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Sample records for aqueous organic sulfur

  1. Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

    NASA Technical Reports Server (NTRS)

    Schulte, Mitchell; Rogers, Karyn L.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard

  2. Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

    NASA Technical Reports Server (NTRS)

    Schulte, Mitchell; Rogers, Karyn L.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard

  3. The influence of hydroxyl volatile organic compounds on the oxidation of aqueous sulfur dioxide by oxygen.

    PubMed

    Dhayal, Yogpal; Chandel, C P S; Gupta, K S

    2014-01-01

    Although the effect of volatile organic compounds (VOCs) on the oxidation of dissolved sulfur dioxide by oxygen has been the subject of many investigations, this is the first study which examines the effect of a large number of precisely 16 hydroxy compounds. The kinetics both in the absence and the presence of VOCs was defined by rate laws (A and B): -d[S(IV)]dt = R₀ = k₀[S(IV)] (A) -d[S(IV)]dt = R(i) = k(i)[S(IV)] (B) where R₀ and k₀ are the initial rate and first-order rate constant, respectively, in the absence of VOCs, R(i), and k(i) are the initial rate and the first-order rate constant, respectively, in the presence of VOCs, and [S(IV)] is the concentration of dissolved sulfur dioxide, sulfur(IV). The nature of the dependence of k(i) on the concentration of inhibitor, [Inh], was defined by Eq. (C). [k(i) = k₀/(1 + B[Inh]) (C) where B is an empirical inhibition parameter. The values of B have been determined from the plots of 1/k(i) versus [Inh]. Among aliphatic and aromatic hydroxy compounds studied, t-butyl alcohol and pinacol were without any inhibition effect due to the absence of secondary or tertiary hydrogen. The values of inhibition parameter, B, were related to k(inh), the rate constant for the reaction of SO₄(-) radical with the inhibitor, by Eq. (D). B = (9 ± 2) x 10⁻⁴ x k(inh) (D) Equation (D) may be used to calculate the values of either of B or k(inh) provided that the other is known. The extent of inhibition depends on the value of the composite term, B[Inh]. However, in accordance with Eq. (C), the extent of inhibition would be sizeable and measurable when B[Inh] > 0.1 and oxidation of S(IV) would be almost completely stopped when B[Inh] ≥ 10. B[Inh] value can be used as a guide whether the reaction step: SO4 (-) + organics → SO₄(2-) + non-chain products: should be included in the multiphase models or not.

  4. Organic sulfur compounds resulting from the interaction of iron sulfide, hydrogen sulfide and carbon dioxide in an anaerobic aqueous environment.

    PubMed

    Heinen, W; Lauwers, A M

    1996-04-01

    The reaction of iron sulfide (FeS) with H2S in water, in presence of CO2 under anaerobic conditions was found to yield H2 and a variety of organic sulfur compounds, mainly thiols and small amounts of CS2 and dimethyldisulfide. The same compounds were produced when H2S was replaced by HCl, in the H2S-generating system FeS/HCl/CO2. The identification of the products was confirmed by GC-MS analyses and the incorporation of H2 in the organic sulfur compounds was demonstrated by experiments in which all hydrogen compounds were replaced by deuterium compounds. Generation of H2 and the synthesis of thiols were both dependent upon the relative abundance of FeS and HCl or H2S, i.e. the FeS/HCl- or FeS/H2S-proportions. Whether thiols or CS2 were formed as the main products depended also on the FeS/HCl-ratio: All conditions which create a H2 deficiency were found to initiate a proportional increase in the amount of CS2. The quantities of H2 and thiols generated depended on temperature: the production of H2 was significantly accelerated from 50 degrees C onward and thiol synthesis above 75 degrees C. The yield of thiols increased with the amount of FeS and HCl (H2S), given a certain FeS/HCl-ratio and a surplus of CO2. A deficiency of CO2 results in lower thiol synthesis. The end product, pyrite (FeS2), was found to appear as a silvery granular layer floating on the aqueous surface. The identity of the thiols was confirmed by mass spectrometry, and the reduction of CO2 demonstrated by the determination of deuterium incorporation with DCl and D2O. The described reactions can principally proceed under the conditions comparable to those obtaining around submarine hydrothermal vents, or the global situation about 4 billion years ago, before the dawn of life, and could replace the need for a reducing atmosphere on the primitive earth.

  5. Infrared titration of aqueous sulfuric acid

    SciTech Connect

    Max, J.J.; Menichelli, C.; Chapados, C.

    2000-03-30

    This paper presents the infrared (IR) titration of aqueous sulfuric acid solutions (0.50 M) obtained by the attenuated total reflection (ATR) sampling technique. After subtracting the water spectra, the spectra of the ionic species of H{sub 2}SO{sub 4} in the 0--14 pH range were separated by factor analysis (FA) which also gave their abundance. The results were in agreement with the theoretical calculation of the distribution of the species. Three sulfate species were found: HSO{sub 4}{sup {minus}}, SO{sub 4}{sup 2{minus}}, and HSO{sub 4}{sup {minus}}/HCl. The latter stands for the bisulfate--hydronium complex formed by the addition of HCl to obtain measurements in the 0--0.47 pH range. For 0.50 M sulfuric acid, the comparison between the experimentally IR-determined quantities and the theoretical values gave a mean activity coefficient of 0.12 {+-} 0.04, a value comparable to that from electrochemical measurements. Three types of water were quantitatively determined in the solutions: acidic water, basic water, and neutral water. The latter is always present while the two others are present in the low and high pH range, respectively. Another type of water strongly associated with the sulfates is also present. Moreover, knowledge of the behavior of the different types of water as the titration proceeded permitted us to give the details of the neutralization reactions of aqueous sulfuric acid by sodium hydroxide.

  6. Supercapacitance of nitrogen-sulfur-oxygen co-doped 3D hierarchical porous carbon in aqueous and organic electrolyte

    NASA Astrophysics Data System (ADS)

    Yang, Wang; Yang, Wu; Song, Ailing; Gao, Lijun; Su, Li; Shao, Guangjie

    2017-08-01

    This work report the synthesis of porous carbon with hierarchical pore structure and uniform nitrogen-sulfur-oxygen doping. The favorable pore structure (micro-, meso-, and macro-pores) is beneficial to ion adsorption and transportation, and the doping heteroatoms can introduce electrochemical active sites which contribute to additional pseudocapacitance. Therefore, the carbon material shows good electrochemical performance when employed as supercapacitor electrode. High specific capacitance (367 F g-1 at 0.3 A g-1), good rate performance and stable cycling characteristics are obtained in 6 M KOH. In addition, when tested in 1 M H2SO4, a higher specific capacitance (382 F g-1 at 0.3 A g-1) is delivered. Furthermore, the assembled symmetric cell yields a maximum specific energy of 35.3 W h kg-1 in 1 M TEABF4/AN, significantly improving the specific energy of carbon-based supercapacitors.

  7. Aqueous process for recovering sulfur from hydrogen sulfide-bearing gas

    SciTech Connect

    Basu, Arunabha

    2015-05-05

    A process for recovering sulfur from a hydrogen sulfide-bearing gas utilizes an aqueous reaction medium, a temperature of about 110-150.degree. C., and a high enough pressure to maintain the aqueous reaction medium in a liquid state. The process reduces material and equipment costs and addresses the environmental disadvantages associated with known processes that rely on high boiling point organic solvents.

  8. The iron catalyzed oxidation of sulfur(IV) in aqueous solution: Differing effects of organics at high and low pH

    NASA Astrophysics Data System (ADS)

    Martin, L. R.; Hill, M. W.; Tai, A. F.; Good, T. W.

    1991-02-01

    We have studied the oxidation of sulfur dioxide by dissolved oxygen in highly dilute solutions with a new differential optical absorption technique. We measured the rate of oxidation catalyzed by iron(III) over a wide range of pH, ionic strength, and in the presence of various organic materials. The studies indicate that noncomplexing organic molecules are highly inhibiting at "high" pH values of 5 and above and are not inhibiting at "low" pH values of 3 and below. Furthermore, the order of the reaction with respect to iron is different in the two pH regimes. This suggests that the mechanism of this reaction differs in the two pH regimes and is probably a free radical chain at high pH and a nonradical mechanism at low pH. Some of the mechanisms proposed in the literature are discussed in the light of these new data. None of the proposed mechanisms give completely satisfactory agreement with the data. We propose a modified free radical chain mechanism for the high pH regime, which correctly predicts the organic inhibitions. For the low pH regime, mechanisms proposed by Conklin and Hoffmann (1988) and by Hoffmann and Jacob (1984) give fair agreement with the pH data and correctly predict the self-inhibition, the sulfate inhibition, and the ionic strength inhibition. In view of the new data we believe that the iron(III) catalyzed reaction in tropospheric clouds can be a major contributor to the rate of sulfate formation, but there will be significant inhibition of this process by formic acid in some situations.

  9. Solubility of uranous sulfate in aqueous sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Suzuki, Shigeru; Hirono, Shuichiro; Awakura, Yasuhiro; Majima, Hiroshi

    1990-10-01

    To provide important thermodynamic data for use in uranium hydrometallurgy, solubilities of uranous sulfate were determined as a function of free acid concentration and temperature. Two sets of experiments were performed in this study. One set was the precipitation experiments of uranous sulfate crystals, in which concentrated uranous sulfate solution was mixed with sulfuric acid solution of suitable concentration. The other set was the dissolution experiments of uranous sulfate crystals in aqueous sulfuric acid solutions. It is noteworthy that good agreement exists between the solubilities determined by the two methods. At elevated temperatures, say, 363 K, the presence of free sulfuric acid is required to avoid precipitation of uranous hydroxide resulting from the hydrolysis of uranous sulfate. Generally speaking, however, an increase in free sulfuric acid concentration results in a slight decrease in uranous sulfate solubility. The elevation of solution temperature causes a decrease in solubility of uranous sulfate. It should be noted that the solid uranous sulfates equilibrated with saturated solutions at 298 K were U(SO4)2 2H2O in dilute sulfuric acid solution and U(SO4)2 4H2O in concentrated sulfuric acid solution, while those at 333 K and 363 K were mainly U(SO4)2 4H2O.

  10. A critique of homogeneous freezing measurements of aqueous sulfuric acid

    NASA Astrophysics Data System (ADS)

    Alofs, Darryl J.; Vandike, John L.

    2000-08-01

    Two laboratory measurements of homogeneous freezing of aqueous sulfuric acid particles are critiqued: The first by Bertram et al., 1996, J. Phys. Chem., vol. 100, pp. 2376-2383: the second by Koop et al., 1998, J. Phys. Chem. A, vol. 102, pp. 8924-8931. Calculations for a proposed experimental artifact are inconclusive for Bertram et al. A proposed artifact for Koop et al. is shown to be insignificant.

  11. Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

  12. Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

  13. Protonation Dynamics and Hydrogen Bonding in Aqueous Sulfuric Acid.

    PubMed

    Niskanen, Johannes; Sahle, Christoph J; Juurinen, Iina; Koskelo, Jaakko; Lehtola, Susi; Verbeni, Roberto; Müller, Harald; Hakala, Mikko; Huotari, Simo

    2015-09-03

    Hydration of sulfuric acid plays a key role in new-particle formation in the atmosphere. It has been recently proposed that proton dynamics is crucial in the stabilization of these clusters. One key question is how water molecules mediate proton transfer from sulfuric acid, and hence how the deprotonation state of the acid molecule behaves as a function concentration. We address the proton transfer in aqueous sulfuric acid with O K edge and S L edge core-excitation spectra recorded using inelastic X-ray scattering and with ab initio molecular dynamics simulations in the concentration range of 0-18.0 M. Throughout this range, we quantify the acid-water interaction with atomic resolution. Our simulations show that the number of donated hydrogen bonds per Owater increases from 1.9 to 2.5 when concentration increases from 0 to 18.0 M, in agreement with a rapid disappearance of the pre-edge feature in the O K edge spectrum. The simulations also suggest that for 1.5 M sulfuric acid SO4(2-) is most abundant and that its concentration falls monotonously with increasing concentration. Moreover, the fraction of HSO4(-) peaks at ∼12 M.

  14. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-08-01

    Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10) and ketones (C3 and C9) on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s) at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point) were found to play a dominant role in determining the inferred mode of nucleation (homogenous or heterogeneous) and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures) nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  15. Ice nucleation in sulfuric acid/organic aerosols: implications for cirrus cloud formation

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-03-01

    Using an aerosol flow tube apparatus, we have studied the effects of aliphatic aldehydes (C3 to C10) and ketones (C3 and C9) on ice nucleation in sulfuric acid aerosols. Mixed aerosols were prepared by combining an organic vapor flow with a flow of sulfuric acid aerosols over a small mixing time (~60 s) at room temperature. No acid-catalyzed reactions were observed under these conditions, and physical uptake was responsible for the organic content of the sulfuric acid aerosols. In these experiments, aerosol organic content, determined by a Mie scattering analysis, was found to vary with the partial pressure of organic, the flow tube temperature, and the identity of the organic compound. The physical properties of the organic compounds (primarily the solubility and melting point) were found to play a dominant role in determining the mode of nucleation (homogenous or heterogeneous) and the specific freezing temperatures observed. Overall, very soluble, low-melting organics, such as acetone and propanal, caused a decrease in aerosol ice nucleation temperatures when compared with aqueous sulfuric acid aerosol. In contrast, sulfuric acid particles exposed to organic compounds of eight carbons and greater, of much lower solubility and higher melting temperatures, nucleate ice at temperatures above aqueous sulfuric acid aerosols. Organic compounds of intermediate carbon chain length, C4-C7, (of intermediate solubility and melting temperatures) nucleated ice at the same temperature as aqueous sulfuric acid aerosols. Interpretations and implications of these results for cirrus cloud formation are discussed.

  16. Sulfur monochloride in organic synthesis

    NASA Astrophysics Data System (ADS)

    Konstantinova, L. S.; Rakitin, O. A.

    2014-03-01

    The data on the reactivity of sulfur monochloride published in the past 15 years have been reviewed and systematized. The review focuses on the synthesis of acyclic and heterocyclic compounds with the use of S2Cl2. The bibliography includes 154 references.

  17. Metabolic Reactions among Organic Sulfur Compounds

    NASA Technical Reports Server (NTRS)

    Schulte, M.; Rogers, K.

    2005-01-01

    Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. Numerous authors have addressed the energy available from a variety of inorganic sulfur redox pairs. Less attention has been paid, however, to the energy required or gained from metabolic reactions among organic sulfur compounds. Work in this area has focused on the oxidation of alkyl sulfide or disulfide to thiol and formaldehyde, e.g. (CH3)2S + H2O yields CH3SH + HCHO + H2, eventually resulting in the formation of CO2 and SO4(-2). It is also found that reactions among thiols and disulfides may help control redox disequilibria between the cytoplasm and the periplasm. Building on our earlier efforts for thiols, we have compiled and estimated thermodynamic properties for alkyl sulfides. We are investigating metabolic reactions among various sulfur compounds in a variety of extreme environments, ranging from sea floor hydrothermal systems to organic-rich sludge. Using thermodynamic data and the revised HKF equation of state, along with constraints imposed by the geochemical environments sulfur-metabolizing organisms inhabit, we are able to calculate the amount of energy available to these organisms.

  18. Metabolic Reactions among Organic Sulfur Compounds

    NASA Technical Reports Server (NTRS)

    Schulte, M.; Rogers, K.

    2005-01-01

    Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. Numerous authors have addressed the energy available from a variety of inorganic sulfur redox pairs. Less attention has been paid, however, to the energy required or gained from metabolic reactions among organic sulfur compounds. Work in this area has focused on the oxidation of alkyl sulfide or disulfide to thiol and formaldehyde, e.g. (CH3)2S + H2O yields CH3SH + HCHO + H2, eventually resulting in the formation of CO2 and SO4(-2). It is also found that reactions among thiols and disulfides may help control redox disequilibria between the cytoplasm and the periplasm. Building on our earlier efforts for thiols, we have compiled and estimated thermodynamic properties for alkyl sulfides. We are investigating metabolic reactions among various sulfur compounds in a variety of extreme environments, ranging from sea floor hydrothermal systems to organic-rich sludge. Using thermodynamic data and the revised HKF equation of state, along with constraints imposed by the geochemical environments sulfur-metabolizing organisms inhabit, we are able to calculate the amount of energy available to these organisms.

  19. Organic Sulfur Gas Production in Sulfidic Caves

    NASA Astrophysics Data System (ADS)

    Stern, L. A.; Engel, A. S.; Bennett, P. C.

    2001-12-01

    Lower Kane Cave, Big Horn Basin, WY, permits access to an environment where anaerobic sulfide-rich groundwater meets the aerobic vadose zone. At this interface microorganisms thrive on diverse metabolic pathways including autotrophic sulfur oxidation, sulfate reduction, and aerobic heterotrophy. Springs introduce groundwater rich in H2S to the cave where it both degasses into the cave atmosphere and is used by chemautotrophic sulfur oxidizing bacteria in the cave spring and stream habitat. The cave atmosphere in the immediate vicinity of the springs has elevated levels of CO2, H2S and methane, mirroring the higher concentration of H2S and methane in the spring water. The high CO2 concentrations are attenuated toward the two main sources of fresh air, the cave entrance and breathing holes at the rear of the cave. Conventional toxic gas monitors permit estimations of H2S concentrations, but they have severe cross sensitivity with other reduced sulfur gases, and thus are inadequate for characterization of sulfur cave gases. However employment of a field-based GC revealed elevated concentrations of carbonyl sulfide in cave atmosphere. Cultures of microorganisms collected from the cave optimized for enriching fermenters and autotrophic and heterophic sulfate reducing bacteria each produced carbonyl sulfide suggesting a biogenic in origin of the COS in addition to H2S. Enrichment cultures also produced methanethiol (methyl mercaptan) and an additional as yet undetermined volatile organic sulfur compound. In culture, the organo-sulfur compounds were less abundant than H2S, whereas in the cave atmosphere the organo-sulfur compounds were the dominant sulfur gases. Thus, these organo-sulfur gases may prove to be important sources of both reduced sulfur and organic carbon to microorganisms living on the cave wall in a subaerial habitat. Moreover groundwater has not yet been recognized as a source of sulfur gases to the atmosphere, but with the abundance of sulfidic

  20. Organic Sulfur Associated with Aquatic Humic Substances

    NASA Astrophysics Data System (ADS)

    Aiken, G.; Vairavamurthy, M. A.; Ravichandran, M.

    2003-12-01

    This study examines the speciation and reactivity of organic sulfur associated with dissolved organic matter isolated from a variety of freshwater environments and the Pacific Ocean. The isolates, which included aquatic humic substances, were obtained using XAD resins and exhibited a wide range of elemental compositions, aromatic carbon contents, and molecular weights. Organic sulfur contents for the samples ranged from 0.4% to 1.9% of the atomic composition and were strongly dependent on the redox chemistry of the environments whence the samples originated, especially with regard to potential interactions with sulfide in sulfate reducing environments. The speciation of the sulfur associated with these samples was investigated using X-ray adsorption near edge spectroscopy (XANES). The samples, all obtained from oxic environments, contained reduced sulfur moieties. Reduced sulfur content (thiophene, organic sulfides and thiols) ranged from 22-70%. In general, humic acid fractions were found to have the largest percentage of reduced sulfur, followed by the fulvic acid and hydrophobic acid fractions. Hydrophilic fractions of the DOC contained a large percentage of oxidized organic sulfur (sulfonate and sulfate moieties). To assess the significance of reduced S content on interactions with soft metals, an environmentally significant process, the binding strength and binding capacity of Hg with organic matter isolated from the Florida Everglades were determined using equilibrium dialysis ligand exchange. Based on elemental analyses and XANES, the DOM sample from the Everglades used in our binding experiments had a reduced-S content of approximately 1.0%. Very strong interactions (KDOM' = 1023.2+/-0.5 L kg-1) were observed at Hg/DOM ratios below approximately 1 μ g Hg per mg DOM. Only a small fraction (approximately 2%) of the reduced-S groups were involved with the strongest interactions between Hg and DOM, suggesting that the binding of Hg to DOM under natural

  1. Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

  2. Combined chemical and microbiological removal of organic sulfur from coal

    SciTech Connect

    Raphaelian, L.A.

    1991-01-01

    The objective of this work is to investigate techniques for chemically converting the sulfur containing organic compounds in coal to compounds that can be treated microbiologically to remove the organically bound sulfur. The goal is to achieve an economically feasible mild chemical oxidation of the organic sulfur in a representative Illinois Basin coal by converting the sulfur to sulfoxides and sulfones; the carbon sulfur bond in the sulfoxides and sulfones would then be broken microbiologically and the sulfur removed from the coal as sulfate.

  3. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    ERIC Educational Resources Information Center

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  4. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    ERIC Educational Resources Information Center

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  5. Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Michelsen, R. R.; Ashbourn, S. F. M.; Staton, S. J. R.

    2003-01-01

    To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

  6. Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Michelsen, R. R.; Ashbourn, S. F. M.; Staton, S. J. R.

    2003-01-01

    To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

  7. Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

    PubMed

    Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

    2017-06-13

    Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

  8. DOE workshop: Sedimentary systems, aqueous and organic geochemistry

    SciTech Connect

    Not Available

    1993-07-01

    A DOE workshop on sedimentary systems, aqueous and organic geochemistry was held July 15-16, 1993 at Lawrence Berkeley Laboratory. Papers were organized into several sections: Fundamental Properties, containing papers on the thermodynamics of brines, minerals and aqueous electrolyte solutions; Geochemical Transport, covering 3-D imaging of drill core samples, hydrothermal geochemistry, chemical interactions in hydrocarbon reservoirs, fluid flow model application, among others; Rock-Water Interactions, with presentations on stable isotope systematics of fluid/rock interaction, fluid flow and petotectonic evolution, grain boundary transport, sulfur incorporation, tracers in geologic reservoirs, geothermal controls on oil-reservoir evolution, and mineral hydrolysis kinetics; Organic Geochemistry covered new methods for constraining time of hydrocarbon migration, kinetic models of petroleum formation, mudstones in burial diagenesis, compound-specific carbon isotope analysis of petroleums, stability of natural gas, sulfur in sedimentary organic matter, organic geochemistry of deep ocean sediments, direct speciation of metal by optical spectroscopies; and lastly, Sedimentary Systems, covering sequence stratigraphy, seismic reflectors and diagenetic changes in carbonates, geochemistry and origin of regional dolomites, and evidence of large comet or asteroid impacts at extinction boundaries.

  9. A novel non-aqueous aluminum sulfur battery

    NASA Astrophysics Data System (ADS)

    Cohn, Gil; Ma, Lin; Archer, Lynden A.

    2015-06-01

    An aluminum-sulfur battery comprised of a composite sulfur cathode, aluminum anode and an ionic liquid electrolyte of AlCl3/1-ethyl-3-methylimidazolium chloride is described. The electrochemical reduction of elemental sulfur has been studied in different molar ratios of the electrolyte, and aluminum tetrachloride ions have been identified at the electroactive ionic species. The Al/S battery exhibits a discharge voltage plateau of 1.1-1.2 V, with extremely high charge storage capacity of more than 1500 mAh g-1, relative to the mass of sulfur in the cathode. The energy density of the Al/S cell is estimated to be 1700 Wh kg-1 sulfur, which is competitive with the most attractive battery chemistries targeted for high-energy electrochemical storage. Characterization by means of SEM, XRD and XPS of the battery components reveal complete dissolution of sulfur-based discharge products to the electrolyte. The low cost, natural abundance and high volumetric energy density of both anode and cathode materials define a research path for new materials and cell designs for next-generation Al/S battery systems.

  10. Porous Organic Cages for Sulfur Hexafluoride Separation

    PubMed Central

    2016-01-01

    A series of porous organic cages is examined for the selective adsorption of sulfur hexafluoride (SF6) over nitrogen. Despite lacking any metal sites, a porous cage, CC3, shows the highest SF6/N2 selectivity reported for any material at ambient temperature and pressure, which translates to real separations in a gas breakthrough column. The SF6 uptake of these materials is considerably higher than would be expected from the static pore structures. The location of SF6 within these materials is elucidated by X-ray crystallography, and it is shown that cooperative diffusion and structural rearrangements in these molecular crystals can rationalize their superior SF6/N2 selectivity. PMID:26757885

  11. Thermodynamic Properties of the Aqueous Sulfuric Acid System to 350 K

    NASA Astrophysics Data System (ADS)

    Zeleznik, Frank J.

    1991-11-01

    Experimental measurements for aqueous sulfuric acid and its related pure, solid phases have been thermodynamically analyzed and correlated as a function of temperature and composition from pure water to pure acid. The pure phases included anhydrous sulfuric acid, five of its hydrates and ice. Experimental data which were used in the correlation included measurements of the enthalpy of dilution, both solution and pure phase heat capacities, electromotive force and solution freezing points. The correlation yielded mutually consistent expressions for the Gibbs energy of each phase and these functions generally reproduce the experimental data to ±0.75 percent. The Gibbs energy functions of the pure solid phases were used to generate tables of their thermodynamic properties from 0 K to the melting points. The Gibbs energy function for aqueous sulfuric acid was used to produce tables of both integral and partial molar solution properties as a function of sulfuric acid mole fraction every 50° from 200 to 350 K.

  12. VOLATILE ORGANIC ANALYSIS BY DIRECT AQUEOUS INJECTION

    EPA Science Inventory

    Gas chromatographic environmental analysis by direct aqueous injection (DAI) was studied for 24 volatile organic analytes (VOAs). Internal standardization was used to determine the precision of analyzing these compounds by DAI. Aequous samples were directly introduced to a gas ch...

  13. Uptake of methacrolein into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Wu, Ling-Yan; Wang, Tian-He; Ge, Mao-Fa; Wang, Wei-Gang

    2012-01-12

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol (SOA) formation from isoprene and its gas-phase oxidation products, but the kinetics and chemical mechanism remain largely uncertain. Here we report the first measurement of uptake of methacrolein into aqueous solutions of sulfuric acid and hydrogen peroxide in the temperature range of 253-293 K. The steady-state uptake coefficients were acquired and increased quickly with increasing sulfuric acid concentration and decreasing temperature. Propyne, acetone, and 2,3-dihydroxymethacrylic acid were suggested as the products. The chemical mechanism is proposed to be the oxidation of carbonyl group and C═C double bonds by peroxide hydrogen in acidic environment, which could explain the large content of polyhydroxyl compounds in atmospheric fine particles. These results indicate that multiphase acid-catalyzed oxidation of methacrolein by hydrogen peroxide can contribute to SOA mass in the atmosphere, especially in the upper troposphere.

  14. The x-ray absorption spectroscopy model of solvation about sulfur in aqueous L-cysteine.

    PubMed

    Sarangi, Ritimukta; Frank, Patrick; Benfatto, Maurizio; Morante, Silvia; Minicozzi, Velia; Hedman, Britt; Hodgson, Keith O

    2012-11-28

    The environment of sulfur in dissolved aqueous L-cysteine has been examined using K-edge x-ray absorption spectroscopy (XAS), extended continuum multiple scattering (ECMS) theory, and density functional theory (DFT). For the first time, bound-state and continuum transitions representing the entire XAS spectrum of L-cysteine sulfur are accurately reproduced by theory. Sulfur K-edge absorption features at 2473.3 eV and 2474.2 eV represent transitions to LUMOs that are mixtures of S-C and S-H σ∗ orbitals significantly delocalized over the entire L-cysteine molecule. Continuum features at 2479, 2489, and 2530 eV were successfully reproduced using extended continuum theory. The full L-cysteine sulfur K-edge XAS spectrum could not be reproduced without addition of a water-sulfur hydrogen bond. Density functional theory analysis shows that although the Cys(H)S⋯H-OH hydrogen bond is weak (∼2 kcal) the atomic charge on sulfur is significantly affected by this water. MXAN analysis of hydrogen-bonding structures for L-cysteine and water yielded a best fit model featuring a tandem of two water molecules, 2.9 Å and 5.8 Å from sulfur. The model included a S(cys)⋯H-O(w1)H hydrogen-bond of 2.19 Å and of 2.16 Å for H(2)O(w1)⋯H-O(w2)H. One hydrogen-bonding water-sulfur interaction alone was insufficient to fully describe the continuum XAS spectrum. However, density functional theoretical results are convincing that the water-sulfur interaction is weak and should be only transient in water solution. The durable water-sulfur hydrogen bond in aqueous L-cysteine reported here therefore represents a break with theoretical studies indicating its absence. Reconciling the apparent disparity between theory and result remains the continuing challenge.

  15. Biocatalytic removal of organic sulfur from coal

    SciTech Connect

    Webster, D.A.; Kilbane, J.J. II

    1994-09-09

    The objective is to characterize more completely the biochemical ability of the bacterium, Rhodococcus rhodochrous IGTS8, to cleave carbon-sulfur bonds with emphasis on data that will allow the development of a practical coal biodesulfurization process. Another approach for increasing the desulfurization activity of the IGTS8 cultures is to produce strains genetically that have higher activity. The goal of this part of research is to achieve strain improvement by introducing a stronger promoter using genetic engineering techniques. The promoter regulates the transcription of the genes for the desulfurization enzymes, and a stronger promoter, would up-regulate the expression of these genes, resulting in cells with higher desulfurization activity. Promoter probe vectors are used to identify and isolate promoters from a DNA library of the experimental organism. The major accomplishments have been to obtain high biodesulfurization activity in nonaqueous, media, especially using freeze-dried cells, and to have isolated strong promoters from R. rhodochrous IGTS8 which will be used to engineer the organism to produce strains with higher biocatalytic activity.

  16. Evaluating the Effects of Sediment Reworking on the Sulfur Isotopic Composition of Aqueous and Mineral Sulfides

    NASA Astrophysics Data System (ADS)

    Johnson, D.; Rose, C.; Fike, D. A.

    2014-12-01

    The sulfur isotopic compositions of sulfide minerals preserved in the rock record are widely used in reconstructions of past ocean and atmospheric chemistry, but little is known about how syn- and post-depositional processes may affect these compositions. Furthermore, recent discoveries of pyrite more enriched in 34S than coeval sulfate in the rock record (e.g., Ries et al., 2009) and in modern deltaic sediments (e.g., Aller et al., 2010) have indicated a need to develop a better understanding of the controls on isotopic fractionation during sulfur cycling in natural environments. Here, we report the results of a controlled laboratory experiment designed to simulate the repeated oxidative reworking of sediments using a series of sediment columns constructed with bulk carbonate mud from Florida Bay, Florida. A rapid decline in [H2S] was observed in reworked sediments during the first 12 weeks of the experiment. Decreases in the δ34S of sulfide phases and increases in Δ34SSO4-H2S (i.e., the difference between the δ34S of sulfate, δ34SSO4, and that of hydrogen sulfide, δ34SH2S, at a given depth) were also documented across all columns. These results indicate a decline in labile organic matter concentrations within the sediments and a corresponding decrease in MSR rates with time. Complete reoxidation did not generate superheavy pyrite in this study, but did stimulate biological activity through the generation of sharp redox boundaries. Partial oxidation of aqueous sulfide and an associated increase in residual δ34SH2S must thus be key if oxidation itself is important to superheavy pyrite formation. These findings further suggest that organic matter lability may have played a more fundamental role than [SO42-] in regulating MSR fractionation throughout Earth history and provide motivation for future research.

  17. Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

    DOE PAGES

    Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; ...

    2014-12-02

    A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

  18. Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

    SciTech Connect

    Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; Li, Chao; McKinnon, Meaghan E.; Sadok, Rachel G.; Qu, Deyu; Yu, Xiqian; Lee, Hung-Sui; Qu, Deyang

    2014-12-02

    A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility of the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.

  19. Secondary organic material formed by methylglyoxal in aqueous aerosol mimics

    NASA Astrophysics Data System (ADS)

    Sareen, N.; Schwier, A. N.; Shapiro, E. L.; Mitroo, D.; McNeill, V. F.

    2010-02-01

    We show that methylglyoxal forms light-absorbing secondary organic material in aqueous ammonium sulfate and ammonium nitrate solutions mimicking tropospheric aerosol particles. The kinetics were characterized using UV-Vis spectrophotometry. The results suggest that the bimolecular reaction of methylglyoxal with an ammonium or hydronium ion is the rate-limiting step for the formation of light-absorbing species, with kNH4+II=5×10-6 M-1 min-1 and kH3O+II≤10-3 M-1 min-1. Evidence of aldol condensation products and oligomeric species up to 759 amu was found using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS). Tentative identifications of carbon-nitrogen species and a sulfur-containing compound were also made using Aerosol-CIMS. Aqueous solutions of methylglyoxal, with and without inorganic salts, exhibit significant surface tension depression. These observations add to the growing body of evidence that dicarbonyl compounds may form secondary organic material in the aerosol aqueous phase, and that secondary organic aerosol formation via heterogeneous processes may affect seed aerosol properties.

  20. Preservation of organic matter on Mars by sulfur

    NASA Astrophysics Data System (ADS)

    Eigenbrode, J. L.; Steele, A.; Summons, R. E.; McAdam, A.; Sutter, B.; Franz, H. B.; Freissinet, C.; Millan, M.; Glavin, D. P.; Szopa, C.; Conrad, P. G.; Mahaffy, P. R.

    2016-12-01

    Deltaic-lacustrine mudstones at Pahrump Hills, Gale Crater, Mars yielded a variety of sulfur-containing volatiles upon heating to 500-860°C, as detected by the Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover. The detection of organosulfur compounds comprising thiophenes, dimethylsulfide and thiols by gas chromatography-mass spectrometry and evolved gas analyses, together with aromatic and other hydrocarbon molecules with distributions specific to the sample (i.e., not from the SAM background) indicate that some or all of these organic fragments released at high temperatures are indigenous to the mudstones. The organosulfur compounds are most likely derived from sulfur organics in the sediments. However, there is a possibility that sulfurization of some organic fragments occurred in the oven. On Earth, sulfurization of organic matter is a key process that aids preservation over geological time-scales. This is because it reduces reactive functional groups and adds cross links between small unstable molecules thereby converting them into recalcitrant macromolecules. Sulfurization of organic materials prior to deposition and during early diagenesis may have been a key mechanism responsible for organic matter preservation in the Murray formation mudstones. Sulfur-bearing organics have also been observed in carbonaceous meteorites and there is indication of their presence in the Tissint martian meteorite. A quantitative assessment of organosulfur compounds relative to their non-organic counterparts will be presented for the Murray formation mudstones analyzed by SAM and meteorites analyzed in the laboratory under similar analytical conditions.

  1. Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

    NASA Technical Reports Server (NTRS)

    Fry, B.; Ruf, W.; Gest, H.; Hayes, J. M.

    1988-01-01

    Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

  2. Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

    NASA Technical Reports Server (NTRS)

    Fry, B.; Ruf, W.; Gest, H.; Hayes, J. M.

    1988-01-01

    Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

  3. Biodesulfurization of refractory organic sulfur compounds in fossil fuels.

    PubMed

    Soleimani, Mehran; Bassi, Amarjeet; Margaritis, Argyrios

    2007-01-01

    The stringent new regulations to lower sulfur content in fossil fuels require new economic and efficient methods for desulfurization of recalcitrant organic sulfur. Hydrodesulfurization of such compounds is very costly and requires high operating temperature and pressure. Biodesulfurization is a non-invasive approach that can specifically remove sulfur from refractory hydrocarbons under mild conditions and it can be potentially used in industrial desulfurization. Intensive research has been conducted in microbiology and molecular biology of the competent strains to increase their desulfurization activity; however, even the highest activity obtained is still insufficient to fulfill the industrial requirements. To improve the biodesulfurization efficiency, more work is needed in areas such as increasing specific desulfurization activity, hydrocarbon phase tolerance, sulfur removal at higher temperature, and isolating new strains for desulfurizing a broader range of sulfur compounds. This article comprehensively reviews and discusses key issues, advances and challenges for a competitive biodesulfurization process.

  4. Improving rubber concrete by waste organic sulfur compounds.

    PubMed

    Chou, Liang-Hisng; Lin, Chun-Nan; Lu, Chun-Ku; Lee, Cheng-Haw; Lee, Maw-Tien

    2010-01-01

    In this study, the use of crumb tyres as additives to concrete was investigated. For some time, researchers have been studying the physical properties of concrete to determine why the inclusion of rubber particles causes the concrete to degrade. Several methods have been developed to improve the bonding between rubber particles and cement hydration products (C-S-H) with the hope of creating a product with an improvement in mechanical strength. In this study, the crumb tyres were treated with waste organic sulfur compounds from a petroleum refining factory in order to modify their surface properties. Organic sulfur compounds with amphiphilic properties can enhance the hydrophilic properties of the rubber and increase the intermolecular interaction forces between rubber and C-S-H. In the present study, a colloid probe of C-S-H was prepared to measure these intermolecular interaction forces by utilizing an atomic force microscope. Experimental results showed that rubber particles treated with waste organic sulfur compounds became more hydrophilic. In addition, the intermolecular interaction forces increased with the adsorption of waste organic sulfur compounds on the surface of the rubber particles. The compressive, tensile and flexural strengths of concrete samples that included rubber particles treated with organic sulfur compound also increased significantly.

  5. Selective oxidations of organosulfur model compounds and coal for the removal of organic sulfur

    SciTech Connect

    Fauth, D.J.; Baltrus, J.P.; Nowak, M.A.; Olson, G.J.

    1991-01-01

    Investigations with organosulfur compounds have established that potassium monopersulfate (Oxone) in aqueous ethanol and sodium perborate in glacial acetic acid are highly selective oxidants for the oxidation of organic sum ides and aromatic sulfur heterocycles to their corresponding sulfoxides and sulfones. In a series of selective oxidations, dibenzothiophene in ethanol, fluorene in ethanol, and a 50:50 mol mixture of dibenzothiophene (DBT) and fluoresce in ethanol were reacted with aqueous Oxone under mild conditions. Capillary gas chromatographic analyses showed conversions of DBT to DBT-5,5-dioxide, while its carbon analog, fluorene was recovered quantitatively in every case. Furthermore, selective oxidations with Oxone of a triboelectrostatically cleaned Illinois {number sign}6 ultrafine coal (400 mesh {times} 0) and an Illinois {number sign}6 coal (IBC-101) (200 mesh {times} 0) depyritized via microorganisms were investigated. X-ray photoelectron spectroscopic (XPS) data indicated oxidation of a large fraction of the organic sulfur on the coal surface. Approximately 55--85% of the total S 2p area could be attributed to oxidized organic sulfur in the form of sulfones.

  6. A Systematic Presentation of Organic Phosphorus and Sulfur Compounds.

    ERIC Educational Resources Information Center

    Hendrickson, James B.

    1985-01-01

    Because the names, interrelations, and oxidation levels of the organic compounds of phosphorus and sulfur tend to confuse students, a simple way to organize these compounds has been developed. The system consists of grouping them by oxidation state and extent of carbon substitution. (JN)

  7. A Systematic Presentation of Organic Phosphorus and Sulfur Compounds.

    ERIC Educational Resources Information Center

    Hendrickson, James B.

    1985-01-01

    Because the names, interrelations, and oxidation levels of the organic compounds of phosphorus and sulfur tend to confuse students, a simple way to organize these compounds has been developed. The system consists of grouping them by oxidation state and extent of carbon substitution. (JN)

  8. Hematin crystallization from aqueous and organic solvents

    NASA Astrophysics Data System (ADS)

    Ketchum, Megan A.; Olafson, Katy N.; Petrova, Elena V.; Rimer, Jeffrey D.; Vekilov, Peter G.

    2013-09-01

    Hematin crystallization is the main mechanism of detoxification of heme that is released in malaria-infected erythrocytes as a byproduct of the hemoglobin catabolism by the parasite. A controversy exists over whether hematin crystals grow from the aqueous medium of the parasite's digestive vacuole or in the lipid bodies present in the vacuole. To this end, we compare the basic thermodynamic and structural features of hematin crystallization in an aqueous buffer at pH 4.8, as in the digestive vacuole, and in water-saturated octanol that mimics the environment of the lipid nanospheres. We show that in aqueous solutions, hematin aggregation into mesoscopic disordered clusters is insignificant. We determine the solubility of the β-hematin crystals in the pH range 4.8-7.6. We image by atomic force microscopy crystals grown at pH 4.8 and show that their macroscopic and mesoscopic morphology features are incompatible with those reported for biological hemozoin. In contrast, crystals grown in the presence of octanol are very similar to those extracted from parasites. We determine the hematin solubility in water-saturated octanol at three temperatures. These solubilities are four orders of magnitude higher than that at pH 4.8, providing for faster crystallization from organic than from aqueous solvents. These observations further suggest that the lipid bodies play a role in mediating biological hemozoin crystal growth to ensure faster heme detoxification.

  9. Organic Sulfur and HAP Removal from Coal with Subcritical Water

    SciTech Connect

    1996-12-31

    To date, no economically feasible organic sulfur and hazardous air pollutant (HAP) precursor removal process has been developed; however, an effective sulfur and selected HAP removal process is needed to enhance the utilization of high-sulfur coals and to comply with increasingly stringent regulations. Subcritical water has been shown by the Energy & Environmental Research Center (EERC) researchers on this project to be an extremely effective fluid for the removal of organic sulfur from coals. A multigram reactor designed and built at the EERC for supercritical water extraction was used to scale up from milligram-sized samples to 10-20 grams of coal charge. Work performed during this project year resulted in production of low-sulfur (as low as 0.5% S) extracted coal first at supercritical conditions, i.e., 450{degrees}C and 400 atm (5880 psig), but then at conditions below the critical conditions, i.e., 420{degrees}C and 156 atm (2300 psig). Still milder conditions of 400{degrees}C and 156 atm (2300 psig) resulted in sulfur values similar to those of obtained under the supercritical conditions. IBC-102 extracted with supercritical water had a sulfur value of 0.7 wt%. Extraction of IBC-102 at subcritical conditions of 420{degrees}C and 156 atm (2300 psig) resulted in a sulfur content of 0.490A. The tar obtained from the extracted coal had sulfur values ranging from 1.4 to 6.5 wt% and when treated by catalytic desulfurization, tar was quantitatively recovered with a sulfur value of 0.6 wt%. Float-sink physical cleaning of IBC-102 with Certigrav 1.4 reduced the sulfur content of the coal to 1.5 wt% in a recovered float fraction of 83.3%. Approximately 300 lb of IBC-102 was obtained for use in preparing 100 lb of low-sulfur fuel. Float- sink cleaning on a sample of this new coal returned 87.1 wt% as float fraction, with 1.7 wt% sulfur. 158 lb of physically cleaned IBC-102 was used for the continuous process test on the pilot scale. An additional 150 lb of physically

  10. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid

    PubMed Central

    Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-01-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range. PMID:26888159

  11. Sulfur

    USGS Publications Warehouse

    Apodaca, L.E.

    2012-01-01

    In 2011, elemental sulfur and the byproduct sulfuric acid were produced at 109 operations in 29 states and the U.S. Virgin Islands. Total shipments were valued at about $1.6 billion. Elemental sulfur production was 8.2 Mt (9 million st); Louisiana and Texas accounted for about 53 percent of domestic production.

  12. Multidimensional Polycation β-Cyclodextrin Polymer as an Effective Aqueous Binder for High Sulfur Loading Cathode in Lithium-Sulfur Batteries.

    PubMed

    Zeng, Fanglei; Wang, Weikun; Wang, Anbang; Yuan, Keguo; Jin, Zhaoqing; Yang, Yu-sheng

    2015-12-02

    Although the lithium-sulfur battery has attracted significant attention because of its high theoretical energy density and low cost of elemental sulfur, its real application is still hindered by multiple challenges, especially the polysulfides shuttled between the cathode and anode electrodes. By originating from β-cyclodextrin and introducing a quaternary ammonium cation into β-cyclodextrin polymer, a new multifunctional aqueous polycation binder (β-CDp-N(+)) for the sulfur cathode is obtained. The unique hyperbranched network structure of the new binder β-CDp-N(+) as well as its multidimensional noncovalent interactions and the introduced cations endowed β-CDp-N(+) with some new abilities: a sulfur-electrode-stabilized ability, a polysulfides-immobilized ability, and a volume-accommodated ability, which help to ease the primary problems of the lithium-sulfur battery, i.e., the shuttle of polysulfides and the volume change of the sulfur during charge and discharge. It is demonstrated that cycling performance and rate capability of the cathodes can be the improved by using β-CDp-N(+) as the binder compared to other well-known binders. Even with high sulfur loading of 5.5 mg cm(-2), the cathode with β-CDp-N(+) still can deliver an areal capacity of 4.4 mAh cm(-2) at 50 mA g(-1) after 45 cycles, which is much higher than that achieved using the cathode with the conventional binder (0.9 mAh cm(-2)).

  13. The infrared optical constants of sulfuric acid at 250 K. [spectral reflectance measurement of aqueous solutions

    NASA Technical Reports Server (NTRS)

    Pinkley, L. W.; Williams, D.

    1976-01-01

    Results are presented for measurements of the IR spectral reflectance at near-normal incidence of aqueous solutions of sulfuric acid with acid concentrations of 75% and 95.6% by weight. Kramers-Kronig analyses of the reflectance data are employed to obtain values of the optical constants n(nu) and k(nu) in the spectral range from 400 to 6000 cm to the -1 power. The optical constants of these solutions at 250 K and 300 K are compared. It is found that in spectral regions remote from strong absorption bands, the values of the n(nu) indices obtained at 250 K agree with the values given by Lorentz-Lorenz correction of the same indices at 300 K. All absorption bands observed at 300 K are found to be present at 250 K with slight shifts in frequency and with significant differences in the k(nu) indices at the band maxima. Based on these results, it is concluded that the clouds of Venus probably consist of droplets of aqueous solutions of sulfuric acid with acid concentrations of about 75% by weight.

  14. Sulfur removal from coal

    SciTech Connect

    Lompa-Krzymien, L.

    1985-01-01

    Coal is treated to remove both pyritic and organic sulfur by contacting with an aqueous solution comprising cupric ions at temperatures of about 140/sup 0/ C.-200/sup 0/ C. under autogenic pressure, until substantial amounts of the sulfur are solubilized, separating the coal solids, and washing the solids with water to remove soluble forms of sulfur, iron and copper therefrom. The copper can be recovered and recycled as a cupric salt.

  15. Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Michelsen, Rebecca R.; Ashbourn, Samatha F. M.; Rammer, Thomas A.; Golden, David M.

    2005-01-01

    Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

  16. Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases

    NASA Astrophysics Data System (ADS)

    Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.

    2016-03-01

    Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.

  17. Volatile organic sulfur compounds in a stratified lake.

    PubMed

    Hu, Haiying; Mylon, Steven E; Benoit, Gaboury

    2007-03-01

    Three volatile organic sulfur compounds (VOSCs), dimethyl sulfide (DMS), carbon disulfide (CS(2)), and dimethyl disulfide (DMDS), were detected in the stratified water column of a lake (Linsley Pond) in Connecticut. The compounds DMS and DMDS appeared in both the oxic and the anoxic portions of the water column, CS(2) was primarily found in anoxic hypolimnion. Algal metabolism and/or bacterial degradation of sulfur-containing amino acids or other organic materials are potential sources of VOSCs in the oxic lake water. Reactions of hydrogen sulfide with organic compounds and microbial degradation of organic matter may be responsible for the production of VOSCs in the anoxic lake water. The vertical distribution patterns of these three VOSCs varied from month to month in the summer, but the daily profiles obtained in one 5-day period in the summer displayed consistency. No clear diurnal pattern for any of the three VOSCs was observed. Based on observation that these VOSCs were not present in surface and near surface waters of Linsley Pond, freshwater inputs of reduced sulfur compounds to the atmosphere may be insignificant.

  18. Adsorption of cadmium from aqueous solutions on sulfurized activated carbon prepared from nut shells.

    PubMed

    Fouladi Tajar, Amir; Kaghazchi, Tahereh; Soleimani, Mansooreh

    2009-06-15

    Low-cost activated carbon, derived from nut shells, and its modified sample have been used as replacements for the current expensive methods of removing cadmium from aqueous solutions and waste waters. Adsorption of cadmium onto four kinds of activated carbons has been studied; prepared activated carbon (PAC), commercial activated carbon (CAC), and the sulfurized ones (SPAC & SCAC). The activated carbon has been derived, characterized, treated with sulfur and then utilized for the removal of Cd(2+). Sulfurizing agent (SO(2) gas) was successfully used in adsorbents' modification process at the ambient temperature. Samples were then characterized and tested as adsorbents of cadmium. Effect of some parameters such as contact time, initial concentration and pH were examined. With increasing pH, the adsorption of cadmium ions was increased and maximum removal, 92.4% for SPAC, was observed in pH>8.0 (C(0)=100mg/L). The H-type adsorption isotherms, obtained for the adsorbents, indicated a favorable process. Adsorption data on both prepared and commercial activated carbon, before and after sulfurization, followed both the Frendlich and Langmuir models. They were better fitted by Frendlich isotherm as compared to Langmuir. The maximum adsorption capacities were 90.09, 104.17, 126.58 and 142.86 mg/g for CAC, PAC, SCAC and SPAC, respectively. Accordingly, surface modification of activated carbons using SO(2) greatly enhanced cadmium removal. The reversibility of the process has been studied in a qualitative manner and it shows that the spent SPAC can be effectively regenerated for further use easily.

  19. Rapid determination of organic matter in spent sulfuric acid

    SciTech Connect

    Petrenko, V.G.; Takhtaeva, A.Ya.; Frolova, R.P.

    1981-01-01

    Ammonium sulfate is produced with the aid of spent sulfuric acid which averages 0.3 to 0.7% (and sometimes up to 2.5%) of carbon in the form of organic impurities. In the saturator, the latter upset the processing conditions and lower the quality (size analysis, etc.) of the ammonium sulfate. A rapid quality control procedure is essential to obtain timely warning of increased organic matter contents in the acid. On the other hand, the standard procedure in current use (TU38-2-3-1-68), based on the oxidation of organic substances with potassium bichromate in an acid medium, takes 3 hr to complete. Observations have revealed a correlation between the color of the acid and its organic impurity contents. On this basis, we have developed a rapid photocolorimetric procedure for determining the organic impurity contents of sulfuric acid, based on the known proportionality between optical density (light absorption) and solute (dye) content. A calibration curve is used to convert optical density readings to organic impurity contents. It should be pointed out that in contrast to the standard procedure, our procedure only determines the concentration of organic matter in solution in the acid. However, the amounts of insoluble organic matter are negligible compared with the amounts in solution and therefore do not affect the final results.

  20. Isolation and separation of transplutonium elements from other actinides on ion exchange resins from aqueous and aqueous ethanol solutions of sulfuric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1987-11-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on an anion exchange resin and a cation exchange resin in aqueous and aqueous alcohol solutions of sulfuric acid was investigated as a function of the concentration of various components of the solution. It was found that the presence of alcohol in sulfuric acid solutions leads to an increase in the distribution coefficients both on cation exchange resins and on anion exchange resins. The possibility of using ion exchange resins for the concentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements that form strong complexes with sulfate ions in a wide range of sulfuric acid concentrations was demonstrated.

  1. New organic chemistry of sulfur dioxide.

    PubMed

    Vogel, Pierre; Turks, Maris; Bouchez, Laure; Marković, Dean; Varela-Alvarez, Adrián; Sordo, José Angel

    2007-10-01

    Simple 1,3-dienes undergo highly stereoselective hetero-Diels-Alder additions with SO2 at low temperature giving sultines. These reactions that are faster than the more exothermic cheletropic additions of SO2-producing sulfolenes. This has led to the invention of a new C-C bond-forming reaction combining electron-rich dienes and alkenes with SO2. The reaction cascade has been exploited to develop combinatorial, one-pot, four-component syntheses of polyfunctional sulfones, sulfonamides, and sulfonic esters. It also allows us to generate, in one-pot operations, enantiomerically enriched polypropionate fragments containing up to three contiguous stereogenic centers and a (E)-alkene unit. These fragments can be used directly in further C-C bond-forming reactions, such as cross-aldol condensations, thus permitting the expeditious construction of complicated natural products of biological interest (e.g., Baconipyrones, Rifamycin S, Apoptolidinone) and analogues. New ene reactions of SO2 have also been discovered; they open new avenues to organic synthesis.

  2. Non-steady state diagenesis of organic and inorganic sulfur in lake sediments

    NASA Astrophysics Data System (ADS)

    Couture, Raoul-Marie; Fischer, Rachele; Van Cappellen, Philippe; Gobeil, Charles

    2016-12-01

    Sulfur controls the fate of many geochemical elements in lake sediments, including iron, phosphorus and environmentally important trace elements. We measured the speciation of pore-water and sediment-bound sulfur (aqueous sulfate and sulfides, elemental sulfur, iron monosulfide, pyrite, organic sulfur) and supporting geochemical variables (carbon, oxygen, iron) in the sediments of a perennially oxygenated and a seasonally anoxic basin of an oligotrophic lake in Québec, using a combination of pore-water analyses, sequential extractions and X-ray absorption near edge structure. A non-steady state early diagenetic model was developed and calibrated against this extensive dataset to help unravel the pathways and quantify the rates of S transformations. Results suggest that the main source of S to the sediments is the settling of organic ester-sulfate (R-O-SO3-H). Hydrolysis of these compounds provides an additional source of sulfate for anaerobic microbial oxidation of sedimentary organic matter, releasing sulfide to the pore-water. Reduced solid-bound S species accumulate as thiols (R-SH) and iron sulfides in the perennially oxygenated and seasonally anoxic basin, respectively. The model-estimated rate constant for R-SH formation is lower than previously estimated for this particular lacustrine site, but similar to that proposed for marine shelf sediments. The solid sediment S profiles, however, carry the imprint of the time-dependent sulfate input to the lake. Iron sulfide enrichments formed during past decades of elevated atmospheric SO4 deposition are presently dissolving. In the sediments of the perennially oxygenated basin this reaction hampers the build-up of Fe(III) (oxy)hydroxide near the sediment-water interface.

  3. Method and apparatus for destroying organic contaminants in aqueous liquids

    DOEpatents

    Donaldson, Terrence L.; Wilson, James H.

    1993-01-01

    A method and apparatus for destroying organic contaminants, such as trichloroethylene, in aqueous liquids, such as groundwater, utilizing steam stripping integrated with biodegradation. The contaminated aqueous liquid is fed into a steam stripper causing the volatilization of essentially all of the organic contaminants and a portion of the aqueous liquid. The majority of the aqueous liquid is discharged from the steam stripper. The volatilized vapors are then condensed to the liquid phase and introduced into a bioreactor. The bioreactor contains methanotrophic microorganisms which convert the organic contaminants into mainly carbon dioxide. The effluent from the bioreactor is then recycled back to the steam stripper for further processing.

  4. Method and apparatus for destroying organic contaminants in aqueous liquids

    DOEpatents

    Donaldson, T.L.; Wilson, J.H.

    1993-09-21

    A method and apparatus for destroying organic contaminants, such as trichloroethylene, in aqueous liquids, such as groundwater, utilizing steam stripping integrated with biodegradation. The contaminated aqueous liquid is fed into a steam stripper causing the volatilization of essentially all of the organic contaminants and a portion of the aqueous liquid. The majority of the aqueous liquid is discharged from the steam stripper. The volatilized vapors are then condensed to the liquid phase and introduced into a bioreactor. The bioreactor contains methanotrophic microorganisms which convert the organic contaminants into mainly carbon dioxide. The effluent from the bioreactor is then recycled back to the steam stripper for further processing. 2 figures.

  5. Chemistry in the Venus clouds: Sulfuric acid reactions and freezing behavior of aqueous liquid droplets

    NASA Astrophysics Data System (ADS)

    Delitsky, M. L.; Baines, K. H.

    2015-11-01

    Venus has a thick cloud deck at 40-70 km altitude consisting of liquid droplets and solid particles surrounded by atmospheric gases. The liquid droplets are highly concentrated aqueous solutions of sulfuric acid ranging in concentration from 70-99 wt%. Weight percent drops off with altitude (Imamura and Hashimoto 2001). There will be uptake of atmospheric gases into the droplet solutions and the ratios of gas-phase to liquid-phase species will depend on the Henry’s Law constant for those solutions. Reactions of sulfuric acid with these gases will form products with differing solubilities. For example, uptake of HCl by H2SO4/H2O droplets yields chlorosulfonic acid, ClSO3H (Robinson et al 1998) in solution. This may eventually decompose to thionyl- or sulfuryl chlorides, which have UV absorbances. HF will also uptake, creating fluorosulfonic acid, FSO3H, which has a greater solubility than the chloro- acid. As uptake continues, there will be many dissolved species in the cloudwaters. Baines and Delitsky (2013) showed that uptake will have a maximum at ~62 km and this is very close to the reported altitude for the mystery UV absorber in the Venus atmosphere. In addition, at very strong concentrations in lower altitude clouds, sulfuric acid will form hydrates such as H2SO4.H2O and H2SO4.4H2O which will have very different freezing behavior than sulfuric acid, with much higher freezing temperatures (Carslaw et al, 1997). Using temperature data from Venus Express from Tellmann et al (2009), and changes in H2SO4 concentrations as a function of altitude (James et al 1997), we calculate that freezing out of sulfuric acid hydrates can be significant down to as low as 56 km altitude. As a result, balloons, aircraft or other probes in the Venus atmosphere may be limited to flying below certain altitudes. Any craft flying at altitudes above ~55 km may suffer icing on the wings, propellers, balloons and instruments which could cause possible detrimental effects (thermal

  6. Reactive uptake of organic compounds by liquid sulfuric acid.

    NASA Astrophysics Data System (ADS)

    Roberts, J.; Michelsen, R.

    2003-04-01

    The uptake of several organic compounds by laboratory surrogates for tropospheric sulfuric acid particles were investigated by mass spectrometry and infrared reflection-absorption spectroscopy. Among the compounds studied were acetone [(CH_3)_2CO], 2,4-hexanedione [CH_3CO(CH_2)_2COCH_3, MBO], and 2-methyl-3-buten-2-ol [CH_2CHC(CH_3)_2OH]. Experiments were carried out on ultrathin sulfuric acid films (ca. 10-100 monolayer equivalents thick) as functions of organic partial pressure, temperature, and acid composition. Acetone uptake is irreversible for acids that contain >70 weight percent (wt. %) H_2SO4, with kinetics that are second-order in concentration of dissolved acetone. Hexanedione and MBO are irreversibly taken for all acid compositions investigated (60-96 wt. %), with first-order uptake kinetics. In all cases, the irreversible uptake is a consequence of sulfuric acid catalyzed reactions that lead to the formation of new C-C bonds. Implications of these results for heterogeneous tropospheric chemistry will be discussed.

  7. Sulfur and carbon cycling in organic-rich marine sediments

    NASA Technical Reports Server (NTRS)

    Martens, C. S.

    1985-01-01

    Nearshore, continental shelf, and slope sediments are important sites of microbially mediated carbon and sulfur cycling. Marine geochemists investigated the rates and mechanisms of cycling processes in these environments by chemical distribution studies, in situ rate measurements, and steady state kinetic modeling. Pore water chemical distributions, sulfate reduction rates, and sediment water chemical fluxes were used to describe cycling on a ten year time scale in a small, rapidly depositing coastal basin, Cape Lookout Bight, and at general sites on the upper continental slope off North Carolina, U.S.A. In combination with 210 Pb sediment accumulation rates, these data were used to establish quantitative carbon and sulfur budgets as well as the relative importance of sulfate reduction and methanogeneis as the last steps in the degradation of organic matter.

  8. Activity and osmotic coefficients of aqueous sulfuric acid at 298.15 K

    NASA Astrophysics Data System (ADS)

    Staples, Bert R.

    1981-07-01

    A critical evaluation of the mean activity coefficient, γ±, and osmotic coefficient, φ, of aqueous sulfuric acid at 298.15 K is presented for the molality range of 0 to 28 molṡkg-1. Osmotic coefficients were calculated from direct vapor pressure measurements, from isopietic measurements or from freezing point depression measurements. Activity coefficients were calculated from electromotive force measurements of galvanic cells. A least-squares program was used to fit data from all sources using both φ and ln γ± as functions of molality. A nine parameter equation describes the osmotic coefficient, the mean activity coefficient, and the excess. Gibbs energy as a function of the one-half power of molality. The scientific literature has been covered through January, 1979.

  9. Aqueous leaching on high sulfur sub-bituminous coals, in Assam, India

    SciTech Connect

    Bimala P. Baruah; Binoy K. Saikia; Prabhat Kotoky; P. Gangadhar Rao

    2006-08-15

    Aqueous leaching of high sulfur sub-bituminous coals from Ledo and Baragolai collieries of Makum coal fields, in Assam, India, has been investigated with respect to time at different temperatures. Leaching at 25{sup o}C up to 120 h showed that the physicochemical characteristics viz., conductivity, acidity, TDS, and SO{sub 4}-2 ions, increase with the increase in time of leaching. The generation of highly acidic leachates at 1-1.5 h (pH 2.5) and 2 h (pH 3.1) for Ledo and Baragolai coals was observed, respectively. However, it remains stable up to 120 h. The concentration of major, minor, and trace elements and their mobility along with the loss of pyritic sulfur or depyritization were also reported. The release of metals (Fe, Mg, Bi, Al, V, Cu, Cd, Ni, Pb, and Mn) above the regulatory levels during leaching was evidenced. Depyritization was found to be 79.8, 82.9, 84.7, and 89.7% for Ledo and 70.49, 73.77, 75.41, and 77.05% for Baragolai coal at 15, 25, 35, and 45 {sup o}C, respectively. A pseudo-first-order kinetic relationship with activation energies (E) of 8.1477 and 5.2378 kJ mol{sup -1} with frequency factors (A) of 8.8405 x 10{sup -4} and 2.6494 x 10{sup -4} dm{sup 3} mol{sup -1} s{sup -1} was attributed to aqueous oxidation of pyrites in Ledo and Baragolai coals, respectively. The X-ray diffraction analysis and Fourier transform infrared spectroscopy patterns indicate the presence of illite, {alpha}-quartz, hematite, chlorite, rutile, calcite, and albite as mineral phases. This investigation justifies the formation of acid mine drainage by weathering of pyrites from coal during the mining of high sulfur Makum coal fields, in Assam, India, and demonstrates one of the possible routes for its formation. 39 refs., 3 figs. 9 tabs.

  10. Sulfur species behavior in soil organic matter during decomposition

    USGS Publications Warehouse

    Schroth, A.W.; Bostick, B.C.; Graham, M.; Kaste, J.M.; Mitchell, M.J.; Friedland, A.J.

