Sample records for carbonyl sulfide ocs

  1. Carbonyl sulfide (OCS) in the Archean atmosphere

    DEFF Research Database (Denmark)

    Ueno, Yuichiro; Danielache, Sebastian Oscar; Johnson, Matthew Stanley


    The mass independent fractionation of sulfur isotopes (S-MIF) in geological samples would provide a record of the past atmospheric composition, though the mechanism of photochemical S-MIF is still poorly understood [1]. We determined the high-precision UV absorption spectra of SO2 isotopologues [2......] and calculated isotope fractionation factor of SO2 photolysis as a function of wavelength. Using these results, we show that the estimated fractionation factors give mass independent distributions and are highly sensitive to the atmospheric concentrations of O2, O3, CO2, H2O, CS2, NH4, N2O, H2S, OCS and SO2...... itself, because these molecules can modify spectra of actinic UV flux. Although various UVshielding scenarios can be considered, we found that the negative ¿33S observed in all the Archean sulfate deposits [1,3] could be expected only when OCS was present in the atmosphere. This is because OCS uniquely...

  2. Carbonyl sulfide (OCS) in the Archean atmosphere

    DEFF Research Database (Denmark)

    Ueno, Yuichiro; Danielache, Sebastian Oscar; Johnson, Matthew Stanley


    also has absorption band in lethal UVC region like ozone, thus could be an alternative UV-shielding molecule in an ozonefree reducing atmosphere. The decline of OCS might have coursed the late Archean Pongola glaciation (2.9 Ga) and possibly resulted in UV crisis of terrestrial and shallow water...

  3. Exchange of carbonyl sulfide (OCS) between soils and atmosphere under various CO2 concentrations (United States)

    Bunk, Rüdiger; Behrendt, Thomas; Yi, Zhigang; Andreae, Meinrat O.; Kesselmeier, Jürgen


    A new continuous integrated cavity output spectroscopy analyzer and an automated soil chamber system were used to investigate the exchange processes of carbonyl sulfide (OCS) between soils and the atmosphere under laboratory conditions. The exchange patterns of OCS between soils and the atmosphere were found to be highly dependent on soil moisture and ambient CO2 concentration. With increasing soil moisture, OCS exchange ranged from emission under dry conditions to an uptake within an optimum moisture range, followed again by emission at high soil moisture. Elevated CO2 was found to have a significant impact on the exchange rate and direction as tested with several soils. There is a clear tendency toward a release of OCS at higher CO2 levels (up to 7600 ppm), which are typical for the upper few centimeters within soils. At high soil moisture, the release of OCS increased sharply. Measurements after chloroform vapor application show that there is a biotic component to the observed OCS exchange. Furthermore, soil treatment with the fungi inhibitor nystatin showed that fungi might be the dominant OCS consumers in the soils we examined. We discuss the influence of soil moisture and elevated CO2 on the OCS exchange as a change in the activity of microbial communities. Physical factors such as diffusivity that are governed by soil moisture also play a role. Comparing KM values of the enzymes to projected soil water CO2 concentrations showed that competitive inhibition is unlikely for carbonic anhydrase and PEPCO but might occur for RubisCO at higher CO2 concentrations.

  4. Dimers of fluorinated methanes with carbonyl sulfide: the rotational spectrum and structure of difluoromethane-OCS. (United States)

    Serafin, Michal M; Peebles, Sean A


    The pure rotational spectra of four isotopologues of the difluoromethane-carbonyl sulfide dimer have been measured in the 5-15 GHz region with use of pulsed-nozzle Fourier-transform microwave spectroscopy. The complex was determined to possess an ab plane of symmetry with a center of mass separation of 3.41(2) A and dipole moment components mu(a) = 1.1386(18) D, mu(b) = 0.4840(63) D, mu(total) = 1.2372(41) D. Experimental planar moments indicate that the two fluorine atoms straddle the symmetry plane while one of the C-H bonds of the difluoromethane monomer is aligned to interact with the oxygen atom of the OCS molecule. The assignment of the rotational spectrum for this dimer completes the experimental studies of the series of dimers involving fluorinated methanes (HCF(3), H(2)CF(2), and H(3)CF) complexed with OCS and makes possible a comparison of properties within this series.

  5. Influence of Elevated CO2 on the Carbonyl Sulfide (OCS, COS) Exchange between Plants, Soils and the Atmosphere (United States)

    Bunk, R.; Behrendt, T.; Yi, Z.; Andreae, M. O.; Kesselmeier, J.


    Carbonyl sulfide (OCS) is a sulfur-containing trace gas with an atmospheric concentration of about 500 ppt. As it has some impact on the tropospheric greenhouse effect as well as on the stratospheric cooling effect by aerosols, its biogeochemical cycling if of high interest. Furthermore, in view of the close similarities between the assimilation of CO2 and OCS, terrestrial vegetation is regarded as the main global sink for OCS. Within this context, there is an increasing interest to use OCS as a proxy for CO2 to study ecosystem or global CO2 fluxes, exploiting the parallels between CO2 and OCS uptake by plants. However, the exchange of OCS between an ecosystem and the atmosphere does not only depend on vegetation but also on soils. We investigated the exchange processes between soils and the atmosphere and report on the impact of high but realistic CO2 concentrations on soil/atmosphere exchange and its relation to the soil water content. Not only competitive inhibition (same enzymes for CO2 and OCS uptake) but an influence on OCS production could be found. We compare these environmental effects on soils with the exchange processes between plants and the atmosphere demonstrating similar effects reaching from competitive inhibition to production of OCS.

