Carolin R; Paulmier, Aurélien; Contreras, Sergio; Siegel, Herbert; Holtappels, Moritz; Rosenstiel, Philip; Schilhabel, Markus B; Graco, Michelle; Schmitz, Ruth A; Kuypers, Marcel M M; Laroche, Julie

2013-01-01

In Eastern Boundary Upwelling Systems nutrient-rich waters are transported to the ocean surface, fuelling high photoautotrophic primary production. Subsequent heterotrophic decomposition of the produced biomass increases the oxygen-depletion at intermediate water depths, which can result in the formation of oxygen minimum zones (OMZ). OMZs can sporadically accumulate hydrogen sulfide (H2S), which is toxic to most multicellular organisms and has been implicated in massive fish kills. During a cruise to the OMZ off Peru in January 2009 we found a sulfidic plume in continental shelf waters, covering an area >5500 km(2), which contained ∼2.2×10(4) tons of H2S. This was the first time that H2S was measured in the Peruvian OMZ and with ∼440 km(3) the largest plume ever reported for oceanic waters. We assessed the phylogenetic and functional diversity of the inhabiting microbial community by high-throughput sequencing of DNA and RNA, while its metabolic activity was determined with rate measurements of carbon fixation and nitrogen transformation processes. The waters were dominated by several distinct γ-, δ- and ε-proteobacterial taxa associated with either sulfur oxidation or sulfate reduction. Our results suggest that these chemolithoautotrophic bacteria utilized several oxidants (oxygen, nitrate, nitrite, nitric oxide and nitrous oxide) to detoxify the sulfidic waters well below the oxic surface. The chemolithoautotrophic activity at our sampling site led to high rates of dark carbon fixation. Assuming that these chemolithoautotrophic rates were maintained throughout the sulfidic waters, they could be representing as much as ∼30% of the photoautotrophic carbon fixation. Postulated changes such as eutrophication and global warming, which lead to an expansion and intensification of OMZs, might also increase the frequency of sulfidic waters. We suggest that the chemolithoautotrophically fixed carbon may be involved in a negative feedback loop that could fuel

Effect of sulfide on As(III) and As(V) sequestration by ferrihydrite.

PubMed

Zhao, Zhixi; Wang, Shaofeng; Jia, Yongfeng

2017-10-01

The sulfide-induced change in arsenic speciation is often coupled to iron geochemical processes, including redox reaction, adsorption/desorption and precipitation/dissolution. Knowledge about how sulfide influenced the coupled geochemistry of iron and arsenic was not explored well up to now. In this work, retention and mobilization of As(III) and As(V) on ferrihydrite in sulfide-rich environment was studied. The initial oxidation states of arsenic and the contact order of sulfide notably influenced arsenic sequestration on ferrihydrite. For As(III) systems, pre-sulfidation of As(III) decreased arsenic sequestration mostly. The arsenic adsorption capacity decreased about 50% in comparison with the system without sulfide addition. For As(V) systems, pre-sulfidation of ferrihydrite decreased 30% sequestration of arsenic on ferrihydrite. Reduction of ferrihydrite by sulfide in As(V) system was higher than that in As(III) system. Geochemical modeling calculations identified formation of thioarsenite in the pre-sulfidation of As(III) system. Formation of arsenic thioanions enhanced As solubility in the pre-sulfidation of As(III) system. The high concentration of sulfide and Fe(II) in pre-sulfidation of ferrihydrite system contributed to saturation of FeS. This supplied new solid phase to immobilize soluble arsenic in aqueous phase. X-ray absorption near edge spectroscopy (XANES) of sulfur K-edge, arsenic K-edge and iron L-edge analysis gave the consistent evidence for the sulfidation reaction of arsenic and ferrihydrite under specific geochemical settings. Copyright © 2017 Elsevier Ltd. All rights reserved.

Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands.

PubMed

Kaeser, Adrien; Mohankumar, Meera; Mohanraj, John; Monti, Filippo; Holler, Michel; Cid, Juan-José; Moudam, Omar; Nierengarten, Iwona; Karmazin-Brelot, Lydia; Duhayon, Carine; Delavaux-Nicot, Béatrice; Armaroli, Nicola; Nierengarten, Jean-François

2013-10-21

Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2](+) and [Cu(PP)2](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.

Tetra­chlorido[(diphenyl­phosphino)diphenyl­phosphine oxide-κO]zirconium(IV) benzene monosolvate

PubMed Central

Ogawa, Takahiko; Kajita, Yuji; Masuda, Hideki

2009-01-01

In the title centrosymmetric mononuclear ZrIV compound, [ZrCl4{P(O)(C6H5)2P(C6H5)2}2]·C6H6, the central ZrIV ion is coordinated by two O atoms from two symmetry-related (diphenyl­phosphino)diphenyl­phosphine ligands and four Cl atoms in a distorted octahedral geometry with the four Cl atoms in the equatorial positions. The mol­ecule lies about a center of inversion and the benzene solvent mol­ecule about another center of inversion. The P=O bond [1.528 (2) Å] is slightly longer than a typical P=O double bond (average 1.500 ). PMID:21577468

Biaryl Phosphine Ligands in Palladium-Catalyzed Amination

PubMed Central

Surry, David S.

2012-01-01

Palladium-catalyzed amination of aryl halides has undergone rapid development in the last 12 years. This has been largely driven by implementation of new classes of ligands. Biaryl phosphines have proven to provide especially active catalysts in this context. This review discusses the applications that these catalysts have found in C-N cross-coupling in heterocycle synthesis, pharmaceuticals, materials science and natural product synthesis. PMID:18663711

Hydroxyalkyl phosphine compounds for use as diagnostic and therapeutic pharmaceuticals

DOEpatents

Katti, K.V.; Singh, P.R.; Reddy, V.S.; Katti, K.K.; Volkert, W.A.; Ketring, A.R.

1999-03-02

This research discloses a compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical comprises a functionalized hydroxyalkyl phosphine ligand and a metal combined with the ligand. 16 figs.

Detection of the Free-Living Forms of Sulfide-Oxidizing Gill Endosymbionts in the Lucinid Habitat (Thalassia testudinum Environment)

PubMed Central

Gros, Olivier; Liberge, Martine; Heddi, Abdelaziz; Khatchadourian, Chaqué; Felbeck, Horst

2003-01-01

Target DNA from the uncultivable Codakia orbicularis endosymbiont was PCR amplified from sea-grass sediment. To confirm that such amplifications originated from intact bacterial cells rather than free DNA, whole-cell hybridization (fluorescence in situ hybridization technique) with the specific probe Symco2 was performed along with experimental infection of aposymbiotic juveniles placed in contact with the same sediment. Taken together, the data demonstrate that the sulfide-oxidizing gill endosymbiont of Codakia orbicularis is present in the environment as a free-living uncultivable form. PMID:14532089

Detection of the free-living forms of sulfide-oxidizing gill endosymbionts in the lucinid habitat (Thalassia testudinum environment).

PubMed

Gros, Olivier; Liberge, Martine; Heddi, Abdelaziz; Khatchadourian, Chaqué; Felbeck, Horst

2003-10-01

Target DNA from the uncultivable Codakia orbicularis endosymbiont was PCR amplified from sea-grass sediment. To confirm that such amplifications originated from intact bacterial cells rather than free DNA, whole-cell hybridization (fluorescence in situ hybridization technique) with the specific probe Symco2 was performed along with experimental infection of aposymbiotic juveniles placed in contact with the same sediment. Taken together, the data demonstrate that the sulfide-oxidizing gill endosymbiont of Codakia orbicularis is present in the environment as a free-living uncultivable form.

The Determination of Hydrogen Sulfide in Stack Gases, Iodometric Titration After Sulfite Removal.

ERIC Educational Resources Information Center

Robles, E. G.

The determination of hydrogen sulfide in effluents from coal-fired furnaces and incinerators is complicated by the presence of sulfur oxides (which form acids). Organic compounds also may interfere with or prevent the formation of the cadmium sulfide precipitate or give false positive results because of reaction with iodine. The report presents a…

Synthesis and structural characterisation of a novel phosphine-borane-stabilised dicarbanion and an unusual bis(phosphine-borane).

PubMed

Izod, Keith; McFarlane, William; Tyson, Brent V; Clegg, William; Harrington, Ross W

2004-03-07

The reaction between the phosphine-borane-substituted alkene [Pr(n)(2)P(BH(3))](Me(3)Si)C[double bond]CH(2) and elemental lithium in THF yields the complex [(pmdeta)Li[Pr(n)(2)P(BH(3))](Me(3)Si)CCH(2)](2)(2b) after recrystallisation; an X-ray crystallographic study of 2b reveals that the lithium is bound to the BH(3) hydrogens of the ligand, with no Li-C(carbanion) contact.

Iron sulfide deposits at Wadi Wassat, Kingdom of Saudi Arabia

USGS Publications Warehouse

Roberts, R.J.; Rossman, D.L.; Bagdady, A.Y.; Conway, C.M.; Helaby, A.M.

1981-01-01

Massive and disseminated iron sulfide deposits in Wadi Wassat form lenticular, stratabound deposits in cherty Precambrian sedimentary rocks interlayered with Precambrian calcareous sedimentary rocks, pyroclastic rocks, and andesitic flow rocks. These rocks have been cut by a wide variety of plutonic and dike rocks including gabbro, diorite, granodiorite, diabase, rhyolite, and granite. The zone containing the sulfide lenses is nearly 16 km long and is cut off by granitic rocks at both the northern and southern ends. The lenses are as much as 200 m thick; one can be traced along strike for more than 4 km. The lenses consist mostly of iron sulfides. Pyrite is the principal sulfide mineral; near intrusive bodies the pyrite has been partially converted to pyrrhotite and locally mobilized into fractures. The sulfides have been oxidized to a depth of about 25 m. Preliminary calculations indicate that about 107,500,000 tons of sulfides, averaging 40 percent iron and 35 percent sulfur, are available to a depth of i00 m. Small amounts of nickel, cobalt, zinc, and copper are also present, but at metal prices prevailing in early 1981, these do not constitute significant resources.

Zelda and company - Petrogenesis of sulfide-rich Fremdlinge and constraints on solar nebula processes

NASA Technical Reports Server (NTRS)

Armstrong, John T.; Hutcheon, Ian D.; Wasserburg, G. J.

1987-01-01

A detailed petrographic and chemical study of Zelda (a gigantic sulfide-rich Fremdling from the Allende Ca-rich inclusion, CAI, Egg 6) and its contact with the host was conducted using analytical SEM and electron-microprobe techniques, and the results were compared with those obtained on other sulfide-rich and oxide-rich Fremdlinge. Strong evidence is presented that Zelda, a type-example of sulfide-rich Fremdlinge, has been formed from a preexisting Ur-Fremdling, similar by composition to Willy, by closed-system sulfidization of magnetite and metal. At least two different sulfidization mechanisms appear to have occurred in altering Fremdlinge: one producing compositionally homogeneous equigranular objects such as Zelda, the other producing compositionally and texturally heterogeneous objects.

Volcanogenic massive sulfide occurrence model: Chapter C in Mineral deposit models for resource assessment

USGS Publications Warehouse

Shanks, W.C. Pat; Koski, Randolph A.; Mosier, Dan L.; Schulz, Klaus J.; Morgan, Lisa A.; Slack, John F.; Ridley, W. Ian; Dusel-Bacon, Cynthia; Seal, Robert R.; Piatak, Nadine M.; Shanks, W.C. Pat; Thurston, Roland

2012-01-01

An unusual feature of VMS deposits is the common association of stratiform "exhalative" deposits precipitated from hydrothermal fluids emanating into bottom waters. These deposits may extend well beyond the margins of massive sulfide and are typically composed of silica, iron, and manganese oxides, carbonates, sulfates, sulfides, and tourmaline.

Sulfide Homeostasis and Nitroxyl Intersect via Formation of Reactive Sulfur Species in Staphylococcus aureus.

PubMed

Peng, Hui; Shen, Jiangchuan; Edmonds, Katherine A; Luebke, Justin L; Hickey, Anne K; Palmer, Lauren D; Chang, Feng-Ming James; Bruce, Kevin A; Kehl-Fie, Thomas E; Skaar, Eric P; Giedroc, David P

2017-01-01

Staphylococcus aureus is a commensal human pathogen and a major cause of nosocomial infections. As gaseous signaling molecules, endogenous hydrogen sulfide (H 2 S) and nitric oxide (NO·) protect S. aureus from antibiotic stress synergistically, which we propose involves the intermediacy of nitroxyl (HNO). Here, we examine the effect of exogenous sulfide and HNO on the transcriptome and the formation of low-molecular-weight (LMW) thiol persulfides of bacillithiol, cysteine, and coenzyme A as representative of reactive sulfur species (RSS) in wild-type and Δ cstR strains of S. aureus . CstR is a per- and polysulfide sensor that controls the expression of a sulfide oxidation and detoxification system. As anticipated, exogenous sulfide induces the cst operon but also indirectly represses much of the CymR regulon which controls cysteine metabolism. A zinc limitation response is also observed, linking sulfide homeostasis to zinc bioavailability. Cellular RSS levels impact the expression of a number of virulence factors, including the exotoxins, particularly apparent in the Δ cstR strain. HNO, like sulfide, induces the cst operon as well as other genes regulated by exogenous sulfide, a finding that is traced to a direct reaction of CstR with HNO and to an endogenous perturbation in cellular RSS, possibly originating from disassembly of Fe-S clusters. More broadly, HNO induces a transcriptomic response to Fe overload, Cu toxicity, and reactive oxygen species and reactive nitrogen species and shares similarity with the sigB regulon. This work reveals an H 2 S/NO· interplay in S. aureus that impacts transition metal homeostasis and virulence gene expression. IMPORTANCE Hydrogen sulfide (H 2 S) is a toxic molecule and a recently described gasotransmitter in vertebrates whose function in bacteria is not well understood. In this work, we describe the transcriptomic response of the major human pathogen Staphylococcus aureus to quantified changes in levels of cellular

Study on the surface sulfidization behavior of smithsonite at high temperature

NASA Astrophysics Data System (ADS)

Lv, Jin-fang; Tong, Xiong; Zheng, Yong-xing; Xie, Xian; Wang, Cong-bing

2018-04-01

Surface sulfidization behavior of smithsonite at high temperature was investigated by X-ray powder diffractometer (XRD) along with thermodynamic calculation, X-ray photoelectron spectroscopy (XPS) and electron probe microanalysis (EPMA). The XRD and thermodynamic analyses indicated that the smithsonite was decomposed into zincite at high temperatures. After introducing a small amount of pyrite, artificial sulfides were formed at surface of the obtained zincite. The XPS analyses revealed that the sulfide species including zinc sulfide and zinc disulfide were generated at the zincite surface. The EPMA analyses demonstrated that the film of sulfides was unevenly distributed at the zincite surface. The average concentration of elemental sulfur at the sample surface increased with increasing of pyrite dosage. A suitable mole ratio of FeS2 to ZnCO3 for the surface thermal modification was determined to be about 0.3. These findings can provide theoretical support for improving the process during which the zinc recovery from refractory zinc oxide ores is achieved by xanthate flotation.

Effect of Nitrogen Oxides on Elemental Mercury Removal by Nanosized Mineral Sulfide.

PubMed

Li, Hailong; Zhu, Lei; Wang, Jun; Li, Liqing; Lee, Po-Heng; Feng, Yong; Shih, Kaimin

2017-08-01

Because of its large surface area, nanosized zinc sulfide (Nano-ZnS) has been demonstrated in a previous study to be efficient for removal of elemental mercury (Hg 0 ) from coal combustion flue gas. The excellent mercury adsorption performance of Nano-ZnS was found to be insusceptible to water vapor, sulfur dioxide, and hydrogen chloride. However, nitrogen oxides (NO X ) apparently inhibited mercury removal by Nano-ZnS; this finding was unlike those of many studies on the promotional effect of NO X on Hg 0 removal by other sorbents. The negative effect of NO X on Hg 0 adsorption over Nano-ZnS was systematically investigated in this study. Two mechanisms were identified as primarily responsible for the inhibitive effect of NO X on Hg 0 adsorption over Nano-ZnS: (1) active sulfur sites on Nano-ZnS were oxidized to inactive sulfate by NO X ; and (2) the chemisorbed mercury, i.e., HgS, was reduced to Hg 0 by NO X . This new insight into the role of NO X in Hg 0 adsorption over Nano-ZnS can help to optimize operating conditions, maximize Hg 0 adsorption, and facilitate the application of Nano-ZnS as a superior alternative to activated carbon for Hg 0 removal using existing particulate matter control devices in power plants.

Sulfur-Oxidizing Bacteria in Soap Lake (Washington State), a Meromictic, Haloalkaline Lake with an Unprecedented High Sulfide Content▿

PubMed Central

Sorokin, Dimitry Y.; Foti, Mirjam; Pinkart, Holly C.; Muyzer, Gerard

2007-01-01

Culture-dependent and -independent techniques were used to study the diversity of chemolithoautotrophic sulfur-oxidizing bacteria in Soap Lake (Washington State), a meromictic, haloalkaline lake containing an unprecedentedly high sulfide concentration in the anoxic monimolimnion. Both approaches revealed the dominance of bacteria belonging to the genus Thioalkalimicrobium, which are common inhabitants of soda lakes. A dense population of Thioalkalimicrobium (up to 107 cells/ml) was found at the chemocline, which is characterized by a steep oxygen-sulfide gradient. Twelve Thioalkalimicrobium strains exhibiting three different phenotypes were isolated in pure culture from various locations in Soap Lake. The isolates fell into two groups according to 16S rRNA gene sequence analysis. One of the groups was closely related to T. cyclicum, which was isolated from Mono Lake (California), a transiently meromictic, haloalkaline lake. The second group, consisting of four isolates, was phylogenetically and phenotypically distinct from known Thioalkalimicrobium species and unique to Soap Lake. It represented a new species, for which we suggest the name Thioalkalimicrobium microaerophilum sp. nov. PMID:17114324

Nucleophilic Chiral Phosphines: Powerful and Versatile Catalysts for Asymmetric Annulations

PubMed Central

Xiao, Yumei; Guo, Hongchao; Kwon, Ohyun

2016-01-01

Recent advances in chiral-phosphine-catalyzed asymmetric annulation reactions; including annulations of allenes, alkynes, Morita–Baylis–Hillman (MBH) carbonates, and ketenes; and their applications in the synthesis of bioactive molecules and natural products are reviewed. PMID:28077882

Competition for sulfide among colorless and purple sulfur bacteria in cyanobacterial mats

NASA Technical Reports Server (NTRS)

Jorgensen, B. B.; Des Marais, D. J.

1986-01-01

The vertical zonation of light, O2, H2S, pH, and sulfur bacteria was studied in two benthic cyanobacterial mats from hypersaline ponds at Guerrero Negro, Baja California, Mexico. The physical-chemical gradients were analyzed in the upper few mm at < or = 100 micrometers spatial resolution by microelectrodes and by a fiber optic microprobe. In mats, where oxygen produced by photosynthesis diffused far below the depth of the photic zone, colorless sulfur bacteria (Beggiatoa sp.) were the dominant sulfide oxidizing organisms. In a mat, where the O2-H2S interface was close to the photic zone, but yet received no significant visible light, purple sulfur bacteria (Chromatium sp.) were the dominant sulfide oxidizers. Analysis of the spectral light distribution here showed that the penetration of only 1% of the incident near-IR light (800-900 nm) into the sulfide zone was sufficient for the mass development of Chromatium in a narrow band of 300 micromoles thickness. The balance between O2 and light penetration down into the sulfide zone thus determined in micro-scale which type of sulfur bacteria became dominant.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

The hydrogen sulfide metabolite trimethylsulfonium is found in human urine

NASA Astrophysics Data System (ADS)

Lajin, Bassam; Francesconi, Kevin A.

2016-06-01

Hydrogen sulfide is the third and most recently discovered gaseous signaling molecule following nitric oxide and carbon monoxide, playing important roles both in normal physiological conditions and disease progression. The trimethylsulfonium ion (TMS) can result from successive methylation reactions of hydrogen sulfide. No report exists so far about the presence or quantities of TMS in human urine. We developed a method for determining TMS in urine using liquid chromatography-electrospray ionization-triple quadrupole mass spectrometry (LC-ESI-QQQ), and applied the method to establish the urinary levels of TMS in a group of human volunteers. The measured urinary levels of TMS were in the nanomolar range, which is commensurate with the steady-state tissue concentrations of hydrogen sulfide previously reported in the literature. The developed method can be used in future studies for the quantification of urinary TMS as a potential biomarker for hydrogen sulfide body pools.

Temperature and cell-type dependency of sulfide effects on mitochondrial respiration.

PubMed

Groeger, Michael; Matallo, Jose; McCook, Oscar; Wagner, Florian; Wachter, Ulrich; Bastian, Olga; Gierer, Saskia; Reich, Vera; Stahl, Bettina; Huber-Lang, Markus; Szabó, Csaba; Georgieff, Michael; Radermacher, Peter; Calzia, Enrico; Wagner, Katja

2012-10-01

Previous studies suggest that sulfide-induced inhibition of cytochrome c oxidase (cCox) and, consequently, the metabolic and toxic effects of sulfide are less pronounced at low body temperature. Because the temperature-dependent effects of sulfide on the inflammatory response are still a matter of debate, we investigated the impact of varying temperature on the cCox excess capacity and the mitochondrial sulfide oxidation by the sulfide-ubiquinone oxidoreductase in macrophage-derived cell lines (AMJ2-C11 and RAW 264.7). Using an oxygraph chamber, the inhibition of mitochondrial respiration was measured by stepwise titrations with sulfide and the nonmetabolizable cCox inhibitor sodium azide at 25°C and 37°C. Using the latter of the two inhibitors, the excess capacity of the cCox was obtained. Furthermore, we quantified the capacity of these cells to withstand sulfide inhibition by measuring the amount required to inhibit respiration by 50% and 90% and the viability of the cells after 24-h exposure to 100 ppm of hydrogen sulfide. At low titration rates, the AMJ2-C11 cells, but not the RAW 264.7 cells, increased their capacity to withstand exogenously added sulfide. This effect was even greater at 25°C than at 37°C. Furthermore, only the AMJ2-C11 cells remained viable after sulfide exposure for 24 h. In contrast, only in the RAW 264.7 cells that an increase in cCox excess capacity was found at low temperatures. In macrophage-derived cell lines, both the excess capacity of cCox and the efficiency of sulfide elimination may increase at low temperatures. These properties may modify the effects of sulfide in immune cells and, potentially, the inflammatory response during sulfide exposure at different body temperatures.