    2007-01-01

    Soil organic matter (SOM) is a primary re??servoir of terrestrial sulfur (S), but its role in the global S cycle remains poorly understood. We examine S speciation by X-ray absorption near-edge structure (XANES) spectroscopy to describe S species behavior during SOM decomposition. Sulfur species in SOM were best represented by organic sulfide, sulfoxide, sulfonate, and sulfate. The highest fraction of S in litter was organic sulfide, but as decomposition progressed, relative fractions of sulfonate and sulfate generally increased. Over 6-month laboratory incubations, organic sulfide was most reactive, suggesting that a fraction of this species was associated with a highly labile pool of SOM. During humification, relative concentrations of sulfoxide consistently decreased, demonstrating the importance of sulfoxide as a reactive S phase in soil. Sulfonate fractional abundance increased during humification irrespective of litter type, illustrating its relative stability in soils. The proportion of S species did not differ systematically by litter type, but organic sulfide became less abundant in conifer SOM during decomposition, while sulfate fractional abundance increased. Conversely, deciduous SOM exhibited lesser or nonexistent shifts in organic sulfide and sulfate fractions during decomposition, possibly suggesting that S reactivity in deciduous litter is coupled to rapid C mineralization and independent of S speciation. All trends were consistent in soils across study sites. We conclude that S reactivity is related to spqciation in SOM, particularly in conifer forests, and S species fractions in SOM change, during decomposition. Our data highlight the importance of intermediate valence species (sulfoxide and sulfonate) in the pedochemical cycling of organic bound S. Copyright 2007 by the American Geophysical Union.

  11. Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Ge, Maofa; Wang, Weigang

    2012-01-01

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.

  12. Quadruple sulfur isotope constraints on the origin and cycling of volatile organic sulfur compounds in a stratified sulfidic lake

    NASA Astrophysics Data System (ADS)

    Oduro, Harry; Kamyshny, Alexey; Zerkle, Aubrey L.; Li, Yue; Farquhar, James

    2013-11-01

    We have quantified the major forms of volatile organic sulfur compounds (VOSCs) distributed in the water column of stratified freshwater Fayetteville Green Lake (FGL), to evaluate the biogeochemical pathways involved in their production. The lake's anoxic deep waters contain high concentrations of sulfate (12-16 mmol L-1) and sulfide (0.12 μmol L-1 to 1.5 mmol L-1) with relatively low VOSC concentrations, ranging from 0.1 nmol L-1 to 2.8 μmol L-1. Sulfur isotope measurements of combined volatile organic sulfur compounds demonstrate that VOSC species are formed primarily from reduced sulfur (H2S/HS-) and zero-valent sulfur (ZVS), with little input from sulfate. Thedata support a role of a combination of biological and abiotic processes in formation of carbon-sulfur bonds between reactive sulfur species and methyl groups of lignin components. These processes are responsible for very fast turnover of VOSC species, maintaining their low levels in FGL. No dimethylsulfoniopropionate (DMSP) was detected by Electrospray Ionization Mass Spectrometry (ESI-MS) in the lake water column or in planktonic extracts. These observations indicate a pathway distinct from oceanic and coastal marine environments, where dimethylsulfide (DMS) and other VOSC species are principally produced via the breakdown of DMSP by plankton species.

  13. Adsorption of the complex ion Au(CN)2- onto sulfur-impregnated activated carbon in aqueous solutions.

    PubMed

    Ramírez-Muñiz, Kardia; Song, Shaoxian; Berber-Mendoza, Selene; Tong, Shitang

    2010-09-15

    The adsorption of the gold-cyanide complex ion (Au(CN)(2)(-)) on sulfur-impregnated activated carbon in aqueous solution has been studied in order to find a better adsorbent for the gold cyanidation process for extracting gold from ores. This study was performed using sulfur-impregnated activated carbon (SIAC 8.0) made from high-sulfur petroleum coke and an artificial aqueous solution of Au(CN)(2)(-). The experimental results have shown that Au(CN)(2)(-) strongly adsorbed onto the SIAC 8.0, leading the gold adsorption capacity of the SIAC 8.0 to be 2.25x that on conventional activated carbon. It has been also found that the adsorption fit the Langmuir isotherm well, and the adsorption density of Au(CN)(2)(-) on the SIAC 8.0 in aqueous solution increased with increasing temperature, suggesting chemical adsorption. The chemical adsorption might be attributed to the formation of S-Au-CN on SIAC 8.0 surfaces through the covalent bond between the gold atom of the ion and the sulfur in the molecular structure of the SIAC 8.0. In addition, the desorption test has demonstrated that the majority of the adsorption was irreversible, which depended on the density of the adsorption sites on the SIAC.

  14. Characterization of the organic-sulfur-degrading enzymes

    SciTech Connect

    Ho, N.W.Y.

    1993-01-01

    The objective of this project is to characterize and purify the enzymes involved in degrading organic sulfur in coal from two well characterized organic sulfur degrading strains, IGTS8 and K3B. We believe that characterization and purification of these enzymes may provide valuable information that will lead to developing or isolating better strains for desulfurization of coal. Our recent results imply that the IGTS8 enzymes are firmly attached to the cell wall, most likely that they are covalently bonded to the cell wall. We believe that for coal desulfurization, it is better to have a microorganism that can secrete its desulfurization enzymes into the medium. The enzymes can penetrate into coal hundreds of times better than a bacterial cell. Thus we have changed the priority of this project. We believe that the isolation of a mutant of IGTS8 which can release the desulfurization enzymes into the cultural medium will be able to develop a much improved microbial process for coal desulfurization. Furthermore, the isolation of sucha mutant will be able to shed some light on how the wild type IGTS8 desulfurization enzyme are attached to the cell wall and make the purification of these enzymes much easier to accomplish.

  15. Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Farquhar, J.; Guo, W.

    2015-12-01

    Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate

  16. Variation of organic sulfur in macerals of selected Illinois Basin coals

    USGS Publications Warehouse

    Demir, I.; Harvey, R.D.

    1991-01-01

    An electron microbeam technique was used to determine the distribution of organic sulfur in the main macerals of five Illinois Basin coals. On average, sporinites are the highest, inertinites the lowest, and vitrinites intermediate in organic sulfur for each coal. The observed differences are likely due to varying affinities of the different pre-maceral materials for sulfur and/or local variation in the production of H2S primarily during the peat stage. Investigation of molecular structures of individual macerals in relation to the findings of this study may delineate the relative abundance of organic sulfur in various organic compounds and thus lead to the development of efficient desulfurization processes. ?? 1991.

  17. [Influence of exogenous sulfur-containing compounds on the exchange fluxes of volatile organic sulfur compounds].

    PubMed

    Yi, Zhi-Gang; Wang, Xin-Ming

    2011-08-01

    The influences of cysteine, sodium sulfide (Na2S) and sodium sulfate (Na2SO4) on the soil-air exchange fluxes of volatile organic sulfur compounds (VOSCs), including carbonyl sulfide (COS), dimethyl sulfide (DMS), carbon disulfide (CS2) and dimethyl disulfide (DMDS), were studied employing static chamber enclosure followed by laboratory determination using an Entech 7100 preconcentrator coupled with an Agilent 5973 GC-MSD. The results showed that after the addition of cysteine, the soil for the exchange fluxes of COS and CS2 shifted to be the source from sink and the emissions of DMS and DMDS increased significant. The emission amount of DMS and CS2 accounted for 89.2% to the total VOSCs after the addition of cysteine, implying that cysteine is an important precursor for DMS and CS2 in the soil. The amount of DMDS accounted for 93.2% to the total sulfur from the soil after addition of Na2S, indicating that Na2S is a key precursor for DMDS. No significant difference of VOSCs fluxes was found between the controlled soil and the soil with addition of Na2SO4, suggesting Na2SO4 was not the direct precursor for VOSCs in soil. VOSCs exchange rates reached the maximum at 6 to 8 days after addition of cysteine. As for addition of Na2S, the maximal emission rates of different VOSCs appeared at different dates, and the dates differed significantly from those after addition of cysteine, implying that the formation process of VOSCs from the soil with addition of Na2S was more complex and different from the soil with addition of cysteine.

  18. Dimethylmercury Formation Mediated by Inorganic and Organic Reduced Sulfur Surfaces

    NASA Astrophysics Data System (ADS)

    Jonsson, Sofi; Mazrui, Nashaat M.; Mason, Robert P.

    2016-06-01

    Underlying formation pathways of dimethylmercury ((CH3)2Hg) in the ocean are unknown. Early work proposed reactions of inorganic Hg (HgII) with methyl cobalamin or of dissolved monomethylmercury (CH3Hg) with hydrogen sulfide as possible bacterial mediated or abiotic pathways. A significant fraction (up to 90%) of CH3Hg in natural waters is however adsorbed to reduced sulfur groups on mineral or organic surfaces. We show that binding of CH3Hg to such reactive sites facilitates the formation of (CH3)2Hg by degradation of the adsorbed CH3Hg. We demonstrate that the reaction can be mediated by different sulfide minerals, as well as by dithiols suggesting that e.g. reduced sulfur groups on mineral particles or on protein surfaces could mediate the reaction. The observed fraction of CH3Hg methylated on sulfide mineral surfaces exceeded previously observed methylation rates of CH3Hg to (CH3)2Hg in seawaters and we suggest the pathway demonstrated here could account for much of the (CH3)2Hg found in the ocean.

  19. Dimethylmercury Formation Mediated by Inorganic and Organic Reduced Sulfur Surfaces

    PubMed Central

    Jonsson, Sofi; Mazrui, Nashaat M.; Mason, Robert P.

    2016-01-01

    Underlying formation pathways of dimethylmercury ((CH3)2Hg) in the ocean are unknown. Early work proposed reactions of inorganic Hg (HgII) with methyl cobalamin or of dissolved monomethylmercury (CH3Hg) with hydrogen sulfide as possible bacterial mediated or abiotic pathways. A significant fraction (up to 90%) of CH3Hg in natural waters is however adsorbed to reduced sulfur groups on mineral or organic surfaces. We show that binding of CH3Hg to such reactive sites facilitates the formation of (CH3)2Hg by degradation of the adsorbed CH3Hg. We demonstrate that the reaction can be mediated by different sulfide minerals, as well as by dithiols suggesting that e.g. reduced sulfur groups on mineral particles or on protein surfaces could mediate the reaction. The observed fraction of CH3Hg methylated on sulfide mineral surfaces exceeded previously observed methylation rates of CH3Hg to (CH3)2Hg in seawaters and we suggest the pathway demonstrated here could account for much of the (CH3)2Hg found in the ocean. PMID:27302323

  20. Recovery of transplutonium elements from aqueous and water-ethanol solutions of sulfuric acid and their separation from other actinides

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-05-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on anion and cation exchangers in aqueous and water-ethanol solutions of sulfuric acid as a function of the various components of the solution has been investigated. It has been discovered that the presence of ethanol in sulfuric acid solutions causes an increase in the distribution coefficients both on cation exchangers and on anion exchangers. The possibility of the use of ion exchangers for the preconcentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements which form strong complexes with sulfate ions over a broad range of concentrations of sulfuric acid has been demonstrated.

  1. Evidence for organic synthesis in high temperature aqueous media--facts and prognosis.

    PubMed

    Simoneit, B R

    1995-06-01

    Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to >400 degrees C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. Heterocyclic sulfur compounds have been identified in high temperature zones and hydrothermal petroleums of the Guaymas Basin vent systems. They can be interpreted as being synthesized from formaldehyde and sulfur or HS kappa- in the hydrothermal fluids. Other products from potential synthesis reactions have not yet been found in the natural systems but are expected based on known industrial processes and inferences from experimental simulation data. Various industrial processes have been reviewed and are of relevance to hydrothermal synthesis of organic compounds. The reactivity of organic compounds in hot water (200-350 degrees C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to >400 degrees C.

  2. Molecular Modeling of Ammonium, Calcium, Sulfur, and Sodium Lignosulphonates in Acid and Basic Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Salazar Valencia, P. J.; Bolívar Marinez, L. E.; Pérez Merchancano, S. T.

    2015-12-01

    Lignosulphonates (LS), also known as lignin sulfonates or sulfite lignin, are lignins in sulfonated forms, obtained from the "sulfite liquors," a residue of the wood pulp extraction process. Their main utility lies in its wide range of properties, they can be used as additives, dispersants, binders, fluxing, binder agents, etc. in fields ranging from food to fertilizer manufacture and even as agents in the preparation of ion exchange membranes. Since they can be manufactured relatively easy and quickly, and that its molecular size can be manipulated to obtain fragments of very low molecular weight, they are used as transport agents in the food industry, cosmetics, pharmaceutical and drug development, and as molecular elements for the treatment of health problems. In this paper, we study the electronic structural and optical characteristics of LS incorporating ammonium, sulfur, calcium, and sodium ions in acidic and basic aqueous media in order to gain a better understanding of their behavior and the very interesting properties exhibit. The studies were performed using the molecular modeling program HyperChem 5 using the semiempirical method PM3 of the NDO Family (neglect of differential overlap), to calculate the structural properties. We calculated the electronic and optical properties using the semiempirical method ZINDO / CI.

  3. Sulfur-Doped Graphene Oxide Quantum Dots as Photocatalysts for Hydrogen Generation in the Aqueous Phase.

    PubMed

    Gliniak, Jacek; Lin, Jia-Hoa; Chen, Yi-Ting; Li, Chuen-Ru; Jokar, Efat; Chang, Chin-Hao; Peng, Chun-Sheng; Lin, Jui-Nien; Lien, Wan-Hsiang; Tsai, Hui-Min; Wu, Tung-Kung

    2017-08-24

    Sulfur-doped graphene oxide quantum dots (S-GOQDs) were synthesized and investigated for efficient photocatalytic hydrogen generation application. The UV/Vis, FTIR, and photoluminescence spectra of the synthesized S-GOQDs exhibit three absorption bands at 333, 395, and 524 nm, characteristic of C=S and C-S stretching vibration signals at 1075 and 690 cm(-1) , and two excitation-wavelength-independent emission signals with maxima at 451 and 520 nm, respectively, confirming the successful doping of S atom into the GOQDs. Electronic structural analysis suggested that the S-GOQDs exhibit conduction band minimum (CBM) and valence band maximum (VBM) levels suitable for water splitting. Under direct sunlight irradiation, an initial rate of 18 166 μmol h(-1)  g(-1) in pure water and 30 519 μmol h(-1)  g(-1) in 80 % ethanol aqueous solution were obtained. Therefore, metal-free and inexpensive S-GOQDs hold great potential in the development of sustainable and environmentally friendly photocatalysts for efficient hydrogen generation from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Method for removing organic liquids from aqueous solutions and mixtures

    DOEpatents

    Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.

    2004-03-23

    A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.

  5. Organic volatile sulfur compounds in inland aquatic systems

    SciTech Connect

    Richards, S.R.

    1991-01-01

    The speciation, concentration, and fluxes of organic volatile sulfur compounds (VSCs) in a wide variety of inland aquatic systems wee studied. Dissolved VSCs were sparged from water samples, trapped cryogenically, and quantified by gas chromatograph equipped with a flame photometric detector. Species detected and mean surface water concentrations were: carbonyl sulfide (COS), 0.091-7.6 nM; methanethiol (MSH), undetected-180 nM; dimethyl sulfide (DMS), 0.48-1290 nM; carbon disulfide (CS[sub 2]), undetected-69 nM; dimethyl disulfide (DMDS), undetected-68 nM. The range in surface water concentrations of over five orders of magnitude was influenced principally by lake depth and sulfate concentration ([SO[sub 4][sup 2[minus

  6. Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Guo, W.; Farquhar, J.

    2016-12-01

    We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30-40H2O clusters spanning the range of sulfur oxidation state (Sn, n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34β values based on major isotope (34S/32S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values (x/34κ = ln(xβ)/ln(34β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds (33/34κ ≈ 0.5148-0.5159, 36/34κ ≈ 1.89-1.90 from T ⩾ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit (33/34κT→∞ = 0.51587 ± 0.00003 and 36/34κT→∞ = 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO3-T(aq)/SO2(g, aq), SO2(aq)/SO2(g), H2S(aq)/H2S(g), H2S(aq)/HS-(aq), SO42-(aq)/H2ST(aq), S2O32-(aq) (intramolecular), and S2O32-(aq)/H2ST(aq), and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO3-T/SO32- major isotope (34S/32S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O3

  7. Experiments on δ34S mixing between organic and inorganic sulfur species during thermal maturation

    USGS Publications Warehouse

    Amrani, Alon; Said-Ahamed, Ward; Lewan, Michael D.; Aizenshtat, Zeev

    2006-01-01

    Reduced sulfur species were studied to constrain isotopic exchange-mixing with synthetic polysulfide cross-linked macromolecules (PCLM), model sulfur containing molecules and natural sulfur-rich kerogen, asphalt and oil of the Dead Sea area. PCLM represents protokerogens that are rich in sulfur and thermally unstable. Mixing rates of PCLM with HS-(aq) (added as (NH4)2S(aq)) at low to moderate temperatures (50–200 °C) are rapid. Elemental sulfur and H2S(gas) fully mix isotopes with PCLM during pyrolysis conditions at 200 °C. During these reactions significant structural changes of the PCLM occur to form polysulfide dimers, thiolanes and thiophenes. As pyrolysis temperatures or reaction times increase, the PCLM thermal products are transformed to more aromatic sulfur compounds. Isotopic mixing rates increase with increasing pyrolysis temperature and time. Polysulfide bonds (S–S) in the PCLM are responsible for most of these structural and isotopic changes because of their low stability. Conversely, sulfur isotope mixing does not occur between dibenzothiophene (aromatic S) or hexadecanthiol (C–SH) and HS-(aq) at 200 °C after 48 h. This shows that rates of sulfur isotope mixing are strongly dependent on the functionality of the sulfur in the organic matter. The order of isotopic mixing rates for organic matter is kerogen > asphalt > oil, which is inverse to their sulfur thermal stability. Asphalt and oil with more refractory sulfur show significantly lower isotopes mixing rates than the kerogen with more labile sulfur. Based on the findings of the present study we suggest that sulfur isotopes mixing can occur from early diagenesis into catagenesis and result in isotopic homogenization of the inorganic and organic reduced sulfur pools.

  8. Fossil bacterial ecosystem at methane seeps - Origin of organic matter from Be'eri sulfur deposit, Israel

    NASA Astrophysics Data System (ADS)

    Burhan, R. Y. P.; Trendel, J. M.; Adam, P.; Wehrung, P.; Albrecht, P.; Nissenbaum, A.

    2002-12-01

    The Be'eri sulfur mine (Israel) is a unique deposit mainly composed of sandstone intercalated with biogenic mats and possessing organic matter exceptionally depleted in 13C. Molecular and isotopic studies of free and bound biomarkers were performed to unravel the source of the organic matter co-occurring with sulfur in this deposit and to propose a paleoenvironmental model of bacterial life in a type of extreme environment. They showed that the biomarkers are all extremely 13C-depleted and almost exclusively composed of hopanoids and biphytane derivatives of bacterial origin, notably methanotrophic bacteria and acidophilic archaea. δ 13C values of individual components and of bulk organic carbon are in the -80% to -90% range and are among the lowest values ever measured for hopanoids. Organic matter in the sandstone and the mats differ mainly by the occurrence of 3-methylated hopanoids in the mats, which may reflect either different bacterial populations or different conditions of growth. These data demonstrate that the complete biomass of this deposit primarily derives from methanotrophic hopanoid-synthesizing bacteria consuming methane having seeped toward the surface, and that all other organisms - apparently only archaea and bacteria - must have been thriving on methane-derived carbon (methane, CO 2, biomass of methanotrophic bacteria). Unambiguous evidence for photosynthetic organisms in the environment of deposition could not be found. The Be'eri sulfur deposit is thus a fossil remain of an exclusively bacterial ecosystem fueled by methane as sole carbon source and having developed in an interstitial aqueous medium within the sandstone. Elemental sulfur from the deposit probably originates from the oxidation of hydrogen sulfide seeping along with methane, which could have been oxidized either abiotically or biologically by sulfur-oxidizing Beggiatoa-like bacteria and archaea. Further oxidation of elemental sulfur might explain the high acidity of the deposit

  9. Aqueous phase processing of secondary organic aerosol from isoprene photooxidation

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Monod, A.; Tritscher, T.; Praplan, A. P.; DeCarlo, P. F.; Temime-Roussel, B.; Quivet, E.; Marchand, N.; Dommen, J.; Baltensperger, U.

    2012-07-01

    Transport of reactive air masses into humid and wet areas is highly frequent in the atmosphere, making the study of aqueous phase processing of secondary organic aerosol (SOA) very relevant. We have investigated the aqueous phase processing of SOA generated from gas-phase photooxidation of isoprene using a smog chamber. The SOA collected on filters was extracted by water and subsequently oxidized in the aqueous phase either by H2O2 under dark conditions or by OH radicals in the presence of light, using a photochemical reactor. Online and offline analytical techniques including SMPS, HR-AMS, H-TDMA, TD-API-AMS, were employed for physical and chemical characterization of the chamber SOA and nebulized filter extracts. After aqueous phase processing, the particles were significantly more hygroscopic, and HR-AMS data showed higher signal intensity at m/z 44 and a lower signal intensity at m/z 43, thus showing the impact of aqueous phase processing on SOA aging, in good agreement with a few previous studies. Additional offline measurement techniques (IC-MS, APCI-MS2 and HPLC-APCI-MS) permitted the identification and quantification of sixteen individual chemical compounds before and after aqueous phase processing. Among these compounds, small organic acids (including formic, glyoxylic, glycolic, butyric, oxalic and 2,3-dihydroxymethacrylic acid (i.e. 2-methylglyceric acid)) were detected, and their concentrations significantly increased after aqueous phase processing. In particular, the aqueous phase formation of 2-methylglyceric acid and trihydroxy-3-methylbutanal was correlated with the consumption of 2,3-dihydroxy-2-methyl-propanal, and 2-methylbutane-1,2,3,4-tetrol, respectively, and an aqueous phase mechanism was proposed accordingly. Overall, the aging effect observed here was rather small compared to previous studies, and this limited effect could possibly be explained by the lower liquid phase OH concentrations employed here, and/or the development of oligomers

  10. Degradation of organic sulfur compounds by a coal-solubilizing fungus

    SciTech Connect

    Faison, B.D.; Clark, T.M.; Lewis, S.N.; Sharkey, D.M.; Woodward, C.A.; Ma, C.Y.

    1990-01-01

    Paecilomyces sp. TLi, a coal-solubilizing fungus, was shown to degrade organic sulfur-containing coal substructure compounds. Dibenzothiophene was degraded via a sulfur-oxidizing pathway to 2.2'-biphenol. No further metabolism of the biphenol was observed. Ethyl phenyl sulfide and phenyl sulfide were degraded to the corresponding sulfones. A variety of products were formed from benzyl sulfide, presumably via free radical intermediates. Phenyl disulfide and benzyl disulfide were cleaved to the corresponding thiols and other single-ring products. It was concluded that degradation of organic sulfur compounds by Paecilomyces involves an oxidative attack localized at the sulfur atom. 21 refs., 3 figs., 2 tabs.

  11. Sulfonates: A novel class of organic sulfur compounds in marine sediments

    NASA Astrophysics Data System (ADS)

    Vairavamurthy, Appathurai; Zhou, Weiqing; Eglinton, Timothy; Manowitz, Bernard

    1994-11-01

    X-ray absorption near-edge structure spectroscopy (XANES) used to measure sulfur speciation in a variety of organic-rich marine sediments has established sulfonates as a novel and major component of sedimentary organic sulfur. The origins of sulfonates in sediments are not clear, although both biological and geochemical mechanisms are possible. The accumulation of oxidized sulfonate sulfur in reducing marine sediments was not known previously; hence, a new perspective in sulfur geochemistry is established. The biogeochemical implications of the presence of sulfonates in marine sediments are discussed.

  12. Microbial cycling of volatile organic sulfur compounds in anoxic environments.

    PubMed

    Lomans, B P; Pol, A; Op den Camp, H J M

    2002-01-01

    Microbial cycling of volatile organic sulfur compounds (VOSC) is investigated due to the impact these compounds are thought to have on environmental processes like global temperature control, acid precipitation and the global sulfur cycle. Moreover, in several kinds of industries like composting plants and the paper industry VOSC are released causing odor problems. Waste streams containing these compounds must be treated in order to avoid the release of these compounds to the atmosphere. This paper describes the general mechanisms for the production and degradation of methanethiol (MT) and dimethyl sulfide (DMS), two ubiquitous VOSC in anaerobic environments. Slurry incubations indicated that methylation of sulfide and MT resulting in MT and DMS, respectively, is one of the major mechanisms for VOSC in sulfide-rich anaerobic environments. An anaerobic bacterium that is responsible for the formation of MT and DMS through the anaerobic methylation of H2S and MT was isolated from a freshwater pond after enrichment with syringate as a methyl group donating compound and sole carbon source. In spite of the continuous formation of MT and DMS, steady state concentrations are generally very low. This is due to the microbial degradation of these compounds. Experiments with sulfate-rich and sulfate-amended sediment slurries demonstrated that besides methanogens, sulfate-reducing bacteria can also degrade MT and DMS, provided that sulfate is available. A methanogen was isolated that is able to grow on DMS as the sole carbon source. A large survey of sediments slurries of various origin demonstrated that both isolates are commonly occurring inhabitants of anaerobic environments.

  13. Hydrogen generation by electrolysis of aqueous organic solutions

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

    2002-01-01

    A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

  14. Hydrogen generation by electrolysis of aqueous organic solutions

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

    2006-01-01

    A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

  15. Hydrogen generation by electrolysis of aqueous organic solutions

    NASA Technical Reports Server (NTRS)

    Narayanan, Sekharipuram R. (Inventor); Chun, William (Inventor); Jeffries-Nakamura, Barbara (Inventor); Valdez, Thomas I. (Inventor)

    2002-01-01

    A device for electrolysis of an aqueous solution of an organic fuel. The electrolyte is a solid-state polymer membrane with anode and cathode catalysts on both surfaces for electro-oxidization and electro-reduction. A low-cost and portable hydrogen generator can be made based on the device with organic fuels such as methanol.

  16. Kinetics of the reduction of nitrite oil by sulfur dioxide in aqueous solution

    SciTech Connect

    Oblath, S.B.

    1981-08-01

    Reactions between nitrite and bisulfite ions in aqueous solutions were studied in which sulfur (IV) species are oxidized to sulfate ions and nitrogen (III) species are reduced. The dependence on temperature, ionic strength, acidity, and solution composition was determined. The actual products formed depend primarily on the concentration of bisulfite ion. The importance of these reactions to atmospheric aerosol formation processes is discussed. Under most conditions, the nitrogen product is hydroxylamine-N, N-disulfonate. Two processes are responsible for its formation. The first process (when the bisulfite concentration is greater than 0.1 M) is first order in nitrite ion, second order in bisulfite ion, and independent of acidity and temperature. It has a strong dependence on the ionic strength. The second and dominant process contributes to the product formation under all conditions and is first order in nitrite, bisulfite, and hydrogen ions. This process is independent of ionic strength and has a 12 kcal/mole activation energy. Both processes are insensitive to the choice of buffer. Whenever the hydrogen ion concentraion is nearly equal to that of the bisulfite ion, nitrous oxide is also a product. A mechanism is proposed to account for these results. It consists of a direct reaction of nitrite ion with metabisulfite ion to form hydroxylamine disulfonate, in parallel with a reaction between nitrous acid and bisulfite ion to form nitrososulfonic acid. This rapidly adds a bisulfite ion to form hydroxylamine disulfonate or undergoes hydrolysis to form nitrous oxide. The reaction between nitrite ion and hydroxylamine-N-sulfonate to produce nitrous oxide was also investigated. The reaction is first order in nitrite ion, second order in hydrogen ion, and between zero and first order in hydroxylamine monosulfonate, depending on the concentration.

  17. Sulfur isotope fractionation during incorporation of sulfur nucleophiles into organic compounds.

    PubMed

    Amrani, Alon; Ma, Qisheng; Ahmad, Ward Said; Aizenshtat, Zeev; Tang, Yongchun

    2008-03-21

    (34)S enrichment is shown to occur during sulfurization reactions and for the first time conclusively attributed to an isotope equilibrium effect rather than selective addition of (34)S enriched nucleophiles.

  18. Research on the Composition and Distribution of Organic Sulfur in Coal.

    PubMed

    Zhang, Lanjun; Li, Zenghua; Yang, Yongliang; Zhou, Yinbo; Li, Jinhu; Si, Leilei; Kong, Biao

    2016-05-13

    The structure and distribution of organic sulfur in coals of different rank and different sulfur content were studied by combining mild organic solvent extraction with XPS technology. The XPS results have shown that the distribution of organic sulfur in coal is related to the degree of metamorphism of coal. Namely, thiophenic sulfur content is reduced with decreasing metamorphic degree; sulfonic acid content rises with decreasing metamorphic degree; the contents of sulfate sulfur, sulfoxide and sulfone are rarely related with metamorphic degree. The solvent extraction and GC/MS test results have also shown that the composition and structure of free and soluble organic sulfur small molecules in coal is closely related to the metamorphic degree of coal. The free organic sulfur small molecules in coal of low metamorphic degree are mainly composed of aliphatic sulfides, while those in coal of medium and high metamorphic degree are mainly composed of thiophenes. Besides, the degree of aromatization of organic sulfur small molecules rises with increasing degree of coalification.

  19. Spatial Dependence of Reduced Sulfur in Everglades Dissolved Organic Matter Controlled by Sulfate Enrichment.

    PubMed

    Poulin, Brett A; Ryan, Joseph N; Nagy, Kathryn L; Stubbins, Aron; Dittmar, Thorsten; Orem, William; Krabbenhoft, David P; Aiken, George R

    2017-04-04

    Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

  20. Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

    USGS Publications Warehouse

    Poulin, Brett A.; Ryan, Joseph N.; Nagy, Kathryn L.; Stubbins, Aron; Dittmar, Thorsten; Orem, William H.; Krabbenhoft, David P.; Aiken, George R.

    2017-01-01

    Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

  1. Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory.

    PubMed

    Ksionzek, Kerstin B; Lechtenfeld, Oliver J; McCallister, S Leigh; Schmitt-Kopplin, Philippe; Geuer, Jana K; Geibert, Walter; Koch, Boris P

    2016-10-28

    Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of nonvolatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid-phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. Although molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (sulfur/nitrogen ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 petagrams of sulfur, exceeding all other marine organic sulfur reservoirs by an order of magnitude. Copyright © 2016, American Association for the Advancement of Science.

  2. Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory

    NASA Astrophysics Data System (ADS)

    Ksionzek, Kerstin B.; Lechtenfeld, Oliver J.; McCallister, S. Leigh; Schmitt-Kopplin, Philippe; Geuer, Jana K.; Geibert, Walter; Koch, Boris P.

    2016-10-01

    Although sulfur is an essential element for marine primary production and critical for climate processes, little is known about the oceanic pool of nonvolatile dissolved organic sulfur (DOS). We present a basin-scale distribution of solid-phase extractable DOS in the East Atlantic Ocean and the Atlantic sector of the Southern Ocean. Although molar DOS versus dissolved organic nitrogen (DON) ratios of 0.11 ± 0.024 in Atlantic surface water resembled phytoplankton stoichiometry (sulfur/nitrogen ~ 0.08), increasing dissolved organic carbon (DOC) versus DOS ratios and decreasing methionine-S yield demonstrated selective DOS removal and active involvement in marine biogeochemical cycles. Based on stoichiometric estimates, the minimum global inventory of marine DOS is 6.7 petagrams of sulfur, exceeding all other marine organic sulfur reservoirs by an order of magnitude.

  3. Organic non-aqueous cation-based redox flow batteries

    DOEpatents

    Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai; Zhang, Lu; Brushett, Fikile R.

    2016-03-29

    The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturated moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.

  4. Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

    NASA Astrophysics Data System (ADS)

    Chen, Renjie; Zhao, Teng; Tian, Tian; Cao, Shuai; Coxon, Paul R.; Xi, Kai; Fairen-Jimenez, David; Vasant Kumar, R.; Cheetham, Anthony K.

    2014-12-01

    A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/CZIF8-D) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/CZIF8-D) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/CZIF8-D sample, Li-S batteries with the GS-S/CZIF8-D composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

  5. Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

    SciTech Connect

    Chen, Renjie E-mail: chenrj@bit.edu.cn; Zhao, Teng; Tian, Tian; Fairen-Jimenez, David; Cao, Shuai; Coxon, Paul R.; Xi, Kai E-mail: chenrj@bit.edu.cn; Vasant Kumar, R.; Cheetham, Anthony K.

    2014-12-01

    A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

  6. A Study on the Aqueous Formation of Secondary Organic Aerosols

    NASA Astrophysics Data System (ADS)

    Sinclair, K.; Tsigaridis, K.

    2013-12-01

    The effect aerosols have on radiative forcing in the atmosphere is recognized as one of the largest uncertainties in the radiation budget. About 80% of organic aerosol mass in the atmosphere is estimated to be created though secondary processes. Recently, the aqueous formation of secondary organic aerosols (SOA) has become recognized as important when considering the source, transformation and radiative impacts of SOA. This work focuses on implementing a mechanism for aqueous SOA formation that can be used in atmospheric chemistry and models of all scales, from box to global. A box model containing a simplified chemical mechanism for the aqueous production of precursors of aqueous SOA (Myriokefalitakis et al. (2011) is coupled to gas-phase chemistry which uses the carbon bond mechanism (CBM) IV is presented. The model implements aqueous chemistry of soluble gases, both in-cloud and aerosol water, including organic compounds such as glyoxal and methylglyoxal, which have been shown as potentially significant sources for dissolved secondary organic aerosols. This mechanism implements aqueous phase mass transfer and molecular dissociation. The model's performance is evaluated against previous box model studies from the literature. A comparison is conducted between the detailed GAMMA model (McNeill et al., 2012), which is constrained with chamber experiments and the one developed here. The model output under different atmospheric conditions is explored and differences and sensitivities are assessed. The objective of this work is to create a robust framework for simulating aqueous phase formation of SOA and maximizing the computational efficiency of the model, while maintaining accuracy, in order to later use the exact mechanism in global climate simulations.

  7. 4-Carboxybenzophenone-sensitized photooxidation of sulfur-containing amino acids in alkaline aqueous solutions. Secondary photoreactions kinetics

    SciTech Connect

    Bobrowski, K.; Hug, G.L. ); Marciniak, B. A. Mickiewicz Univ., Poznan ); Kozubek, H. )

    1994-01-13

    Sulfur-containing amino acids and alanine were oxidized via photosensitization by 4-carboxybenzophenone (CB) in alkaline aqueous solutions. The mechanism of this reaction was examined using steady-state and laser flash photolysis techniques. The rate constants were determined for the quenching of the CB triplet state by five sulfur-containing amino acids and alanine and were found to be approximately 10[sup 9] and 1.8 x 10[sup 8] M[sup [minus]1] s[sup [minus]1], respectively. The observation of the (S therefore S)[sup +] radical cations of some of the amino acids showed that the quenching process involves an electron transfer from the sulfur atom to the triplet state of CB. A show process of formation of the ketyl radical anion occurring on the microsecond time scale was assigned to the one-electron reduction of CB by the [alpha]-aminoalkyl radicals that were formed earlier as a result of an intramolecular electron transfer from the carboxyl group to the sulfur-centered radical cation followed by decarboxylation. For thiaproline, the pseudo-first-order rate constant, k[prime][sub obs], which characterizes the slow process of secondary ketyl radical anion formation, is linearly dependent on the CB concentration over the pH region 9.4-13.4. A detailed mechanism for the primary and the secondary photoreduction of CB is proposed and discussed. 32 refs., 7 figs., 5 tabs.

  8. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium–sulfur batteries

    PubMed Central

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-01-01

    Lithium–sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium–sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density. PMID:28262801

  9. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries.

    PubMed

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-06

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  10. Foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Mao, Yiyin; Li, Gaoran; Guo, Yi; Li, Zhoupeng; Liang, Chengdu; Peng, Xinsheng; Lin, Zhan

    2017-03-01

    Lithium-sulfur batteries are promising technologies for powering flexible devices due to their high energy density, low cost and environmental friendliness, when the insulating nature, shuttle effect and volume expansion of sulfur electrodes are well addressed. Here, we report a strategy of using foldable interpenetrated metal-organic frameworks/carbon nanotubes thin film for binder-free advanced lithium-sulfur batteries through a facile confinement conversion. The carbon nanotubes interpenetrate through the metal-organic frameworks crystal and interweave the electrode into a stratified structure to provide both conductivity and structural integrity, while the highly porous metal-organic frameworks endow the electrode with strong sulfur confinement to achieve good cyclability. These hierarchical porous interpenetrated three-dimensional conductive networks with well confined S8 lead to high sulfur loading and utilization, as well as high volumetric energy density.

  11. VHF EPR analysis of organic sulfur in coal

    SciTech Connect

    Clarkson, R.B.

    1991-01-01

    This report covers progress made in the first yearly quarter of a two year investigation using novel, very high frequency electron paramagnetic resonance (VHF EPR) spectroscopy techniques and instrumentation (one of only two W-band spectrometers in existence) developed earlier by these authors, to conduct further qualitative and quantitative studies of heteroatomic organic molecules in coal with particular emphasis on sulfur. Previous W-band (96 GHz) work is being extended to studies of new model compounds as well as coal and desulfurized coal samples. Typically, the model compounds under investigation and their analogues are found in coals as stable free radicals which give rise to an EPR signal. The preparation of radicals from compounds having widely varying structures and physical properties in a stable environment has long been a very difficult task. To address this problem, the refinement of several new and very useful methods of preparing of these stable free radicals in various glasses, at catalytic surfaces, and in solution, are presented in this first report. Free radical generation was accomplished by both UV photolysis as well as chemical oxidation/reduction techniques. By these methods, over 25 new compounds, often commercially derived from coal extracts, have been prepared and studied by conventional X-band EPR (9 GHz). Several representative W-band spectra are also presented.

  12. Metastable Equilibria Among Aqueous Organic Compounds

    NASA Astrophysics Data System (ADS)

    Shock, E.; Shipp, J.; Yang, Z.; Gould, I. R.

    2011-12-01

    Metastable equilibrium states exist when reactions among a subset of compounds in a chemical system are reversible even though other irreversible reactions exist in the same system. The existence of metastable equilibrium among organic compounds was initially detected by comparing ratios of organic acid concentrations reported for oil-field brines (Shock, 1988, Geology 16, 886-890; Shock, 1989, Geology 17, 572-573), and calculating the same ratios for likely oxidation states determined by mineral assemblages and mixtures of hydrocarbons in coexisting petroleum (Shock, 1994, in: The Role of Organic Acids in Geological Processes, Springer). This led to the notion of extending the concept of metastable equilibrium states to explicitly account for petroleum compositions (Helgeson et al., 1993, GCA, 57, 3295-3339), which eventually yielded the concept of hydrolytic disproportionation of kerogens to produce petroleum and CO2(g) (Helgeson et al., 2009, GCA, 73, 594-695). Experimental tests of metastable equilibrium among organic compounds began with the identification of reversible reactions between alkanes and alkenes that are dependent on the H2 fugacity of the experimental system (Seewald, 1994, Nature 370, 285-287). These were followed with a comprehensive series of long-term experiments leading to the hypothesis that reversible reactions include alkanes, alkenes, alcohol, aldehydes, ketones and carboxylic acids (e.g., Seewald, 2001, GCA 65, 1641-1664; 2003, Nature 426, 327-333; McCollom & Seewald, 2003, GCA 67, 3645-3664). We have conducted sets of hydrothermal organic transformation experiments that test the extent to which these reactions are indeed reversible using aromatic and cyclic compounds. Results demonstrate reversibility for reactions among dibenzyl ketone, 1,3-diphenyl-2-propanol, 1,3-diphenylpropene and 1,3-diphenylpropane, as well as among methylcyclohexanes, methylcyclohexenes, methylcyclohexanols, methylcyclohexanones and methylcyclohexadienes. The

  13. Combined chemical and microbiological removal of organic sulfur from coal. Technical report, September 1, 1990--August 31, 1991

    SciTech Connect

    Raphaelian, L.A.

    1991-12-31

    The objective of this work is to investigate techniques for chemically converting the sulfur containing organic compounds in coal to compounds that can be treated microbiologically to remove the organically bound sulfur. The goal is to achieve an economically feasible mild chemical oxidation of the organic sulfur in a representative Illinois Basin coal by converting the sulfur to sulfoxides and sulfones; the carbon sulfur bond in the sulfoxides and sulfones would then be broken microbiologically and the sulfur removed from the coal as sulfate.

  14. Sorption of tetracycline antibiotics on hyper-crosslinked polystyrene from aqueous and aqueous-organic media

    NASA Astrophysics Data System (ADS)

    Udalova, A. Yu.; Dmitrienko, S. G.; Apyari, V. V.

    2015-06-01

    The sorption of tetracycline, oxytetracycline, chlortetracycline, and doxycycline on hyper-cross-linked polystyrene from aqueous and aqueous-organic solutions is studied under static and dynamic conditions in order to extend the range of the sorbents suitable for sorption isolation and the preconcentration of tetracycline antibiotics. Features of tetracycline sorption depending on the acidity of a solution and the nature and concentration of the compounds are explained. It is shown that hyper-crosslinked polystyrene can be used for the group sorption preconcentration of these compounds.

  15. Synthesis of copper monolayer and particles at aqueous organic interface

    NASA Astrophysics Data System (ADS)

    Yang, Jian-guang; Yang, Sheng-hai; Okamoto, Takeshi; Bessho, Takeshi; Satake, Shigeru; Ichino, Ryoichi; Okido, Masazumi

    2006-12-01

    Using aqueous-organic interface (water-oleic acid) reduction of Cu 2+ by ascorbic acid, hydrophobic copper monolayer and copper particles have been prepared and characterized. The resultant monolayer could be transferred from the interface onto solid substrate or be dissolved to yield an organosol and copper nanoparticles.

  16. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    PubMed Central

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A.R.

    2017-01-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects. PMID:28198376

  17. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series

    NASA Astrophysics Data System (ADS)

    Rodríguez-Albelo, L. Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A. Rabdel; Calero, Sofia; Navarro, Jorge A. R.

    2017-02-01

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  18. Selective sulfur dioxide adsorption on crystal defect sites on an isoreticular metal organic framework series.

    PubMed

    Rodríguez-Albelo, L Marleny; López-Maya, Elena; Hamad, Said; Ruiz-Salvador, A Rabdel; Calero, Sofia; Navarro, Jorge A R

    2017-02-15

    The widespread emissions of toxic gases from fossil fuel combustion represent major welfare risks. Here we report the improvement of the selective sulfur dioxide capture from flue gas emissions of isoreticular nickel pyrazolate metal organic frameworks through the sequential introduction of missing-linker defects and extra-framework barium cations. The results and feasibility of the defect pore engineering carried out are quantified through a combination of dynamic adsorption experiments, X-ray diffraction, electron microscopy and density functional theory calculations. The increased sulfur dioxide adsorption capacities and energies as well as the sulfur dioxide/carbon dioxide partition coefficients values of defective materials compared to original non-defective ones are related to the missing linkers enhanced pore accessibility and to the specificity of sulfur dioxide interactions with crystal defect sites. The selective sulfur dioxide adsorption on defects indicates the potential of fine-tuning the functional properties of metal organic frameworks through the deliberate creation of defects.

  19. Geologic settings for aqueous organic synthesis on Titan revisited.

    PubMed

    Lorenz, R D; Lunine, J I; McKay, C P

    2001-01-01

    The photochemistry in Titan's cold reducing atmosphere is an evolutionary dead end. However, the hydrocarbons and nitriles deposited from the atmosphere can undergo aqueous synthesis into prebiotic molecules in ephemeral settings such as impact melt sheets. We re-examine the longevity of aqueous solutions on Titan, noting that recent measurements of the thermal conductivity of ammonia-rich ices suggest that the melt pockets may be longer-lived than previously thought. We propose an important role in surface organic reactions for ultraviolet sunlight transported to the surface as chemical energy stored in acetylene and released by polymerization at Titan's surface.

  20. Analysis of organic sulfur compounds in atmospheric aerosols at the HKUST supersite in Hong Kong using HR-ToF-AMS.

    PubMed

    Huang, Dan Dan; Li, Yong Jie; Lee, Berto P; Chan, Chak K

    2015-03-17

    Organic sulfur compounds have been identified in ambient secondary organic aerosols, but their contribution to organic mass is not well quantified. In this study, using a high-resolution time-of-flight aerosol mass spectrometer (AMS), concentrations of organic sulfur compounds were estimated based on the high-resolution fragmentation patterns of methanesulfonic acid (MSA), and organosulfates (OS), including alkyl, phenyl, and cycloalkyl sulfates, obtained in laboratory experiments. Mass concentrations of MSA and minimum mass concentrations of OS were determined in a field campaign conducted at a coastal site of Hong Kong in September 2011. MSA and OS together accounted for at least 5% of AMS detected organics. MSA is of marine origin with its formation dominated by local photochemical activities and enhanced by aqueous phase processing. OS concentrations are better correlated with particle liquid water content (LWC) than with particle acidity. High-molecular-weight OS were detected in the continental influenced period probably because they had grown into larger molecules during long-range transport or they were formed from large anthropogenic precursors. This study highlights the importance of both aqueous-phase processing and regional influence, i.e., different air mass origins, on organic sulfur compound formation in coastal cities like Hong Kong.

  1. Sulfur geochemistry of organic-rich sediments from Mud Lake, Florida, USA

    USGS Publications Warehouse

    Bates, A.L.; Spkker, E.C.; Hatcher, P.G.; Stout, S.A.; Weintraub, V.C.

    1995-01-01

    The cores include the upper 4 m of sediment, which consist of four major horizons based on petrographic analyses of the organic material. Systematic changes in the isotopic composition of sedimentary disulfide and organic sulfur coincide with variations in the sulfur species and vegetation types. The transition to sapropel is accompanied by a large negative shift in disulfide ??34S- values, consistent with an increase in sulfate availability and a slower rate of sulfate reduction. -from Authors

  2. Dissolved organic sulfur in streams draining forested catchments in southern China.

    PubMed

    Wang, Zhanyi; Zhang, Xiaoshan; Wang, Zhangwei; Zhang, Yi; Li, Bingwen; Vogt, Rolf

    2012-01-01

    Dissolved organic sulfur (DOS) is an important fraction for sulfur mobilization in ecosystem. In this work stream waters were sampled in 25 forested sites in southern China to study the dissolved sulfur fractions. Dissolved sulfur was fractionated into dissolved organic sulfur (DOS) and inorganic sulfate (SO4(2-)) for 95 stream water samples. The results showed that the concentration of DOS ranged from 0 to 13.1 mg/L (average 1.3 mg/L) in all the streams. High concentrations of DOS in stream waters were found in the sites with high concentrations of sulfate. DOS constituted less than 60.1% of dissolved sulfur (average 17.9%). Statistical analysis showed that DOS concentration was correlated with SO4(2-) in streams waters and total sulfur in surface layer soils. The results also showed that DOS concentration in stream waters had a seasonal variation, but no trends were found with it. The implication was that the long term sulfur deposition had led the increase of the concentration and fraction of DOS in stream waters in acid rain prevailing regions

  3. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods

    SciTech Connect

    Kruge, M.A.

    1991-01-01

    With the recent increase in concern for environmental issues and the implication of sulfur and nitrogen in coal combustion products as prime causes of acid rain, it has become clear that there is an urgent need for alternative methods for determining the nature of organic sulfur and nitrogen compounds in coal. The present study couples mold oxidative and reductive procedures to enhance the depolymerization of coal and its constituent macerals and the quantities of produces amenable to analysis. The study also seeks to apply the degradative techniques to coal asphaltenes, since they are believed to be polymeric structures similar to the whole coal, but smaller and more readily analyzed. While the research effort will focus on Illinois coal, additional samples with even higher sulfur contents will also used, allowing for much easier detection and characterization of organic sulfur structures. A preliminary tests of this hypothesis indicates that many of the same sulfur compounds are present in both the Illinois and in an extremely sulfur-rich coal and that the more complex sulfur compounds are indeed more concentrated in the sulfur-rich sample.

  4. The use of hydrophilic groups in aqueous organic reactions.

    PubMed

    Itami, Kenichiro; Yoshida, Jun-Ichi

    2002-01-01

    The representative examples of beneficial effects of hydrophilic groups in aqueous organic reactions are described, including the Diels-Alder reactions, hetero Diels-Alder reactions, Claisen rearrangement, radical reactions, and transition metal-catalyzed reactions. Although the low solubility of organic molecules in water has been a bane in aqueous organic reactions, the incorporation of hydrophilic groups into the substrate structure can overcome the solubility problem and at the same time enhance the hydrophobic effect. In some cases, interesting micellar effects are observed because of the amphiphilic natures of such molecules. The emerging concept of "removable hydrophilic group," in which the solubility problems have been alleviated, yet the initial product can still be transformed into a variety of products with the removal of the hydrophilic groups, is also described. Copyright 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

  5. Rapid, direct determination of organic sulfur in coal using electron-probe microanalysis

    SciTech Connect

    Raymond, R. Jr.

    1981-01-01

    Electron probe microanalysis (EPM) for organic sulfur content can be performed easily on -20 to -100 mesh coal samples. Samples need only be mounted in epoxy and polished as coal samples are commonly prepared for petrographic examination. 15 areas within non-contiguous vitrinite grains are analyzed with the EPM. Without the need to produce a photomosaic, the organic sulfur content of vitrinite, and therefore of a coal, may be determined in less than 10 minutes. To test the EPM method coals were analyzed for which the ASTM organic sulfur values were corrected for unextracted iron. Such a correction would take into account the effect of any pyrite that remained unextracted following the ASTM Standard Method D2492-68. As shown from the data the EPM organic sulfur contents are very close to those of the corrected ASTM values. Using the EPM method, the potential exists to achieve very rapid, multiple organic sulfur analyses, which in turn will allow for rapid, detailed measurements of variations in organic sulfur content occurring across coal seams.

  6. Characterization of the organic-sulfur-degrading enzymes. [IGTS8: a derivative of Rhodococcus rhodochrous

    SciTech Connect

    Ho, N.W.Y.

    1991-01-01

    The objective of the proposed research is to first characterize the enzymes involved in degrading organic sulfur in coal from some of the well-characterized organic sulfur-degrading strains. After the enzymes have been successfully purified, the genes encoding these enzymes will be cloned and the suitability of these microorganisms for recombinant manipulation will also be studied. Initially, the enzymes involved in the removal of organic sulfur from coal and from model compounds in two particular strains, IGTS8 and K3B, will be characterized and analyzed. The scope of the proposed study covers the following: (1) Characterization, purification, and partial sequence analysis of the enzymes involved in the removal of organic sulfur from coal. (2) Cloning of the genes encoding the organic sulfur-degrading enzymes from these two selected species in E. coli. (3) Sequence analysis of the cloned genes. (4) Attempting to clone and overexpress the organic sulfur degrading genes in their parent hosts as well as in other hosts.

  7. Characterization of the organic-sulfur-degrading enzymes. Technical report, September 1, 1991--November 30, 1991

    SciTech Connect

    Ho, N.W.Y.

    1991-12-31

    The objective of the proposed research is to first characterize the enzymes involved in degrading organic sulfur in coal from some of the well-characterized organic sulfur-degrading strains. After the enzymes have been successfully purified, the genes encoding these enzymes will be cloned and the suitability of these microorganisms for recombinant manipulation will also be studied. Initially, the enzymes involved in the removal of organic sulfur from coal and from model compounds in two particular strains, IGTS8 and K3B, will be characterized and analyzed. The scope of the proposed study covers the following: (1) Characterization, purification, and partial sequence analysis of the enzymes involved in the removal of organic sulfur from coal. (2) Cloning of the genes encoding the organic sulfur-degrading enzymes from these two selected species in E. coli. (3) Sequence analysis of the cloned genes. (4) Attempting to clone and overexpress the organic sulfur degrading genes in their parent hosts as well as in other hosts.

  8. Photocatalytic transformations of organic sulfur compounds and H2S

    NASA Astrophysics Data System (ADS)

    Vorontsov, A. V.

    2008-10-01

    Modern views on the products, pathways and kinetic features of liquid- and gas-phase photocatalytic reactions of sulfur compounds in the presence of heterogeneous and homogeneous photocatalysts are generalised. Attention is focussed on the aliphatic and aromatic reduced sulfur compounds and pesticides. The reaction rate in the liquid and gas phases are analysed as function of solution pH, temperature, catalyst content, substrate concentration, solvent type, air moisture and added oxidants. Photocatalyst deactivation and the ways for recovery of its activity are considered.

  9. Sulfur-rich Sediments

    NASA Astrophysics Data System (ADS)

    Goldhaber, M. B.

    2003-12-01

    Marine sediments with more than a few tenths of a percent of organic carbon, as well as organic-matter-bearing, nonmarine sediments with significant concentrations of sulfate in the depositional waters contain the mineral pyrite (FeS2). Pyrite, along with sulfur-bearing organic compounds, form indirectly through the metabolic activities of sulfate-reducing microorganisms. The geochemical transformations of sulfur in sediments leading to these products significantly impact the pathway of early sedimentary diagenesis, conditions for the localization of mineral deposits (Ohmoto and Goldhaber, 1997), the global cycling of sulfur and carbon, the abundance of oxygen in the Earth's atmosphere, and perhaps even the emergence of life on Earth (e.g., Russell and Hall, 1997). This chapter provides an overview of sedimentary-sulfur geochemistry from its microbial and abiologic pathways to the global consequences of these processes.The geochemistry of sulfur is complicated by its wide range of oxidation states (Table 1). Under oxidizing conditions (e.g., in the presence of atmospheric oxygen) sulfate, with sulfur in the +6 valence state, is the stable form of sulfur. Under reducing conditions (e.g., in the presence of H2), sulfide (S=-2 valent) is the stable oxidation state. However, a range of additional aqueous and solid-phase sulfur species exist with valences between these two end-members. What makes the study of sulfur geochemistry so exciting and challenging is that many of these intermediate-valent forms play key roles in sedimentary-sulfur transformations. Furthermore, many of these reactions are microbially mediated. As detailed below, these complex biogeochemical pathways are now yielding to research whose scope ranges from molecular to global level. Table 1. Forms of sulfur in marine sediments and their oxidation states Aqueous species or mineralFormulaOxidation state(s) of sulfur SulfideH2S(aq), HS-(aq)-2 Iron sulfideaFeS(s)-2 GreigiteFe3S4(s)-2, 0 PyriteFeS2(s)-2

  10. Electromembrane extraction from aqueous samples containing polar organic solvents.

    PubMed

    Seip, Knut Fredrik; Gjelstad, Astrid; Pedersen-Bjergaard, Stig

    2013-09-20

    Electromembrane extraction (EME) was performed from aqueous samples and from aqueous samples containing methanol, ethanol, dimethyl sulfoxide, and acetonitrile. The basic drugs pethidine, haloperidol, nortriptyline, methadone and loperamide were used as model analytes. Reversed phase (C18) HPLC with UV (235 nm) and MS detection was used for analysis of the samples. With no organic solvent in the sample, maximum recoveries were obtained after 5-10 min. The maximum recoveries ranged between 83 and 95%. With 50% (v/v) methanol, ethanol, or dimethyl sulfoxide in the sample, recoveries were comparable to those from an aqueous sample, but the time required reaching maximum recovery increased to 15-25 min. With 2-nitrophenyl octyl ether (NPOE) as the supported liquid membrane (SLM), a stable EME system was obtained for 50% (v/v) methanol, 50% (v/v) ethanol, or 75% (v/v) dimethyl sulfoxide in the sample solution. On the other hand, the EME system was unstable with acetonitrile in the sample, as this solvent partly dissolved the SLM. In addition, acetonitrile migrated through the SLM and caused a volume expansion of the acceptor solution. Other SLMs were also tested (ethyl nitrobenzene, isopropyl nitrobenzene, and dodecyl nitrobenzene), but were inferior to NPOE. As a practical example, EME on dried blood spot extracts (80% methanol) were tested, and proved highly successful. These observations showed that EME can be an effective way of preparing aqueous samples containing substantial amounts of an organic solvent.

  11. Solubility, stability, and electrochemical studies of sulfur-sulfide solutions in organic solvents

    NASA Technical Reports Server (NTRS)

    Fielder, W. L.; Singer, J.

    1978-01-01

    A preliminary study of the sulfur electrode in organic solvents suggests that the system warrants further investigation for use in a low temperature (100 deg to 120 C) Na-S secondary battery. A qualitative screening was undertaken at 120 C to determine the solubilities and stabilities of Na2S and Na2S2 in representatives of many classes of organic solvents. From the screening and quantitative studies, two classes of solvents were selected for work; amides and cyclic polyalcohols. Voltammetric and Na-S cell charge discharge studies of sulfide solutions in organic solvents (e.g., N, N-dimethylformamide) at 120 C suggested that the reversibilities of the reactions on Pt or high density graphite were moderately poor. However, the sulfur electrode was indeed reducible (and oxidizable) through the range of elemental sulfur to Na2S. Reactions and mechanisms are proposed for the oxidation reduction processes occurring at the sulfur electrode.

  12. Coal desulfurization by aqueous chlorination

    NASA Technical Reports Server (NTRS)

    Kalvinskas, J. J.; Vasilakos, N.; Corcoran, W. H.; Grohmann, K.; Rohatgi, N. K. (Inventor)

    1982-01-01

    A method of desulfurizing coal is described in which chlorine gas is bubbled through an aqueous slurry of coal at low temperature below 130 degrees C., and at ambient pressure. Chlorinolysis converts both inorganic and organic sulfur components of coal into water soluble compounds which enter the aqueous suspending media. The media is separated after chlorinolysis and the coal dechlorinated at a temperature of from 300 C to 500 C to form a non-caking, low-sulfur coal product.

  13. Aqueous organic chemistry in the atmosphere: sources and chemical processing of organic aerosols.

    PubMed

    McNeill, V Faye

    2015-02-03

    Over the past decade, it has become clear that aqueous chemical processes occurring in cloud droplets and wet atmospheric particles are an important source of organic atmospheric particulate matter. Reactions of water-soluble volatile (or semivolatile) organic gases (VOCs or SVOCs) in these aqueous media lead to the formation of highly oxidized organic particulate matter (secondary organic aerosol; SOA) and key tracer species, such as organosulfates. These processes are often driven by a combination of anthropogenic and biogenic emissions, and therefore their accurate representation in models is important for effective air quality management. Despite considerable progress, mechanistic understanding of some key aqueous processes is still lacking, and these pathways are incompletely represented in 3D atmospheric chemistry and air quality models. In this article, the concepts, historical context, and current state of the science of aqueous pathways of SOA formation are discussed.

  14. A comparison of dilute aqueous p-toluenesulfonic and sulfuric acid pretreatments and saccharification of corn stover at moderate temperatures and pressures.

    PubMed

    Amarasekara, Ananda S; Wiredu, Bernard

    2012-12-01

    Single step pretreatment-saccharification of corn stover was investigated in aqueous p-toluenesulfonic and sulfuric acid media. Dilute aqueous solution of p-toluenesulfonic acid was a better catalyst than aqueous sulfuric acid of the same H(+) ion concentration for single step pretreatment-saccharification of corn stover at moderate temperatures and pressures. For example, 100mg corn stover heated at 150°C for 1h in 0.100 M H(+) aqueous sulfuric acid produced 64 μmol of total reducing sugars (TRS), whereas the sample heated in 0.100 M H(+)p-toluenesulfonic acid produced 165 μmol of TRS under identical conditions. Glucose yield showed a similar trend, as aq. sulfuric acid and p-toluene sulfonic acid media produced 29 and 35 μmol of glucose respectively after 2.5h. Higher catalytic activity of p-toluenesulfonic acid may be due to an interaction with biomass, supported by repulsion of hydrophobic tolyl group by the aqueous phase. Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Biodesulfurization techniques: Application of selected microorganisms for organic sulfur removal from coals. Final report

    SciTech Connect

    Elmore, B.B.

    1993-08-01

    As an alternative to post-combustion desulfurization of coal and pre-combustion desulfurization using physicochemical techniques, the microbial desulfurization of coal may be accomplished through the use of microbial cultures that, in an application of various microbial species, may remove both the pyritic and organic fractions of sulfur found in coal. Organisms have been isolated that readily depyritize coal but often at prohibitively low rates of desulfurization. Microbes have also been isolated that may potentially remove the organic-sulfur fraction present in coal (showing promise when acting on organic sulfur model compounds such as dibenzothiophene). The isolation and study of microorganisms demonstrating a potential for removing organic sulfur from coal has been undertaken in this project. Additionally, the organisms and mechanisms by which coal is microbially depyritized has been investigated. Three cultures were isolated that grew on dibenzothiophene (DBT), a model organic-sulfur compound, as the sole sulfur source. These cultures (UMX3, UMX9, and IGTS8) also grew on coal samples as the sole sulfur source. Numerous techniques for pretreating and ``cotreating`` coal for depyritization were also evaluated for the ability to improve the rate or extent of microbial depyritization. These include prewashing the coal with various solvents and adding surfactants to the culture broth. Using a bituminous coal containing 0.61% (w/w) pyrite washed with organic solvents at low slurry concentrations (2% w/v), the extent of depyritization was increased approximately 25% in two weeks as compared to controls. At slurry concentrations of 20% w/v, a tetrachloroethylene treatment of the coal followed by depyritization with Thiobacillus ferrooxidans increased both the rate and extent of depyritization by approximately 10%.

  16. Selective aqueous extraction of organics coupled with trapping by membrane separation

    SciTech Connect

    van Eikeren, P.; Brose, D.J.; Ray, R.J.

    1991-08-20

    This patent describes improvement in an organic/aqueous extraction process for the extraction of an organic solute from an organic solvent or solvent mixture with an aqueous-based extractant. The improvement comprises continuously recycling the aqueous-based extractant through a membrane separation process that selectively removes the organic solute from the aqueous-based extractant, the membrane separation process being selected from at least one of reverse osmosis, nanofiltration, ultrafiltration, membrane distillation, pervaporation, membrane contactor and supported-liquid membrane.

  17. Quartz dissolution in organic-rich aqueous systems

    USGS Publications Warehouse

    Bennett, Philip C.