  6. Continuous In-situ Measurements of Carbonyl Sulfide (OCS) and Carbon Dioxide Isotopes to Constrain Ecosystem Carbon and Water Exchanges (United States)

    Rastogi, B.; Still, C. J.; Noone, D. C.; Berkelhammer, M. B.; Whelan, M.; Lai, C. T.; Hollinger, D. Y.; Gupta, M.; Leen, J. B.; Huang, Y. W.


    Understanding the processes that control the terrestrial exchange of carbon and water are critical for examining the role of forested ecosystems in changing climates. A small but increasing number of studies have identified Carbonyl Sulfide (OCS) as a potential tracer for photosynthesis. OCS is hydrolyzed by an irreversible reaction in leaf mesophyll cells that is catalyzed by the enzyme, carbonic anhydrase. Leaf- level field and greenhouse studies indicate that OCS uptake is controlled by stomatal activity and that the ratio of OCS and CO2 uptake is reasonably constant. Existing studies on ecosystem OCS exchange have been based on laboratory measurements or short field campaigns and therefore little information on OCS exchange in a natural ecosystem over longer timescales is available. The objective of this study is to further assess the stability of OCS as a tracer for canopy photosynthesis in an active forested ecosystem and also to assess its utility for constraining transpiration, since both fluxes are mediated by canopy stomatal conductance. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W). Canopy air was sampled from four heights as well as the soil to measure vertical gradients of OCS within the canopy, and OCS exchange between the forest and the atmosphere for the growing season. Here we take advantage of simultaneous measurements of the stable isotopologues of H2O and CO2 at corresponding heights as well as NEE (Net Ecosystem Exchange) from eddy covariance measurements to compare GPP (Gross Primary Production) and transpiration estimates from a variety of independent techniques. Our findings also seek to allow assessment of the environmental and ecophysicological controls on evapotranspiration rates, which are projected to change in coming decades, and are otherwise poorly constrained.

  7. Atmospheric carbonyl sulfide (OCS measured remotely by FTIR solar absorption spectrometry

    Directory of Open Access Journals (Sweden)

    G. C. Toon


    Full Text Available Atmospheric OCS abundances have been retrieved from infrared spectra measured by the Jet Propulsion Laboratory (JPL MkIV Fourier transform infra-red (FTIR spectrometer during 24 balloon flights and during nearly 1100 days of ground-based observations since 1985. Our spectral fitting approach uses broad windows to enhance the precision and robustness of the retrievals. Since OCS has a vertical profile similar in shape to that of N2O, and since tropospheric N2O is very stable, we reference the OCS observations to those of N2O, measured simultaneously in the same air mass, to remove the effects of stratospheric transport, allowing a clearer assessment of secular changes in OCS. Balloon measurements reveal less than 5 % change in stratospheric OCS amounts over the past 25 years. Ground-based measurements reveal a springtime peak of tropospheric OCS, followed by a rapid early-summer decrease, similar to the behavior of CO2. This results in a peak-to-peak seasonal cycle of 5–6 % of the total OCS column at northern mid-latitudes. In the long-term tropospheric OCS record, a 5 % decrease is seen from 1990 to 2002, followed by a 5 % increase from 2003 to 2012.

  8. Atmospheric carbonyl sulfide (OCS) measured remotely by FTIR solar absorption spectrometry (United States)

    Toon, Geoffrey C.; Blavier, Jean-Francois L.; Sung, Keeyoon


    Atmospheric OCS abundances have been retrieved from infrared spectra measured by the Jet Propulsion Laboratory (JPL) MkIV Fourier transform infra-red (FTIR) spectrometer during 24 balloon flights and during nearly 1100 days of ground-based observations since 1985. Our spectral fitting approach uses broad windows to enhance the precision and robustness of the retrievals. Since OCS has a vertical profile similar in shape to that of N2O, and since tropospheric N2O is very stable, we reference the OCS observations to those of N2O, measured simultaneously in the same air mass, to remove the effects of stratospheric transport, allowing a clearer assessment of secular changes in OCS. Balloon measurements reveal less than 5 % change in stratospheric OCS amounts over the past 25 years. Ground-based measurements reveal a springtime peak of tropospheric OCS, followed by a rapid early-summer decrease, similar to the behavior of CO2. This results in a peak-to-peak seasonal cycle of 5-6 % of the total OCS column at northern mid-latitudes. In the long-term tropospheric OCS record, a 5 % decrease is seen from 1990 to 2002, followed by a 5 % increase from 2003 to 2012.

  9. Atmospheric carbonyl sulfide (OCS) variation from 1992-2004 by ground-based solar FTIR spectrometry (United States)

    Deutscher, N. M.; Jones, N. B.; Griffith, D. W. T.; Wood, S. W.; Murcray, F. J.