Oxidative degradation of benzene rings using iron sulfide activated by hydrogen peroxide/ozone.

PubMed

Hara, Junko

2017-12-01

Mineral pyrites-metal sulfides abundant in the earth's crust-exhibit oxidative ability when exposed to water. This oxidizing ability makes mineral pyrites suitable for the natural and enhanced remediation of environmentally hazardous materials. Herein, we evaluate the benzene ring degradation ability of iron bisulfide activated by H 2 O 2 and O 3 and elucidate the corresponding reaction pathways. A set of control experiments was conducted to optimize the reaction conditions, i.e., the FeS 2 /H 2 O ratio under aerobic conditions and the H 2 O 2 and/or O 3 dosages. Benzene ring was successfully decomposed to CO 2 via organic acids even by the simplest FeS 2 /H 2 O combination. This process was accelerated by the addition of both O 3 and H 2 O 2 . The extent of degradation to CO 2 increased in the presence of O 3 , while oxalic acid generation increased in the presence of H 2 O 2 . The reaction proceeded via the radicals generated on FeS 2 /H 2 O, which is enhanced by O 3 , and a Fenton-like reaction using the iron obtained from FeS 2 dissolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Garlic extracts prevent oxidative stress, hypertrophy and apoptosis in cardiomyocytes: a role for nitric oxide and hydrogen sulfide

PubMed Central

2012-01-01

Background In ancient times, plants were recognized for their medicinal properties. Later, the arrival of synthetic drugs pushed it to the backstage. However, from being merely used for food, plants are now been widely explored for their therapeutic value. The current study explores the potential of skin and flesh extracts from a hard-necked Rocambole variety of purple garlic in preventing cardiomyocyte hypertrophy and cell death. Methods Norepinephrine (NE) was used to induce hypertrophy in adult rat cardiomyocytes pretreated with garlic skin and flesh extracts. Cell death was measured as ratio of rod to round shaped cardiomyocytes. Fluorescent probes were used to measure apoptosis and oxidative stress in cardiomyocytes treated with and without extracts and NE. Pharmacological blockade of nitric oxide (NO) and hydrogen sulfide (H2S) were used to elucidate the mechanism of action of garlic extracts. Garlic extract samples were also tested for alliin and allicin concentrations. Results Exposure of cardiomyocytes to NE induced an increase in cell size and cell death; this increase was significantly prevented upon treatment with garlic skin and flesh extracts. Norepinephrine increased apoptosis and oxidative stress in cardiomyocytes which was prevented upon pretreatment with skin and flesh extracts; NO, and H2S blockers significantly inhibited this beneficial effect. Allicin and alliin concentration were significantly higher in garlic flesh extract when compared to the skin extract. Conclusion These results suggest that both skin and flesh garlic extracts are effective in preventing NE induced cardiomyocyte hypertrophy and cell death. Reduction in oxidative stress may also play an important role in the anti-hypertrophic and anti-apoptotic properties of garlic extracts. These beneficial effects may in part be mediated by NO and H2S. PMID:22931510

Hydrogen sulfide removal from sediment and water in box culverts/storm drains by iron-based granules.

PubMed

Sun, J L; Shang, C; Kikkert, G A

2013-01-01

A renewable granular iron-based technology for hydrogen sulfide removal from sediment and water in box culverts and storm drains is discussed. Iron granules, including granular ferric hydroxide (GFH), granular ferric oxide (GFO) and rusted waste iron crusts (RWIC) embedded in the sediment phase removed aqueous hydrogen sulfide formed from sedimentary biological sulfate reduction. The exhausted iron granules were exposed to dissolved oxygen and this regeneration process recovered the sulfide removal capacities of the granules. The recovery is likely attributable to the oxidation of the ferrous iron precipitates film and the formation of new reactive ferric iron surface sites on the iron granules and sand particles. GFH and RWIC showed larger sulfide removal capacities in the sediment phase than GFO, likely due to the less ordered crystal structures on their surfaces. This study demonstrates that the iron granules are able to remove hydrogen sulfide from sediment and water in box culverts and storm drains and they have the potential to be regenerated and reused by contacting with dissolved oxygen.

Sulfide chemiluminescence detection

DOEpatents

Spurlin, Stanford R.; Yeung, Edward S.

1985-01-01

A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

Mineralogy and Geochemical Processes of Carbonate Mineral-rich Sulfide Mine Tailings, Zimapan, Mexico

NASA Astrophysics Data System (ADS)

McClure, R. J.; Deng, Y.; Loeppert, R.; Herbert, B. E.; Carrillo, R.; Gonzalez, C.

2009-12-01

Mining for silver, lead, zinc, and copper in Zimapan, Hidalgo State, Mexico has been ongoing since 1576. High concentrations of heavy metals have been found in several mine tailing heaps in the Zimapan area, with concentrations of arsenic observed as high as 28,690 mg/kg and levels of Pb as high as 2772 mg/kg. Unsecured tailings heaps and associated acid mine drainage has presented tremendous problems to revegetation, water quality, and dust emission control in the Zimapan area. Although acid mine drainage problems related to weathering of sulfide minerals have been extensively studied and are well known, the weathering products of sulfides in areas with a significant presence of carbonate minerals and their effect on the mobility of heavy metals warrant further study. Carbonate minerals are expected to neutralize sulfuric acid produced from weathering of sulfide minerals, however, in the Zimapan area localized areas of pH as low as 1.8 were observed within carbonate mineral-rich tailing heaps. The objectives of this study are to characterize (1) the heavy metal-containing sulfide minerals in the initial tailing materials, (2) the intermediate oxidation products of sulfide minerals within the carbonate-rich tailings, (3) chemical species of heavy metals within pH gradients between 1.8 and 8.2, the approximate natural pH of limestone, and (4) the mobility of soluble and colloidal heavy metals and arsenic within the carbonate-rich tailings. Representative mine tailings and their intermediate oxidation products have been sampled from the Zimapan area. Mineralogical characterization will be conducted with X-ray diffraction, infrared spectroscopy, electron microscopes and microprobes, and chemical methods. Chemical species will be extracted by selective dissolution methods. Preliminary results have identified calcite as the dominant mineral in the tailing heaps with a pH of 7, suggesting non-equilibrium with the acidic weathering products. Other minerals identified in

Decomposition Products of Phosphine Under Pressure: PH 2 Stable and Superconducting?

DOE PAGES

Shamp, Andrew; Terpstra, Tyson; Bi, Tiange; ...

2016-02-17

Evolutionary algorithms (EA) coupled with Density Functional Theory (DFT) calculations have been used to predict the most stable hydrides of phosphorous (PH n, n = 1 - 6) at 100, 150 and 200 GPa. At these pressures phosphine is unstable with respect to decomposition into the elemental phases, as well as PH 2 and H 2. Three metallic PH 2 phases were found to be dynamically stable and superconducting between 100-200 GPa. One of these contains five formula units in the primitive cell and has C2=m symmetry (5FU-C2=m). It is comprised of 1D periodic PH 3-PH-PH 2-PH-PH 3 oligomers. Twomore » structurally related phases consisting of phosphorous atoms that are octahedrally coordinated by four phosphorous atoms in the equatorial positions and two hydrogen atoms in the axial positions (I4=mmm and 2FU-C 2=m) were the most stable phases between 160-200 GPa. Their superconducting critical temperatures (Tc) were computed as being 70 and 76 K, respectively, via the Allen-Dynes modified McMillan formula and using a value of 0.1 for the Coulomb pseudopotential, . Our results suggest that the superconductivity recently observed by Drozdov, Eremets and Troyan when phosphine was subject to pressures of 207 GPa in a diamond anvil cell may result from these, and other, decomposition products of phosphine.« less

Decomposition Products of Phosphine Under Pressure: PH 2 Stable and Superconducting?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shamp, Andrew; Terpstra, Tyson; Bi, Tiange

Evolutionary algorithms (EA) coupled with Density Functional Theory (DFT) calculations have been used to predict the most stable hydrides of phosphorous (PH n, n = 1 - 6) at 100, 150 and 200 GPa. At these pressures phosphine is unstable with respect to decomposition into the elemental phases, as well as PH 2 and H 2. Three metallic PH 2 phases were found to be dynamically stable and superconducting between 100-200 GPa. One of these contains five formula units in the primitive cell and has C2=m symmetry (5FU-C2=m). It is comprised of 1D periodic PH 3-PH-PH 2-PH-PH 3 oligomers. Twomore » structurally related phases consisting of phosphorous atoms that are octahedrally coordinated by four phosphorous atoms in the equatorial positions and two hydrogen atoms in the axial positions (I4=mmm and 2FU-C 2=m) were the most stable phases between 160-200 GPa. Their superconducting critical temperatures (Tc) were computed as being 70 and 76 K, respectively, via the Allen-Dynes modified McMillan formula and using a value of 0.1 for the Coulomb pseudopotential, . Our results suggest that the superconductivity recently observed by Drozdov, Eremets and Troyan when phosphine was subject to pressures of 207 GPa in a diamond anvil cell may result from these, and other, decomposition products of phosphine.« less

Sulfide chemiluminescence detection

DOEpatents

Spurlin, S.R.; Yeung, E.S.

1985-11-26

A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

Sulfide mineralization: Its role in chemical weathering of Mars

NASA Technical Reports Server (NTRS)

Burns, Roger G.

1988-01-01

Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produced degradation products in the Martian regolith. By analogy with terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato- and hydroxo-complex ions and sols formed gossans above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite) and silica (opal). Underlying groundwater, now permafrost, contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, etc., which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates and phyllosilicates during dust storms on Mars.

Isolation and Characterization of Strains CVO and FWKO B, Two Novel Nitrate-Reducing, Sulfide-Oxidizing Bacteria Isolated from Oil Field Brine

PubMed Central

Gevertz, Diane; Telang, Anita J.; Voordouw, Gerrit; Jenneman, Gary E.

2000-01-01

Bacterial strains CVO and FWKO B were isolated from produced brine at the Coleville oil field in Saskatchewan, Canada. Both strains are obligate chemolithotrophs, with hydrogen, formate, and sulfide serving as the only known energy sources for FWKO B, whereas sulfide and elemental sulfur are the only known electron donors for CVO. Neither strain uses thiosulfate as an energy source. Both strains are microaerophiles (1% O2). In addition, CVO grows by denitrification of nitrate or nitrite whereas FWKO B reduces nitrate only to nitrite. Elemental sulfur is the sole product of sulfide oxidation by FWKO B, while CVO produces either elemental sulfur or sulfate, depending on the initial concentration of sulfide. Both strains are capable of growth under strictly autotrophic conditions, but CVO uses acetate as well as CO2 as its sole carbon source. Neither strain reduces sulfate; however, FWKO B reduces sulfur and displays chemolithoautotrophic growth in the presence of elemental sulfur, hydrogen, and CO2. Both strains grow at temperatures between 5 and 40°C. CVO is capable of growth at NaCl concentrations as high as 7%. The present 16s rRNA analysis suggests that both strains are members of the epsilon subdivision of the division Proteobacteria, with CVO most closely related to Thiomicrospira denitrifcans and FWKO B most closely related to members of the genus Arcobacter. The isolation of these two novel chemolithotrophic sulfur bacteria from oil field brine suggests the presence of a subterranean sulfur cycle driven entirely by hydrogen, carbon dioxide, and nitrate. PMID:10831429

Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

NASA Technical Reports Server (NTRS)

Righter, Kevin

2009-01-01

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation

New reactions involving the oxidative O-, N-, and C-phosphorylation of organic compounds by phosphorus and phosphides in the presence of metal complexes

NASA Astrophysics Data System (ADS)

Dorfman, Ya A.; Aleshkova, M. M.; Polimbetova, G. S.; Levina, L. V.; Petrova, T. V.; Abdreimova, R. R.; Doroshkevich, D. M.

1993-09-01

The mechanisms of new catalytic reactions leading to the formation of di-, and tri-alkyl phosphates, di- and tri-alkyl phosphites, phosphoramidites, phosphazenes, phosphines, and phosphine oxides from hydrogen, copper, and zinc phosphides and white and red phosphorus are analysed. The mechanisms of the activation of the reactants by metal complexes and of the reactions involving the oxidative P-O, P-N, and P-C coupling of organic compounds to phosphorus and phosphides are considered. The bibliography includes 124 references.

Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties.

PubMed

David, Tomáš; Procházková, Soňa; Havlíčková, Jana; Kotek, Jan; Kubíček, Vojtěch; Hermann, Petr; Lukeš, Ivan

2013-02-21

Three symmetrical methylene-bis[(aminomethyl)phosphinic acids] bearing different substituents on the central carbon atom, (NH(2)CH(2))PO(2)H-C(R(1))(R(2))-PO(2)H(CH(2)NH(2)) where R(1) = OH, R(2) = Me (H(2)L(1)), R(1) = OH, R(2) = Ph (H(2)L(2)) and R(1),R(2) = H (H(2)L(3)), were synthesized. Acid-base and complexing properties of the ligands were studied in solution as well as in the solid state. The ligands show unusually high basicity of the nitrogen atoms (log K(1) = 9.5-10, log K(2) = 8.5-9) if compared with simple (aminomethyl)phosphinic acids and, consequently, high stability constants of the complexes with studied divalent metal ions. The study showed the important role of the hydroxo group attached to the central carbon atom of the geminal bis(phosphinate) moiety. Deprotonation of the hydroxo group yields the alcoholate anion which tends to play the role of a bridging ligand and induces formation of polynuclear complexes. Solid-state structures of complexes [H(2)N=C(NH(2))(2)][Cu(2)(H(-1)L(2))(2)]CO(3)·10H(2)O and Li(2)[Co(4)(H(-1)L(1))(3)(OH)]·17.5H(2)O were determined by X-ray diffraction. The complexes show unexpected geometries forming dinuclear and cubane-like structures, respectively. The dinuclear copper(II) complex contains a bridging μ(2)-alcoholate group with the (-)O-P(=O)-CH(2)-NH(2) fragments of each ligand molecule chelated to the different central ion. In the cubane cobalt(II) complex, one μ(3)-hydroxide and three μ(3)-alcoholate anions are located in the cube vertices and both phosphinate groups of one ligand molecule are chelating the same cobalt(II) ion while each of its amino groups are bound to different neighbouring metal ions. All such three metal ions are bridged by the alcoholate group of a given ligand.

Improved sulfide mitigation in sewers through on-line control of ferrous salt dosing.

PubMed

Ganigué, Ramon; Jiang, Guangming; Liu, Yiqi; Sharma, Keshab; Wang, Yue-Cong; Gonzalez, José; Nguyen, Tung; Yuan, Zhiguo

2018-05-15

Water utilities worldwide spend annually billions of dollars to control sulfide-induced corrosion in sewers. Iron salts chemically oxidize and/or precipitate dissolved sulfide in sewage and are especially used in medium- and large-size sewers. Iron salt dosing rates are defined ad hoc, ignoring variation in sewage flows and sulfide levels. This often results in iron overdosing or poor sulfide control. Online dosing control can adjust the chemical dosing rates to current (and future) state of the sewer system, allowing high-precision, stable and cost-effective sulfide control. In this paper, we report a novel and robust online control strategy for the dosing of ferrous salt in sewers. The control considers the fluctuation of sewage flow, pH, sulfide levels and also the perturbation from rainfall. Sulfide production in the pipe is predicted using auto-regressive models (AR) based on current flow measurements, which in turn can be used to determine the dose of ferrous salt required for cost-effective sulfide control. Following comprehensive model-based assesment, the control was successfully validated and its effectiveness demonstrated in a 3-week field trial. The online control algorithm controlled sulfide below the target level (0.5 mg S/L) while reducing chemical dosing up to 30%. Copyright © 2018 Elsevier Ltd. All rights reserved.

Hydrogen sulfide ameliorated L-NAME-induced hypertensive heart disease by the Akt/eNOS/NO pathway.

PubMed

Jin, Sheng; Teng, Xu; Xiao, Lin; Xue, Hongmei; Guo, Qi; Duan, Xiaocui; Chen, Yuhong; Wu, Yuming

2017-12-01

Reductions in hydrogen sulfide (H 2 S) production have been implicated in the pathogenesis of hypertension; however, no studies have examined the functional role of hydrogen sulfide in hypertensive heart disease. We hypothesized that the endogenous production of hydrogen sulfide would be reduced and exogenous hydrogen sulfide would ameliorate cardiac dysfunction in N ω -nitro- L-arginine methyl ester ( L-NAME)-induced hypertensive rats. Therefore, this study investigated the cardioprotective effects of hydrogen sulfide on L-NAME-induced hypertensive heart disease and explored potential mechanisms. The rats were randomly divided into five groups: Control, Control + sodium hydrosulfide (NaHS), L-NAME, L-NAME + NaHS, and L-NAME + NaHS + glibenclamide (Gli) groups. Systolic blood pressure was monitored each week. In Langendorff-isolated rat heart, cardiac function represented by ±LV dP/dt max and left ventricular developing pressure was recorded after five weeks of treatment. Hematoxylin and Eosin and Masson's trichrome staining and myocardium ultrastructure under transmission electron microscopy were used to evaluate cardiac remodeling. The plasma nitric oxide and hydrogen sulfide concentrations, as well as nitric oxide synthases and cystathionine-γ-lyase activity in left ventricle tissue were determined. The protein expression of p-Akt, Akt, p-eNOS, and eNOS in left ventricle tissue was analyzed using Western blot. After five weeks of L-NAME treatment, there was a time-dependent hypertension, cardiac remodeling, and dysfunction accompanied by a decrease in eNOS phosphorylation, nitric oxide synthase activity, and nitric oxide concentration. Meanwhile, cystathionine-γ-lyase activity and hydrogen sulfide concentration were also decreased. NaHS treatment significantly increased plasma hydrogen sulfide concentration and subsequently promoted the Akt/eNOS/NO pathway which inhibited the development of hypertension and attenuated cardiac remodeling and

Phosphines bearing alkyne substituents: synthesis and hydrophosphination polymerization.

PubMed

Greenberg, Sharonna; Stephan, Douglas W

2009-09-07

A synthetic route is described for a series of phosphines bearing pendant alkyne substituents, from the conversion of BrC(6)H(2)R(2)C[triple bond]CR' (R = Me, i-Pr; R' = Ph, SiMe(3)) to [(mu-Br)Cu(Et(2)N)(2)PC(6)H(2)R(2)C[triple bond]CR'](2) and subsequently to Cl(2)PC(6)H(2)R(2)C[triple bond]CR' and H(2)PC(6)H(2)R(2)C[triple bond]CR'. Lithiation and subsequent alkylation yield the secondary phosphines R(H)PC(6)H(2)(i-Pr)(2)C[triple bond]CPh (R = CH(2)i-Pr, CH(2)Ph). Intermolecular hydrophosphination-polymerization is used to prepare the polymeric species [RPC(6)H(2)(i-Pr)(2)CH=CPh](n), which can then be sulfurized to give [RP(S)C(6)H(2)(i-Pr)(2)CH=CPh](n). The polymeric products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography. These data indicate a degree of polymerization (DP(n)) of up to 60. Discussion of the mechanism is augmented with gas-phase density functional theory calculations.

Iron Sulfide Minerals Record Microbe-Mineral Interactions in Anoxic Environments

NASA Astrophysics Data System (ADS)

Picard, A.; Gartman, A.; Cosmidis, J.; Clarke, D. R.; Girguis, P. R.

2017-12-01

The precipitation of most minerals in low-temperature environments on Earth is directly or indirectly influenced by the presence of organic substances and/or microbial biomass. Notably, the influence of microorganisms on the formation of Mn and Fe oxides/oxyhydroxides at the surface of the Earth has been well characterized (Chan et al., 2011; Estes et al., 2017). However, an oxygenated atmosphere is a unique feature of planet Earth. It is therefore critical for the search of life on other planetary bodies to characterize microbe-mineral interactions that form in anoxic conditions. Here we explore the role of microorganisms on the formation of iron sulfide minerals, which form under anoxic conditions. On modern Earth, sulfate-reducing microorganisms (SRM) are the major source of dissolved sulfide in low-temperature sedimentary environments. We experimentally demonstrate that SRM play a role in the nucleation and growth of iron sulfide minerals by acting as organic templates. The physical characteristics of the resulting minerals are different from those formed under abiotic conditions. Moreover, upon forming, iron sulfide minerals become associated with organic carbon, producing a potential organo-mineral signature. We also evaluate how the presence of various organic substances affect the formation of abiotic minerals and how this could produce false biosignatures that could be mistaken as biogenic minerals. Chan, C.S., Fakra, S.C., Emerson, D., Fleming, E.J. and Edwards, K.J. (2011) Lithotrophic iron-oxidizing bacteria produce organic stalks to control mineral growth: implications for biosignature formation. Isme Journal 5, 717-727. Estes, E.R., Andeer, P.F., Nordlund, D., Wankel, S.D. and Hansel, C.M. (2017) Biogenic manganese oxides as reservoirs of organic carbon and proteins in terrestrial and marine environments. Geobiology 15, 158-172.

Protective Effects of Hydrogen Sulfide in the Ageing Kidney.

PubMed

Hou, Cui-Lan; Wang, Ming-Jie; Sun, Chen; Huang, Yong; Jin, Sheng; Mu, Xue-Pan; Chen, Ying; Zhu, Yi-Chun

2016-01-01

Aims . The study aimed to examine whether hydrogen sulfide (H 2 S) generation changed in the kidney of the ageing mouse and its relationship with impaired kidney function. Results . H 2 S levels in the plasma, urine, and kidney decreased significantly in ageing mice. The expression of two known H 2 S-producing enzymes in kidney, cystathionine γ -lyase (CSE) and cystathionine- β -synthase (CBS), decreased significantly during ageing. Chronic H 2 S donor (NaHS, 50  μ mol/kg/day, 10 weeks) treatment could alleviate oxidative stress levels and renal tubular interstitial collagen deposition. These protective effects may relate to transcription factor Nrf2 activation and antioxidant proteins such as HO-1, SIRT1, SOD1, and SOD2 expression upregulation in the ageing kidney after NaHS treatment. Furthermore, the expression of H 2 S-producing enzymes changed with exogenous H 2 S administration and contributed to elevated H 2 S levels in the ageing kidney. Conclusions . Endogenous hydrogen sulfide production in the ageing kidney is insufficient. Exogenous H 2 S can partially rescue ageing-related kidney dysfunction by reducing oxidative stress, decreasing collagen deposition, and enhancing Nrf2 nuclear translocation. Recovery of endogenous hydrogen sulfide production may also contribute to the beneficial effects of NaHS treatment.