    1991-01-01

    Organic electrolytes are a common component of natural waters and are known to be important in many rock-water interactions. The influence of organic electrolytes on silica mobility, quartz solubility, and quartz dissolution kinetics, however, is less well understood. While there is mounting evidence supporting the presence of an aqueous organic-silica complex in natural waters, the significance of this species is difficult to characterize because of competing interactions in mixed inorganic-organic electrolyte environments. In the experiments reported here, the kinetics of quartz dissolution in dilute aqueous organic-acid solutions between 25 and 70°C were investigated to determine the influence of both organic and inorganic electrolytes.Batch-reactor dissolution experiments in inorganic and organic electrolyte solutions were designed to investigate the hypothesis that organic acids at circum-neutral pH accelerate the dissolution and increase the solubility of quartz in water. Results suggest that multi-functional organic acids such as citrate and oxalate accelerate quartz dissolution by decreasing the activation energy by approximately 20%. The increase in dissolution rate was accompanied by a 100% increase in apparent quartz solubility at 25°C. Experiments using inorganic electrolytes, in contrast, increase the rate of quartz dissolution without decreasing the activation energy, and without increasing solubility.From these data, a model for both a solution complex between dissolved organic acid and monomeric silicic acid, and an activated complex on quartz surfaces is proposed. The model suggests that dissolved organic compounds in natural waters at near-neutral pH and low temperatures are capable of accelerating the dissolution of quartz and increasing its solubility.

  18. Prehydrolysis of aspen wood with water and with dilute aqueous sulfuric acid

    Treesearch

    Edward L. Springer; John F. Harris

    1982-01-01

    Water prehydrolysis of aspen wood was compared with 0.40% sulfuric acid prehydrolysis at a reaction temperature of 170°C. Acid prehydrolysis gave much higher yields of total anhydroxylose units in the prehydrolyzate and removed significantly less anhydroglucose from the wood than did the water treatment. At maximum yields of total anhydroxylose units in the...

  19. Aqueous adsorption and removal of organic contaminants by carbon nanotubes.

    PubMed

    Yu, Jin-Gang; Zhao, Xiu-Hui; Yang, Hua; Chen, Xiao-Hong; Yang, Qiaoqin; Yu, Lin-Yan; Jiang, Jian-Hui; Chen, Xiao-Qing

    2014-06-01

    Organic contaminants have become one of the most serious environmental problems, and the removal of organic contaminants (e.g., dyes, pesticides, and pharmaceuticals/drugs) and common industrial organic wastes (e.g., phenols and aromatic amines) from aqueous solutions is of special concern because they are recalcitrant and persistent in the environment. In recent years, carbon nanotubes (CNTs) have been gradually applied to the removal of organic contaminants from wastewater through adsorption processes. This paper reviews recent progress (145 studies published from 2010 to 2013) in the application of CNTs and their composites for the removal of toxic organic pollutants from contaminated water. The paper discusses removal efficiencies and adsorption mechanisms as well as thermodynamics and reaction kinetics. CNTs are predicted to have considerable prospects for wider application to wastewater treatment in the future.

  20. Laboratory evidence of organic peroxide and peroxyhemiacetal formation in the aqueous phase and implications for aqueous OH

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Turpin, B. J.

    2015-11-01

    Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is considered a potentially important atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2-C3) are precursors for SOAaq; products include organic acids, organic sulfates, and high-molecular-weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra-high-resolution Fourier transform ion cyclotron resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals and epoxides (i.e., IEPOX), and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.

  1. Sulfur diagenesis in marine sediments

    NASA Technical Reports Server (NTRS)

    Goldhaber, M.

    1985-01-01

    Bacterial sulfate reduction occurs in all marine sediments that contain organic matter. Aqueous sulfide (HS-, H2S), one of the initial products of bacterial sulfide reduction, is extremely reactive with iron bearing minerals: sulfur is fixed into sediments as iron sulfide (first FeS and then Fe2S2). A working definition is given of sulfur diagenesis in marine sediments. Controls and consequences of sulfate reduction rates in marine sediments are examined.

  2. Trace Metal Associations in an Anoxic Lake: the Relative Roles of Organic Carbon and Reduced Sulfur

    NASA Astrophysics Data System (ADS)

    Poulson Brucker, R.; McManus, J.; Severmann, S.; Owens, J.; Lyons, T.

    2008-12-01

    We investigate the geochemistry of the trace elements Mo, U, and Re in sediments from a transect through the chemocline of Lake Tanganyika, East Africa. In addition to these relatively shallow cores (70 to 330m), we present data from a longer core representing ~30,000 years of lake history, which was taken within the sulfidic waters that lie well below the chemocline (~900m water depth). Our goal is to establish a framework for trace metal deposition within the context of organic carbon and sulfur burial - two important carrier phases for these metals. Sediment organic carbon contents are high, generally between 5 and 10 wt% at the shallow sites, and up to 16 wt% in the deep basin. Despite the very low sulfate (~35 μM) and sulfide (~30 μM) concentrations in the lake water, sediment reduced sulfur contents are up to 1.5 wt% in the shallow sites and as high as 5 wt% in the deepest sediments. Sediment C:S ratios for all study sites are consistent with these sediments generally being sulfur limited. Sediment C:S ratios decrease from ~22, which agree well with previously published freshwater values, to ~6 with increasing site depth. The lower C:S ratios are more comparable to the marine value (2.8), and suggest that a considerable amount of organic carbon must be decomposing via sulfate reduction. C:S ratios in the deepest site are highly variable, with some even lower than the marine threshold. In light of the sedimentary organic carbon and sulfur data, trace metal distributions imply that U deposition is closely associated with organic carbon deposition and is independent of sulfur cycling. In contrast, Mo behavior suggests both an association with organic carbon as well as sulfur, but is subject to poor preservation where the sediment C:S ratios are highest. Rhenium accumulation only appears significant at the deepest most sulfur-rich site, and there is a close correspondence between Mo and Re distributions. These latter observations suggest that sulfur burial is

  3. Contemporaneous early diagenetic formation of organic and inorganic sulfur in estuarine sediments from St. Andrew Bay, Florida, USA

    NASA Astrophysics Data System (ADS)

    Brüchert, Volker; Pratt, Lisa M.

    1996-07-01

    Estuarine sediment samples were collected from nine stations in St. Andrew Bay near Panama City, Florida, USA. Contrasting grain size and varying concentration of organic carbon allowed a comparative study of the relationships among organic degradation processes, sulfur cycling, and diagenetic removal of dissolved sulfide produced by bacterial sulfate reduction. Abundance and sulfur isotopic composition were determined for dissolved sulfide, dissolved sulfate, pyrite, humic-acid sulfur, fulvic-acid sulfur, and elemental sulfur. Presence of free dissolved sulfide and enrichment in 34S of porewater sulfate in samples from organic-rich, muddy sediments of St. Andrew Bay indicate high rates of sulfate reduction and anoxic conditions below 5 mm depth. Such conditions are not reflected in samples from organic-poor, sandy, near-shore sediments collected from highly productive areas occupied by seagrass beds. In this estuarine system, pyrite and fulvic-acid sulfur are the largest sinks for sulfide produced by bacterial sulfate reduction. Strong correlation between abundances of pyrite and fulvic-acid sulfur suggests coincident formation in the uppermost 10 cm of sediment. Large differences in isotopic composition between these two species and consistent enrichment in 34S of the fulvic-acid fraction, however, indicate two different reaction pathways. Abundance and sulfur isotopic composition of humic-acid and fulvic-acid sulfur suggest that organic sulfur is derived from mixing between (1) 34S-depleted sulfur with an unknown oxidation state that was recycled from bacterial hydrogen sulfide and (2) 34S-enriched sulfur interpreted as primary biosynthetic sulfur originally assimilated from dissolved sulfate. Samples taken from sandy sediment localities where aquatic vascular plants are rooted in the anoxic zone show a strong depletion in 34S in the fulvic-acid sulfur fraction suggesting recycled hydrogen sulfide as the dominant source of organic sulfur.

  4. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    NASA Astrophysics Data System (ADS)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  5. Manganese-catalysed autoxidation of dissolved sulfur dioxide in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Berglund, Johan; Elding, Lars I.

    Autoxidation of SO 2(aq) in the presence of manganese(II) is one of the important pathways for sulfuric acid formation in atmospheric clouds and fogs. Recent experimental results indicating that the catalyzed reaction takes place via a complex free-radical mechanism are discussed. Previous literature is reviewed in the light of this mechanism. Under atmospheric conditions of low total concentrations of manganese(II) ( < 2 × 10 -5 M) and sulfur(IV) ( ≤ 10 -5 M) and 2.5 < pH < 5, the rate law for conversion of SO 2(aq) to SO 3(aq) is reduced to d[S(IV)]/d t = k[Mn(II)][S(IV)], where [S(IV)] denotes the total concentration. A value of the overall rate constant k of 1.4 × 10 3 M -1s -1 is recommended for use in atmospheric model calculations.

  6. Kinetics and mechanism of hydration of o-thioquinone methide in aqueous solution. Rate-determining protonation of sulfur.

    PubMed

    Chiang, Yvonne; Kresge, A Jerry; Sadovski, Oleg; Zhan, Hao-Qiang

    2005-03-04

    o-Thioquinone methide, 2, was generated in aqueous solution by flash photolysis of benzothiete, 1, and rates of hydration of this quinone methide to o-mercaptobenzyl alcohol, 3, were measured in perchloric acid solutions, using H2O and D2O as the solvent, and also in acetic acid and tris(hydroxymethyl)methylammonium ion buffers, using H2O as the solvent. The rate profiles constructed from these data show hydronium-ion-catalyzed and uncatalyzed hydration reaction regions, just like the rate profiles based on literature data for hydration of the oxygen analogue, o-quinone methide, of the presently examined substrate. Solvent isotope effects on hydronium-ion catalysis of hydration for the two substrates, however, are quite different: k(H)/k(D) = 0.42 for the oxygen quinone methide, whereas k(H)/k(D) = 1.66 for the sulfur substrate. The inverse nature (k(H)/k(D) < 1) of the isotope effect in the oxygen system indicates that this reaction occurs by a preequilibrium proton-transfer reaction mechanism, with protonation of the substrate on its oxygen atom being fast and reversible and capture of the benzyl-type carbocationic intermediate so formed being rate-determining. The normal direction (k(H)/k(D) > 1) of the isotope effect in the sulfur system, on the other hand, suggests that protonation of the substrate on its sulfur atom is in this case rate-determining, with carbocation capture a fast following step. A semiquantitative argument supporting this hypothesis is presented.

  7. Quantitative analysis of sulfur functional groups in natural organic matter by XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Manceau, Alain; Nagy, Kathryn L.

    2012-12-01

    Two new approaches to quantify sulfur functionalities in natural organic matter from S K-edge XANES spectroscopy are presented. In the first, the K-edge spectrum is decomposed into Gaussian and two arctangent functions, as in the usual Gaussian curve fitting (GCF) method, but the applicability of the model is improved by a rigorous simulation procedure that constrains the model-fit to converge toward chemically and physically realistic values. Fractions of each type of functionality are obtained after spectral decomposition by correcting Gaussian areas for the change in X-ray absorption cross-section with increasing oxidation state. This correction is made using published calibration curves and a new curve obtained in this study. Calibration-induced errors, inherent to the choice of a particular curve, are typically lower than 5% of total sulfur for oxidized species (e.g., sulfate), may reach 10% for organic reduced sulfur, and may be as high as 30-40% for inorganic reduced sulfur. A generic curve, which reduces the calibration-induced uncertainty by a factor of two on data collected to avoid X-ray overabsorption, is derived. In the second analytical scheme, the K-edge spectrum is partitioned into a weighted sum of component species, as in the usual linear combination fitting (LCF) method, but is fit to an extended database of reference spectra under the constraint of non-negativity in the loadings (Combo fit). The fraction of each sulfur functionality is taken as the sum of all positive fractions of references with similar oxidation state of sulfur. The two proposed methods are applied to eight humic and fulvic acids from the International Humic Substances Society (IHSS). The nature and fractions of sulfur functionalities obtained by the two analytical approaches are consistent with each other. The accuracy of the derived values, expressed as the difference in values of a fraction obtained on the same material by the two independent methods, is on average 4.5 ± 3

  8. Sulfur-Containing Organic-Inorganic Hybrid Gel Compositions and Aerogels

    NASA Technical Reports Server (NTRS)

    Evans, Owen R. (Inventor); Dong, Wenting (Inventor); Deshpande, Kiranmayi (Inventor)

    2015-01-01

    Methods and materials are described for preparing organic-inorganic hybrid gel compositions where a sulfur-containing cross-linking agent covalently links the organic and inorganic components. The gel compositions are further dried to provide porous gel compositions and aerogels. The mechanical and thermal properties of the dried gel compositions are also disclosed.

  9. Simultaneous Separation of Manganese, Cobalt, and Nickel by the Organic-Aqueous-Aqueous Three-Phase Solvent Extraction

    NASA Astrophysics Data System (ADS)

    Shirayama, Sakae; Uda, Tetsuya

    2016-04-01

    This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.

  10. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    NASA Astrophysics Data System (ADS)

    Riccobono, F.; Rondo, L.; Sipilä, M.; Barmet, P.; Curtius, J.; Dommen, J.; Ehn, M.; Ehrhart, S.; Kulmala, M.; Kürten, A.; Mikkilä, J.; Petäjä, T.; Weingartner, E.; Baltensperger, U.

    2012-05-01

    Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to formation and to the early growth of nucleated particles, respectively. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene) showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two Chemical Ionization Mass Spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene. New analysis methods were applied to the data collected with a Condensation Particle Counter battery and a Scanning Mobility Particle Sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ), defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is dominated by organic compounds already at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particles growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. The size resolved growth analysis finally indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  11. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    NASA Astrophysics Data System (ADS)

    Riccobono, F.; Rondo, L.; Sipilä, M.; Barmet, P.; Curtius, J.; Dommen, J.; Ehn, M.; Ehrhart, S.; Kulmala, M.; Kürten, A.; Mikkilä, J.; Paasonen, P.; Petäjä, T.; Weingartner, E.; Baltensperger, U.

    2012-10-01

    Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene) showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene. New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ), defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  12. Contributions of organic matter and organic sulfur redox processes to electron flow in anoxic incubations of peat

    NASA Astrophysics Data System (ADS)

    YU, Zhiguo; Peiffer, Stefan; Göttlicher, Jörg; Knorr, Klaus-Holger

    2015-04-01

    Anaerobic decomposition of peat soils involves a number of interdependent microbial processes that ultimately generate CO2 and CH4. In many peat soils, a high ratio of CO2:CH4 was reported, which presumably results from a direct or indirect role of soil organic matter serving as an electron acceptor. Therefore, in this study we intended to test the hypothesis that organic matter (OM) suppresses methanogenesis and sustains anaerobic CO2 production, serving as i) direct electron acceptor or ii) via supporting internal sulfur cycling to maintains CO2 production through bacterial sulfate reduction (BSR). We incubated peat samples of commercial bog peat, inoculated with a small amount of fresh peat to introduce an active microbial community. Samples were amended with sulfate or sulfide and incubated under anoxic conditions for 6 weeks at 30 ° C. Upon anaerobic incubation of peat virtually devoid of inorganic electron acceptors, CO2 and CH4 were produced at a ratio of 3.2. According to the electron budget, the calculated electron accepting capacity (EAC) of OM was 2.36 μeq cm3 d-1. Addition of sulfate significantly increased CO2 production and effectively suppressed CH4 production. After subtracting the EAC provided though sulfate addition (0.97~2.81 μeq cm-3 d-1), EACs supplied by OM reached 3.88 to 4.85 μeq cm-3 d-1.The contribution of organic sulfur was further evaluated by XANES spectroscopy and using natural abundance of δ34S as a tracer. Results demonstrated that BSR involved both addition of H2S and sulfate to OM leading to a formation of reduced organic sulfur and partial changes of oxidized organic sulfur species. The original peat prior to incubation contained 70.5% reduced organic S (R-S-H, R-S-R, R-S-S-R), and 25.9% oxidized S (R-SO3, R-SO2-R, R-SO4-R), whereas the treatment with H2S or sulfate addition comprised 75.7~ 81.1% reduced organic S, and only 21.1~18.9 % oxidized S. Our results imply that that organic matter contributes to anaerobic respiration

  13. Secondary organic aerosol production from aqueous reactions of atmospheric phenols with an organic triplet excited state.

    PubMed

    Smith, Jeremy D; Sio, Vicky; Yu, Lu; Zhang, Qi; Anastasio, Cort

    2014-01-21

    Condensed-phase chemistry plays a significant role in the formation and evolution of atmospheric organic aerosols. Past studies of the aqueous photoformation of secondary organic aerosol (SOA) have largely focused on hydroxyl radical oxidation, but here we show that triplet excited states of organic compounds ((3)C*) can also be important aqueous oxidants. We studied the aqueous photoreactions of three phenols (phenol, guaiacol, and syringol) with the aromatic carbonyl 3,4-dimethoxybenzaldehyde (DMB); all of these species are emitted by biomass burning. Under simulated sunlight, DMB forms a triplet excited state that rapidly oxidizes phenols to form low-volatility SOA. Rate constants for these reactions are fast and increase with decreasing pH and increasing methoxy substitution of the phenols. Mass yields of aqueous SOA are near 100% for all three phenols. For typical ambient conditions in areas with biomass combustion, the aqueous oxidation of phenols by (3)C* is faster than by hydroxyl radical, although rates depend strongly on pH, oxidant concentrations, and the identity of the phenol. Our results suggest that (3)C* can be the dominant aqueous oxidant of phenols in areas impacted by biomass combustion and that this is a significant pathway for forming SOA.

  14. Supercritical aqueous fluids in subduction zones carrying carbon and sulfur: oxidants for the mantle wedge?

    NASA Astrophysics Data System (ADS)

    Sverjensky, Dimitri; Manning, Craig

    2014-05-01

    Much speculation surrounds the nature of aqueous fluids in subduction zones. Aqueous fluids likely trigger partial melting in the mantle wedge, influencing the chemistry of the magmas that erupt in island arcs. They also may play a role in transporting elements that could metasomatize and oxidize the overlying mantle wedge, most importantly C, S and Fe. However, full coupling of aqueous fluid chemistry with the silicate, carbonate, C, sulfide and sulfate minerals has remained limited to pressures of 0.5 GPa because of limitations on the HKF aqueous ion equation of state. Recent progress in developing a Deep Earth Water model (Sverjensky et al., 2014), calibrated with new experimental data, now enables a detailed evaluation of the evolution of aqueous fluid chemistry to a pressure of 6 GPa, well into subduction zone conditions. We report aqueous speciation models for eclogitic aqueous fluids constrained by model mineral assemblages that give preliminary indications of the solubilities of elements that could contribute to mass transfer and redox changes in the mantle wedge. For example, at 600 °C and 2.5 GPa, an aqueous fluid in equilibrium with jadeite, paragonite, muscovite, quartz, lawsonite, almandine, talc, magnesite and pyrite at QFM oxidation state with 0.1 molal total Cl, contains 5.5 molal C, 0.04 molal S, and 9 micromolal Fe. The fluid has a pH of 4.7, much greater than the neutral pH of 3.3; the predominant species and molalities are CO2 (5.0), Na+ (0.44), Si(OH)4 (0.36), HCO3- (0.26), H3SiO4- (0.23), CaHCO3+ (0.18), silica dimer (0.10), Cl- (0.09), K+ (0.08), HCOO- (0.06), H2S (0.03). Calculations for model eclogitic fluids at the higher pressures and temperatures of subarc conditions also show that the solubility of C is much greater than either S or Fe at QFM. However, in subarc eclogitic fluids of higher oxidation state (QFM +3 to +4) in equilibrium with hematite, anhydrite, jadeite, kyanite, phlogopite, coesite, lawsonite, almandine-pyrope, and

  15. Oxygenation of methylarenes to benzaldehyde derivatives by a polyoxometalate mediated electron transfer-oxygen transfer reaction in aqueous sulfuric Acid.

    PubMed

    Sarma, Bidyut Bikash; Efremenko, Irena; Neumann, Ronny

    2015-05-13

    The synthesis of benzaldehyde derivatives by oxygenation of methylarenes is of significant conceptual and practical interest because these compounds are important chemical intermediates whose synthesis is still carried out by nonsustainable methods with very low atom economy and formation of copious amounts of waste. Now an oxygenation reaction with a 100% theoretical atom economy using a polyoxometalate oxygen donor has been found. The product yield is typically above 95% with no "overoxidation" to benzoic acids; H2 is released by electrolysis, enabling additional reaction cycles. An electrocatalytic cycle is also feasible. This reaction is possible through the use of an aqueous sulfuric acid solvent, in an aqueous biphasic reaction mode that also allows simple catalyst recycling and recovery. The solvent plays a key role in the reaction mechanism by protonating the polyoxometalate thereby enabling the activation of the methylarenes by an electron transfer process. After additional proton transfer and oxygen transfer steps, benzylic alcohols are formed that further react by an electron transfer-proton transfer sequence forming benzaldehyde derivatives.

  16. A thermodynamic model for organic and aqueous tablet film coating.

    PubMed

    am Ende, Mary Tanya; Berchielli, Alfred

    2005-01-01

    A tablet film-coating model for aqueous- and/or organic-based systems is shown to predict exhaust stream conditions thereby facilitating process optimization and scale-up. This coating model uses the First Law of Thermodynamics and conservation of mass principles to complete a material-energy balance on the coating unit operation for a closed, non-isolated system. Heat loss from the coating pan is incorporated into the model through a parameter called a heat loss factor (HLF) that is directly related to the heat transfer coefficient and pan surface area. For a mixed organic-aqueous coating formulation, the outlet air temperature and humidity are most notably affected by the coating composition and the inlet drying air temperature, which controls the evaporative cooling rate. The coating solution temperature and inlet air relative humidity do not significantly influence the exhaust air temperature, Tair,out. The HLF was determined to be 24 to 62 cal/min degrees C for the LDCS-20 to HCT-30, 360 cal/min degrees C for the HCT-60, 0 cal/min degrees C for the HC-130L and 945 to 1322 cal/min degrees C for the Accela-Cota-48 to Compulab-36 coating pans. This model successfully predicts Tair,out within 3 degrees C for a given coating pan, and within 6 degrees C scaling up from one to 220 kg pans for both organic- and aqueous-based coatings. The model is also useful for probing process and formulation variable sensitivity critical to establishing process robustness.

  17. Estimation of aqueous solubility of organic compounds with QSPR approach.

    PubMed

    Gao, Hua; Shanmugasundaram, Veerabahu; Lee, Pil

    2002-04-01

    To derive a QSPR model for estimation of aqueous solubility of organic compounds. Solubility data for 930 diverse compounds was investigated with principal component regression analysis. This set of compounds consists of pharmaceuticals, pollutants, nutrients, herbicides, and pesticides. The diversity of this collection was analyzed using MACCS fingerprint and BCUT chemistry space. The training set of the solubility data is as diverse as the Available Chemicals Directory, and more diverse than the MDL Drug Data Report. Forty-six molecular descriptors were screened using a genetic algorithm. A QSPR model with a squared correlation coefficient (r2) of 0.92, a root mean square error of 0.53 log molar solubility (log S(w)), an average absolute estimation error of 0.36 log S(w), and a cross-validated q2 of 0.91 was derived. The QSPR model was validated with a test set of 249 compounds not included in the training set. The absolute estimation error for the test set of compounds was 0.39 log S(w). A highly predictive QSPR model for estimating aqueous solubility was derived and validated. This model can be used to estimate aqueous solubility for virtual screening and combinatorial library design.

  18. Carbinolamines and Geminal Diols in Aqueous Environmental Organic Chemistry

    NASA Astrophysics Data System (ADS)

    Urbansky, Edward T.

    2000-12-01

    Organic chemistry textbooks generally treat geminal diols as curiosities--exceptions to the stability of the C=O double bond. However, most aldehydes of environmental significance, to wit, trichloroethanal (chloral), methanal (formaldehyde), ethanal (acetaldehyde), and propanal (propionaldehyde), exhibit this behavior. Carbinolamines (hemiaminals) are usually considered to be unstable reaction intermediates of very short lifetime, despite a considerable volume of literature that suggests otherwise. In aqueous solution, carbinolamines can build up to substantial concentrations and play important roles in kinetics of aldehyde reactions, subsequent to formation of aldehydes as ozonation by-products during drinking water disinfection. A few carbinolamines are isolable, although these are not encountered in environmental systems. In general, the minimal conceptual treatment of these chemical species results from the central theme of synthetic utility that quite reasonably dominates organic chemistry courses and textbooks. Nonetheless, a pedagogical consequence is that students may be left with an incorrect perception that these species are unlikely to be encountered in common situations. Accordingly, it is important for teachers and students of environmental chemistry to remember that aqueous chemistry can be quite different from that observed in less polar and sometimes aprotic organic solvents.

  19. Gas solubilities in aqueous solutions of organic substances

    SciTech Connect

    Rischbieter, E.; Schumpe, A.; Wunder, V.

    1996-07-01

    The solubilities of He, N{sub 2}, O{sub 2}, CH{sub 4}, and CO{sub 2} in aqueous solutions of glycerol, acetic acid, glucose, sucrose, and lactose were measured at 303.2 K. Additional data were generated for CO{sub 2} at 293.2 K and 323.2 K. The present results and literature data were analyzed to develop an empirical model. The parameter set allows predictions for 15 gases and 63 organic substances at temperatures between 273 K and 343 K.

  20. Aldol Condensation Products and Polyacetals in Organic Films Formed from Reactions of Propanal in Sulfuric Acid at Upper Troposphere/Lower Stratosphere (UT/LS) Aerosol Acidities

    NASA Astrophysics Data System (ADS)

    Bui, J. V. H.; Perez-Montano, S.; Li, E. S. W.; Nelson, T. E.; Ha, K. T.; Leong, L.; Iraci, L. T.; Van Wyngarden, A. L.

    2015-12-01

    Aerosols in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt. %) which is highly reflective towards UV and visible radiation. However, airborne measurements have shown that these particles may also contain a significant amount of organic material. Experiments combining organics (propanal, glyoxal and/or methylglyoxal) with sulfuric acid at concentrations typical of UT/LS aerosols produced highly colored surface films (and solutions) that have the potential to impact chemical, optical and/or cloud-forming properties of aerosols. In order to assess the potential for such films to impact aerosol chemistry or climate properties, experiments were performed to identify the chemical processes responsible for film formation. Surface films were analyzed via Attenuated Total Reflectance-FTIR and Nuclear Magnetic Resonance spectroscopies and are shown to consist primarily of aldol condensation products and cyclic and linear polyacetals, the latter of which are likely responsible for separation from the aqueous phase.

  1. CHLORPYRIFOS TRANSFORMATION BY AQUEOUS CHLORINE IN THE PRESENCE OF BROMIDE AND NATURAL ORGANIC MATTER

    EPA Science Inventory

    The aqueous chlorination of chlorpyrifos (CP) was investigated in the presence of bromide and natural organic matter (NOM), which were identified as naturally occurring aqueous constituents that could impact CP transformation rates to the toxic product chlorpyrifos oxon (CPO). Br...

  2. CHLORPYRIFOS TRANSFORMATION BY AQUEOUS CHLORINE IN THE PRESENCE OF BROMIDE AND NATURAL ORGANIC MATTER

    EPA Science Inventory

    The aqueous chlorination of chlorpyrifos (CP) was investigated in the presence of bromide and natural organic matter (NOM), which were identified as naturally occurring aqueous constituents that could impact CP transformation rates to the toxic product chlorpyrifos oxon (CPO). Br...

  3. Sulfur Assimilation in Developing Lupin Cotyledons Could Contribute Significantly to the Accumulation of Organic Sulfur Reserves in the Seed

    PubMed Central

    Tabe, Linda Marie; Droux, Michel

    2001-01-01

    It is currently assumed that the assimilation of sulfur into reduced forms occurs predominantly in the leaves of plants. However, developing seeds have a strong requirement for sulfur amino acids for storage protein synthesis. We have assessed the capacity of developing seeds of narrow-leaf lupin (Lupinus angustifolius) for sulfur assimilation. Cotyledons of developing lupin seeds were able to transfer the sulfur atom from 35S-labeled sulfate into seed proteins in vitro, demonstrating the ability of the developing cotyledons to perform all the steps of sulfur reduction and sulfur amino acid biosynthesis. Oxidized sulfur constituted approximately 30% of the sulfur in mature seeds of lupins grown in the field and almost all of the sulfur detected in phloem exuded from developing pods. The activities of three enzymes of the sulfur amino acid biosynthetic pathway were found in developing cotyledons in quantities theoretically sufficient to account for all of the sulfur amino acids that accumulate in the protein of mature lupin seeds. We conclude that sulfur assimilation by developing cotyledons is likely to be an important source of sulfur amino acids for the synthesis of storage proteins during lupin seed maturation. PMID:11351081

  4. Inorganic and organic sulfur cycling in salt-marsh pore waters

    SciTech Connect

    Luther, G.W. III; Church, T.M.; Scudlark, J.R.; Cosman, M.

    1986-05-09

    Sulfur species in pore waters of the Great Marsh, Delaware, were analyzed seasonally by polarographic methods. The species determined (and their concentrations in micromoles per liter) included inorganic sulfides (less than or equal to3360), polysulfides (less than or equal to326), thiosulfate (less than or equal to104), tetrathionate (less than or equal to302), organic thiols (less than or equal to2411), and organic disulfides (less than or equal to139). Anticipated were bisulfide increases with depth due to sulfate reduction and subsurface sulfate excesses and pH minima, the result of a seasonal redox cycle. Unanticipated was the pervasive presence of thiols (for example, glutathione), particularly during periods of biological production. Salt marshes appear to be unique among marine systems in producing high concentrations of thiols. Polysulfides, thiosulfate, and tetrathionate also exhibited seasonal subsurface maxima. These results suggest a dynamic seasonal cycling of sulfur in salt marshes involving abiological and biological reactions and dissolved and solid sulfur species. The chemosynthetic turnover of pyrite to organic sulfur is a likely pathway for this sulfur cycling. Thus, material, chemical, and energy cycles in wetlands appear to be optimally synergistic.

  5. Catalytic destruction of hazardous organics in aqueous solutions

    SciTech Connect

    Baker, E.G.; Sealock, L.J. Jr.

    1988-04-01

    Pacific Northwest Laboratory (PNL) is developing a process for destroying hazardous organics and chlorinated organics in aqueous solutions. The process is targeted at liquid waste streams that are difficult and costly to treat with conventional or developing technologies. Examples of these waste streams include contaminated groundwater and surface water and industrial wastewater. Aqueous solutions are treated with a transition metal catalyst at 300/degree/C to 460/degree/C and 2000 to 5000 psig pressure to convert the wastes to innocuous gases. During proof-of-principle tests conducted in a 1-L batch reactor, destruction of over 99/percent/ (in most cases approaching 99.9/percent/) of the organic material was achieved. Hexone (methyl is isobutyl ketone, MIBK), p-cresol, hexane, benzene, and naphthalene were used as model waste materials. The only major product with all of the organic compounds was a gas containing 50/percent/ to 75/percent/ methane, 25/percent/ to 45/percent/ carbon dioxide, and 0/percent) to 5/percent/ hydrogen. Reduced nickel was the only effective catalyst and that the optimal operating conditions for destroying nonchlorinated organics were 350/degree/C to 400/degree/C, 2000 to 4000 psig, and 30/endash/ to 60/endash/min residence time. These tests also indicated that catalyst deactivation or fouling would not be a problem at these conditions. Chlorobenzene and trichloroethylene (TEC), were also tested. Destruction of both compounds was 99/percent/ or greater, but the products were different from those obtained from hydrocarbons. With TCE, the major product was carbon dioxide; with chlorobenzene the major product identified was benzene. In the tests with the chlorinated hydrocarbons, the chlorine was converted to HC1 and the reduced nickel was converted to nickel hydroxide, which may be detrimental to long-term catalyst activity. (15 refs., 8 figs., 6 tabs).

  6. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

    PubMed

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-10-22

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

  7. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules

    PubMed Central

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K.; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J.; Dunne, Eimear M.; Flagan, Richard C.; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P.; Rondo, Linda; Santos, Filipe D.; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S.; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M.; Worsnop, Douglas R.

    2013-01-01

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions. PMID:24101502

  8. Aqueous-phase mechanism for secondary organic aerosol ...

    EPA Pesticide Factsheets

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observati

  9. Aqueous-phase mechanism for secondary organic aerosol ...

    EPA Pesticide Factsheets

    Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx  ≡  NO + NO2) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observati

  10. VHF EPR determination of the chemical forms of organic sulfur in coal

    SciTech Connect

    Clarkson, R.B.

    1991-01-01

    This program addresses the need for innovative approaches to characterize the organic sulfur in Illinois Basin coals. We have developed a very high frequency electron paramagnetic resonance (EPR) spectrometer operating at the W-band of microwave frequencies (96 GHz). This instrument has shown unique sensitivity to heteroatoms in coal, and we believe the technique can be successfully applied for the non-destructive, direct determination of organic sulfur in coal. Preliminary data from Illinois coals and separated macerals indicate that the method also may be able to distinguish aromatic from aliphatic sulfur, and may be useful in assessing the extent of conjugation in aromatic portions of the coal. These high energy spectroscopic techniques, however invariably suffer from the fact that they are not truly non-destructive. By contrast, the low powers and relatively low energy radiation used in magnetic resonance techniques have virtually no effect on the physical structure or chemical composition of coal.

  11. Reevaluating the contribution of sulfuric acid and the origin of organic compounds in atmospheric nanoparticle growth

    NASA Astrophysics Data System (ADS)

    Vakkari, Ville; Tiitta, Petri; Jaars, Kerneels; Croteau, Philip; Beukes, Johan Paul; Josipovic, Miroslav; Kerminen, Veli-Matti; Kulmala, Markku; Venter, Andrew D.; Zyl, Pieter G.; Worsnop, Douglas R.; Laakso, Lauri

    2015-12-01

    Aerosol particles formed in the atmosphere are important to the Earth's climate system due to their ability to affect cloud properties. At present, little is known about the atmospheric chemistry responsible for the growth of newly formed aerosol particles to climate-relevant sizes. Here combining detailed aerosol measurements with a theoretical framework we found that depending on the gaseous precursors and size of the newly formed particles, the growth was dominated by either sulfuric acid accompanied by ammonium or organic compounds originating in either biogenic emissions or savannah fires. The contribution of sulfuric acid was larger during the early phases of the growth, but in clean conditions organic compounds dominated the growth from 1.5 nm up to climatically relevant sizes. Furthermore, our analysis indicates that in polluted environments the contribution of sulfuric acid to the growth may have been underestimated by up to a factor of 10.

  12. Removal of sulfur-containing organic molecules adsorbed on inorganic supports by Rhodococcus Rhodochrous spp.

    PubMed

    Carvajal, P; Dinamarca, M Alejandro; Baeza, P; Camú, E; Ojeda, J

    2017-02-01

    To remove dibenzothiophene (DBT) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) adsorbed on alumina, silica and sepiolite through biodesulfurization (BDS) using Rhodococcus Rhodochrous spp., that selectively reduce sulfur molecules without generating of gaseous pollutants. The adsorption of DBT and 4,6-DMDBT was affected by the properties of the supports, including particle size and the presence of surface acidic groups. The highest adsorption of both sulfur-containing organic molecules used particle sizes of 0.43-0.063 mm. The highest percentage removal was with sepiolite (80 % for DBT and 56 % for 4,6-DMDBT) and silica (71 % for DBT and 37 % for 4,6-DMDBT). This is attributed to the close interaction between these supports and the bacteria. Biodesulfurization is effective for removing the sulfur-containing organic molecules adsorbed on inorganic materials and avoids the generation of gaseous pollutants.

  13. Evaluation of sulfur-reducing microorganisms for organic desulfurization. [Pyrococcus furiosus

    SciTech Connect

    Miller, K.W.

    1991-01-01

    Because of substantial portion of the sulfur in Illinois coal is organic, microbial desulfurization of sulfidic and thiophenic functionalities could hold great potential for completing pyritic sulfur removal. We are testing the hypothesis that organic sulfur can be reductively removed as H{sub 2}S through the activities of anaerobic microorganisms. Our objectives for this year include the following: (1) To obtain cultures that will reductively desulfurize thiophenic model compounds. In addition to crude oil enrichments begun last year, we sampled municipal sewage sludge. (2) To continue to work toward optimizing the activity of the DBDS-reducing cultures obtained during the previous year. (3) To expand coal desulfurization work to include other coals including Illinois Basin Coal 101 and a North Dakota lignite, which might be more susceptible to the dibenzyldisulfide reducing cultures due to its lower rank. (4) To address the problem of sulfide sorption, by investigating the sorption capacity of coals in addition to Illinois Basin Coal 108.

  14. Pervaporation of Water from Aqueous Sulfuric Acid at Elevated Temperatures Using Nafion® Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2009-01-01

    The concentration of sulfuric acid by pervaporation has been studied using Nafion-112® and Nafion-117® membranes, which have been characterized in terms of flux, permeability, and selectivity at 100 ºC and 120 ºC. Feed concentrations investigated ranged from 40 to over 80 weight percent. In general, water fluxes ranged from 100-8000 g/m2h, depending on feed acid concentration and separations factors as high as 104 were observed. Membrane stability was probed using Dynamic Mechanical Analysis that revealed some embrittlement of the membranes during use. Further studies showed that the embrittlement was due to an interaction with the acid and was not induced by the operating temperature.

  15. [Research on determination of total volatile organic sulfur compounds in the atmosphere].

    PubMed

    Wang, Yan-Jun; Zheng, Xiao-Ling; He, Ying; Zhang, Dong; Wang, Bao-Dong

    2011-12-01

    A detection technology was established comprising trap, desorption, oxidation and UV fluorescence determination process, and used for the test of total concentration of trace volatile sulfur compounds (VSCs) in the atmosphere. A cryogenic trap-thermal desorption device was developed, integrating the advantages of solid retention method and cryogenic condensation method, which was applied to capture and enrich trace volatile organic sulfur compounds. Under high temperature and combustion-supporting gas, the VSCs were completely oxidized into sulfur dioxide. By analyzing the content of sulfur dioxide through ultraviolet fluorescence method indirectly calculated to gain the total concentration of volatile organic sulfur compounds. The trapping temperature, desorption temperature and the oxidation temperature were 5 degrees C, 150 degrees C and 1 000 degrees C, and the precision and recovery of the method were 5.46% and 99.6%-109.2%, respectively. The content of trace amounts of atmospheric VSCs determined from February to April at Qingdao was 42-195 ng x m(-3).

  16. Interfacial Chemistry of Aqueous Sulfur/Iodide Aerosol Microdroplets in Gaseous Ozone

    NASA Astrophysics Data System (ADS)

    Enami, S.; Vecitis, C. D.; Cheng, J.; Colussi, A. J.; Hoffmann, M. R.

    2007-12-01

    The intermediates ISO3- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (iodide - thiosulfate) microdroplets traversing dilute ozone gas plumes at atmospheric pressure are detected via online electrospray mass spectrometry within 1 ms, and their stabilities gauged by collision-induced dissociation. The simultaneous detection of anionic reactants and the S2O62-, HSO4-, IO3- and I3- products as a function of experimental conditions provides evidence of unique interfacial reaction kinetics. Although ozone reacts ~3-4 times faster with I- than S2O332- in bulk solution, only S2O32- is apparently oxidized in [I--]o/[S2O32- ]o = 10 microdroplets below [O3(g)] ~ 50 ppm. The sulfite to sulfate and iodide to triiodide and iodate oxidations in the interfacial layers of aqueous thiosulfate or mixed thiosulfate and iodide microdroplets briefly exposed to dilute O3(g) gas mixtures are also investigated. S(IV) oxidation kinetics in sodium thiosulfate solutions, where the rates are proportional to [S(IV)] [O3(g)] in the ranges investigated, correspond to a surface-specific reaction. I3-/IO3- yields based on interfacial I- losses exceed their stoichiometric limits in the presence of excess S(IV), revealing that interfacial I- is competitively replenished from the microdroplets inner layers. Present results provide unequivocal evidence of distinct interfacial chemistry in gas-aerosol reactions of atmospheric relevance.

  17. Isotopic evidence for determining the sources of dissolved organic sulfur in a forested catchment

    Treesearch

    Phil-Goo Kang; Myron J. Mitchell; Bernhard Mayer; John L. Campbell

    2014-01-01

    Understanding sulfur (S) biogeochemistry, especially in those watersheds subject to elevated levels of atmospheric S inputs, is needed for determining the factors that contribute to acidification, nutrient losses and the mobilization of toxic solutes (e.g., monomeric aluminum and methylmercury). S is found in a variety of both organic and inorganic forms undergoing a...

  18. Comment on “Dissolved organic sulfur in the ocean: Biogeochemistry of a petagram inventory”

    NASA Astrophysics Data System (ADS)

    Dittmar, Thorsten; Stubbins, Aron; Ito, Takamitsu; Jones, Daniel C.

    2017-05-01

    Ksionzek et al. (Reports, 28 October 2016, p. 456) provide important data describing the distribution of dissolved organic sulfur (DOS) in the Atlantic Ocean. Here, we show that mixing between water masses is sufficient to explain the observed distribution of DOS, concluding that the turnover time of refractory DOS that Ksionzek et al. present cannot be deduced from their data.

  19. Volatile Organic Sulfur Compounds of Environmental Interest: Dimethyl Sulfide and Methanethiol

    ERIC Educational Resources Information Center

    Chasteen, Thomas G.; Bentley, Ronald

    2004-01-01

    Volatile organic sulfur compounds (VOSCs) have been assigned environmental roles in global warming, acid precipitation, and cloud formation where two important members dimethyl sulfide (CH3)2 S, DMS, and methanethiol, CH3SH, MT, of VOSC group are involved.

  20. Volatile Organic Sulfur Compounds of Environmental Interest: Dimethyl Sulfide and Methanethiol

    ERIC Educational Resources Information Center

    Chasteen, Thomas G.; Bentley, Ronald

    2004-01-01

    Volatile organic sulfur compounds (VOSCs) have been assigned environmental roles in global warming, acid precipitation, and cloud formation where two important members dimethyl sulfide (CH3)2 S, DMS, and methanethiol, CH3SH, MT, of VOSC group are involved.

  1. The effect of moderate coal cleaning on microbial removal of organic sulfur. [Rhodococcus rhodochrous

    SciTech Connect

    Srivastava, V.J.

    1991-01-01

    The objective of this research is to provide data relevant to the development of an integrated physical, chemical, and microbiological process for the desulfurization of coal, utilizing existing technologies insofar as is possible. Specifically, the effect of increased surface area and porosity achieved by physical, chemical, and microbial treatments of coal on the subsequent microbiological removal of organic sulfur will be evaluated.

  2. Solubility of volatile organic compounds in aqueous ammonia solution.

    PubMed

    Görgényi, Miklós; Dewulf, Jo; Van Langenhove, Herman; Király, Zoltán

    2005-05-01

    The Ostwald solubility coefficient, L of 17 volatile organic compounds (VOCs) from the gas phase into water and dilute aqueous ammonia solutions was determined by the equilibrium partitioning in closed system-solid phase micro extraction (EPICS-SPME) method at 303 K and at 0-2.5 mol dm(-3) ammonia concentrations. Ammonia increased the solubility of all VOCs nearly linearly, but to a different extent. The difference in the solubility values in aqueous ammonia solutions (Lmix) compared to pure water (L) is explained on the basis of a Linear Solvation Energy Relationship (LSER) equation made applicable for solvent mixtures, logLmix - logL = x((sNH3 - sH2O)pi2H + (aNH3 - aH2O)Sigma2H + (bNH3 - bH2O)Sigmabeta2H + (vNH3 - VH2O)Vx). sNH3 - sH2O, aNH3 - aH2O, bNH3 - bH2O, vNH3 - vH2O are the differences of solvent parameters, x is the mole fraction, pi2H is the solute dipolarity-polarizability, Sigmaalpha2H is the effective hydrogen bond acidity of the solute, Sigmabeta2H is the effective hydrogen bond basicity of the solute and Vx, the McGowan characteristic volume. The most significant term was v, the phase hydrophobicity. The solubility behavior was explained by the change in structure of the aqueous solution: the presence of ammonia reduces the cavity effect. These findings show that the presence of compounds such as ammonia, frequently observed in environmental waters, especially wastewaters, affect the fugacity of VOCs, having consequences for the environmental partitioning of VOCs and having technical consequences towards wastewater treatment technologies.

  3. Sulfur cathode hosted in porous organic polymeric matrices

    SciTech Connect

    Zhang, Zhengcheng; Weng, Wei; Yuan, Shengwen; Amine, Khalil

    2016-02-09

    A composite material includes a porous organic polymer and an electrochemically active material, wherein the porous organic polymer contains a plurality of pores having a diameter of from about 0.1 nm to about 100 nm, and the electrochemically active material is disposed within the pores.

  4. Aqueous processing of organic compounds in carbonaceous asteroids

    NASA Astrophysics Data System (ADS)

    Trigo-Rodríguez, Josep Maria; Rimola, Albert; Martins, Zita

    2015-04-01

    There is growing evidence pointing towards a prebiotic synthesis of complex organic species in water-rich undifferentiated bodies. For instance, clays have been found to be associated with complex organic compounds (Pearson et al. 2002; Garvie & Buseck 2007; Arteaga et al. 2010), whereas theoretical calculations have studied the interaction between the organic species and surface minerals (Rimola et al., 2013) as well as surface-induced reactions (Rimola at al. 2007). Now, we are using more detailed analytical techniques to study the possible processing of organic molecules associated with the mild aqueous alteration in CR, CM and CI chondrites. To learn more about these processes we are studying carbonaceous chondrites at Ultra High-Resolution Transmission Electron Microscopy (UHR-TEM). We are particularly interested in the relationship between organics and clay minerals in carbonaceous chondrites (CCs) matrixes (Trigo-Rodríguez et al. 2014, 2015).We want to address two goals: i) identifying the chemical steps in which the organic molecules could have increased their complexity (i.e., surface interaction and catalysis); and ii) studying if the organic matter present in CCs experienced significant processing concomitant to the formation of clays and other minerals at the time in which these planetary bodies experienced aqueous alteration. Here, these two points are preliminarily explored combing experimental results with theoretical calculations based on accurate quantum mechanical methods. References Arteaga O, Canillas A, Crusats J, El-Hachemi Z, Jellison GE, Llorca J, Ribó JM (2010) Chiral biases in solids by effect of shear gradients: a speculation on the deterministic origin of biological homochirality. Orig Life Evol Biosph 40:27-40. Garvie LAJ, Buseck PR (2007) Prebiotic carbon in clays from Orgueil and Ivuna (CI) and Tagish lake (C2 ungrouped) meteorites. Meteorit Planet Sci 42:2111-2117. Pearson VK, Sephton MA, Kearsley AT, Bland AP, Franchi IA, Gilmour

  5. BIOGEOCHEMICAL CONTROLS ON REACTION OF SEDIMENTARY ORGANIC MATTER AND AQUEOUS SULFIDES IN HOLOCENE SEDIMENTS OF MUD LAKE FLORIDA

    EPA Science Inventory

    The distribution and quantity of organic sulfur and iron sulfur species were determined in the
    Holocene sediments from Mud Lake, Florida. The sediments of this shallow, sinkhole lake are characterized by high sulfur and organic carbon contents as well as active sulfate reducti...

  6. BIOGEOCHEMICAL CONTROLS ON REACTION OF SEDIMENTARY ORGANIC MATTER AND AQUEOUS SULFIDES IN HOLOCENE SEDIMENTS OF MUD LAKE FLORIDA

    EPA Science Inventory

    The distribution and quantity of organic sulfur and iron sulfur species were determined in the
    Holocene sediments from Mud Lake, Florida. The sediments of this shallow, sinkhole lake are characterized by high sulfur and organic carbon contents as well as active sulfate reducti...

  7. Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution

    DTIC Science & Technology

    1990-03-01

    IIC FILE COPY Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution Susan Taylor and Louise Parker March...Engineers Cold Regions Research & Engineering Laboratory Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution...14 iii Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution SUSAN TAYLOR AND LOUISE

  8. Stabilization of Gold Nanorods (GNRs) in Aqueous and Organic Environments by Select Surface Functionalization

    DTIC Science & Technology

    2016-01-01

    ARL-TR-7581 ● JAN 2016 US Army Research Laboratory Stabilization of Gold Nanorods (GNRs) in Aqueous and Organic Environments by...7581 ● JAN 2016 US Army Research Laboratory Stabilization of Gold Nanorods (GNRs) in Aqueous and Organic Environments by Select Surface... Gold Nanorods (GNRs) in Aqueous and Organic Environments by Select Surface Functionalization 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM

  9. Microbial removal of organic sulfur from coal (bacterial degradation of sulfur-containing heterocyclic compounds): Final report, March 1--December 31, 1987

    SciTech Connect

    Klubek, B.; Clark, D.

    1988-03-01

    The presence of levels of sulfur in coal is a major source of air pollution and considerable efforts are being made to devise a cost-effective way of removing it. One promising method is microbial desulfurization. Almost all of the inorganic sulfur can be removed from coal by the bacteria Thiobacillus or Sulfolobus, which convert sulfide to sulfate but leave the organic sulfur untouched. If strains of bacteria are developed which remove organic sulfur from coal and are used in conjunction with inorganic sulfur-oxidizing bacteria, the result should be an effective desulfurization method. We are using two approaches to develop bacteria which remove organic sulfur. One method is to mutate a laboratory species, Escherichia coli, an organism which is genetically well understood and whose pathways for the metabolism of sulfur-containing amino acids have been extensively investigated. Such thiophene degraders can be genetically analyzed, and the genes involved can be cloned in order to amplify their products. The second approach is the development of naturally occurring bacteria capable of thiophene degradation. Enrichment culture techniques, mutagenesis of current isolated strains, and mixed culture studies with crushed coal comprise an alternative approach in our study. The degradation rates of our model-thiophene compounds and the preliminary testing of our isolates with coal will index the efficiency of our strains in coal desulfurization. Ultimately, the genes responsible for thiophene degradation by our isolated strains will be transferred to our E. coli strain, creating a single organism capable of degrading a broad spectrum of thiophene compounds. 14 refs., 5 tabs.

  10. Kinetics and mechanism of the degradation of methyl parathion in aqueous hydrogen sulfide solution: investigation of natural organic matter effects.

    PubMed

    Guo, Xiaofen; Jans, Urs

    2006-02-01

    The kinetics of the transformation of methyl parathion have been investigated in aqueous solution containing reduced sulfur species and small concentrations of natural organic matter (NOM) from different sources such as soil, river, and peat. It was shown that NOM mediates the degradation of methyl parathion in aqueous solutions containing hydrogen sulfide. After evaluating and quantifying the effect of the NOM concentration on the degradation kinetics of methyl parathion in the presence of hydrogen sulfide, it was found that the observed pseudo-first-order reaction rate constants (k(obs)) were proportional to NOM concentrations. The influence of pH on the degradation of methyl parathion in the aqueous solutions containing hydrogen sulfide and NOM has been studied. The rate of degradation of methyl parathion was strongly pH dependent. The results indicate k(obs) with a commercially available humic acid has a maximum value at approximately pH 8.3. Two main reaction mechanisms are identified to dominate the degradation of methyl parathion in aqueous solution containing hydrogen sulfide and NOM based on the products aminomethyl parathion and desmethyl methyl parathion. The two mechanisms are nitro-group reduction and nucleophilic attack at the methoxy-carbon. The reduction of the nitro-group is only observed in the presence of NOM. The results of this study form an important base for the evaluation and interpretation of transformation processes of methyl parathion in the environment.

  11. Biodegradability of organic nanoparticles in the aqueous environment.

    PubMed

    Kümmerer, Klaus; Menz, Jakob; Schubert, Thomas; Thielemans, Wim

    2011-03-01

    Synthetic nanoparticles have already been detected in the aquatic environment. Therefore, knowledge on their biodegradability is of utmost importance for risk assessment but such information is currently not available. Therefore, the biodegradability of fullerenes, single, double, multi-walled as well as COOH functionalized carbon nanotubes and cellulose and starch nanocrystals in aqueous environment has been investigated according to OECD standards. The biodegradability of starch and cellulose nanoparticles was also compared with the biodegradability of their macroscopic counterparts. Fullerenes and all carbon nanotubes did not biodegrade at all, while starch and cellulose nanoparticles biodegrade to similar levels as their macroscopic counterparts. However, neither comfortably met the criterion for ready biodegradability (60% after 28 days). The cellulose and starch nanoparticles were also found to degrade faster than their macroscopic counterparts due to their higher surface area. These findings are the first report of biodegradability of organic nanoparticles in the aquatic environment, an important accumulation environment for manmade compounds.

  12. Metal-organic framework-based separator for lithium-sulfur batteries

    NASA Astrophysics Data System (ADS)

    Bai, Songyan; Liu, Xizheng; Zhu, Kai; Wu, Shichao; Zhou, Haoshen

    2016-07-01

    Lithium-sulfur batteries are a promising energy-storage technology due to their relatively low cost and high theoretical energy density. However, one of their major technical problems is the shuttling of soluble polysulfides between electrodes, resulting in rapid capacity fading. Here, we present a metal-organic framework (MOF)-based battery separator to mitigate the shuttling problem. We show that the MOF-based separator acts as an ionic sieve in lithium-sulfur batteries, which selectively sieves Li+ ions while efficiently suppressing undesired polysulfides migrating to the anode side. When a sulfur-containing mesoporous carbon material (approximately 70 wt% sulfur content) is used as a cathode composite without elaborate synthesis or surface modification, a lithium-sulfur battery with a MOF-based separator exhibits a low capacity decay rate (0.019% per cycle over 1,500 cycles). Moreover, there is almost no capacity fading after the initial 100 cycles. Our approach demonstrates the potential for MOF-based materials as separators for energy-storage applications.

  13. Rapid organic matter sulfurization in sinking particles from the Cariaco Basin water column

    NASA Astrophysics Data System (ADS)

    Raven, Morgan Reed; Sessions, Alex L.; Adkins, Jess F.; Thunell, Robert C.

    2016-10-01

    Organic matter (OM) burial in marine sediments is a potentially important control on global climate and the long-term redox state of the earth's surface. Still, we have only a limited understanding of the processes that stabilize OM and facilitate its preservation in the geologic record. Abiotic reactions with (poly)sulfides can enhance the preservation potential of OM, but for this process to be significant it needs to compete with OM remineralization, the majority of which occurs before sinking particles reach the sea floor. Here we investigate whether OM sulfurization occurs within sinking particles in the Cariaco Basin, a modern sulfidic marine environment with high rates of OM burial. Proto-kerogen in sinking particles is frequently more sulfur-rich and 34S-depleted than expectations for biomass, with a composition that is difficult to explain by mixing with resuspended or terrigenous material. Instead, it appears that sulfur is being incorporated into OM on a timescale of days in sinking particles. The flux of this abiogenic organic S from particles is equivalent to approximately two-thirds of the total amount of proto-kerogen S at 10 cm depth in underlying sediments (ODP Core 1002B); after 6000 years of more gradual sulfurization reactions, potential water column sources are still equivalent to nearly half of the total proto-kerogen S in Cariaco sediments. Water column sulfurization is most extensive during periods of upwelling and high primary productivity and appears to involve elemental S, possibly via polysulfides. This process has the potential to deliver large amounts of OM to the sediments by making it less available for remineralization, generating OM-rich deposits. It represents a potentially dynamic sink in the global carbon cycle that can respond to changes in environmental conditions, including the size and intensity of O2-depleted environments. Water column OM sulfurization could also have played a more significant role in the carbon cycle

  14. Molecular evidence for abiotic sulfurization of dissolved organic matter in marine shallow hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Gomez-Saez, Gonzalo V.; Niggemann, Jutta; Dittmar, Thorsten; Pohlabeln, Anika M.; Lang, Susan Q.; Noowong, Ann; Pichler, Thomas; Wörmer, Lars; Bühring, Solveig I.

    2016-10-01

    Shallow submarine hydrothermal systems are extreme environments with strong redox gradients at the interface of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids are often depleted in sulfate when compared to surrounding seawater and can contain high concentrations of hydrogen sulfide (H2S). It is well known that sulfur in its various oxidation states plays an important role in processing and transformation of organic matter. However, the formation and the reactivity of dissolved organic sulfur (DOS) in the water column at hydrothermal systems are so far not well understood. We investigated DOS dynamics and its relation to the physicochemical environment by studying the molecular composition of dissolved organic matter (DOM) in three contrasting shallow hydrothermal systems off Milos (Eastern Mediterranean), Dominica (Caribbean Sea) and Iceland (North Atlantic). We used ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the DOM on a molecular level. The molecular information was complemented with general geochemical data, quantitative dissolved organic carbon (DOC) and DOS analyses as well as isotopic measurements (δ2H, δ18O and F14C). In contrast to the predominantly meteoric fluids from Dominica and Iceland, hydrothermal fluids from Milos were mainly fed by recirculating seawater. The hydrothermal fluids from Milos were enriched in H2S and DOS, as indicated by high DOS/DOC ratios and by the fact that >90% of all assigned DOM formulas that were exclusively present in the fluids contained sulfur. In all three systems, DOS from hydrothermal fluids had on average lower O/C ratios (0.26-0.34) than surrounding surface seawater DOS (0.45-0.52), suggesting shallow hydrothermal systems as a source of reduced DOS, which will likely get oxidized upon contact with oxygenated seawater. Evaluation of hypothetical sulfurization reactions suggests DOM reduction and sulfurization during seawater

  15. Gas chromatography combined with mass spectrometry for the identification of organic sulfur compounds in shellfish and fish

    SciTech Connect

    Ogata, M.; Miyake, Y.

    1980-11-01

    The authors determined that the organic sulfur compounds usually contained in crude oil can be used as a marker of oil pollution in shellfish and fish. Short-necked clams and eels were maintained in a controlled laboratory environment in water with suspension of crude oil. Mass spectra and mass chromatograms of short-necked clam extract showed the presence of organic sulfur compounds. Capillary column gas chromatography-mass chromatograms of crude oil and extract from the soft body of a short-necked clam showed the presence of organic sulfur compounds. Besides sulfur components, various other compounds were contained in crude oil and short-necked clam. Mass chromatograms of crude oil and the extract from eel flesh showed the presence of alkyl benzothiophene, dibenzothiophene, naphthalene, and alkyl naphthalene. Data indicated that the organic sulfur compounds and polyaromatic compounds could serve as markers of oil pollution in shellfish and fish.

  16. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

    1996-01-01

    Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are

  17. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, Sherwood

    1996-01-01

    Isotopic measurements have been made on organic sulfur and phosphorus compounds recently discovered in the Murchison meteorite. Carbon, hydrogen and sulfur measurements were performed on individual members of the organic sulfur compounds, alkyl sulfonates; and carbon and hydrogen measurements were made on bulk alkyl phosphonates. Cooper and Chang reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into the potential synthetic mechanisms of these and, possibly, other organic species. Hydrogen isotopic measurements of the sulforiates now reveal deuterium excesses ranging from +660 to +2730 %. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurements of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson have shown that some bulk ureilites possess excess S-33 and Thiemens et al. have reported excess S-33 in an oldhamite separate from the Norton County meteorite. Rees and Thode reported a large S-33 excess in an Allende acid residue, however, attempts to verify this measurements have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect chemistry in the protosolar nebula or the precursor molecular cloud, identification of potential carriers is of considerable interest. In the present study, the stable isotopes of sulfur were measured in methane sulfonic acid extracted from the Murchison meteorite. The isotopic composition was found to be: (delta)S-33 = 2.48 %, (delta)S-34 = 2.49 % and (delta)S-36 = 6.76 %. Based upon analysis of more than 60 meteoritic and numerous terrestrial samples, the mass fractionation lines are

  18. Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

    NASA Astrophysics Data System (ADS)

    Luo, Chao

    To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit

  19. Uptake of organic sulfur and nitrogen compounds by aerosols

    USDA-ARS?s Scientific Manuscript database

    Efforts have been undertaken to monitor and model the uptake of medium-sized organic compounds found above agricultural waste. Field effects performed by our collaborators monitor both the gas phase compounds present in a chicken house in Kentucky; using PILS-IC sampling, the contents of PM2.5 parti...

  20. Volatile Organic Sulfur Compounds of Environmental Interest: Dimethyl Sulfide and Methanethiol. An Introductory Overview

    NASA Astrophysics Data System (ADS)

    Chasteen, Thomas G.; Bentley, Ronald

    2004-10-01

    Volatile organic sulfur compounds and their degradation products play important environmental roles in global warming, acid precipitation, and cloud formation. Two important members of this group, dimethyl sulfide, DMS, and methanethiol, MT, are formed by living organisms as well as by abiotic processes. DMS is synthesized by various organisms in the marine environment and large quantities of it are released to the atmosphere. One key precursor for DMS synthesis is the sulfonium salt, dimethylsulfoniopropionate. MT, also formed in marine environments, can be further converted to DMS. The chemical reactions responsible for the biosynthesis of DMS and MT are emphasized here, as well as means for their degradation. Since sulfur compounds are often ignored in normal course work, this article provides a basic foundation for an understanding of these interesting and environmentally significant compounds.

  1. Sulfur organic compounds in bottom sediments of the eastern Gulf of Finland.

    PubMed

    Khoroshko, Larisa O; Petrova, Varvara N; Takhistov, Viatcheslav V; Viktorovskii, Igor V; Lahtiperä, Mirja; Paasivirta, Jaakko

    2007-09-01

    Despite the large number of studies on the forms of sulfur in marine deposits, investigations on sulfur organic compounds are still rare. It is known that the processes leading to formation of intermediate and final sulfur compounds (including organic ones) in modern deposits are the results of microbiological transformation of sulfur containing proteins, as well as the microbiological reduction of sulfate ions. The latter are finally reduced by anaerobic sulfate-reducing bacteria to H2S, HS- and S2-; the total sum of these is referred to as 'hydrogen sulfide' in chemical oceanography. Further, the formation of reduced sulfur organic derivatives (sulfides and polysulfides) is the result of interaction of the organic substance destruction products with the sulfide ions. In such cases, the main source of organic substances, as well as sulfates for the sulfur reducing processes, is the pore water in the sediments. The choice of the target of our study is based on the fact that the eastern part of the Gulf of Finland water area receives the bulk of the anthropogenic load of the St. Petersburg region. Low vertical intermixing of the water thickness is observed there (thus creating a deficiency of oxygen near the bottom), and the bottom sea current transfers the polluted salty water of the Baltic Sea into the Neva Bay. The whole of the above are the preconditions for the formation of sulfur-bearing organic compounds. A great number of bottom sediment samples for analytical surveys were collected in the Eastern Gulf of Finland during research expeditions in the years of 1997 and 2001. These were screened for structures of sulfur organic microcontaminants, including organic forms of sulfur, using advanced instrumentation and experienced personnel in our two, cooperating laboratories. This work is a part of the research being carried out on organic micro-admixtures present in bottom sediments, and is the summary of our findings on previously unstudied sulfur organic

  2. Sources and Fate of Dissolved Organic Sulfur at the Redox Interface of Marine Shallow Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Gomez-Saez, G. V.; Niggemann, J.; Dittmar, T.; Pohlabeln, A. M.; Lang, S. Q.; Noowong, A.; Pichler, T.; Wörmer, L.; Bühring, S. I.