    Analysis of ground-based high-resolution solar FTIR absorption spectra from four sites was performed to determine trends and variability in OCS columns over the period 1992-2004. The sites were Wollongong, Australia (34.45° S, 150.88° E), Lauder, New Zealand (45.0° S, 169.7° E), Arrival Heights, Antarctica (77.8° S, 166.6° E) and Mauna Loa, Hawaii (19.5° N, 155.6° W). Small but significant long-term trends of -0.18±0.02% yr-1 above Hawaii, -0.30±0.12% yr-1 above Wollongong and -0.29±0.14% yr-1 above Lauder, were seen. No significant trend was seen above Arrival Heights. A large peak-to-peak seasonal difference observed in 1996-1997 above Wollongong and reported earlier was confirmed, but not repeated in later years. This seasonal feature correlated with particularly high water vapour columns present during late summer and early autumn, and suggests a link to warm oceanic airmasses. Seasonal variation of approximately 6% per year is observed in the total column in other years for all four locations.

  10. Marine cycling of the climate relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2) in the Peruvian upwelling regime (United States)

    Lennartz, Sinikka; von Hobe, Marc; Booge, Dennis; Gonçalves-Araujo, Rafael; Bracher, Astrid; Röttgers, Rüdiger; Ksionzek, Kerstin B.; Koch, Boris P.; Fischer, Tim; Bittig, Henry; Quack, Birgit; Krüger, Kirstin; Marandino, Christa A.


    The ocean is a major source for the climate relevant trace gases carbonyl sulfide (OCS) and carbon disulfide (CS2). While the greenhouse gas CS2 quickly oxidizes to OCS in the atmosphere, the atmospheric lifetime of OCS of 2-7 years leads to an accumulation of this gas and makes it the most abundant reduced sulfur compound in the atmosphere. OCS has a counteracting effect on the climate: in the troposphere, it acts as a greenhouse gas causing warming, whereas it also sustains the stratospheric aerosol layer, and thus increases Earth's albedo causing cooling. To better constrain the important oceanic source of these trace gases, the marine cycling needs to be well understood and quantified. For OCS, the production and consumption processes are identified, but photoproduction and light-independent production rates remain to be quantified across different regions. In contrast, the processes that influence the oceanic cycling of CS2 are less well understood. Here we present new data from a cruise to the Peruvian upwelling regime and relate measurements of OCS and CS2 to key parameters, such as dissolved organic sulfur, chromophoric and fluorescent dissolved organic matter. We use a 1D water column model to further constrain their production and degradation rates. A focus is set on the influence of oxygen on the marine cycling of these two gases in oxygen depleted zones in the ocean, which are expected to expand in the future.

  11. Carbonyl sulfide (OCS) as a proxy for GPP: Complications derived from studies on the impact of CO2, soil humidity and sterilization on the OCS exchange between soils and atmosphere (United States)

    Bunk, Rüdiger; Behrendt, Thomas; Yi, Zhigang; Kesselmeier, Jürgen


    Carbonyl sulfide is discussed to be used as a proxy for gross primary productivity (GPP) of forest ecosystems. However, soils may interfere. Soils play an important role in budgeting global and local carbonyl sulfide (OCS) fluxes, yet the available data on the uptake and emission behavior of soils in conjunction with environmental factors is limited. The work of many authors has shown that the OCS exchange of soils depends on various factors, such as soil type, atmospheric OCS concentrations, temperature or soil water content (Kesselmeier et al., J. Geophys. Res., 104, No. D9, 11577-11584, 1999; Van Diest & Kesselmeier, Biogeosciences, 5, 475-483, 2008; Masyek et al., PNAS, 111, No 25, 9064-9069, doi: 10.1073/pnas.1319132111, 2014; Whelan and Rhew, J. Geophys. Res. Biogeosciences., 120, 54-62, doi: 10.1002/2014JG002661, 2015) and the light dependent and obviously abiotic OCS production as reported by Whelan and Rhew (2015). To get a better constraint on the impact of some environmental factors on the OCS exchange of soils we used a new laser based integrated cavity output spectroscopy instrument (LGR COS/CO Analyzer Model 907-0028, Los Gatos, Mountain View, California, USA) in conjunction with an automated soil chamber system (as described in Behrendt et al, Biogeosciences, 11, 5463-5492, doi: 10.5194/bg-11-5463-2014, 2014). The OCS exchange of various soils under the full range of possible soil humidity and various CO2 mixing ratios was examined. Additionally OCS exchange of chloroform sterilized subsamples was compared to their live counterparts to illuminate the influence of microorganisms. Results were quite heterogeneous between different soils. With few exceptions, all examined soils show dependence between OCS exchange and soil humidity, usually with strongest uptake at a certain humidity range and less uptake or even emission at higher and lower humidity. Differences in CO2 mixing ratio also clearly impacts on OCS exchange, but trends for different soils

  12. Oxidation of Reduced Sulfur Species: Carbonyl Sulfide

    DEFF Research Database (Denmark)

    Glarborg, Peter; Marshall, Paul


    A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts satisfact......A detailed chemical kinetic model for oxidation of carbonyl sulfide (OCS) has been developed, based on a critical evaluation of data from the literature. The mechanism has been validated against experimental results from batch reactors, flow reactors, and shock tubes. The model predicts...... satisfactorily oxidation of OCS over a wide range of stoichiometric air–fuel ratios (0.5 ≤λ≤7.3), temperatures (450–1700 K), and pressures (0.02–3.0 atm) under dry conditions. The governing reaction mechanisms are outlined based on calculations with the kinetic model. The oxidation rate of OCS is controlled...