Sulfide Homeostasis and Nitroxyl Intersect via Formation of Reactive Sulfur Species in Staphylococcus aureus

PubMed Central

Peng, Hui; Shen, Jiangchuan; Edmonds, Katherine A.; Luebke, Justin L.; Hickey, Anne K.; Palmer, Lauren D.; Chang, Feng-Ming James; Bruce, Kevin A.; Kehl-Fie, Thomas E.; Skaar, Eric P.

2017-01-01

ABSTRACT Staphylococcus aureus is a commensal human pathogen and a major cause of nosocomial infections. As gaseous signaling molecules, endogenous hydrogen sulfide (H2S) and nitric oxide (NO·) protect S. aureus from antibiotic stress synergistically, which we propose involves the intermediacy of nitroxyl (HNO). Here, we examine the effect of exogenous sulfide and HNO on the transcriptome and the formation of low-molecular-weight (LMW) thiol persulfides of bacillithiol, cysteine, and coenzyme A as representative of reactive sulfur species (RSS) in wild-type and ΔcstR strains of S. aureus. CstR is a per- and polysulfide sensor that controls the expression of a sulfide oxidation and detoxification system. As anticipated, exogenous sulfide induces the cst operon but also indirectly represses much of the CymR regulon which controls cysteine metabolism. A zinc limitation response is also observed, linking sulfide homeostasis to zinc bioavailability. Cellular RSS levels impact the expression of a number of virulence factors, including the exotoxins, particularly apparent in the ΔcstR strain. HNO, like sulfide, induces the cst operon as well as other genes regulated by exogenous sulfide, a finding that is traced to a direct reaction of CstR with HNO and to an endogenous perturbation in cellular RSS, possibly originating from disassembly of Fe-S clusters. More broadly, HNO induces a transcriptomic response to Fe overload, Cu toxicity, and reactive oxygen species and reactive nitrogen species and shares similarity with the sigB regulon. This work reveals an H2S/NO· interplay in S. aureus that impacts transition metal homeostasis and virulence gene expression. IMPORTANCE Hydrogen sulfide (H2S) is a toxic molecule and a recently described gasotransmitter in vertebrates whose function in bacteria is not well understood. In this work, we describe the transcriptomic response of the major human pathogen Staphylococcus aureus to quantified changes in levels of cellular

Microbial communities and arsenic biogeochemistry at the outflow of an alkaline sulfide-rich hot spring.

PubMed

Jiang, Zhou; Li, Ping; Van Nostrand, Joy D; Zhang, Ping; Zhou, Jizhong; Wang, Yanhong; Dai, Xinyue; Zhang, Rui; Jiang, Dawei; Wang, Yanxin

2016-04-29

Alkaline sulfide-rich hot springs provide a unique environment for microbial community and arsenic (As) biogeochemistry. In this study, a representative alkaline sulfide-rich hot spring, Zimeiquan in the Tengchong geothermal area, was chosen to study arsenic geochemistry and microbial community using Illumina MiSeq sequencing. Over 0.26 million 16S rRNA sequence reads were obtained from 5-paired parallel water and sediment samples along the hot spring's outflow channel. High ratios of As(V)/AsSum (total combined arsenate and arsenite concentrations) (0.59-0.78), coupled with high sulfide (up to 5.87 mg/L), were present in the hot spring's pools, which suggested As(III) oxidation occurred. Along the outflow channel, AsSum increased from 5.45 to 13.86 μmol/L, and the combined sulfide and sulfate concentrations increased from 292.02 to 364.28 μmol/L. These increases were primarily attributed to thioarsenic transformation. Temperature, sulfide, As and dissolved oxygen significantly shaped the microbial communities between not only the pools and downstream samples, but also water and sediment samples. Results implied that the upstream Thermocrinis was responsible for the transformation of thioarsenic to As(III) and the downstream Thermus contributed to derived As(III) oxidation. This study improves our understanding of microbially-mediated As transformation in alkaline sulfide-rich hot springs.

Microbial communities and arsenic biogeochemistry at the outflow of an alkaline sulfide-rich hot spring

PubMed Central

Jiang, Zhou; Li, Ping; Van Nostrand, Joy D.; Zhang, Ping; Zhou, Jizhong; Wang, Yanhong; Dai, Xinyue; Zhang, Rui; Jiang, Dawei; Wang, Yanxin

2016-01-01

Alkaline sulfide-rich hot springs provide a unique environment for microbial community and arsenic (As) biogeochemistry. In this study, a representative alkaline sulfide-rich hot spring, Zimeiquan in the Tengchong geothermal area, was chosen to study arsenic geochemistry and microbial community using Illumina MiSeq sequencing. Over 0.26 million 16S rRNA sequence reads were obtained from 5-paired parallel water and sediment samples along the hot spring’s outflow channel. High ratios of As(V)/AsSum (total combined arsenate and arsenite concentrations) (0.59–0.78), coupled with high sulfide (up to 5.87 mg/L), were present in the hot spring’s pools, which suggested As(III) oxidation occurred. Along the outflow channel, AsSum increased from 5.45 to 13.86 μmol/L, and the combined sulfide and sulfate concentrations increased from 292.02 to 364.28 μmol/L. These increases were primarily attributed to thioarsenic transformation. Temperature, sulfide, As and dissolved oxygen significantly shaped the microbial communities between not only the pools and downstream samples, but also water and sediment samples. Results implied that the upstream Thermocrinis was responsible for the transformation of thioarsenic to As(III) and the downstream Thermus contributed to derived As(III) oxidation. This study improves our understanding of microbially-mediated As transformation in alkaline sulfide-rich hot springs. PMID:27126380

Sulfidation behavior and mechanism of zinc silicate roasted with pyrite

NASA Astrophysics Data System (ADS)

Ke, Yong; Peng, Ning; Xue, Ke; Min, Xiaobo; Chai, Liyuan; Pan, Qinglin; Liang, Yanjie; Xiao, Ruiyang; Wang, Yunyan; Tang, Chongjian; Liu, Hui

2018-03-01

Sulfidation roasting followed by flotation is widely known as a possible generic technology for enriching valuable metals in low-grade Zn-Pb oxide ores. Zn2SiO4 is the primary Zn phase in willemite. Zn4Si2O7(OH)2(H2O), the main Zn phase in hemimorphite, transforms into Zn2SiO4 at temperatures above 600 °C. To enrich the Zn in willemite and hemimorphite, the Zn species should first be converted to ZnS. Therefore, a thorough understanding of the sulfidation reaction of Zn2SiO4 during roasting with pyrite is of vital important. In this study, the sulfidation behavior and reaction mechanisms of a Zn2SiO4-pyrite roasting system were determined using HSC 5.0 software, TG-FTIR spectroscopy, XRD, XPS and SEM-EDS. The results indicate that the sulfidation process can be divided into three steps: the decomposition of pyrite and formation of a sulfur-rich environment, the sulfur-induced migration of O2- and transformation of sulfur vapor, and the sulfidation reaction via oxygen-sulfur exchange. During the sulfidation roasting process, pyrite was converted to loose and porous Fe3O4, whereas Zn2SiO4 was transformed into ZnS and SiO2 in situ. These findings provide theoretical support for controlling the sulfidation roasting process of willemite and hemimorphite.

Influence of oxygenation on chromium redox reactions with manganese sulfide (MnS(s)).

PubMed

Wadhawan, Amar R; Livi, Kenneth J; Stone, Alan T; Bouwer, Edward J

2015-03-17

Manganese sulfide (MnS(s)) minerals exist in sulfidic environments and can have unique reactive abilities because of sulfide, which is a known reductant, and Mn, the oxyhydroxides of which are known oxidants. This study elucidated the role of MnS(s) in controlling Cr speciation with implications on its fate and toxicity in the natural environment, specifically sulfidic sediments that undergo biogeochemical changes due to sediment resuspension during dredging, bioturbation, and flood events. In continuously mixed batch reaction experiments, aqueous CrVI reduction under anaerobic conditions occurred primarily on the surface of MnS(s) displaying a biphasic behavior- the initial rapid removal of CrVI from solution was followed by a slow decline due to surface passivation by reaction products, mainly sorbed or precipitated CrIII. The reaction progress increased with MnS(s) surface area loading but decreased on increasing CrVI concentration and pH, suggesting that surface site regeneration through product desorption was the rate-controlling mechanism. Below circum-neutral pH, higher solubility of MnS(s) resulted in additional CrVI reduction by reduced sulfur species in solution, whereas increased CrIII solubility lowered surface passivation allowing for more reactive sites to participate in the reaction. Aeration of MnS(s) at pH≥7 caused the formation of a heterogeneous MnIII(hydr)oxide that was composed of hausmanite and manganite. CrVI reoccurrence was observed on aeration of CrVI-spiked MnS(s) from the oxidation of product CrIII. The reoccurrence at pH≥7 was attributed to the oxidation of product CrIII by MnIII(hydr)oxide, whereas the reoccurrence at pH<7 was hypothesized from the oxidation of product CrIII by intermediate aqueous MnIII and/or sulfur species. Just as with Cr, MnS(s) may play an important role in speciation, fate, and transport of other environmental contaminants.

Redox processes in subducting oceanic crust recorded by sulfide-bearing high-pressure rocks and veins (SW Tianshan, China)

NASA Astrophysics Data System (ADS)

Li, Ji-Lei; Gao, Jun; Klemd, Reiner; John, Timm; Wang, Xin-Shui

2016-09-01

The oxidized nature of the sub-arc mantle and hence arc magmas is generally interpreted as a result of the migration of subduction-related oxidizing fluids or melts from the descending slab into the mantle wedge. This is of particular importance seeing that the oxidization state of sub-arc magmas seems to play a key role in the formations of arc-related ore deposits. However, direct constraints on the redox state of subducted oceanic crust are sparse. Here, we provide a detailed petrological investigation on sulfide- and oxide-bearing eclogites, blueschists, micaschists, eclogite-facies and retrograde veins from the Akeyazi high-pressure (HP) terrane (NW China) in order to gain insight into the redox processes recorded in a subducting oceanic slab. Sulfides in these rocks are mainly pyrite and minor pyrrhotite, chalcopyrite, bornite, molybdenite, sphalerite and chalcocite, including exsolution textures of bornite-chalcopyrite intergrowth. Magnetite, ilmenite and pyrite occur as inclusions in garnet, whereas sulfides are dominant in the matrix. Large pyrite grains in the matrix contain inclusions of garnet, omphacite and other HP index minerals. However, magnetite replacing pyrite textures are commonly observed in the retrograded samples. The eclogite-facies and retrograde veins display two fluid events, which are characterized by an early sulfide-bearing and a later magnetite-bearing mineral assemblage, respectively. Textural and petrological evidences show that the sulfides were mainly formed during HP metamorphism. Mineral assemblage transitions reveal that the relative oxygen fugacity of subducted oceanic crust decreases slightly with increasing depths. However, according to oxygen mass balance calculations, based on the oxygen molar quantities ( nO2), the redox conditions remain constant during HP metamorphism. At shallow levels (<60 km) in the subduction channel, interaction with oxidized fluid seems to have caused an increase of the oxygen fugacity and the

Evaluation of phosphine genotoxicity at occupational levels of exposure in New South Wales, Australia.

PubMed Central

Barbosa, A; Bonin, A M

1994-01-01

Phosphine has been claimed to cause chromosomal damage at exposures close to the current time weighted average exposure standard of 0.3 ppm (0.4 mg/m3). The current study involved 31 phosphine fumigators and 21 controls during the high fumigation season. All were volunteers and were evaluated for genotoxicity variables, including micronuclei in peripheral blood lymphocytes and urine mutagenicity. In parallel, all fumigators and 17 controls were evaluated for full haematology, multiple biochemical analysis, whole blood organochlorines, and whole blood and serum cholinesterase activity. The results for micronuclei showed no significant differences between fumigators and controls, but detected a strong association between age and increased frequency of micronuclei. Measurement of urine mutagenicity did not show any significant difference between fumigators and controls, but did show increased excretion of mutagens in smokers. All haematological and biochemical variables were within normal ranges, except for some non-specific changes in biochemistry. At monitored occupational exposures of < 2.4 ppm/h our results show no association between phosphine exposure and genotoxic or toxicological effects in fumigators. PMID:8000496

Sulfidation Roasting of Hemimorphite with Pyrite for the Enrichment of Zn and Pb

NASA Astrophysics Data System (ADS)

Min, Xiao-Bo; Xue, Ke; Ke, Yong; Zhou, Bo-Sheng; Li, Yang-Wen-Jun; Wang, Qing-Wei

2016-09-01

With the increasing consumption of zinc and the depletion of zinc sulfide ores, the exploitation of low-grade zinc oxide ores may be important for the sustainability of the zinc industry. Hemimorphite, a zinc hydroxyl silicate hydrate, is a significant source of Zn and Pb. It is difficult to obtain Zn and Pb from the hemimorphite using traditional technology. In this work, for the first time, sulfidation roasting of hemimorphite with pyrite was studied for the enrichment of Zn and Pb by a flotation process. Four stages of sulfidation roasting were determined based on x-ray diffraction and thermogravimetry analysis. Then, the effects of sulfidation temperature, pyrite dosage and reaction time on the sulfidation percentages were investigated at the laboratory scale. The experimental results showed that the sulfidation percentages of Pb and Zn were as high as 98.08% and 90.55% under optimum conditions, respectively. Finally, a flotation test was performed to enrich Zn and Pb in the sulfidation product. A flotation concentrate with 8.78% Zn and 9.25% Pb was obtained, and the recovery of Zn and Pb reached 56.14% and 75.94%, respectively.

A hypothesis for treating inflammation and oxidative stress with hydrogen sulfide during age-related macular degeneration.

PubMed

George, Akash K; Singh, Mahavir; Homme, Rubens Petit; Majumder, Avisek; Sandhu, Harpal S; Tyagi, Suresh C

2018-01-01

Age-related macular degeneration (AMD) is a leading cause of blindness and is becoming a global crisis since affected people will increase to 288 million by 2040. Genetics, age, diabetes, gender, obesity, hypertension, race, hyperopia, iris-color, smoking, sun-light and pyroptosis have varying roles in AMD, but oxidative stress-induced inflammation remains a significant driver of pathobiology. Eye is a unique organ as it contains a remarkable oxygen-gradient that generates reactive oxygen species (ROS) which upregulates inflammatory pathways. ROS becomes a source of functional and morphological impairments in retinal pigment epithelium (RPE), endothelial cells and retinal ganglion cells. Reports demonstrated that hydrogen sulfide (H 2 S) acts as a signaling molecule and that it may treat ailments. Therefore, we propose a novel hypothesis that H 2 S may restore homeostasis in the eyes thereby reducing damage caused by oxidative injury and inflammation. Since H 2 S has been shown to be a powerful antioxidant because of its free-radicals' inhibition properties in addition to its beneficial effects in age-related conditions, therefore, patients may benefit from H 2 S salubrious effects not only by minimizing their oxidant and inflammatory injuries to retina but also by lowering retinal glutamate excitotoxicity.

Evaluation of Degradation Inhibitors in Poly(Hexafluoropropene Oxide) Fluids

NASA Technical Reports Server (NTRS)

Jones, William R., Jr.; Paciorek, Kazimiera J. L.; Lin, Wen-Huey; Masuda, Steven R.; Nakahara, James H.

1996-01-01

The action of various alloys: 440C steel, M-50 steel, Pyrowear 675, Cronidur 30 and Ti(4Al,4Mn); the effect of decradation inhibitors: mono- and diphospha-s-triazines, diphosphatetraazacyclooctatetraene, phosphate esters, phosphate/ diester rust inhibiting mixtures, and a phosphine were evaluated in two poly(hexafluoropropene oxide) fluids (143AC and 16256). The degradation promoting action of the ferrous alloys in 16256 fluid were comparable; Ti(4Al,4Mn) alloy was significantly more detrimental. The overall rating of the additives was: phosphates (greater than) phosphate/diester mixture (greater than) phosphine (greater than or equal to) phospha-s-triazines. The 16256 fluid was less responsive to additive inhibition than 143AC. Phosphate esters were fully effective over 24 hour exposure in the 16256/440C steel and the 16256/Ti(4Al,4Mn) systems at 330 C. In general, the phosphine was less effective in the presence of ferrous alloys than the phosphates and phospha-s-triazines.

ISOLATION AND PROPERTIES OF AN IRON-OXIDIZING THIOBACILLUS

PubMed Central

Razzell, W. E.; Trussell, P. C.

1963-01-01

Razzell, W. E. (British Columbia Research Council, Vancouver, Canada) and P. C. Trussell. Isolation and properties of an iron-oxidizing Thiobacillus. J. Bacteriol. 85:595–603. 1963. — An organism isolated from acidic copper-leaching waters has been shown to oxidize ferrous ions, sulfur, and metallic sulfides but exhibit peculiar responses to thiosulfate. The name Thiobacillus ferrooxidans has been used to describe it. A pH of 2.5 is optimal for growth on iron, sulfur, and metallic sulfides, but cells free from iron can be obtained from growth at pH 1.6, and sulfur cultures adjusted to pH 5.5 readily attain a pH of 1.8. A stationary cultivation procedure appears superior to percolation techniques for studying the oxidation of finely divided metallic sulfides. Concentrations of soluble copper in excess of 1 g per liter were obtained from chalcopyrite in less than 4 weeks. Chalcocite oxidation proceeded in the absence of iron. Sodium chloride inhibits iron oxidation without preventing oxidation of metallic sulfides by the organism. PMID:14042937

Chemistry and mineralogy of pyrite-enriched sediments at a passive margin sulfide brine seep: abyssal Gulf of Mexico

USGS Publications Warehouse

Commeau, R.F.; Paull, C.K.; Commeau, J.A.; Poppe, L.J.

1987-01-01

Pyrite is rapidly accumulating at the contact between the Cretaceous limestones of the Florida Platform and the hemipelagic sediments of the abyssal Gulf of Mexico. Sediments sampled with the submersible "Alvin" in 3266 m of water are associated with a dense community of organisms that depend on chemosynthetic primary production as a food source. Analysis of the chemistry, mineralogy, and textural composition of these sediments indicate that iron sulfide mineralization is occurring at the seafloor within an anoxic micro-habitat sustained by the advection of hydrogen sulfide-charged saline brines from the adjacent platform. The chemosynthetic bacteria that directly overlie the sediments oxidize hydrogen sulfide for energy and provide elemental sulfur that reacts with iron monosulfide to form some of the pyrite. The sediments are mixtures of pyrite (??? 30 wt.%), BaSr sulfates (??? 4 wt.%), clays, and locally derived biogenic carbonates and are progressively being cemented by iron sulfides. Oxidation of hydrogen sulfide produces locally acidic conditions that corrode the adjacent limestones. Potential sources of S, H2S, Fe, Ba, and Sr are discussed. ?? 1987.

Analytical Measurement of Discrete Hydrogen Sulfide Pools in Biological Specimens

PubMed Central

Shen, Xinggui; Peter, Elvis A.; Bir, Shyamal; Wang, Rui; Kevil, Christopher G.

2015-01-01

Hydrogen sulfide (H2S) is a ubiquitous gaseous signaling molecule that plays a vital role in numerous cellular functions and has become the focus of many research endeavors including pharmaco-therapeutic manipulation. Amongst the challenges facing the field is the accurate measurement of biologically active H2S. We have recently reported that the typically used methylene blue method and its associated results are invalid and do not measure bonafide H2S. The complexity of analytical H2S measurement reflects the fact that hydrogen sulfide is a volatile gas and exists in the body in different forms, including a free form, an acid labile pool and as bound sulfane sulfur. Here we describe a new protocol to discretely measure specific H2S pools using the monobromobimane method coupled with RP-HPLC. This new protocol involves selective liberation, trapping and derivatization of H2S. Acid-labile H2S is released by incubating the sample in an acidic solution (pH 2.6) of 100 mM phosphate buffer with 0.1 mM DTPA, in an enclosed system to contain volatilized H2S. Volatilized H2S is then trapped in 100 mM Tris-HCl (pH 9.5, 0.1 mM DTPA) and then reacted with excess monobromobimane. In a separate aliquot, the contribution of bound sulfane sulfur pool was measured by incubating the sample with 1 mM TCEP (Tris(2-carboxyethyl)phosphine hydrochloride), a reducing agent to reduce disulfide bonds, in 100 mM phosphate buffer (pH 2.6, 0.1 mM DTPA), and H2S measurement performed in an analogous manner to the one described above. The acid labile pool was determined by subtracting the free hydrogen sulfide value from the value obtained by the acid liberation protocol. The bound sulfane sulfur pool was determined by subtracting the H2S measurement from the acid liberation protocol alone compared to that of TCEP plus acidic conditions. In summary, our new method protocol allows very sensitive and accurate measurement of the three primary biological pools of H2S including free, acid labile

Dibenzyl sulfide metabolism by white rot fungi.

PubMed

Van Hamme, Jonathan D; Wong, Eddie T; Dettman, Heather; Gray, Murray R; Pickard, Michael A

2003-02-01

Microbial metabolism of organosulfur compounds is of interest in the petroleum industry for in-field viscosity reduction and desulfurization. Here, dibenzyl sulfide (DBS) metabolism in white rot fungi was studied. Trametes trogii UAMH 8156, Trametes hirsuta UAMH 8165, Phanerochaete chrysosporium ATCC 24725, Trametes versicolor IFO 30340 (formerly Coriolus sp.), and Tyromyces palustris IFO 30339 all oxidized DBS to dibenzyl sulfoxide prior to oxidation to dibenzyl sulfone. The cytochrome P-450 inhibitor 1-aminobenzotriazole eliminated dibenzyl sulfoxide oxidation. Laccase activity (0.15 U/ml) was detected in the Trametes cultures, and concentrated culture supernatant and pure laccase catalyzed DBS oxidation to dibenzyl sulfoxide more efficiently in the presence of 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) than in its absence. These data suggest that the first oxidation step is catalyzed by extracellular enzymes but that subsequent metabolism is cytochrome P-450 mediated.