    2016-02-01

    Shallow hydrothermal systems are extreme environments with strong redox gradients at the interface of hot, reduced fluids and cold, oxygenated seawater. Hydrothermal fluids are often depleted in sulfate and can contain high concentrations of hydrogen sulfide (H2S). It is well known that sulfur plays an important role in processing and transformation of organic matter. However, the formation and the reactivity of dissolved organic sulfur (DOS) in the water column at hydrothermal systems are not well understood. We investigated DOS dynamics by studying the molecular composition of DOM in three contrasting systems off Milos (Aegean Sea), Dominica (Lesser Antilles) and Iceland (North Atlantic). We used ultra-high resolution mass spectrometry (FTICR-MS) to characterize the DOM on a molecular level. The molecular information was complemented with geochemical data, quantitative DOC and DOS analyses and isotopic measurements (δ2H, δ18O, F14C). In contrast to the predominantly meteoric fluids from Dominica and Iceland, fluids from Milos were mainly fed by recirculating seawater. Milos hydrothermal fluids were enriched in H2S and DOS, as indicated by high DOS/DOC ratios and by the fact that 93% of all assigned DOM molecular formulas exclusively present in the fluids contained sulfur. In all three systems, DOS from the fluids had on average lower O/C ratios (0.31-0.33) than surrounding seawater DOS (0.47-0.49), suggesting shallow hydrothermal systems as a marine source of reduced DOS, which will likely get oxidized upon contact with oxygenated seawater. Evaluation of hypothetical pathways suggested DOM reduction and sulfurization during seawater recirculation in Milos. The four most effective pathways were those exchanging an O atom by one S atom in the formula or the equivalent +H2S reaction. In conclusion, our study reveals novel insights about DOS dynamics in marine hydrothermal environments and provides a conceptual framework for molecular-scale mechanisms in organic

  3. Organic Matter Sulfurization in the Water Column and Its Effect on Sedimentary Processes

    NASA Astrophysics Data System (ADS)

    Raven, M. R.; Sessions, A. L.; Adkins, J. F.; Thunell, R.

    2016-02-01

    An essential characteristic of marine organic matter (OM) is its lability, which is typically taken to mean its susceptibility to remineralization by microorganisms. OM that is more highly condensed or polymerized is less available for heterotrophs and is therefore associated with lower rates of microbial metabolisms and inorganic carbon release than fresh, lower molecular weight material. Accordingly, understanding the mechanisms driving the transformation of OM into recalcitrant `proto-kerogen' will greatly improve our understanding of sedimentary metabolic rates and carbon burial. One important set of reactions driving proto-kerogen formation in O2-limited environments are abiotic reactions between sulfide and/or polysulfides and functionalized OM. We investigate this process in sinking particles from the modern Cariaco basin. We find evidence for rapid sulfurization in the water column based on the concentrations and sulfur-isotopic compositions of organic fractions and individual organosulfur compounds. More extensive sulfurization in Cariaco Basin is associated with high OM export from the surface ocean, low terrestrial inputs, and high concentrations of both elemental S and the dominant non-polar organosulfur compound, C20 thiophene. Depending on the frequency of high OM export events, we estimate that water column sulfurization delivers roughly half of the total organic S present at 5 cm depth in underlying sediments. We compare these data to results from Santa Barbara Basin and find that similar processes may be responsible for low rates of heterotrophy in this environment. OM sulfurization during sedimentation and very early diagenesis will have many implications for biogeochemical cycles in sediments during later diagenesis and burial.

  4. Evidence for abiotic sulfurization of marine dissolved organic matter in sulfidic environments

    NASA Astrophysics Data System (ADS)

    Pohlabeln, A. M.; Niggemann, J.; Dittmar, T.

    2016-02-01

    Sedimentary organic matter abiotically sulfurizes in sulfidic marine environments. Here we hypothesize that sulfurization also affects dissolved organic matter (DOM), and that sulfidic marine environments are sources of dissolved organic sulfur (DOS) to the ocean. To test these hypotheses we studied solid-phase extractable (SPE) DOS in the Black Sea at various water column depths (oxic and anoxic) and in sediment porewaters from the German Wadden Sea. The concentration and molecular composition of SPE-DOS from these sites and from the oxic water columns of the North Sea (Germany) and of the North Pacific were compared. In support of our hypotheses, SPE-DOS concentrations were elevated in sulfidic waters compared to oxic waters. For a detailed molecular characterization of SPE-DOS, selective wet-chemical alteration experiments targeting different sulfur-containing functional groups were applied prior to Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). These experiments included harsh hydrolysis, selective derivatization of thiols, oxidation, and deoxygenation to test for thioesters, sulfonic acid esters, alkylsulfates, thiols, non-aromatic thioethers, and sulfoxides. Additionally, collision-induced fragmentation experiments were applied to test for sulfonic acids. The tests revealed that the sulfonic acid group was the main structural feature in SPE-DOS, independent of the environmental conditions of the sampling site. Only in Wadden Sea anoxic porewater also non-aromatic thioethers were found which are presumably not stable in oxic waters. The findings from our field studies were confirmed in laboratory experiments, where we abiotically sulfurized marine and algal-derived DOM under conditions similar to that in anoxic marine sediments.

  5. Formation of Nitrogen- and Sulfur-Containing Light-Absorbing Compounds Accelerated by Evaporation of Water from Secondary Organic Aerosols

    SciTech Connect

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey

    2012-01-14

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of dlimonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (< 2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>10{sup 5} L mol{sup -1} cm{sup -1} at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 10{sup 3} cm{sup 2} g{sup -1} - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH {approx} 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  6. Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A.

    2012-01-01

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of d-limonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (<2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>105 L mol-1 cm-1 at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 103 cm2 g-1 - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH ˜ 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  7. Secondary organic material formed by methylglyoxal in aqueous aerosol mimics - Part 2: Product identification using Aerosol-CIMS

    NASA Astrophysics Data System (ADS)

    Sareen, N.; Shapiro, E. L.; Schwier, A. N.; McNeill, V. F.

    2009-07-01

    We used chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS) to characterize secondary organic material formed by methylglyoxal with ammonium sulfate in aqueous aerosol mimics. Bulk reaction mixtures were diluted and atomized to form submicron aerosol particles. Organics were detected using Aerosol-CIMS in positive and negative ion mode using I- and H3O+·(H2O)n as reagent ions. The results are consistent with aldol condensation products, carbon-nitrogen species, sulfur-containing compounds, and oligomeric species up to 759 amu. These results support previous observations by us and others that ammonium sulfate plays a critical role in the SOA formation chemistry of dicarbonyl compounds.

  8. Aqueous photolysis of the organic ultraviolet filter chemical octyl methoxycinnamate.

    PubMed

    MacManus-Spencer, Laura A; Tse, Monica L; Klein, Jacob L; Kracunas, Alison E

    2011-05-01

    Organic UV filter chemicals are the active ingredients in personal care products designed to protect the skin from UV radiation, and hundreds of tons are estimated to be produced annually. Despite their entrance into the aquatic environment by both direct and indirect routes and their detection in surface waters and fish, little is known about their environmental fate. UV filter chemicals are designed to be photostable, but some undergo transformation upon exposure to UV light. Octyl methoxycinnamate (OMC), a commonly used UV filter chemical, degrades rapidly by direct photolysis; previous studies have focused on its photoisomerization, and a few investigators have reported the formation of cyclodimers. Here, we present the kinetics and quantum efficiency of the direct photolysis of OMC and confirm that dimerization occurs as a result of direct photolysis in aqueous solution. Likely identities of the dimers are offered based on comparison to reported results for other cinnamate derivatives. We have identified additional products of direct photolysis that have not been previously reported and investigated their photostability, as well as the mechanism of product formation. There is also some evidence of indirect photolysis in the presence of dissolved natural organic matter.

  9. SEM-EDX and isotope characterization of the organic sulfur in macerals and chars in Illinois Basin coals

    USGS Publications Warehouse

    Demir, I.; Harvey, R.D.; Hackley, Keith C.

    1993-01-01

    Two samples of the Herrin (Illinois No. 6) Coal and one sample of the Colchester (Illinois No. 2) Coal from the Illinois Basin were studied to evaluate the spatial distribution of organic sulfur within macerals occurring next to pyrite grains, both in the raw coal and their chars. The chars were produced by pyrolysing the coal at 250-550??C in a nitrogen atmosphere. Representative splits of the coals and their chars were mounted in epoxy and polished for optical microscopy and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDX). Determinations of organic sulfur concentrations were made at 996 locations within macerals, mostly vitrinite, around 115 grains of pyrite and at 50 locations around 5 pores in chars. The pyrite considered here is restricted to the disseminated type within macerals. On the average, the organic sulfur content increased near pyrite grains after the coals were charred at 550??C, indicating that some of the pyritic sulfur released during charring was retained within the organic matrix rather than being emitted to the atmosphere. One of the coal samples and its chars were isotopically characterized by chemically separating the pyritic and organic sulfur fractions, followed by analyzing the isotopes of the sulfur forms with a Nuclide 6-60 ratio mass spectrometer. The sulfur isotope (??34S) data confirmed the movement of pyritic sulfur into the macerals after charring to 550??C. About 18% of the organic sulfur that remained in the 550??C char had originally been pyritic sulfur in the untreated coal. ?? 1993.

  10. Sulfur and Hydrogen Isotope Anomalies in Organic Compounds from the Murchison Meteorite

    NASA Astrophysics Data System (ADS)

    Cooper, G. W.; Thiemens, M. H.; Jackson, T.; Chang, S.

    1995-09-01

    Carbon, hydrogen and sulfur isotopic measurements have been made on individual members of a recently discovered class of organic sulfur compounds, alkyl sulfonates, in the Murchison meteorite. Cooper and Chang (1) reported the first carbon isotopic measurements of Murchison organic sulfonates, providing insight into potential synthetic mechanisms of these, and possibly other, organic species. Hydrogen isotopic measurements of the sulfonates now reveal deuterium excesses ranging from +660 to +2730 per mil. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of dense molecular clouds. Measurement of the sulfur isotopes provide further constraints on the origin and mechanism of formation of these organic molecules. Recently, there has been growing documentation of sulfur isotopic anomalies in meteoritic material. Thiemens and Jackson (2) have shown that some bulk ureilites possess excess 33S and Thiemens et al. (3) have reported excess 33S in an oldhamite separate from Norton County. Rees and Thode (4) reported a large 33S excess in an Allende acid residue, however, attempts to verify this measurement have been unsuccessful, possibly due to the heterogeneous nature of the carrier phase. With the recognition that sulfur isotopes may reflect nebular chemistry, identification of potential carriers is of considerable interest. In the present study the three stable isotopes of sulfur were measured in methane sulfonate extracted from the Murchison meteorite. The isotopic composition was found to be delta 33S=2.48, delta 34S=2.49 and delta 36S = 6.76 per mil. Based upon analysis of more than 60 meteoritic, and numerous terrestrial samples, the mass fractionation lines are defined by 33Delta = delta 33S-0.50 delta 34S and 36Delta = delta 36S -1.97 delta 34S. From these relations a 33Delta = 1.24 per mil and 36Delta = 0.89 per mil is observed. These anomalies

  11. Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution

    DTIC Science & Technology

    1990-03-01

    CRREL *) Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution Susan Taylor and Louise Parker March...Engineering Laboratory Surface Changes in Well Casing Pipe Exposed to High Concentrations of Organics in Aqueous Solution Susan Taylor and Louise Parker March...SS304 (2000x) ..................................................................................... 14 iii Surface Changes in Well Casing Pipe Exposed to

  12. Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of captopril by acidified bromate and aqueous bromine.

    PubMed

    Kapungu, G P; Rukweza, G; Tran, Thai; Mbiya, Wilbes; Adigun, Risikat; Ndungu, Patrick; Martincigh, Bice; Simoyi, Reuben H

    2013-04-04

    By nature of their nucleophilicity, all thiol-based drugs are oxidatively metabolized in the physiological environment. The key to understanding the physiological role of a hypertension drug, (2S)-1-[(2S)-2-methyl-3-sulfanylpropanoyl]pyrrolidine-2-carboxylic acid, medically known as captopril is through studying its oxidation pathway: its reactive intermediates and oxidation products. The oxidation of captopril by aqueous bromine and acidified bromate has been studied by spectrophotometric and electrospray ionization techniques. The stoichiometry for the reaction of acidic bromate with captopril is 1:1, BrO3(-) + (C4H6N)(COOH)(COCHCH3CH2)-SH → (C4H6N)(COOH)(COCHCH3CH2)-SO3H + Br(-), with reaction occurring only at the thiol center. For the direct reaction of bromine with captopril, the ratio is 3:1; 3Br2 + (C4H6N)(COOH)(COCHCH3CH2)-SH + 3H2O → (C4H6N)(COOH)(COCHCH3CH2)-SO3H + 6HBr. In excess acidic bromate conditions the reaction displays an initial induction period followed by a sharp rise in absorbance at 390 nm due to rapid formation of bromine. The direct reaction of aqueous bromine with captopril was much faster than oxidation of the thiol by acidified bromate, with a bimolecular rate constant of (1.046 (±0.08) × 10(5) M(-1) s(-1). The detection of thiyl radicals confirms the involvement of radicals as intermediates in the oxidation of Captopril by acidified BrO3(-). The involvement of thiyl radicals in oxidation of captopril competes with a nonradical pathway involving 2-electron oxidations of the sulfur center. The oxidation product of captopril under these strong oxidizing conditions is a sulfonic acid as confirmed by electrospray ionization mass spectrometry (ESI-MS), iodometric titrations, and proton nuclear magnetic resonance ((1)H NMR) results. There was no evidence from ESI-MS for the formation of the sulfenic and sulfinic acids in the oxidation pathway as the thiol group is rapidly oxidized to the sulfonic acid. A computer simulation analysis of

  13. Significant role of organic sulfur in supporting sedimentary sulfate reduction in low-sulfate environments

    NASA Astrophysics Data System (ADS)

    Fakhraee, Mojtaba; Li, Jiying; Katsev, Sergei

    2017-09-01

    Dissimilatory sulfate reduction (DSR) is a major carbon mineralization pathway in aquatic sediments, soils, and groundwater, which regulates the production of hydrogen sulfide and the mobilization rates of biologically important elements such as phosphorus and mercury. It has been widely assumed that water-column sulfate is the main sulfur source to fuel this reaction in sediments. While this assumption may be justified in high-sulfate environments such as modern seawater, we argue that in low-sulfate environments mineralization of organic sulfur compounds can be an important source of sulfate. Using a reaction-transport model, we investigate the production of sulfate from sulfur-containing organic matter for a range of environments. The results show that in low sulfate environments (<500 μM) the in-sediment production of sulfate can support a substantial portion (>50%) of sulfate reduction. In well-oxygenated systems, porewater sulfate profiles often exhibit sub-interface peaks so that sulfate fluxes are directed out of the sediment. Our measurements in Lake Superior, the world's largest lake, corroborate this conclusion: offshore sediments act as sources rather than sinks of sulfate for the water column, and sediment DSR is supported entirely by the in-sediment production of sulfate. Sulfate reduction rates are correlated to the depth of oxygen penetration and strongly regulated by the supply of reactive organic matter; rate co-regulation by sulfate availability becomes appreciable below 500 μM level. The results indicate the need to consider the mineralization of organic sulfur in the biogeochemical cycling in low-sulfate environments, including several of the world's largest freshwater bodies, deep subsurface, and possibly the sulfate-poor oceans of the Early Earth.

  14. Emission of volatile organic sulfur compounds (VOSCs) during aerobic decomposition of food wastes

    NASA Astrophysics Data System (ADS)

    Wu, Ting; Wang, Xinming; Li, Dejun; Yi, Zhigang

    2010-12-01

    Food wastes collected from typical urban residential communities were investigated for the emission of volatile organic sulfur compounds (VOSCs) during laboratory-controlled aerobic decomposition in an incubator for a period of 41 days. Emission of VOSCs from the food wastes totaled 409.9 mg kg -1 (dry weight), and dimethyl disulfide (DMDS), dimethyl sulfide (DMS), methyl 2-propenyl disulfide, carbonyl sulfide and methyl 1-propenyl sulfide were the five most abundant VOSCs, with shares of 75.5%, 13.5%, 4.8%, 2.2% and 1.3% in total 15 VOSCs released, respectively. The emission fluxes of major VOSCs were very low at the beginning (day 0). They peaked at days 2-4 and then decreased sharply until they leveled off after 10 days of incubation. For most VOSCs, over 95% of their emission occurred in the first 10 days. The time series of VOSC emission fluxes, as well as their significant correlation with internal food waste temperature ( p < 0.05) during incubation, suggested that production of VOSC species was induced mainly by microbial activities during the aerobic decomposition instead of as inherited. Released VOSCs accounted for 5.3% of sulfur content in the food wastes, implying that during aerobic decomposition considerable portion of sulfur in food wastes would be released into the atmosphere as VOSCs, primarily as DMDS, which is very short-lived in the atmosphere and thus usually less considered in the sources and sinks of reduced sulfur gases.

  15. Enhanced formation of isoprene-derived organic aerosol in sulfur-rich power plant plumes during Southeast Nexus

    NASA Astrophysics Data System (ADS)

    Xu, Lu; Middlebrook, Ann M.; Liao, Jin; Gouw, Joost A.; Guo, Hongyu; Weber, Rodney J.; Nenes, Athanasios; Lopez-Hilfiker, Felipe D.; Lee, Ben H.; Thornton, Joel A.; Brock, Charles A.; Neuman, J. Andrew; Nowak, John B.; Pollack, Ilana B.; Welti, Andre; Graus, Martin; Warneke, Carsten; Ng, Nga Lee

    2016-09-01

    We investigate the effects of anthropogenic sulfate on secondary organic aerosol (SOA) formation from biogenic isoprene through airborne measurements in the southeastern United States as part of the Southeast Nexus (SENEX) field campaign. In a flight over Georgia, organic aerosol (OA) is enhanced downwind of the Harllee Branch power plant but not the Scherer power plant. We find that the OA enhancement is likely caused by the rapid reactive uptake of isoprene epoxydiols (IEPOX) in the sulfate-rich plume of Harllee Branch, which was emitting at least 3 times more sulfur dioxide (SO2) than Scherer, and more aerosol sulfate was produced downwind. The contrast in the evolution of isoprene-derived OA concentration between two power plants with different SO2 emissions provides an opportunity to investigate the magnitude and mechanisms of particle sulfate on isoprene-derived OA formation. We estimate that 1 µg sm-3 reduction of sulfate would decrease the isoprene-derived OA by 0.23 ± 0.08 µg sm-3. Based on a parameterization of the IEPOX heterogeneous reactions, we find that the effects of sulfate on isoprene-derived OA formation in the power plant plume arises from enhanced particle surface area and particle acidity, which increases both IEPOX uptake to particles and subsequent aqueous-phase reactions, respectively. The observed relationships between isoprene-OA, sulfate, particle pH, and particle water in previous field studies are explained using these findings.

  16. Effects of paleolatitude on coal quality - model for organic sulfur distribution in US coal

    SciTech Connect

    Affolter, R.H.; Stricker, G.D.

    1989-03-01

    In the conterminous US, most Carboniferous peats accumulated at latitudes of 0/degrees/-15/degrees/S, Cretaceous Rocky Mountain province peats at 30/degrees/-45/degrees/N, Tertiary northern Great Plains peats at 40/degrees/-55/degrees/N, and Tertiary Gulf Coast peats at 30/degrees/-40/degrees/N. Alaskan Cretaceous and Tertiary peats accumulated at latitudes above 70/degrees/N. A comparison of paleolatitudes calculated from paleomagnetic poles and organic sulfur contents for more than 7000 coal samples indicates that the higher the latitude in which a peat swamp developed, the lower the mean organic sulfur content of the subsequent coal (correlation coefficient - 0.4; significant at the 99% confidence level). Mean organic sulfur contents range from 0.90% (range = 0.01-5.08%, standard deviation = 0.56) in low-latitude Carboniferous coal to 0.25% (range = 0.01-1.41%, standard deviation = 0.23) in high-latitude Alaskan Cretaceous and Tertiary coal.

  17. Fluctuating confinement of water in aqueous organic nanodroplets

    NASA Astrophysics Data System (ADS)

    Wilemski, Gerald; Hrahsheh, Fawaz

    2013-03-01

    Supercooled and nano-confined water occurs frequently as nanometer-sized aqueous-organic aerosol droplets that are ubiquitous in the atmosphere and in many industrial processes. Nanodroplet structure is important because it influences droplet growth and evaporation rates, heterogeneous reaction rates, and radiative properties. We use classical molecular dynamic simulations to study the structure of ternary water-butanol-nonane nanodroplets for several temperatures and droplet sizes. We study the effects of butanol on the wetting of the water/butanol core-shell droplet by the nonane lens. At low concentrations, butanol acts as a surfactant to significantly enhance the wetability of the water droplet by nonane. At 250 K, with sufficient butanol and nonane, perfect wetting (thin film formation by nonane) occurs. Perfect wetting also occurs at higher temperatures, 270 K to 300 K, but this wetting state is progressively destabilized at higher temperature. All of the nanodroplets studied undergo distinct transitions between partial dewetting and perfect wetting states due to isothermal fluctuations in the local distribution of butanol on the surface of the water core. These fluctuations favor the wetted state at lower temperatures and the dewetted state at higher temperatures. Supported by NSF Grant CBET 1033387

  18. Two-Step Enzymatic Modification of Solid-Supported Bergenin in Aqueous and Organic Media

    PubMed Central

    Akbar, Umar; Shin, Dong-Sik; Schneider, Elizabeth; Dordick, Jonathan S.; Clark, Douglas S.

    2010-01-01

    The natural flavonoid bergenin was directly immobilized onto carboxylic acid functionalized controlled pore glass (carboxy-CPG) at 95% yield. Immobilized bergenin was brominated via chloroperoxidase in aqueous solution and then transesterified with vinyl butyrate in diisopropyl ether by subtilisin carslberg (SC) extracted into the organic solvent via ion pairing. Enzymatic cleavage of 7-bromo-4-butyrylbergenin from carboxy-CPG (9.6% final yield) was accomplished using lipase B (LipB) in an aqueous/organic mixture (90/10 v/v of water/acetonitrile), demonstrating the feasibility of solid phase biocatalysis of a natural product in aqueous and non-aqueous media. PMID:20174610

  19. A method for separating water soluble organics from a process stream by aqueous biphasic extraction

    SciTech Connect

    Chaiko, David J.; Mego, William A.

    1997-12-01

    The present invention relates to a method for separating water-miscible organic species from a process stream by aqueous biphasic extraction. In particular, the method includes extracting the organic species into a polymer-rich phase of an aqueous biphase system in which the process stream comprises the salt-rich phase, and, next, separating the polymer from the extracted organic species by contacting the loaded, polymer-rich phase with a water-immiscible organic phase. Alternatively, the polymer can be separated from the extracted organic species by raising the temperature of the loaded, polymer-rich phase above the cloud point, such that the polymer and the water-soluble organic species separate into two distinct aqueous phases. In either case, a substantially salt-free, concentrated aqueous solution containing the organic species is recovered.

  20. Effect of Bisulfate, Ammonia, and Ammonium on the Clustering of Organic Acids and Sulfuric Acid.

    PubMed

    Myllys, Nanna; Olenius, Tinja; Kurtén, Theo; Vehkamäki, Hanna; Riipinen, Ilona; Elm, Jonas

    2017-06-29

    We investigate the effect of the bisulfate anion HSO4(-), ammonium cation NH4(+), and ammonia NH3 on the clustering of sulfuric acid and pinic acid or 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA). The systems were chosen based on their expected relevance in atmospheric new particle formation. Using quantum chemical methods together with kinetic calculations, we study the ability of these compounds to enhance cluster formation and growth. The cluster structures are obtained and frequencies are calculated using three different DFT functionals (M06-2X, PW91, and ωB97X-D) with the 6-31++G(d,p) basis set. The electronic energies are corrected using an accurate DLPNO-CCSD(T)/def2-QZVPP level of theory. The evaporation rates are evaluated based on the calculated Gibbs free energies. The interaction between the ions and sulfuric acid or carboxylic acid group is strong, and thereby small two-component ionic clusters are found to be very stable against evaporation. The presence of bisulfate stimulates the cluster formation through addition of the sulfuric acid, whereas the presence of ammonium favors the addition of organic acids. Bisulfate and ammonium enhance the first steps of cluster formation; however, at atmospheric conditions further cluster growth is limited due to the weak interaction and fast evaporation of the larger three-component clusters. On the basis of our results it is therefore unlikely that the studied organic acids and sulfuric acid, even together with bisulfate, ammonia, or ammonium can drive new-particle formation via clustering mechanisms. Other mechanisms such as chemical reactions are needed to explain observed new-particle formation events in the presence of oxidized organic compounds resembling the acids studied here.

  1. Observation of dipropenyldisulfide and other organic sulfur compounds in the atmosphere of a beech forest with Allium ursinum ground cover

    NASA Astrophysics Data System (ADS)

    Puxbaum, H.; König, G.

    Dipropenyldisulfide, methylpropenyldisulfide, cis-propenylpropyldisulfide, diallylsulfide, dimethyldisulfide and 3-methylthiopropene were detected in the atmosphere of a beech forest with Allium ursinum (broad-leaved garlic) ground cover plants. Furthermore, it was shown that the Allium plants were the source of the organic sulfur compounds. The atmospheric concentrations of the organic sulfur observed on one day in May 1994 in a suburban forest in Vienna ranged from 0.3 to 7.8 ppb S with an average level of 2.9 ppb S. The atmospheric emission rate of organic sulfur species from A. ursinum determined with an enclosure box was the highest ever reported for terrestrial continental plants. The total organic sulfur flux on the average was at least 1 jug g-1h-1 (plant dry weight) or 60 gmgm-2 h-1 (per unit of ground area).

  2. Organic peroxide and OH formation in aerosol and cloud water: laboratory evidence for this aqueous chemistry

    NASA Astrophysics Data System (ADS)

    Lim, Y. B.; Turpin, B. J.

    2015-06-01

    Aqueous chemistry in atmospheric waters (e.g., cloud droplets or wet aerosols) is well accepted as an atmospheric pathway to produce secondary organic aerosol (SOAaq). Water-soluble organic compounds with small carbon numbers (C2-C3) are precursors for SOAaq and products include organic acids, organic sulfates, and high molecular weight compounds/oligomers. Fenton reactions and the uptake of gas-phase OH radicals are considered to be the major oxidant sources for aqueous organic chemistry. However, the sources and availability of oxidants in atmospheric waters are not well understood. The degree to which OH is produced in the aqueous phase affects the balance of radical and non-radical aqueous chemistry, the properties of the resulting aerosol, and likely its atmospheric behavior. This paper demonstrates organic peroxide formation during aqueous photooxidation of methylglyoxal using ultra high resolution Fourier Transform Ion Cyclotron Resonance electrospray ionization mass spectrometry (FTICR-MS). Organic peroxides are known to form through gas-phase oxidation of volatile organic compounds. They contribute secondary organic aerosol (SOA) formation directly by forming peroxyhemiacetals, and epoxides, and indirectly by enhancing gas-phase oxidation through OH recycling. We provide simulation results of organic peroxide/peroxyhemiacetal formation in clouds and wet aerosols and discuss organic peroxides as a source of condensed-phase OH radicals and as a contributor to aqueous SOA.

  3. Nitrogen, Sulfur, and Oxygen Isotope Ratios of Animal- and Plant-Based Organic Fertilizers Used in South Korea.

    PubMed

    Shin, Woo-Jin; Ryu, Jong-Sik; Mayer, Bernhard; Lee, Kwang-Sik; Kim, Insu

    2017-05-01

    Organic fertilizers are increasingly used in agriculture in Asia and elsewhere. Tracer techniques are desirable to distinguish the fate of nutrients added to agroecosystems with organic fertilizers from those contained in synthetic fertilizers. Therefore, we determined the nitrogen, sulfur, and oxygen isotope ratios of nitrogen- and sulfur-bearing compounds in animal- and plant-based organic fertilizers (ABOF and PBOF, respectively) used in South Korea to evaluate whether they are isotopically distinct. The δN values of total and organic nitrogen for ABOF ranged from +7 to +19‰ and were higher than those of PBOF (generally <+6‰). This suggests that ABOFs have distinct δN values suitable for tracing these fertilizer compounds in the plant-soil-water system, whereas PBOFs have similar δN values to synthetic fertilizers. However, δO values for nitrate (δO) from organic fertilizer samples (<+17.0‰) were consistently lower than those of synthetic nitrate-containing fertilizers. The δS values of total sulfur, organic sulfur compounds (e.g., carbon-bonded sulfur and hydriodic acid-reducible sulfur), and sulfate for ABOFs yielded wide and overlapping ranges of +0.3 to +6.3, +0.9 to +7.2, and -2.6 to +14.2‰, whereas those for PBOFs varied from -3.4 to +7.7, +1.4 to +9.4, and -4.1 to +12.5‰, respectively, making it challenging to distinguish the fate of sulfur compounds from ABOF and PBOF in the environment using sulfur isotopes. We conclude that the δN values of ABOFs and the O values of organic fertilizers are distinct from those of synthetic fertilizers and are a promising tool for tracing the fate of nutrients added by organic fertilizers to agroecosystems. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  4. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Technical report, 1 September--30 November 1991

    SciTech Connect

    Kruge, M.A.

    1991-12-31

    With the recent increase in concern for environmental issues and the implication of sulfur and nitrogen in coal combustion products as prime causes of acid rain, it has become clear that there is an urgent need for alternative methods for determining the nature of organic sulfur and nitrogen compounds in coal. The present study couples mold oxidative and reductive procedures to enhance the depolymerization of coal and its constituent macerals and the quantities of produces amenable to analysis. The study also seeks to apply the degradative techniques to coal asphaltenes, since they are believed to be polymeric structures similar to the whole coal, but smaller and more readily analyzed. While the research effort will focus on Illinois coal, additional samples with even higher sulfur contents will also used, allowing for much easier detection and characterization of organic sulfur structures. A preliminary tests of this hypothesis indicates that many of the same sulfur compounds are present in both the Illinois and in an extremely sulfur-rich coal and that the more complex sulfur compounds are indeed more concentrated in the sulfur-rich sample.

  5. A metal-free organic-inorganic aqueous flow battery

    SciTech Connect

    Huskinson, B; Marshak, MP; Suh, C; Er, S; Gerhardt, MR; Galvin, CJ; Chen, XD; Aspuru-Guzik, A; Gordon, RG; Aziz, MJ

    2014-01-08

    As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output(1,2). In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form(3-5). Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts(6,7). Here we describe a class of energy storage materials that exploits the favourable chemical and electro-chemical properties of a family of molecules known as quinones. The example we demonstrate is ametal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br-2/Br- redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals(8). This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of p-aromatic redox-active organic molecules instead of redox-active metals

  6. A metal-free organic-inorganic aqueous flow battery.

    PubMed

    Huskinson, Brian; Marshak, Michael P; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R; Galvin, Cooper J; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G; Aziz, Michael J

    2014-01-09

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br(-) redox couple, yields a peak galvanic power density exceeding 0.6 W cm(-2) at 1.3 A cm(-2). Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals

  7. A metal-free organic-inorganic aqueous flow battery

    NASA Astrophysics Data System (ADS)

    Huskinson, Brian; Marshak, Michael P.; Suh, Changwon; Er, Süleyman; Gerhardt, Michael R.; Galvin, Cooper J.; Chen, Xudong; Aspuru-Guzik, Alán; Gordon, Roy G.; Aziz, Michael J.

    2014-01-01

    As the fraction of electricity generation from intermittent renewable sources--such as solar or wind--grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br2/Br- redox couple, yields a peak galvanic power density exceeding 0.6Wcm-2 at 1.3Acm-2. Cycling of this quinone-bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals represents a new and

  8. Organic reactions increasing the absorption index of atmospheric sulfuric acid aerosols

    NASA Astrophysics Data System (ADS)

    Nozière, B.; Esteve, W.

    2005-02-01

    Unlike most environments present at Earth's surface atmospheric aerosols can be favorable to organic reactions. Among them, the acid-catalyzed aldol condensation of aldehydes and ketones produces light-absorbing compounds. In this work the increase of the absorption index of sulfuric acid solutions 50-96 wt. % resulting from the uptake of gas-phase acetaldehyde, acetone, and 2-butanone (methyl ethyl ketone), has been measured in the near UV and visible range. Our results indicate that the absorption index between 200 and 500 nm for stratospheric sulfuric aerosols exposed to 100 pptV of acetaldehyde (1 pptV = 10-12 v/v) would increase by four orders of magnitude over a two-year lifetime. Rough estimates based on previous radiative calculations suggest that this reaction could result in an increase of the radiative forcing of sulfate aerosols of the order of 0.01 W m-2, and that these processes are worth further investigation.

  9. Why sulfuric acid forms particles so extremely well, and how organics might still compete

    NASA Astrophysics Data System (ADS)

    Kurten, T.; Ehn, M.; Kupiainen, O.; Olenius, T.; Rissanen, M.; Thornton, J. A.; Nielsen, L.; Jørgensen, S.; Ortega Colomer, I. K.; Kjaergaard, H. G.; Vehkamäki, H.

    2013-12-01

    It is a well-known result in aerosol science that the single most important molecule for the first steps of new-particle formation in our atmosphere is sulfuric acid, H2SO4. From a chemical perspective, this seems somewhat counterintuitive: the atmosphere contains thousands of different organic compounds, many of which can potentially form oxidation products with even lower volatility than H2SO4. The unique role of sulfuric acid is due to its formation kinetics. The conversion of sulfur dioxide, SO2 to H2SO4 requires only a single oxidant molecule (e.g. OH), as subsequent steps are extremely rapid. Still, the saturation vapor pressure of H2SO4 is over 108 times lower than that of SO2. In contrast, the oxidation reactions of organic molecules typically lower their saturation vapor pressure by only a factor of 10-1000 per oxidation step. Therefore, organic compounds are usually lost to pre-existing aerosol surfaces before they have undergone sufficiently many oxidation reactions to nucleate on their own. The presence of strong nitrogen-containing base molecules such as amines enhances the particle-forming advantages of sulfuric acid even further. Quantum chemical calculations indicate that the evaporation rate of sulfuric acid from key clusters containing two acid molecules may decrease by a factor of 108 in the presence of ppt-level concentrations of amines, implying a total decrease of up to 1016 in the effective vapor pressure going from SO2 to H2SO4. In some circumstances, this decrease causes the energy barrier for new-particle formation to disappear: the process is no longer nucleation, and some common applications of e.g. the nucleation theorem cease to apply. Cluster kinetic models combined with first-principles evaporation rates appear to describe this sulfuric acid - base clustering reasonably well, and result in cluster formation rates close to those measured at the CLOUD experiment in CERN. There may nevertheless exist exceptions to the general rule that

  10. Determination of Dissolved Organic Sulfur in Seawater, and its Distribution in the Chesapeake Bay

    NASA Astrophysics Data System (ADS)

    Chavous, B.; Filippino, K. C.; Cutter, G. A.

    2001-12-01

    Although there are measurements of specific organic sulfur compounds in marine waters, the total concentration of dissolved organic sulfur (DOS) is unknown. However, this poorly quantified component in the global sulfur cycle is the precursor to the radiatively important gas, carbonyl sulfide, and contains very strong ligands that complex trace metals, affecting their bioavailability/cycling. Nevertheless, the high concentration of sulfate in seawater (28 mM) has hampered efforts to determine DOS. In order to obtain DOS data for different marine regimes, we have developed a novel analytical method that employs: (1) sulfate removal using Ba, followed by ion exchange; (2) determination of the nanomolar concentrations of residual sulfate; and (3) reductive pyrolysis (combustion at 1050 C in pure hydrogen) of a treated (as in (1)) sample to quantitatively produce hydrogen sulfide from all forms of sulfur, which is then quantified using GC/flame photometric detection. A wide variety of model S compounds (e.g., DMSP, glutathione, taurine, marine and freshwater humics) have been analyzed to test the efficiency of the method with good results. The method's detection limit is 15 nM S, the precision is <10% RSD at 100 nM S, and it is highly linear (>2000 nM S). To examine the estuarine distribution of DOS, water samples from the Chesapeake Bay were taken in July 1997 (earlier version of the method) and June 2001. These were 0.4 um filtered, placed in glass vials, and quick frozen for temporary storage (<2 months). In 2001, DOS concentrations in the Bay averaged 312+/-75 nM S, in close agreement with those in 1997 except in the uppermost (riverine) Bay. The distributions show slightly decreasing concentrations from the riverine to the seaward end of the Bay. No obvious correlations with nutrients or chlorophyll are apparent. However, the distributions do appear to be affected by higher concentrations in the rivers (S-containing humic acids?).

  11. Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains.

    PubMed

    Schmatz, Brian; Yuan, Zhibo; Lang, Augustus W; Hernandez, Jeff L; Reichmanis, Elsa; Reynolds, John R

    2017-09-27

    The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer's side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics.

  12. Aqueous Processing for Printed Organic Electronics: Conjugated Polymers with Multistage Cleavable Side Chains

    PubMed Central

    2017-01-01

    The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer’s side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics. PMID:28979937

  13. Aqueous sulfuric acid as the mobile phase in cation ion chromatography for determination of histamine, putrescine, and cadaverine in fish samples.

    PubMed

    Liao, Benjamin S; Sram, Jackie; Cain, Teresa T; Halcrow, Kenneth R

    2011-01-01

    Aqueous sulfuric acid can be used as the mobile phase in cation ion chromatography to separate the three biogenic amines, putrescine, cadaverine, and histamine, from fish. Various concentrations of aqueous sulfuric acid were investigated to optimize the separation of these three biogenic amines. Aqueous sulfuric acid (5.0 mM) was found to be optimum for the separation and was used to determine the three biogenic amines in fish. The LOQ, defined as the lowest level of the standard calibration curve, was 0.055 ppm (equivalent to 0.55 microg/g sample) for putrescine, 0.05 ppm (equivalent to 0.5 microg/g sample) for cadaverine, and 1.0 ppm (equivalent to 10 microg/g sample) for histamine. From statistical analysis of the LOQ, the method detection limit was 0.003 ppm for putrescine, 0.009 ppm for cadaverine, and 0.16 ppm for histamine. For sample preparation, the fish was composited, homogenized in methanol-water (75 + 25, v/v), incubated for 15 min at 60 degrees C, and centrifuged. The sample solution was micron-filtered before injection. The mobile phase flow rate was 0.8 mL/min under isocratic conditions at room temperature (15-25 degrees C). The three biogenic amines were separated in the order of increasing retention time, i.e., putrescine, cadaverine, and histamine, within 30 min. The chromatograms showed complete peak separation of the three amines regardless of the difference in fish matrixes.

  14. Determination of pKa values of organic bases in aqueous acetonitrile solutions using capillary electrophoresis.

    PubMed

    Buckenmaier, Stephan M C; McCalley, David V; Euerby, Melvin R

    2003-07-04

    Capillary electrophoresis (CE) was used for the determination of ionisation constants (pKa) of a variety of organic bases in aqueous acetonitrile solutions over the range 0-60% (v/v) acetonitrile. These bases are used as test compounds in HPLC column evaluation, thus knowledge of their pKa in hydro-organic solutions is useful. The base pKa decreased with acetonitrile concentration and significant shifts from the aqueous pKa (up to -0.8) were found using 60% acetonitrile. The CE application was confirmed to be very suitable for fast and accurate pKa measurement in aqueous organic solutions.

  15. Biocatalysis of Steroids with Mycobacterium sp. in Aqueous and Organic Media.

    PubMed

    de Carvalho, Carla C C R; Fernandes, Pedro

    2017-01-01

    Mycobacterium sp. can convert steroids such as β-sitosterol, campesterol, and cholesterol into commercially interesting products. In aqueous systems, the biocatalysis is limited by the low solubility of the steroids in water. This may be overcome by the introduction of an organic phase acting as a substrate and/or product reservoir.In this chapter, we describe the biocatalysis of β-sitosterol to 4-androstene-3,17-dione (AD) and 1,4-androstadiene-3,17-dione (ADD) both in aqueous and organic-aqueous systems. In the latter case, both traditional organic solvents and green solvents are proposed.

  16. VHF EPR analysis of organic sulfur in coal. Final technical report, September 1, 1992--August 31, 1993

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1993-12-31

    A direct and non-destructive technique called very High Frequency Electron Paramagnetic Resonance (VHF EPR) utilizing instrumentation and application techniques developed in this laboratory, is proving to be a practical and sensitive analytical method for the organic sulfur in coal. Research during this past year (1992--1993) was very successful in terms of obtaining spectrochemical information on organic sulfur in coal both quantitatively (amount of organic sulfur) and qualitatively (form and distribution of organic sulfur). Starting in this funding year, the authors have begun to develop and use a two-species model (non-exchanging and axially symmetric) for the simulation of VHF EPR coal spectra. Such a model provides quantitative information on the total concentration of sulfur species that can be directly related to the organic sulfur content as measured by conventional chemical methods. Utilizing the newly developed method, they have analyzed the VHF EPR spectra from some sub-bituminous coals containing organic sulfur in the range from 2% to 12% and a number of maceral blends. Excellent quantitative agreement is achieved between VHF EPR results and chemical analyses. In addition, the modelling of VHF EPR spectra of coal provides detailed spectral parameters. These parameters can be related to the molecular structures of the paramagnetic species giving rise to the EPR signals, as demonstrated by our study of the model compounds. The foundation of VHF EPR analysis of aromatic sulfur radicals has been firmly established based on careful investigations of the molecular and electronic structures of the thiophenic model compounds. The results validate the theoretical soundness of the method and carry important practical implications.

  17. Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Hariss, R.; Niki, H.

    1985-01-01

    Among the general categories of tropospheric sulfur sources, anthropogenic sources have been quantified the most accurately. Research on fluxes of sulfur compounds from volcanic sources is now in progress. Natural sources of reduced sulfur compounds are highly variable in both space and time. Variables, such as soil temperature, hydrology (tidal and water table), and organic flux into the soil, all interact to determine microbial production and subsequent emissions of reduced sulfur compounds from anaerobic soils and sediments. Available information on sources of COS, CS2, DMS, and H2S to the troposphere in the following paragraphs are summarized; these are the major biogenic sulfur species with a clearly identified role in tropospheric chemistry. The oxidation of SO2 to H2SO4 can often have a significant impact on the acidity of precipitation. A schematic representation of some important transformations and sinks for selected sulfur species is illustrated.

  18. On-line sulfur isotope analysis of organic material by direct combustion: Preliminary results and potential applications

    USGS Publications Warehouse

    Kester, C.L.; Rye, R.O.; Johnson, C.A.; Schwartz, C.H.; Holmes, C.H.

    2001-01-01

    Sulfur isotopes have received little attention in ecology studies because plant and animal materials typically have low sulfur concentrations (< 1 wt.%) necessitating labor-intensive chemical extraction prior to analysis. To address the potential of direct combustion of organic material in an elemental analyzer coupled with a mass spectrometer, we compared results obtained by direct combustion to results obtained by sulfur extraction with Eschka's mixture. Direct combustion of peat and animal tissue gave reproducibility of better than 0.5??? and on average, values are 0.8??? higher than values obtained by Eschka extraction. Successful direct combustion of organic material appears to be a function of sample matrix and sulfur concentration. Initial results indicate that direct combustion provides fast, reliable results with minimal preparation. Pilot studies underway include defining bear diets and examining fluctuations between freshwater and brackish water in coastal environments.

  19. Analysis of Direct Samples of Extraterrestrial, Organic-Bearing, Aqueous Fluids

    NASA Technical Reports Server (NTRS)

    Zolensky, Michael

    2016-01-01

    I will describe water we have found in 4.5 billion year old extraterrestrial salt, and the organics that are also present. We hypothesize that organics being carried through the parent body of the halite have been deposited adjacent to the fluid inclusions, where they have been preserved against any thermal metamorphism. We are making bulk compositional, carbon and hydrogen isotopic measurements of solid organic phases associated with the aqueous fluid inclusions in the meteorites. We will compare these organics with those found in chondrites and Wild-2 comet coma particles to determine whether these classes of organics had an origin within aqueous solutions.

  20. Examination of Organic Reactions in UT/LS Aerosols: Temperature Dependence in Sulfuric Acid Solution

    NASA Astrophysics Data System (ADS)

    Iraci, L. T.; Michelsen, R. R.

    2004-12-01

    Sulfuric acid has been used for decades as an industrial catalyst for organic reactions, but its parallel role in atmospheric aerosols is relatively unexplored, despite identification of a wide array of organic compounds in particles. Several recent studies have demonstrated possible reactions in acidic particles, generally involving carbonyl groups (C=O) and leading to the formation of larger molecules. Reactions of oxygenated organic compounds in acidic solution are most often studied near room temperature, while the sulfate particles of the upper troposphere and lower stratosphere are significantly colder. Our studies of ethanal (acetaldehyde) suggest that reactivity in ~50 wt% H2SO4 solutions may be enhanced at lower temperatures, contrary to expectations. We will present temperature-dependent results of acid catalyzed condensation reactions, leading to formation of higher molecular weight products. Implications for aerosol composition and reactivity will be discussed.

  1. Self-organized highly ordered TiO{sub 2} nanotubes in organic aqueous system

    SciTech Connect

    Wan Jun; Yan Xia; Ding Junjie; Wang Meng; Hu Kongcheng

    2009-12-15

    A simple method to achieve self-organized, freestanding TiO{sub 2} nanotube array was constructed, free of corrosive etching process which was traditionally employed to separate TiO{sub 2} nanotubes from the metallic Ti substrate. The TiO{sub 2} nanotube arrays were constructed through potentiostatic anodization of Ti foil in aqueous electrolyte containing NH{sub 4}F and ethylene glycol. The nanotubes in the array were of 45 {mu}m lengths and 100 nm average pore diameters. The effect of NH{sub 4}F concentration on the length of the self-organized nanotube arrays was investigated. Electrochemical and spectroscopic measurements showed that the as-prepared nanotubes possessed large surface areas, good uniformity, and were ready for enzyme immobilization. The as-prepared nanotube arrays were amorphous, but crystallized with annealing at elevated temperatures, as demonstrated by X-ray diffraction (XRD).

  2. Factors controlling the abundance of organic sulfur in flash pyrolyzates of Upper Cretaceous kerogens from Sergipe Basin, Brazil

    USGS Publications Warehouse

    Carmo, A.M.; Stankiewicz, B.A.; Mastalerz, Maria; Pratt, L.M.

    1997-01-01

    The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene + dec-1-ene) in the pyrolyzates is variable and may be related to changes in the type of primary organic input and/or to variations in rates of bacterial sulfate reduction. A concomitant increase in S/C and O/C ratios determined in situ using the electron microprobe is observed in AOM and alginites and may be related to a progressive oxidation of the organic matter during sulfurization. The S/C ratio of the AOM is systematically higher than the S C ratio of the alginites. Combined with a thiophene distribution characteristic of pyrolyzates of Type II organic matter, the higher S/C of AOM in Sergipe kerogens suggests that sulfurization and incorporation of low-molecular weight lipids derived from normal marine organic matter into the kerogen structure predominated over direct sulfurization of highly aliphatic algal biomacromolecules.The molecular and elemental composition of immature kerogens isolated from Upper Cretaceous marine carbonates from Sergipe Basin, Brazil were investigated using combined pyrolysis-gas chromatography/mass spectrometry and organic petrographic techniques. The kerogens are predominantly composed of reddish-fluorescing amorphous organic matter (AOM) and variable amounts of yellow-fluorescing alginite and liptodetrinite. The abundance of organic sulfur in the kerogens inferred from the ratio 2-ethyl-5-methylthiophene/(1,2-dimethylbenzene+dec-1-ene) in the pyrolyzates is variable and may be related to changes in

  3. Interfacial stabilization of organic-aqueous two-phase microflows for a miniaturized DNA extraction module.

    PubMed

    Reddy, Varun; Zahn, Jeffrey D

    2005-06-01

    Organic-aqueous liquid (phenol) extraction is one of many standard techniques to efficiently purify DNA directly from cells. The cell components naturally distribute themselves into the two fluid phases in order to minimize interaction energies of the biological components with the surrounding solvents. The membrane components and protein partition to the interface between the organic and aqueous phases while the DNA stays in the aqueous phase. The aqueous phase is then removed with a purified DNA sample. This work studies the first steps towards miniaturizing this liquid extraction technique in a microfluidic device. The first step is to understand how the two liquid phases behave in microchannels. Due to the interfacial tension between the two liquid phases, novel approaches must be examined in order to obtain interfacial stability under flow conditions. The stability of the organic-aqueous interface is improved by reducing the interfacial tension between the two phases by incorporating a surfactant into the aqueous phase. The variation of the interfacial tension as a function of surfactant concentration is also quantified in this work. This has led to the ability to create stable stratified microflows in both a dual inlet and three inlet microfluidic systems. Also, the first step in understanding biological interactions at the organic-aqueous interface is investigated using a fluorescently labeled bovine serum albumin protein.

  4. Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism

    PubMed Central

    Bontognali, Tomaso R. R.; Sessions, Alex L.; Allwood, Abigail C.; Fischer, Woodward W.; Grotzinger, John P.; Summons, Roger E.; Eiler, John M.

    2012-01-01

    The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities. PMID:22949693

  5. Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism.

    PubMed

    Bontognali, Tomaso R R; Sessions, Alex L; Allwood, Abigail C; Fischer, Woodward W; Grotzinger, John P; Summons, Roger E; Eiler, John M

    2012-09-18

    The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ(33)S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ(33)S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H(2)S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ(33)S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities.

  6. The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases.

    PubMed

    Slater, Anthony Michael

    2014-10-01

    Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases.

  7. The IUPAC aqueous and non-aqueous experimental pKa data repositories of organic acids and bases

    NASA Astrophysics Data System (ADS)

    Slater, Anthony Michael

    2014-10-01

    Accurate and well-curated experimental pKa data of organic acids and bases in both aqueous and non-aqueous media are invaluable in many areas of chemical research, including pharmaceutical, agrochemical, specialty chemical and property prediction research. In pharmaceutical research, pKa data are relevant in ligand design, protein binding, absorption, distribution, metabolism, elimination as well as solubility and dissolution rate. The pKa data compilations of the International Union of Pure and Applied Chemistry, originally in book form, have been carefully converted into computer-readable form, with value being added in the process, in the form of ionisation assignments and tautomer enumeration. These compilations offer a broad range of chemistry in both aqueous and non-aqueous media and the experimental conditions and original reference for all pKa determinations are supplied. The statistics for these compilations are presented and the utility of the computer-readable form of these compilations is examined in comparison to other pKa compilations. Finally, information is provided about how to access these databases.

  8. Effect of organics and alkalinity on the sulfur oxidizing bacteria (SOB) biosensor.

    PubMed

    Hassan, Sedky H A; Van Ginkel, Steven W; Oh, Sang-Eun

    2013-01-01

    The environmental risk assessment of toxic chemicals in stream water requires the use of a low cost standardized toxicity bioassay. Here, a biosensor for detection of toxic chemicals in stream water was studied using sulfur oxidizing bacteria (SOB) in continuous mode. The biosensor depends on the ability of SOB to oxidize sulfur particles under aerobic conditions to produce sulfuric acid. The reaction results in an increase in electrical conductivity (EC) and a decrease in pH. The biosensor is based on the inhibition of SOB in the presence of toxic chemicals by measuring changes in EC and pH. We found that the SOB biosensor can detect Cr(6+)at a low concentration (50 ppb) which is lower than many whole-cell biosensors. The effect of organic material in real stream water on SOB activity was studied. Due to the presence of mixotrophic SOB, we found that the presence of organic matter increases SOB activity which decreases the biosensor start up period. Low alkalinity (22 mg L(-1) CaCO(3)) increased effluent EC and decreased effluent pH which is optimal for biosensor operation. While at high alkalinity (820 mg L(-1) CaCO(3), the activity of SOB little decreased. We found that system can detect 50 ppb of Cr(6+) at low alkalinity (22 mg L(-1) CaCO(3)) in few hours while, complete inhibition was observed after 35 h of operation at high alkalinity (820 mg L(-1) CaCO(3)). Copyright © 2012 Elsevier Ltd. All rights reserved.

  9. Experimental determination of the temperature dependence of water activities for a selection of aqueous organic solutions

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Stratmann, G.; Peter, T.

    2014-05-01

    This work presents experimental data of the temperature dependence of water activity in aqueous organic solutions relevant for tropospheric conditions (200-273 K). Water activity (aw) at low temperatures (T) is a crucial parameter for predicting homogeneous ice nucleation. We investigated temperature dependent water activities, ice freezing and melting temperatures of solutions, and vapour pressures of a selection of atmospherically relevant aqueous organic systems. To measure aw over a wide composition range and with a focus on low temperatures, we use various aw measurement techniques and instruments: a dew point water activity meter, an electrodynamic balance (EDB), differential scanning calorimetry (DSC), and a setup to measure the total gas phase pressure at equilibrium over aqueous solutions. Water activity measurements were performed for aqueous multicomponent and multifunctional organic mixtures containing the functional groups typically found in atmospheric organic aerosols, such as hydroxyl, carboxyl, ketone, ether, ester, and aromatic groups. The aqueous organic systems studied at several fixed compositions over a considerable temperature range differ significantly in their temperature dependence. Aqueous organic systems of 1,4-butanediol and methoxyacetic acid show a moderate decrease in aw with decreasing temperature. The aqueous M5 system (a multicomponent system containing five different dicarboxylic acids) and aqueous 2-(2-ethoxyethoxy)ethanol solutions both show a strong increase of water activity with decreasing temperature at high solute concentrations for T<270 K and T<260 K, respectively. These measurements show that the temperature trend of aw can be reversed at low temperatures and that linear extrapolations of high temperature data may lead to erroneous predictions. To avoid this, experimentally determined aw at low temperature are needed to improve thermodynamic models towards lower temperatures and for improved predictions of the ice

  10. Experimental determination of the temperature dependence of water activities for a selection of aqueous organic solutions

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Marcolli, C.; Krieger, U. K.; Zuend, A.; Stratmann, G.; Peter, T.

    2014-09-01

    This work presents experimental data of the temperature dependence of water activity in aqueous organic solutions relevant for tropospheric conditions (200-273 K). Water activity (aw) at low temperatures (T) is a crucial parameter for predicting homogeneous ice nucleation. We investigated temperature-dependent water activities, ice freezing and melting temperatures of solutions, and vapour pressures of a selection of atmospherically relevant aqueous organic systems. To measure aw over a wide composition range and with a focus on low temperatures, we use various aw measurement techniques and instruments: a dew point water activity meter, an electrodynamic balance (EDB), differential scanning calorimetry (DSC), and a setup to measure the total gas phase pressure at equilibrium over aqueous solutions. Water activity measurements were performed for aqueous multicomponent and multifunctional organic mixtures containing the functional groups typically found in atmospheric organic aerosols, such as hydroxyl, carboxyl, ketone, ether, ester, and aromatic groups. The aqueous organic systems studied at several fixed compositions over a considerable temperature range differ significantly in their temperature dependence. Aqueous organic systems of 1,4-butanediol and methoxyacetic acid show a moderate decrease in aw with decreasing temperature. The aqueous M5 system (a multicomponent system containing five different dicarboxylic acids) and aqueous 2-(2-ethoxyethoxy)ethanol solutions both show a strong increase of water activity with decreasing temperature at high solute concentrations for T < 270 K and T < 260 K, respectively. These measurements show that the temperature trend of aw can be reversed at low temperatures and that linear extrapolations of high-temperature data may lead to erroneous predictions. To avoid this, experimentally determined aw at low temperature are needed to improve thermodynamic models towards lower temperatures and for improved predictions of the ice

  11. Formation and burial of pyrite and organic sulfur in mud sediments of the East China Sea inner shelf: Constraints from solid-phase sulfur speciation and stable sulfur isotope

    NASA Astrophysics Data System (ADS)

    Zhu, Mao-Xu; Shi, Xiao-Ning; Yang, Gui-Peng; Hao, Xiao-Chen

    2013-02-01

    Solid-phase sulfur speciation and stable sulfur isotopic compositions are used to elucidate the formation and burial of pyrite-sulfur (Spy) and organic sulfur (OS) at three selected sites in mud sediments of the East China Sea (ECS) inner shelf, and to infer potential factors influencing the preservation of Spy and OS in the sediments. Our results in combination with previous studies show that the overall reactivity of sedimentary organic matter (OM) is low, while OM at the site impacted by frequent algal-bloom events displays somewhat enhanced reactivity. We observed characteristically low contents of acid volatile sulfide (AVS) and Spy in the sediments, which can be attributed to low sulfate reduction rate due to high redox potential together with limited availability of labile OM. Several geochemical features, for example, persistent occurrence of S0, good coupling among the profiles of AVS, S0 and Spy, and large 34Spy depletion, all suggest that the polysulfide pathway and disproportionation are likely involved in the pyrite formation. Organic sulfur amounts in the sediments are at the lower end of OS contents reported in many other marine sediments around the world. The sources of OS are both biosynthetic and diagenetic, with the biosynthetic OS being the major share (59-73%). In one site studied (C702), enhanced accumulation of OS within the upper layers (14 cm) is believed to be associated with frequent algal-bloom events. Net burial fluxes of Spy and OS in the three sites studied range from 0.27 to 0.82 mmol/m2/d and from 0.22 to 0.74 mmol/m2/d, respectively. Sedimentation rate and algal-bloom events are two important factors influencing the spatial variability of Spy and OS burial fluxes in the whole shelf.

  12. Refined Sulfur Nanoparticles Immobilized in Metal-Organic Polyhedron as Stable Cathodes for Li-S Battery.

    PubMed

    Bai, Linyi; Chao, Dongliang; Xing, Pengyao; Tou, Li Juan; Chen, Zhen; Jana, Avijit; Shen, Ze Xiang; Zhao, Yanli

    2016-06-15

    The lithium-sulfur (Li-S) battery presents a promising rechargeable energy storage technology for the increasing energy demand in a worldwide range. However, current main challenges in Li-S battery are structural degradation and instability of the solid-electrolyte interphase caused by the dissolution of polysulfides during cycling, resulting in the corrosion and loss of active materials. Herein, we developed novel hybrids by employing metal-organic polyhedron (MOP) encapsulated PVP-functionalized sulfur nanoparticles (S@MOP), where the active sulfur component was efficiently encapsulated within the core of MOP and PVP as a surfactant was helpful to stabilize the sulfur nanoparticles and control the size and shape of corresponding hybrids during their syntheses. The amount of sulfur embedded into MOP could be controlled according to requirements. By using the S@MOP hybrids as cathodes, an obvious enhancement in the performance of Li-S battery was achieved, including high specific capacity with good cycling stability. The MOP encapsulation could enhance the utilization efficiency of sulfur. Importantly, the structure of the S@MOP hybrids was very stable, and they could last for almost 1000 cycles as cathodes in Li-S battery. Such high performance has rarely been obtained using metal-organic framework systems. The present approach opens up a promising route for further applications of MOP as host materials in electrochemical and energy storage fields.

  13. VHF EPR quantitation and speciation of organic sulfur in coal. Technical report, September 1, 1993--November 30, 1993

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1993-12-31

    Over the last few years, we have developed a non-destructive technique called Very High Frequency Electron Paramagnetic Resonance (VHF-EPR) that is proving to be a practical and very sensitive analytical method for the organic sulfur in coal. Already, although still under development, the technique rapidly can quantify organic sulfur, and perhaps provide information on organic oxygen and nitrogen, in typical Illinois coals. At this stage, the precision is not well enough calibrated, and specificity for particular species needs more development. This year`s proposal outlined a 12 month work plan designed to improve and extend the utility of VHF-EPR. Two main goals of the work are: (1) refinement and calibration of organic sulfur analysis, in coals of differing rank, over a concentration range from 0.1% to 5%, and (2) better utilization of VHF-EPR coal spectral data for sulfur speciation. This quarter, goal (1) is being pursued; results will be ready to describe in a future report. Meanwhile, work toward goal (2) has produced detailed information about the VHF-EPR spectral behavior of several comparison compounds -- sulfur -- containing thiophenic fused-ring molecules.

  14. Nanocrystalline ceria coatings on solid oxide fuel cell anodes: the role of organic surfactant pretreatments on coating microstructures and sulfur tolerance

    PubMed Central

    Wu, Chieh-Chun; Tang, Ling

    2014-01-01

    Summary Treatments with organic surfactants, followed by the deposition of nanocrystalline ceria coatings from aqueous solution, were applied to anodes of solid oxide fuel cells. The cells were then operated in hydrogen/nitrogen fuel streams with H2S contents ranging from 0 to 500 ppm. Two surfactant treatments were studied: immersion in dodecanethiol, and a multi-step conversion of a siloxy-anchored alkyl bromide to a sulfonate functionality. The ceria coatings deposited after the thiol pretreatment, and on anodes with no pretreatment, were continuous and uniform, with thicknesses of 60–170 nm and 100–140 nm, respectively, and those cells exhibited better lifetime performance and sulfur tolerance compared to cells with untreated anodes and anodes with ceria coatings deposited after the sulfonate pretreatment. Possible explanations for the effects of the treatments on the structure of the coatings, and for the effects of the coatings on the performance of the cells, are discussed. PMID:25383282

  15. Mechanistic roles of soil humus and minerals in the sorption of nonionic organic compounds from aqueous and organic solutions

    USGS Publications Warehouse

    Chiou, C.T.; Shoup, T.D.; Porter, P.E.