  13. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase I (United States)

    National Aeronautics and Space Administration — Southwest Sciences proposes to develop small, low power instrumentation for the real-time direct measurement of carbonyl sulfide (OCS) in the atmosphere, especially...

  14. Interhemispheric ratio and annual cycle of carbonyl sulfide (OCS) total column from ground-based solar FTIR spectra (United States)

    Griffith, David W. T.; Jones, Nicholas B.; Matthews, W. Andrew


    We have made extensive measurements of total column OCS by ground-based high-resolution solar Fourier transform infrared absorption spectroscopy from two southern hemisphere sites to complement earlier measurements in the northern hemisphere and to investigate the interhemispheric ratio, variability, and seasonal cycles of OCS in the atmosphere. The measurements were made at Lauder, New Zealand (45.0°S, 169.7°E, 370 m asl, 547 spectra March 1993 through April 1997), and Wollongong, Australia (34.45°S, 150.88°E, 30 m asl, 358 spectra May 1996 through April 1997). The annual mean column amounts are 9.15×1015 molecules cm-2 above Lauder and 9.84×1015 molecules cm-2 above Wollongong, corresponding to tropospheric mixing ratios of 480 and 490 parts per trillion by volume, respectively, with the assumed mixing ratio vertical profiles. The secular trend in total column OCS is less than 1% per year. Variability of all measurements about the means implies an atmospheric lifetime for OCS of at least 2.8 years. Comparison with earlier measurements in the northern hemisphere yields a north/south interhemispheric ratio in the range 1.1-1.2. There are peak-to-peak apparent annual cycles in total column OCS of 6% at Lauder and 18% at Wollongong with a late summer maximum. Seasonal tropopause height variation accounts for a 5-6% amplitude, and the remainder of the amplitude in Wollongong is assumed to be due to changes in the tropospheric mixing ratio.

  15. Positive trends in Southern Hemisphere carbonyl sulfide (United States)

    Kremser, Stefanie; Jones, Nicholas B.; Palm, Mathias; Lejeune, Bernard; Wang, Yuting; Smale, Dan; Deutscher, Nicholas M.


    Transport of carbonyl sulfide (OCS) from the troposphere to the stratosphere contributes sulfur to the stratospheric aerosol layer, which reflects incoming short-wave solar radiation, cooling the climate system. Previous analyses of OCS observations have shown no significant trend, suggesting that OCS is unlikely to be a major contributor to the reported increases in stratospheric aerosol loading and indicating a balanced OCS budget. Here we present analyses of ground-based Fourier transform spectrometer measurements of OCS at three Southern Hemisphere sites spanning 34.45°S to 77.80°S. At all three sites statistically significant positive trends are seen from 2001 to 2014 with an observed overall trend in total column OCS at Wollongong of 0.73 ± 0.03%/yr, at Lauder of 0.43 ± 0.02%/yr, and at Arrival Heights of 0.45 ± 0.05%/yr. These observed trends in OCS imply that the OCS budget is not balanced and could contribute to constraints on current estimates of sources and sinks.

  16. Positive trends in Southern Hemisphere observations of carbonyl sulfide (United States)

    Kremser, Stefanie; Jones, Nicholas; Smale, Dan; Palm, Mathias; Lejeune, Bernard; Wang, Yuting; Deutscher, Nicholas


    Carbonyl sulfide (OCS; lifetime of about 5.7 years) is the longest lived reduced sulfur-containing gas in the atmosphere. The primary source of OCS is the ocean, which is both a direct source (through OCS emission) and an indirect source (due to oxidation of carbon disulfide, CS2, and dimethyl sulfide). Other natural sources of OCS include volcanic outgassing and direct fluxes from wetland regions. The removal of OCS from the atmosphere is dominated by soil and vegetation uptake, with minor contributions from reactions with the hydroxyl radical. Small anthropogenic sources of OCS are coal combustion, biomass burning, and aluminum production. A dominant indirect source results from CS2 emissions from the rayon industry. Transport of tropospheric OCS to the stratosphere during volcanically quiescent periods has been suggested to contribute sulfur to the stratospheric aerosol layer which affects atmospheric radiative balance. If, however, production of stratospheric aerosols from OCS oxidation is smaller than typical estimates, this OCS contribution would be overestimated. The magnitude of the OCS flux to the stratosphere is currently not well quantified as is the relative contribution of OCS to background aerosol loading. While earlier model simulations indicate OCS fluxes into the atmosphere exceeding removal, past total column observations of OCS show no significant trend. Analysis of tropospheric OCS columns at Arrival Heights (Antarctica) and Lauder (New Zealand) show strong positive trends from 2001-2008 followed by weaker trends to 2015, with unexpected temporal coherence. Since trends in ocean and land sources/sinks at these two sites, respectively, are unlikely to be similar, the coherence in trend structure likely results from changes in transport of OCS from the tropics to middle and high latitudes. Potential causes for OCS increases are (i) increases in tropical lower stratospheric OCS and/or (ii) strengthening of the large-scale circulation which