Luminescence in Sulfides: A Rich History and a Bright Future

PubMed Central

Smet, Philippe F.; Moreels, Iwan; Hens, Zeger; Poelman, Dirk

2010-01-01

Sulfide-based luminescent materials have attracted a lot of attention for a wide range of photo-, cathodo- and electroluminescent applications. Upon doping with Ce3+ and Eu2+, the luminescence can be varied over the entire visible region by appropriately choosing the composition of the sulfide host. Main application areas are flat panel displays based on thin film electroluminescence, field emission displays and ZnS-based powder electroluminescence for backlights. For these applications, special attention is given to BaAl2S4:Eu, ZnS:Mn and ZnS:Cu. Recently, sulfide materials have regained interest due to their ability (in contrast to oxide materials) to provide a broad band, Eu2+-based red emission for use as a color conversion material in white-light emitting diodes (LEDs). The potential application of rare-earth doped binary alkaline-earth sulfides, like CaS and SrS, thiogallates, thioaluminates and thiosilicates as conversion phosphors is discussed. Finally, this review concludes with the size-dependent luminescence in intrinsic colloidal quantum dots like PbS and CdS, and with the luminescence in doped nanoparticles.

Synthesis and Structural Studies of Calcium and Magnesium Phosphinate and Phosphonate Compounds

NASA Astrophysics Data System (ADS)

Bampoh, Victoria Naa Kwale

The work presented herein describes synthetic methodologies leading to the design of a wide array of magnesium and calcium based phosphinate and phosphonates with possible applications as bone scaffolding materials or additives to bone cements. The challenge to the chemistry of the alkaline earth phosphonate target compounds includes poor solubility of compounds, and poorly understood details on the control of the metal's coordination environment. Hence, less is known on phosphonate based alkaline earth metal organic frameworks as compared to transition metal phosphonates. Factors governing the challenges in obtaining crystalline, well-defined magnesium and calcium solids lie in the large metal diameters, the absence of energetically available d-orbitals to direct metal geometry, as well as the overall weakness of the metal-ligand bonds. A significant part of this project was concerned with the development of suitable reaction conditions to obtain X-ray quality crystals of the reaction products to allow for structural elucidation of the novel compounds. Various methodologies to aid in crystal growth including hydrothermal methods and gel crystallization were employed. We have used phosphinate and phosphonate ligands with different number of phosphorus oxygen atoms as well as diphosphonates with different linker lengths to determine their effects on the overall structural features. An interesting correlation is observed between the dimensionality of products and the increasing number of donor oxygen atoms in the ligands as we progress from phosphinic acid to the phosphorous acids. As an example, monophosphinate ligand only yielded one-dimensional compounds, whereas the phosphonates crystallize as one and two-dimensional compounds, and the di- and triphosphonate based compounds display two or three-dimensional geometries. This thesis provides a selection of calcium and magnesium compounds with one-dimensional geometry, as represented in a calcium phosphinate to novel

Aerobic and anaerobic degradation of a range of alkyl sulfides by a denitrifying marine bacterium

USGS Publications Warehouse

Visscher, P.T.; Taylor, B.F.

1993-01-01

A pure culture of a bacterium was obtained from a marine microbial mat by using an anoxic medium containing dimethyl sulfide (DMS) and nitrate. The isolate grew aerobically or anaerobically as a denitrifier on alkyl sulfides, including DMS, dimethyl disulfide, diethyl sulfide (DES), ethyl methyl sulfide, dipropyl sulfide, dibutyl sulfide, and dibutyl disulfide. Cells grown on an alkyl sulfide or disulfide also oxidized the corresponding thiols, namely, methanethiol, ethanethiol, propanethiol, or butanethiol. Alkyl sulfides were metabolized by induced or derepressed cells with oxygen, nitrate, or nitrite as electron acceptor. Cells grown on DMS immediately metabolized DMS, but there was a lag before DES was consumed; with DES-grown cells, DES was immediately used but DMS was used only after a lag. Chloramphenicol prevented the eventual use of DES by DMS-grown cells and DMS use by DES-grown cells, respectively, indicating separate enzymes for the metabolism of methyl and ethyl groups. Growth was rapid on formate, acetate, propionate, and butyrate but slow on methanol. The organism also grew chemolithotrophically on thiosulfate with a decrease in pH; growth required carbonate in the medium. Growth on sulfide was also carbonate dependent but slow. The isolate was identified as a Thiobacillus sp. and designated strain ASN-1. It may have utility for removing alkyl sulfides, and also nitrate, nitrite, and sulfide, from wastewaters.

Synthesis of (Silylamino)phosphines by the Wilburn Method.

DTIC Science & Technology

1982-08-01

by the addi- tion of two equivalents of an alkyl Grignard reagent at 0 0C affords the [bis(trimethylsilyl)aminoldialkylphosphines 1 -3 (eq 1). Simi...larly, the use of dichlorophenylphosphine and one equivalent of Grignard reagent permits the convenient preparation of the corres- ponding alkyl(phenyl...Received The importance of (silylamino)phosphines, e.g. (Me3Si)2NPMe2, as reagents for the synthesis of organo-substituted phosphazene 1 2,3 polymers

Hexagonal AlN Layers Grown on Sulfided Si(100) Substrate

NASA Astrophysics Data System (ADS)

Bessolov, V. N.; Gushchina, E. V.; Konenkova, E. V.; L'vova, T. V.; Panteleev, V. N.; Shcheglov, M. P.

2018-01-01

We have studied the influence of sulfide passivation on the initial stages of aluminum nitride (AlN)-layer nucleation and growth by hydride vapor-phase epitaxy (HVPE) on (100)-oriented single-crystalline silicon substrates. It is established that the substrate pretreatment in (NH4)2S aqueous solution leads to the columnar nucleation of hexagonal AlN crystals of two modifications rotated by 30° relative to each other. Based on the sulfide treatment, a simple method of oxide removal from and preparation of Si(100) substrate surface is developed that can be used for the epitaxial growth of group-III nitride layers.

Factors affecting activated carbon-based catalysts for selective hydrogen sulfide oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Huixing; Monnell, J.D.; Alvin, M.A.

2008-09-01

The primary product of coal gasification processes is synthesis gas (syngas), a mixture of CO, H2, CO2, H2O and a number of minor components. Among the most significant minor components in syngas is hydrogen sulfide (H2S). In addition to its adverse environmental impact, H2S poisons the catalysts and hydrogen purification membranes, and causes severe corrosion in gas turbines. Technologies that can remove H2S from syngas and related process streams are, therefore, of considerable practical interest. To meet this need, we work towards understanding the mechanism by which prospective H2S catalysts perform in simulated fuel gas conditions. Specifically, we show thatmore » for low-temperature gas clean-up (~1408C) using activated carbon fibers and water plays a significant role in H2S binding and helps to prolong the lifetime of the material. Basic surface functional groups were found to be imperative for significant conversion of H2S to daughter compounds, whereas metal oxides (La and Ce) did little to enhance this catalysis. We show that although thermal regeneration of the material is possible, the regenerated material has a substantially lower catalytic and sorption capacity.« less

Selenium Sulfide

MedlinePlus

... minutes.Do not leave selenium sulfide on your hair, scalp, or skin for long periods (e.g., ... jewelry; selenium sulfide may damage it. Wash your hair with ordinary shampoo and rinse it well. Shake ...

Chiral and achiral phosphine derivatives of alkylidyne tricobalt carbonyl clusters as catalyst precursors for (asymmetric) inter- and intramolecular Pauson-Khand reactions.

PubMed

Moberg, Viktor; Mottalib, M Abdul; Sauer, Désirée; Poplavskaya, Yulia; Craig, Donald C; Colbran, Stephen B; Deeming, Antony J; Nordlander, Ebbe

2008-05-14

Phosphine derivatives of alkylidyne tricobalt carbonyl clusters have been tested as catalysts/catalyst precursors in intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. A number of new phosphine derivatives of the tricobalt alkylidyne clusters [Co3(micro3-CR)(CO)9] (R = H, CO2Et) were prepared and characterised. The clusters [Co3(micro3-CR)(CO)9-x(PR'3)x] (PR'3 = achiral or chiral monodentate phosphine, x = 1-3) and [Co3(micro3-CR)(CO)7)(P-P)] (P-P = chiral diphosphine; 1,1'- and 1,2-structural isomers) were assayed as catalysts for intermolecular and (asymmetric) intramolecular Pauson-Khand reactions. The phosphine-substituted tricobalt clusters proved to be viable catalysts/catalyst precursors that gave moderate to very good product yields (up to approximately 90%), but the enantiomeric excesses were too low for the clusters to be of practical use in the asymmetric reactions.

C6, C7, and C8 perfluoroalkyl-substituted phosphinic acids.

PubMed

Singh, R P; Shreeve, J M

2000-04-17

Reaction of red phosphorus with RfI in a 1:2 molar ratio at 230 degrees C led to the formation of a mixture of (Rf)2PI and (Rf)PI2 (Rf = C6F13, C7F15, C8F17) in about a 70:30 ratio, respectively. These mixtures were separated by vacuum distillation. (Rf)2PI (Rf = C6F13, C7F15) are yellow liquids whereas (C8F17)2PI is a yellow solid. Oxidation of (Rf)2PI with excess NO2 led to (Rf)2P(O)OH (Rf = C6F13, C7F15, C8F17) in > 90% isolated yields after aqueous hydrolysis of the anhydride intermediates. These highly fluorinated phosphinic acids are white solids with sharp melting points and are highly soluble in methyl sulfoxide (DMSO) and 1,1,2-trichlorotrifluoroethane. However, solubility in chloroform and methylene dichloride is low. These perfluoroalkylphosphinic acids were characterized by IR, NMR (1H, 19F, and 31P), and mass spectra and elemental analysis.

Electrochemical hydrogen sulfide biosensors.

PubMed

Xu, Tailin; Scafa, Nikki; Xu, Li-Ping; Zhou, Shufeng; Abdullah Al-Ghanem, Khalid; Mahboob, Shahid; Fugetsu, Bunshi; Zhang, Xueji

2016-02-21

The measurement of sulfide, especially hydrogen sulfide, has held the attention of the analytical community due to its unique physiological and pathophysiological roles in biological systems. Electrochemical detection offers a rapid, highly sensitive, affordable, simple, and real-time technique to measure hydrogen sulfide concentration, which has been a well-documented and reliable method. This review details up-to-date research on the electrochemical detection of hydrogen sulfide (ion selective electrodes, polarographic hydrogen sulfide sensors, etc.) in biological samples for potential therapeutic use.

Feasibility of sulfide control in sewers by reuse of iron rich drinking water treatment sludge.

PubMed

Sun, Jing; Pikaar, Ilje; Sharma, Keshab Raj; Keller, Jürg; Yuan, Zhiguo

2015-03-15

Dosage of iron salt is the most commonly used method for sulfide control in sewer networks but incurs high chemical costs. In this study, we experimentally investigate the feasibility of using iron rich drinking water treatment sludge for sulfide control in sewers. A lab-scale rising main sewer biofilm reactor was used. The sulfide concentration in the effluent decreased from 15.5 to 19.8 mgS/L (without dosing) to below 0.7-2.3 mgS/L at a sludge dosing rate achieving an iron to total dissolved inorganic sulfur molar ratio (Fe:S) of 1:1, with further removal of sulfide possible by prolonging the reaction time. In fact, batch tests revealed an Fe consumption to sulfide removal ratio of 0.5 ± 0.02 (mole:mole), suggesting the possible occurrence of other reactions involving the removal of sulfide. Modelling revealed that the reaction between iron in sludge and sulfide has reaction orders of 0.65 ± 0.01 and 0.77 ± 0.02 with respect to the Fe and sulfide concentrations, respectively. The addition of sludge slightly increased the total chemical oxidation demand (tCOD) concentration (by approximately 12%) as expected, but decreased the soluble chemical oxidation demand (sCOD) concentration and methane formation by 7% and 20%, respectively. Some phosphate removal (13%) was also observed at the sludge dosing rate of 1:1 (Fe:S), which is beneficial to nutrient removal from the wastewater. Overall, this study suggests that dosing iron-rich drinking water sludge to sewers could be an effective strategy for sulfide removal in sewer systems, which would also reduce the sludge disposal costs for drinking water treatment works. However, its potential side-effects on sewer sedimentation and on the wastewater treatment plant effluent remain to be investigated. Copyright © 2015 Elsevier Ltd. All rights reserved.

LOW TEMPERATURE PHOSPHINE FUMIGATION FOR POSTHARVEST PEST CONTROL ON FRESH VEGETABLES

USDA-ARS?s Scientific Manuscript database

U.S. exported lettuce, broccoli, asparagus, and strawberries often harbor western flower thrips (Frankliniella occidentalis), a quarantined pest in Taiwan, and therefore require quarantine treatment. Fumigation with pure phosphine at a low temperature of 2°C was studied to control western flower t...

Communication: Tunnelling splitting in the phosphine molecule

NASA Astrophysics Data System (ADS)

Sousa-Silva, Clara; Tennyson, Jonathan; Yurchenko, Sergey N.

2016-09-01

Splitting due to tunnelling via the potential energy barrier has played a significant role in the study of molecular spectra since the early days of spectroscopy. The observation of the ammonia doublet led to attempts to find a phosphine analogous, but these have so far failed due to its considerably higher barrier. Full dimensional, variational nuclear motion calculations are used to predict splittings as a function of excitation energy. Simulated spectra suggest that such splittings should be observable in the near infrared via overtones of the ν2 bending mode starting with 4ν2.

Another side of the oxazaphospholidine oxide chiral ortho-directing group.

PubMed

Martins, Nelson; Mateus, Nuno; Vinci, Daniele; Saidi, Ourida; Brigas, Amadeu; Bacsa, John; Xiao, Jianliang

2012-05-28

A new ferrocenyl oxazaphospholidine oxide 3 was synthesized together with its P-epimer 2 in the reaction of ferrocene lithium with phosphoramidite chloride 1. 3 was successfully derivatized into planar chiral 1,2-ferrocenes, including phosphine ligands, via highly diastereoselective ortho-lithiation and subsequent functionalization; these compounds display opposite planar chirality to those obtained from 2. Some of these 1,2-ferrocenes were further lithiated, allowing for the introduction of a free phosphine group at the oxazaphospholidine ring. The X-ray structures of the compounds 2 and 3 as well as those of the new 1,2-ferrocenes 4 and 7 have been determined.

Dibenzyl Sulfide Metabolism by White Rot Fungi

PubMed Central

Van Hamme, Jonathan D.; Wong, Eddie T.; Dettman, Heather; Gray, Murray R.; Pickard, Michael A.

2003-01-01

Microbial metabolism of organosulfur compounds is of interest in the petroleum industry for in-field viscosity reduction and desulfurization. Here, dibenzyl sulfide (DBS) metabolism in white rot fungi was studied. Trametes trogii UAMH 8156, Trametes hirsuta UAMH 8165, Phanerochaete chrysosporium ATCC 24725, Trametes versicolor IFO 30340 (formerly Coriolus sp.), and Tyromyces palustris IFO 30339 all oxidized DBS to dibenzyl sulfoxide prior to oxidation to dibenzyl sulfone. The cytochrome P-450 inhibitor 1-aminobenzotriazole eliminated dibenzyl sulfoxide oxidation. Laccase activity (0.15 U/ml) was detected in the Trametes cultures, and concentrated culture supernatant and pure laccase catalyzed DBS oxidation to dibenzyl sulfoxide more efficiently in the presence of 2,2′-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS) than in its absence. These data suggest that the first oxidation step is catalyzed by extracellular enzymes but that subsequent metabolism is cytochrome P-450 mediated. PMID:12571066

Nano sulfide and oxide semiconductors as promising materials for studies by positron annihilation

NASA Astrophysics Data System (ADS)

Nambissan, P. M. G.

2013-06-01

A number of wide band gap sulfide and oxide semiconducting nanomaterial systems were investigated using the experimental techniques of positron lifetime and coincidence Doppler broadening measurements. The results indicated several features of the nanomaterial systems, which were found strongly related to the presence of vacancy-type defects and their clusters. Quantum confinement effects were displayed in these studies as remarkable changes in the positron lifetimes and the lineshape parameters around the same grain sizes below which characteristic blue shifts were observed in the optical absorption spectra. Considerable enhancement in the band gap and significant rise of the positron lifetimes were found occurring when the particle sizes were reduced to very low sizes. The results of doping or substitutions by other cations in semiconductor nanosystems were also interesting. Variously heat-treated TiO2 nanoparticles were studied recently and change of positron annihilation parameters across the anatase to rutile structural transition are carefully analyzed. Preliminary results of positron annihilation studies on Eu-doped CeO nanoparticles are also presented.

Cadmium sulfide membranes

DOEpatents

Spanhel, Lubomir; Anderson, Marc A.

1992-07-07

A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

Cadmium sulfide membranes

DOEpatents

Spanhel, Lubomir; Anderson, Marc A.

1991-10-22

A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

Protective effects of hydrogen sulfide on chronic kidney disease by reducing oxidative stress, inflammation and apoptosis

PubMed Central

Askari, Hassan; Seifi, Behjat; Kadkhodaee, Mehri; Sanadgol, Nima; Elshiekh, Mohammed; Ranjbaran, Mina; Ahghari, Parisa

2018-01-01

The current study aimed to examine the renoprotective effects of long-term treatment with sodium hydrosulfide (NaHS), a prominent hydrogen sulfide donor, in 5/6 nephrectomy animal model. Twenty-four rats were randomly divided into 3 groups including sham-operated group (Sham), 5/6-nephrectomized group (5/6 Nx), and NaHS-treated group (5/6Nx+NaHS). NaHS (30 micromol/l) was added twice daily into the drinking water and renal failure was induced by 5/6 nephrectomy. Twelve weeks after surgical procedure, blood pressure, creatinine clearance (CCr), urine concentration of neutrophil gelatinase associated lipocalin (NGAL) and tissue concentration of malondialdehyde (MDA), superoxide dismutase (SOD), as well as renal morphological changes, apoptosis (cleaved caspase-3) and inflammation (p-NF-κB) were measured. Five-sixth nephrectomy induced severe renal damage as indicated by renal dysfunction, hypertension and significant histopathological injury which were associated with increased NGAL and MDA levels, oxidant/antioxidant imbalance, decreased SOD activity and CCr and also overexpression of p-NF-κB and cleaved caspase-3 proteins. Instead, NaHS treatment attenuated renal dysfunction through reduction of NGAL concentration, hypertension, CCr, oxidant/antioxidant imbalance, inflammation and apoptosis. These findings suggest that long term NaHS treatment can be useful in preventing the progression of CKD by improving oxidant/antioxidant balance and reducing inflammation and apoptosis in the kidney. PMID:29383015

Adsorption-oxidation of hydrogen sulfide on Fe/walnut-shell activated carbon surface modified by NH3-plasma.

PubMed

Ning, Ping; Liu, Sijian; Wang, Chi; Li, Kai; Sun, Xin; Tang, Lihong; Liu, Gui

2018-02-01

Walnut-shell activated carbon (WSAC) supported ferric oxide was modified by non-thermal plasma (NTP), and the removal efficiency for hydrogen sulfide over Fe/WSAC modified by dielectric barrier discharge (DBD) was significantly promoted. The sample modified for 10min and 6.8kV output (30V input voltage) maintained 100% H 2 S conversion over a long reaction time of 390min. The surface properties of adsorbents modified by NTP under different conditions were evaluated by the methods of X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) analysis and in-situ Fourier transform infrared spectroscopy (FTIR), to help understand the effect of the NTP treatment. NTP treatment enhanced the adsorption capacity of Fe/WSAC, which could due to the formation of micro-pores with sizes of 0.4, 0.5 and 0.75nm. XPS revealed that chemisorbed oxygen changed into lattice oxygen after NTP treatment, and lattice oxygen is beneficial for H 2 S oxidation. From the in-situ FTIR result, transformation of the reaction path on Fe/WSAC was observed after NTP modification. The research results indicate that NTP is an effective method to improve the surface properties of the Fe/WSAC catalyst for H 2 S adsorption-oxidation. Copyright © 2017. Published by Elsevier B.V.

Removal of dimethyl sulfide by the combination of non-thermal plasma and biological process.

PubMed

Wei, Z S; Li, H Q; He, J C; Ye, Q H; Huang, Q R; Luo, Y W

2013-10-01

A bench scale system integrated with a non-thermal plasma (NTP) and a biotricking filtration (BTF) unit for the treatment of gases containing dimethyl sulfide (DMS) was investigated. DMS removal efficiency in the integrated system was up to 96%. Bacterial communities in the BTF were assessed by PCR-DGGE, which play the dominant role in the biological processes of metabolism, sulfur oxidation, sulfate-reducing and carbon oxidation. The addition of ozone from NTP made microbial community in BTF more complicated and active for DMS removal. The NTP oxidize DMS to simple compounds such as methanol and carbonyl sulfide; the intermediate organic products and DMS are further oxidized to sulfate, carbon dioxide, water vapors by biological degradation. These results show that NTP-BTF is achievable and open new possibilities for applying the integrated with NTP and BTF to odour gas treatment. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a "Smart" Probe Answer!

PubMed

Ali, Moussa; Dondaine, Lucile; Adolle, Anais; Sampaio, Carla; Chotard, Florian; Richard, Philippe; Denat, Franck; Bettaieb, Ali; Le Gendre, Pierre; Laurens, Véronique; Goze, Christine; Paul, Catherine; Bodio, Ewen

2015-06-11

Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. The in vitro biological action of the gold complexes and the phosphonium derivative were investigated, and a preliminary in vivo study in healthy zebrafish larvae allowed us to evaluate gold complex biodistribution and toxicity. The different analyses carried out showed that these gold complexes were stable and behaved differently from phosphonium and auranofin, both in vitro and in vivo. Two-photon microscopy experiments demonstrated that the cellular targets of these gold complexes are not the same as those of the phosphonium analogue. Moreover, despite similar IC50 values in some cancer cell lines, gold complexes displayed a low toxicity in vivo, in contrast to the phosphonium salt. They are therefore suitable for future in vivo investigations.

Emission and distribution of phosphine in paddy fields and its relationship with greenhouse gases.