    1985-01-01

    Mechanistic roles of soil humus and soil minerals and their contributions to soil sorption of nonionic organic compounds from aqueous and organic solutions are illustrated. Parathion and lindane are used as model solutes on two soils that differ greatly in their humic and mineral contents. In aqueous systems, observed sorptive characteristics suggest that solute partitioning into the soil-humic phase is the primary mechanism of soil uptake. By contrast, data obtained from organic solutions on dehydrated soil partitioning into humic phase and adsorption by soil minerals is influenced by the soil-moisture content and by the solvent medium from which the solute is sorbed. ?? 1985.

  16. Secondary Organic Aerosol Produced from Aqueous Reactions of Phenols in Fog Drops and Deliquesced Particles

    NASA Astrophysics Data System (ADS)

    Smith, J.; Anastasio, C.

    2014-12-01

    The formation and evolution of secondary organic aerosol (SOA) in atmospheric condensed phases (i.e., aqueous SOA) can proceed rapidly, but relatively little is known of the important aqueous SOA precursors or their reaction pathways. In our work we are studying the aqueous SOA formed from reactions of phenols (phenol, guaiacol, and syringol), benzene-diols (catechol, resorcinol, and hydroquinone), and phenolic carbonyls (e.g., vanillin and syringaldehyde). These species are potentially important aqueous SOA precursors because they are released in large quantities from biomass burning, have high Henry's Law constants (KH = 103 -109 M-1 atm-1) and are rapidly oxidized. To evaluate the importance of aqueous reactions of phenols as a source of SOA, we first quantified the kinetics and SOA mass yields for 11 phenols reacting via direct photodegradation, hydroxyl radical (•OH), and with an excited organic triplet state (3C*). In the second step, which is the focus of this work, we use these laboratory results in a simple model of fog chemistry using conditions during a previously reported heavy biomass burning event in Bakersfield, CA. Our calculations indicate that under aqueous aerosol conditions (i.e., a liquid water content of 100 μg m-3) the rate of aqueous SOA production (RSOA(aq)) from phenols is similar to the rate in the gas phase. In contrast, under fog/cloud conditions the aqueous RSOA from phenols is 10 times higher than the rate in the gas phase. In both of these cases aqueous RSOA is dominated by the oxidation of phenols by 3C*, followed by direct photodegradation of phenolic carbonyls, and then •OH oxidation. Our results suggest that aqueous oxidation of phenols is a significant source of SOA during fog events and also during times when deliquesced aerosols are present.

  17. Properties of Sulfur Concrete.

    DTIC Science & Technology

    1979-07-06

    This report summarizes the state of the art of sulfur concrete . Sulfur concrete is created by mixing molten sulfur with aggregate and allowing the...and many organic compounds. It works well as a rapid runway repair material. Sulfur concrete also has unfavorable properties. It has poor durability

  18. Observations of some oxygen-containing and sulfur-containing organic molecules in cold dark clouds

    NASA Technical Reports Server (NTRS)

    Irvine, W. M.; Friberg, P.; Kaifu, N.; Kitamura, Y.; Kawaguchi, K.

    1989-01-01

    Observations of nine oxygen- and sulfur-containing organic molecules have been made toward the cold dark clouds TMC-1 and L134N. The presence of paraketene (H2C2O) in TMC-1 is confirmed for orthoketene, and has been observed for the first time and a total ketene column density of about 10 to the 13th/sq cm is found. Thioformaldehyde (H2CS) is easily detectable in both TMC-1 and L134N, with a column density about five times larger in the former source. The fractional abundance of ketene is comparable to the predictions of ion-molecule chemistry, while that of thioformaldehyde in TMC-1 is one to two orders of magnitude greater than that expected from such models at steady state. Interstellar sulfur chemistry thus continues to be poorly understood. Upper limits are set for the column densities of formic acid (HCOOH), vinyl alcohol (CH2CHOH), methyl formate (HCO2CH3), formamide (NH2CHO), methyl mercaptan (CH3SH), isothiocyanic acid (HNCS), and thioketene (H2C2S) in both sources.

  19. Lewis Acid–Base Interactions between Polysulfides and Metal Organic Framework in Lithium Sulfur Batteries

    SciTech Connect

    Zheng, Jianming; Tian, Jian; Wu, Dangxin; Gu, Meng; Xu, Wu; Wang, Chongmin; Gao, Fei; Engelhard, Mark H.; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2014-05-14

    Lithium–sulfur (Li–S) battery is one of the most promising energy storage systems because of its high specific capacity of 1675 mAh g–1 based on sulfur. However, the rapid capacity degradation, mainly caused by polysulfide dissolution, remains a significant challenge prior to practical applications. This work demonstrates that a novel Ni-based metal organic framework (Ni-MOF), Ni6(BTB)4(BP)3 (BTB = benzene-1,3,5-tribenzoate and BP = 4,4'-bipyridyl), can remarkably immobilize polysulfides within the cathode structure through physical and chemical interactions at molecular level. The capacity retention achieves up to 89% after 100 cycles at 0.1 C. Finally, the excellent performance is attributed to the synergistic effects of the interwoven mesopores (~2.8 nm) and micropores (~1.4 nm) of Ni-MOF, which first provide an ideal matrix to confine polysulfides, and the strong interactions between Lewis acidic Ni(II) center and the polysulfide base, which significantly slow down the migration of soluble polysulfides out of the pores, leading to the excellent cycling performance of Ni-MOF/S composite.

  20. Lewis acid-base interactions between polysulfides and metal organic framework in lithium sulfur batteries.

    PubMed

    Zheng, Jianming; Tian, Jian; Wu, Dangxin; Gu, Meng; Xu, Wu; Wang, Chongmin; Gao, Fei; Engelhard, Mark H; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

    2014-05-14

    Lithium-sulfur (Li-S) battery is one of the most promising energy storage systems because of its high specific capacity of 1675 mAh g(-1) based on sulfur. However, the rapid capacity degradation, mainly caused by polysulfide dissolution, remains a significant challenge prior to practical applications. This work demonstrates that a novel Ni-based metal organic framework (Ni-MOF), Ni6(BTB)4(BP)3 (BTB = benzene-1,3,5-tribenzoate and BP = 4,4'-bipyridyl), can remarkably immobilize polysulfides within the cathode structure through physical and chemical interactions at molecular level. The capacity retention achieves up to 89% after 100 cycles at 0.1 C. The excellent performance is attributed to the synergistic effects of the interwoven mesopores (∼2.8 nm) and micropores (∼1.4 nm) of Ni-MOF, which first provide an ideal matrix to confine polysulfides, and the strong interactions between Lewis acidic Ni(II) center and the polysulfide base, which significantly slow down the migration of soluble polysulfides out of the pores, leading to the excellent cycling performance of Ni-MOF/S composite.

  1. VHF EPR analysis of organic sulfur in coal. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1992-12-31

    The development of very High Frequency Electron Paramagnetic Resonance (VHF-EPR) into an analytical technique that holds great promise for the non-destructive determination of the amount and structure of organic sulfur in both native and desulfurized coal advanced considerably during the past year. The VHF-EPR spectrometer built with funds from the CRSC is one of two operating near 96 GHz, and the only such instrument in the United States. Earlier work has shown that W-band spectra of Illinois coals and separated macerals shows good sensitivity to forms of organic sulfur present. This work has been extended to improve the use of W-band spectra to provide quantitative as well as qualitative information regarding different sulfur species and, in collaboration with other researchers, their fate during various desulfurizing techniques. A key approach is to synthesize various model compounds, both those from known precursors and those made as sulfurized chars, and to compare their respective W-band spectra (1) with each other, (2) with the predictions of theoretical models, and (3) with the W-band spectra of coal specimens. The quantitative measurement of aromatic sulfur in these compounds has improved as different methods of calibration and indexing are evaluated. Work is also being conducted on apparent variations in spectral line-shapes on evacuation of coal samples. Corroborations of many aspects of W-band organic sulfur interpretation in both raw and desulfurized coals as well as in model compounds are also being carried out by microanalysis and by high-temperature mass spectroscopy. The determination of populations of groups or species of aromatic sulfur molecules is being refined. Especially promising are methods to improve discrimination by differing saturation rates, and by second-derivative spectra.

  2. Method for separating water soluble organics from a process stream by aqueous biphasic extraction

    DOEpatents

    Chaiko, David J.; Mego, William A.

    1999-01-01

    A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

  3. Method for separating water soluble organics from a process stream by aqueous biphasic extraction

    SciTech Connect

    Chaiko, D.J.; Mego, W.A.

    1999-09-07

    A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

  4. Biological activities of aqueous and organic extracts from tropical marine sponges.

    PubMed

    Sepcić, Kristina; Kauferstein, Silke; Mebs, Dietrich; Turk, Tom

    2010-04-28

    We report on screening tests of 66 extracts obtained from 35 marine sponge species from the Caribbean Sea (Curaçao) and from eight species from the Great Barrier Reef (Lizard Island). Extracts were prepared in aqueous and organic solvents and were tested for hemolytic, hemagglutinating, antibacterial and anti-acetylcholinesterase (AChE) activities, as well as their ability to inhibit or activate cell protein phosphatase 1 (PP1). The most interesting activities were obtained from extracts of Ircinia felix, Pandaros acanthifolium, Topsentia ophiraphidites, Verongula rigida and Neofibularia nolitangere. Aqueous and organic extracts of I. felix and V. rigida showed strong antibacterial activity. Topsentia aqueous and some organic extracts were strongly hemolytic, as were all organic extracts from I. felix. The strongest hemolytic activity was observed in aqueous extracts from P. acanthifolium. Organic extracts of N. nolitangere and I. felix inhibited PP1. The aqueous extract from Myrmekioderma styx possessed the strongest hemagglutinating activity, whilst AChE inhibiting activity was found only in a few sponges and was generally weak, except in the methanolic extract of T. ophiraphidites.

  5. Removal of sulfur-organic polar micropollutants in a membrane bioreactor treating industrial wastewater.

    PubMed

    Reemtsma, Thorsten; Zywicki, Britta; Stueber, Markus; Kloepfer, Achim; Jekel, Martin

    2002-03-01

    While membrane bioreactors (MBR) have proven their large potential to remove bulk organic matter from municipal as well as industrial wastewater, their suitability to remove poorly degradable polar wastewater contaminants is yet unknown. However, this is an important aspect for the achievable effluent quality and in terms of wastewater reuse. We have analyzed two classes of polar sulfur-organic compounds, naphthalene sulfonates and benzothiazoles, by liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS) over a period of 3 weeks in the influent and effluent of a full-scale MBR with external ultrafiltration that treats tannery wastewater. While naphthalene monosulfonates were completely removed, total naphthalene disulfonate removal was limited to about 40%, and total benzothiazoles concentration decreased for 87%. Quantitative as well as qualitative data did not indicate an adaptation to or a more complete removal of these polar aromatic compounds by the MBR as compared to literature data on conventional activated sludge treatment. While quality improvements in receiving waters for bulk organic matter are documented and the same can be anticipated for apolar particle-associated contaminants, these data provide no indication that MBR will improve the removal of polar poorly biodegradable organic pollutants.

  6. Predicting liquid densities of organic compounds: II, Nitrogen and sulfur compounds

    SciTech Connect

    Wood, G.O.; Weaver, T.B.

    1993-02-01

    Correlations of liquid densities have been extended to more classes of organic compounds. The products of liquid density and molecular weight at or near 20{degrees}C were previously found to be linear functions of the number and types of carbon atoms in the molecule. Cyclic carbon atoms contributed more to density than carbon atoms not part of a ring structure. Carbon atoms which occupy two rings have since been found to contribute even different increments. Additional databases of liquid densities have been set up for compounds with cyclic oxygen atoms, cyclic and noncyclic nitrogen atoms, and cyclic and noncyclic sulfur atoms. Correlation parameters have been obtained by fitting these data by least squares minimization.

  7. Evaluation of sulfur-reducing microorganisms for organic desulfurization. Final technical report, September 1, 1990--August 31, 1991

    SciTech Connect

    Miller, K.W.

    1991-12-31

    Because of substantial portion of the sulfur in Illinois coal is organic, microbial desulfurization of sulfidic and thiophenic functionalities could hold great potential for completing pyritic sulfur removal. We are testing the hypothesis that organic sulfur can be reductively removed as H{sub 2}S through the activities of anaerobic microorganisms. Our objectives for this year include the following: (1) To obtain cultures that will reductively desulfurize thiophenic model compounds. In addition to crude oil enrichments begun last year, we sampled municipal sewage sludge. (2) To continue to work toward optimizing the activity of the DBDS-reducing cultures obtained during the previous year. (3) To expand coal desulfurization work to include other coals including Illinois Basin Coal 101 and a North Dakota lignite, which might be more susceptible to the dibenzyldisulfide reducing cultures due to its lower rank. (4) To address the problem of sulfide sorption, by investigating the sorption capacity of coals in addition to Illinois Basin Coal 108.

  8. Aqueous photooxidation of ambient Po Valley Italy air samples: Insights into secondary organic aerosol formation

    NASA Astrophysics Data System (ADS)

    Kirkland, J. R.; Lim, Y. B.; Sullivan, A. P.; Decesari, S.; Facchini, C.; Collett, J. L.; Keutsch, F. N.; Turpin, B. J.

    2012-12-01

    In this work, we conducted aqueous photooxidation experiments with ambient samples in order to develop insights concerning the formation of secondary organic aerosol through gas followed by aqueous chemistry (SOAaq). Water-soluble organics (e.g., glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone) are formed through gas phase oxidation of alkene and aromatic emissions of anthropogenic and biogenic origin. Their further oxidation in clouds, fogs and wet aerosols can form lower volatility products (e.g., oligomers, organic acids) that remain in the particle phase after water evaporation, thus producing SOA. The aqueous OH radical oxidation of several individual potentially important precursors has been studied in the laboratory. In this work, we used a mist-chamber apparatus to collect atmospheric mixtures of water-soluble gases from the ambient air at San Pietro Capofiume, Italy during the PEGASOS field campaign. We measured the concentration dynamics after addition of OH radicals, in order to develop new insights regarding formation of SOA through aqueous chemistry. Specifically, batch aqueous reactions were conducted with 33 ml mist-chamber samples (TOC ~ 50-100μM) and OH radicals (~10-12M) in a new low-volume aqueous reaction vessel. OH radicals were formed in-situ, continuously by H2O2 photolysis. Products were analyzed by ion chromatography (IC), electrospray ionization mass spectrometry (ESI-MS +/-), and ESI-MS with IC pre-separation (IC/ESI-MS-). Reproducible formation of pyruvate and oxalate were observed both by IC and ESI-MS. These compounds are known to form from aldehyde oxidation in the aqueous phase. New insights regarding the aqueous chemistry of these "more atmospherically-realistic" experiments will be discussed.

  9. Autotrophic and heterotrophic denitrification for simultaneous removal of nitrogen, sulfur and organic matter.

    PubMed

    Guerrero, Lorna; Aguirre, Juan P; Muñoz, Maria A; Barahona, Andrea; Huiliñir, Cesar; Montalvo, Silvio; Borja, Rafael

    2016-07-02

    The aim of this investigation was to assess the startup and operation of a laboratory-scale hybrid UASB-Anaerobic Filter Reactor (UASFB) of 1 L volume, kept at 30°C, in order to carry out a simultaneous autotrophic and heterotrophic denitrification process. First, the heterotrophic and autotrophic populations were separately enriched, with specific cultures and subsequently the UASFB was inoculated with 2 g L(-1) of volatile suspended solids (VSS), with a ratio of 1.5:1 (autotrophs: heterotrophs). The influent or synthetic wastewater used was composed of: Na2S2O3·5H2O, CH3COOK, NaNO3, NaHCO3, K2HPO4, NH4Cl and saline solution. The concentrations varied depending on the organic loading rate (OLR), nitrogen loading rate (NLR) and sulfur loading rate (SLR) applied. In the UASFB reactor, two experimental conditions were tested and assessed: (i) COD/N ratio of 3.6 and SLR of 0.75 kg S m(-3) d(-1); and (ii) COD/N ratio of 5.8 and SLR of 0.25 kg S m(-3) d(-1). The results obtained demonstrated that an inoculum coming from an anaerobic reactor was able to carry out the process, obtaining a maximum nitrate removal of 85.3% in the first stage of operation and 99.5% in the second stage. The recovery of sulfur in form of sulfate in the effluent did not present a tendency to stabilize during the measured time, with a maximum thiosulfate removal of 32.5%, when the SLR was lowered to 0.25 kg S m(-3) d(-1). The maximum organic matter elimination, measured as COD, was 75.8%, which indicates the relatively good performance and behavior of the heterotrophic microorganisms.

  10. Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

    1988-01-01

    Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

  11. Efficient catalytic hydration of cyanamides in aqueous medium and in the presence of Naringin sulfuric acid or green synthesized silver nanoparticles by using Gongronema latifolium leaf extract.

    PubMed

    Issaabadi, Zahra; Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

    2017-10-01

    In this paper, a novel, efficient and green method for the preparation of Naringin sulfuric acid (NSA) as a Brønsted acid organocatalyst and silver nanoparticles (Ag NPs) by using Gongronema latifolium leaf extract as a reducing and stabilizing agent is introduced. The catalysts were characterized using the powder XRD, SEM, EDS, TEM, UV-Vis and FT-IR spectroscopy. Afterward, the catalytic activity of synthesized NSA and Ag NPs were investigated for the synthesis of N-monosubstituted ureas via the hydration of cyanamides in aqueous medium. All products were obtained in good to excellent yields. These methods provided several advantages such as shorter reaction time, simpler work-up and higher yield. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. Secondary organic aerosol production from aqueous photooxidation of glycolaldehyde: Laboratory experiments

    NASA Astrophysics Data System (ADS)

    Perri, Mark J.; Seitzinger, Sybil; Turpin, Barbara J.

    Organic particulate matter (PM) formed in the atmosphere (secondary organic aerosol; SOA) is a substantial yet poorly understood contributor to atmospheric PM. Aqueous photooxidation in clouds, fogs and aerosols is a newly recognized SOA formation pathway. This study investigates the potential for aqueous glycolaldehyde oxidation to produce low volatility products that contribute SOA mass. To our knowledge, this is the first confirmation that aqueous oxidation of glycolaldehyde via the hydroxyl radical forms glyoxal and glycolic acid, as previously assumed. Subsequent reactions form formic acid, glyoxylic acid, and oxalic acid as expected. Unexpected products include malonic acid, succinic acid, and higher molecular weight compounds, including oligomers. Due to (1) the large source strength of glycolaldehyde from precursors such as isoprene and ethene, (2) its water solubility, and (3) the aqueous formation of low volatility products (organic acids and oligomers), we predict that aqueous photooxidation of glycolaldehyde and other aldehydes in cloud, fog, and aerosol water is an important source of SOA and that incorporation of this SOA formation pathway in chemical transport models will help explain the current under-prediction of organic PM concentrations.

  13. SULFUR POLYMER ENCAPSULATION.

    SciTech Connect

    KALB, P.

    2001-08-22

    Sulfur polymer cement (SPC) is a thermoplastic polymer consisting of 95 wt% elemental sulfur and 5 wt% organic modifiers to enhance long-term durability. SPC was originally developed by the U.S. Bureau of Mines as an alternative to hydraulic cement for construction applications. Previous attempts to use elemental sulfur as a construction material in the chemical industry failed due to premature degradation. These failures were caused by the internal stresses that result from changes in crystalline structure upon cooling of the material. By reacting elemental sulfur with organic polymers, the Bureau of Mines developed a product that successfully suppresses the solid phase transition and significantly improves the stability of the product. SPC, originally named modified sulfur cement, is produced from readily available, inexpensive waste sulfur derived from desulfurization of both flue gases and petroleum. The commercial production of SPC is licensed in the United States by Martin Resources (Odessa, Texas) and is marketed under the trade name Chement 2000. It is sold in granular form and is relatively inexpensive ({approx}$0.10 to 0.12/lb). Application of SPC for the treatment of radioactive, hazardous, and mixed wastes was initially developed and patented by Brookhaven National Laboratory (BNL) in the mid-1980s (Kalb and Colombo, 1985; Colombo et al., 1997). The process was subsequently investigated by the Commission of the European Communities (Van Dalen and Rijpkema, 1989), Idaho National Engineering Laboratory (Darnell, 1991), and Oak Ridge National Laboratory (Mattus and Mattus, 1994). SPC has been used primarily in microencapsulation applications but can also be used for macroencapsulation of waste. SPC microencapsulation has been demonstrated to be an effective treatment for a wide variety of wastes, including incinerator hearth and fly ash; aqueous concentrates such as sulfates, borates, and chlorides; blowdown solutions; soils; and sludges. It is not

  14. Aqueous synthesis of Cu-doped ZnCdS/ZnS core/shell nanocrystals with a new and highly reactive sulfur source

    NASA Astrophysics Data System (ADS)

    Zeng, Ruosheng; Shen, Rongan; Zhao, Yunqiang; Li, Xingsheng; Sun, Zhiguo; Shen, Yayun

    2014-04-01

    A new sulfur precursor with a highly reactive chemical nature was prepared with S powder and NaBH4 at the high temperature of 180 °C in a closed autoclave and made it possible to carry out the synthesis of high quality metal sulfide nanocrystals (NCs) with diverse composition and structure. Using this new sulfur source, we demonstrated aqueous synthesis of colloidal Cu-doped ZnCdS NCs (d-dots) with pure, color-tunable photoluminescence (PL) in a wide spectral range (from 517 to 650 nm) based on the ‘co-nucleation doping’ strategy. The influences of the various experimental variables, including Cd/Zn ratio, Cu-doping concentration, pH value and amount of mercaptopropionic acid (MPA), on the optical properties of Cu-doped ZnCdS NCs were systematically investigated. Furthermore, highly efficient and stable dopant emission from Cu:ZnCdS/ZnS core/shell d-dots with PL quantum yield as high as 40% was achieved by the deposition of a ZnS shell around the bare Cu:ZnCdS cores; this is the highest reported to date for aqueous doped NCs. The optical properties and structure of the d-dots were characterized by UV-vis absorption spectra, PL spectra, x-ray photoelectron spectroscopy, powder x-ray diffraction, and transmission electron microscopy. The experimental results indicated that this facile synthesis route would provide a versatile approach for the preparation of other water-soluble sulfide NCs.

  15. Enhanced Ga2O3-photocatalyzed and photochemical degradation of the Fipronil insecticide by UVC irradiation in mixed aqueous/organic media under an inert atmosphere.

    PubMed

    Hidaka, Hisao; Tsukamoto, Tohru; Mitsutsuka, Yoshihiro; Oyama, Toshiyuki; Serpone, Nick

    2015-05-01

    Agrochemicals such as the insecticide Fipronil that bear fluoro groups are generally fat-soluble and nearly insoluble in water, so that their photodegradation in a heterogeneous aqueous gallium oxide dispersion presents some challenges. This article examined the photodegradation of this insecticide by solubilizing it through the addition of organic solvents (EtOH, MeOH, THF, 1,4-dioxane and ethylene glycol) to an aqueous medium and then subjecting the insecticide to 254 nm UVC radiation under photocatalytically inert (Ga2O3/N2) and air-equilibrated (Ga2O3/O2) conditions, as well as photochemically in the absence of Ga2O3 but also under inert and air-equilibrated conditions. Defluorination, dechlorination, desulfonation and denitridation of Fipronil were examined in mixed aqueous/organic media (10, 25 and 50 vol% in organic solvent). After 3 h of UVC irradiation (50 vol% mixed media) defluorination with Ga2O3/N2 was ∼65% greater than in aqueous media, and ca. 80% greater than the direct photolysis of Fipronil under inert (N2) conditions; under air-equilibrated conditions both Ga2O3-photocatalyzed and photochemical defluorination were significantly lower than in aqueous media. Dechlorination of Fipronil was ∼160% (Ga2O3/N2) and 140% (photochemically, N2) greater than in aqueous media; under air-equilibrated conditions, both photocatalyzed and photochemical formation of Cl(-) ions in mixed media fell rather short relative to aqueous media. The photocatalyzed (Ga2O3/N2) and photochemical (N2) conversion of the sulfur group in Fipronil to SO4(2(-)) ions was ca. 20% and 30% greater, respectively, in mixed media, while under air-equilibrated conditions photocatalyzed desulfonation was nearly twofold less than in the aqueous phase; direct photolysis showed little variations in mixed media. Denitridation of the nitrogens in Fipronil occurred mostly through the formation of ammonia (as NH4(+)) under all conditions with negligible quantities of NO3(-); again mixed media

  16. Identifying precursors and aqueous organic aerosol formation pathways during the SOAS campaign

    NASA Astrophysics Data System (ADS)

    Sareen, Neha; Carlton, Annmarie G.; Surratt, Jason D.; Gold, Avram; Lee, Ben; Lopez-Hilfiker, Felipe D.; Mohr, Claudia; Thornton, Joel A.; Zhang, Zhenfa; Lim, Yong B.; Turpin, Barbara J.

    2016-11-01

    Aqueous multiphase chemistry in the atmosphere can lead to rapid transformation of organic compounds, forming highly oxidized, low-volatility organic aerosol and, in some cases, light-absorbing (brown) carbon. Because liquid water is globally abundant, this chemistry could substantially impact climate, air quality, and health. Gas-phase precursors released from biogenic and anthropogenic sources are oxidized and fragmented, forming water-soluble gases that can undergo reactions in the aqueous phase (in clouds, fogs, and wet aerosols), leading to the formation of secondary organic aerosol (SOAAQ). Recent studies have highlighted the role of certain precursors like glyoxal, methylglyoxal, glycolaldehyde, acetic acid, acetone, and epoxides in the formation of SOAAQ. The goal of this work is to identify additional precursors and products that may be atmospherically important. In this study, ambient mixtures of water-soluble gases were scrubbed from the atmosphere into water at Brent, Alabama, during the 2013 Southern Oxidant and Aerosol Study (SOAS). Hydroxyl (OH⚫) radical oxidation experiments were conducted with the aqueous mixtures collected from SOAS to better understand the formation of SOA through gas-phase followed by aqueous-phase chemistry. Total aqueous-phase organic carbon concentrations for these mixtures ranged from 92 to 179 µM-C, relevant for cloud and fog waters. Aqueous OH-reactive compounds were primarily observed as odd ions in the positive ion mode by electrospray ionization mass spectrometry (ESI-MS). Ultra high-resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) spectra and tandem MS (MS-MS) fragmentation of these ions were consistent with the presence of carbonyls and tetrols. Products were observed in the negative ion mode and included pyruvate and oxalate, which were confirmed by ion chromatography. Pyruvate and oxalate have been found in the particle phase in many locations (as salts and complexes). Thus

  17. Enzymatic hydrolysis of organic-core microcapsules to produce aqueous-core microcapsules.

    PubMed

    Breguet, Veronique; Vojinovic, Vojislav; Von Stockar, Urs; Marison, Ian W

    2008-05-01

    This paper describes the development of a new method to obtain aqueous-core microcapsules from organic-core capsules. The direct production of microcapsules, using tripropionin as organic material, followed by the hydrolysis of the core by a lipase was investigated. The enzymatic study showed that the enzyme obeyed a Michaelis-Menten mechanism and conditions for optimal activity were pH 7.5, 25-37 degrees C and 0% NaCl. Under these conditions, incubation of tripropionin-alginate microcapsules in a buffer containing the enzyme successfully produced aqueous-core capsules with reduced accumulation of alginate in the core in approximately 3 h.

  18. CARBINOLAMINES AND GEMINAL DIOLS IN AQUEOUS ENVIRONMENTAL ORGANIC CHEMISTRY

    EPA Science Inventory

    Organic chemistry textbooks generally treat geminal diols as curiosities-exceptions to the stability of the C=O double bond. However, most aldehydes of environmental significance, to wit, trichloroethanal (chloral), methanala (formaldehyde), ethanal (acetaldehyde), and propanal ...

  19. CARBINOLAMINES AND GEMINAL DIOLS IN AQUEOUS ENVIRONMENTAL ORGANIC CHEMISTRY

    EPA Science Inventory

    Organic chemistry textbooks generally treat geminal diols as curiosities-exceptions to the stability of the C=O double bond. However, most aldehydes of environmental significance, to wit, trichloroethanal (chloral), methanala (formaldehyde), ethanal (acetaldehyde), and propanal ...

  20. Heterogeneous Chemistry of Carbonyls and Alcohols With Sulfuric Acid: Implications for Secondary Organic Aerosol Formation

    NASA Astrophysics Data System (ADS)

    Zhao, J.; Levitt, N.; Zhang, R.

    2006-12-01

    Recent environmental chamber studies have suggested that acid-catalyzed particle-phase reactions of organic carbonyls lead to multifold increases in secondary organic aerosol (SOA) mass and acid-catalyzed reactions between alcohols and aldehydes in the condensed phase lead to the formation of hemiacetals and acetals, also enhancing secondary organic aerosol growth. The kinetics and mechanism of the heterogeneous chemistry of carbonyls and alcohols with sulfuric acid, however, remain largely uncertain. In this talk, we present measurements of heterogeneous uptake of several carbonyls and alcohols on liquid H2SO4 in a wide range of acid concentrations and temperatures. The results indicate that uptake of larger carbonyls is explained by aldol condensation. For small dicarbonyls, heterogeneous reactions are shown to decrease with acidity and involve negligible formation of sulfate esters. Hydration and polymerization likely explain the measured uptake of such small dicarbonyls on H2SO4 and the measurements do not support an acid- catalyzed uptake. Atmospheric implications from our findings will be discussed.

  1. Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds.

    PubMed

    Zhang, Lanjun; Li, Zenghua; Li, Jinhu; Zhou, Yinbo; Yang, Yongliang; Tang, Yibo

    2015-12-11

    This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30°C to 80°C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80°C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO₂ being released at 130°C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS). The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What's more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal.

  2. Aqueous organic dye discoloration induced by contact glow discharge electrolysis.

    PubMed

    Wang, Lei

    2009-11-15

    In this study, effects of applied voltage, types of electrolytes, initial substrate concentration, radical scavengers and iron salts on the aqueous polar brilliant B (PBB) discoloration induced by contact glow discharge electrolysis (CGDE) were examined. Experimental results showed that the PBB discoloration proceeded faster in chloride solution than in phosphate or sulfate solutions. Increasing the applied voltage from 450V to 550V did not enhance the discoloration when the applied current was kept constant. Addition of a small amount of hydroxyl scavengers (methanol) to the solution decreased the discoloration, whereas addition of a large amount of methanol increased the discoloration. During the treatment, TOC of the solution smoothly decreased whereas COD of the solution gradually increased due to the production of H(2)O(2) in the liquid phase. Iron salts enhanced the discoloration significantly due to the additional Fenton reaction. Higher initial PBB concentration resulted in lower color removal efficiency, indicating that the PBB discoloration by CGDE did not observe the first-order reaction kinetics in inert electrolytic solutions.

  3. Morphologies of mixed organic/inorganic/aqueous aerosol droplets.

    PubMed

    Song, Mijung; Marcolli, Claudia; Krieger, Ulrich K; Lienhard, Daniel M; Peter, Thomas

    2013-01-01

    Despite major progress in the understanding of properties of tropospheric aerosol particles, it remains challenging to understand their physical state and morphology. To obtain more detailed knowledge of the phases, phase transitions and morphologies of internally mixed organic/inorganic aerosol particles, we evaluated liquid-liquid phase separation (LLPS), deliquescence relative humidity (DRH) and efflorescence relative humidity (ERH) of 33 organic/ammonium sulfate (AS)/H2O systems from our own and literature data. The organic fraction consists of single compounds or mixtures with up to ten aliphatic and/or aromatic components with carboxylic acid, hydroxyl, carbonyl, ether, and ester functionalities, covering O : C ratios between 0.29 and 1.33. Thirteen out of these 33 systems did not show LLPS for any of the studied organic-to-inorganic mixing ratios, sixteen underwent LLPS showing core-shell morphology, and four showed both core-shell and partially engulfed configurations depending on the organic-to-inorganic ratio and RH. In all cases the organic fractions of the systems with partially engulfed configurations consisted of dicarboxylic acids. AS in mixed organic/AS/H2O particles deliquesced between 70 and 84% RH. AS effloresced below 58% RH or remained in a one-liquid-phase state. AS in droplets with LLPS always showed efflorescence with ERH between 30 and 50% RH, providing clear evidence that the presence of LLPS facilitates AS efflorescence. Spreading coefficients of the organic-rich phase on the AS-rich phase for systems containing polyethylene glycol 400 (PEG-400) and a mixture of dicarboxylic acids are in agreement with the optically observed morphologies of droplets deposited on the hydrophobic substrate. Analysis of high resolution elastic Mie resonance spectra allowed the detection of LLPS for single levitated droplets consisting of PEG-400/AS/ H2O, whereas LLPS was difficult to detect in (2-methylglutaric acid + 3-methylglutaric acid + 2

  4. Sulfur MIF, Organic Haze, and the Gaia Hypothesis in the Archean

    NASA Astrophysics Data System (ADS)

    Domagal-Goldman, S.; James, K. F.

    2006-05-01

    The presence of mass-independent fractionation (MIF) of sulfur isotopes in Archean sedimentary rocks provides evidence for a low-O2 atmosphere prior to 2.4 Ga. Recent data suggest that S-MIF vanished transiently between ~3.2 Ga and 2.8 Ga. The absence of S-MIF after 2.4 Ga is commonly attributed to the rise of O2 in the atmosphere, as the presence of free O2 would have oxidized all sulfur species, thereby erasing any MIF created by atmospheric photochemistry. However, if free O2 did not appear in the atmosphere until 2.4 Ga, then why did S-MIF disappear transiently much earlier? Could S-MIF have been eliminated from the rock record without the presence of free atmospheric O2? We used a 1-dimensional photochemical model to demonstrate how this might have happened. Increasing the CH4/CO2 ratio in the model atmosphere results in the formation of organic haze. If the haze was sufficiently thick, it would have blocked out much of the solar UV radiation shortward of 220 nm that dissociates SO2 and SO, and thereby causes MIF. The haze should also have caused anti-greenhouse cooling and may have triggered the (putative) 2.8-Ga glaciations. Speculatively, an increase in CH4 at 3.0 Ga could have been caused by the evolution of methanogens, while a CH4 decrease at 2.7 Ga could correspond to the evolution of cyanobacteria. The presence of an optically thin organic haze between 2.4 and 2.7 Ga may explain the larger S-MIF values seen at this time, as compared to the early Archean. If such an organic haze existed, it could have resulted in a biologically-mediated negative feedback loop that stabilized the Archean climate. This feedback loop would have operated as follows: an increase in the biological CH4 flux would have led to an increase in haze thickness and a stronger anti-greenhouse effect, cooling the surface. The surface cooling would have caused a reduction of methanogen productivity, thus offsetting the original increase in the CH4 flux. Such stabilizing feedbacks

  5. Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of N-acetyl homocysteine thiolactone by acidified bromate and aqueous bromine.

    PubMed

    Mbiya, Wilbes; Choi, Boyoung; Martincigh, Bice S; Morakinyo, Moshood K; Simoyi, Reuben H

    2013-12-12

    N-acetyl homocysteine thiolactone (NAHT), medically known as citiolone, can be used as a mucolytic agent and for the treatment of certain hepatic disorders. We have studied the kinetics and mechanisms of its oxidation by acidic bromate and aqueous bromine. In acidic bromate conditions the reaction is characterized by a very short induction period followed by a sudden and rapid formation of bromine and N-acetyl homocysteine sulfonic acid. The stoichiometry of the bromate-NAHT reaction was deduced to be: BrO3(-) + H2O + CH3CONHCHCH2CH2SCO → CH3CONHCHCH2CH2(SO3H)COOH + Br(-) (S1) while in excess bromate it was deduced to be: 6BrO3(-) + 5CH3CONHCHCH2CH2SCO + 6H(+) → 3Br2 + 5CH3CONHCHCH2CH2(SO3H)COOH + 2H2O (S2). For the reaction of NAHT with bromine, a 3:1 stoichiometric ratio of bromine to NAHT was obtained: 3Br2 + CH3CONHCHCH2CH2SCO + 4H2O → 6Br(-) + CH3CONHCHCH2CH2(SO3H)COOH + 6H(+) (S3). Oxidation occurred only on the sulfur center where it was oxidized to the sulfonic acid. No sulfate formation was observed. The mechanism involved an initial oxidation to a relatively stable sulfoxide without ring-opening. Further oxidation of the sulfoxide involved two pathways: one which involved intermediate formation of an unstable sulfone and the other involves ring-opening coupled with oxidation through to the sulfonic acid. There was oligooscillatory production of aqueous bromine. Bromide produced in S1 reacts with excess bromate to produce aqueous bromine. The special stability associated with the sulfoxide allowed it to coexist with aqueous bromine since its further oxidation to the sulfone was not as facile. The direct reaction of aqueous bromine with NAHT was fast with an estimated lower limit bimolecular rate constant of 2.94 ± 0.03 × 10(2) M(-1) s(-1).

  6. Vhf EPR analysis of organic sulfur in coal. [Quarterly] technical report, March 1, 1992--May 31, 1992

    SciTech Connect

    Clarkson, R.B.; Belford, R.L.

    1992-10-01

    This third quarterly report of the project`s first year reports that, consonant with our research goals, we have refined the quantitative measurement of organic sulfur in coals, and extended this technique to analysis of treated and desulfurized coals, using either low temperature pyrolysis in our labs, or other techniques as supplied by DOE-PETC. The evolution of the central carbon and downfield sulfur peak amplitudes vs pyrolysis temperature support both the hypothesis of increase in aromatic carbon radicals and the evolution of some sulfur, even at low temperatures. The examination of evacuation effects, and differentiation of species by microwave power saturation levels and second derivative W-band detection also continued. Finally, model sulfur-containing carbonaceous solids -- chars from sucrose or cellulose, and various model sulfur compounds (elemental, mono- and di-thiophenic, and thiosulfidal) - are under development. Already, the W-band spectra of some of these char models show striking similarities to those of whole and treated coals. The further development of these models in conjunction with all other aspects of this program are progressing steadily toward the goal of better quantitative md qualitative differentiation of aromatic heteroatoms in coal.

  7. Malodorous volatile organic sulfur compounds: Sources, sinks and significance in inland waters.

    PubMed

    Watson, Susan B; Jüttner, Friedrich

    2017-03-01

    Volatile Organic Sulfur Compounds (VOSCs) are instrumental in global S-cycling and greenhouse gas production. VOSCs occur across a diversity of inland waters, and with widespread eutrophication and climate change, are increasingly linked with malodours in organic-rich waterbodies and drinking-water supplies. Compared with marine systems, the role of VOSCs in biogeochemical processes is far less well characterized for inland waters, and often involves different physicochemical and biological processes. This review provides an updated synthesis of VOSCs in inland waters, focusing on compounds known to cause malodours. We examine the major limnological and biochemical processes involved in the formation and degradation of alkylthiols, dialkylsulfides, dialkylpolysulfides, and other organosulfur compounds under different oxygen, salinity and mixing regimes, and key phototropic and heterotrophic microbial producers and degraders (bacteria, cyanobacteria, and algae) in these environs. The data show VOSC levels which vary significantly, sometimes far exceeding human odor thresholds, generated by a diversity of biota, biochemical pathways, enzymes and precursors. We also draw attention to major issues in sampling and analytical artifacts which bias and preclude comparisons among studies, and highlight significant knowledge gaps that need addressing with careful, appropriate methods to provide a more robust understanding of the potential effects of continued global development.

  8. Isotopic evidence for determining the sources of dissolved organic sulfur in a forested catchment.

    PubMed

    Kang, Phil-Goo; Mitchell, Myron J; Mayer, Bernhard; Campbell, John L

    2014-10-07

    Understanding sulfur (S) biogeochemistry, especially in those watersheds subject to elevated levels of atmospheric S inputs, is needed for determining the factors that contribute to acidification, nutrient losses and the mobilization of toxic solutes (e.g., monomeric aluminum and methylmercury). S is found in a variety of both organic and inorganic forms undergoing a range of biotic and abiotic transformations. In watersheds with decreasing atmospheric S inputs, internal cycling is becoming dominant in affecting whether there is net loss or retention of S. Little attention has been given to the role of dissolved organic S (DOS) in affecting S biogeochemistry. DOS originates from assimilatory and bacterial dissimilatory S reduction (BDSR), the latter of which produces (34)S-depleted S. Within groundwater of the Archer Creek Catchment in the Adirondack Mountains (New York) there was reoxidation of reduced S, which was an important source of SO4(2-). DOS in surface waters had a higher variation of δ(34)S-DOS values (-6.0 to +8.4‰) than inorganic S with δ(34)S-SO4(2-) values ranging from +1.0 to +5.8‰. Inverse correlations between δ(34)S values of SO4(2-) and DOS suggested that BDSR played an important role in producing DOS.

  9. Complexation of zinc in organic soils--EXAFS evidence for sulfur associations.

    PubMed

    Karlsson, Torbjörn; Skyllberg, Ulf

    2007-01-01

    Even if it is generally accepted that associations with natural organic matter (NOM) to a great extent determine the bioavailability and mobility of trace metals in soils and waters, the knowledge about the identity of NOM functional groups involved is still limited. In this study, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the coordination chemistry of zinc (Zn) in two organic soils (500-10,000 microg Zn g(-), pH 5.6-7.3). In both soils Zn was coordinated by a mixture of oxygen/nitrogen (O/N) and sulfur (S) ligands in the first coordination shell. In average, 0.4-0.9 S atoms were located at a distance of 2.29-2.33 angstom, well in agreement with a 4-fold coordination with thiolates (RS-) in proteins. In addition 2.7-3.7 O/N atoms were located at 1.99-2.04 angstrom. The improved merit of fit by inclusion of S atoms was shown to be significant after adjusting for the improvement caused merely by increasing the number of fitting parameters. Two second shell Zn-C distances were used in our model: 3.0-4.2 carbon (C) atoms, associated to first shell O/N, were encountered at an average distance of 2.84 amgstrom, and 0.4-0.9 C atoms, associated to first shell S, were encountered at an average distance of 3.32 angstrom. These Zn-C distances are well in agreement with distances determined in well-defined organic molecules. It is concluded that Zn forms mainly inner-sphere complexes with a mixture of 4-fold coordination with S and O/N ligands and 6-fold coordination with O ligands in organic soils.

  10. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

    2013-01-01

    The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  11. Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

    2012-09-01

    The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

  12. Quantification of volatile-alkylated selenium and sulfur in complex aqueous media using solid-phase microextraction.

    PubMed

    Vriens, Bas; Mathis, Marcel; Winkel, Lenny H E; Berg, Michael

    2015-08-14

    Biologically produced volatile-alkylated Se and S compounds play an important role in the global biogeochemical Se and S cycles, are important constituents of odorous industrial emissions, and contribute to (off-)flavors in food and beverages. This study presents a fully automated direct-immersion solid-phase microextraction (DI-SPME) method coupled with capillary gas chromatography-mass spectrometry (GC/MS) for the simultaneous quantification of 10 volatile-alkylated Se and S compounds in complex aqueous media. Instrumental parameters of the SPME procedure were optimized to yield extraction efficiencies of up to 96% from complex aqueous matrices. The effects of sample matrix composition and analyte transformation during sample storage were critically assessed. With the use of internal standards and procedural calibrations, the DI-SPME-GC/MS method allows for trace-level quantification of volatile Se and S compounds in the ng/L range (e.g. down to 30 ng/L dimethyl sulfide and 75 ng/L dimethyl selenide). The applicability and robustness of the presented method demonstrate that the method may be used to quantify volatile Se and S compounds in complex aqueous samples, such as industrial effluents or food and beverage samples.

  13. Method for removing and decolorizing aqueous waste effluents containing dissolved or dispersed organic matter

    DOEpatents

    Case, F.N.; Ketchen, E.E.

    1975-10-14

    A method is provided for treating organic waste material dissolved or dispersed in an aqueous effluent, which comprises contacting the effluent with an inert particulate carbonaceous sorbent at an oxygen pressure up to 2000 psi, irradiating the resultant mixture with high energy radiation until a decolorized liquid is produced, and then separating the decolorized liquid.

  14. Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction

    DOE PAGES

    Ren, Shoujie; Ye, Philip; Borole, Abhijeet P

    2017-01-05

    Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less

  15. Aggregation of Montmorillonite and Organic Matter in Aqueous Media Containing Artificial Seawater

    DTIC Science & Technology

    2009-01-23

    laboratory kaolinite and montmorillonite aggregation in which the dispersion-aggregation properties of pure clay suspensions were found to be primarily...Article 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Aggregation of montmorillonite and organic matter in aqueous media containing...properties of suspended colloids and aggregates) were determined for systems containing suspended montmorillonite , humic acid, and/or chitin at the

  16. Aqueous phase sensing of cyanide ions using a hydrolytically stable metal-organic framework.

    PubMed

    Karmakar, Avishek; Joarder, Biplab; Mallick, Abhik; Samanta, Partha; Desai, Aamod V; Basu, Sudipta; Ghosh, Sujit K

    2017-01-19

    A pure aqueous phase recognition and corresponding detoxification of highly toxic cyanide ions has been achieved by a fluorescent metal-organic framework (MOF). The cyanide detoxification has been shown to be effective even in in vitro studies and the MOF could be recycled to show the same efficiency of detoxification.

  17. Single step signal group-imidazole labeling of organic phosphate groups under aqueous conditions

    DOEpatents

    Giese, R.W.; Wang, P.

    1996-04-30

    Compounds and methods for single step, covalent labeling of the phosphate group of an organic substance under aqueous conditions are described. The labeling compound includes any kind of detectable signal group covalently bound to an imidazole moiety, which can be imidazole or a substituted imidazole. A preferred labeling compound has the formula shown in the accompanying diagram. 4 figs.

  18. Single step signal group-imidazole labeling of organic phosphate groups under aqueous conditions

    DOEpatents

    Giese, Roger W.; Wang, Poguang

    1996-01-01

    Compounds and methods for single step, covalent labeling of the phosphate group of an organic substance under aqueous conditions are described. The labeling compound includes any kind of detectable signal group covalently bound to an imidazole moiety, which can be imidazole or a substituted imidazole. A preferred labeling compound has the formula ##STR1##

  19. High organic sulfur removal performance of a cobalt based metal-organic framework.

    PubMed

    Bagheri, Minoo; Masoomi, Mohammad Yaser; Morsali, Ali

    2017-06-05

    Synthesis of a new porous cobalt based metal-organic framework, [Co6(oba)6(CH3O)4(O)2]n·3DMF (TMU-11) has been carried out to introduce a new and highly efficient adsorbent of dibenzothiophene (DBT). This compound has been synthesized by solvothermal method using a nonlinear dicarboxylate ligand and characterized by single-crystal X-ray crystallography. To study the adsorption properties of the synthesized compound, TMU-11, for DBT removal, various factors, such as amount of adsorbent, contact time and temperature were examined. On the basis of the results, maximum efficiency and reusability in DBT removal occur under the mild reaction conditions. Furthermore, the DBT removal follows the pseudo-second order reaction kinetic. The maximum adsorption value is 825mg/g. The selectivity test of DBT over naphthalene (NA) clearly shows that π-π interactions between organic linkers of TMU-11 and the aromatic ring of DBT are not responsible for the adsorption desulfurization (ADS) process and the main part of adsorption takes place on unsaturated site around Co centres. Our findings may provide some insight into the preparation of the adsorbent with superior performance in practical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  20. Solubility of sulfur dioxide in aqueous solutions of acetic acid, sodium acetate, and ammonium acetate in the temperature range from 313 to 393 K at pressures up to 3.3 MPa: Experimental results and comparison with correlations/predictions

    SciTech Connect

    Xia, J.; Rumpf, B.; Maurer, G.

    1999-03-01

    In many chemical plants, for example in coal gasification processes or desulfurization equipment, sour gas absorption columns and sour water strippers are used to remove weak electrolyte gases like sulfur dioxide, hydrogen cyanide, hydrogen sulfide or carbon dioxide from aqueous solutions. The basic design of such equipment requires physico-chemical models to describe the phase equilibrium as well as the caloric properties of such mixtures. New experimental results for the solubility of sulfur dioxide in aqueous solutions of single solutes acetic acid, sodium acetate and ammonium acetate at temperatures from 313 to 393 K and total pressures up to 3.3 MPa are reported. Similar to the system sulfur dioxide-water, also in such systems with acetic acid and sodium or ammonium acetate a second (sulfur dioxide rich) liquid phase is observed at high sulfur dioxide concentrations. A model to describe the phase equilibrium is presented and calculated (i.e., predicted as well as correlated) phase equilibria are compared to the new experimental data.

  1. A non-aqueous procedure to synthesize amino group bearing nanostructured organic-inorganic hybrid materials.

    PubMed

    Göring, M; Seifert, A; Schreiter, K; Müller, P; Spange, S

    2014-09-04

    Amino-functionalized organic-inorganic hybrid materials with a narrow distributed nanostructure of 2-4 nm in size were obtained by means of a template-free and non-aqueous procedure. Simultaneous twin polymerization of novel amino group containing twin monomers with 2,2'-spirobi[4H-1,3,2-benzodioxasiline] has been applied for this purpose. The amino groups of the organic-inorganic hybrid material are useful for post derivatization.

  2. Micro-organization of humic acids in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Klučáková, Martina; Věžníková, Kateřina

    2017-09-01

    The methods of dynamic light scattering and micro-rheology were used to investigate the molecular organization of humic acids in solutions. The obtained results were supplemented by ultraviolet/visible spectrometry and measurement of the zeta potential. Particle tracking micro-rheology was used for the first time as a novel method in humic research. Solutions of humic acids were prepared in three different mediums: NaOH, NaCl, and NaOH neutralized by HCl after dissolution of the humic sample. The molecular organization of humic acids was studied over a wide concentration range (0.01-10 g dm-3). Two breaks were detected in the obtained concentration dependencies. The rearrangements were observed at concentrations around 0.02 g dm-3 and 1 g dm-3. Changes in the measured values observed at around 0.02 g dm-3 were less noticeable and were related to the formation of particles between 100 and 1000 nm in size and the strong bimodal character of humic systems diluted by NaCl. The ;switch-over point; at around 1 g dm-3 indicated changes in the secondary structure of humic acids connected with the increase in colloidal stability (decrease of zeta potential), the decrease in polydispersity, and minimal values of viscosity.

  3. Mid-Infrared Sensing of Organic Pollutants in Aqueous Environments

    PubMed Central

    Pejcic, Bobby; Myers, Matthew; Ross, Andrew

    2009-01-01

    The development of chemical sensors for monitoring the levels of organic pollutants in the aquatic environment has received a great deal of attention in recent decades. In particular, the mid-infrared (MIR) sensor based on attenuated total reflectance (ATR) is a promising analytical tool that has been used to detect a variety of hydrocarbon compounds (i.e., aromatics, alkyl halides, phenols, etc.) dissolved in water. It has been shown that under certain conditions the MIR-ATR sensor is capable of achieving detection limits in the 10–100 ppb concentration range. Since the infrared spectral features of every single organic molecule are unique, the sensor is highly selective, making it possible to distinguish between many different analytes simultaneously. This review paper discusses some of the parameters (i.e., membrane type, film thickness, conditioning) that dictate MIR-ATR sensor response. The performance of various chemoselective membranes which are used in the fabrication of the sensor will be evaluated. Some of the challenges associated with long-term environmental monitoring are also discussed. PMID:22454582

  4. The surface tension of aqueous solutions of some atmospheric water-soluble organic compounds

    NASA Astrophysics Data System (ADS)

    Tuckermann, Rudolf; Cammenga, Heiko K.

    The surface tensions of aqueous solutions of levoglucosan, 3-hydroxybutanoic acid, 3-hydroxybenzoic acid, azelaic acid, pinonic acid, and humic acid have been measured. These compounds are suggested as model substances for the water-soluble organic compounds (WSOC) in atmospheric aerosols and droplets which may play an important role in the aerosol cycle because of their surface-active potentials. The reductions in surface tension induced by single and mixed WSOC in aqueous solution of pure water is remarkable. However, the results of this investigation cannot explain the strong reduction in surface tension in real cloud and fog water samples at concentrations of WSOC below 1 mg/mL.

  5. A Bifunctional Dimethylsulfoxide Substitute Enhances the Aqueous Solubility of Small Organic Molecules

    PubMed Central

    Sprachman, Melissa M.

    2012-01-01

    Abstract An oxetane-substituted sulfoxide has demonstrated potential as a dimethylsulfoxide substitute for enhancing the dissolution of organic compounds with poor aqueous solubilities. This sulfoxide may find utility in applications of library storage and biological assays. For the model compounds studied, significant solubility enhancements were observed using the sulfoxide as a cosolvent in aqueous media. Brine shrimp, breast cancer (MDA-MB-231), and liver cell line (HepG2) toxicity data for the new additive are also presented, in addition to comparative IC50 values for a series of PKD1 inhibitors. PMID:22192308

  6. Homogeneously catalyzed oxidation for the destruction of aqueous organic wastes

    SciTech Connect

    Leavitt, D.D.; Horbath, J.S.; Abraham, M.A. )

    1990-11-01

    Several organic species, specifically atrazine, 2,4-dichlorophenozyacetic acid, and biphenyl, were converted to CO{sub 2} and other non-harmful gases through oxidation catalyzed by inorganic acid. Nearly complete conversion was obtained through homogeneous liquid-phase oxidation with ammonium nitrate. The kinetics of reaction have been investigated and indicate parallel oxidation and thermal degradation of the oxidant. This results in a maximum conversion at an intermediate temperature. Increasing oxidant concentration accelerates the rate of conversion and shifts the location of the optimum temperature. Reaction at varying acid concentration revealed that conversion increased with an approximately linear relationship as the pH of the solution was increased. Conversion was increased to greater than 99% through the addition of small amounts of transition metal salts demonstrating the suitability of a treatment process based on this technology for wastestreams containing small quantities of heavy metals.

  7. Measurements of thermodynamic and optical properties of selected aqueous organic and organic-inorganic mixtures of atmospheric relevance.

    PubMed

    Lienhard, Daniel M; Bones, David L; Zuend, Andreas; Krieger, Ulrich K; Reid, Jonathan P; Peter, Thomas

    2012-10-11

    Atmospheric aerosol particles can exhibit liquid solution concentrations supersaturated with respect to the dissolved organic and inorganic species and supercooled with respect to ice. In this study, thermodynamic and optical properties of sub- and supersaturated aqueous solutions of atmospheric interest are presented. The density, refractive index, water activity, ice melting temperatures, and homogeneous ice freezing temperatures of binary aqueous solutions containing L(+)-tartaric acid, tannic acid, and levoglucosan and ternary aqueous solutions containing levoglucosan and one of the salts NH(4)HSO(4), (NH(4))(2)SO(4), and NH(4)NO(3) have been measured in the supersaturated concentration range for the first time. In addition, the density and refractive index of binary aqueous citric acid and raffinose solutions and the glass transition temperatures of binary aqueous L(+)-tartaric acid and levoglucosan solutions have been measured. The data presented here are derived from experiments on single levitated microdroplets and bulk solutions and should find application in thermodynamic and atmospheric aerosol models as well as in food science applications.

  8. Selection of Xenobiotic-Degrading Microorganisms in a Biphasic Aqueous-Organic System

    PubMed Central

    Ascon-Cabrera, Miguel; Lebeault, Jean-Michel

    1993-01-01

    Microbial selection on mixtures of chlorinated and nonchlorinated compounds that are poorly soluble in water and/or toxic to growing microbial cells was examined in both biphasic aqueous-organic and monophasic aqueous systems. A biphasic system in which silicone oil was used as the organic phase permitted the acceleration of acclimation, leading to rapid selection and to an increase in xenobiotic compound degradation. In contrast, acclimation, selection, and degradation were very slow in the monophasic aqueous system. The variation in microbial growth rate with the degree of dispersion (i.e., dispersion at different silicone oil concentrations and agitation rates), and cell adhesion to the silicone oil indicate that the performance of the biphasic aqueous-organic system is dependent on the interfacial area between the two phases and that microbial activity is important at this interface. Therefore, the biphasic water-silicone oil system could be used for microbial selection in the presence of xenobiotic compounds that are toxic and have low water solubility. PMID:16348949

  9. Aqueous Reaction of Dicarbonyls with Ammonia as a Potential Source of Organic Nitrogen in Airborne Nanoparticles.

    PubMed

    Stangl, Christopher M; Johnston, Murray V

    2017-05-18

    Nitrogen-containing organic species such as imines and imidazoles can be formed by aqueous reactions of carbonyl-containing compounds in the presence of ammonia. In the work described here, these reactions are studied in airborne aqueous nanodroplets containing ammonium sulfate and glyoxal, methylglyoxal, or glycolaldehyde using a combination of online and offline mass spectrometry. N/C ratios attributed to the organic fraction of the particles (N/Corg) produced from glyoxal and methylglyoxal were quantified across a wide relative humidity (RH) range. As the RH was lowered, glyoxal was found to increase N/Corg, attributed to "salting-in" with increasing solute concentration, while methylglyoxal led to a decrease in N/Corg, attributed to "salting-out". Glycolaldehyde was found to evaporate from the droplets rather than react in the aqueous phase and did not form particulate-phase organic matter from aerosol drying under any of the conditions studied. The results are discussed in the context of ambient nanoparticle composition measurements and suggest that aqueous chemistry may significantly impact nanoparticle composition and growth during new particle formation in locations where emissions of water-soluble dicarbonyls are high, such as the eastern United States.

  10. The abiotic degradation of methyl parathion in anoxic sulfur-containing system mediated by natural organic matter.

    PubMed

    Liao, Xiaoping; Zhang, Caixiang; Wang, Yanxin; Tang, Mi

    2017-06-01

    Although the kinetics and transformation of methyl parathion have been investigated extensively, its abiotic degradation mechanism in anoxic sulfur-containing groundwater system is still not clear. In this work, the abiotic degradation of methyl parathion in anoxic sulfur-containing system mediated by natural organic matter (NOM) was investigated in batch experiments. It was found that the removal of methyl parathion (up to 80.7%) was greatly improved in sulfide containing NOM compared to those in sulfide alone (with 15.5%) and in NOM alone (almost negligible). Various sulfur species presented significant differences in behaviors methyl parathion degradation, but followed by the pseudo-first-order model well. No facilitated degradation of methyl parathion was observed in sulfite (SO3(2-)) or thiosulfate (S2O3(2-)) containing NOM such as anthraquinone. Although elemental sulfur (S(0)) and cysteine could further improve the degradation rate of methyl parahtion, their impacts was very limited. The removal efficiency of methyl parathion in anoxic sulfur-containing system were related remarkably with NOM concentration and solution pH. Based on the transformation products identified by gas chromatography-mass spectrometer (GC/MS) and liquid chromatography high resolution mass spectrometer (LC/HRMS), both the nitro group reduction and hydrolysis (SN@C) processes by sulfide (HS(-)) were further proved to be two predominant reaction mechanisms for the abiotic degradation of methyl parathion in anoxic sulfur-containing system. The results of this study help to understand the natural attenuation of methyl parathion under anoxic sulfide-containing groundwater system mediated by NOM.

  11. NOCHAR Polymers: An Aqueous and Organic Liquid Solidification Process for Cadarache LOR (Liquides Organiques Radioactifs) - 13195

    SciTech Connect

    Vaudey, Claire-Emilie; Renou, Sebastien; Porco, Julien; Kelley, Dennis; Cochaud, Chantal

    2013-07-01

    To handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW) in France, two options can be considered: the incineration at CENTRACO facility and the disposal facility on ANDRA sites. The waste acceptance in these radwaste routes is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the radwaste route specifications. If the waste characteristics are incompatible with the radwaste route specifications (presence of significant quantities of chlorine, fluorine, organic component etc or/and high activity limits), it is necessary to find an alternative solution that consists of a waste pre-treatment process. In the context of the problematic Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. The first one is composed of organic liquids at 13.1 % (diphenyloxazol, mesitylene, TBP, xylene) and water at 86.9 %. The second one is composed of TBP at 8.6 % and water at 91.4 %. They contain chlorine, fluorine and sulphate and have got alpha/beta/gamma spectra with mass activities equal to some kBq.g{sup -1}. Therefore, tritium is present and creates the second problematic waste stream. As a consequence, in order for disposal acceptance at the ANDRA site, it is necessary to pre-treat the waste. The NOCHAR polymers as an aqueous and organic liquid solidification process seem to be an adequate solution. Indeed, these polymers constitute an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing etc) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and immobilise the liquid. Then as the

  12. VHF EPR analysis of organic sulfur in coal. [Quarterly] technical report, September 1--November 20, 1991

    SciTech Connect

    Clarkson, R.B.

    1991-12-31

    This report covers progress made in the first yearly quarter of a two year investigation using novel, very high frequency electron paramagnetic resonance (VHF EPR) spectroscopy techniques and instrumentation (one of only two W-band spectrometers in existence) developed earlier by these authors, to conduct further qualitative and quantitative studies of heteroatomic organic molecules in coal with particular emphasis on sulfur. Previous W-band (96 GHz) work is being extended to studies of new model compounds as well as coal and desulfurized coal samples. Typically, the model compounds under investigation and their analogues are found in coals as stable free radicals which give rise to an EPR signal. The preparation of radicals from compounds having widely varying structures and physical properties in a stable environment has long been a very difficult task. To address this problem, the refinement of several new and very useful methods of preparing of these stable free radicals in various glasses, at catalytic surfaces, and in solution, are presented in this first report. Free radical generation was accomplished by both UV photolysis as well as chemical oxidation/reduction techniques. By these methods, over 25 new compounds, often commercially derived from coal extracts, have been prepared and studied by conventional X-band EPR (9 GHz). Several representative W-band spectra are also presented.

  13. Measurements of Volatile Organic Compounds and Gaseous Sulfuric Acid During the 2008 CAREBEIJING Campaign

    NASA Astrophysics Data System (ADS)

    Zhang, R.; Zheng, J.; Hu, M.; Zhu, T.

    2009-05-01

    Air quality in Beijing has been a hot topic recently, because Beijing hosted the 2008 summer Olympics. To combat the problem, China ordered numerous factories shut down or used only sporadically during the games to limit air pollution in the area. Another major step involved ordering about one-half of the city's 3.3 million vehicles off the road during the games, allowing only cars on roads with odd or even-numbered license plates on alternate days until the games were over. In addition, China has implemented new auto emission standards since March 2009 with regulations that are similar to those used throughout Europe. Our team at the Texas A&M participated in the 2008 CAREBEIJING campaign, with the objectives of studying the complex chemistry of the air in Beijing, looking at emission controls and their effectiveness, studying the surrounding air from other regions and how it can affect Beijing's air, and comparing all of our findings with air quality in other cities we have examined, such as Mexico City and Houston. In this talk, preliminary results of measurements of volatile organic compounds (VOCs) and gaseous sulfuric acid will be presented to discuss the trends of VOCs and new particle formation associated with the traffic control.