  17. The Potential of Carbonyl Sulfide as a Proxy for Gross Primary Production at Flux Tower Sites (United States)

    Regional and continental scale studies of the seasonal dynamics of atmospheric carbonyl sulfide (OCS) mole fractions and leaf-level studies of plant OCS exchange have shown a close relationship with those for CO2. CO2 has sinks and sources within terrestrial ecosystems, but the primary terrestrial e...

  18. Acute inhalation toxicity of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Benson, J.M.; Hahn, F.F.; Barr, E.B. [and others


    Carbonyl sulfide (COS), a colorless gas, is a side product of industrial procedures sure as coal hydrogenation and gasification. It is structurally related to and is a metabolite of carbon disulfide. COS is metabolized in the body by carbonic anhydrase to hydrogen sulfide (H{sub 2}S), which is thought to be responsible for COS toxicity. No threshold limit value for COS has been established. Results of these studies indicate COS (with an LC{sub 50} of 590 ppm) is slightly less acutely toxic than H{sub 2}S (LC{sub 50} of 440 ppm).

  19. The Hydrolysis of Carbonyl Sulfide at Low Temperature: A Review (United States)

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


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

  20. Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles (United States)

    Hattori, Shohei; Kamezaki, Kazuki; Ogawa, Takahiro; Toyoda, Sakae; Katayama, Yoko; Yoshida, Naohiro


    Carbonyl sulfide (OCS or COS) is the most abundant gas containing sulfur in the atmosphere, with an average mixing ratio of 500 p.p.t.v. in the troposphere. OCS is suggested as a sulfur source of the stratospheric sulfate aerosols (SSA) which plays an important role in Earth's radiation budget and ozone depletion. Therefore, OCS budget should be validated for prediction of climate change, but the global OCS budget is imbalance. Recently we developed a promising new analytical method for measuring the stable sulfur isotopic compositions of OCS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ (Hattori et al., 2015). The first measurement of the δ34S value for atmospheric OCS coupled with isotopic fractionation for OCS sink reactions in the stratosphere (Hattori et al., 2011; Schmidt et al., 2012; Hattori et al., 2012) explains the reported δ34S value for background stratospheric sulfate, suggesting that OCS is a potentially important source for background (nonepisodic or nonvolcanic) stratospheric sulfate aerosols. This new method measuring δ34S values of OCS can be used to investigate OCS sources and sinks in the troposphere to better understand its cycle. It is known that some microorganisms in soil can degrade OCS, but the mechanism and the contribution to the OCS in the air are still uncertain. In order to determine sulfur isotopic enrichment factor of OCS during degradation via microorganisms, incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia and Cupriavidus, isolated from natural soil environments (Kato et al., 2008). As a result, sulfur isotope ratios of OCS were increased during degradation of OCS, indicating that reaction for OC32S is faster than that for OC33S and OC34S. OCS degradation via microorganisms is not mass-independent fractionation (MIF) process, suggesting that this

  1. Isotope effect in the carbonyl sulfide reaction with O(3P)

    DEFF Research Database (Denmark)

    Hattori, Shohei; Schmidt, Johan Albrecht; Mahler, Denise W.


    The sulfur kinetic isotope effect (KIE) in the reaction of carbonyl sulfide (OCS) with O((3)P) was studied in relative rate experiments at 298 ± 2 K and 955 ± 10 mbar. The reaction was carried out in a photochemical reactor using long path FTIR detection, and data were analyzed using a nonlinear......; at 300 K, the isotopic fractionation was found to be (34)e = -14.8‰. The OCS sink reaction with O((3)P) cannot explain the large fractionation in (34)S, over +73‰, indicated by remote sensing data. In addition, (34)e in OCS photolysis and OH oxidation are not larger than 10‰, indicating that...

  2. Multiple-sulfur isotope effects during photolysis of carbonyl sulfide

    Directory of Open Access Journals (Sweden)