PubMed

Chen, Weiyi; Niu, Xiaojun; An, Shaorong; Sheng, Hong; Tang, Zhenghua; Yang, Zhiquan; Gu, Xiaohong

2017-12-01

Phosphine (PH 3 ), as a gaseous phosphide, plays an important role in the phosphorus cycle in ecosystems. In this study, the emission and distribution of phosphine, carbon dioxide (CO 2 ) and methane (CH 4 ) in paddy fields were investigated to speculate the future potential impacts of enhanced greenhouse effect on phosphorus cycle involved in phosphine by the method of Pearson correlation analysis and multiple linear regression analysis. During the whole period of rice growth, there was a significant positive correlation between CO 2 emission flux and PH 3 emission flux (r=0.592, p=0.026, n=14). Similarly, a significant positive correlation of emission flux was also observed between CH 4 and PH 3 (r=0.563, p=0.036, n=14). The linear regression relationship was determined as [PH 3 ] flux =0.007[CO 2 ] flux +0.063[CH 4 ] flux -4.638. No significant differences were observed for all values of matrix-bound phosphine (MBP), soil carbon dioxide (SCO 2 ), and soil methane (SCH 4 ) in paddy soils. However, there was a significant positive correlation between MBP and SCO 2 at heading, flowering and ripening stage. The correlation coefficients were 0.909, 0.890 and 0.827, respectively. In vertical distribution, MBP had the analogical variation trend with SCO 2 and SCH 4 . Through Pearson correlation analysis and multiple stepwise linear regression analysis, pH, redox potential (Eh), total phosphorus (TP) and acid phosphatase (ACP) were identified as the principal factors affecting MBP levels, with correlative rankings of Eh>pH>TP>ACP. The multiple stepwise regression model ([MBP]=0.456∗[ACP]+0.235∗[TP]-1.458∗[Eh]-36.547∗[pH]+352.298) was obtained. The findings in this study hold great reference values to the global biogeochemical cycling of phosphorus in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaluation of P1'-diversified phosphinic peptides leads to the development of highly selective inhibitors of MMP-11.

PubMed

Matziari, Magdalini; Beau, Fabrice; Cuniasse, Philippe; Dive, Vincent; Yiotakis, Athanasios

2004-01-15

Phosphinic peptides were previously reported to be potent inhibitors of several matrixins (MMPs). To identify more selective inhibitors of MMP-11, a matrixin overexpressed in breast cancer, a series of phosphinic pseudopeptides bearing a variety of P(1)'-side chains has been synthesized, by parallel diversification of a phosphinic template. The potencies of these compounds were evaluated against a set of seven MMPs (MMP-2, MMP-7, MMP-8, MMP-9, MMP-11, MMP-13, and MMP-14). The chemical strategy applied led to the identification of several phosphinic inhibitors displaying high selectivity toward MMP-11. One of the most selective inhibitors of MMP-11 in this series, compound 22, exhibits a K(i) value of 0.23 microM toward MMP-11, while its potency toward the other MMPs tested is 2 orders of magnitude lower. This remarkable selectivity may rely on interactions of the P(1)'-side chain atoms of these inhibitors with residues located at the entrance of the S(1)'-cavity of MMP-11. The design of inhibitors able to interact with residues located at the entrance of MMPs' S(1)'-cavity might represent an alternative strategy to identify selective inhibitors that will fully differentiate one MMP among the others.

Facile Synthesis of Flower-Like Copper-Cobalt Sulfide as Binder-Free Faradaic Electrodes for Supercapacitors with Improved Electrochemical Properties

PubMed Central

Wang, Tianlei; Liu, Meitang; Ma, Hongwen

2017-01-01

Supercapacitors have been one of the highest potential candidates for energy storage because of their significant advantages beyond rechargeable batteries in terms of large power density, short recharging time, and long cycle lifespan. In this work, Cu–Co sulfides with uniform flower-like structure have been successfully obtained via a traditional two-step hydrothermal method. The as-fabricated Cu–Co sulfide vulcanized from precursor (P–Cu–Co sulfide) is able to deliver superior specific capacitance of 592 F g−1 at 1 A g−1 and 518 F g−1 at 10 A g−1 which are surprisingly about 1.44 times and 2.39 times higher than those of Cu–Co oxide electrode, respectively. At the same time, excellent cycling stability of P–Cu–Co sulfide is indicated by 90.4% capacitance retention at high current density of 10 A g−1 after 3000 cycles. Because of the introduction of sulfur during the vulcanization process, these new developed sulfides can get more flexible structure and larger reaction surface area, and will own richer redox reaction sites between the interfaces of active material/electrolyte. The uniform flower-like P–Cu–Co sulfide electrode materials will have more potential alternatives for oxides electrode materials in the future. PMID:28590417

Facile Synthesis of Flower-Like Copper-Cobalt Sulfide as Binder-Free Faradaic Electrodes for Supercapacitors with Improved Electrochemical Properties.

PubMed

Wang, Tianlei; Liu, Meitang; Ma, Hongwen

2017-06-07

Supercapacitors have been one of the highest potential candidates for energy storage because of their significant advantages beyond rechargeable batteries in terms of large power density, short recharging time, and long cycle lifespan. In this work, Cu-Co sulfides with uniform flower-like structure have been successfully obtained via a traditional two-step hydrothermal method. The as-fabricated Cu-Co sulfide vulcanized from precursor (P-Cu-Co sulfide) is able to deliver superior specific capacitance of 592 F g -1 at 1 A g -1 and 518 F g -1 at 10 A g -1 which are surprisingly about 1.44 times and 2.39 times higher than those of Cu-Co oxide electrode, respectively. At the same time, excellent cycling stability of P-Cu-Co sulfide is indicated by 90.4% capacitance retention at high current density of 10 A g -1 after 3000 cycles. Because of the introduction of sulfur during the vulcanization process, these new developed sulfides can get more flexible structure and larger reaction surface area, and will own richer redox reaction sites between the interfaces of active material/electrolyte. The uniform flower-like P-Cu-Co sulfide electrode materials will have more potential alternatives for oxides electrode materials in the future.

Blood oxidative stress (BLOS) is a secondary host defense system responding normally to anaerobic wound infection and inadvertently to dietary ultra-exogenous sulfide formation (USF).

PubMed

Stroot, Peter G

2017-01-01

Blood oxidative stress (BLOS) is the presence of white blood cells and platelets that are generating high levels of reactive oxygen species (ROS). A mathematical model links the level of BLOS or BLOS# and plasma sulfide concentration. An increase in the BLOS# reduces the plasma sulfide concentration. The reported maximum plasma sulfide concentration for defined health conditions were used to calculate the minimum BLOS#. Elevated BLOS generates high plasma concentration of ROS, which triggers multiple responses in the body that protect the host. First, insulin production by the pancreas is inhibited, which results in elevated blood glucose levels. This results in advanced glycation end products (AGE), which thicken the blood vessel wall. Elevated blood glucose levels also increases urination, which reduces the availability of substrates for infectious bacteria. Second, one or more signaling molecules are stimulated to produce vascular hypertrophy resulting in hypertension. Third, the initial stage of atherosclerosis thickens the blood vessel wall while also protecting the inner surface of the blood vessels from localized infection. The first three mechanisms provide added protection against pathogen migration through the blood vessel wall and reduce the cross-sectional area of blood vessels, which increases the retention time (RT) for improved ROS inactivation of pathogens. Fourth, genes expressed in the liver, which are associated with drug oxidation and uptake transport, are inhibited. This inhibition protects the host from any toxins produced by an anaerobic infection. Elevated BLOS also reduces plasma sulfide concentration, which inhibits wound healing and extends aerobic conditions of the wound. The normal induction of BLOS offers a short-term, cascade of several primary mechanisms for secondary defense against anaerobic infection of a wound. Normal induction of BLOS is due to ultra-exogenous sulfide formation (USF) generated by a local anaerobic infection of a

Reactions of Mono(disilylamino)phosphines with Carbon Tetrachloride.

DTIC Science & Technology

1984-05-18

and LiN(SiMe 3 )2 . Allyl and benzyl Grignard reagents were used in the Wilburn synthesis 6 to prepare phosphines L5-18. Compounds 15, 16, and 17, each...Section General Procedures. The following reagents were purchased from commercial sources and used without further purification: MeMgBr(Et20), PhCH...2.7 M, 99 mmol) was added dropwise via the addition funnel. The mixture was allowed to warm to room temperature and to stir overnight. The Grignard

Particle Geochemistry of Hydrothermal Systems and Implications for Mining Seafloor Massive Sulfides

NASA Astrophysics Data System (ADS)

Gartman, A.; Hein, J. R.

2016-12-01

Seafloor massive sulfide deposits form due to high-temperature hydrothermal venting that occurs globally, in every ocean basin, along plate boundaries and intra-plate hotspots. At these sites, the rapid mixing of hot, metal- and sulfur-rich reduced fluids into cold, oxygenated ocean water results in abundant mineral precipitation. The mining of seafloor massive sulfides is likely to occur in the near future and will generate a new class of mainly inorganic particulates, different from those formed in hydrothermal `black smoke.' While the major components of both black smoke & SMS tailings are Cu, Fe and Zn sulfides, many other minerals, including those containing technology critical elements, especially tellurium, are present. A comparison of these two classes of particulates will be presented, including chemical composition and reactivity to oxidative dissolution.

Evaluation of feed COD/sulfate ratio as a control criterion for the biological hydrogen sulfide production and lead precipitation.

PubMed

Velasco, Antonio; Ramírez, Martha; Volke-Sepúlveda, Tania; González-Sánchez, Armando; Revah, Sergio

2008-03-01

The ability of sulfate-reducing bacteria to produce hydrogen sulfide and the high affinity of sulfide to react with divalent metallic cations represent an excellent option to remove heavy metals from wastewater. Different parameters have been proposed to control the hydrogen sulfide production by anaerobic bacteria, such as the organic and sulfate loading rates and the feed COD/SO4(2-) ratio. This work relates the feed COD/SO4(2-) ratio with the hydrogen sulfide production and dissolved lead precipitation, using ethanol as carbon and energy source in an up-flow anaerobic sludge blanket reactor. A maximum dissolved sulfide concentration of 470+/-7 mg S/L was obtained at a feed COD/SO4(2-) ratio of 2.5, with sulfate and ethanol conversions of approximately 94 and 87%, respectively. The lowest dissolved sulfide concentration (145+/-10 mg S/L) was observed with a feed COD/SO4(2-) ratio of 0.67. Substantial amounts of acetate (510-1730 mg/L) were produced and accumulated in the bioreactor from ethanol oxidation. Although only incomplete oxidation of ethanol to acetate was observed, the consortium was able to remove 99% of the dissolved lead (200 mg/L) with a feed COD/SO4(2-) ratio of 1.5. It was found that the feed COD/SO4(2-) ratio could be an adequate parameter to control the hydrogen sulfide production and the consequent precipitation of dissolved lead.

The effects of oxygen scavenging on jet fuel thermal stability

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heneghan, S.P.; Williams, T.F.; Whitacre, S.

1996-10-01

Preliminary tests with a proposed oxygen scavenger (triphenyl-phosphine, TPP) have been done in closed static and flowing systems to study its effects on the oxidation and the deposit formation of jet fuel. TPP was found to significantly slow the oxidation of hexadecane or jet fuel at some temperatures/concentrations and increase the oxidation rate at other conditions. The additive helped decrease the formation of deposits at higher concentrations (200 mg/l) but not at lower concentrations. No evidence of phosphorous was observed in the deposits that were formed. Gas chomatography combined with mass spectrometry and atomic emission detection showed that TPP producedmore » the expected oxidation product (triphenylphosphineoxide) and an unexpected triphenylphosphine-sulfide. The GC/AED allowed A quantitative analysis of the conversion efficiency of TPP to TPPO upon stressing in a closed system.« less

Phosphine Resistance in Adult and Immature Life Stages of Tribolium castaneum (Coleoptera: Tenebrionidae) and Plodia interpunctella (Lepidoptera: Pyralidae) Populations in California.

PubMed

Gautam, S G; Opit, G P; Hosoda, E

2016-12-01

Phosphine resistance in stored-product insects occurs worldwide and is a major challenge to continued effective use of this fumigant. We determined resistance frequencies and levels of resistance in Tribolium castaneum and Plodia interpunctella collected from California almond storage and processing facilities. Discriminating doses of phosphine were established for eggs and larvae of P. interpunctella and eggs of T. castaneum using laboratory susceptible strains of the two species. For T. castaneum and P. interpunctella eggs, discriminating doses were 62.4 and 107.8 ppm, respectively, over a 3-d fumigation period, and for P. interpunctella larvae, discriminating dose was 98.7 ppm over a 20-h fumigation period. Discriminating dose tests on adults and eggs showed that 4 out of 11 T. castaneum populations tested had resistance frequencies that ranged from 42 to 100% for adults and 54 to 100% for eggs. LC99 values for the susceptible and the most resistant adults of T. castaneum were 7.4 and 356.9 ppm over 3 d, respectively. LC99 values for T. castaneum eggs were 51.5 and 653.9 ppm, respectively. Based on adult data, the most resistant T. castaneum beetle population was 49× more resistant than the susceptible strain. Phosphine resistance frequencies in P. interpunctella eggs ranged from 4 to 20%. Results show phosphine resistance is present in both species in California. Future research will investigate phosphine resistance over a wider geographic area. In addition, the history of pest management practices in facilities where insects tested in this study originated will be determined in order to develop phosphine resistance management strategies for California almond storage and processing facilities. © The Authors 2016. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Long-term effects of sulfidized silver nanoparticles in sewage sludge on soil microflora.

PubMed

Kraas, Marco; Schlich, Karsten; Knopf, Burkhard; Wege, Franziska; Kägi, Ralf; Terytze, Konstantin; Hund-Rinke, Kerstin

2017-12-01

The use of silver nanoparticles (AgNPs) in consumer products such as textiles leads to their discharge into wastewater and consequently to a transfer of the AgNPs to soil ecosystems via biosolids used as fertilizer. In urban wastewater systems (e.g., sewer, wastewater treatment plant [WWTP], anaerobic digesters) AgNPs are efficiently converted into sparingly soluble silver sulfides (Ag 2 S), mitigating the toxicity of the AgNPs. However, long-term studies on the bioavailability and effects of sulfidized AgNPs on soil microorganisms are lacking. Thus we investigated the bioavailability and long-term effects of AgNPs (spiked in a laboratory WWTP) on soil microorganisms. Before mixing the biosolids into soil, the sludges were either anaerobically digested or directly dewatered. The effects on the ammonium oxidation process were investigated over 140 d. Transmission electron microscopy (TEM) suggested an almost complete sulfidation of the AgNPs analyzed in all biosolid samples and in soil, with Ag 2 S predominantly detected in long-term incubation experiments. However, despite the sulfidation of the AgNPs, soil ammonium oxidation was significantly inhibited, and the degree of inhibition was independent of the sludge treatment. The results revealed that AgNPs sulfidized under environmentally relevant conditions were still bioavailable to soil microorganisms. Consequently, Ag 2 S may exhibit toxic effects over the long term rather than the short term. Environ Toxicol Chem 2017;36:3305-3313. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC. © 2017 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

Surface modifications of steels to improve corrosion resistance in sulfidizing-oxidizing environments

NASA Astrophysics Data System (ADS)

Behrani, Vikas

Industrial and power generation processes employ units like boilers and gasifiers to burn sulfur containing fuels to produce steam and syn gas (H 2 and CO), which can generate electricity using turbines and fuel cells. These units often operate under environments containing gases such as H 2S, SO2, O2 etc, which can attack the metallic structure and impose serious problems of corrosion. Corrosion control in high temperature sulfur bearing environments is a challenging problem requiring information on local gaseous species at the surface of alloy and mechanisms of degradation in these environments. Coatings have proved to be a better alternative for improving corrosion resistance without compromising the bulk mechanical properties. Changes in process conditions may result in thermal and/or environment cycling between oxidizing and sulfidizing environments at the alloy surface, which can damage the protective scale formed on the alloy surface, leading to increase in corrosion rates. Objective of this study was to understand the effect of fluctuating environments on corrosion kinetics of carbon steels and develop diffusion based coatings to mitigate the high temperatures corrosion under these conditions. More specifically, the focus was: (1) to characterize the local gaseous environments at the surface of alloys in boilers; (2) optimizing diffusion coatings parameters for carbon steel; (3) understand the underlying failure mechanisms in cyclic environments; (4) to improve aluminide coating behavior by co-deposition of reactive elements such as Yttrium and Hafnium; (5) to formulate a plausible mechanism of coating growth and effects of alloying elements on corrosion; and (6) to understand the spallation behavior of scale by measuring stresses in the scales. The understanding of coating mechanism and effects of fluctuating gaseous environments provides information for designing materials with more reliable performance. The study also investigates the mechanism behind

Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

NASA Technical Reports Server (NTRS)

Miller, Scott R.; Bebout, Brad M.

2004-01-01

Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

SULFIDE MINERALS IN SEDIMENTS

EPA Science Inventory

The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

Siderophile-element Anomalies in CK Carbonaceous Chondrites: Implications for Parent-body Aqueous Alteration and Terrestrial Weathering of Sulfides

NASA Technical Reports Server (NTRS)

Huber, Heinz; Rubin, Alan E.; Kallemeyn, Gregory W.; Wasson, John T.

2006-01-01

CK chondrites constitute the most oxidized anhydrous carbonaceous chondrite group; most of the Fe occurs in magnetite and in FeO-rich mafic silicates. The two observed CK falls (Karoonda and Kobe), along with thirteen relatively unweathered CK finds, have unfractionated siderophile-element abundance patterns. In contrast, a sizable fraction of CK finds (9 of 24 investigated) shows fractionated siderophile abundance patterns including low abundances of Ni, Co, Se and Au; the most extreme depletions are in Ni (0.24 of normal CK) and Au (0.14 of normal CK). This depletion pattern has not been found in other chondrite groups. Out of the 74 CK chondrites listed in the Meteoritical Bulletin Database (2006; excluded considerably paired specimens; see http://tin.er.usgs.gov/meteor/ metbull.php) we analyzed 24 and subclassified the CK chondrites in terms of their chemical composition and sulfide mineralogy: sL (siderophiles low; six samples) for large depletions in Ni, Co, Se and Au (>50% of sulfides lost); sM (siderophiles medium; two CKs) for moderately low Ni and Co abundances (sulfides are highly altered or partly lost); sH (siderophiles high; one specimen) for enrichments in Ni, Co, Se and Au; 'normal' for unfractionated samples (13 samples). The sole sH sample may have obtained additional sulfide from impact redistribution in the parent asteroid. We infer that these elements became incorporated into sulfides after asteroidal aqueous processes oxidized nebular metal; thermal metamorphism probably also played a role in their mineral siting. The siderophile losses in the SL and sM samples are mainly the result of oxidation of pentlandite, pyrite and violarite by terrestrial alteration followed by leaching of the resulting phases. Some Antarctic CK chondrites have lost most of their sulfides but retained Ni, Co, Se and Au, presumably as insoluble weathering products.

Transition of Blast Furnace Slag from Silicate Based to Aluminate Based: Sulfide Capacity

NASA Astrophysics Data System (ADS)

Yan, Zhiming; Lv, Xuewei; Pang, Zhengde; He, Wenchao; Liang, Dong; Bai, Chenguang

2017-10-01

The effect of Al2O3 and Al2O3/SiO2 ratio on the sulfide capacity of the molten aluminosilicate CaO-SiO2-Al2O3-MgO-TiO2 slag system with high Al2O3 content was measured at 1773 K (1500 °C) using a metal-slag equilibration method. The sulfide capacity between silicate-based and aluminate-based slag was also compared based on the thermodynamic analysis and structural characteristics of melts. At a fixed CaO/SiO2 ratio of 1.20, the sulfide capacity decreases with increasing Al2O3 content primarily due to the decrease of free oxygen (FO) and the activity of O2-. Increasing the Al2O3/SiO2 ratio from 0.47 to 0.79 causes a significant increase in the sulfide capacity of the slags, and a slight increase is found when the Al2O3/SiO2 ratio is more than 0.79. The effect of the substitution of silica by alumina on the sulfide capacity of the slags was not only due to an increase in the activity of basic oxides ( a_{{{O}^{2 - } }} ) but also to a decrease in the stability of sulfide ( γ_{{{S}^{2 - } }} ). Moreover, a_{{{O}^{2 - } }} and γ_{{{S}^{2 - } }} increase in a similar degree, and the weaker binding electronegativity of Al3+ with oxygen atoms results in a slight increase in the final sulfide capacity in the aluminate-based slag system with Al2O3 ↔ SiO2 substitution. Five different sulfide capacity models were employed to predict the sulfide capacity, and the iso-sulfide capacity distribution diagram based on the Young's model was obtained in the high Al2O3 corner of the diagram.

Novel unsymmetrical P/O substituted ferrocene ligands and the first structurally characterised hydroxyferrocene derivative.

PubMed

Atkinson, Robert C J; Gibson, Vernon C; Long, Nicholas J; White, Andrew J P; Williams, David J

2004-06-21

Two new unsymmetrical 1'-substituted hydroxyferrocene ligands featuring either phosphine or phosphine oxide substituents have been synthesised and the phosphine oxide derivative has been structurally characterised. A nickel complex of the hydroxyl/phosphine ligand has been formed, along with preliminary evaluation of the complex for catalysis of ethylene polymerisation.

Regeneration of sulfated metal oxides and carbonates

DOEpatents

Hubble, Bill R.; Siegel, Stanley; Cunningham, Paul T.

1978-03-28

Alkali metal or alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate found in dolomite or limestone are employed for removal of sulfur dioxide from combustion exhaust gases. The sulfated carbonates are regenerated to oxides through use of a solid-solid reaction, particularly calcium sulfide with calcium sulfate to form calcium oxide and sulfur dioxide gas. The regeneration is performed by contacting the sulfated material with a reductant gas such as hydrogen within an inert diluent to produce calcium sulfide in mixture with the sulfate under process conditions selected to permit the sulfide-sulfate, solid-state reaction to occur.

Biogeographic congruency among bacterial communities from terrestrial sulfidic springs

PubMed Central

Headd, Brendan; Engel, Annette S.