  14. Volatile organic sulfur compounds in anaerobic sludge and sediments: biodegradation and toxicity.

    PubMed

    van Leerdam, Robin C; de Bok, Frank A M; Lomans, Bart P; Stams, Alfons J M; Lens, Piet N L; Janssen, Albert J H

    2006-12-01

    A variety of environmental samples was screened for anaerobic degradation of methanethiol, ethanethiol, propanethiol, dimethylsulfide, and dimethyldisulfide. All sludge and sediment samples degraded methanethiol, dimethylsulfide, and dimethyldisulfide anaerobically. In contrast, ethanethiol and propanethiol were not degraded by the samples investigated under any of the conditions tested. Methanethiol, dimethylsulfide, and dimethyldisulfide were mainly degraded by methanogenic archaea. In the presence of sulfate and the methanogenic inhibitor bromoethane sulfonate, degradation of these compounds coupled to sulfate reduction occurred as well, but at much lower rates. Besides their biodegradability, also the toxicity of methanethiol, ethanethiol, and propanethiol to methanogenesis with methanol, acetate, and H2/CO2 as the substrates was assessed. The 50% inhibition concentration of methanethiol on the methane production from these substrates ranged between 7 and 10 mM. The 50% inhibition concentration values of ethanethiol and propanethiol for the degradation of methanol and acetate were between 6 and 8 mM, whereas hydrogen consumers were less affected by ethanethiol and propanethiol, as indicated by their higher 50% inhibition concentration (14 mM). Sulfide inhibited methanethiol degradation already at relatively low concentrations: methanethiol degradation was almost completely inhibited at an initial sulfide concentration of 8 mM. These results define the operational limits of anaerobic technologies for the treatment of volatile organic sulfur compounds in sulfide-containing wastewater streams.

  15. Process for preparing organoclays for aqueous and polar-organic systems

    DOEpatents

    Chaiko, David J.

    2001-01-01

    A process for preparing organoclays as thixotropic agents to control the rheology of water-based paints and other aqueous and polar-organic systems. The process relates to treating low-grade clay ores to achieve highly purified organoclays and/or to incorporate surface modifying agents onto the clay by adsorption and/or to produce highly dispersed organoclays without excessive grinding or high shear dispersion. The process involves the treatment of impure, or run-of-mine, clay using an aqueous biphasic extraction system to produce a highly dispersed clay, free of mineral impurities and with modified surface properties brought about by adsorption of the water-soluble polymers used in generating the aqueous biphasic extraction system. This invention purifies the clay to greater than 95%.

  16. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2014-06-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~275 to ~400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures with the introduction of a new temperature dependence parameterisation. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multicomponent system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~190 to ~440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 25% in comparison to

  17. Evidence for organic synthesis in high temperature aqueous media - facts and prognosis

    NASA Technical Reports Server (NTRS)

    Simoneit, Bernd R. T.

    1995-01-01

    Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to greater than 400 C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. The reactivity of organic compounds in hot water (200-350 C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to greater than 400 C.

  18. Evidence for organic synthesis in high temperature aqueous media - facts and prognosis

    NASA Technical Reports Server (NTRS)

    Simoneit, Bernd R. T.

    1995-01-01

    Hydrothermal systems are common along the active tectonic areas of the earth. Potential sites being studied for organic matter alteration and possible organic synthesis are spreading ridges, off-axis systems, back-arc activity, hot spots, volcanism, and subduction. Organic matter alteration, primarily reductive and generally from immature organic detritus, occurs in these high temperature and rapid fluid flow hydrothermal regimes. Hot circulating water (temperature range - warm to greater than 400 C) is responsible for these molecular alterations, expulsion and migration. Compounds that are obviously synthesized are minor components because they are generally masked by the pyrolysis products formed from contemporary natural organic precursors. The reactivity of organic compounds in hot water (200-350 C) has been studied in autoclaves, and supercritical water as a medium for chemistry has also been evaluated. This high temperature aqueous organic chemistry and the strong reducing conditions of the natural systems suggest this as an important route to produce organic compounds on the primitive earth. Thus a better understanding of the potential syntheses of organic compounds in hydrothermal systems will require investigations of the chemistry of condensation, autocatalysis, catalysis and hydrolysis reactions in aqueous mineral buffered systems over a range of temperatures from warm to greater than 400 C.

  19. Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter

    USGS Publications Warehouse

    Fleck, Jacob A.; Gill, Gary W.; Bergamaschi, Brian A.; Kraus, Tamara E.C.; Downing, Bryan D.; Alpers, Charles N.

    2014-01-01

    Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5 × 10-3 m2 mol-1 (s.d. 3.5 × 10-3) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg–DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

  20. Concurrent photolytic degradation of aqueous methylmercury and dissolved organic matter.

    PubMed

    Fleck, Jacob A; Gill, Gary; Bergamaschi, Brian A; Kraus, Tamara E C; Downing, Bryan D; Alpers, Charles N

    2014-06-15

    Monomethyl mercury (MeHg) is a potent neurotoxin that threatens ecosystem viability and human health. In aquatic systems, the photolytic degradation of MeHg (photodemethylation) is an important component of the MeHg cycle. Dissolved organic matter (DOM) is also affected by exposure to solar radiation (light exposure) leading to changes in DOM composition that can affect its role in overall mercury (Hg) cycling. This study investigated changes in MeHg concentration, DOM concentration, and the optical signature of DOM caused by light exposure in a controlled field-based experiment using water samples collected from wetlands and rice fields. Filtered water from all sites showed a marked loss in MeHg concentration after light exposure. The rate of photodemethylation was 7.5×10(-3)m(2)mol(-1) (s.d. 3.5×10(-3)) across all sites despite marked differences in DOM concentration and composition. Light exposure also caused changes in the optical signature of the DOM despite there being no change in DOM concentration, indicating specific structures within the DOM were affected by light exposure at different rates. MeHg concentrations were related to optical signatures of labile DOM whereas the percent loss of MeHg was related to optical signatures of less labile, humic DOM. Relationships between the loss of MeHg and specific areas of the DOM optical signature indicated that aromatic and quinoid structures within the DOM were the likely contributors to MeHg degradation, perhaps within the sphere of the Hg-DOM bond. Because MeHg photodegradation rates are relatively constant across freshwater habitats with natural Hg-DOM ratios, physical characteristics such as shading and hydrologic residence time largely determine the relative importance of photolytic processes on the MeHg budget in these mixed vegetated and open-water systems.

  1. Immobilization of trypsin in organic and aqueous media for enzymatic peptide synthesis and hydrolysis reactions.

    PubMed

    Stolarow, Julia; Heinzelmann, Manuel; Yeremchuk, Wladimir; Syldatk, Christoph; Hausmann, Rudolf

    2015-08-19

    Immobilization of enzymes onto different carriers increases enzyme's stability and reusability within biotechnological and pharmaceutical applications. However, some immobilization techniques are associated with loss of enzymatic specificity and/or activity. Possible reasons for this loss are mass transport limitations or structural changes. For this reason an immobilization method must be selected depending on immobilisate's demands. In this work different immobilization media were compared towards the synthetic and hydrolytic activities of immobilized trypsin as model enzyme on magnetic micro-particles. Porcine trypsin immobilization was carried out in organic and aqueous media with magnetic microparticles. The immobilization conditions in organic solvent were optimized for a peptide synthesis reaction. The highest carrier activity was achieved at 1 % of water (v/v) in dioxane. The resulting immobilizate could be used over ten cycles with activity retention of 90 % in peptide synthesis reaction in 80 % (v/v) ethanol and in hydrolysis reaction with activity retention of 87 % in buffered aqueous solution. Further, the optimized method was applied in peptide synthesis and hydrolysis reactions in comparison to an aqueous immobilization method varying the protein input. The dioxane immobilization method showed a higher activity coupling yield by factor 2 in peptide synthesis with a maximum activity coupling yield of 19.2 % compared to aqueous immobilization. The hydrolysis activity coupling yield displayed a maximum value of 20.4 % in dioxane immobilization method while the aqueous method achieved a maximum value of 38.5 %. Comparing the specific activity yields of the tested immobilization methods revealed maximum values of 5.2 % and 100 % in peptide synthesis and 33.3 % and 87.5 % in hydrolysis reaction for the dioxane and aqueous method, respectively. By immobilizing trypsin in dioxane, a beneficial effect on the synthetic trypsin activity resilience

  2. Sulfur cycling in freshwater sediments

    NASA Technical Reports Server (NTRS)

    Klug, M. J.

    1985-01-01

    Organic sulfur containing compounds represent greater than 80% of the total sulfur in sediments of eutrophic freshwater lakes. Although sedimentary sulfur is predominantly in the form of organic compounds, more sulfur is transformed by sulfate reduction than by any other process. Rates of sulfate reduction in these sediments average 7 mmol/sq m/day. This rate is 19 times greater than the net rate of production of inorganic sulfur from organic compounds on an annual basis.

  3. From Conventional to Phase-Sensitive Vibrational Sum Frequency Generation Spectroscopy: Probing Water Organization at Aqueous Interfaces.

    PubMed

    Verreault, Dominique; Hua, Wei; Allen, Heather C

    2012-10-18

    Elucidation of water organization at aqueous interfaces has remained a challenging problem. Conventional vibrational sum frequency generation (VSFG) spectroscopy and its most recent extension, phase-sensitive VSFG (PS-VSFG), have emerged as powerful experimental methods for unraveling structural information at various aqueous interfaces. In this Perspective, we briefly describe the two possible VSFG detection modes, and we point out features that make these methods highly suited to address questions about water organization at air/aqueous interfaces. Several important aqueous interfacial systems are discussed to illustrate the versatility of these methods. Remaining challenges and exciting prospective directions are also presented.

  4. Removal of organic and inorganic sulfur compounds by ozone and granular activated carbon

    SciTech Connect

    Shepherd, B.; Ball, G.W.

    1996-11-01

    Most groundwater supplies in the western U.S. are relatively low in dissolved organic matter, are generally free of bacteria, and are platable to their consumers. In areas of western Nevada, certain groundwaters are near active geothermal areas, which can produce sulfurous types of tastes and odors (T&Os) in the water. Other water quality characteristics can consist of either relatively low or highly mineralized waters, variations in pH, and temperatures ranging from those slightly above normal groundwaters to pressurized steam. Watersource Consulting Engineers (WCE) and Shepherd Laboratories (SL) conducted an engineering study of a high-capacity well for a local northwestern Nevada utility. WCE`s original task had been to design pumping and storage facilities for the well, in addition to evaluating basic treatment. Originally, WCE anticipated designing facilities to remove hydrogen sulfide (H{sub 2}S) and reduce color, primarily with chlorination and aeration. SL was requested to evaluate existing water quality and eventually conduct bench-scale testing of several treatment processes. As the study proceeded, the original goals were modified when it became evident that water quality conditions required more extensive evaluation. The study was done in several stages, reflecting the information gained during each stage. The final recommended design criteria included treatment for improving water quality relative to T&O, color, total organic carbon (TOC), and, to a limited extent, fluoride. The water quality goals adopted by the utility encompassed primary maximum contaminant levels (MCLs) for regulatory compliance and secondary MCLs for aesthetically pleasing water. The treatment processes evaluated and recommended in this study were designed primarily to improve the aesthetic qualities of color, taste, and odor. Fluoride reduction was evaluated but was not included in the final design requirements, except for the overall reduction provided by the recommended process.

  5. Sulfur Earth

    NASA Astrophysics Data System (ADS)

    de Jong, B. H.

    2007-12-01

    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  6. Advanced characterization of forms of chlorine, organic sulfur and trace elements in available coals from operating Illinois mines. Quarterly report, 1 December 1994--28 February 1995

    SciTech Connect

    Chou, M.I.M.; Demir, I.; Ruch, R.R.; Lytle, S.

    1995-12-31

    The goals of the study are (1) to use X-ray absorption near-edge spectroscopy (XANES) to determine forms of chlorine (inorganic, ionic, and organic) and forms of organic sulfur (organic sulfide and thiophenic sulfur) in as-shipped coals from Illinois mines, (2) to obtain basic data on chlorine removal via froth flotation at fine ({minus}200 mesh) and ultrafine ({minus}400 mesh) particle sizes, and (3) to evaluate XANES for direct assessment of the organic/inorganic affinities of trace elements. This is a cooperative effort among the Illinois State Geological Survey, the University of Kentucky, and Western Kentucky University. In this quarter, chlorine leachability during fine wet grinding of 21 coal samples was examined. The results show a general improvement in chlorine removal by grinding coals to {minus}200 mesh, but do not show further improvement by additional grinding to {minus}400 mesh. The chlorine and sulfur spectra of five coals , each from a distinct geographic location in Illinois, were examined. The chlorine XANES spectra for the five coals are similar and chloride anion was determined to be the predominant form of chlorine. The sulfur XANES data for the same coals show that a majority (61% to 82%) of organic sulfur in the coals is contributed from thiophenic sulfur. The distribution of organic sulfur shows that the high sulfur coals tend to have more organic sulfide than low sulfur coals. A more detailed interpretation may be possible after a complete analysis of all the samples selected. Evaluating the possibility of XANES for direct assessment of the organic/inorganic affinities of trace elements in an Illinois coal was completed.

  7. An alternative method to remove PEO-PPO-PEO template in organic-inorganic mesoporous nanocomposites by sulfuric acid extraction

    NASA Astrophysics Data System (ADS)

    Zhuang, Xin; Qian, Xufang; Lv, Jiahui; Wan, Ying

    2010-06-01

    Sulfuric acid is used as an extraction agent to remove PEO-PPO-PEO templates in the organic-inorganic mesoporous nanocomposites from the triconstituent co-assembly which includes the low-polymerized phenolic resins, TEOS and triblock copolymer F127. The XRD and TEM results show well ordered mesostructure after extraction with sulfuric acid. As followed from the N 2 sorption isotherms the extracted composites possess high surface areas (332-367 m 2/g), large pore volumes (0.66-0.78 cm 3/g), and large pore sizes (about 10.7 nm). The FT-IR analysis reveals almost complete elimination of triblock copolymer F127, and the maintenance of organic groups. This method shows potentials in removing templates from nanocomposites containing functional moieties.

  8. Analysis of sulfur-organic compounds in jet fuel by chromatographic sniffing and gas chromatography with atomic emission detector

    SciTech Connect

    Skoog, P.A.

    1995-04-01

    When the Swedish Air Force changed fuel from Jet B to Jet A-1 during 1991-1992, a working environmental problem was reported from the military air force bases. The symptoms were unpleasant odor, headache and indisposition. This problem arose from some batches of the new fuel, Jet A-1. In order to investigate the compounds in the fuel which gave rise to this problem a chromatographic sniffing technique (sensory analysis) was used. The identification of the compounds from the sniffing analysis was done with a atomic emission detector for gas chromatography. The problem stemmed from relatively volatile sulfur-organic compounds. An interesting question is if these compounds also are strongly involved in the fuel system deposit formation. This presentation shows this new analysis technique and the complex pattern of sulfur-organic compounds related to fuels from different refinery processes.

  9. Analyzing organic sulfur in coal/char: Integrated mild degradation/XANES methods. Final technical report, September 1, 1993--November 30, 1994

    SciTech Connect

    Palmer, S.R.; Huffman, G.P.

    1994-12-31

    The overall goal of this study is to improve the understanding of sulfur in coals/chars via the use of combined advanced nondestructive and advanced destructive methods of sulfur analysis. This study combines selective oxidation, analytical pyrolysis, and sulfur X-ray Absorption Near Edge Structure Spectroscopy (XANES) analysis. Samples with a wide variety of sulfur contents, (0.63%--4.40%) have been prepared for use in this study. This includes steam gasification chars, oxidized coals and desulfurized coals as well of the original unaltered coals. Mild pyrolysis and XANES data shows that the sulfur chemistry of gasification chars is significantly different from that of the original coals. Mild pyrolysis of the samples that were oxidized with peroxyacetic acid showed that the level of simple thiophene structures observed in the pyrolysis products declines with increasing levels of oxidation. Sulfur XANES spectra of treated samples showed various effects depending on the treatment severity. The XANES spectra of less severely treated samples were similar, although not identical, to the untreated coal spectra. XANES of gasification chars indicated conversion of pyrite to pyrrhotite, removal of organic sulfide sulfur and dissolution of soluble inorganic sulfur species during gasification. Mild oxidation with peroxyacetic acid results in preferential oxidation of sulfide forms before thiophene forms but increasing oxidation severity leads to virtually all sulfur species being oxidized. Good agreement between W-band EPR and XANES data for aromatic sulfur contents were obtained. The TPR analysis of coal indicated that organic sulfur was present as alkyl-aryl sulfide, aryl-aryl sulfides, simple thiophenes and condensed thiophenes. TPR shows that non-thiophenic compounds are removed by PAA oxidation, and that the longer the oxidation is performed the greater is the removal of non-thiophenic sulfur structures.

  10. Water as a Promoter and Catalyst for Dioxygen Electrochemistry in Aqueous and Organic Media [Water as Promoter and Catalyst in Dioxygen Electrochemistry at Aqueous and Organic Electrified Interfaces].

    DOE PAGES

    Staszak-Jirkovský, Jakub; Subbaraman, Ram; Strmcnik, Dusan; ...

    2015-11-06

    Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad···H2O (aqueous solutions) and LiO2···H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even atmore » low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.« less

  11. Oxidation of Organic Compoundsin the Atmospheric Aqueous Phase: Development of a New Explicit Oxidation Mechanism

    NASA Astrophysics Data System (ADS)

    Mouchel-Vallon, C.; Bregonzio-Rozier, L.; Monod, A.; Leriche, M.; Doussin, J. F.; Chaumerliac, N. M.; Deguillaume, L.

    2014-12-01

    Current 3D models tend to underestimate the production of secondary organic aerosol (SOA) in the atmosphere (Volkamer et al., 2006). Recent studies argue that aqueous chemistry in clouds could be responsible for a significant production of SOA (Ervens et al., 2011; Carlton and Turpin, 2013) through oxidative and non-oxidative processes. Aqueous phase reactivity of organic compounds needs to be thoroughly described in models to identify organic molecules available to contribute to SOA mass. Recently, new empirical methods have been developed to allow the estimate of HO·reaction rates in the aqueous phase (Doussin and Monod, 2013, Minakata et al., 2009). These methods provide global rate constants together with branching ratios for HO·abstraction and addition on organic compounds of atmospheric interests. Current cloud chemistry mechanisms do not take the different possible pathways into account. Based on these structure-activity relationships, a new detailed aqueous phase mechanism describing the oxidation of hydrosoluble organic compounds resulting from isoprene oxidation is proposed. This new aqueous phase mechanism is coupled with the detailed gas phase mechanism MCM v3.2 (Jenkin et al., 1997; Saunders et al., 2003) through a kinetic of mass transfer parameterization for the exchange between gas phase and aqueous phase. The GROMHE SAR (Raventos-Duran et al., 2010) allows the evaluation of Henry's law constants for organic compounds. Variable photolysis in both phases using the TUV 4.5 radiative transfer model (Madronich and Flocke, 1997) is also calculated. The resulting multiphase mechanism has been implemented in a cloud chemistry model. Focusing on oxygenated compounds produced from the isoprene oxidation, sensitivity tests and comparisons with multiphase experiments performed in the framework of the CUMULUS project in the CESAM atmospheric simulation chamber (Wang et al., 2011) will be presented. Volkamer et al., GRL, 33, L17811, 2006. Carlton and Turpin

  12. Self-organization of poly(ethylene oxide) on the surface of aqueous salt solutions.

    PubMed

    Fuchs, Christian; Hussain, Hazrat; Amado, Elkin; Busse, Karsten; Kressler, Joerg

    2015-01-01

    It is demonstrated that stable Langmuir films of poly(ethylene oxide) (PEO) can be formed up to surface pressures of 30 mN m(-1) when potassium carbonate K2CO3 is added to the aqueous subphase. Generally, PEO homopolymer cannot stay on the water surface at a surface pressure ≥10 mN m(-1) due to its high water solubility. To prepare stable monolayer films, PEO can be modified with hydrophobic moieties. However, by exploiting the salting out effect by adding certain salts (K2CO3 or MgSO4) into the aqueous subphase, not only very stable films but also unusual self-organization can be achieved by the PEO homopolymer on the surface of the aqueous solution. Thus, a series of OH-terminated PEOs is found to form a stable monolayer at K2CO3 concentrations of 2 M and above in the aqueous subphase, and the stability of the film increases with an increase in K2CO3 concentration. Hysteresis experiments are also carried out. During the phase transition induced by progressive compression, self-organization into well-defined domains with sizes in the micrometer range are observed, and with further compression and holding of the film for 30 min and above the microdomains transform into a crystalline morphology as visualized by Brewster angle microscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Chemical properties and mechanisms determining the anti-cancer action of garlic-derived organic sulfur compounds.

    PubMed

    Cerella, Claudia; Dicato, Mario; Jacob, Claus; Diederich, Marc

    2011-03-01

    Organic sulfur compounds (OSCs) derived from plants, fungi or bacteria can serve as chemopreventive and/or chemotherapeutic agents and have been attracting medical and research interest as a promising source for novel anti-cancer agents. Garlic, which has long been used as a medicinal plant in different cultures due to its multiple beneficial effects, contains a consistent number of OSCs, the majority of which are currently under investigation for their biological activities. Experimental animal and laboratory studies have shown strong evidence that garlic OSCs may affect cancer cells by promoting early mitotic arrest followed by apoptotic cell death without affecting healthy cells. The ability of OSCs to hinder cancer cell proliferation and viability tightly correlates with the length of the sulfur chain. Current data support a mechanism of mitotic arrest of cancer cells due to the alteration of the microtubule network, possibly as a consequence of the high reactivity of sulfur atoms against the thiol groups of different cellular macromolecules controlling crucial regulatory functions. Taken together, these findings indicate a promising potential for the use of garlic-derived sulfur compounds in chemoprevention and chemotherapy.

  14. Monitoring changes in soil organic carbon pools, nitrogen, phosphorus, and sulfur under different agricultural management practices in the tropics.

    PubMed

    Verma, Bibhash C; Datta, Siba Prasad; Rattan, Raj K; Singh, Anil K

    2010-12-01

    Soil organic matter not only affects sustainability of agricultural ecosystems, but also extremely important in maintaining overall quality of environment as soil contains a significant part of global carbon stock. Hence, we attempted to assess the influence of different tillage and nutrient management practices on various stabilized and active soil organic carbon pools, and their contribution to the extractable nitrogen phosphorus and sulfur. Our study confined to the assessment of impact of agricultural management practices on the soil organic carbon pools and extractable nutrients under three important cropping systems, viz. soybean-wheat, maize-wheat, and rice-wheat. Results indicated that there was marginal improvement in Walkley and Black content in soil under integrated and organic nutrient management treatments in soybean-wheat, maize-wheat, and rice-wheat after completion of four cropping cycles. Improvement in stabilized pools of soil organic carbon (SOC) was not proportional to the applied amount of organic manures. While, labile pools of SOC were increased with the increase in amount of added manures. Apparently, green manure (Sesbania) was more effective in enhancing the lability of SOC as compared to farmyard manure and crop residues. The KMnO(4)-oxidizable SOC proved to be more sensitive and consistent as an index of labile pool of SOC compared to microbial biomass carbon. Under different cropping sequences, labile fractions of soil organic carbon exerted consistent positive effect on the extractable nitrogen, phosphorus, and sulfur in soil.

  15. Membrane air stripping: A process for removal of organics from aqueous solutions

    SciTech Connect

    Mahmud, H.; Kumar, A.; Narbaitz, R.M.; Matsuura, T.

    1998-10-01

    The membrane air-stripping (MAS) process using microporous polypropylene hollow fiber membranes has shown potential for the removal of volatile organics from aqueous streams over conventional treatment processes, particularly in reducing the size of the equipment. This paper reviews the theoretical aspects and experimental investigations on the performance of these membranes in terms of overall mass transfer capabilities in the removal of organics from aqueous solutions. The reported findings of the effect of pH, ozone, chlorine, influence of packing density and possible fouling on the performance of these hollow fibers membranes are presented. The fate of the stripped air is discussed. Other possible applications as well as the future research needs are highlighted, along with critical assessment of the reported work.

  16. Mercury retention in soil in association with organic matter decomposition and sulfur cycle

    NASA Astrophysics Data System (ADS)

    Bajracharya, U.; Feng, X.; Jackson, B.

    2016-12-01

    Soil is the largest sink for mercury (Hg), and it is important to understand mechanisms that retain or mobilize this element. Hg binds to soil organic matter (SOM), and is particularly associated with organic sulfur (S). It is expected, therefore, that Hg retention and mobilization is strongly controlled by C and S cycles. When carbon is converted to CO2 by decomposition, at least some Hg that was bound to the lost C is retained in the soil. Therefore, the Hg/C ratio increases as SOM ages. Some Hg is lost with dissolved organic matter (DOM). We report a study that examines the importance of SOM decomposition, S content, land use, and soil type on retention of Hg indicated by changes in Hg/C ratios. Soil samples were collected from Bartlett experimental forest, NH with three age groups - 120 yrs (OG), 40 yrs (MG) and 15 yrs (YG) after clear cutting, and two soil types - spodosol and inceptisol. A multiple regression was conducted with Hg/C against four explanatory variables, δ13C, S/C, age group and soil type. All four variables significantly contribute to the explanation of the Hg/C variance with an overall R2 = 0.89 (p<0.0001). As expected, the partial coefficients for δ13C and S/C ratio are both positive. These two variables explain 83% of the total variance. The soil type explains 3% of the total variance. The inceptisol soil type had a higher mean Hg/C ratio (2.8 ug/g) than spodosol soils (1.3 ug/g). This difference could result from greater leaching potential of spodosol soil as indicated by Kd values. Age also explains 3% of the total variance. The mean Hg/C ratio is highest in OG (2.6 ug/g) followed by YG (1.5 ug/g) and MG (1.2 ug/g). This may result from vegetation type, hill slope, or other variables not explicitly controlled in the multiple regression analysis. We conclude that SOM decomposition and S/C ratio are the most important factors for Hg retention in the soil, while the soil type and growth age have limited but significant influences.

  17. Mechanistic investigation of Fe(III) oxide reduction by low molecular weight organic sulfur species

    NASA Astrophysics Data System (ADS)

    Eitel, Eryn M.; Taillefert, Martial

    2017-10-01

    Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

  18. Modeling phase distribution of water-soluble organics in aqueous solutions using surface tension data

    NASA Astrophysics Data System (ADS)

    Cline, B.; Hiatt, J.; Aumann, E.; Cabrera, J.; Tabazadeh, A.

    2006-12-01

    A good fraction (greater than 30 percent) of submicron particle mass in the atmosphere is often composed of water-soluble organic carbon. Identifiable, water-miscible organics, such as, known sugars, small alcohols, small diacids, etc. comprise only a small fraction of the water-soluble mass (about 1-2 percent). Most of the water-soluble mass is often composed of unidentifiable, humic-like materials, which are commonly refereed to as HULIS. Humic substances are known to form colloids in aqueous solutions at very low aqueous concentrations. Thus, it is likely for HULIS to also be colloid-forming in aqueous solutions. Here, we present surface tension measurements of water-miscible and colloid-forming organics, using methanol and sodium laurate as analogs, respectively. By relating the change in surface tension to chemical potential of the solution, we determine a relationship between surface tension and the surface excess of solute; that is, the number of molecules of solute adsorbed at the surface. Assuming surface acts as a monolayer, we model the adsorption with a Langmuir isotherm to extract the surface excess as a function of solute mole fraction. This relationship allows us to calculate the solute's distribution between bulk and surface phases for methanol, and in bulk, surface and colloid phases for sodium laurate. A colloid of sodium laurate contains approximately 100 laurate anions in a spherical cluster. We present adsorption constants for methanol and sodium laurate (derived from our surface tension data), critical micelle concentration for sodium laurate (derived from our surface tension data), and all the other thermocehmical constants (obtained from the literature) required to constrain a model for determining phase partitioning of organics in aqueous solutions.

  19. Fast and ultrafast spectroscopic investigation of tetracycline derivatives in organic and aqueous media.

    PubMed

    Carlotti, Benedetta; Fuoco, Domenico; Elisei, Fausto

    2010-12-28

    The photophysical properties of seven tetracycline derivatives (tetracycline, oxytetracycline, demeclocycline, chlortetracycline, doxycycline, minocycline and meclocycline) in organic solvents and aqueous solution were studied using steady-state absorption and fluorescence techniques and transient absorption spectroscopies with nanosecond and femtosecond time resolution. The molecular structure, solvent and pH effects on the optical properties of this class of pharmaceutically interesting compounds were investigated in detail. The investigation furnished a complete description of the nature, the spectral and kinetic properties of the excited states formed upon irradiation. All the tetracycline derivatives exhibited a similar behaviour, and the photophysics of these molecules is different in organic solvents and in aqueous medium, where they exhibit a significant pH dependence. In water, compared to organic solvents, these compounds showed a blue-shifted bathochromic absorption band, a red-shifted emission spectrum, an increased Stokes shift and a decreased fluorescence quantum yield. These findings, together with the overall investigated solvent effect, suggested that in aqueous solvent additional fast and non-radiative deactivation processes, responsible for the large Stokes Shift and for the reduced fluorescence efficiency, are present. In fact, in organic media just two transients were observed during the ultrafast time-resolved investigation: the vibrationally hot S(1) state which was quickly stabilized by solvent reorganization to the relaxed S(1) state. This state showed lifetimes of tens of picoseconds and relaxed by fluorescence and internal conversion. No longer-lived transients were detected. In aqueous solution the excited-state deactivation of tetracyclines was found to be more complicated. Different protonated and tautomeric forms of the S(1) state were detected: a component which showed decay times of tens of picoseconds and a component which was

  20. Importance of Aqueous-phase Secondary Organic Aerosol Formation from Aromatics in an Atmospheric Hydrocarbon Mixture

    NASA Astrophysics Data System (ADS)

    Parikh, H. M.; Carlton, A. G.; Vizuete, W.; Zhang, H.; Zhou, Y.; Chen, E.; Kamens, R. M.

    2010-12-01

    Two new secondary organic aerosol (SOA) modeling frameworks are developed, one based on an aromatic gas and particle-phase kinetic mechanism and another based on a parameterized SOA model used in conjunction with an underlying gas-phase mechanism, both of which simulate SOA formation through partitioning to two stable liquid phases: one hydrophilic containing particle aqueous-phase and the other hydrophobic comprising mainly organic components. The models were evaluated against outdoor smog chamber experiments with different combinations of initial toluene, o-xylene, p-xylene, toluene and xylene mixtures, NOx, non-SOA-forming hydrocarbon mixture, initial seed type, and humidity. Aerosol data for experiments with either ammonium sulfate or initial background seed particles, in the presence of an atmospheric hydrocarbon mixture, NOx and in sunlight under a dry atmosphere (RH = 6 to 10%) show reduced SOA formation when compared to experiments with similar initial gas and particle concentrations at higher relative humidities (RH = 40 to 90%). Both frameworks simulated reasonable fits to the total observed SOA concentrations under all conditions. For both dry and wet experiments with low initial seed, semi-volatile product partitioning in particle organic-phase is mass-transfer limited and is modeled using a dynamic gas-particle partitioning algorithm with accommodation coefficient as the primary pseudo-transport parameter. Further, the modeled SOA product distributions for both frameworks clearly show the importance of the contribution of aqueous-phase SOA particularly under conditions of low initial seed concentrations and high-humidity. For both models, under these conditions, aqueous-phase SOA from uptake of glyoxal, methylglyoxal and related polar products to particle water phase dominates as compared to the partitioning of semi-volatiles to particle organic phase. Interestingly, both the kinetic and parameterized SOA frameworks simulate similar amounts of aqueous

  1. Gold nanoparticle chemiresistor sensors: direct sensing of organics in aqueous electrolyte solution.

    PubMed

    Raguse, Burkhard; Chow, Edith; Barton, Christopher S; Wieczorek, Lech

    2007-10-01

    A novel chemiresistor sensor for detection of organic analytes in high-conductivity aqueous electrolyte solution is reported. The chemiresistor sensor is based on thin films of gold nanoparticles capped with a 1-hexanethiol monolayer that is inkjet printed onto a microelectrode. In order for a change in nanoparticle film resistance to be measured, the electronic conduction must preferentially occur through the nanoparticle film rather than through the high-conductivity electrolyte solution. This was achieved by miniaturizing the chemiresistor device such that the double layer capacitance of the electrodes in contact with the electrolyte solution gives rise to a significantly larger impedance compared to the nanoparticle film resistance. This system was shown to be sensitive to simple organics dissolved in an aqueous electrolyte solution. The organic analytes, dissolved in the aqueous solution, partition into the hydrophobic nanoparticle film causing the nanoparticle film to swell, resulting in an increase in the low-frequency impedance of the sensor. An increase in the impedance, at 1 Hz, of the gold nanoparticle chemiresistor on exposure to toluene, dichloromethane, and ethanol dissolved in 1 M KCl solution was demonstrated with detection limits of 0.1, 10, and 3000 ppm, respectively. Titration curves over 3 orders of magnitude could be obtained for analytes such as toluene.

  2. LONG-TERM STABILITY TESTING RESULTS USING SURROGATES AND SORBENTS FOR SAVANNAH RIVER SITE ORGANIC AND AQUEOUS WASTESTREAMS - 10016

    SciTech Connect

    Burns, H.

    2009-11-10

    The U.S. Department of Energy (DOE) has tasked MSE Technology Applications, Inc. (MSE) with evaluating the long-term stability of various commercially available sorbent materials to solidify two organic surrogate wastestreams (both volatile and nonvolatile), a volatile organic surrogate with a residual aqueous phase, an aqueous surrogate, and an aqueous surrogate with a residual organic phase. The Savannah River Site (SRS) Legacy and F-Canyon plutonium/uranium extraction (PUREX) process waste surrogates constituted the volatile organic surrogates, and various oils constituted the nonvolatile organic surrogates. The aqueous surrogates included a rainwater surrogate and an aqueous organic surrogate. MSE also evaluated the PUREX surrogate with a residual aqueous component with and without aqueous type sorbent materials. Solidification of the various surrogate wastestreams listed above was performed from 2004 to 2006 at the MSE Test Facility located in Butte, Montana. This paper summarizes the comparison of the initial liquid release test (LRT) values with LRT results obtained during subsequent sampling events in an attempt to understand and define the long-term stability characteristics for the solidified wastestreams.

  3. Degradation/oxidation susceptibility of organic photovoltaic cells in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Habib, K.; Husain, A.; Al-Hazza, A.

    2015-12-01

    A criterion of the degradation/oxidation susceptibility of organic photovoltaic (OPV) cells in aqueous solutions was proposed for the first time. The criterion was derived based on calculating the limit of the ratio value of the polarization resistance of an OPV cell in aqueous solution (Rps) to the polarization resistance of the OPV cell in air (Rpair). In other words, the criterion lim(Rps/Rpair) = 1 was applied to determine the degradation/oxidation of the OPV cell in the aqueous solution when Rpair became equal (increased) to Rps as a function of time of the exposure of the OPV cell to the aqueous solution. This criterion was not only used to determine the degradation/oxidation of different OPV cells in a simulated operational environment but also it was used to determine the electrochemical behavior of OPV cells in deionized water and a polluted water with fine particles of sand. The values of Rps were determined by the electrochemical impedance spectroscopy at low frequency. In addition, the criterion can be applied under diverse test conditions with a predetermined period of OPV operations.

  4. Electrosprayed molybdenum trioxide aqueous solution and its application in organic photovoltaic cells.

    PubMed

    Suzuki, Katsumi; Fukuda, Takeshi; Liao, Yingjie

    2014-01-01

    A molybdenum trioxide thin film with smooth surface and uniform thickness was successfully achieved by an electrospray deposition method using an aqueous solution with a drastically low concentration of 0.05 wt%. Previous papers demonstrated that an additive solvent technique is useful for depositing the thin film by the electrospray deposition, and the high vapor pressure and a low surface tension of an additive solvent were found to be important factors. As a result, the smooth molybdenum trioxide thin film was obtained when the acetonitrile was used as the additive solvent. Furthermore, the vapor pressure of acetone is much higher than that of aqueous solution, and this indicates that the acetone is easily evaporated after spraying from the glass capillary. By optimizing a concentration of acetone in the molybdenum aqueous solution, a minimum root mean square roughness of the MoO3 thin film became 3.7 nm. In addition, an organic photovoltaic cell was also demonstrated using the molybdenum trioxide as a hole transport layer. Highest photoconversion efficiency was 1.72%, a value comparable to that using conventional thermal evaporation process even though the aqueous solution was used for the solution process. The photovonversion efficiency was not an optimized value, and the higher value can be achieved by optimizing the coating condition of the active layer.

  5. Aqueous-phase secondary organic aerosol and organosulfate formation in atmospheric aerosols: a modeling study.

    PubMed

    McNeill, V Faye; Woo, Joseph L; Kim, Derek D; Schwier, Allison N; Wannell, Neal J; Sumner, Andrew J; Barakat, Joseph M

    2012-08-07

    We have examined aqueous-phase secondary organic aerosol (SOA) and organosulfate (OS) formation in atmospheric aerosols using a photochemical box model with coupled gas-phase chemistry and detailed aqueous aerosol chemistry. SOA formation in deliquesced ammonium sulfate aerosol is highest under low-NO(x) conditions, with acidic aerosol (pH = 1) and low ambient relative humidity (40%). Under these conditions, with an initial sulfate loading of 4.0 μg m(-3), 0.9 μg m(-3) SOA is predicted after 12 h. Low-NO(x) aqueous-aerosol SOA (aaSOA) and OS formation is dominated by isoprene-derived epoxydiol (IEPOX) pathways; 69% or more of aaSOA is composed of IEPOX, 2-methyltetrol, and 2-methyltetrol sulfate ester. 2-Methyltetrol sulfate ester comprises >99% of OS mass (66 ng m(-3) at 40% RH and pH 1). In urban (high-NO(x)) environments, aaSOA is primarily formed via reversible glyoxal uptake, with 0.12 μg m(-3) formed after 12 h at 80% RH, with 20 μg m(-3) initial sulfate. OS formation under all conditions studied is maximum at low pH and lower relative humidities (<60% RH), i.e., when the aerosol is more concentrated. Therefore, OS species are expected to be good tracer compounds for aqueous aerosol-phase chemistry (vs cloudwater processing).

  6. Sulfidization of Organic Freshwater Flocs from a Minerotrophic Peatland: Speciation Changes of Iron, Sulfur, and Arsenic.

    PubMed

    ThomasArrigo, Laurel K; Mikutta, Christian; Lohmayer, Regina; Planer-Friedrich, Britta; Kretzschmar, Ruben

    2016-04-05

    Iron-rich organic flocs are frequently observed in surface waters of wetlands and show a high affinity for trace metal(loid)s. Under low-flow stream conditions, flocs may settle, become buried, and eventually be subjected to reducing conditions facilitating trace metal(loid) release. In this study, we reacted freshwater flocs (704-1280 mg As/kg) from a minerotrophic peatland (Gola di Lago, Switzerland) with sulfide (5.2 mM, S(-II)spike/Fe = 0.75-1.62 mol/mol) at neutral pH and studied the speciation changes of Fe, S, and As at 25 ± 1 °C over 1 week through a combination of synchrotron X-ray techniques and wet-chemical analyses. Sulfidization of floc ferrihydrite and nanocrystalline lepidocrocite caused the rapid formation of mackinawite (52-81% of Fesolid at day 7) as well as solid-phase associated S(0) and polysulfides. Ferrihydrite was preferentially reduced over lepidocrocite, although neoformation of lepidocrocite from ferrihydrite could not be excluded. Sulfide-reacted flocs contained primarily arsenate (47-72%) which preferentially adsorbed to Fe(III)-(oxyhydr)oxides, despite abundant mackinawite precipitation. At higher S(-II)spike/Fe molar ratios (≥1.0), the formation of an orpiment-like phase accounted for up to 35% of solid-phase As. Despite Fe and As sulfide precipitation and the presence of residual Fe(III)-(oxyhydr)oxides, mobilization of As was recorded in all samples (Asaq = 0.45-7.0 μM at 7 days). Aqueous As speciation analyses documented the formation of thioarsenates contributing up to 33% of Asaq. Our findings show that freshwater flocs from the Gola di Lago peatland may become a source of As under sulfate-reducing conditions and emphasize the pivotal role Fe-rich organic freshwater flocs play in trace metal(loid) cycling in S-rich wetlands characterized by oscillating redox conditions.

  7. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Technical report, 1 December 1992--28 February 1993

    SciTech Connect

    Kruge, M.A.; Palmer, S.R.; Ho, K.

    1993-05-01

    N/C and S/C ratios show only minor differences between asphaltenes and coal on this basis, the asphaltenes continue to appear to be good surrogates for the characterization of organic acid rain precursors in coal. Alkylmethoxythiophene carboxylic acids (ATCA) are detected in all dichromate oxidation products analyzed to date. Relative concentrations of ATCA compounds are directly proportional to the sample`s bulk organic sulfur contents. Concentrations of ATCA compounds in oxidation products decrease upon repeated oxidation. This may indicate that the thiophenic groups tend to be located in external positions on the coal macromolecular structure and a high proportion of them can be stripped away with only one mild oxidation step. If true, this may make industrial-scale removal of organic sulfur easier than expected. Using analytical micropyrolysis-gas chromatography with a sulfur-selective flame photometric detector, it is possible to easily see a full distribution of organic sulfur forms in a one-step analysis. The predominance of alkylthiophenes in the pyrolyzates lends credence to the discovery of thiophenic compounds in the dichromate oxidation products. The thiophene concentrations in pyrolyzates are directly proportional to bulk organic sulfur values. However, thiophene distributions in IBCSP coals are remarkably similar, regardless of organic sulfur content. It is thus possible to distinguish Illinois Basin coals from foreign coals on the basis of thiophene ``fingerprints.`` To examine rank effects, we have started analysis on a group of five Appalachian coals ranging from high-volatile C to medium-volatile bituminous rank.

  8. The study of CdSe colloidal quantum dots synthesized in aqueous and organic media

    NASA Astrophysics Data System (ADS)

    Mikhailov, I. I.; Tarasov, S. A.; Solomonov, A. V.; Aleksandrova, O. A.; Matyushkin, L. B.; Mazing, D. S.

    2014-12-01

    The samples of CdSe colloidal quantum dots (CQDs) synthesized in aqueous and organic media are studied. The possibility of luminescence peak position control depending on nanoparticle growth process is demonstrated. The samples synthesized in organic medium revealed the luminescence color variation effect with nanoparticle growth. The relation of this effect with processes of nucleation and defect formation in nanoparticles is considered. The CQDs of CdSe coated with CdS shell are fabricated. The use of inorganic shell can provide a double increase of the luminescence quantum yield.

  9. Osmotic potential calculations of inorganic and organic aqueous solutions over wide solute concentration levels and temperatures.

    PubMed

    Cochrane, T T; Cochrane, T A

    2016-01-01

    To demonstrate that the authors' new "aqueous solution vs pure water" equation to calculate osmotic potential may be used to calculate the osmotic potentials of inorganic and organic aqueous solutions over wide ranges of solute concentrations and temperatures. Currently, the osmotic potentials of solutions used for medical purposes are calculated from equations based on the thermodynamics of the gas laws which are only accurate at low temperature and solute concentration levels. Some solutions used in medicine may need their osmotic potentials calculated more accurately to take into account solute concentrations and temperatures. The authors experimented with their new equation for calculating the osmotic potentials of inorganic and organic aqueous solutions up to and beyond body temperatures by adjusting three of its factors; (a) the volume property of pure water, (b) the number of "free" water molecules per unit volume of solution, "Nf," and (c) the "t" factor expressing the cooperative structural relaxation time of pure water at given temperatures. Adequate information on the volume property of pure water at different temperatures is available in the literature. However, as little information on the relative densities of inorganic and organic solutions, respectively, at varying temperatures needed to calculate Nf was available, provisional equations were formulated to approximate values. Those values together with tentative t values for different temperatures chosen from values calculated by different workers were substituted into the authors' equation to demonstrate how osmotic potentials could be estimated over temperatures up to and beyond bodily temperatures. The provisional equations formulated to calculate Nf, the number of free water molecules per unit volume of inorganic and organic solute solutions, respectively, over wide concentration ranges compared well with the calculations of Nf using recorded relative density data at 20 °C. They were

  10. Adsorption and Unfolding of Lysozyme at a Polarized Aqueous-Organic Liquid Interface.

    PubMed

    Arooj, Mahreen; Gandhi, Neha S; Kreck, Cara A; Arrigan, Damien W M; Mancera, Ricardo L

    2016-03-31

    The adsorption of proteins at the interface between two immiscible electrolyte solutions has been found to be key to their bioelectroactivity at such interfaces. Combined with interfacial complexation of organic phase anions by cationic proteins, this adsorption process may be exploited to achieve nanomolar protein detection. In this study, replica exchange molecular dynamics simulations have been performed to elucidate for the first time the molecular mechanism of adsorption and subsequent unfolding of hen egg white lysozyme at low pH at a polarized 1,2-dichloroethane/water interface. The unfolding of lysozyme was observed to occur as soon as it reaches the organic-aqueous interface, which resulted in a number of distinct orientations at the interface. In all cases, lysozyme interacted with the organic phase through regions rich in nonpolar amino acids, such that the side chains are directed toward the organic phase, whereas charged and polar residues were oriented toward the aqueous phase. By contrast, as expected, lysozyme in neat water at low pH does not exhibit significant structural changes. These findings demonstrate the key influence of the organic phase upon adsorption of lysozyme under the influence of an electric field, which results in the unfolding of its structure.

  11. The dissolution of quartz in dilute aqueous solutions of organic acids at 25 degree C

    SciTech Connect

    Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P. )

    1988-06-01

    The dissolution of quartz in dilute aqueous solutions of organic acids at 25{degree}C and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 {mu}mole/Kg compared to 50 {mu}mole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH. The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

  12. The dissolution of quartz in dilute aqueous solutions of organic acids at 25°C

    USGS Publications Warehouse

    Bennett, P.C.; Melcer, M.E.; Siegel, D.I.; Hassett, J.P.

    1988-01-01

    The dissolution of quartz in dilute aqueous solutions of organic acids at 25° and standard pressure was investigated by the batch dissolution method. The bulk dissolution rate of quartz in 20 mmole/Kg citrate solutions at pH 7 was 8 to 10 times faster than that in pure water. After 1750 hours the concentration of dissolved silica in the citrate solution was 167 μmole/Kg compared to 50 μmole/Kg in water and a 20 mmole/Kg solution of acetate at pH 7. Solutions of salicylic, oxalic, and humic acids also accelerated the dissolution of quartz in aqueous solution at pH 7. The rate of dissolution in organic acids decreased sharply with decreasing pH.The possibility of a silica-organic acid complex was investigated using UV-difference spectroscopy. Results suggest that dissolved silica is complexed by citrate, oxalate and pyruvate at pH 7 by an electron-donor acceptor complex, whereas no complexation occurs between silica and acetate, lactate, malonate, or succinate. Three models are proposed for the solution and surface complexation of silica by organic acid anions which result in the accelerated dissolution and increased solubility of quartz in organic rich water.

  13. Chemical Characterization of Secondary Organic Aerosol Formed from Atmospheric Aqueous-phase Reactions of Phenolic Compounds

    NASA Astrophysics Data System (ADS)

    Yu, L.; Smith, J.; Anastasio, C.; Zhang, Q.

    2012-12-01

    Phenolic compounds, which are released in significant amounts from biomass burning, may undergo fast aqueous-phase reactions to form secondary organic aerosol (SOA) in the atmosphere. Understanding the aqueous-phase reaction mechanisms of these compounds and the composition of their reaction products is thus important for constraining SOA sources and predicting organic aerosol properties in models. In this study, we investigate the aqueous-phase reactions of three phenols (phenol, guaiacol and syringol) with two oxidants - excited triplet states (3C*) of non-phenolic aromatic carbonyls and hydroxyl radical (OH). By employing four analytical methods including high-resolution aerosol mass spectrometry, total organic carbon analysis, ion chromatography, and liquid chromatography-mass spectrometry, we thoroughly characterize the chemical compositions of the low volatility reaction products of phenols and propose formation mechanisms based on this information. Our results indicate that phenolic SOA is highly oxygenated, with O/C ratios in the range of 0.83-1.03, and that the SOA of phenol is usually more oxidized than those of guaiacol and syringol. Among the three precursors, syringol generates the largest fraction of higher molecular weight (MW) products. For the same precursor, the SOA formed via reaction with 3C* is less oxidized than that formed via reaction with OH. In addition, oxidation by 3C* enhances the formation of higher MW species, including phenolic dimers, higher oligomers and hydroxylated products, compared to reactions initiated by OH, which appear to favor the formation of organic acids. However, our results indicate that the yields of small organic acids (e.g., formate, acetate, oxalate, and malate) are low for both reaction pathways, together accounting for less than 5% of total SOA mass.

  14. Unexpected toxicity to aquatic organisms of some aqueous bisphenol A samples treated by advanced oxidation processes.

    PubMed

    Tišler, Tatjana; Erjavec, Boštjan; Kaplan, Renata; Şenilă, Marin; Pintar, Albin

    2015-01-01

    In this study, photocatalytic and catalytic wet-air oxidation (CWAO) processes were used to examine removal efficiency of bisphenol A from aqueous samples over several titanate nanotube-based catalysts. Unexpected toxicity of bisphenol A (BPA) samples treated by means of the CWAO process to some tested species was determined. In addition, the CWAO effluent was recycled five- or 10-fold in order to increase the number of interactions between the liquid phase and catalyst. Consequently, the inductively coupled plasma mass spectrometry (ICP-MS) analysis indicated higher concentrations of some toxic metals like chromium, nickel, molybdenum, silver, and zinc in the recycled samples in comparison to both the single-pass sample and the photocatalytically treated solution. The highest toxicity of five- and 10-fold recycled solutions in the CWAO process was observed in water fleas, which could be correlated to high concentrations of chromium, nickel, and silver detected in tested samples. The obtained results clearly demonstrated that aqueous samples treated by means of advanced oxidation processes should always be analyzed using (i) chemical analyses to assess removal of BPA and total organic carbon from treated aqueous samples, as well as (ii) a battery of aquatic organisms from different taxonomic groups to determine possible toxicity.

  15. Analysis of synthetic peptides by capillary zone electrophoresis in organic/aqueous buffers.

    PubMed

    Miller, C; Rivier, J

    1998-06-01

    Whereas synthetic peptides have been routinely analyzed for purity by reverse phase high performance liquid chromatography (RPHPLC) for a number of years, it is only in the last decade that the use of capillary zone electrophoresis (CZE) in aqueous buffers has been taken advantage of as an orthogonal method for the detection of impurities. However, we have found that hydrophobic amino acids and peptides often migrate as very broad, tailing absorbances or even precipitate in the aqueous buffers during CZE analysis. As a result, alternative buffer systems containing organic modifiers were sought. Varying concentrations of acetonitrile, methanol and isopropanol in sodium phosphate and triethylammonium phosphate buffers were used to study their effects on the electrophoretic migration of several synthetic peptides [gonadotropin releasing hormone (GnRH), corticotropin releasing factor (CRF) and analogs] and an enantiomeric synthetic amino acid. The organic/aqueous buffers used to obtain the best conditions for separation of porcine gonadotropin-releasing hormone (GnRH) and chicken II GnRH were then used to optimize a separation of nine native forms of GnRH decapeptides. Interestingly, several of these GnRHs have identical formal charges and yet could be separated. This suggests a mixed mechanism of separation that discriminates not only on the basis of peptide charge and structure but also of adsorptive properties (Van der Waals forces, dipole-dipole interactions and hydrogen bonding) of the capillaries.

  16. Immunomodulatory effects of aqueous and organic fractions from Petiveria alliacea on human dendritic cells.

    PubMed

    Santander, Sandra Paola; Hernández, John Fredy; Barreto, Claudia Cifuentes; Cifuentes B, Claudia; Masayuki, Aoki; M, Aoki; Moins-Teisserenc, Hélène; H, Moins-Teisserenc; Fiorentino, Susana

    2012-01-01

    Petiveria alliacea is a plant traditionally known for its anti-inflammatory and anti-tumor activities; however, the molecular and cellular mechanisms of its immunomodulatory properties are still unknown. Dendritic cells (DC) promote adaptive immune response by activating T lymphocytes, inducing an effector response or tolerance depending on the DC differentiation level. Herein, we evaluated the immunomodulatory activity of aqueous and organic plant fractions from P. alliacea using human monocyte-derived dendritic cells. The phenotype, cytokine secretion and gene expression were estimated after treatment with the plant fractions. We found that P. alliacea aqueous fraction induced morphological changes and co-stimulatory expression of CD86, indicating partial DC maturation. In addition, pro-inflammatory cytokines such as IL-1β, IL-6, IL-8, IL-10, IL-12p70, and TNF-α were secreted. The fraction also increased NF-κB gene expression while down-regulating TGFβ gene expression. These results suggest that the aqueous fraction can induce partial DC activation, a situation that can be relevant in tolerance induction. It is important to state that the organic fraction by itself does not show any immunomodulatory activity. This study provides evidence for possible immunomodulatory activity of P. alliacea extracts which has been used in traditional medicine in Colombia.

  17. Structural properties of the inner coordination sphere of indium chloride complexes in organic and aqueous solutions.

    PubMed

    Narita, Hirokazu; Tanaka, Mikiya; Shiwaku, Hideaki; Okamoto, Yoshihiro; Suzuki, Shinichi; Ikeda-Ohno, Atsushi; Yaita, Tsuyoshi

    2014-01-28

    The nature of the inner coordination sphere of In(3+) present in both the organic and aqueous solutions during the solvent extraction of In(3+) from an aqueous HCl solution with tri-n-octyl amine (TOA) was investigated by In K-edge XAFS. This information was then used to clarify the details of the extraction properties of indium chloride anion complexes with TOA. In aqueous HCl solution (0.1-10 M), In(3+) exists as octahedral anion complexes, [InCln(H2O)6-n](3-n) (n ≥ 4); the [InCl6](3-) complex is dominant at 10 M HCl. The extraction of In(3+) from HCl solution with TOA was performed using two kinds of diluents: nitrobenzene (NB) or n-dodecane (DD), which contained 20 vol% of 2-ethylhexanol as an additive. The stoichiometric composition of the extracted complexes, which is estimated from the distribution ratios of In(3+), is affected by the diluents and the HCl concentration of the aqueous phase; the apparent values of TOA/In(3+) in the extracted complex are 3 for DD-1 M HCl (diluent-aqueous phase) and DD-5 M HCl, 2 for NB-1 M HCl and NB-5 M HCl, and 1 for NB-10 M HCl. The EXAFS analysis of these extracted complexes shows that the In(3+) has ∼4 Cl(-) at ∼2.336 Å and no H2O in the inner coordination sphere; additionally, the shape of the XANES suggests that their coordination geometry is tetrahedral. Therefore, the same tetrahedral [InCl4](-) complex is formed during the extraction in spite of the variation in the stoichiometric composition (TOA/In(3+) = 1-3) of the extracted complexes.

  18. Sulfur metabolism in phototrophic sulfur bacteria.

    PubMed

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2009-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative of the Chromatiaceae), and many are well characterized also on a molecular genetic level. Complete genome sequence data are currently available for 10 strains of GSB and for one strain of PSB. We present here a genome-based survey of the distribution and phylogenies of genes involved in oxidation of sulfur compounds in these strains. It is evident from biochemical and genetic analyses that the dissimilatory sulfur metabolism of these organisms is very complex and incompletely understood. This metabolism is modular in the sense that individual steps in the metabolism may be performed by different enzymes in different organisms. Despite the distant evolutionary relationship between GSB and PSB, their photosynthetic nature and their dependency on oxidation of sulfur compounds resulted in similar ecological roles in the sulfur cycle as important anaerobic oxidizers of sulfur compounds.

  19. Complexation of Mercury(II) in Soil Organic Matter: EXAFS Evidence for Linear Two-Coordination with Reduced Sulfur Groups

    SciTech Connect

    Skyllberg,U.; Bloom, P.; Qian, J.; Lin, C.; Bleam, W.

    2006-01-01

    The chemical speciation of inorganic mercury (Hg) is to a great extent controlling biologically mediated processes, such as mercury methylation, in soils, sediments, and surface waters. Of utmost importance are complexation reactions with functional groups of natural organic matter (NOM), indirectly determining concentrations of bioavailable, inorganic Hg species. Two previous extended X-ray absorption fine structure (EXAFS) spectroscopic studies have revealed that reduced organic sulfur (S) and oxygen/nitrogen (O/N) groups are involved in the complexation of Hg(II) to humic substances extracted from organic soils. In this work, covering intact organic soils and extending to much lower concentrations of Hg than before, we show that Hg is complexed by two reduced organic S groups (likely thiols) at a distance of 2.33 Angstroms in a linear configuration. Furthermore, a third reduced S (likely an organic sulfide) was indicated to contribute with a weaker second shell attraction at a distance of 2.92-3.08 Angstroms. When all high-affinity S sites, corresponding to 20-30% of total reduced organic S, were saturated, a structure involving one carbonyl-O or amino-N at 2.07 Angstroms and one carboxyl-O at 2.84 Angstroms in the first shell, and two second shell C atoms at an average distance of 3.14 Angstroms, gave the best fit to data. Similar results were obtained for humic acid extracted from an organic wetland soil. We conclude that models that are in current use to describe the biogeochemistry of mercury and to calculate thermodynamic processes need to include a two-coordinated complexation of Hg(II) to reduced organic sulfur groups in NOM in soils and waters.

  20. Prediction of capacity factors for aqueous organic solutes adsorbed on a porous acrylic resin

    USGS Publications Warehouse

    Thurman, E.M.

    1978-01-01

    The capacity factors of 20 aromatic, allphatic, and allcycllc organic solutes with carboxyl, hydroxyl, amine, and methyl functional groups were determined on Amberlite XAD-8, a porous acrylic resin. The logarithm of the capacity factor, k???, correlated inversely with the logarithm of the aqueous molar solubility with significance of less than 0.001. The log k???-log solubility relationship may be used to predict the capacity of any organic solute for XAD-8 using only the solubility of the solute. The prediction is useful as a guide for determining the proper ratio of sample to column size In the preconcentration of organic solutes from water. The inverse relationship of solubility and capacity is due to the unfavorable entropy of solution of organic solutes which affects both solubility and sorption.

  1. Extending the analytical window for water-soluble organic matter in sediments by aqueous Soxhlet extraction

    NASA Astrophysics Data System (ADS)

    Schmidt, Frauke; Koch, Boris P.; Witt, Matthias; Hinrichs, Kai-Uwe

    2014-09-01

    Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 μm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased

  2. Proteomic analysis of organic sulfur compound utilisation in Advenella mimigardefordensis strain DPN7T

    PubMed Central

    Meinert, Christina; Brandt, Ulrike; Heine, Viktoria; Beyert, Jessica; Schmidl, Sina; Wübbeler, Jan Hendrik; Voigt, Birgit; Riedel, Katharina; Steinbüchel, Alexander

    2017-01-01

    2-Mercaptosuccinate (MS) and 3,3´-ditiodipropionate (DTDP) were discussed as precursor substance for production of polythioesters (PTE). Therefore, degradation of MS and DTDP was investigated in Advenella mimigardefordensis strain DPN7T, applying differential proteomic analysis, gene deletion and enzyme assays. Protein extracts of cells cultivated with MS, DTDP or 3-sulfinopropionic acid (SP) were compared with those cultivated with propionate (P) and/or succinate (S). The chaperone DnaK (ratio DTDP/P 9.2, 3SP/P 4.0, MS/S 6.1, DTDP/S 6.2) and a Do-like serine protease (DegP) were increased during utilization of all organic sulfur compounds. Furthermore, a putative bacterioferritin (locus tag MIM_c12960) showed high abundance (ratio DTDP/P 5.3, 3SP/P 3.2, MS/S 4.8, DTDP/S 3.9) and is probably involved in a thiol-specific stress response. The deletion of two genes encoding transcriptional regulators (LysR (MIM_c31370) and Xre (MIM_c31360)) in the close proximity of the relevant genes of DTDP catabolism (acdA, mdo and the genes encoding the enzymes of the methylcitric acid cycle; prpC,acnD, prpF and prpB) showed that these two regulators are essential for growth of A. mimigardefordensis strain DPN7T with DTDP and that they most probably regulate transcription of genes mandatory for this catabolic pathway. Furthermore, proteome analysis revealed a high abundance (ratio MS/S 10.9) of a hypothetical cupin-2-domain containing protein (MIM_c37420). This protein shows an amino acid sequence similarity of 60% to a newly identified MS dioxygenase from Variovorax paradoxus strain B4. Deletion of the gene and the adjacently located transcriptional regulator LysR, as well as heterologous expression of MIM_c37420, the putative mercaptosuccinate dioxygenase (Msdo) from A. mimigardefordensis, showed that this protein is the key enzyme of MS degradation in A. mimigardefordensis strain DPN7T (KM 0.2 mM, specific activity 17.1 μmol mg-1 min-1) and is controlled by LysR (MIM_c37410

  3. Sorption of hydrophobic organic compounds on natural sorbents and organoclays from aqueous and non-aqueous solutions: a mini-review.