    Y. Lin


    Full Text Available Laboratory experiments were carried out to determine sulfur isotope effects during ultraviolet photolysis of carbonyl sulfide (OCS to carbon monoxide (CO and elemental sulfur (S0. The OCS gas at 3.7 to 501 mbar was irradiated with or without a N2 bath gas using a 150 W Xe arc lamp. Sulfur isotope ratios for the product S0 and residual OCS were analyzed by an isotope ratio mass-spectrometer with SF6 as the analyte gas. The isotope fractionation after correction for the reservoir effects is −6.8‰ for the ratio 34S/32S, where product S0 is depleted in heavy isotopes. The magnitude of the overall isotope effect is not sensitive to the addition of N2 but increases to −9.5‰ when radiation of λ > 285 nm is used. The measured isotope effect reflects that of photolysis as well as the subsequent sulfur abstraction (from OCS reaction. The magnitude of isotope effects for the abstraction reaction is estimated by transition state theory to be between −18.9 and −3.1‰ for 34S which gives the photolysis isotope effect as −10.5 to +5.3‰. The observed triple isotope coefficients are ln(δ34S + 1/ln(δ34S + 1 = 0.534 ± 0.005 and ln(δ36S + 1/ln(δ34S + 1 = 1.980 ± 0.021. These values differ from canonical values for mass-dependent fractionation of 0.515 and 1.90, respectively. The result demonstrates that the OCS photolysis does not produce large isotope effects of more than about 10‰ for 34S/32S, and can be the major source of background stratospheric sulfate aerosol (SSA during volcanic quiescence.

  3. Plant Uptake of Atmospheric Carbonyl Sulfide in Coast Redwood Forests (United States)

    Campbell, J. E.; Whelan, M. E.; Berry, J. A.; Hilton, T. W.; Zumkehr, A.; Stinecipher, J.; Lu, Y.; Kornfeld, A.; Seibt, U.; Dawson, T. E.; Montzka, S. A.; Baker, I. T.; Kulkarni, S.; Wang, Y.; Herndon, S. C.; Zahniser, M. S.; Commane, R.; Loik, M. E.


    The future resilience of coast redwoods (Sequoia sempervirens) is now of critical concern due to the detection of a 33% decline in California coastal fog over the 20th century. However, ecosystem-scale measurements of photosynthesis and stomatal conductance are challenging in coast redwood forests, making it difficult to anticipate the impacts of future changes in fog. To address this methodological problem, we explore coastal variations in atmospheric carbonyl sulfide (COS or OCS), which could potentially be used as a tracer of these ecosystem processes. We conducted atmospheric flask campaigns in coast redwood sites, sampling at surface heights and in the canopy ( 70 m), at the University of California Landels-Hill Big Creek Reserve and Big Basin State Park. We simulated COS atmosphere-biosphere exchange with a high-resolution 3-D model to interpret these data. Flask measurements indicated a persistent daytime drawdown between the coast and the downwind forest (45 ± 6 ppt COS) that is consistent with the expected relationship between COS plant uptake, stomatal conductance, and gross primary production. Other sources and sinks of COS that could introduce noise to the COS tracer technique (soils, anthropogenic activity, nocturnal plant uptake, and surface hydrolysis on leaves) are likely to be small relative to daytime COS plant uptake. These results suggest that COS measurements may be useful for making ecosystem-scale estimates of carbon, water, and energy exchange in coast redwood forests.


    Carbonyl sulfide (COS) is an intermediate in the production of pesticides and herbicides, and is a metabolite of the neurotoxicant carbon disulfide. The potential neurotoxicity of inhaled COS was investigated in F344 rats. Male rats were exposed to 0, 75, 150, 300, or 600 ppm COS...

  5. Carbonyl Sulfides as Possible Intermediates in the Photolysis of Oxathiiranes

    DEFF Research Database (Denmark)

    Carlsen, Lars; Snyder, J. P.; Holm, A.


    Diphenyl oxathiirane, formed by irradiation of thiobenzophenone S-oxide at 77 K, is photochemically converted into a blue, thermally unstable compound which decomposes at ca 100–110 K (λmax 550 nm, (ϵ ca 11,000). Lack of change in magnetic susceptibility during the light induced conversion...... of sulfine to ketone via the oxathiirane and the subsequent blue intermediate implies the absence of triplet and biradical singlet transients. The unknown carbonyl sulfide functionality, R2C&z.dbnd;O&z.dbnd;S, thereby emerges as a strong candidate for producing the visible absorption. Comparison of the wave...... functions for CH2&z.dbnd;S&z.dbnd;O and CH2&z.dbnd;O&z.dbnd;S arising from MNDO limited CI geometry optimizations leads to the conclusion that the carbonyl sulfide structure is best described as a zwitterion rather than as a singlet biradical. The failure to observe cycloaddition products between the blue...

  6. Continuous In-situ Measurements of Carbonyl Sulfide to Constrain Ecosystem Carbon and Water Exchange (United States)

    Rastogi, B.; Kim, Y.; Berkelhammer, M. B.; Noone, D. C.; Lai, C. T.; Hollinger, D. Y.; Bible, K.; Leen, J. B.; Gupta, M.; Still, C. J.