2014-01-01

Terrestrial sulfidic springs support diverse microbial communities by serving as stable conduits for geochemically diverse and nutrient-rich subsurface waters. Microorganisms that colonize terrestrial springs likely originate from groundwater, but may also be sourced from the surface. As such, the biogeographic distribution of microbial communities inhabiting sulfidic springs should be controlled by a combination of spring geochemistry and surface and subsurface transport mechanisms, and not necessarily geographic proximity to other springs. We examined the bacterial diversity of seven springs to test the hypothesis that occurrence of taxonomically similar microbes, important to the sulfur cycle, at each spring is controlled by geochemistry. Complementary Sanger sequencing and 454 pyrosequencing of 16S rRNA genes retrieved five proteobacterial classes, and Bacteroidetes, Chlorobi, Chloroflexi, and Firmicutes phyla from all springs, which suggested the potential for a core sulfidic spring microbiome. Among the putative sulfide-oxidizing groups (Epsilonproteobacteria and Gammaproteobacteria), up to 83% of the sequences from geochemically similar springs clustered together. Abundant populations of Hydrogenimonas-like or Sulfurovum-like spp. (Epsilonproteobacteria) occurred with abundant Thiothrix and Thiofaba spp. (Gammaproteobacteria), but Arcobacter-like and Sulfurimonas spp. (Epsilonproteobacteria) occurred with less abundant gammaproteobacterial populations. These distribution patterns confirmed that geochemistry rather than biogeography regulates bacterial dominance at each spring. Potential biogeographic controls were related to paleogeologic sedimentation patterns that could control long-term microbial transport mechanisms that link surface and subsurface environments. Knowing the composition of a core sulfidic spring microbial community could provide a way to monitor diversity changes if a system is threatened by anthropogenic processes or climate change. PMID

Metagenomic and Biochemical Characterizations of Sulfur Oxidation Metabolism in Uncultured Large Sausage-Shaped Bacterium in Hot Spring Microbial Mats

PubMed Central

Tamaki, Hideyuki; Kamagata, Yoichi; Hanada, Satoshi

2012-01-01

So-called “sulfur-turf” microbial mats in sulfide containing hot springs (55–70°C, pH 7.3–8.3) in Japan were dominated by a large sausage-shaped bacterium (LSSB) that is closely related to the genus Sulfurihydrogenibium. Several previous reports proposed that the LSSB would be involved in sulfide oxidation in hot spring. However, the LSSB has not been isolated yet, thus there has been no clear evidence showing whether it possesses any genes and enzymes responsible for sulfide oxidation. To verify this, we investigated sulfide oxidation potential in the LSSB using a metagenomic approach and subsequent biochemical analysis. Genome fragments of the LSSB (a total of 3.7 Mb sequence including overlapping fragments) were obtained from the metagenomic fosmid library constructed from genomic DNA of the sulfur-turf mats. The sequence annotation clearly revealed that the LSSB possesses sulfur oxidation-related genes coding sulfide dehydrogenase (SD), sulfide-quinone reductase and sulfite dehydrogenase. The gene encoding SD, the key enzyme for sulfide oxidation, was successfully cloned and heterologously expressed in Escherichia coli. The purified recombinant enzyme clearly showed SD activity with optimum temperature and pH of 60°C and 8.0, respectively, which were consistent with the environmental conditions in the hot spring where the sulfur-turf thrives. Furthermore, the affinity of SD to sulfide was relatively high, which also reflected the environment where the sulfide could be continuously supplied. This is the first report showing that the LSSB harbors sulfide oxidizing metabolism adapted to the hot spring environment and can be involved in sulfide oxidation in the sulfur-turf microbial mats. PMID:23185438

Control of morphology and crystal purity of InP nanowires by variation of phosphine flux during selective area MOMBE

NASA Astrophysics Data System (ADS)

Kelrich, A.; Dubrovskii, V. G.; Calahorra, Y.; Cohen, S.; Ritter, D.

2015-02-01

We present experimental results showing how the growth rate, morphology and crystal structure of Au-catalyzed InP nanowires (NWs) fabricated by selective area metal organic molecular beam epitaxy can be tuned by the growth parameters: temperature and phosphine flux. The InP NWs with 20-65 nm diameters are grown at temperatures of 420 and 480 °C with the PH3 flow varying from 1 to 9 sccm. The NW tapering is suppressed at a higher temperature, while pure wurtzite crystal structure is preferred at higher phosphine flows. Therefore, by combining high temperature and high phosphine flux, we are able to fabricate non-tapered and stacking fault-free InP NWs with the quality that other methods rarely achieve. We also develop a model for NW growth and crystal structure which explains fairly well the observed experimental tendencies.

Convergent modulation of singlet and triplet excited states of phosphine-oxide hosts through the management of molecular structure and functional-group linkages for low-voltage-driven electrophosphorescence.

PubMed

Han, Chunmiao; Zhang, Zhensong; Xu, Hui; Xie, Guohua; Li, Jing; Zhao, Yi; Deng, Zhaopeng; Liu, Shiyong; Yan, Pengfei

2013-01-02

The controllable tuning of the excited states in a series of phosphine-oxide hosts (DPExPOCzn) was realized through introducing carbazolyl and diphenylphosphine-oxide (DPPO) moieties to adjust the frontier molecular orbitals, molecular rigidity, and the location of the triplet excited states by suppressing the intramolecular interplay of the combined multi-insulating and meso linkage. On increasing the number of substituents, simultaneous lowering of the first singlet energy levels (S(1)) and raising of the first triplet energy levels (T(1), about 3.0 eV) were achieved. The former change was mainly due to the contribution of the carbazolyl group to the HOMOs and the extended conjugation. The latter change was due to an enhanced molecular rigidity and the shift of the T(1) states from the diphenylether group to the carbazolyl moieties. This kind of convergent modulation of excited states not only facilitates the exothermic energy transfer to the dopants in phosphorescent organic light-emitting diodes (PHOLEDs), but also realizes the fine-tuning of electrical properties to achieve the balanced carrier injection and transportation in the emitting layers. As the result, the favorable performance of blue-light-emitting PHOLEDs was demonstrated, including much-lower driving voltages of 2.6 V for onset and 3.0 V at 100 cd m(-2), as well as a remarkably improved E.Q.E. of 12.6%. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanochemical processing of molybdenum and vanadium sulfides for metal recovery from spent catalysts wastes.

PubMed

Li, Zhao; Chen, Min; Zhang, Qiwu; Liu, Xinzhong; Saito, Fumio

2017-02-01

This work describes the mechanochemical transformations of molybdenum and vanadium sulfides into corresponding molybdate and vanadate, to serve as a new environment-friendly approach for processing hazardous spent hydrodesulphurization (HDS) catalysts solid waste to achieve an easy recovery of not only molybdenum and vanadium but also nickel and cobalt. Co-grinding the molybdenum and vanadium sulfides with oxidants and sodium carbonate stimulates solid-state reactions without any heating aid to form metal molybdates and vanadates. The reactions proceed with an increase in grinding time and were enhanced by using more sodium carbonate and stronger oxidant. The necessary conditions for the successful transformation can be explained on the basis of thermodynamic analyses, namely a negative change in Gibbs free energy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Nitrosopersulfide (SSNO(-)) accounts for sustained NO bioactivity of S-nitrosothiols following reaction with sulfide.

PubMed

Cortese-Krott, Miriam M; Fernandez, Bernadette O; Santos, José L T; Mergia, Evanthia; Grman, Marian; Nagy, Péter; Kelm, Malte; Butler, Anthony; Feelisch, Martin

2014-01-01

Sulfide salts are known to promote the release of nitric oxide (NO) from S-nitrosothiols and potentiate their vasorelaxant activity, but much of the cross-talk between hydrogen sulfide and NO is believed to occur via functional interactions of cell regulatory elements such as phosphodiesterases. Using RFL-6 cells as an NO reporter system we sought to investigate whether sulfide can also modulate nitrosothiol-mediated soluble guanylyl cyclase (sGC) activation following direct chemical interaction. We find a U-shaped dose response relationship where low sulfide concentrations attenuate sGC stimulation by S-nitrosopenicillamine (SNAP) and cyclic GMP levels are restored at equimolar ratios. Similar results are observed when intracellular sulfide levels are raised by pre-incubation with the sulfide donor, GYY4137. The outcome of direct sulfide/nitrosothiol interactions also critically depends on molar reactant ratios and is accompanied by oxygen consumption. With sulfide in excess, a 'yellow compound' accumulates that is indistinguishable from the product of solid-phase transnitrosation of either hydrosulfide or hydrodisulfide and assigned to be nitrosopersulfide (perthionitrite, SSNO(-); λ max 412 nm in aqueous buffers, pH 7.4; 448 nm in DMF). Time-resolved chemiluminescence and UV-visible spectroscopy analyses suggest that its generation is preceded by formation of the short-lived NO-donor, thionitrite (SNO(-)). In contrast to the latter, SSNO(-) is rather stable at physiological pH and generates both NO and polysulfides on decomposition, resulting in sustained potentiation of SNAP-induced sGC stimulation. Thus, sulfide reacts with nitrosothiols to form multiple bioactive products; SSNO(-) rather than SNO(-) may account for some of the longer-lived effects of nitrosothiols and contribute to sulfide and NO signaling.

Pediatric Cystic Fibrosis Sputum Can Be Chemically Dynamic, Anoxic, and Extremely Reduced Due to Hydrogen Sulfide Formation

PubMed Central

Cowley, Elise S.; Kopf, Sebastian H.; LaRiviere, Alejandro

2015-01-01

ABSTRACT Severe and persistent bacterial lung infections characterize cystic fibrosis (CF). While several studies have documented the microbial diversity within CF lung mucus, we know much less about the inorganic chemistry that constrains microbial metabolic processes and their distribution. We hypothesized that sputum is chemically heterogeneous both within and between patients. To test this, we measured microprofiles of oxygen and sulfide concentrations as well as pH and oxidation-reduction potentials in 48 sputum samples from 22 pediatric patients with CF. Inorganic ions were measured in 20 samples from 12 patients. In all cases, oxygen was depleted within the first few millimeters below the sputum-air interface. Apart from this steep oxycline, anoxia dominated the sputum environment. Different sputum samples exhibited a broad range of redox conditions, with either oxidizing (16 mV to 355 mV) or reducing (−300 to −107 mV) potentials. The majority of reduced samples contained hydrogen sulfide and had a low pH (2.9 to 6.5). Sulfide concentrations increased at a rate of 0.30 µM H2S/min. Nitrous oxide was detected in only one sample that also contained sulfide. Microenvironmental variability was observed both within a single patient over time and between patients. Modeling oxygen dynamics within CF mucus plugs indicates that anoxic zones vary as a function of bacterial load and mucus thickness and can occupy a significant portion of the mucus volume. Thus, aerobic respiration accounts only partially for pathogen survival in CF sputum, motivating research to identify mechanisms of survival under conditions that span fluctuating redox states, including sulfidic environments. PMID:26220964

A paradox resolved: Sulfide acquisition by roots of seep tubeworms sustains net chemoautotrophy

PubMed Central

Freytag, John K.; Girguis, Peter R.; Bergquist, Derk C.; Andras, Jason P.; Childress, James J.; Fisher, Charles R.

2001-01-01

Vestimentiferan tubeworms, symbiotic with sulfur-oxidizing chemoautotrophic bacteria, dominate many cold-seep sites in the Gulf of Mexico. The most abundant vestimentiferan species at these sites, Lamellibrachia cf. luymesi, grows quite slowly to lengths exceeding 2 meters and lives in excess of 170–250 years. L. cf. luymesi can grow a posterior extension of its tube and tissue, termed a “root,” down into sulfidic sediments below its point of original attachment. This extension can be longer than the anterior portion of the animal. Here we show, using methods optimized for detection of hydrogen sulfide down to 0.1 μM in seawater, that hydrogen sulfide was never detected around the plumes of large cold-seep vestimentiferans and rarely detectable only around the bases of mature aggregations. Respiration experiments, which exposed the root portions of L. cf. luymesi to sulfide concentrations between 51–561 μM, demonstrate that L. cf. luymesi use their roots as a respiratory surface to acquire sulfide at an average rate of 4.1 μmol⋅g−1⋅h−1. Net dissolved inorganic carbon uptake across the plume of the tubeworms was shown to occur in response to exposure of the posterior (root) portion of the worms to sulfide, demonstrating that sulfide acquisition by roots of the seep vestimentiferan L. cf. luymesi can be sufficient to fuel net autotrophic total dissolved inorganic carbon uptake. PMID:11687647

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.

PubMed

Kreitman, Gal Y; Danilewicz, John C; Jeffery, David W; Elias, Ryan J

2016-05-25

Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.

Corrosion behavior of an HVOF-sprayed Fe3Al coating in a high-temperature oxidizing/sulfidizing environment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Covino, Bernard S., Jr.; Bullard, Sophie J.; Cramer, Stephen D.

An iron aluminide (Fe3Al) intermetallic coating was deposited onto a F22 (2.25Cr-1Mo) steel substrate using a JP-5000 high velocity oxy-fuel (HVOF) thermal spray system. The as-sprayed coating was examined by electron microscopy and X-ray diffraction and was characterized in terms of oxidation and adhesion. Fe3Al-coated steel specimens were exposed to a mixed oxidizing/sulfidizing environment at 500, 600, 700, and 800DGC for approximately seven days. The gaseous environment consisted of N2-10%CO-5%CO2-2%H2O-0.12%H2S (by volume). All specimens gained mass after exposure to the environment and the mass gains were found to be inversely proportional to temperature increases. Representative specimens exposed at each temperaturemore » were cross-sectioned and subjected to examination under a scanning electron microscope (SEM) and X-ray mapping. Results are presented in terms of corrosion weight gain and corrosion product formation. The purpose of the research presented here was to evaluate the effectiveness of an HVOF-sprayed Fe3Al coating in protecting a steel substrate exposed to a fossil energy environment.« less

Selective extraction of metal ions with polymeric extractants by ion exchange/redox

DOEpatents

Alexandratos, Spiro D.

1987-01-01

The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

Novel Microbial Assemblages Dominate Weathered Sulfide-Bearing Rock from Copper-Nickel Deposits in the Duluth Complex, Minnesota, USA

PubMed Central

Lapakko, Kim A.; Wenz, Zachary J.; Olson, Michael C.; Roepke, Elizabeth W.; Novak, Paige J.; Bailey, Jake V.

2017-01-01

ABSTRACT The Duluth Complex in northeastern Minnesota hosts economically significant deposits of copper, nickel, and platinum group elements (PGEs). The primary sulfide mineralogy of these deposits includes the minerals pyrrhotite, chalcopyrite, pentlandite, and cubanite, and weathering experiments show that most sulfide-bearing rock from the Duluth Complex generates moderately acidic leachate (pH 4 to 6). Microorganisms are important catalysts for metal sulfide oxidation and could influence the quality of water from mines in the Duluth Complex. Nevertheless, compared with that of extremely acidic environments, much less is known about the microbial ecology of moderately acidic sulfide-bearing mine waste, and so existing information may have little relevance to those microorganisms catalyzing oxidation reactions in the Duluth Complex. Here, we characterized the microbial communities in decade-long weathering experiments (kinetic tests) conducted on crushed rock and tailings from the Duluth Complex. Analyses of 16S rRNA genes and transcripts showed that differences among microbial communities correspond to pH, rock type, and experimental treatment. Moreover, microbial communities from the weathered Duluth Complex rock were dominated by taxa that are not typically associated with acidic mine waste. The most abundant operational taxonomic units (OTUs) were from the genera Meiothermus and Sulfuriferula, as well as from diverse clades of uncultivated Chloroflexi, Acidobacteria, and Betaproteobacteria. Specific taxa, including putative sulfur-oxidizing Sulfuriferula spp., appeared to be primarily associated with Duluth Complex rock, but not pyrite-bearing rocks subjected to the same experimental treatment. We discuss the implications of these results for the microbial ecology of moderately acidic mine waste with low sulfide content, as well as for kinetic testing of mine waste. IMPORTANCE Economic sulfide mineral deposits in the Duluth Complex may represent the largest

Novel Microbial Assemblages Dominate Weathered Sulfide-Bearing Rock from Copper-Nickel Deposits in the Duluth Complex, Minnesota, USA.

PubMed

Jones, Daniel S; Lapakko, Kim A; Wenz, Zachary J; Olson, Michael C; Roepke, Elizabeth W; Sadowsky, Michael J; Novak, Paige J; Bailey, Jake V

2017-08-15

The Duluth Complex in northeastern Minnesota hosts economically significant deposits of copper, nickel, and platinum group elements (PGEs). The primary sulfide mineralogy of these deposits includes the minerals pyrrhotite, chalcopyrite, pentlandite, and cubanite, and weathering experiments show that most sulfide-bearing rock from the Duluth Complex generates moderately acidic leachate (pH 4 to 6). Microorganisms are important catalysts for metal sulfide oxidation and could influence the quality of water from mines in the Duluth Complex. Nevertheless, compared with that of extremely acidic environments, much less is known about the microbial ecology of moderately acidic sulfide-bearing mine waste, and so existing information may have little relevance to those microorganisms catalyzing oxidation reactions in the Duluth Complex. Here, we characterized the microbial communities in decade-long weathering experiments (kinetic tests) conducted on crushed rock and tailings from the Duluth Complex. Analyses of 16S rRNA genes and transcripts showed that differences among microbial communities correspond to pH, rock type, and experimental treatment. Moreover, microbial communities from the weathered Duluth Complex rock were dominated by taxa that are not typically associated with acidic mine waste. The most abundant operational taxonomic units (OTUs) were from the genera Meiothermus and Sulfuriferula , as well as from diverse clades of uncultivated Chloroflexi , Acidobacteria , and Betaproteobacteria Specific taxa, including putative sulfur-oxidizing Sulfuriferula spp., appeared to be primarily associated with Duluth Complex rock, but not pyrite-bearing rocks subjected to the same experimental treatment. We discuss the implications of these results for the microbial ecology of moderately acidic mine waste with low sulfide content, as well as for kinetic testing of mine waste. IMPORTANCE Economic sulfide mineral deposits in the Duluth Complex may represent the largest

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Calculation of the visible-UV absorption spectra of hydrogen sulfide, bisulfide, polysulfides, and As and Sb sulfides, in aqueous solution

PubMed Central

Tossell, JA

2003-01-01

Recently we showed that visible-UV spectra in aqueous solution can be accurately calculated for arsenic (III) bisulfides, such as As(SH)3, As(SH)2S- and their oligomers. The calculated lowest energy transitions for these species were diagnostic of their protonation and oligomerization state. We here extend these studies to As and Sb oxidation state III and v sulfides and to polysulfides Sn2-, n = 2–6, the bisulfide anion, SH-, hydrogen sulfide, H2S and the sulfanes, SnH2, n = 2–5. Many of these calculations are more difficult than those performed for the As(iii) bisulfides, since the As and Sb(v) species are more acidic and therefore exist as highly charged anions in neutral and basic solutions. In general, small and/or highly charged anions are more difficult to describe computationally than larger, monovalent anions or neutral molecules. We have used both Hartree-Fock based (CI Singles and Time-Dependent HF) and density functional based (TD B3LYP) techniques for the calculations of absorption energy and intensity and have used both explicit water molecules and a polarizable continuum to describe the effects of hydration. We correctly reproduce the general trends observed experimentally, with absorption energies increasing from polysulfides to As, Sb sulfides to SH- to H2S. As and Sb(v) species, both monomers and dimers, also absorb at characteristically higher energies than do the analogous As and Sb(III)species. There is also a small reduction in absorption energy from monomeric to dimeric species, for both As and Sb III and v. The polysufides, on the other hand, show no simple systematic changes in UV spectra with chain length, n, or with protonation state. Our results indicate that for the As and Sb sulfides, the oxidation state, degree of protonation and degree of oligomerization can all be determined from the visible-UV absorption spectrum. We have also calculated the aqueous phase energetics for the reaction of S8 with SH- to produce the polysulfides

Using phosphine ligands with a biological role to modulate reactivity in novel platinum complexes

NASA Astrophysics Data System (ADS)

Echeverri, Marcelo; Alvarez-Valdés, Amparo; Navas, Francisco; Perles, Josefina; Sánchez-Pérez, Isabel; Quiroga, A. G.

2018-02-01

Three platinum complexes with cis and trans configuration cis-[Pt(TCEP)2Cl2], cis-[Pt(tmTCEP)2Cl2] and trans-[Pt(TCEP)2Cl2], where TCEP is tris(2-carboxyethyl)phosphine, have been synthesized and fully characterized by usual techniques including single-crystal X-ray diffraction for trans-[Pt(TCEP)2Cl2] and cis-[Pt(tmTCEP)2Cl2]. Here, we also report on an esterification process of TCEP, which takes place in the presence of alcohols, leading to a platinum complex coordinated to an ester tmTCEP (2-methoxycarbonylethyl phosphine) ligand. The stability in solution of the three compounds and their interaction with biological models such as DNA (pBR322 and calf thymus DNA) and proteins (lysozyme and RNase) have also been studied.

Case Study: Microbial Ecology and Forensics of Chinese Drywall-Elemental Sulfur Disproportionation as Primary Generator of Hydrogen Sulfide.

PubMed

Tomei Torres, Francisco A

2017-06-21

Drywall manufactured in China released foul odors attributed to volatile sulfur compounds. These included hydrogen sulfide, methyl mercaptan, and sulfur dioxide. Given that calcium sulfate is the main component of drywall, one would suspect bacterial reduction of sulfate to sulfide as the primary culprit. However, when the forensics, i.e., the microbial and chemical signatures left in the drywall, are studied, the evidence suggests that, rather than dissimilatory sulfate reduction, disproportionation of elemental sulfur to hydrogen sulfide and sulfate was actually the primary cause of the malodors. Forensic evidence suggests that the transformation of elemental sulfur went through several abiological and microbial stages: (1) partial volatilization of elemental sulfur during the manufacture of plaster of Paris, (2) partial abiotic disproportionation of elemental sulfur to sulfide and thiosulfate during the manufacture of drywall, (3) microbial disproportionation of elemental sulfur to sulfide and sulfate resulting in neutralization of all alkalinity, and acidification below pH 4, (4) acidophilic microbial disproportionation of elemental sulfur to sulfide and sulfuric acid, and (5) hydrogen sulfide volatilization, coating of copper fixtures resulting in corrosion, and oxidation to sulfur dioxide.

Studies on the effects of phosphine on Salmonella enterica serotype Enteritidis in culture medium and in black pepper (Piper nigrum).