    PubMed

    Moyo, Francis; Tandlich, Roman; Wilhelmi, Brendan S; Balaz, Stefan

    2014-05-09

    Renewed focus on the sorption of hydrophobic organic chemicals (HOCs) onto mineral surfaces and soil components is required due to the increased and wider range of organic pollutants being released into the environment. This mini-review examines the possibility of the contribution and mechanism of HOC sorption onto clay mineral sorbents such as kaolinite, and soil organic matter and the possible role of both in the prevention of environmental contamination by HOCs. Literature data indicates that certain siloxane surfaces can be hydrophobic. Therefore soils can retain HOCs even at low soil organic levels and the extent will depend on the structure of the pollutant and the type and concentration of clay minerals in the sorbent. Clay minerals are wettable by nonpolar solvents and so sorption of HOCs onto them from aqueous and non-aqueous solutions is possible. This is important for two reasons: firstly, the movement and remediation of soil environments will be a function of the concentration and type of clay minerals in the soil. Secondly, low-cost sorbents such as kaolinite and expandable clays can be added to soils or contaminated environments as temporary retention barriers for HOCs. Inorganic cations sorbed onto the kaolinite have a strong influence on the rate and extent of sorption of hydrophobic organic pollutants onto kaolinite. Structural sorbate classes that can be retained by the kaolinite matrix are limited by hydrogen bonding between hydroxyl groups of the octahedral alumosilicate sheet and the tetrahedral sheet with silicon. Soil organic carbon plays a key role in the sorption of HOCs onto soils, but the extent will be strongly affected by the structure of the organic soil matter and the presence of soot. Structural characterisation of soil organic matter in a particular soil should be conducted during a particular contamination event. Contamination by mining extractants and antibiotics will require renewed focus on the use of the QSAR approaches in the

  4. Thorough removal of inorganic and organic mercury from aqueous solutions by adsorption on Lemna minor powder.

    PubMed

    Li, Shun-Xing; Zheng, Feng-Ying; Yang, Huang; Ni, Jian-Cong

    2011-02-15

    The adsorption ability of duckweed (Lemna minor) powders for removing inorganic and organic mercury (methyl and ethyl mercury) has been studied using cold vapour atomic absorption spectrometry. The optimal adsorption conditions were: (a) the pH value of the solution 7.0 for inorganic and ethyl mercury, 9.0 for methyl mercury, and (b) equilibrium adsorption time 10, 20, and 40 min for inorganic mercury, methyl mercury, and ethyl mercury, respectively. After adsorption by L. minor powder for 40 min, when the initial concentrations of inorganic and organic mercury were under 12.0 μg L(-1) and 50.0 μg L(-1), respectively, the residual concentrations of mercury could meet the criterion of drinking water (1.0 μg L(-1)) and the permitted discharge limit of wastewater (10.0 μg L(-1)) set by China and USEPA, respectively. Thorough removal of both inorganic and organic mercury from aqueous solutions was reported for the first time. The significant adsorption sites were C-O-P and phosphate groups by the surface electrostatic interactions with aqueous inorganic and organic mercury cations, and then the selective adsorption was resulted from the strong chelating interaction between amine groups and mercury on the surface of L. minor cells.

  5. Measuring and Modeling the Surface Tensions of Organic Aqueous Solutions With Atmospheric Significance

    NASA Astrophysics Data System (ADS)

    Aumann, E.; Tabazadeh, A.

    2008-12-01

    Organic compounds account for a substantial fraction of dry submicron atmospheric aerosol mass. Additionally, single particle composition data suggest that individual aerosols are often mixtures of organic and inorganic components. This study measured the surface tensions of atmospherically relevant pure and mixed organic / inorganic aqueous solutions. Measurements were performed using the Wilhelmy plate method at 25°C and 5°C. Small water-soluble organic compounds previously identified in aerosols (i.e. sugars, dicarboxylic acids) were found to alter the surface tension of water to a limited extent. Humic and fulvic acids were used as analog species for the unidentifiable humic-like substances (HULIS) found in atmospheric particles. Natural humic substances were considerably more effective at reducing the surface tension of water than small water-soluble species. However, humic matter reduced the surface tension of water to a lesser degree than measurements reported for atmospheric HULIS. The addition of inorganic species was found to significantly affect the surface activity of natural humic materials. Surface tension data were fit to the Szyszkowski equation to extract Langmuir adsorption parameters (maximum surface excess, Γmax, and the adsorption constant, β) for the aqueous systems. Adsorption parameters were used to model the surface tensions of multi-component solutions.

  6. Removal of organic and inorganic sulfur from Ohio coal by combined physical and chemical process. Final report

    SciTech Connect

    Attia, Y.A.; Zeky, M.El.; Lei, W.W.; Bavarian, F.; Yu, S.

    1989-04-28

    This project consisted of three sections. In the first part, the physical cleaning of Ohio coal by selective flocculation of ultrafine slurry was considered. In the second part, the mild oxidation process for removal of pyritic and organic sulfur.was investigated. Finally, in-the third part, the combined effects of these processes were studied. The physical cleaning and desulfurization of Ohio coal was achieved using selective flocculation of ultrafine coal slurry in conjunction with froth flotation as flocs separation method. The finely disseminated pyrite particles in Ohio coals, in particular Pittsburgh No.8 seam, make it necessary to use ultrafine ({minus}500 mesh) grinding to liberate the pyrite particles. Experiments were performed to identify the ``optimum`` operating conditions for selective flocculation process. The results indicated that the use of a totally hydrophobic flocculant (FR-7A) yielded the lowest levels of mineral matters and total sulfur contents. The use of a selective dispersant (PAAX) increased the rejection of pyritic sulfur further. In addition, different methods of floc separation techniques were tested. It was found that froth flotation system was the most efficient method for separation of small coal flocs.

  7. Molecular characterization of phytoplankton dissolved organic matter (DOM) and sulfur components using high resolution Orbitrap mass spectrometry.

    PubMed

    Mangal, Vaughn; Stock, Naomi L; Guéguen, Celine

    2016-03-01

    Orbitrap high resolution mass spectrometry (HRMS) with electrospray ionization in both positive and negative polarity was conducted on Suwannee River fulvic acid (SRFA), Pony Lake fulvic acid (PLFA) standards, and dissolved organic matter (DOM) released by freshwater phytoplankton (Scenedesmus obliquus, Euglena mutabilis, and Euglena gracilis). Three-dimensional van Krevelen diagrams expressing various oxygenation states of sulfur molecules and abundance plots of sulfur-containing species were constructed. Orbitrap HRMS analysis of SRFA found a high density of peaks in the lignin region (77 %) and low density of protein material (6.53 %), whereas for PLFA, 25 % of the total peaks were lignin related compared to 56 % of peaks in protein regions, comparable with other HRMS studies. Phytoplankton-derived DOM of S. obliquus, E. mutabilis, and E. gracilis was dominated by protein molecules at respective percentages of 36, 46, and 49 %, and is consistent with previous experiments examining phytoplankton-derived DOM composition. The normalized percentage of SO-containing compounds was determined among the three phytoplankton to be 56 % for Scenedesmus, 54 % for E. mutabilis, and 47 % for E. gracilis, suggesting variation between sulfur content in phytoplankton-derived DOM and differences in metal binding capacities. These results suggest the level of resolution by Orbitrap mass spectrometry is sufficient for preliminary characterization of phytoplankton DOM at an affordable cost relative to other HRMS techniques.

  8. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. [Quarterly] technical report, March 1--May 31, 1993

    SciTech Connect

    Kruge, M.A.; Palmer, S.R.

    1993-09-01

    There is need for alternative methods for determining the nature of organic sulfur and nitrogen compounds in coal. In our research, we apply chemical and thermal degradation techniques to render coal amenable to standard gas chromatography characterization. Standard density gradient centrifugation successfully isolated vitrinite from the IBC101 coal, whereas the multi-step high resolution method was required to isolate liptinite and inertinite macerals, which are minority constituents. Analytical pyrolysis-gas chromatography, operating with either the sulfur selective flame photometric detector (py-GC-PFD) or a mass spectrometer (py-GC/MS), provides distinctive organosulfur ``fingerprints`` for all coal, asphaltene and maceral samples analyzed to date. PY-GC/MS permits ready differentiation of asphaltenes from low and high rank coals. Of the two pyrolysis techniques, py-GC-FPD is simpler and less expensive, and is the recommended method for situations in which sulfur content is the prime concern. Both py-GC methods are superior to oxidative degradation techniques in that they are permit direct, one-step micro-scale analysis, requiring only a minimum of sample preparation. Distinctive chromatographic profiles are also achieved using the methylated dichromate oxidation products of coals, asphaltenes and macerals, but the extensive wet chemical preparation required is a serious disadvantage. Reasonable matches for the expected masses of alkylthiophene carboxylic acid derivatives have been found in the direct probe, low voltage, high resolution mass spectral data set collected on the methylated dichromate oxidation products of the sulfur-rich Spanish lignite sample, providing an additional line of evidence confirming the presence of such compounds.

  9. Preparation of organic sulfur adsorbent from coal for adsorption of dibenzothiophene-type compounds in diesel fuel

    SciTech Connect

    Cigdem Shalaby; Xiaoliang Ma; Anning Zhou; Chunshan Song

    2009-05-15

    High-performance organic sulfur adsorbents (OSA) have been prepared from coal by chemical activation for selective adsorption of the refractory sulfur compounds, such as 4-methyl dibenzothiophene and 4,6-dimethyldibenzothiophene, in diesel fuel. The performance of the prepared OSAs for adsorptive desulfurization (ADS) was evaluated in batch and flow adsorption systems at room temperature using a model diesel fuel. It was found that coal rank and preparation conditions, including activation agents (NaOH, KOH, and NaOH + KOH) and their ratio to coal, activation temperature, and time have significant impacts on the yield and ADS performance of the OSAs. The high-performance OSAs can be prepared from different ranks of coal by using NaOH + KOH as an activation agent with an activating-agent-to-coal ratio of 3.5. The yield of OSA increased in the order of lignite < high volatile bituminous coal < medium volatile bituminous coal < anthracite. The OSA-A, which was derived from an anthracite with the highest yield (68 wt %) by the activation at 650{sup o}C for 1 h, gave the best ADS performance among the OSAs from all coal samples tested. The sulfur adsorption capacity of OSA-A reached 0.281 mmol-S/g-A at an equilibrium sulfur concentration of 50 ppmw in the model diesel fuel, which was 155% higher than a commercial coal-derived activated carbon and 35% higher than the best commercial activated carbon among all commercial activated carbons examined in our laboratory. The higher ADS capacity of OSA-A can be attributed to its significantly higher density (2.77 {mu}mol/m{sup 2}) of the adsorption sites on the surface as determined by Langmuir adsorption isotherm, which is related to its oxygen-containing functional groups on the carbonaceous surface as revealed by temperature-programmed desorption analysis. 57 refs., 10 figs., 6 tabs.

  10. Vhf EPR quantitation and speciation of organic sulfur in coal. [Quarterly] technical report, December 1, 1993--February 28, 1994

    SciTech Connect

    Clarkson, R.B.; Belford, R.I.

    1994-06-01

    The existence of free electrons in coals` natural site offers a great attraction for Electron Paramagnetic Resonance (EPR) analysis to aid in the study of the structure and composition of coal. This direct and non-destructive approach to coal analysis has been hindered by the problem of resolution using the conventional 9.5 GHz EPR spectrometers. In the past few years, we have developed techniques including W-band Very High Frequency EPR spectroscopy as a means of determining the quantity and structure of organic sulfur in native and desulfurized coals. The state of the art 95 GHz (W-band) EPR spectrometer which we have constructed shows a well resolved spectrum including the interaction between unpaired electrons and the heteroatom like sulfur. The spectra also provide quantitative as well as qualitative information regarding different sulfur species. In collaboration with researchers at the University of Kentucky, we are also analyzing the result of desulfurization techniques on the presence of various sulfur species in coal. In the past, we have tried to synthesize various model compounds comparing their W-band spectra with other models, the predictions of theoretical models, and with the W-band spectra of coal specimens. In this quarter, we have been concentrating our efforts on developing a new standard protocol in handling and preparing the coal samples for EPR measurements to provide a quantitative comparison between the EPR spectra of coal in the natural state and desulfurized. Ten coal samples, both native and desulfurized, have been provided to us. These samples have been run in both laboratories. The simulation of coal EPR spectra has been carried out using several mathematical models. EPR results now are being compared with XANES data.

  11. Aqueous liquid feed organic fuel cell using solid polymer electrolyte membrane

    NASA Technical Reports Server (NTRS)

    Surampudi, Subbarao (Inventor); Narayanan, Sekharipuram R. (Inventor); Vamos, Eugene (Inventor); Frank, Harvey A. (Inventor); Halpert, Gerald (Inventor); Olah, George A. (Inventor); Prakash, G. K. Surya (Inventor)

    1997-01-01

    A liquid organic fuel cell is provided which employs a solid electrolyte membrane. An organic fuel, such as a methanol/water mixture, is circulated past an anode of a cell while oxygen or air is circulated past a cathode of the cell. The cell solid electrolyte membrane is preferably fabricated from Nafion.TM.. Additionally, a method for improving the performance of carbon electrode structures for use in organic fuel cells is provided wherein a high surface-area carbon particle/Teflon.TM.-binder structure is immersed within a Nafion.TM./methanol bath to impregnate the electrode with Nafion.TM.. A method for fabricating an anode for use in a organic fuel cell is described wherein metal alloys are deposited onto the electrode in an electro-deposition solution containing perfluorooctanesulfonic acid. A fuel additive containing perfluorooctanesulfonic acid for use with fuel cells employing a sulfuric acid electrolyte is also disclosed. New organic fuels, namely, trimethoxymethane, dimethoxymethane, and trioxane are also described for use with either conventional or improved fuel cells.

  12. Laboratory Measurements of the Effect of Sulfuric and Organic Acid Coatings on the Optical Properties of Carbon Soot Aerosols

    NASA Astrophysics Data System (ADS)

    Xue, H.; Khalizov, A.; Zhang, R.

    2008-12-01

    Aerosol particles perturb the Earth-atmosphere radiative balance through scattering and absorption of the solar energy. Soot or black carbon, produced during combustion of fossil fuels and biofuels, is the major component responsible for light absorption by aerosol particles. The variation in the reported mass-specific absorption cross-sections (MAC) of fresh soot and increased light absorption by aged soot aerosols internally mixed with non-absorbing materials are the major factors leading to large uncertainties in the evaluation of the aerosol optical effects. We have investigated the optical properties of submicron carbon soot aerosols during simulated atmospheric processing with sulfuric acid and dicarboxylic organic acids. Internally mixed soot particles with known size, morphology, and the mixing state were produced by exposing the size-classified, flame-generated soot to sulfuric acid and organic acid vapor. Light extinction and scattering by fresh and internally mixed soot were measured at 532 nm wavelength using a cavity ring-down spectrometer and an integrating nephelometer, respectively; light absorption was derived as the difference between extinction and scattering. Mass-specific absorption cross-sections for fresh and internally mixed soot aggregates were calculated using the measured effective densities of soot cores. The optical properties of fresh soot were independent of the relative humidity (RH). Internally mixed soot exhibited significant enhancement in light absorption and scattering, increasing with the mass fraction of the coating material and RH. Sulfuric acid was found to cause greater enhancement in soot optical properties than organic acids. The higher absorption and scattering resulted in the increased single scattering albedo of coated soot aerosol. The measurements indicate that the irreversible restructuring of soot aggregates to more compact globules is a major contributor to the enhanced optical properties of internally mixed soot.

  13. Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol.

    PubMed

    Smith, Jeremy D; Kinney, Haley; Anastasio, Cort

    2015-04-21

    Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

  14. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    SciTech Connect

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program's Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment.

  15. Current emission trends for nitrogen oxides, sulfur dioxide, and volatile organic compounds by month and state: Methodology and results

    SciTech Connect

    Kohout, E.J.; Miller, D.J.; Nieves, L.A.; Rothman, D.S.; Saricks, C.L.; Stodolsky, F.; Hanson, D.A.

    1990-08-01

    This report presents estimates of monthly sulfur dioxide (SO{sub 2}), nitrogen oxides (NO{sub x}), and nonmethane voltatile organic compound (VOC) emissions by sector, region, and state in the contiguous United States for the years 1975 through 1988. This work has been funded as part of the National Acid Precipitation Assessment Program`s Emissions and Controls Task Group by the US Department of Energy (DOE) Office of Fossil Energy (FE). The DOE project officer is Edward C. Trexler, DOE/FE Office of Planning and Environment.

  16. Photoinduced reactions between Pb3O4 and organic dyes in aqueous solution under visible light.

    PubMed

    Zhou, Yangen; Long, Jinlin; Gu, Quan; Lin, Huaxiang; Lin, Huan; Wang, Xuxu

    2012-12-03

    Pb(3)O(4) could react with organic dyes in aqueous solution under visible light irradiation, in which Pb(3)O(4) was transformed into Pb(3)(CO(3))(2)(OH)(2) along with oxidation of the organic dyes. Cu(2+) has considerable effect on the reaction. In the presence of Cu(2+), MO (20 ppm) and RhB (10(-5) mol L(-1)) were completely degraded under visible light within 6 and 20 min, respectively, while both Pb(3)O(4) and Cu(2+) keep almost stable during photodegradation. The mechanisms of the reactions with and without Cu(2+) ions were studied. The photochemical system of Pb(3)O(4) cooperating with Cu(2+) ions is probably used for the treatment of organic pollutants in water under visible light.

  17. Versatile phase transfer of gold nanoparticles from aqueous media to different organic media.

    PubMed

    Karg, Matthias; Schelero, Natascha; Oppel, Claudia; Gradzielski, Michael; Hellweg, Thomas; von Klitzing, Regine

    2011-04-11

    A novel, simple, and very efficient method to prepare hydrophobically modified gold particles is presented. Gold nanoparticles of different sizes and polydispersities were prepared. The diameter of the gold particles ranges from 5 to 37 nm. All systems were prepared in aqueous solution stabilized by citrate and afterwards transferred into an organic phase by using amphiphilic alkylamine ligands with different alkyl chain lengths. The chain length was varied between 8 and 18 alkyl groups. Depending on the particle size and the alkylamine, different transfer efficiencies were obtained. In some cases, the phase transfer has a yield of about 100%. After drying, the particles can be redispersed in different organic solvents. Characterization of the particles before and after transfer was performed by using UV/Vis spectroscopy, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS) techniques. The effect of organic solvents with various refractive indices on the plasmon band position was investigated.

  18. Aqueous Oxidation of Green Leaf Volatiles as a Source of Secondary Organic Aerosol

    NASA Astrophysics Data System (ADS)

    Richards-Henderson, N. K.; Hansel, A.; Pham, A. T.; Vempati, H. S.; Valsaraj, K. T.; Anastasio, C.

    2013-12-01

    Vegetation emits volatile oxygenated hydrocarbons - the green leaf volatiles (GLVs) - which are formed from the biochemical conversion of linoleic and linolenic acids within plant cells. Stress or damage to vegetation can significantly elevate emission fluxes of these compounds, some of which are fairly water soluble. Aqueous-phase reactions of the GLVs with photochemically generated oxidants - such as hydroxyl radical (OH), singlet oxygen (1O2) and excited triplet states of organic compounds (3C*) _ might then form low-volatility products that can act as secondary organic aerosol (SOA). In order to determine if GLVs can be a significant source of secondary organic carbon in fogwater, studies of GLVs in laboratory solutions are needed to elucidate the oxidation kinetics and the corresponding SOA mass yields. In this study we are determining the second-order rate constants, and SOA mass yields, for five GLVs (cis-3-hexen-1-ol, cis-3-hexenylacetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol) reacting with OH,1O2 and 3C*. Experiments are performed at relevant fog water pHs, temperatures, and oxidant concentrations. Rate constants are determined using a relative rate approach in which the decay of GLVs and reference compounds are monitored as function of time by HPLC. The capacity of GLVs to form aqueous SOA was determined by following the formation of their decomposition products with HPLC-UV/DAD and HPLC-ESI/MS. SOA mass yields are measured gravimetrically from laboratory solutions containing atmospherically relevant concentrations of photooxidants and GLVs, and irradiated with simulated sunlight. We will use our results to assess the potential contribution of aqueous GLV reactions as a source of SOA in cloudy or foggy atmospheres.

  19. Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics

    NASA Astrophysics Data System (ADS)

    Shapiro, E. L.; Szprengiel, J.; Sareen, N.; Jen, C. N.; Giordano, M. R.; McNeill, V. F.

    2009-01-01

    Light-absorbing and high-molecular-weight secondary organic products were observed to result from the reaction of glyoxal in mildly acidic (pH=4) aqueous inorganic salt solutions mimicking aqueous tropospheric aerosol particles. High-molecular-weight (500-600 amu) products were observed when ammonium sulfate ((NH4)2SO4) or sodium chloride (NaCl) was present in the aqueous phase. The products formed in the (NH4)2SO4 solutions absorb light at UV and visible wavelengths. Substantial absorption at 300-400 nm develops within two hours, and absorption between 400-600 nm develops within days. Pendant drop tensiometry measurements show that the products are not surface-active. The experimental results along with ab initio predictions of the UV/Vis absorption of potential products suggest that an aldol condensation mechanism is active in the glyoxal-(NH4)2SO4system, resulting in the formation of pi-conjugated products. If similar products are formed in atmospheric aerosol particles, they could change the optical properties of the seed aerosol over its lifetime.

  20. Effects of Chromophoric Dissolved Organic Matter on Anthracene Photolysis Kinetics in Aqueous Solution and Ice.

    PubMed

    Malley, Philip P A; Grossman, Jarod N; Kahan, Tara F

    2017-09-27

    We measured photolysis kinetics of the PAH anthracene in aqueous solution, in bulk ice, and at ice surfaces in the presence and absence of chromophoric dissolved organic matter (CDOM). Self-association, which occurs readily at ice surfaces, may be responsible for the faster anthracene photolysis observed there. Photolysis rate constants in liquid water increased under conditions where anthracene self-association was observed. Concomitantly, kinetics changed from first-order to second-order, indicating that the photolysis mechanism at ice surfaces might be different than that in aqueous solution. Other factors that could lead to faster photolysis at ice surfaces were also investigated. Increased photon fluxes due to scattering in the ice samples can account for at most 20% of the observed rate increase, and other factors including singlet oxygen ((1)O2*) production and changes in pH and polarity were determined not to be responsible for the faster photolysis. CDOM (in the form of fulvic acid (FA)) did not affect anthracene photolysis kinetics in aqueous solution but suppressed photolysis in ice cubes and ice granules (by 30% and 56%, respectively). This was primarily due to competitive photon absorption (the inner filter effect). Freeze-concentration (or "salting out") appears to slightly increase the suppressing effects of FA on anthracene photolysis. This may be due to increased competitive photon absorption or to physical interactions between anthracene and FA.

  1. Principles for Manipulation of the Lateral Organization of Aqueous-Soluble Surface-Active Molecules at the Liquid Crystal-Aqueous Interface

    PubMed Central

    Gupta, Jugal K.; Abbott, Nicholas L.

    2011-01-01

    We report an investigation of the lateral organization of water-soluble, surface-active molecules within monolayers formed spontaneously at interfaces between aqueous phases and immiscible, micrometer-thick films of nematic liquid crystals (LCs; 4′-pentyl-4-cyanobiphenyl and TL205, a mixture of cyclohexanefluorinated biphenyls and fluorinated terphenyls). Using both anionic (sodium dodecylsulfate) and cationic surfactants (dodecyltrimethylammonium bromide), we demonstrate that the nematic order of the LCs can direct monolayers of surfactant in dynamic equilibria with bulk aqueous solutions to phase separate and assume lateral organizations at the interfaces of the LCs that are not seen in the absence of the nematic order. The lateral organization of the surfactants is readily evidenced by the patterned orientations assumed by the LCs, and can be manipulated reversibly by changes in the bulk concentrations of the surfactants. Experimental observations of the effects of bulk surfactant concentration, thickness of the film of LC, nematic order, and aqueous electrolyte concentration are placed within the framework of a simple thermodynamic model. The model incorporates the dynamic equilibration of surfactant between the bulk and interface as well as the coupling between the elasticity of nematic LCs and the lateral organization of the water-soluble surfactants within the monolayers. Qualitative agreement is found between the model predictions and experimental observations, thus supporting our conclusion that LCs offer the basis of general and facile methods to direct the lateral organization of interfacial molecular assemblies. PMID:19140731

  2. Microwave-induced carbon nanotubes catalytic degradation of organic pollutants in aqueous solution.

    PubMed

    Chen, Jing; Xue, Shuang; Song, Youtao; Shen, Manli; Zhang, Zhaohong; Yuan, Tianxin; Tian, Fangyuan; Dionysiou, Dionysios D

    2016-06-05

    In this study, a new catalytic degradation technology using microwave induced carbon nanotubes (MW/CNTs) was proposed and applied in the treatment of organic pollutants in aqueous solution. The catalytic activity of three CNTs of 10-20nm, 20-40nm, and 40-60nm diameters were compared. The results showed that organic pollutants such as methyl orange (MO), methyl parathion (MP), sodium dodecyl benzene sulfonate (SDBS), bisphenol A (BPA), and methylene blue (MB) in aqueous solution could be degraded effectively and rapidly in MW/CNTs system. CNTs with diameter of 10-20nm exhibited the highest catalytic activity of the three CNTs under MW irradiation. Further, complete degradation was obtained using 10-20nm CNTs within 7.0min irradiation when 25mL MO solution (25mg/L), 1.2g/L catalyst dose, 450W, 2450MHz, and pH=6.0 were applied. The rate constants (k) for the degradation of SDBS, MB, MP, MO and BPA using 10-20nm CNTs/MW system were 0.726, 0.679, 0.463, 0.334 and 0.168min(-1), respectively. Therefore, this technology may have potential application for the treatment of targeted organic pollutants in wastewaters.

  3. Volatility of organic aerosol: evaporation of ammonium sulfate/succinic acid aqueous solution droplets.

    PubMed

    Yli-Juuti, Taina; Zardini, Alessandro A; Eriksson, Axel C; Hansen, Anne Maria K; Pagels, Joakim H; Swietlicki, Erik; Svenningsson, Birgitta; Glasius, Marianne; Worsnop, Douglas R; Riipinen, Ilona; Bilde, Merete

    2013-01-01

    Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol.

  4. Volatility of Organic Aerosol: Evaporation of Ammonium Sulfate/Succinic Acid Aqueous Solution Droplets

    PubMed Central

    2013-01-01

    Condensation and evaporation modify the properties and effects of atmospheric aerosol particles. We studied the evaporation of aqueous succinic acid and succinic acid/ammonium sulfate droplets to obtain insights on the effect of ammonium sulfate on the gas/particle partitioning of atmospheric organic acids. Droplet evaporation in a laminar flow tube was measured in a Tandem Differential Mobility Analyzer setup. A wide range of droplet compositions was investigated, and for some of the experiments the composition was tracked using an Aerosol Mass Spectrometer. The measured evaporation was compared to model predictions where the ammonium sulfate was assumed not to directly affect succinic acid evaporation. The model captured the evaporation rates for droplets with large organic content but overestimated the droplet size change when the molar concentration of succinic acid was similar to or lower than that of ammonium sulfate, suggesting that ammonium sulfate enhances the partitioning of dicarboxylic acids to aqueous particles more than currently expected from simple mixture thermodynamics. If extrapolated to the real atmosphere, these results imply enhanced partitioning of secondary organic compounds to particulate phase in environments dominated by inorganic aerosol. PMID:24107221

  5. Study of organic compounds-water interactions by partition in aqueous two-phase systems.

    PubMed

    Madeira, Pedro P; Bessa, Ana; Teixeira, Miguel A; Álvares-Ribeiro, Luís; Aires-Barros, M Raquel; Rodrigues, Alírio E; Zaslavsky, Boris Y

    2013-12-27

    Partition coefficients of fourteen organic compounds were determined in 10 or 20 different polymer/polymer aqueous two-phase systems (ATPS) all at physiological pH (0.15M NaCl in 0.01M phosphate buffer, pH 7.4). Solute-specific coefficients characterizing different types of solute-water interactions for the compounds examined were determined by the multiple linear regression analysis. It is shown that (i) the partition behavior for the polar organic compounds is affected not only by dipole-dipole and hydrogen-bond interactions with aqueous environment but, notably, in most cases also by dipole-ion interactions; (ii) it is possible to predict partition behavior for compounds with pre-determined solute-specific coefficients in ATPS with characterized solvent features; and (iii) linear combinations of the solute-specific coefficients for the organic compounds might be useful in the development of quantitative structure-activity relationship (QSAR) analysis to describe their odor detection threshold.

  6. Combinatorial synthesis by nature: volatile organic sulfur-containing constituents of Ruta chalepensis L.

    PubMed

    Escher, Sina; Niclass, Yvan; van de Waal, Matthijs; Starkenmann, Christian

    2006-09-01

    Ongoing interest in discovering new natural fragrance and flavor ingredients prompted us to examine a solvent extract of sulfurous-sweaty smelling Ruta chalepensis L. (Rutaceae) plant material more closely. Twenty-one sulfur-containing constituents of similar structures were identified by GC/MS techniques. Amongst them, 14 have never been described to occur in nature. The compounds 1-18 belong to a family of natural flavor and fragrance molecules having a 1,3-positioned O,S moiety in common. The identities of the natural constituents were confirmed by comparison with synthetic reference samples, and the organoleptic properties of the latter were studied. The relative and absolute configurations of the four stereoisomers of 4-methyl-3-sulfanylhexan-1-ol (5) were established by stereoselective synthesis. The natural isomers consisted of a 65 : 35 mixture of (3R,4S)-5 and (3S,4S)-5.

  7. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Final technical report, 1 September 1991--31 August 1992

    SciTech Connect

    Kruge, M.A.; Palmer, S.R.

    1992-12-31

    With the recent increase in concern for environmental issues and the implication of sulfur and nitrogen in coal combustion products as prime causes of acid rain, it has become clear that there is an urgent need for alternative methods for de g the nature of organic sulfur and nitrogen compounds in coal. The principal impediment to the molecular characterization of organic sulfur and nitrogen forms in coal is the polymeric nature of coal`s molecular structure, ordering coal insoluble and impossible to analyze by the necessary gas chromatographic (GC) methods. In our research, we apply mild chemical degradation techniques in order to render coal soluble in common organic solvents and thus amenable to standard GC characterization. The study also seeks to apply the degradative techniques to coal asphaltenes, since they are believed to be polymeric structures similar to the whole coal, but smaller and more readily analyzed. Of the degradation techniques used to date, oxidation by sodium dichromate provides the best chemical structural information. A variety of major sulfur compounds were detected in the dichromate oxidation products of demineralized IBC101 coal, including thiazoles (compounds which contains both sulfur and nitrogen) and a series of isomers of C{sub 2}-, C{sub 3}and C{sub 4}-alkylthiophene derivatives. Precise agreement between GC-MS and sulfur-selective GC-FPD data was obtained for these compounds, which probably originated as short alkyl chains on exterior portions of the original peat macromolecular structure that were sulfurized shortly after burial by H{sub 2}S. The results were further confirmed by the analysis of a non-Illinois Basin coal with nearly twice the organic sulfur content of IBC101.

  8. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Final technical report, 1 September 1991--31 October 1992

    SciTech Connect

    Kruge, M.A.; Palmer, S.R.

    1992-12-31

    With the recent increase in concern for environmental issues and the implication of sulfur and nitrogen in coal combustion preducts as prime causes of acid rain, it has become clear that there is an urgent need for alternative methods for determining the nature of organic sulfur and nitrogen compounds in coal. The principal impediment to the molecular characterization of organic sulfur and nitrogen forms in coal is the polymeric nature of coal`s molecular structure, rendering coal insoluble and impossible to analyze by the necessary gas chromatographic (GC) methods. In our research, we apply mild chemical degradation techniques in order to render coal soluble in common organic solvents and thus amenable to standard GC characterization. The study also seeks to apply the degradative techniques to coal asphaltenes, since they are believed to be polymeric structures similar to the whole coal, but smaller and more readily analyzed. Of the degradation techniques used to date, oxidation by sodium dichromate provides the best chemical structure information. A variety of major sulfur compounds were detected in the dichromate oxidation products of demineralized IBC101 coal, including thiazoles (compounds which contains both sulfur and nitrogen) and a series of isomers of C{sub 2}-, C{sub 3}- and C{sub 4}-alkylthiophene derivatives. Precise agreement between GC-MS and sulfur-selective GC-FPD data was obtained for these compounds, which probably originated as short alkyl chains on exterior portions of the original peat macromolecular structure that were sulfurized shortly after burial by H{sub 2}S. The results were further confirmed by the analysis of a non-Illinois Basin coal with nearly twice the organic sulfur content of IBC101.

  9. Organic Matter Sulfurization in the Cariaco Water Column Revealed by High-Sensitivity and Compound-Specific d34S Analyses.

    NASA Astrophysics Data System (ADS)

    Raven, M. R.; Sessions, A. L.; Adkins, J. F.; Thunell, R.

    2015-12-01

    Organic matter burial in marine sediments is a major process in the global carbon cycle, and enhanced organic matter burial is often associated with periods of global climatic and ecological change. Still, we have only a limited understanding of the processes that drive enhanced OM burial during oxygen-deficient conditions. Abiotic OM sulfurization has the potential to enhance the preservation of OM, but for this process to be significant it must compete with heterotrophic remineralization, most of which occurs before sinking particles reach the sea floor. We investigate the sources of sulfur to sinking particles in a modern marine basin using samples from the CARIACO fixed sediment trap time-series, applying recently developed methods for d34S analysis of small (≥20 nmol) sulfur pools and individual volatile organosulfur compounds. Relative to expectations for planktonic biomass, we find that sinking particles are both sulfur-rich and 34S-depleted. Higher apparent fluxes of 34S-depleted organic sulfur are associated with high OM export from the surface ocean, low terrestrial inputs, and high concentrations of both elemental S and the dominant non-polar organosulfur compound, C20 thiophene. We conclude that OM sulfurization is occurring in particles sinking through the Cariaco water column on timescales of days or less. Depending on the frequency of high OM export events, we estimate that this rapid sulfurization delivers roughly half of the total organic S present at 5 cm depth in underlying sediments. Accordingly, many OM-rich deposits in the geologic record may represent the products of water column sulfurization. This process provides a strong mechanistic feedback between oxygen deficiency and OM preservation.

  10. Reactions of potential organic water contaminants with aqueous chlorine and monochloramine. Final report

    SciTech Connect

    Scully, F.E.; White, W.N.

    1991-09-01

    Aqueous chlorine and monochloramine are the two most widely used disinfectants of drinking waters in the U.S. The reactions of these two disinfectants with various organic functional groups in order to predict which classes of chemical substrates might be most likely to undergo transformations under drinking water conditions are reviewed. For those reactions for which kinetic data are available, the half-lives of substances containing these functional groups is estimated. Where possible, known reaction mechanisms are identified and structure activity relationships are discussed.

  11. SEPARATION OF PLUTONIUM FROM AQUEOUS SOLUTIONS BY ION-EXCHANGE

    DOEpatents

    Schubert, J.

    1958-06-01

    A process is described for the separation of plutonium from an aqueous solution of a plutonium salt, which comprises adding to the solution an acid of the group consisting of sulfuric acid, phosphoric acid, and oxalic acid, and mixtures thereof to provide an acid concentration between 0.0001 and 1 M, contacting the resultant solution with a synthetic organic anion exchange resin, and separating the aqueous phase and the resin which contains the plutonium.

  12. The Relative Importance of Aqueous vs. Vapor-Pressure Dependent Pathways for Particulate Organic Nitrate Formation

    NASA Astrophysics Data System (ADS)

    Zare, A.; Pye, H. O. T.; Cohen, R. C.

    2016-12-01

    Formation of biogenic derived organic nitrates is known as an important immediate sink of atmospheric nitrogen oxides. Although, subsequent oxidation and photolysis of organic nitrates can return a part of the sequestered NOx to the atmosphere, other removal pathways in combination with wet and dry deposition and hydrolysis of particulate organic nitrates is of central importance in irreversible NOx removal from the atmosphere. The aim of this work is to understand how and to what degree the particle phase participates in removal of NOx. We implement a new BVOC oxidation gas phase mechanism (including a detailed representation of OH- and NO3-initiated organic nitrates) and an explicit representation of organic nitrate aerosols formation, including irreversible aqueous-phase uptake and reversible partitioning onto pre-existing organic aerosol, into the CMAQ model. Using these mechanisms, we simulate observations from the SOAS field campaigns over the southeast US in summer 2013 and examine the relative role of water-mediated vs vapor pressure processes in determining aerosol from organic nitrates.

  13. From the Cover: Sulfur isotopes of organic matter preserved in 3.45-billion-year-old stromatolites reveal microbial metabolism

    NASA Astrophysics Data System (ADS)

    Bontognali, Tomaso R. R.; Sessions, Alex L.; Allwood, Abigail C.; Fischer, Woodward W.; Grotzinger, John P.; Summons, Roger E.; Eiler, John M.

    2012-09-01

    The 3.45-billion-year-old Strelley Pool Formation of Western Australia preserves stromatolites that are considered among the oldest evidence for life on Earth. In places of exceptional preservation, these stromatolites contain laminae rich in organic carbon, interpreted as the fossil remains of ancient microbial mats. To better understand the biogeochemistry of these rocks, we performed microscale in situ sulfur isotope measurements of the preserved organic sulfur, including both Δ33S and . This approach allows us to tie physiological inference from isotope ratios directly to fossil biomass, providing a means to understand sulfur metabolism that is complimentary to, and independent from, inorganic proxies (e.g., pyrite). Δ33S values of the kerogen reveal mass-anomalous fractionations expected of the Archean sulfur cycle, whereas values show large fractionations at very small spatial scales, including values below -15‰. We interpret these isotopic patterns as recording the process of sulfurization of organic matter by H2S in heterogeneous mat pore-waters influenced by respiratory S metabolism. Positive Δ33S anomalies suggest that disproportionation of elemental sulfur would have been a prominent microbial process in these communities.

  14. Aboveground and Belowground Herbivores Synergistically Induce Volatile Organic Sulfur Compound Emissions from Shoots but Not from Roots.

    PubMed

    Danner, Holger; Brown, Phil; Cator, Eric A; Harren, Frans J M; van Dam, Nicole M; Cristescu, Simona M

    2015-07-01

    Studies on aboveground (AG) plant organs have shown that volatile organic compound (VOC) emissions differ between simultaneous attack by herbivores and single herbivore attack. There is growing evidence that interactive effects of simultaneous herbivory also occur across the root-shoot interface. In our study, Brassica rapa roots were infested with root fly larvae (Delia radicum) and the shoots infested with Pieris brassicae, either singly or simultaneously, to study these root-shoot interactions. As an analytical platform, we used Proton Transfer Reaction Mass Spectrometry (PTR-MS) to investigate VOCs over a 3 day time period. Our set-up allowed us to monitor root and shoot emissions concurrently on the same plant. Focus was placed on the sulfur-containing compounds; methanethiol, dimethylsulfide (DMS), and dimethyldisulfide (DMDS), because these compounds previously have been shown to be biologically active in the interactions of Brassica plants, herbivores, parasitoids, and predators, yet have received relatively little attention. The shoots of plants simultaneously infested with AG and belowground (BG) herbivores emitted higher levels of sulfur-containing compounds than plants with a single herbivore species present. In contrast, the emission of sulfur VOCs from the plant roots increased as a consequence of root herbivory, independent of the presence of an AG herbivore. The onset of root emissions was more rapid after damage than the onset of shoot emissions. The shoots of double infested plants also emitted higher levels of methanol. Thus, interactive effects of root and shoot herbivores exhibit more strongly in the VOC emissions from the shoots than from the roots, implying the involvement of specific signaling interactions.

  15. Sedimentary pyrite δ34S differs from porewater sulfide in Santa Barbara Basin: Proposed role of organic sulfur

    NASA Astrophysics Data System (ADS)

    Raven, Morgan Reed; Sessions, Alex L.; Fischer, Woodward W.; Adkins, Jess F.

    2016-08-01

    Santa Barbara Basin sediments host a complex network of abiotic and metabolic chemical reactions that knit together the carbon, sulfur, and iron cycles. From a 2.1-m sediment core collected in the center of the basin, we present high-resolution profiles of the concentrations and isotopic compositions of all the major species in this system: sulfate, sulfide (∑H2S), elemental sulfur (S0), pyrite, extractable organic sulfur (OS), proto-kerogen S, total organic and dissolved inorganic carbon, and total and reducible iron. Below 10 cm depth, the core is characterized by low apparent sulfate reduction rates (<0.01 mM/yr) except near the sulfate-methane transition zone. Surprisingly, pyrite forming in shallow sediments is ∼30‰ more 34S-depleted than coexisting ∑H2S in porewater. S0 has the same strongly 34S-depleted composition as pyrite where it forms near the sediment-water interface, though not at depth. This pattern is not easily explained by conventional hypotheses in which sedimentary pyrite derives from abiotic reactions with porewater ∑H2S or from the products of S0 disproportionation. Instead, we propose that pyrite formation in this environment occurs within sulfate reducing microbial aggregates or biofilms, where it reflects the isotopic composition of the immediate products of bacterial sulfate reduction. Porewater ∑H2S in Santa Barbara Basin may be more 34S-enriched than pyrite due to equilibration with relatively 34S-enriched OS. The difference between OS and pyrite δ34S values would then reflect the balance between microbial sulfide formation and the abundance of exchangeable OS. Both OS and pyrite δ34S records thus have the potential to provide valuable information about biogeochemical cycles and redox structure in sedimentary paleoenvironments.

  16. Advanced characterization of forms of chlorine, organic sulfur, and trace elements in available coals from operating Illinois mines. [Quarterly] technical report, September 1--November 30, 1994

    SciTech Connect

    Chou, M.I.M.; Demir, I.; Ruch, J.M.

    1994-12-31

    A set of 34 as-shipped coal samples from operating Illinois mines is available for this study to determine the forms of chlorine and sulfur and leachability of chlorine during wet grinding and froth flotation. The forms of chlorine may be inorganic, ionic, and organic. The forms of organic sulfur will include organic sulfide and thiophenic sulfur. Chlorine can be leached from coal during wet grinding. The potential for removal of chlorine from the samples during fine ({minus}200 mesh) and ultrafine ({minus}400 mesh) wet-grinding and during froth flotation designed primarily for removal of pyrite and ash will be determined. In addition, the organic/inorganic affinities of trace elements in as-shipped Illinois coals will be assessed so that the current physical coal cleaning results may be better interpreted.

  17. Photo-induced valence change of the sulfur atom in an L-cysteine thin film grown on a silver metal substrate in a saliva-emulated aqueous solution

    NASA Astrophysics Data System (ADS)

    Tsujibayashi, Toru; Azuma, Junpei; Yamamoto, Isamu; Takahashi, Kazutoshi; Kamada, Masao

    2015-04-01

    A thin film of L-cysteine (HSCH2CH(NH2)COOH) is grown on a silver substrate in saliva-emulated aqueous solution. X-ray photoemission spectroscopic measurements have revealed that the sulfur atom shows valence change under IR laser irradiation at 825 nm. The valence change maintains for about a minute at room temperature and more than an hour between 110 and 250 K after stopping the laser irradiation. It is not observed at all at temperatures lower than 110 K. This temperature-dependent behavior indicates that the photo-excited electronic change should be accompanied by a conformational change in the L-cysteine molecule. It is strongly suggested that the reversible valence change of the sulfur atom is applicable to a memory used around room temperature.

  18. Photo-induced valence change of the sulfur atom in an L-cysteine thin film grown on a silver metal substrate in a saliva-emulated aqueous solution

    SciTech Connect

    Tsujibayashi, Toru; Azuma, Junpei; Yamamoto, Isamu; Takahashi, Kazutoshi; Kamada, Masao

    2015-04-27

    A thin film of L-cysteine (HSCH{sub 2}CH(NH{sub 2})COOH) is grown on a silver substrate in saliva-emulated aqueous solution. X-ray photoemission spectroscopic measurements have revealed that the sulfur atom shows valence change under IR laser irradiation at 825 nm. The valence change maintains for about a minute at room temperature and more than an hour between 110 and 250 K after stopping the laser irradiation. It is not observed at all at temperatures lower than 110 K. This temperature-dependent behavior indicates that the photo-excited electronic change should be accompanied by a conformational change in the L-cysteine molecule. It is strongly suggested that the reversible valence change of the sulfur atom is applicable to a memory used around room temperature.

  19. Analyzing organic sulfur in coal/char: Integrated mild degradation/XANES methods. [Quarterly] technical report, December 1, 1993--February 28, 1994

    SciTech Connect

    Palmer, S.R.; Huffman, G.P.

    1994-06-01

    The cost effective removal of sulfur from coal has been very difficult to accomplish. Perhaps the single most important reason for this is the fact that the organic sulfur in coal remains very poorly characterized. The overall goal of this study is to improve our understanding of sulfur in coals/chars via the use of combined advanced non-destructive and advanced destructive methods of sulfur analysis. This study combines selective oxidation, analytical pyrolysis, and sulfur X-ray Absorption Near Edge Structure Spectroscopy (XANES) analysis. Examination of samples that were oxidized with peroxyacetic acid using the analytical pyrolysis technique showed that the level of simple thiophene structures observed in the pyrolysis products declines with increasing levels of oxidation. Sulfur XANES spectra of treated samples showed various effects depending on the treatment severity. For the less severely treated samples (demineralization and solvent extraction), the XANES spectra were similar, although not identical, to the untreated coal spectra, whereas the more severe treatments (steam at 450{degree}C; peroxyacetic acid at 25{degree}C) showed preferential oxidation of one or more sulfur-bearing phases in the original coal.

  20. Investigation on thiosulfate-involved organics and nitrogen removal by a sulfur cycle-based biological wastewater treatment process.

    PubMed

    Qian, Jin; Lu, Hui; Cui, Yanxiang; Wei, Li; Liu, Rulong; Chen, Guang-Hao

    2015-02-01

    Thiosulfate, as an intermediate of biological sulfate/sulfite reduction, can significantly improve nitrogen removal potential in a biological sulfur cycle-based process, namely the Sulfate reduction-Autotrophic denitrification-Nitrification Integrated (SANI(®)) process. However, the related thiosulfate bio-activities coupled with organics and nitrogen removal in wastewater treatment lacked detailed examinations and reports. In this study, S2O3(2-) transformation during biological SO4(2-)/SO3(2-) co-reduction coupled with organics removal as well as S2O3(2-) oxidation coupled with chemolithotrophic denitrification were extensively evaluated under different experimental conditions. Thiosulfate is produced from the co-reduction of sulfate and sulfite through biological pathway at an optimum pH of 7.5 for organics removal. And the produced S2O3(2-) may disproportionate to sulfide and sulfate during both biological S2O3(2-) reduction and oxidation most possibly carried out by Desulfovibrio-like species. Dosing the same amount of nitrate, pH was found to be the more direct factor influencing the denitritation activity than free nitrous acid (FNA) and the optimal pH for denitratation (7.0) and denitritation (8.0) activities were different. Spiking organics significantly improved both denitratation and denitritation activities while minimizing sulfide inhibition of NO3(-) reduction during thiosulfate-based denitrification. These findings in this study can improve the understanding of mechanisms of thiosulfate on organics and nitrogen removal in biological sulfur cycle-based wastewater treatment.

  1. Determination of trace organic pollutants in aqueous samples using GC/MS and SPE techniques

    SciTech Connect

    Yoo, L.J.; Yamamoto, M.; Fitzsimmons, S.; Shen, Y.

    1996-11-01

    This study evaluates the advantage of using GC/MS (ion trap) and solid phase extraction (SPE) for the determination of semi-volatile organics which cover priority pollutants, such as polycyclic aromatic hydrocarbons, pesticides, phthalates, and synthetic organic analytes. SPE of trace organic compounds using reverse phase sorbent is attractive compared to the more traditional methods that utilize liquid-liquid extraction or microextraction for the removal of these pollutants from aqueous samples. GC/MS method involving SPE for sample preparation reduces manual labor, speed sample processing,and substantially reduces the volume of solvent required. Also, the application of axial modulation ion trap mass spectrometry improved sensitivity in GC/MS analysis and the method accuracy and precision of semi-volatile organics from GC/MS (ion trap) are very competitive with electron capture detector and photo ionization detector. Systematic studies were done to determine the factors that effect the optimum disk sampling/elution conditions to achieve the quality control requirements for the compliance monitoring. The recoveries of phthalates, polycyclic aromatic hydrocarbons (PAH`s) and most of the organic pesticides, which have very hydrophobic nature and high boiling points, are very acceptable. Consequently GC/MS analysis using solid phase extraction (SPE) techniques can be applied as the primary analytical method and final conformation tool for the routine monitoring samples such as ground water, surface water and reclaimed water for the determination of trace organic pollutants with improved sensitivity, reduced extraction time and monitoring expense.

  2. Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling

    SciTech Connect

    Boone, Eric J.; Laskin, Alexander; Laskin, Julia; Wirth, Christopher; Shepson, Paul B.; Stirm, Brian H.; Pratt, Kerri A.

    2015-07-21

    Cloud water and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry with nanospray desorption electrospray ionization and direct infusion electrospray ionization were utilized to compare the organic composition of the particle and cloud water samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloud water, showing the significant influence of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloud water samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloud water when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.

  3. Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling.

    PubMed

    Boone, Eric J; Laskin, Alexander; Laskin, Julia; Wirth, Christopher; Shepson, Paul B; Stirm, Brian H; Pratt, Kerri A

    2015-07-21

    Cloudwater and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry (HRMS) with nanospray desorption electrospray ionization (nano-DESI) and direct infusion electrospray ionization (ESI) were utilized to compare the organic composition of the particle and cloudwater samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloudwater, showing the significant influence of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloudwater samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloudwater when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.

  4. Characterization of the organic-sulfur-degrading enzymes. [Quarterly] technical report, December 1, 1992--February 28, 1993

    SciTech Connect

    Ho, N.W.Y.

    1993-06-01

    The objective of this project is to characterize and purify the enzymes involved in degrading organic sulfur in coal from two well characterized organic sulfur degrading strains, IGTS8 and K3B. We believe that characterization and purification of these enzymes may provide valuable information that will lead to developing or isolating better strains for desulfurization of coal. Our recent results imply that the IGTS8 enzymes are firmly attached to the cell wall, most likely that they are covalently bonded to the cell wall. We believe that for coal desulfurization, it is better to have a microorganism that can secrete its desulfurization enzymes into the medium. The enzymes can penetrate into coal hundreds of times better than a bacterial cell. Thus we have changed the priority of this project. We believe that the isolation of a mutant of IGTS8 which can release the desulfurization enzymes into the cultural medium will be able to develop a much improved microbial process for coal desulfurization. Furthermore, the isolation of sucha mutant will be able to shed some light on how the wild type IGTS8 desulfurization enzyme are attached to the cell wall and make the purification of these enzymes much easier to accomplish.

  5. Antimicrobial activity of aqueous and organic extracts of a Saudi medicinal plant: Rumex nervosus

    PubMed Central

    Al-Asmari, Abdul Rahman K.; Siddiqui, Yunus M.; Athar, Md. Tanwir; Al-Buraidi, Ahmed; Al-Eid, A. S.; Horaib, Ghalib B.

    2015-01-01

    Objective: The antimicrobial effect of aerial part of Rumex nervosus obtained from the Southern region of Saudi Arabia was evaluated on bacterial strains Staphylococcus aureus, methicillin resistant S. aureus, Enterococcus faecalis, Escherichia coli, Pseudomonas Aeruginosa, and fungal strain Candida albicans. Materials and Methods: The solvents used for the extraction were aqueous, hexane, and methanol. The in vitro antimicrobial activity was performed by agar diffusion and disk diffusion methods and the confirmation of this activity was done by the enumeration of colony forming units (CFU). Results: The aqueous extract showed the growth inhibitory effect on Gram-positive bacteria while the Gram-negative P. aeruginosa was the most sensitive microorganism as determined by the agar diffusion technique. Surprisingly, the extract showed little antibacterial activity on other Gram-negative bacteria (E. coli) by this technique. Ethanolic extract was also found to be inhibitory to the growth of microorganisms. Hexane extract was relatively low in antimicrobial activity on Gram-negative E. coli and P. aeruginosa, while both the organic extracts were inhibitory to the growth of the fungus, C. albicans. Hexane gave no conclusive results with agar or disk diffusion methods, but showed the microbial growth inhibition in CFU enumeration. The antibacterial activity of active extracts was compared with vancomycin while antifungal activity of was compared with amphotericin B. Conclusion: The results obtained in the present study suggest that R. nervosus showed a marked antimicrobial activity with the test organisms. PMID:26681888

  6. Peptide environment specifies conformation. Helicity of hydrophobic segments compared in aqueous, organic, and membrane environments.

    PubMed

    Li, S C; Deber, C M

    1993-11-05

    Transmembrane segments in integral membrane proteins exist characteristically as helices in lipid bilayers, yet are often rich in residues considered helix-destabilizing (Val, Ile, Gly) in soluble proteins. We propose that helicity of a transmembrane segment is likely to be affected by factors other than the "intrinsic" helical propensities of its component amino acids. This hypothesis is tested by comparing the conformation(s) in aqueous, organic, membrane-mimetic (micellar), and membrane (bilayer) environments of designed model peptides with systematically altered helical propensity and/or segmental hydrophobicity. Peptides of prototypic sequence NH2-(Ser-Lys)2-Ala5-Leu6-Ala7-Ala8-Leu9-Ala10-++ +Trp11-Ala12-Leu13-Ala14- (Lys-Ser)3-OH were synthesized, which incorporate a hydrophobic core "guest" segment (residues 5-14) into a water-soluble hydrophilic host matrix. Related peptides featured substitution of Leu6,9,13-->Gly, Leu6,9,13-->Ala, and Ala7,10,14-->Gly. Circular dichroism spectra revealed that algorithms for soluble proteins correctly predicted peptide helical proclivities in aqueous solutions, but peptide helicity in organic (trifluoroethanol) solvents, membrane-mimetic SDS micelles, and negatively charged lipid bilayer vesicles, was found to be governed almost exclusively by the segmental hydrophobicity of the peptide mid-hydrophobic core segment. In related Trp fluorescence studies, peptide-membrane association was similarly correlated with extent of hydrophobic interaction.

  7. Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media.

    SciTech Connect

    Staszak-Jirkovsky, Jakub; Subbaraman, Ram; Strmcnik, Dusan; Harrison, Katherine L.; Diesendruck, Charles E.; Assary, Rajeev; Frank, Otakar; Kobr, Lukas; Wiberg, Gustav K.H; Genorio, Bostjan; Connell, Justin G.; Lopes, Pietro P.; Stamenkovic, Vojislav R.; Curtiss, Larry; Moore, Jeffrey S.; Zavadil, Kevin R.; Markovic, Nenad M.

    2015-11-01

    Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad center dot center dot center dot H2O (aqueous solutions) and LiO2 center dot center dot center dot H2O (organic solvents) complexes that place water in a configurationally favorable position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.

  8. Water as a promoter and catalyst for dioxygen electrochemistry in aqueous and organic media.

    DOE PAGES

    Staszak-Jirkovsky, Jakub; Subbaraman, Ram; Strmcnik, Dusan; ...

    2015-11-01

    Water and oxygen electrochemistry lies at the heart of interfacial processes controlling energy transformations in fuel cells, electrolyzers, and batteries. Here, by comparing results for the ORR obtained in alkaline aqueous media to those obtained in ultradry organic electrolytes with known amounts of H2O added intentionally, we propose a new rationale in which water itself plays an important role in determining the reaction kinetics. This effect derives from the formation of HOad center dot center dot center dot H2O (aqueous solutions) and LiO2 center dot center dot center dot H2O (organic solvents) complexes that place water in a configurationally favorablemore » position for proton transfer to weakly adsorbed intermediates. We also find that, even at low concentrations (<10 ppm), water acts simultaneously as a promoter and as a catalyst in the production of Li2O2, regenerating itself through a sequence of steps that include the formation and recombination of H+ and OH-. We conclude that, although the binding energy between metal surfaces and oxygen intermediates is an important descriptor in electrocatalysis, understanding the role of water as a proton-donor reactant may explain many anomalous features in electrocatalysis at metal-liquid interfaces.« less

  9. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    PubMed Central

    Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Pietrogrande, Maria Chiara; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-01-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1–0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4–20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate. PMID:27551086

  10. Magnetic pollen grains as sorbents for facile removal of organic pollutants in aqueous media.

    PubMed

    Thio, Beng Joo Reginald; Clark, Kristin K; Keller, Arturo A

    2011-10-30

    Plant materials have long been demonstrated to sorb organic compounds. However, there are no known reports about pollen grains acting as sorbents to remove hydrophobic organic compounds (HOCs) such as pesticides, polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) from contaminated waters. We report a facile and effective method to remove HOCs from water using magnetized short ragweed (Ambrosia artemisiifolia) pollen grains. We dispersed the magnetized pollen grains in two different water samples - deionized (DI) and natural storm water to mimic real environmental conditions likely to be encountered during treatment. The magnetized pollen grains were readily separated from the aqueous media via a magnetic field after adsorption of the HOCs. We measured the adsorption of five representative HOCs (acenaphthene, phenanthrene, atrazine, diuron, and lindane) onto magnetized ragweed pollen in different aqueous matrices. We demonstrate that the adsorption capacity of the magnetized ragweed pollen can be regenerated to a large extent for reuse as a sorbent. Our results also indicate that the magnetized pollen grains are as effective as activated carbon (AC) in removing HOCs from both types of contaminated waters. The high HOC sorption of the ragweed pollen allows it to have potential remediation application in the field under realistic conditions.

  11. Direct observation of aqueous secondary organic aerosol from biomass-burning emissions

    NASA Astrophysics Data System (ADS)

    Gilardoni, Stefania; Massoli, Paola; Paglione, Marco; Giulianelli, Lara; Carbone, Claudio; Rinaldi, Matteo; Decesari, Stefano; Sandrini, Silvia; Costabile, Francesca; Gobbi, Gian Paolo; Chiara Pietrogrande, Maria; Visentin, Marco; Scotto, Fabiana; Fuzzi, Sandro; Facchini, Maria Cristina

    2016-09-01

    The mechanisms leading to the formation of secondary organic aerosol (SOA) are an important subject of ongoing research for both air quality and climate. Recent laboratory experiments suggest that reactions taking place in the atmospheric liquid phase represent a potentially significant source of SOA mass. Here, we report direct ambient observations of SOA mass formation from processing of biomass-burning emissions in the aqueous phase. Aqueous SOA (aqSOA) formation is observed both in fog water and in wet aerosol. The aqSOA from biomass burning contributes to the “brown” carbon (BrC) budget and exhibits light absorption wavelength dependence close to the upper bound of the values observed in laboratory experiments for fresh and processed biomass-burning emissions. We estimate that the aqSOA from residential wood combustion can account for up to 0.1-0.5 Tg of organic aerosol (OA) per y in Europe, equivalent to 4-20% of the total OA emissions. Our findings highlight the importance of aqSOA from anthropogenic emissions on air quality and climate.

  12. Surface tension depression by low-solubility organic material in aqueous aerosol mimics

    NASA Astrophysics Data System (ADS)

    Schwier, Allison; Mitroo, Dhruv; McNeill, V. Faye

    2012-07-01

    Surface-active material, including long-chain fatty acids (LCFAs), comprises a significant fraction of organic aerosol mass. Surface-active species are thought to form a film at the gas-aerosol interface, with implications for aerosol heterogeneous chemistry and cloud formation. However, LCFA phase behavior and surface-bulk partitioning has not been characterized under most conditions typical of tropospheric aerosol water (i.e. acidic, high ionic content), making it challenging to predict surface film formation in aerosols. In this study, we present measurements of the surface tension of aqueous solutions containing the slightly soluble LCFAs oleic and stearic acid. The effect of varying pH, organic concentration, and inorganic salt content was tested for each system. We observe surface tension depression compared to water of up to ˜30 and 45% for aqueous solutions containing stearic or oleic acid at pH 0-8 and high inorganic salt concentrations (NaCl and (NH4)2SO4). This suggests that surface film formation is favorable for these species in atmospheric aerosols.

  13. Responses of polar organic compounds to different ionic environments in aqueous media are interrelated.

    PubMed

    Ferreira, L A; Chervenak, A; Placko, S; Kestranek, A; Madeira, P P; Zaslavsky, B Y

    2014-11-14

    Solubilities of 17 polar organic compounds in aqueous solutions of Na2SO4, NaCl, NaClO4, and NaSCN at the salt concentrations of up to 1.0-2.0 M were determined and the Setschenow constant, ksalt, values were estimated. It was found that NaClO4 may display both salting-in and salting-out effects depending on the particular compound structure. The Setschenow constant values for all the polar compounds examined in different salt solutions are found to be interrelated. Similar relationships were observed for partition coefficients of nonionic organic compounds in aqueous polyethylene glycol-sodium sulfate two-phase systems in the presence of different salt additives reported previously [Ferreira et al., J. Chromatogr. A, 2011, 1218, 5031], and for the effects of different salts on optical rotation of amino acids reported by Rossi et al. [J. Phys. Chem. B, 2007, 111, 10510]. In order to explain the observed relationships it is suggested that all the effects observed originate as responses of the compounds to the presence of a given ionic environment and its interaction with the compounds by forming direct or solvent-separated ionic pairs. The response is compound-specific and its strength is determined by the compound structure and the type (and concentration) of ions inducing the response.

  14. Organic and aqueous electrolytes used for etching macro- and mesoporous silicon

    NASA Astrophysics Data System (ADS)

    Christophersen, M.; Carstensen, J.; Voigt, K.; Föll, H.

    2003-05-01

    The aim of this work is to explain the influence of the solvent molecules on silicon dissolution using several hydrofluoric acid containing organic electrolytes. The investigations focus on the morphology of the mesopores and macropores and the electrochemical valence of the overall reaction. Some basic properties of the electrolyte (polarity, tendency to form silicon oxide, and the H donor properties) were found to dominate the macropore formation in p-type silicon. For macropore formation the correct balance between the two main dissolution paths (direct silicon dissolution and dissolution via an anodic oxide) is very important. For mesopores in highly doped p- and n-type silicon the direct dissolution is dominant. The consequences of mixing organic and aqueous solutions are discussed.

  15. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    NASA Astrophysics Data System (ADS)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2015-01-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in

  16. Osmotic potential calculations of inorganic and organic aqueous solutions over wide solute concentration levels and temperatures

    SciTech Connect

    Cochrane, T. T.; Cochrane, T. A.