    Understanding the processes that control the terrestrial exchange of carbon and water are critical for examining the role of forested ecosystems in changing climates. A small but increasing number of studies have identified Carbonyl Sulfide (OCS) as a potential tracer for photosynthesis. OCS is hydrolyzed by an irreversible reaction in leaf mesophyll cells that is catalyzed by the enzyme, carbonic anhydrase. Leaf-level field and greenhouse studies indicate that OCS uptake is controlled by stomatal activity and that the ratio of OCS and CO2 uptake is reasonably constant. Existing studies on ecosystem OCS exchange have been based on laboratory measurements or short field campaigns and therefore little information on OCS exchange in a natural ecosystem over longer timescales is available. The objective of this study is to further assess the stability of OCS as a tracer for canopy photosynthesis in an active forested ecosystem and also to assess its utility for constraining transpiration, since both fluxes are mediated by canopy stomatal conductance. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W). Canopy air was sampled from three heights to measure vertical gradients of OCS within the canopy, and OCS exchange between the forest and the atmosphere. Here we take advantage of simultaneous measurements of the stable isotopologues of H2O and CO2 at corresponding heights as well as NEE (Net Ecosystem Exchange) from eddy covariance measurements to compare GPP (Gross Primary Production) and transpiration estimates from a variety of independent techniques. Our findings seek to allow assessment of the environmental and ecophysicological controls on evapotranspiration rates, which are projected to change in coming decades, and are otherwise poorly constrained.

  7. Quantification of A Tropical Missing Source From Ocean For The Carbonyl Sulfide Global Budget (United States)

    Kuai, Le; Worden, John; Campbell, Elliott; Kulawik, Susan; Lee, Meemong; Montzka, Stephen; Berry, Joe; Baker, Ian; Denning, Scott; Kawa, Randy; Bian, Huisheng; Yung, Yuk


    Quantifying the carbonyl sulfide (OCS) surface fluxes contributes to the understanding of both sulfur cycle and carbon cycle. Although the major sources and sinks of OCS are well recognized, the uncertainties of individual types of the fluxes remain large. With the understanding of a large underestimate of ecosystem uptake, it suggests a large missing ocean source over tropical region to compensate the increased sink. However before AURA Tropospheric Emissions Spectrometer (TES) OCS data is released, no direct measurements have been taken to test this hypothesis. In this study, we performed a flux inversion to update the fluxes from TES OCS. Then we compared three experimental GEOS-Chem forward model runs driven by different fluxes based on TES inversion to HIPPO aircraft estimates in free troposphere and also to NOAA near surface observations. The TES data supports the hypothesis that a large source from tropical ocean is missing in the current OCS global budget and suggests that the source is even larger than that proposed in Berry et al., (2013). Consequently, it leads to a larger land uptake and increase the estimates of GPP. TES data also suggests the missing oceanic source is not symmetric about equator. It is strong and distributed further north of the equator (to 40°N) but weak and narrow south of the equator (to 20°S).

  8. Rotational spectrum and structure of the carbonyl sulfide-trifluoromethane weakly bound dimer. (United States)

    Serafin, Michal M; Peebles, Sean A


    Pure rotational spectra of five isotopomers of the 1:1 weakly bound complex formed between carbonyl sulfide and trifluoromethane (TFM) have been measured using Fourier transform microwave spectroscopy. The experimental rotational constants and dipole moment components are consistent with a structure of C(s) symmetry in which the dipole moment vectors of OCS and HCF(3) are aligned antiparallel and at an angle of about 40 degrees and with a center of mass separation of 3.965(26) A. The derived H...O distance is 2.90(5) A, which is up to 0.6 A longer than is seen in other similar TFM complexes exhibiting C-H...O interactions. Ab initio calculations at the MP2/6-311++G(2d,2p) level give a structure with rotational constants that are in reasonable agreement with those of the normal isotopic species.

  9. Tropical sources and sinks of carbonyl sulfide observed from space (United States)

    Glatthor, Norbert; Höpfner, Michael; Baker, Ian T.; Berry, Joe; Campbell, Elliott; Kawa, Stephan R.; Krysztofiak, Gisele; Sinnhuber, Björn-Martin; Stiller, Gabriele; Stinecipher, Jim; von Clarmann, Thomas


    According to current budget estimations the seasonal variation of carbonyl sulfide (COS) is governed by oceanic release and vegetation uptake. Its assimilation by plants is assumed to be similar to the photosynthetic uptake of CO2 but, contrary to the latter process, to be irreversible. Therefore COS has been suggested as co-tracer of the carbon cycle. Observations of COS, however, are sparse, especially in tropical regions. We use the comprehensive data set of spaceborne measurements of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) to analyze its global distribution. Two major features are observed in the tropical upper troposphere around 250 hPa: enhanced amounts over the western Pacific and the Maritime Continent, peaking around 550 pptv in boreal summer, and a seasonally varying depletion of COS extending from tropical South America to Africa. The large-scale COS depletion, which in austral summer amounts up to -40 pptv as compared to the rest of the respective latitude band, has not been observed before and reveals the seasonality of COS uptake through tropical vegetation. The observations can only be reproduced by global models, when a large vegetation uptake and a corresponding increase in oceanic emissions as proposed in several recent publications is assumed.

  10. The oceanic cycle and global atmospheric budget of carbonyl sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, P.S.