PubMed

Castro, M F P M; Rezende, A C B; Benato, E A; Valentini, S R T; Furlani, R P Z; Tfouni, S A V

2011-04-01

The effect of phosphine on Salmonella enterica serotype Enteritidis inoculated in culture medium and in black pepper grains (Piper nigrum), as well as on the reduction of the microbial load of the dried and moisturized product, was verified. The postfumigation effect was verified in inoculated samples with 0.92 and 0.97 water activity (a(w)) exposed to 6 g/m(3) phosphine for 72 h, dried to 0.67 a(w), and stored for 24, 48, and 72 h. No decreases were observed in Salmonella Enteritidis populations in culture medium when fumigant concentrations up to 6 g/m(3) were applied for 48 h at 35°C. However, the colonies showed reductions in size and atypical coloration as the phosphine concentration increased. No reduction in Salmonella counts occurred on the inoculated dried samples after fumigation. On the other hand, when phosphine at concentrations of 6 g/m(3) was applied on moisturized black pepper for 72 h, decreases in Salmonella counts of around 80% were observed. The counts of total aerobic mesophilic bacterium populations of the dried and moisturized black pepper were not affected by the fumigant treatment. The results of the postfumigation studies indicated that Salmonella Enteritidis was absent in the fumigated grains after drying and storage for 72 h, indicating a promising application for this technique. It was concluded that for Salmonella Enteritidis control, phosphine fumigation could be applied to black pepper grains before drying and the producers should rigidly follow good agricultural practices, mainly during the drying process, in order to avoid product recontamination. Additional work is needed to confirm the findings with more Salmonella serotypes and strains.

Application of a 2-step process for the biological treatment of sulfidic spent caustics.

PubMed

de Graaff, Marco; Klok, Johannes B M; Bijmans, Martijn F M; Muyzer, Gerard; Janssen, Albert J H

2012-03-01

This research demonstrates the feasibility and advantages of a 2-step process for the biological treatment of sulfidic spent caustics under halo-alkaline conditions (i.e. pH 9.5; Na(+) = 0.8 M). Experiments with synthetically prepared solutions were performed in a continuously fed system consisting of two gas-lift reactors in series operated at aerobic conditions at 35 °C. The detoxification of sulfide to thiosulfate in the first step allowed the successful biological treatment of total-S loading rates up to 33 mmol L(-1) day(-1). In the second, biological step, the remaining sulfide and thiosulfate was completely converted to sulfate by haloalkaliphilic sulfide oxidizing bacteria. Mathematical modeling of the 2-step process shows that under the prevailing conditions an optimal reactor configuration consists of 40% 'abiotic' and 60% 'biological' volume, whilst the total reactor volume is 22% smaller than for the 1-step process. Copyright © 2011 Elsevier Ltd. All rights reserved.

Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center.

PubMed

Chu, Terry; Boyko, Yaroslav; Korobkov, Ilia; Kuzmina, Lyudmila G; Howard, Judith A K; Nikonov, Georgii I

2016-09-06

The aluminum(I) compound NacNacAl (1) reacts with diphenyl disulfide and diethyl sulfide to form the respective four-coordinate bis(phenyl sulfide) complex NacNacAl(SPh)2 (2) and alkyl thiolate aluminum complex NacNacAlEt(SEt) (3). As well, reaction of 1 with tetraphenyl diphosphine furnishes the bis(diphenyl phosphido) complex NacNacAl(PPh2)2 (4). Production of 3 and 4 are the first examples of C(sp(3))-S and R2P-PR2 activation by a main-group element complex. All three complexes were characterized by multinuclear NMR spectroscopy and X-ray crystal structure analysis. Furthermore, a variable-temperature NMR spectroscopic study was undertaken on 4 to study its dynamic behavior in solution.

Nanostructured metal sulfides for energy storage

NASA Astrophysics Data System (ADS)

Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

2014-08-01

Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

Perspective on recent developments on sulfur-containing agents and hydrogen sulfide signaling.

PubMed

Jacob, Claus; Anwar, Awais; Burkholz, Torsten

2008-10-01

The last couple of years have witnessed the coming together of several initially unconnected lines of investigation which now link natural sulfur products to hydrogen sulfide release and wide ranging cardiovascular protection. It has become apparent that sulfur compounds contained within garlic, onions, mushrooms and various edible beans and fruits may be transformed chemically or enzymatically in the human body with subsequent formation of hydrogen sulfide. The latter has emerged during the last decade from a shadowy existence as toxic gas to be recognized as the third gaseous transmitter besides nitric oxide ( (.)NO) and carbon monoxide (CO). Hydrogen sulfide is formed endogenously in the human body by enzymes such as cystathionine beta-synthase (CBS) in the brain and cystathionine gamma-lyase (CSE) in liver, vascular and non-vascular smooth muscle. Although its exact chemical and biochemical modes of action are still not fully understood, levels of hydrogen sulfide in the brain and vasculature have unambiguously been associated with human health and disease. Not surprisingly, agents releasing hydrogen sulfide, as well as inhibitors of hydrogen sulfide synthesis (CBS and CSE inhibitors) have been investigated. Apart from linking our daily diet to a healthy brain and cardiovasculature, these findings may also provide new leads for drug design. Future studies will therefore need to focus on how such compounds are formed and transformed in the relevant plants, how food processing affects their chemical constitution, and how they release hydrogen sulfide (or control its levels) in the human body. Such multidisciplinary research should ultimately answer the all-important question if a hearty diet is also good for the heart.

Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

2013-12-31

This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic andmore » environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe 1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe 3S 4) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe 2+, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe 3(PO 4) 2•8(H 2O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide-based reductions of U(VI) occurred in parallel. The UO 2 produced in

Metal sulfide thin films by chemical spray pyrolysis

NASA Astrophysics Data System (ADS)

Krunks, Malle; Mellikov, Enn

2001-04-01

CdS, ZnS and CuS thin films were prepared by spray pyrolysis method using metal chlorides and thiourea (tu) as starting materials. Metal sulfide films form as products of thermal decomposition of complexes Cd(tu)2Cl2, Zn(tu)2Cl2 and Cu(tu)Cl(DOT)1/2H2O, originally formed in aqueous solution at precursors molar ratio 1:2. The metal-ligand bonding is thermally stable up to 220 degrees Celsius, followed by multistep degradation process of complexes. The TG/DTA analysis show similar thermal behavior of complexes up to 300 degrees Celsius with the formation of metal sulfides in this decomposition step. In air intensive oxidation processes are detected close to 400, 600 and 720 degrees Celsius for Cu, Cd and Zn complexes, respectively. The results of thermoanalytical study and XRD of sprayed films show that CdS and ZnS films could be grown at 450 degrees Celsius even in air while deposition of copper sulfide films should be performed in an inert atmosphere. High total impurities content of 10 wt% in CdS films prepared at 240 degrees Celsius is originated from the precursor and reduced to 2 wt% by increasing the growth temperature up to 400 degrees Celsius.

Bioleaching of a low-grade nickel-copper sulfide by mixture of four thermophiles.

PubMed

Li, Shuzhen; Zhong, Hui; Hu, Yuehua; Zhao, Jiancun; He, Zhiguo; Gu, Guohua

2014-02-01

This study investigated thermophilic bioleaching of a low grade nickel-copper sulfide using mixture of four acidophilic thermophiles. Effects of 0.2g/L l-cysteine on the bioleaching process were further evaluated. It aimed at offering new alternatives for enhancing metal recoveries from nickel-copper sulfide. Results showed a recovery of 80.4% nickel and 68.2% copper in 16-day bioleaching without l-cysteine; while 83.7% nickel and 81.4% copper were recovered in the presence of l-cysteine. Moreover, nickel recovery was always higher than copper recovery. l-Cysteine was found contributing to lower pH value, faster microbial growth, higher Oxidation-Reduction Potential (ORP), higher zeta potential and absorbing on the sulfide surfaces through amino, carboxyl and sulfhydryl groups. X-ray Diffraction (XRD) patterns of leached residues showed generation of S, jarosite and ammoniojarosite. Denaturing Gradient Gel Electrophoresis (DGGE) results revealed that l-cysteine could have variant impacts on different microorganisms and changed the microbial community composition dramatically during nickel-copper sulfide bioleaching. Copyright © 2013 Elsevier Ltd. All rights reserved.

New spectrophotometric methods for the determinations of hydrogen sulfide present in the samples of lake water, industrial effluents, tender coconut, sugarcane juice and egg

NASA Astrophysics Data System (ADS)

Shyla, B.; Nagendrappa, G.

2012-10-01

The new methods are working on the principle that iron(III) is reduced to iron(II) by hydrogen sulfide, catechol and p-toluidine the system 1/hydrogen sulfide the system 2, in acidic medium followed by the reduced iron forming complex with 1,10-phenanthroline with λmax 510 nm. The other two methods are based on redox reactions between electrolytically generated manganese(III) sulfate taken in excess and hydrogen sulfide followed by the unreacted oxidant oxidizing diphenylamine λmax 570 the system 3/barium diphenylamine sulphonate λmax 540 nm, the system 4. The increase/decrease in the color intensity of the dye products of the systems 1 and 2 or 3 and 4 are proportional to the concentration of hydrogen sulfide with its quantification range 0.035-1.40 μg ml-1/0.14-1.40 μg ml-1.

Acute phosphine poisoning on board a bulk carrier: analysis of factors leading to a fatal case.

PubMed

Loddé, Brice; Lucas, David; Letort, Jean-Marie; Jegaden, Dominique; Pougnet, Richard; Dewitte, Jean-Dominique

2015-01-01

To determine accidental factors, clinical presentation and medical care in cases of seafarers presenting phosphine poisoning symptoms on board a bulk carrier. To consider primary prevention of this pathology, which can have extremely severe consequences. To analyse circumstances resulting in toxic exposure to phosphine in the sea transport sector. To obtain information from medical reports regarding the seafarer's rescue. To identify the causes of this accidental poisoning and how to establish an early, appropriate diagnosis thus avoiding other cases. In February 2008, on board a bulk carrier with a cargo of peas, a 56-year-old seafarer with intense abdominal and chest pains, associated with dizziness, was rescued by helicopter 80 miles away from the coast. Despite being admitted rapidly to hospital, his heart rate decreased associated with respiratory distress. He lost consciousness and convulsed. He finally died of pulmonary oedema, major metabolic acidosis and acute multi organ failure. The following day, the captain issued a rescue call from the same vessel for a 41-year-old man also with abdominal pain, vomiting and dizziness. The ECG only revealed type 1 Brugada syndrome. Then 11 other seafarers were evacuated for observation. 3 showed clinical abnormalities. Collective poisoning was suspected. Medical team found out that aluminium phosphide pellets had been put in the ship's hold for pest control before the vessel's departure. Seafarers were poisoned by phosphine gas spreading through cabins above the hold. It was found that the compartments and ducts were not airtight. Unfortunately, a seafarer on board a bulk carrier died in 2008 because of acute phosphine poisoning. Fumigation performed using this gas needs to be done with extreme care. Systematic checks need to be carried out before sailing to ensure that the vessel's compartments are airtight.

Structurally bound sulfide and sulfate in apatite from the Philips Mine iron oxide - apatite deposit, New York, USA: A tracer of redox changes

NASA Astrophysics Data System (ADS)

Sadove, G.; Konecke, B.; Fiege, A.; Simon, A. C.

2017-12-01

Multiple competing hypotheses attempt to explain the genesis of iron oxide-apatite (IOA) ore deposits. Many studies have investigated the chemistry of apatite because the abundances of F and Cl can distinguish magmatic vs. hydrothermal processes. Recent experiments demonstrate that apatite incorporates S6+, S4+, and S2-, and that total sulfur (∑S) as well as the S6+/∑S ratio in apatite vary systematically as a function of oxygen fugacity [1], providing information about sulfur budget and redox. Here, we present results from X-ray absorption near-edge structure (XANES) spectroscopy at the S K-edge, electron microprobe analyses, cathodoluminescence (CL) imaging, and element mapping of apatite from the Philip's Mine IOA deposit, southern Adirondack Mountains, USA. The Philip's Mine apatite contains inclusions of pyrite and pyrrhotite, where the latter includes iron oxide and Ni-rich domains. The apatite also contains inclusions of monazite, and exhibits complex CL zonation coincident with variations in the abundances of REE and S. The presence of monazite fingerprints fluid-mediated dissolution-reprecipitation of originally REE-enriched apatite [2]. The S XANES spectra reveal varying proportions of structurally bound S6+ and S2-, as the S6+/∑S ratio ranges from sulfide-only to sulfate-only. Notably, sulfide-dominated domains contain higher S contents than sulfate-dominated regions. These observations are consistent with co-crystallization of apatite and monosulfide solid solution (MSS) at reducing conditions, followed by decomposition of MSS to pyrrhotite, pyrite and intermediate solid solution (ISS, which is not preserved; [3]). Metasomatism of that assemblage by an oxidized fluid resulted in formation of monazite in apatite and iron oxide domains in pyrrhotite. We conclude that the deposit formed by a H2S-Fe-rich volatile phase, possibly evolved from a rather primitive magmatic source, which is consistent with the low Ti content of magnetite. The deposit was

Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors.

PubMed

Villa-Gomez, D K; Cassidy, J; Keesman, K J; Sampaio, R; Lens, P N L

2014-03-01

Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4(2-) ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing bioreactors. The sulfide was measured using a sulfide ion selective electrode (pS) and the values obtained were used to calculate proportional-integral-derivative (PID) controller parameters. The experiments were performed in an inverse fluidized bed bioreactor with automated operation using the LabVIEW software version 2009(®). A rapid response and high sulfide increment was obtained through a stepwise increase in the CODin concentration, while a stepwise decrease to the HRT exhibited a slower response with smaller sulfide increment. Irrespective of the way the OLR was decreased, the pS response showed a time-varying behavior due to sulfide accumulation (HRT change) or utilization of substrate sources that were not accounted for (CODin change). The pS electrode response, however, showed to be informative for applications in sulfate reducing bioreactors. Nevertheless, the recorded pS values need to be corrected for pH variations and high sulfide concentrations (>200 mg/L). Copyright © 2013 Elsevier Ltd. All rights reserved.

Sulfides of Bottom Sediments in the Northeastern Part of the Black Sea

NASA Astrophysics Data System (ADS)

Rozanov, A. G.

2018-03-01

A study of bottom sediments conducted on the 100th cruise of R/V Professor Shtokman in the northeastern part of the Black Sea along the section from the Kerch Strait to the deep-sea depression allowed estimation of Holocene sulfide sedimentation and consideration of the accompanying diagenetic processes, which involve reactions with C, N, and P. The behavior of dissolved forms of Mn and Fe is considered from the viewpoint of their different solubility and formation of sulfides. The redox system of the Black Sea sediments can significantly be expanded at the expense of the migration methane and hydrogen, which accompanies its anaerobic oxidation.

Benzo[b]phosphole-containing pi-electron systems: synthesis based on an intramolecular trans-halophosphanylation and some insights into their properties.

PubMed

Fukazawa, Aiko; Ichihashi, Yasunori; Kosaka, Youhei; Yamaguchi, Shigehiro

2009-11-02

The intramolecular trans-halophosphanylation of 2-(aminophosphanyl)phenylacetylenes mediated by PBr3 followed by the oxidation with H2O2, produces 3-bromobenzo[b]phosphole oxide derivatives. This cyclization is also used for the synthesis of a 3-iodo derivative by conducting the reaction in the presence of LiI. Based on this synthetic method, various benzophosphole-containing pi-conjugated compounds, including a phosphoryl and methylene-bridged stilbene 10, 2,3,6,7-tetraphenylbenzo[1,2-b:4,5-b']diphosphole-P,P'-dioxides 11, and their phosphine sulfide derivatives 12, are synthesized. The study of the structure-property relationships in a series of the bridged stilbenes, including a bis(methylene)-bridged stilbene 10, and a bis(phosphoryl)-bridged stilbene, reveals that as the contribution of the phosphoryl groups increased, the absorption and emission maxima substantially shift to longer wavelengths. The intrinsic substituent effects of the phosphoryl group in this skeleton are to decrease the oscillator strength of the electronic transition and thus decrease the radiative decay rate constants from the singlet excited state. Nevertheless, these compounds maintain high fluorescence quantum yields (Phi(F)>0.8) owing to the significantly retarded nonradiative decay process. In the study of the benzodiphosphole derivatives 11 and 12, their cyclic voltammetry revealed that both of the phosphoryl and phosphine sulfide derivatives have low reduction potentials (-1.7 to -1.8 V vs ferrocene/ferrocenium couple) with the high reversibility of the redox waves. These compounds also showed high thermal stabilities with the high glass transition temperatures of 147-159 degrees C, indicative of their potential utilities as amorphous materials.

A novel method for improving cerussite sulfidization

NASA Astrophysics Data System (ADS)

Feng, Qi-cheng; Wen, Shu-ming; Zhao, Wen-juan; Cao, Qin-bo; Lü, Chao

2016-06-01

Evaluation of flotation behavior, solution measurements, and surface analyses were performed to investigate the effects of chloride ion addition on the sulfidization of cerussite in this study. Micro-flotation tests indicate that the addition of chloride ions prior to sulfidization can significantly increase the flotation recovery of cerussite, which is attributed to the formation of more lead sulfide species on the mineral surface. Solution measurement results suggest that the addition of chloride ions prior to sulfidization induces the transformation of more sulfide ions from pulp solution onto the mineral surface by the formation of more lead sulfide species. X-ray diffraction and energy-dispersive spectroscopy indicate that more lead sulfide species form on the mineral surface when chloride ions are added prior to sulfidization. These results demonstrate that the addition of chloride ions prior to sulfidization can significantly improve the sulfidization of cerussite, thereby enhancing the flotation performance.

[Investigation of stages of chemical leaching and biooxidation during the extraction of gold from sulfide concentrates].

PubMed

Murav'ev, M I; Fomchenko, N V; Kondrat'eva, T V

2015-01-01

We examined the chemical leaching and biooxidation stages in a two-stage biooxidation process of an auriferous sulfide concentrate containing pyrrhotite, arsenopyrite and pyrite. Chemical leaching of the concentrate (slurry density at 200 g/L) by ferric sulfate biosolvent (initial concentration at 35.6 g/L), which was obtained by microbial oxidation of ferrous sulfate for 2 hours at 70°C at pH 1.4, was allowed to oxidize 20.4% ofarsenopyrite and 52.1% of sulfur. The most effective biooxidation of chemically leached concentrate was observed at 45°C in the presence of yeast extract. Oxidation of the sulfide concentrate in a two-step process proceeded more efficiently than in one-step. In a two-step mode, gold extraction from the precipitate was 10% higher and the content of elemental sulfur was two times lower than in a one-step process.

Sulfide as a Chemoautotrophic Electron Donor for Dissimilatory Arsenate Reduction in Mono Lake, California

NASA Astrophysics Data System (ADS)

Hoeft, S. E.; Kulp, T. R.; Stolz, J. S.; Oremland, R. S.

2003-12-01

In aqueous systems, arsenic occurs as arsenate [As(V)] or as arsenite [As(III)], with the latter form being more toxic and mobile. Mono Lake, California is a meromictic soda lake (pH = 9.8; salinity = 70-90 g/L) with exceptionally high arsenic content ( ˜200 μ M), a consequence of hydrothermal inputs combined with evaporative concentration. Previous work has shown that arsenic speciation changes from As(V) to the more reduced As(III) with vertical transition from the lake's surface oxic waters to its unmixed, anoxic bottom waters and that dissimilatory reduction is responsible for the observed change in arsenic speciation. Rates of in situ dissimilatory As(V) reduction measured by radiotracer ( ˜1- 6 μ mol/L/d) were estimated to be significant enough to mineralize up to 14% of annual primary productivity. Subsequent lab-based investigations with As(V)-amended ( ˜1-2 mM) bottom water displayed significantly higher rates (150-260 μ mol/L/d) of As(V) reduction and were not limited by the availability of organic electron donors such as acetate, lactate, malate and glucose. The focus of this study was to identify a natural source of electrons for As(V) reduction in Mono Lake. While Mono Lake contains plentiful dissolved organic carbon ( ˜7 mM) this material is usually refractory and resistant to bacterial oxidation. Alternatively, the anoxic bottom waters contain high concentrations of sulfide ions ( ˜1-2 mM) that could potentially serve as an electron donor for dissimilatory As(V) reduction. In a time course experiment with As(V)-amended Mono Lake bottom water, we observed oxidation of sulfide linked to the reduction of As(V) to As(III). This reaction did not occur in filter sterilized controls and sulfide loss did not occur in samples lacking As(V). In bottom water amended with additional sulfide (total = 6 mM) and As(V), we observed a linear relationship between rates of dissimilatory As(V) reduction and As(V) concentration. The highest rate observed under

Model-Based Feasibility Assessment of Membrane Biofilm Reactor to Achieve Simultaneous Ammonium, Dissolved Methane, and Sulfide Removal from Anaerobic Digestion Liquor

PubMed Central

Chen, Xueming; Liu, Yiwen; Peng, Lai; Yuan, Zhiguo; Ni, Bing-Jie

2016-01-01

In this study, the membrane biofilm reactor (MBfR) is proposed to achieve simultaneous removal of ammonium, dissolved methane, and sulfide from main-stream and side-stream anaerobic digestion liquors. To avoid dissolved methane stripping, oxygen is introduced through gas-permeable membranes, which also from the substratum for the growth of a biofilm likely comprising ammonium oxidizing bacteria (AOB), anaerobic ammonium oxidation (Anammox) bacteria, denitrifying anaerobic methane oxidation (DAMO) microorganisms, aerobic methane oxidizing bacteria (MOB), and sulfur oxidizing bacteria (SOB). A mathematical model is developed and applied to assess the feasibility of such a system and the associated microbial community structure under different operational conditions. The simulation studies demonstrate the feasibility of achieving high-level (>97.0%), simultaneous removal of ammonium, dissolved methane, and sulfide in the MBfRs from both main-stream and side-stream anaerobic digestion liquors through adjusting the influent surface loading (or hydraulic retention time (HRT)) and the oxygen surface loading. The optimal HRT was found to be inversely proportional to the corresponding oxygen surface loading. Under the optimal operational conditions, AOB, DAMO bacteria, MOB, and SOB dominate the biofilm of the main-stream MBfR, while AOB, Anammox bacteria, DAMO bacteria, and SOB coexist in the side-stream MBfR to remove ammonium, dissolved methane, and sulfide simultaneously. PMID:27112502

Unique Cobalt Sulfide/Reduced Graphene Oxide Composite as an Anode for Sodium-Ion Batteries with Superior Rate Capability and Long Cycling Stability.