    2016-01-15

    Purpose: To demonstrate that the authors’ new “aqueous solution vs pure water” equation to calculate osmotic potential may be used to calculate the osmotic potentials of inorganic and organic aqueous solutions over wide ranges of solute concentrations and temperatures. Currently, the osmotic potentials of solutions used for medical purposes are calculated from equations based on the thermodynamics of the gas laws which are only accurate at low temperature and solute concentration levels. Some solutions used in medicine may need their osmotic potentials calculated more accurately to take into account solute concentrations and temperatures. Methods: The authors experimented with their new equation for calculating the osmotic potentials of inorganic and organic aqueous solutions up to and beyond body temperatures by adjusting three of its factors; (a) the volume property of pure water, (b) the number of “free” water molecules per unit volume of solution, “N{sub f},” and (c) the “t” factor expressing the cooperative structural relaxation time of pure water at given temperatures. Adequate information on the volume property of pure water at different temperatures is available in the literature. However, as little information on the relative densities of inorganic and organic solutions, respectively, at varying temperatures needed to calculate N{sub f} was available, provisional equations were formulated to approximate values. Those values together with tentative t values for different temperatures chosen from values calculated by different workers were substituted into the authors’ equation to demonstrate how osmotic potentials could be estimated over temperatures up to and beyond bodily temperatures. Results: The provisional equations formulated to calculate N{sub f}, the number of free water molecules per unit volume of inorganic and organic solute solutions, respectively, over wide concentration ranges compared well with the calculations of N{sub f

  17. Extraction and isolation of TPE from other elements on ion exchangers in aqueous and aqueous-organic solutions of phosphoric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-07-01

    The behavior of Am-Es and other actinides on anion and cation exchange resins in aqueous and aqueous-organic solutions of phosphoric acid has been studied in a wide range of concentration of various components of the solution. The sorptivity of transplutonium elements (TPE) on anion exchangers from dilute H/sub 3/PO/sub 4/ with a concentration less than or equal to 1 M in presence of organic solvents (alcohols, ketones, etc.) and on cation exchangers from concentrated H/sub 3/PO/sub 4/ has been found to be significant. The possibility of use of phosphoric acid solutions for isolation of TPE from Th, Pa, U, Np, Pu, and Zr and separation of TPE in different oxidation states in presence of a high-purity oxidant has been shown.

  18. Insights Into Atmospheric Aqueous Organic Chemistry Through Controlled Experiments with Cloud Water Surrogates

    NASA Astrophysics Data System (ADS)

    Turpin, B. J.; Ramos, A.; Kirkland, J. R.; Lim, Y. B.; Seitzinger, S.

    2011-12-01

    There is considerable laboratory and field-based evidence that chemical processing in clouds and wet aerosols alters organic composition and contributes to the formation of secondary organic aerosol (SOA). Single-compound laboratory experiments have played an important role in developing aqueous-phase chemical mechanisms that aid prediction of SOA formation through multiphase chemistry. In this work we conduct similar experiments with cloud/fog water surrogates, to 1) evaluate to what extent the previously studied chemistry is observed in these more realistic atmospheric waters, and 2) to identify additional atmospherically-relevant precursors and products that require further study. We used filtered Camden and Pinelands, NJ rainwater as a surrogate for cloud water. OH radical (~10-12 M) was formed by photolysis of hydrogen peroxide and samples were analyzed in real-time by electrospray ionization mass spectroscopy (ESI-MS). Discrete samples were also analyzed by ion chromatography (IC) and ESI-MS after IC separation. All experiments were performed in duplicate. Standards of glyoxal, methylglyoxal and glycolaldehyde and their major aqueous oxidation products were also analyzed, and control experiments performed. Decreases in the ion abundance of many positive mode compounds and increases in the ion abundance of many negative mode compounds (e.g., organic acids) suggest that precursors are predominantly aldehydes, organic peroxides and/or alcohols. Real-time ESI mass spectra were consistent with the expected loss of methylglyoxal and subsequent formation of pyruvate, glyoxylate, and oxalate. New insights regarding other potential precursors and products will be provided.

  19. Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments.

    PubMed

    Habicht, K S; Canfield, D E

    1997-12-01

    Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.

  20. Passage of TBP-uranyl complexes from aqueous-organic interface to the organic phase: insights from molecular dynamics simulation.

    PubMed

    Sahu, Pooja; Ali, Sk Musharaf; Shenoy, Kalasanka Trivikram

    2016-08-24

    The present study reports molecular dynamics simulations for biphasic systems comprising tributyl phosphate (TBP) in dodecane and uranyl nitrate in the aqueous phase, which are key chemical species in the well-known Pu-U extraction (PUREX) process. An attempt has been made to understand the nature of interface and mechanism of 'TBP associated uranyl' crossing under neutral and acidic conditions. Results show that the solvent density undergoes large fluctuation near the interface depending on the nature of the aqueous-organic phase. The study provides compelling evidence of experimentally observed reorganization of interfacial complexes at the interface and their structural reformation during extraction. It has been observed that the surface active nature of TBP and their interfacial coverage is modulated by the nature of incorporated solute species and their location with respect to the interface. Also, the TBP structuring near the interface is destroyed when an acidic interface is considered rather than a neutral one which favors the uranyl extraction. With an acidic interface, the water humidity of organic phase was observed to be increased in the experiments. Furthermore, the acid/water solubility in the organic phase was observed to be influenced by selection of acid models and their concentration. Simulations with high acid concentration show water pocket formation in the organic phase. However, in the case of dissociated ions or a mixture of both, no such water pool is observed and the extracted water remains dispersed in the organic phase, having the tendency to be replaced by HNO3 because of preferred TBP·HNO3 complexation over TBP·H2O. Most remarkably, the present study makes evident the TBP-induced charge redistribution of uranyl complexes during migration from the interface to the bulk organic phase, which contributes to drive uranyl complexes such as UO2·NO3·4TBP, UO2·5TBP and UO2·NO3·3TBP·HNO3 in the organic phase, and this was reestablished by

  1. Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of chemoprotectant, sodium 2-mercaptoethanesulfonate, MESNA, by acidic bromate and aqueous bromine.

    PubMed

    Adigun, Risikat Ajibola; Mhike, Morgen; Mbiya, Wilbes; Jonnalagadda, Sreekanth B; Simoyi, Reuben H

    2014-03-27

    The oxidation of a well-known chemoprotectant in anticancer therapies, sodium 2-mercaptoethanesulfonate, MESNA, by acidic bromate and aqueous bromine was studied in acidic medium. Stoichiometry of the reaction is: BrO3(-) + HSCH2CH2SO3H → Br(-) + HO3SCH2CH2SO3H. In excess bromate conditions the stoichiometry was deduced to be: 6BrO3(-) + 5HSCH2CH2SO3H + 6H(+) → 3Br2 + 5HO3SCH2CH2SO3H + 3H2O. The direct reaction of bromine and MESNA gave a stoichiometric ratio of 3:1: 3Br2 + HSCH2CH2SO3H + 3H2O → HO3SCH2CH2SO3H + 6Br(-) + 6H(+). This direct reaction is very fast; within limits of the mixing time of the stopped-flow spectrophotometer and with a bimolecular rate constant of 1.95 ± 0.05 × 10(4) M(-1) s(-1). Despite the strong oxidizing agents utilized, there is no cleavage of the C-S bond and no sulfate production was detected. The ESI-MS data show that the reaction proceeds via a predominantly nonradical pathway of three consecutive 2-electron transfers on the sulfur center to obtain the product 1,2-ethanedisulfonic acid, a well-known medium for the delivery of psychotic drugs. Thiyl radicals were detected but the absence of autocatalytic kinetics indicated that the radical pathway was a minor oxidation route. ESI-MS data showed that the S-oxide, contrary to known behavior of organosulfur compounds, is much more stable than the sulfinic acid. In conditions where the oxidizing equivalents are limited to a 4-electron transfer to only the sulfinic acid, the products obtained are a mixture of the S-oxide and the sulfonic acid with negligible amounts of the sulfinic acid. It appears the S-oxide is the preferred conformation over the sulfenic acid since no sulfenic acids have ever been stabilized without bulky substituent groups. The overall reaction scheme could be described and modeled by a minimal network of 18 reactions in which the major oxidants are HOBr and Br2(aq).

  2. Effect of organics on the photodeposition of copper in titanium dioxide aqueous suspensions

    SciTech Connect

    Foster, N.S.; Lancaster, A.N.; Noble, R.D.; Koval, C.A.

    1995-11-01

    Semiconductor photoelectrochemistry has been explored in many processes including organic destruction and metal removal in aqueous waste streams. The effect of the organic hole scavenger on copper photodeposition at TiO{sub 2} was investigated as a function of organic concentration and pH. Copper photodeposition was observed in solutions containing sodium formate, sodium oxalate, citric acid, disodium-EDTA, methanol, ethanol, n-propanol, 2-propanol, n-butanol, propiolic acid, isobutyric acid, chloroacetic acid, or DL-lysine monochloride. No copper photodeposition was observed in solutions containing sodium acetate, sodium propionate, sodium butyrate, tert-butyl alcohol, acetone, salicylic acid, ethyl acetate, dichloroacetic acid, trichloroacetic acid, malonic acid, succinic acid, methyl propionate, acrylic acid, methacrylic acid, crotonic acid, phenol, vinyl acetate, chloroform, trichloroethylene, dichloroethane, triethylamine, ethylenediamine, or methylhydroquinone. For solutions containing organics in which copper photodeposition did not occur, addition of small amounts of sodium formate resulted in photodeposition of the copper. The rates of copper photodeposition and subsequent oxidation of the photoreduced copper with oxygen were dependent on the organic hole scavenger. Powder X-ray diffraction was used in an attempt to determine the reduced copper species formed on the TiO{sub 2}.

  3. Type IV kerogens as analogues for organic macromolecular materials in aqueously altered carbonaceous chondrites.

    PubMed

    Matthewman, Richard; Martins, Zita; Sephton, Mark A

    2013-04-01

    Understanding the processes involved in the evolution of organic matter in the early Solar System requires extensive experimental work. The scientifically valuable carbonaceous chondrites are principal targets for organic analyses, but these meteorites are rare. Meteoritic analog materials available in larger quantities, on which experiments can be performed, would be highly beneficial. The bulk of the organic inventory of carbonaceous chondrites is made up of solvent-insoluble macromolecular material. This high-molecular-weight entity provides a record of thermal and aqueous parent-body alteration of precursor organic structures present at the birth of the Solar System. To identify an effective analogue for this macromolecular material, we analyzed a series of terrestrial kerogens by pyrolysis-gas chromatography-mass spectrometry. Type I and II kerogens are unsuitable analogues owing to their highly aliphatic nature. Type III kerogens show some similarities to meteoritic macromolecular materials but display a substantial biological heritage. Type IV kerogens, in this study derived from Mesozoic paleosols and produced by the reworking and oxidation of organic matter, represent an effective analogue. Some isomeric differences exist between meteoritic macromolecular materials and type IV kerogens, and stepped pyrolysis indicates variations in thermal stability. In addition to being a suitable material for novel experimentation, type IV kerogens also have the potential to aid in the optimization of instruments for deployment on Mars.

  4. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. [Quarterly] technical report, 1 March--31 May 1992

    SciTech Connect

    Kruge, M.A.; Palmer, S.R.; Baudet, N.

    1992-10-01

    Sporinite, vitrinite and semi-fusinite single macerals were separated from the IBC 101 coal by the density gradient technique. In addition, a gel permeation chromatography (GPC) system was assembled and the GPC column calibrated with four polystyrene molecular weight standards. A variety of sulfur compounds were identified in the dichromate oxidation products of the IBC 101 coal, including a thiazole and isomers of C2-, C3- and C4-alkyl thiophene carboxylic acids. Precise agreement between GC-MS and FPD chromatograms were obtained for these compounds. These compounds probably originated as short alkyl chains on exterior portions of the original peat macromolecular structures and were sulfurized by H{sub 2}S shortly after burial. Thus the dichromate oxidation appears useful for the characterization of sulfur compounds. Unfortunately, this treatment yields only small amounts of products, but the reaction is relatively mild. On the other hand the peroxyacetic acid gives a very good yield in only a single step, but seems to be very degradative. It was difficult to isolate the products after lithium aluminum hydride reduction of oxidation products. It is believed that this is due to the formation of polyalcohols from polycarboxyl compounds. However polyalcohols were successfully converted to their parent hydrocarbons by the LAH reduction of tosylate intermediates. This allows for much easier separation and characterization and leads to enhanced elucidation of coal structures. To test the hypothesis that asphaltenes are similar in structure to their parent coal, IBC101 asphaltenes and the extracted coal were subjected to PAA oxidation and analytical pyrolysis. The PAA products as well as the pyrolysates show very good correlation. This indicates a very strong relationship between the organic structure of the coal and that of the asphaltenes derived from them.

  5. Sulfurized limonite as material for fast decomposition of organic compounds by heterogeneous Fenton reaction.

    PubMed

    Toda, Kei; Tanaka, Toshinori; Tsuda, Yutaka; Ban, Masahiro; Koveke, Edwin P; Koinuma, Michio; Ohira, Shin-Ichi

    2014-08-15

    Rapid decomposition of wastewater contaminants using sulfurized limonite (S-limonite) was investigated. Limonite is used for desulfurization of biogases, and S-limonite is obtained from desulfurization plants as solid waste. In this work, the profitable use of S-limonite in water treatment was examined. The divalent Fe in S-limonite was expected to produce OH radicals, as Fe(2+) ions and limonite thermally treated with H2 do. Methylene blue was used for batch-wise monitoring of the decomposition performance. The decomposition rate was fast and the methylene blue solution color disappeared in only 10s when a small amount of H2O2 was added (1mM in the sample solution) in the presence of S-limonite. The OH radicals were formed by a heterogeneous reaction on the S-limonite surface and Fenton reaction with dissolved Fe(2+). The decomposition of pentachlorophenol was also examined; it was successfully decomposed in batch-wise tests. The surfaces of limonite before sulfurization, S-limonite, and S-limonite after use for water treatment were performed using scanning electron microscopy and X-ray photoelectron spectroscopy. The results show that S-limonite reverted to limonite after being used for water treatment.

  6. Thiophenes as Indicators of Aqueous Alteration in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Sephton, Mark A.; Perry, Randall S.; Hoover, Richard B.

    2006-01-01

    A common class of organic compound in low petrographic type meteorites is the sulfur-containing thiophenes. The presence of this compound class in organic-rich meteorites which have experienced substantial levels of aqueous alteration is relatively unexplored. Early reports of these compounds attributed them to artifacts brought about by reactions between elemental sulfur and organic matter during high temperature extraction and analysis steps. Subsequent investigations confirmed their indigeneity, yet their environment of formation remained unconstrained. Here we present data which suggests that thiophenes are parent body alteration products that reflect the role of liquid water on asteroids in the early solar system.

  7. Thiophenes as Indicators of Aqueous Alteration in Carbonaceous Meteorites

    NASA Technical Reports Server (NTRS)

    Sephton, Mark A.; Perry, Randall S.; Hoover, Richard B.

    2006-01-01

    A common class of organic compound in low petrographic type meteorites is the sulfur-containing thiophenes. The presence of this compound class in organic-rich meteorites which have experienced substantial levels of aqueous alteration is relatively unexplored. Early reports of these compounds attributed them to artifacts brought about by reactions between elemental sulfur and organic matter during high temperature extraction and analysis steps. Subsequent investigations confirmed their indigeneity, yet their environment of formation remained unconstrained. Here we present data which suggests that thiophenes are parent body alteration products that reflect the role of liquid water on asteroids in the early solar system.

  8. Dermal absorption of neat and aqueous volatile organic chemicals in the Fischer 344 rat

    SciTech Connect

    Morgan, D.L.; Cooper, S.W.; Carlock, D.L.; Sykora, J.J.; Sutton, B.; Mattie, D.R.; McDougal, J.N. )

    1991-06-01

    Quantification of dermal absorption of volatile organic chemicals (VOCs) from aqueous solutions is required to understand the potential health hazards resulting from skin exposure to these chemicals in contaminated water. Male Fischer 344 rats were dermally exposed (3.1-cm2 dorsal skin) to neat, one-third saturated, two-thirds saturated, or saturated aqueous solutions of 14 VOCs for 24 hr. Blood samples were obtained via indwelling jugular catheters during exposure (0, 0.5, 1, 2, 4, 8, 12, and 24 hr), and analyzed for the VOCs by gas chromatography using headspace analysis. Absorption of the neat VOCs in this series of chemicals decreased as water solubility decreased. Peak blood levels of VOCs attained during exposure for 24 hr to neat chemicals were: 1,2-dichloroethane (135.1 micrograms/ml), bromochloromethane (113.3 micrograms/ml), chloroform (51.0 micrograms/ml), benzene (24.2 micrograms/ml), tetrachloroethylene (21.1 micrograms/ml), dibromomethane (18.2 micrograms/ml), trichloroethylene (11.6 micrograms/ml), toluene (9.5 micrograms/ml), xylene (8.8 micrograms/ml), hexane (8.0 micrograms/ml), ethylbenzene (5.6 micrograms/ml), styrene (5.3 micrograms/ml), carbon tetrachloride (5.0 micrograms/ml), and 1,1,1-trichloroethane (3.4 micrograms/ml). Blood levels of 1,2-dichloroethane and benzene continued to increase during the 24-hr exposure to neat chemical, while blood levels of the other neat VOCs peaked within 4 hr and then either decreased or remained about the same for the duration of the exposure. Absorption of VOCs from one-third, two-thirds, or saturated aqueous solutions was rapid, and resulted in depletion of the chemical from the solution although only a small amount of water was absorbed. Blood levels of each VOC were directly related to the exposure concentrations.

  9. Rapid aqueous sample extraction of volatile organic compounds: effect of sample matrix and analyte properties.

    PubMed

    Meyer, M J; Gress, M F; Borgerding, A J

    2001-10-31

    Studies have been done using a rapid aqueous sample extraction (RASE) system to characterize the effects of chemical properties on the time required for removal of volatile organic compounds (VOCs) to the gas phase. These analyses include determinations of the effects that different analytes, and modifications to the matrix, have on extraction time. Experiments were performed to determine the distinct contributions of analyte removal from water and gas-phase transport to the duration of the extracted pulse of analytes. These measured durations were correlated with known values of Henry's law constants (K(H)), boiling points, relative volatilities from modified matrixes, and aqueous diffusion coefficients for cyclohexane, toluene, o-xylene, isopropylbenzene (IPB), and o-dichlorobenzene. Transport time, which was the most significant contributor to the overall duration, correlated well with analyte boiling point. Analyte removal from water correlated better with a modified relative volatility measurement than either K(H) or D(L). IPB extraction was studied in a number of modified matrixes. A 0.1% methanol in water matrix resulted in a 35% decrease in the extraction time of IPB relative to pure water. Extraction time decreased by 22% with the addition of 0.1% NaCl to the aqueous matrix. The addition of 0.01% sodium dodecyl sulfate to the matrix resulted in a 13% increase in the extraction time of IPB relative to water. The RASE system was directly interfaced to a cryofocussing high-speed gas chromatography system to analyze VOCs in wastewater at the low mug l(-1) level.

  10. Organic matrix effects on the formation of light-absorbing compounds from α-dicarbonyls in aqueous salt solution.

    PubMed

    Drozd, Greg T; McNeill, V Faye

    2014-04-01

    Aqueous-phase reactions of organic compounds are of general importance in environmental systems. Reactions of α-dicarbonyl compounds in the aqueous phase of atmospheric aerosols can impact their climate-relevant physical properties including hygroscopicity and absorption of light. Less-reactive water-soluble organic compounds may contribute an organic matrix component to the aqueous environment, potentially impacting the reaction kinetics. In this work we demonstrate the effects of organic matrices on the self-reactions of glyoxal (Gly) and methylglyoxal (mGly) in aqueous solutions containing ammonium sulfate. At an organic-to-sulfate mass ratio of 2 : 1, carbohydrate-like matrices resembling oxidized organic aerosol material reduce the rate of formation of light-absorbing products by up to an order of magnitude. The greatest decreases in the reaction rates were observed for organic matrices with smaller, more linear molecular structures. Initial UV-Vis spectra, product studies, relative rate data, acidity changes, and viscosity measurements suggest that shifts in carbonyl equilibria, due in part to (hemi)acetal formation with the matrix, reduce the rate of formation of light-absorbing imidazole and oligomer species.

  11. Sorption of Hydrophobic Organic Compounds on Natural Sorbents and Organoclays from Aqueous and Non-Aqueous Solutions: A Mini-Review

    PubMed Central

    Moyo, Francis; Tandlich, Roman; Wilhelmi, Brendan S.; Balaz, Stefan

    2014-01-01

    Renewed focus on the sorption of hydrophobic organic chemicals (HOCs) onto mineral surfaces and soil components is required due to the increased and wider range of organic pollutants being released into the environment. This mini-review examines the possibility of the contribution and mechanism of HOC sorption onto clay mineral sorbents such as kaolinite, and soil organic matter and the possible role of both in the prevention of environmental contamination by HOCs. Literature data indicates that certain siloxane surfaces can be hydrophobic. Therefore soils can retain HOCs even at low soil organic levels and the extent will depend on the structure of the pollutant and the type and concentration of clay minerals in the sorbent. Clay minerals are wettable by nonpolar solvents and so sorption of HOCs onto them from aqueous and non-aqueous solutions is possible. This is important for two reasons: firstly, the movement and remediation of soil environments will be a function of the concentration and type of clay minerals in the soil. Secondly, low-cost sorbents such as kaolinite and expandable clays can be added to soils or contaminated environments as temporary retention barriers for HOCs. Inorganic cations sorbed onto the kaolinite have a strong influence on the rate and extent of sorption of hydrophobic organic pollutants onto kaolinite. Structural sorbate classes that can be retained by the kaolinite matrix are limited by hydrogen bonding between hydroxyl groups of the octahedral alumosilicate sheet and the tetrahedral sheet with silicon. Soil organic carbon plays a key role in the sorption of HOCs onto soils, but the extent will be strongly affected by the structure of the organic soil matter and the presence of soot. Structural characterisation of soil organic matter in a particular soil should be conducted during a particular contamination event. Contamination by mining extractants and antibiotics will require renewed focus on the use of the QSAR approaches in the

  12. Multi-stage mixer-settler planet centrifuge. Preliminary studies on partition of macromolecules with organic-aqueous and aqueous-aqueous two-phase solvent systems.

    PubMed

    Ito, Y; Zhang, T Y

    1988-03-11

    A rotary-seal-free planetary centrifuge holds a separation column which consists of multiple partition units (ca. 200) connected in series with transfer tubes. In the cavity of each partition unit the transfer tube extends to form a mixer which vibrates to stir the contents under an oscillating force field generated by the planetary motion of the centrifuge. Consequently, solutes locally introduced at the inlet of the column are subjected to an efficient partition process in each partition unit and separated according to their partition coefficients. The mixer tube equipped with a flexible silicone rubber joint was found to produce excellent results for partition with viscous polymer phase systems. The capability of the method was demonstrated on separation of cytochrome c and lysozyme using a PEG-aqueous dibasic potassium phosphate-aqueous two-phase solvent system.

  13. Synthesis of magnetic nanoporous carbon from metal-organic framework for the fast removal of organic dye from aqueous solution

    NASA Astrophysics Data System (ADS)

    Jiao, Caina; Wang, Yanen; Li, Menghua; Wu, Qiuhua; Wang, Chun; Wang, Zhi

    2016-06-01

    In this paper, a magnetic nanoporous carbon (Fe3O4/NPC) was successfully synthesized by using MOF-5 as carbon precursor and Fe salt as magnetic precursor. The texture properties of the as-synthesized nanocomposite were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibration sample magnetometer (VSM), and N2 adsorption-desorption isotherms. The Fe3O4/NPC had a high surface area with strong magnetic strength. Its adsorption behavior was tested by its adsorption capacity for the removal of methylene blue from aqueous solution. The results demonstrated that the Fe3O4/NPC had a high adsorption capacity, rapid adsorption rate, and easy magnetic separabilty. Moreover, the adsorbent could be easily regenerated by washing it with ethanol. The Fe3O4/NPC can be used as a good alternative for the effective removal of organic dyes from wastewater.

  14. Effects of sulfur dioxide concentration on organic acids and β-carotene in dried apricots during storage.

    PubMed

    Salur-Can, Ayşenur; Türkyılmaz, Meltem; Özkan, Mehmet

    2017-04-15

    The effects of various sulfur dioxide (SO2) concentrations (0, 451, 832, 1594, 2112 and 3241mg/kg) on the profiles and contents of organic acids (OAs) and β-carotene in sulfured dried apricots (SDAs) were investigated during storage at 4, 20 and 30°C for 379days. In all samples, four OAs [malic acid (MA), citric acid (CA), succinic acid (SA) and oxalic acid (OXA)] were identified. SA (13.9-31.8g/kgdw) was the major OA in SDAs containing SO2 at lower than 1594mgSO2/kg, while MA (11.7-11.7g/kgdw) was the major OA in SDAs containing SO2 at higher than 1594mgSO2/kg. As SO2 concentration increased, CA and OXA contents increased whereas MA contents decreased. Moreover, the highest stabilities of β-carotene, MA and SO2 were determined in SDAs containing 1594mgSO2/kg at 4°C. Therefore, we suggest using 1594mgSO2/kg and storing SDAs at 4°C to protect OAs and β-carotene.

  15. Atmospheric So2 Emissions Since the Late 1800s Change Organic Sulfur Forms in Humic Substance Extracts of Soils

    SciTech Connect

    Lehmann,J.; Solomon, D.; Zhao, F.; McGrath, S.

    2008-01-01

    Atmospheric SO2 emissions in the UK and globally increased 6- and 20-fold, respectively, from the mid-1800s to the 1960s resulting in increased S deposition, acid rain, and concurrent acidification of terrestrial and aquatic ecosystems. Structural analyses using synchrotron-based X-ray near-edge spectroscopy (XANES) on humic substance extracts of archived samples from the Rothamsted Park Grass Experiment reveal a significant (R2 = -0.58; P < 0.05; N = 7) shift in soil organic sulfur (S) forms, from reduced to more oxidized organic S between 1876 and 1981, even though soil total S contents remained relatively constant. Over the last 30 years, a decrease in emissions and consequent S deposition has again corresponded with a change of organic S structures of humic extractsreverting in the direction of their early industrial composition. However, the observed reversal lagged behind reductions in emissions by 19 years, which was computed using cross correlations between time series data (R2 = 0.66; P = 0.0024; N = 11). Presently, the ratio of oxidized-to-reduced organic S in humic substance extracts is nearly double that of early industrial times at identical SO2 emission loads. The significant and persistent structural changes of organic S in humic substances as a response to SO2 emissions and S deposition may have effects on recuperation of soils and surface waters from acidification.

  16. Atmospheric SO2 emissions since the late 1800s change organic sulfur forms in humic substance extracts of soils.

    PubMed

    Lehmann, Johannes; Solomon, Dawit; Zhao, Fang-Jie; McGrath, Steve P

    2008-05-15

    Atmospheric SO2 emissions in the UK and globally increased 6- and 20-fold, respectively, from the mid-1800s to the 1960s resulting in increased S deposition, acid rain, and concurrent acidification of terrestrial and aquatic ecosystems. Structural analyses using synchrotron-based X-ray near-edge spectroscopy (XANES) on humic substance extracts of archived samples from the Rothamsted Park Grass Experiment reveal a significant (R2 = -0.58; P < 0.05; N = 7) shift in soil organic sulfur (S) forms, from reduced to more oxidized organic S between 1876 and 1981, even though soil total S contents remained relatively constant. Over the last 30 years, a decrease in emissions and consequent S deposition has again corresponded with a change of organic S structures of humic extracts-reverting in the direction of their early industrial composition. However, the observed reversal lagged behind reductions in emissions by 19 years, which was computed using cross correlations between time series data (R2 = 0.66; P = 0.0024; N = 11). Presently, the ratio of oxidized-to-reduced organic S in humic substance extracts is nearly double that of early industrial times at identical SO2 emission loads. The significant and persistent structural changes of organic S in humic substances as a response to SO2 emissions and S deposition may have effects on recuperation of soils and surface waters from acidification.

  17. Direct Aqueous Photochemistry of Isoprene High-NOx Secondary Organic Aerosol

    SciTech Connect

    Nguyen, Tran B.; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey

    2012-05-17

    Secondary organic aerosol (SOA) generated from the high-NOx photooxidation of isoprene was dissolved in water and irradiated with {lambda} > 290 nm light to simulate direct photolytic processing of organics in atmospheric water droplets. High-resolution mass spectrometry was used to characterize the composition at four time intervals (0, 1, 2, and 4 h). Photolysis resulted in the decomposition of high molecular weight (MW) oligomers, reducing the average length of organics by 2 carbon units. Approximately 65% by count of SOA molecules decomposed during photolysis, accompanied by the formation of new products. An average of 30 % of the organic mass was modified after 4 h of direct photolysis. In contrast, only a small fraction of the mass (<2 %), belonging primarily to organic nitrates, decomposed in the absence of irradiation by hydrolysis. We observed a statistically-significant increase in average O/C, decrease in H/C, and increase in N/C ratios resulting from photolysis. Furthermore, the concentration of aromatic compounds increased significantly during photolysis. Approximately 10 % of photodegraded compounds and 50 % of the photoproducts contain nitrogen. Organic nitrates and multifunctional oligomers were identified as compounds degraded by photolysis. Low-MW 0N (compounds with 0 nitrogen atoms in their structure) and 2N compounds were the dominant photoproducts. Fragmentation experiments using tandem mass spectrometry (MSn, n = 2-3) indicate that the 2N products are likely heterocyclic/aromatic and are tentatively identified as furoxans. Although the exact mechanism is unclear, these 2N heterocyclic compounds are produced by reactions between photochemically-formed aqueous NOx species and SOA organics.

  18. CHARACTERIZATION OF SULFUR CONTAINING ANALOGS OF MONOMETHYLARSONIC ACID IN AQUEOUS PHASE STANDARDS AND CARROT EXTRACTS BY IC-ICP-MS AND IC-ESI-MS/MS

    EPA Science Inventory

    Recently, sulfur analogs of well known arsenicals have been identified, generating a need for stable species-specific standards. This presentation will focus on the identification and characterization of a novel species, monomethylthioarsonic acid (MMTA), in carrots. A standard...

  19. CHARACTERIZATION OF SULFUR CONTAINING ANALOGS OF MONOMETHYLARSONIC ACID IN AQUEOUS PHASE STANDARDS AND CARROT EXTRACTS BY IC-ICP-MS AND IC-ESI-MS/MS

    EPA Science Inventory

    Recently, sulfur analogs of well known arsenicals have been identified, generating a need for stable species-specific standards. This presentation will focus on the identification and characterization of a novel species, monomethylthioarsonic acid (MMTA), in carrots. A standard...

  20. Production of sulfur from sulfur dioxide obtained from flue gas

    SciTech Connect

    Miller, R.

    1989-06-06

    This patent describes a regenerable process for recovery of elemental sulfur from a gas containing sulfur dioxide comprising the steps of: contacting the gas with an aqueous, alkaline reaction medium containing sodium sulfite in concentration sufficient so that a slurry containing solid sodium sulfide is formed to react sulfur dioxide with sodium sulfite to form a solution containing dissolved sodium pyrosulfite and sodium sulfite; separating sulfur dioxide from the solution produced to leave a residual mixture containing water, sodium sulfite and a sodium pyrosulfite, the amount of sulfur dioxide separated being equal to about one-third the amount of sulfur dioxide which reacted with sodium sulfite; adding, in substantial absence of air, sufficient water and sodium bicarbonate to the residual mixture to react with the dissolved sodium pyrsulfide and form a slurry of solid sodium sulfite suspended in the resulting aqueous, alkaline reaction medium and gaseous carbon dioxide; separating the gaseous carbon dioxide; separating the solid sodium sulfite from the aqueous alkaline reaction medium and recycling the separated reaction medium; reducing the separated sodium sulfite to sodium sulfide; adding the sodium sulfide to an aqueous reaction medium containing sodium bicarbonate and, in the substantial absence of air, carbonating the resulting mixture with the gaseous carbon dioxide to form a slurry of solid particles of sodium bicarbonate dispersed in an aqueous reactor medium containing sodium bicarbonate, along with a gas composed primarily of hydrogen sulfide.

  1. Removal of Heavy Metals and Organic Contaminants from Aqueous Streams by Novel Filtration Methods

    SciTech Connect

    Rodriguez, N.M.

    2000-08-01

    The removal of hazardous waste, generated by the dismantling of nuclear weapons is a problem that requires urgent attention by the US Department of Energy. Low levels of radioactive contaminants combined with organic solvent residues have leaked from aging containers into the soil and underground water in the surrounding area. Due to the complexity of the problem, it is evident that traditional adsorption methods are ineffective, since the adsorbent tends to saturate with the aqueous component. It has become apparent that a much more aggressive approach is required which involves the use of specially designed materials. We have investigated the potential of solids that combine high surface area/high pore volume and high electrical conductivity, a rare combination of properties found in a single material. In this program we examined the potential of newly developed materials for the trapping of organic solvents within specially engineered cavities without allowing the material to become saturated with water. Catalytically grown carbon nanofibers are a set of novel structures that are produced by the decomposition of selected carbon-containing gases over metal particles. These materials consist of extremely small graphite platelets stacked in various orientations with respect to the fiber axis. Such an arrangement results in a unique structure that is composed of an infinite number of extremely short and narrow pores, suitable for sequestering small molecules. In addition, when the graphene layers are aligned parallel to the fiber axis, an unusual combination of high surface area and low electrical resistivity solids are attained. We have attempted to capitalize on this blend of properties by using such structures for the selective removal of organic contaminants from aqueous streams. Experimental results indicate that nanofibers possessing a structure in which the graphite platelets are aligned perpendicular to the fiber axis and possessing a high degree of

  2. Organic aqueous tunable solvents (OATS): a vehicle for coupling reactions and separations.

    PubMed

    Pollet, Pamela; Hart, Ryan J; Eckert, Charles A; Liotta, Charles L

    2010-09-21

    In laboratory-based chemical synthesis, the choice of the solvent and the means of product purification are rarely determined by cost or environmental impact considerations. When a reaction is scaled up for industrial applications, however, these choices are critical: the separation of product from the solvent, starting materials, and byproduct usually constitutes 60-80% of the overall cost of a process. In response, researchers have developed solvents and solvent-handling methods to optimize both the reaction and the subsequent separation steps on the manufacturing scale. These include "switchable" solvents, which are designed so that their physical properties can be changed abruptly, as well as "tunable" solvents, wherein the solvent's properties change continuously through the application of an external stimulus. In this Account, we describe the organic aqueous tunable solvent (OATS) system, examining two instructive and successful areas of application of OATS as well as its clear potential for further refinement. OATS systems address the limitations of biphasic processes by optimizing reactions and separations simultaneously. The reaction is performed homogeneously in a miscible aqueous-organic solvent mixture, such as water-tetrahydrofuran (THF). The efficient product separation is conducted heterogeneously by the simple addition of modest pressures of CO(2) (50-60 bar) to the system. Under these conditions, the water-THF phase splits into two relatively immiscible phases: the organic THF phase contains the hydrophobic product, and the aqueous phase contains the hydrophilic catalyst. We take advantage of the unique properties of OATS to develop environmentally benign and cost-competitive processes relevant in industrial applications. Specifically, we describe the use of OATS for optimizing the reaction, separation, design, and recycling of (i) Rh-catalyzed hydroformylation of olefins such as 1-octene and (ii) enzyme-catalyzed hydrolysis of 2-phenylacetate. We

  3. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    PubMed Central

    Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

    2016-01-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V. PMID:27966605

  4. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    NASA Astrophysics Data System (ADS)

    Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

    2016-12-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

  5. High chemiluminescence activity of an Fe(III)-TAML activator in aqueous-organic media and its use in the determination of organic peroxides.

    PubMed

    Demiyanova, Alexandra S; Sakharov, Ivan Yu

    2015-05-07

    High activity of Fe(III)-TAML, peroxidase mimic, upon the catalytic oxidation of luminol in aqueous-organic media (ethanol, isopropanol and acetonitrile) was determined. Using Fe(III)-TAML the sensitive chemiluminescence assays for the determination of benzoyl peroxide and tert-butyl hydroperoxide in the presence of organic solvents were performed.

  6. Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode.

    PubMed

    Apaydin, Dogukan H; Gora, Monika; Portenkirchner, Engelbert; Oppelt, Kerstin T; Neugebauer, Helmut; Jakesova, Marie; Głowacki, Eric D; Kunze-Liebhäuser, Julia; Zagorska, Malgorzata; Mieczkowski, Jozef; Sariciftci, Niyazi Serdar

    2017-04-19

    Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g(-1). This is on par with the best solution-phase amine chemical capture technologies available today.

  7. Nondisruptive Dissolution of Hyperpolarized 129 Xe into Viscous Aqueous and Organic Liquid Crystalline Environments

    SciTech Connect

    Truxal, Ashley E.; Slack, Clancy C.; Gomes, Muller D.; Vassiliou, Christophoros C.; Wemmer, David E.; Pines, Alexander

    2016-03-08

    Studies of hyperpolarized xenon-129 in media such as liquid crystals and cell suspensions are in demand for applications ranging from biomedical imaging to materials engineering but have been hindered by the inability to bubble Xe through the desired media as a result of viscosity or perturbations caused by bubbles. This research reports on a device that can be reliably used to dissolve hp- 129 Xe into viscous aqueous and organic samples without bubbling. This method is robust, requires small sample volumes ( < 60 μL), is compatible with existing NMR hardware, and is made from readily available materials. Experiments show that Xe can be introduced into viscous and aligned media without disrupting molecular order. We detected dissolved xenon in an aqueous liquid crystal that is disrupted by the shear forces of bubbling, and we observed liquid-crystal phase transitions in (MBBA). This tool allows an entirely new class of samples to be investigated by hyperpolarized-gas NMR spectroscopy. Blending into the crowd: A new device that facilitates the direct dissolution of hyperpolarized 129 Xe into viscous liquid-crystalline media is presented. 129 Xe and 2 H NMR spectra show the nondisruptive dissolution of xenon, the presence of ordered phases, and, in the case of the thermotropic liquid crystal N-(4-methoxybenzylidene)-4-butylaniline, a nematic-isotropic phase transition.

  8. Effective Removal of Tetracycline from Aqueous Solution by Organic Acid-Coated Magnetic Nanoparticles.

    PubMed

    Guo, Liang; Liang, Yuyan; Chen, Xuelan; Xu, Wei; Wu, Kesheng; Wei, Hua; Xiong, Yonghua

    2016-03-01

    Self-assembled iron oxide nanocomposites are good magnetic nano-adsorbents that can be prepared using simple methods. Four types of organic acid-functionalised (oleic acid, undecenoic acid, caprylic acid or hexanoic acid) magnetic nanoparticles (MNPs) were synthesised through a one-pot chemisorption method for the removal of tetracycline (TC) from aqueous solution. The undecenoic acid-coated MNPs (UA-MNPs) exhibited the highest adsorption efficiency and can be easily retrieved with a low-gradient magnetic separator (0.4 Tesla) at pH 5.0 aqueous solution. The TC adsorption process on the UA-MNPs followed the Langmuir isotherm and the maximum adsorption capacities increased from 86.96 mg g(-1) to 222.2 mg g(-1) with the increase in temperature from 288 K to 318 K. The kinetics of adsorption fits pseudo-second-order model perfectly with a rate constant, 5.946 g mg(-1) min(-1) at 298 K. The positive values of the enthalpy (AH) and the negative value of the free energy (AG) indicated an endothermic and spontaneous adsorption process of TC on the UA-MNPs. Moreover, the UA-MNPs possessed excellent ability to adsorb the other three major types of TC antibiotics, including chlortetracycline, oxytetracycline and doxycycline.

  9. Electrochemical Capture and Release of CO2 in Aqueous Electrolytes Using an Organic Semiconductor Electrode

    PubMed Central

    2017-01-01

    Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g–1. This is on par with the best solution-phase amine chemical capture technologies available today. PMID:28378994

  10. Investigation of plasma-organic materials interaction in aqueous solution with atmospheric pressure plasmas

    NASA Astrophysics Data System (ADS)

    Takenaka, K.; Miyazaki, A.; Setsuhara, Y.

    2014-06-01

    An investigation was carried out into the interaction of an atmospheric pressure plasma with an organic material in an aqueous solution. The degradation of methylene blue (MB) by plasma exposure through the gas/liquid interface was studied. In the optical emission spectrum of the plasma, in addition to strong He emission lines, emissions due to O and OH radicals formed by dissociation of water were present. The change in the absorbance of a MB aqueous solution during plasma exposure was measured using UV-Vis spectroscopy. The absorption peak intensity decreased with plasma exposure time and complete decolorization occurred after 10 min. Since plasma exposure was found to decrease the pH of water, the effect of changes in pH on MB degradation in the absence of a plasma was investigated using solutions with different pH values. However, varying the pH was found to have no influence on MB degradation. The results indicated that MB degradation occurred due to interactions between MB and radicals across the plasma/liquid interface.

  11. Energy and Angle Resolved Uptake of Organic Gases in Concentrated Sulfuric Acid

    NASA Astrophysics Data System (ADS)

    Fiehrer, Kathleen; Nathanson, Gilbert

    1996-03-01

    We have measured the uptake of reactive gases in concentrated (98.8 wtsulfuric acid at 298 K. Our goal is to determine the fraction of gas molecules that dissolve in and react with concentrated sulfuric acid as a function of impact angle, collision energy, and gas molecule basicity (pKBH+). These gases include olefins, alcohols, ethers, aldehydes, and carboxylic acids. We have investigated how scattering and solvation compete at high and low impact energies and at grazing and perpendicular approach directions. We find that the sticking probability decreases slowly with increasing impact energy and with more grazing angle of incidence. However, the sticking probabilities change dramatically with gas functionality and scale monotonically with the molecule's solution phase basicity. Thus, the sticking probability decreases in the order ethanol, dimethyl ether, formic acid, acetaldehyde, and propene.

  12. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Final technical report, September 1, 1992--August 31, 1993

    SciTech Connect

    Kruge, M.A.; Palmer, S.R.

    1993-12-31

    The principal impediment to the molecular characterization of organic sulfur and nitrogen in coal is the polymeric nature of coal`s molecular structure, rendering coal insoluble and impossible to analyze by the necessary gas chromatographic (GC) methods. In this research, the authors apply chemical and thermal degradation techniques to render coal amenable to standard GC characterization. IBC101 floated coal was oxidized with sodium dichromate in five sequential steps. The SIC ratio in the residues decreases markedly with each successive step. It appears the method is effectively mobilizing the organic sulfur. The NIC ratio shows little change. In the GC/MS analysis of the dichromate oxidation products, alkylmethoxy-thiophene carboxylic acids (ATCA) were found to be major organosulfur compounds. Their relative concentrations also drop markedly with each oxidation step, while the concentration of benzene derivatives progressively increases. It is hypothesized the thiophenic moieties are located on the exterior surfaces of the coal structure, while the core is more aromatic. Using analytical micropyrolysis-gas chromatography with a sulfur-selective flame photometric detector (py-GC-FPD), it is possible to easily see a full distribution of organic sulfur forms in a one-step analysis. The predominance of alkylthiophenes in the pyrolyzates lends support to the recognition of thiophenic compounds in the dichromate oxidation products. The thiophene concentrations in pyrolyzates are directly proportional to bulk organic sulfur values. However, thiophene distributions in Illinois Basin coals are remarkably similar, regardless of organic sulfur content. It is possible to distinguish Illinois Basin coals from foreign coals on the basis of thiophene distributions. The py-GC method has an advantage over oxidative degradation techniques in that it permits direct, one-step micro-scale analysis, requiring only a minimum of sample preparation.

  13. Stable organic field-effect transistors for continuous and nondestructive sensing of chemical and biologically relevant molecules in aqueous environment.

    PubMed

    Yun, Minseong; Sharma, Asha; Fuentes-Hernandez, Canek; Hwang, Do Kyung; Dindar, Amir; Singh, Sanjeev; Choi, Sangmoo; Kippelen, Bernard

    2014-02-12

    The use of organic field-effect transistors (OFETs) as sensors in aqueous media has gained increased attention for environmental monitoring and medical diagnostics. However, stable operation of OFETs in aqueous media is particularly challenging because of electrolytic hydrolysis of water, high ionic conduction through the analyte, and irreversible damage of organic semiconductors when exposed to water. To date, OFET sensors have shown the capability of label-free sensing of various chemical/biological species, but they could only be used once because their operational stability and lifetime while operating in aqueous environments has been poor, and their response times typically slow. Here, we report on OFETs with unprecedented water stability. These OFETs are suitable for the implementation of reusable chemical/biological sensors because they primarily respond to charged species diluted in an aqueous media by rapidly shifting their threshold voltage. These OFET sensors present stable current baselines and saturated signals which are ideal for detection of low concentration of small or large molecules that alter the pH of an aqueous environment. The overall response of these OFET sensors paves the way for the development of continuous chemical/biological nondestructive sensor applications in aqueous media.

  14. Correlation of soil and sediment organic matter polarity to aqueous sorption of nonionic compounds

    USGS Publications Warehouse

    Kile, D.E.; Wershaw, R. L.; Chiou, C.T.

    1999-01-01

    Polarities of the soiL/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment sam pies were determined from solid-state 13C-CP/MAS NMR spectra and compared with published partition coefficients (K(oc)) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct assessment of the polarity of SOM that is not possible by elemental analysis. The percent of organic carbon associated with polar functional groups was estimated from the combined fraction of carbohydrate and carboxylamide-ester carbons. A plot of the measured partition coefficients (K(oc)) of carbon tetrachloride (CT) vs. percent polar organic carbon (POC) shows distinctly different populations of soils and sediments as well as a roughly inverse trend among the soil/sediment populations. Plots of K(oc) values for CT against other structural group carbon fractions did not yield distinct populations. The results indicate that the polarity of SOM is a significant factor in accounting for differences in K(oc) between the organic matter in soils and sediments. The alternate direct correlation of the sum of aliphatic and aromatic structural carbons with K(oc) illustrates the influence of nonpolar hydrocarbon on solute partition interaction. Additional elemental analysis data of selected samples further substantiate the effect of the organic matter polarity on the partition efficiency of nonpolar solutes. The separation between soil and sediment samples based on percent POC reflects definite differences of the properties of soil and sediment organic matters that are attributable to diagenesis.Polarities of the soil/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment samples were determined from solid-state 13C-CP/MAS NMR spectra and compared with published partition coefficients (Koc) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct

  15. Zeolite-type metal organic frameworks immobilized Eu³⁺ for cation sensing in aqueous environment.

    PubMed

    Liu, Chang; Yan, Bing

    2015-12-01

    A novel luminescent lanthanide metal organic framework (Ln-MOF) is synthesized by in situ encapsulating Eu(3+) ions to partial replace the transition-metal clusters in the channels of CPM-17-Zn nanocrystals. The Eu(3+) functionalized zeolite-type MOF hybrid system shows excellent luminescence property and photo-stability in aqueous environment for the sensitization and protection from the host framework. Subsequently, as a highly selective and sensitive sensor, its nanocrystals can be used to detect Cd(2+) in aqueous solution. In addition, the possible sensing mechanism based on ion exchange is discussed in detail. This work is one of the few cases for detecting Cd(2+) in aqueous solution based on a zeolite-type MOF. The good fluorescence stability, low detection limit and broad linear range in aqueous environment make this probe to be expected to have potential application in intracellular sensing and imaging of Cd(2+) potentially.

  16. Correlation of soil and sediment organic matter polarity to aqueous sorption of nonionic compounds

    SciTech Connect

    Kile, D.E. ); Wershaw, R.L.; Chiou, C.T. )

    1999-06-15

    Polarities of the soil/sediment organic matter (SOM) in 19 soil and 9 freshwater sediment samples were determined from solid-state [sup 13]C-CP/MAS NMR spectra and compared with published partition coefficients (K[sub oc]) of carbon tetrachloride (CT) from aqueous solution. Nondestructive analysis of whole samples by solid-state NMR permits a direct assessment of the polarity of SOM that is not possible by elemental analysis. The percent of organic carbon associated with polar functional groups was estimated from the combined fraction of carbohydrate and carboxyl-amide-ester carbons. A plot of the measured partition coefficients (K[sub oc]) of carbon tetrachloride (CT) vs. percent polar organic carbon (POC) shows distinctly different populations of soils and sediments as well as a roughly inverse trend among the soil/sediment populations. Plots of K[sub oc] values for CT against other structural group carbon fractions did not yield distinct populations. The results indicate that the polarity of SOM is a significant factor in accounting for differences in K[sub oc] between the organic matter in soils and sediments. The alternate direct correlation of the sum of aliphatic and aromatic structural carbons with K[sub oc] illustrates the influence of nonpolar hydrocarbon on solute partition interaction. Additional elemental analysis data of selected samples further substantiate the effect of the organic matter polarity on the partition efficiency of nonpolar solutes. The separation between soil and sediment samples based on percent POC reflects definite differences of the properties of soil and sediment organic matters that are attributable to diagenesis.

  17. Lipase in aqueous-polar organic solvents: Activity, structure, and stability

    PubMed Central

    Kamal, Md Zahid; Yedavalli, Poornima; Deshmukh, Mandar V; Rao, Nalam Madhusudhana

    2013-01-01

    Studying alterations in biophysical and biochemical behavior of enzymes in the presence of organic solvents and the underlying cause(s) has important implications in biotechnology. We investigated the effects of aqueous solutions of polar organic solvents on ester hydrolytic activity, structure and stability of a lipase. Relative activity of the lipase monotonically decreased with increasing concentration of acetone, acetonitrile, and DMF but increased at lower concentrations (upto ∼20% v/v) of dimethylsulfoxide, isopropanol, and methanol. None of the organic solvents caused any appreciable structural change as evident from circular dichorism and NMR studies, thus do not support any significant role of enzyme denaturation in activity change. Change in 2D [15N, 1H]-HSQC chemical shifts suggested that all the organic solvents preferentially localize to a hydrophobic patch in the active-site vicinity and no chemical shift perturbation was observed for residues present in protein's core. This suggests that activity alteration might be directly linked to change in active site environment only. All organic solvents decreased the apparent binding of substrate to the enzyme (increased Km); however significantly enhanced the kcat. Melting temperature (Tm) of lipase, measured by circular dichroism and differential scanning calorimetry, altered in all solvents, albeit to a variable extent. Interestingly, although the effect of all organic solvents on various properties on lipase is qualitatively similar, our study suggest that magnitudes of effects do not appear to follow bulk solvent properties like polarity and the solvent effects are apparently dictated by specific and local interactions of solvent molecule(s) with the protein. PMID:23625694

  18. Carboxylate-based receptors for the recognition of carbohydrates in organic and aqueous media.

    PubMed

    Mazik, Monika; Cavga, Hüseyin

    2006-04-14

    Acyclic receptors containing neutral and ionic hydrogen-bonding sites, such as amino-pyridine and carboxylate groups, were prepared and their binding properties toward neutral sugar molecules were studied. The binding studies with disodium and bis(tetramethylammonium) salts containing the dianion 11 have revealed that this type of receptor molecule is able to recognize the selected sugars in both organic and aqueous media. The carboxylate/pyridine-based receptor 11 exhibits in chloroform at least a 100-fold higher affinity for glucopyranosides than the previously described triarmed pyridine-based receptor 1, incorporating only neutral hydrogen-bonding sites. A substantial drop in the association constants is expectedly observed for an ester analogue of 11, compound 9. The dicarboxylate 11 is able to form complexes in water with methyl beta-D-glucopyranoside and D-cellobiose, with a preference for the disaccharide. The studies show the importance of charge-reinforced hydrogen bonds in the recognition of carbohydrates.

  19. Resin-Supported Catalysts for CuAAC Click Reactions in Aqueous or Organic Solvents

    PubMed Central

    Presolski, Stanislav I.; Mamidyala, Sreeman K.; Manzenrieder, Florian

    2012-01-01

    The copper-catalyzed azide-alkyne cycloaddition click reaction is a valuable process for the synthesis of libraries of drug candidates, derivatized polymers and materials, and a wide variety of other functional molecules. In some circumstances, the removal of the copper catalyst is both necessary and inconvenient. We describe here two immobilized forms of a Cu-binding ligand that has been shown to accelerate triazole formation under many different conditions, using different resin supports that are appropriate for aqueous or organic solvents. Copper leaching from these resins was modest, allowing them to be reused in many reaction/filtration cycles without recharging with metal ion. The utility of this catalyst form was demonstrated in the convenient synthesis of 20 N-acetylgalactosamine derivatives for biological testing. PMID:22946559

  20. Solubilization and biodegradation of hydrophobic organic compounds in soil/aqueous systems with nonionic surfactants

    SciTech Connect

    Edwards, D.A.; Laha, S.; Liu, Zhongbao; Luthy, R.G.

    1992-01-01

    Nonionic surfactants may strongly interact with hydrophobic organic compounds (HOCs), soil, and microorganisms in soil/aqueous systems. These interactions affect the potential for surfactant-facilitated HOC transport in soil and groundwater systems, and the feasibility of engineered surfactant cleanup of contaminated sites (McCarthy and Wober, 1991). At sufficiently high bulk liquid concentrations at 25 C, most nonionic surfactants form regular micelles in single-phase solutions, whereas certain surfactants, such as C{sub 12}E{sub 4}, may form bilayer lamellae or other types of aggregates in more complex two-phase solutions. The critical concentrations for the onset of micelle and aggregate formation are termed the critical micelle concentration (CMC) and the critical aggregation concentration (CAC), respectively. Important changes occur in surfactant sorption, surfactant solubilization of HOCs, and microbial mineralization of HOCs in the presence of nonionic surfactants at or near these critical surfactant concentrations.

  1. Solubilization and biodegradation of hydrophobic organic compounds in soil/aqueous systems with nonionic surfactants

    SciTech Connect

    Edwards, D.A.; Laha, S.; Liu, Zhongbao; Luthy, R.G.

    1992-05-01

    Nonionic surfactants may strongly interact with hydrophobic organic compounds (HOCs), soil, and microorganisms in soil/aqueous systems. These interactions affect the potential for surfactant-facilitated HOC transport in soil and groundwater systems, and the feasibility of engineered surfactant cleanup of contaminated sites (McCarthy and Wober, 1991). At sufficiently high bulk liquid concentrations at 25 C, most nonionic surfactants form regular micelles in single-phase solutions, whereas certain surfactants, such as C{sub 12}E{sub 4}, may form bilayer lamellae or other types of aggregates in more complex two-phase solutions. The critical concentrations for the onset of micelle and aggregate formation are termed the critical micelle concentration (CMC) and the critical aggregation concentration (CAC), respectively. Important changes occur in surfactant sorption, surfactant solubilization of HOCs, and microbial mineralization of HOCs in the presence of nonionic surfactants at or near these critical surfactant concentrations.

  2. Photoactivity and stability of Ag2WO4 for organic degradation in aqueous suspensions

    NASA Astrophysics Data System (ADS)

    Chen, Haihang; Xu, Yiming

    2014-11-01

    Silver tungstate as photocatalyst for water splitting and dye degradation has been reported, but the catalyst stability is not known. In this work, we find that both α- and β-Ag2WO4 are not stable under UV light for the photocatalytic degradation of phenol and azo-dye X3B in aqueous solutions. Comparatively, β-Ag2WO4 was more photoactive, but less stable than α-Ag2WO4. Solid characterization with X-ray diffraction and scanning electron microscope showed that metallic silver particles were produced with the two catalysts, consequently resulting into decrease in the activity for organic degradation. Measurement of photoluminescence revealed that β-Ag2WO4 had a weaker band gap emission and higher portion of structural defects than α-Ag2WO4. A possible mechanism responsible for the observed difference in photoactivity and stability between the two tungstates is proposed.

  3. Adsorption of organic acids from dilute aqueous solution onto activated carbon

    SciTech Connect

    Wang, S.W.

    1980-06-01

    The radioisotope technique was used to study the removal of organic acid contaminants from dilute aqueous solutions onto activated carbon. Acetic acid, propionic acid, n-butyric acid, n-hexanoic acid and n-heptanoic acid were studied at 278, 298, and 313/sup 0/K. Three bi-solute acid mixtures (acetic and propionic acids, acetic and butanoic acids, and propionic and butanoic acids) were studied at 278 and 298/sup 0/K. Isotherms of the single-solute systems were obtained at three different temperatures in the very dilute concentration region (less than 1% by weight). These data are very important in the prediction of bi-solute equilibrium data. A Polanyi-based competitive adsorption potential theory was used to predict the bi-solute equilibrium uptakes. Average errors between calculated and experimental data ranges from 4% to 14%. It was found that the competitive adsorption potential theory gives slightly better results than the ideal adsorbed solution theory.

  4. Adsorption of silver nanoparticles from aqueous solution on copper-based metal organic frameworks (HKUST-1).

    PubMed

    Conde-González, J E; Peña-Méndez, E M; Rybáková, S; Pasán, J; Ruiz-Pérez, C; Havel, J

    2016-05-01

    Silver nanoparticles (AgNP) are emerging pollutants. The use of novel materials such as Cu-(benzene 1,3,5-tricarboxylate, BTC) Metal-Organic Framework (MOFs), for AgNP adsorption and their removal from aqueous solutions has been studied. The effect of different parameters was followed and isotherm model was suggested. MOFs adsorbed fast and efficiently AgNP in the range C0 < 10 mg L(-1), being Freundlich isotherm (R = 0.993) these data fitted to. Among studied parameters a remarkable effect of chloride on sorption was found, thus their possible interactions were considered. The high adsorption efficiency of AgNP was achieved and it was found to be very fast. The feasibility of adsorption on Cu-(BTC) was proved in spiked waters. The results showed the potential interest of new material as adsorbent for removing AgNP from environment.

  5. Ruthenium-catalyzed oxidation of alkenes, alkynes, and alcohols to organic acids with aqueous hydrogen peroxide.

    PubMed

    Che, Chi-Ming; Yip, Wing-Ping; Yu, Wing-Yiu

    2006-09-18

    A protocol that adopts aqueous hydrogen peroxide as a terminal oxidant and [(Me3tacn)(CF3CO2)2Ru(III)(OH2)]CF3CO2 (1; Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) as a catalyst for oxidation of alkenes, alkynes, and alcohols to organic acids in over 80% yield is presented. For the oxidation of cyclohexene to adipic acid, the loading of 1 can be lowered to 0.1 mol %. On the one-mole scale, the oxidation of cyclohexene, cyclooctene, and 1-octanol with 1 mol % of 1 produced adipic acid (124 g, 85% yield), suberic acid (158 g, 91% yield), and 1-octanoic acid (129 g, 90% yield), respectively. The oxidative C=C bond-cleavage reaction proceeded through the formation of cis- and trans-diol intermediates, which were further oxidized to carboxylic acids via C-C bond cleavage.

  6. Fluorous oxime palladacycle: a precatalyst for carbon-carbon coupling reactions in aqueous and organic medium.

    PubMed

    Susanto, Woen; Chu, Chi-Yuan; Ang, Wei Jie; Chou, Tzyy-Chao; Lo, Lee-Chiang; Lam, Yulin

    2012-03-16

    To facilitate precatalyst recovery and reuse, we have developed a fluorous, oxime-based palladacycle 1 and demonstrated that it is a very efficient and versatile precatalyst for a wide range of carbon-carbon bond formation reactions (Suzuki-Miyaura, Sonogashira, Stille, Heck, Glaser-type, and Kumada) in either aqueous or organic medium under microwave irradiation. Palladacycle 1 could be recovered through F-SPE in various coupling reactions with recovery ranging from 84 to 95% for the first cycle. Inductively coupled plasma optical emission spectrometry (ICP-OES) analyses of the Pd content in the crude product from each class of transformation indicated extremely low levels of leaching and the palladacycle could be reused four to five times without significant loss of activity.

  7. Resin-supported catalysts for CuAAC click reactions in aqueous or organic solvents.

    PubMed

    Presolski, Stanislav I; Mamidyala, Sreeman K; Manzenrieder, Florian; Finn, M G

    2012-10-08

    The copper-catalyzed azide-alkyne cycloaddition click reaction is a valuable process for the synthesis of libraries of drug candidates, derivatized polymers and materials, and a wide variety of other functional molecules. In some circumstances, the removal of the copper catalyst is both necessary and inconvenient. We describe here two immobilized forms of a Cu-binding ligand that has been shown to accelerate triazole formation under many different conditions, using different resin supports that are appropriate for aqueous or organic solvents. Copper leaching from these resins was modest, allowing them to be reused in many reaction/filtration cycles without recharging with metal ion. The utility of this catalyst form was demonstrated in the convenient synthesis of 20 N-acetylgalactosamine derivatives for biological testing.

  8. Multicatalytic colloids with highly scalable, adjustable, and stable functionalities in organic and aqueous media

    NASA Astrophysics Data System (ADS)

    Kim, Donghee; Cheong, Sanghyuk; Ahn, Yun Gyong; Ryu, Sook Won; Kim, Jai-Kyeong; Cho, Jinhan

    2016-03-01

    Despite a large number of developments of noble metal (or metal oxide) NP-based catalysts, it has been a great challenge to prepare high-performance recyclable catalysts with integrated functionalities that can be used in various solvent media. Here, we report on layer-by-layer (LbL) assembled multicatalysts with high catalytic performance, showing high dispersion and recycling stability in organic and aqueous media. The remarkable advantages of our approach are as follows. (i) Various metal or metal oxide NPs with desired catalytic performance can be easily incorporated into multilayered shells, forming densely packed arrays that allow one colloid to be used as a multicatalyst with highly integrated and controllable catalytic properties. (ii) Additionally, the dispersion stability of catalytic colloids in a desired solvent can be determined by the type of ultrathin outermost layer coating each colloid. (iii) Lastly, the covalent bonding between inorganic NPs and dendrimers within multilayer shells enhances the recycling stability of multicatalytic colloids. The resulting core-shell colloids including OA-Fe3O4 NPs, TOABr-Pd NPs, and OA-TiO2 NPs exhibited excellent performance in the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) and photocatalysis in aqueous media and in the Sonogashira coupling reaction (99% yield) in organic media. Given that the catalytic properties of recyclable colloids reported to date have entirely depended on the functionality of a single catalytic NP layer deposited onto colloids in selective solvent media, our approach provides a basis for the design and exploitation of high-performance recyclable colloids with integrated multicatalytic properties and high dispersion stability in a variety of solvents.Despite a large number of developments of noble metal (or metal oxide) NP-based catalysts, it has been a great challenge to prepare high-performance recyclable catalysts with integrated functionalities that can be used in various solvent

  9. Mass spectral study of organic sulfur in the polymeric matrix of coal. Technical report, December 1, 1992--February 28, 1993

    SciTech Connect

    Hanley, L.; Ho, K.

    1993-05-01

    This report reviews the sixth quarter progress of a two year project t