PubMed

Peng, Shengjie; Han, Xiaopeng; Li, Linlin; Zhu, Zhiqiang; Cheng, Fangyi; Srinivansan, Madhavi; Adams, Stefan; Ramakrishna, Seeram

2016-03-09

Exploitation of high-performance anode materials is essential but challenging to the development of sodium-ion batteries (SIBs). Among all proposed anode materials for SIBs, sulfides have been proved promising candidates due to their unique chemical and physical properties. In this work, a facile solvothermal method to in situ decorate cobalt sulfide (CoS) nanoplates on reduced graphene oxide (rGO) to build CoS@rGO composite is described. When evaluated as anode for SIBs, an impressive high specific capacity (540 mAh g(-1) at 1 A g(-1) ), excellent rate capability (636 mAh g(-1) at 0.1 A g(-1) and 306 mAh g(-1) at 10 A g(-1)), and extraordinarily cycle stability (420 mAh g(-1) at 1 A g(-1) after 1000 cycles) have been demonstrated by CoS@rGO composite for sodium storage. The synergetic effect between the CoS nanoplates and rGO matrix contributes to the enhanced electrochemical performance of the hybrid composite. The results provide a facile approach to fabricate promising anode materials for high-performance SIBs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficacy of Ozone against Phosphine Susceptible and Resistant Strains of Four Stored-Product Insect Species

PubMed Central

E, Xinyi; Subramanyam, Bhadriraju; Li, Beibei

2017-01-01

The efficacy of ozone was evaluated against four economically-important stored-product insect species at 27.2 °C and 20.4% r.h. Adults of phosphine-susceptible laboratory strains and phosphine-resistant field strains of the red flour beetle, Tribolium castaneum (Herbst), saw-toothed grain beetle, Oryzaephilus surinamensis (Linnaeus), maize weevil, Sitophilus zeamais Motschulsky, and rice weevil, Sitophilus oryzae (Linnaeus), were exposed in vials to an ozone concentration of 0.42 g/m3 (200 ppm) for 1, 2, 3, 5, 6, 8, 10 and 12 h with 0 and 10 g of wheat. Initial and final mortalities were assessed 1 and 5 d after exposure to ozone, respectively. After an 8–12-h exposure to ozone, initial mortality of Sitophilus spp. and O. surinamensis was 100%, whereas the highest initial mortality of T. castaneum was 90%. A 3–4-h exposure to ozone resulted in 100% final mortality of Sitophilus spp., whereas O. surinamensis required a 6- to 10-h exposure to ozone. Adults of T. castaneum were least susceptible to ozone, and after a 10-h exposure, mortality ranged between 82 and 95%. Time for the 5 d 99% mortality (LT99) for adults of laboratory and field strains of Sitophilus spp., O. surinamensis and T. castaneum were 2.00–5.56, 4.33–11.18 and 14.35–29.89 h, respectively. The LT99 values for adults of T. castaneum and O. surinamensis were not significantly different between bioassays conducted with 0 and 10 g of wheat. The LT99 values for the laboratory strains of Sitophilus spp. in the absence of wheat were significantly lower than those obtained in the presence of wheat. Both phosphine-susceptible and -resistant strains were equally susceptible to ozone. Ozone effectively suppressed adult progeny production of all four species. Ozone is a viable alternative fumigant to control phosphine-resistant strains of these four species. PMID:28398263

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ57/54Fe Observations

PubMed Central

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; Bach, Wolfgang; Edwards, Katrina J.

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50′N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ 57/54Fe observations

DOE PAGES

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.; ...

2016-05-10

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

PubMed

Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings

Investigation of weldable iron-aluminum alloys for corrosion protection in high temperature oxidizing-sulfidizing environments

NASA Astrophysics Data System (ADS)

Banovic, Stephen William

The objective of the present study was to investigate the corrosion behavior of weldable Fe-Al alloys in environments representative of low NOx gas compositions, i.e., high partial pressures of sulfur [p(S2)] and low partial pressures of oxygen [p(O2)]. Through an integrated experimental approach involving thermogravimetric techniques, post-exposure metallographic examination of the corroded samples, and detailed chemical microanalyses of the reaction scales, the effects of aluminum content, temperature, and gas composition on the corrosion behavior were observed. The corrosion behavior of Fe-Al alloys was found to be directly related to the type and morphology of corrosion product that formed during high temperature exposure in the oxidizing/sulfidizing environment. The inhibition stage was characterized by growth of a thin, gamma alumina scale that suppressed excessive degradation of the substrate at all temperatures. Localized mechanical failure of the initial passive scale, in combination with the inability to re-establish itself, was found to result in nodular growth of non-protective sulfide phases across the sample face due to short circuit diffusion through the gamma alumina layer. With the remnants of the initial gamma scale found between the outer and inner scale, it was concluded that these layers grew by iron diffusion outward and sulfur diffusion inward, respectively. The corrosion rate observed during development of these morphologies was directly related to the density of the nodules on the surface and the exposure temperature. The final period observed was the steady-state stage. This behavior was encountered from the onset of exposure for all Fe-5 wt% Al alloys tested, or upon coalescence of the nodular growths. After initially high corrosion rates, the weight gains were found to increase at a steady rate as subsequent growth occurred via diffusion through the continuous scale. Determination of the corrosion product growth mechanism could not be

The Oxidative Metabolism of Fossil Hydrocarbons and Sulfide Minerals by the Lithobiontic Microbial Community Inhabiting Deep Subterrestrial Kupferschiefer Black Shale.

PubMed

Włodarczyk, Agnieszka; Lirski, Maciej; Fogtman, Anna; Koblowska, Marta; Bidziński, Grzegorz; Matlakowska, Renata

2018-01-01

Black shales are one of the largest reservoirs of fossil organic carbon and inorganic reduced sulfur on Earth. It is assumed that microorganisms play an important role in the transformations of these sedimentary rocks and contribute to the return of organic carbon and inorganic sulfur to the global geochemical cycles. An outcrop of deep subterrestrial ~256-million-year-old Kupferschiefer black shale was studied to define the metabolic processes of the deep biosphere important in transformations of organic carbon and inorganic reduced sulfur compounds. This outcrop was created during mining activity 12 years ago and since then it has been exposed to the activity of oxygen and microorganisms. The microbial processes were described based on metagenome and metaproteome studies as well as on the geochemistry of the rock. The microorganisms inhabiting the subterrestrial black shale were dominated by bacterial genera such as Pseudomonas, Limnobacter, Yonghaparkia, Thiobacillus, Bradyrhizobium , and Sulfuricaulis . This study on black shale was the first to detect archaea and fungi, represented by Nitrososphaera and Aspergillus genera, respectively. The enzymatic oxidation of fossil aliphatic and aromatic hydrocarbons was mediated mostly by chemoorganotrophic bacteria, but also by archaea and fungi. The dissimilative enzymatic oxidation of primary reduced sulfur compounds was performed by chemolithotrophic bacteria. The geochemical consequences of microbial activity were the oxidation and dehydrogenation of kerogen, as well as oxidation of sulfide minerals.

Effect of Ozone Treatment on Nano-Sized Silver Sulfide in Wastewater Effluent.

PubMed

Thalmann, Basilius; Voegelin, Andreas; von Gunten, Urs; Behra, Renata; Morgenroth, Eberhard; Kaegi, Ralf

2015-09-15

Silver nanoparticles used in consumer products are likely to be released into municipal wastewater. Transformation reactions, most importantly sulfidation, lead to the formation of nanoscale silver sulfide (nano-Ag2S) particles. In wastewater treatment plants (WWTP), ozonation can enhance the effluent quality by eliminating organic micropollutants. The effect of ozonation on the fate of nano-Ag2S, however, is currently unknown. In this study, we investigate the interaction of ozone with nano-Ag2S and evaluate the effect of ozonation on the short-term toxicity of WWTP effluent spiked with nano-Ag2S. The oxidation of nano-Ag2S by ozone resulted in a stoichiometric factor (number of moles of ozone required to oxidize one mole of sulfide to sulfate) of 2.91, which is comparable to the results obtained for the reaction of bisulfide (HS(-)) with ozone. The second-order rate constant for the reaction of nano-Ag2S with ozone (k = 3.1 × 10(4) M(-1) s(-1)) is comparable to the rate constant of fast-reacting micropollutants. Analysis of the ozonation products of nano-Ag2S by transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) revealed that ozonation dominantly led to the formation of silver chloride in WWTP effluent. After ozonation of the Ag2S-spiked effluent, the short-term toxicity for the green algae Chlamydomonas reinhardtii increased and reached EC50 values comparable to Ag(+). This study thus reveals that ozone treatment of WWTP effluent results in the oxidation of Ag2S and, hence, an increase of the Ag toxicity in the effluent, which may become relevant at elevated Ag concentrations.

Copper solubility in a basaltic melt and sulfide liquid/silicate melt partition coefficients of Cu and Fe

NASA Astrophysics Data System (ADS)

Ripley, Edward M.; Brophy, James G.; Li, Chusi

2002-09-01

The solubility of copper in a sulfur-saturated basaltic melt has been determined at 1245°C as a function of fO 2 and fS 2. Copper solubilities at log fO 2 values between -8 and -11 fall into two distinct populations as a function of fS 2. At log fS 2 values < -1.65, sulfide liquid that coexists with the basaltic glass quenches to sulfur-poor bornite solid solution. At log fS 2 values in excess of -1.65, the sulfide liquid quenches to a complex intergrowth of sulfur-rich bornite and intermediate solid solution. Copper solubilities in the low-fS 2 population range from 594 to 1550 ppm, whereas those in the high-fS 2 population range from 80 to 768 ppm. Sulfide liquid/silicate liquid partition coefficients (D) for Cu and Fe range from 480 to 1303 and 0.7 to 13.6, respectively. Metal-sulfur complexing in the silicate liquid is shown to be insignificant relative to metal-oxide complexing for Fe but permissible for Cu at high fS 2 values. On log D Fe (sulfide-silicate) and log D Cu (sulfide-silicate) vs. 1/2 (log fS 2 - log fO 2) diagrams, both fS 2 populations show distinct but parallel trends. The observation of two D values for any fS 2/fO 2 ratio indicates nonideal mixing of species involved in the exchange reaction. The two distinct trends observed for both Cu and Fe are thought to be due to variations in activity coefficient ratios (e.g., γ FeO/γ FeS and γ CuO 0.5/γ CuS 0.5). Results of the experiments suggest that accurate assessments of fS 2/fO 2 ratios are required for the successful numerical modeling of processes such as the partial melting of sulfide-bearing mantle and the crystallization of sulfide-bearing magmas, as well as the interpretation of sulfide mineralogical zoning. In addition, the experiments provide evidence for oxide or oxy-sulfide complexing for Cu in silicate magmas and suggest that the introduction of externally derived sulfur to mafic magma may be an important process for the formation of Cu-rich disseminated magmatic sulfide ore

Iron Sulfide Attenuates the Methanogenic Toxicity of Elemental Copper and Zinc Oxide Nanoparticles and their Soluble Metal Ion Analogs

PubMed Central

Gonzalez-Estrella, Jorge; Gallagher, Sara; Sierra-Alvarez, Reyes; Field, Jim A.

2016-01-01

Elemental copper (Cu0) and zinc oxide (ZnO) nanoparticle (NP) toxicity to methanogens has been attributed to the release of soluble metal ions. Iron sulfide (FeS) partially controls the soluble concentration of heavy metals and their toxicity in aquatic environments. Heavy metals displace the Fe from FeS forming poorly soluble metal sulfides in the FeS matrix. Therefore, FeS may be expected to attenuate the NP toxicity. This work assessed FeS as an attenuator of the methanogenic toxicity of Cu0 and ZnO NPs and their soluble salt analogs. The toxicity attenuation capacity of fine (25–75 µm) and coarse (500 to 1200 µm) preparations of FeS (FeS-f and FeS-c respectively) was tested in the presence of highly inhibitory concentrations of CuCl2, ZnCl2 Cu0 and ZnO NPs. FeS-f attenuated methanogenic toxicity better than FeS-c. The results revealed that 2.5× less FeS-f than FeS-c was required to recover the methanogenic activity to 50% (activity normalized to uninhibited controls). The results also indicated that a molar FeS-f/Cu0 NP, FeS-f/ZnO NP, FeS-f/ZnCl2, and FeS-f/CuCl2 ratio of 2.14, 2.14, 4.28, and 8.56 respectively, was necessary to recover the methanogenic activity to >75%. Displacement experiments demonstrated that CuCl2 and ZnCl2 partially displaced Fe from FeS. As a whole, the results indicate that not all the sulfide in FeS was readily available to react with the soluble Cu and Zn ions which may explain the need for a large stoichiometric excesses of FeS to highly attenuate Cu and Zn toxicity. Overall, this study provides evidence that FeS attenuates the toxicity caused by Cu0 and ZnO NPs and their soluble ion analogs to methanogens. PMID:26803736

Metabolism in the Uncultivated Giant Sulfide-Oxidizing Bacterium Thiomargarita Namibiensis Assayed Using a Redox-Sensitive Dye

NASA Astrophysics Data System (ADS)

Bailey, J.; Flood, B.; Ricci, E.

2014-12-01

The colorless sulfur bacteria are non-photosynthetic chemolithotrophs that live at interfaces between nitrate, or oxygen, and hydrogen sulfide. In sulfidic settings such as cold seeps and oxygen minimum zones, these bacteria are thought to constitute a critical node in the geochemical cycling of carbon, sulfur, nitrogen, and phosphorous. Many of these bacteria remain uncultivated and their metabolisms and physiologies are incompletely understood. Thiomargarita namibiensis is the largest of these sulfur bacteria, with individual cells reaching millimetric diameters. Despite the current inability to maintain a Thiomargarita culture in the lab, their large size allows for individual cells to be followed in time course experiments. Here we report on the novel use of a tetrazolium-based dye that measures the flux of NADH production from catabolic pathways via a colorimetric response. Staining with this dye allows for metabolism to be detected, even in the absence of observable cell division. When coupled to microscopy, this approach also allows for metabolism in Thiomargaritato be differentiated from that of epibionts or contaminants in xenic samples. The results of our tetrazolium dye-based assay suggests that Thiomargarita is the most metabolically versatile under anoxic conditions where it appears capable of using acetate, succinate, formate, thiosulfate, citrate, thiotaurine, hydrogen sulfide, and perhaps hydrogen as electron donors. Under hypoxic conditions, staining results suggest the utilization of acetate, citrate, and hydrogen sulfide. Cells incubated under oxic conditions showed the weakest tetrazolium staining response, and then only to hydrogen sulfide and questionably succinate. These initial results using a redox sensitive dye suggest that Thiomargarita is most metabolically versatile under anaerobic and hypoxic conditions. The results of this assay can be further evaluated using molecular approaches such as transcriptomics, as well as provide cultivation

Atomically Precise Growth of Catalytically Active Cobalt Sulfide on Flat Surfaces and within a Metal–Organic Framework via Atomic Layer Deposition

DOE PAGES

Peters, Aaron W.; Li, Zhanyong; Farha, Omar K.; ...

2015-08-04

Atomic layer deposition (ALD) has been employed as a new synthetic route to thin films of cobalt sulfide on silicon and fluorine-doped tin oxide platforms. The self-limiting nature of the stepwise synthesis is established through growth rate studies at different pulse times and temperatures. Additionally, characterization of the materials by X-ray diffraction and X-ray photoelectron spectroscopy indicates that the crystalline phase of these films has the composition Co 9S 8. The nodes of the metal–organic framework (MOF) NU-1000 were then selectively functionalized with cobalt sulfide via ALD in MOFs (AIM). Spectroscopic techniques confirm uniform deposition of cobalt sulfide throughout themore » crystallites, with no loss in crystallinity or porosity. The resulting material, CoS-AIM, is catalytically active for selective hydrogenation of m-nitrophenol to m-aminophenol, and outperforms the analogous oxide AIM material (CoO-AIM) as well as an amorphous CoS x reference material. Here, these results reveal AIM to be an effective method of incorporating high surface area and catalytically active cobalt sulfide in metal–organic frameworks.« less

Sulfur, sulfides, oxides and organic matter aggregated in submarine hydrothermal plumes at 9°50‧N East Pacific Rise

NASA Astrophysics Data System (ADS)

Breier, J. A.; Toner, B. M.; Fakra, S. C.; Marcus, M. A.; White, S. N.; Thurnherr, A. M.; German, C. R.

2012-07-01

Deep-sea hydrothermal plume particles are known to sequester seawater trace elements and influence ocean-scale biogeochemical budgets. The relative importance of biotic versus abiotic oxidation-reduction and other particle-forming reaction, however, and the mechanisms of seawater trace element sequestration remain unknown. Suspended particulate material was collected from a non-buoyant hydrothermal plume by in situ filtration at 9°50‧N East Pacific Rise during a 3-day, 24 sample, time-series. Twenty-three samples were digested for total elemental analysis. One representative sample was selected for particle-by-particle geochemical analyses including elemental composition by X-ray fluorescence, speciation of Fe, S, and C by 1s X-ray absorption near edge structure spectroscopy, and X-ray diffraction. Consistent with past studies, positive linear correlations were observed for P, V, As, and Cr with Fe in the bulk chemistry. Arsenic was associated with both Fe oxyhydroxides and sulfides but not uniformly distributed among either mineral type. Particle aggregation was common. Aggregates were composed of minerals embedded in an organic matrix; the minerals ranged from <20 nm to >10 μm in diameter. The speciation of major mineral forming elements (Fe, Mn, S) was complex. Over 20 different minerals were observed, nine of which were either unpredicted by thermodynamic modeling or had no close match in the thermodynamic database. Sulfur-bearing phases consisted of polysulfides (S6, S8), and metal sulfides (Fe, Cu, Zn, Mn). Four dominant species, Fe oxyhydroxide, Fe monosulfide, pyrrhotite, and pyrite, accounted for >80% of the Fe present. Particulate Mn was prevalent in both oxidized and reduced minerals. The organic matrix was: (1) always associated with minerals, (2) composed of biomolecules, and (3) rich in S. Possible sources of this S-rich organic matter include entrained near vent biomass and in situ production by S-oxidizing microorganisms. These results indicate

[Effect of temperature on the rate of oxidation of pyrrhotite-rich sulfide ore flotation concentrate and the structure of the acidophilic chemolithoautotrophic microbial community].

PubMed

Moshchanetskii, P V; Pivovarova, T A; Belyi, A V; Kondrat'eva, T F

2014-01-01

Oxidation of flotation concentrate of a pyrrhotite-rich sulfide ore by acidophilic chemolithoautotrophic microbial communities at 35, 40, and 45 degrees C was investigated. According to the physicochemical parameters of the liquid phase of the pulp, as well as the results of analysis of the solid residue after biooxidation and cyanidation, the community developed at 40 degrees C exhibited the highest rate of oxidation. The degree of gold recovery at 35, 40, and 45 degrees C was 89.34, 94.59, and 83.25%, respectively. At 40 degrees C, the highest number of microbial cells (6.01 x 10(9) cells/mL) was observed. While temperature had very little effect on the species composition of microbial communities, except for the absence of Leptospirillum ferriphilum at 35 degrees C, the shares of individual species in the communities varied with temperature. Relatively high numbers of Sulfobacillus thermosulfidooxidans, the organism oxidizing iron and elemental sulfur at higher rates than other acidophilic chemolithotrophic species, were observed at 40 degrees C.

Diphosphine is an intermediate in the photolysis of phosphine to phosphorus and hydrogen. [Jupiter atmospheric chemistry

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Benson, R.

1980-01-01

The photolysis of phosphine to red phosphorus (P4) and hydrogen is investigated in light of the potential significance of the reaction in the atmospheric chemistry of Jupiter. It is reported that the photolysis of PH3 at room temperature by a 206.2-nm light source gave rise to a product identified by its UV and IR spectra and gas chromatographic retention time as P2H4, the yield of which is found to increase to a maximum and then decrease to 20% of the maximum value with illumination time. A mechanism for phosphine photolysis including diphosphine formation as an intermediate step is proposed, and it is concluded that P2H4 is a likely constituent of the atmospheres of the Jovian planets.

International Traffic in Arms Regulations (ITAR), (22 CFR 120-130)

DTIC Science & Technology

1996-06-01

Butadienenitrileoxide (BNO); (6) Catocene, N-butyl- ferrocene and other ferrocene derivatives; (7) 3-nitraza-l,5 pentane diisocyanate; (8) Bis(2,2...Tris-l-(2-methyl)aziridinyl phosphine oxide (MAPO), bis(2-methyl aziridinyl) 2-(2-hydroxypropanoxy) propylamino phosphine oxide (BOBBA 8), and...other MAPO derivatives; (22) Bis(2-methyl aziridinyl) methylamino phosphine oxide (methyl BAPO); (23) Organo-metallic coupling agents, specifi

Environmental geochemistry of a Kuroko-type massive sulfide deposit at the abandoned Valzinco mine, Virginia, USA

USGS Publications Warehouse

Seal, R.R.; Hammarstrom, J.M.; Johnson, A.N.; Piatak, N.M.; Wandless, G.A.

2008-01-01

The abandoned Valzinco mine, which worked a steeply dipping Kuroko-type massive sulfide deposit in the Virginia Au-pyrite belt, contributed significant metal-laden acid-mine drainage to the Knight's Branch watershed. The host rocks were dominated by metamorphosed felsic volcanic rocks, which offered limited acid-neutralizing potential. The ores were dominated by pyrite, sphalerite, galena, and chalcopyrite, which represented significant acid-generating potential. Acid-base accounting and leaching studies of flotation tailings - the dominant mine waste at the site - indicated that they were acid generating and therefore, should have liberated significant quantities of metals to solution. Field studies of mine drainage from the site confirmed that mine drainage and the impacted stream waters had pH values from 1.1 to 6.4 and exceeded aquatic ecosystem toxicity limits for Fe, Al, Cd, Cu, Pb and Zn. Stable isotope studies of water, dissolved SO42 -, and primary and secondary sulfate and sulfide minerals indicated that two distinct sulfide oxidation pathways were operative at the site: one dominated by Fe(III) as the oxidant, and another by molecular O2 as the oxidant. Reaction-path modeling suggested that geochemical interactions between tailings and waters approached a steady state within about a year. Both leaching studies and geochemical reaction-path modeling provided reasonable predictions of the mine-drainage chemistry.

Oxidation-promoted activation of a ferrocene C-H bond by a rhodium complex.

PubMed