    A significant portion of stratospheric air chemistry is influenced by the existence of carbonyl sulfide (COS). This ubiquitous sulfur gas represents a major source of sulfur to the stratosphere where it is converted to sulfuric acid aerosol particles. Stratospheric aerosols are climatically important because they scatter incoming solar radiation back to space and are able to increase the catalytic destruction of ozone through gas phase reactions on particle surfaces. COS is primarily formed at the surface of the earth, in both marine and terrestrial environments, and is strongly linked to natural biological processes. However, many gaps in the understanding of the global COS cycle still exist, which has led to a global atmospheric budget that is out of balance by a factor of two or more, and a lack of understanding of how human activity has affected the cycling of this gas. The goal of this study was to focus on COS in the marine environment by investigating production/destruction mechanisms and recalculating the ocean-atmosphere flux.

  11. Assessing canopy performance using carbonyl sulfide (COS) measurements. (United States)

    Yang, Fulin; Qubaja, Rafat; Tatarinov, Fyodor; Rotenberg, Eyal; Yakir, Dan


    Carbonyl sulfide (COS) is a tracer of ecosystem photosynthesis that can advance carbon cycle research from leaf to global scales; however, a range of newly reported caveats related to sink/source strength of various ecosystem components hinder its application. Using comprehensive eddy-covariance and chamber measurements, we systematically measure ecosystem contributions from leaf, stem, soil and litter and were able to close the ecosystem COS budget. The relative contributions of non-photosynthetic components to the overall canopy-scale flux are relatively small (~4% during peak activity season) and can be independently estimated based on their responses to temperature and humidity. Converting COS to photosynthetic CO 2 fluxes based on the leaf relative uptake of COS/CO 2 , faces challenges due to observed daily and seasonal changes. Yet, this ratio converges around a constant value (~1.6), and the variations, dominated by light intensity, were found unimportant on a flux-weighted daily time-scale, indicating a mean ratio of daytime gross-to-net primary productivity of ~2 in our ecosystem. The seasonal changes in the leaf relative uptake ratio may indicate a reduction in mesophyll conductance in winter, and COS-derived canopy conductance permitted canopy temperature estimate consistent with radiative skin temperature. These results support the feasibility of using COS as a powerful and much-needed means of assessing ecosystem function and its response to change. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

  12. Carbonyl Sulfide for Tracing Carbon Fluxes Field Campaign Report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J. Elliott [Univ. of California, Merced, CA (United States); Berry, Joseph A. [Carnegie Inst. of Science, Stanford, CA (United States); Billesbach, Dave [Univ. of Nebraska, Lincoln, NE (United States); Torn, Margaret S [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zahniser, Mark [Aerodyne Research, Inc., Billerica, MA (United States); Seibt, Ulrike [Univ. of California, Los Angeles, CA (United States); Maseyk, Kadmiel [Pierre and Marie Curie Univ., Paris (France)


    The April-June 2012 campaign was located at the U.S. Department of Energy (DOE)’s Atmospheric Radiation Measurement (ARM) Climate Research Facility Southern Great Plains (SGP) site Central Facility and had three purposes. One goal was to demonstrate the ability of current instrumentation to correctly measure fluxes of atmospheric carbonyl sulfide (COS). The approach has been describe previously as a critical approach to advancing carbon cycle science1,2, but requires further investigation at the canopy scale to resolve ecosystem processes. Previous canopy-scale efforts were limited to data rates of 1Hz. While 1 Hz measurements may work in a few ecosystems, it is widely accepted that data rates of 10 to 20 Hz are needed to fully capture the exchange of traces gases between the atmosphere and vegetative canopy. A second goal of this campaign was to determine if canopy observations could provide information to help interpret the seasonal double peak in airborne observations at SGP of CO2 and COS mixing ratios. A third goal was to detect potential sources and sinks of COS that must be resolved before using COS as a tracer of gross primary productivity (GPP).

  13. A top-down approach of surface carbonyl sulfide exchange by a Mediterranean oak forest ecosystem in southern France

    Directory of Open Access Journals (Sweden)

    S. Belviso


    Full Text Available The role that soil, foliage, and atmospheric dynamics have on surface carbonyl sulfide (OCS exchange in a Mediterranean forest ecosystem in southern France (the Oak Observatory at the Observatoire de Haute Provence, O3HP was investigated in June of 2012 and 2013 with essentially a top-down approach. Atmospheric data suggest that the site is appropriate for estimating gross primary production (GPP directly from eddy covariance measurements of OCS fluxes, but it is less adequate for scaling net ecosystem exchange (NEE to GPP from observations of vertical gradients of OCS relative to CO2 during the daytime. Firstly, OCS and carbon dioxide (CO2 diurnal variations and vertical gradients show no net exchange of OCS at night when the carbon fluxes are dominated by ecosystem respiration. This contrasts with other oak woodland ecosystems of a Mediterranean climate, where nocturnal uptake of OCS by soil and/or vegetation has been observed. Since temperature, water, and organic carbon content of soil at the O3HP should favor the uptake of OCS, the lack of nocturnal net uptake would indicate that its gross consumption in soil is compensated for by emission processes that remain to be characterized. Secondly, the uptake of OCS during the photosynthetic period was characterized in two different ways. We measured ozone (O3 deposition velocities and estimated the partitioning of O3 deposition between stomatal and non-stomatal pathways before the start of a joint survey of OCS and O3 surface concentrations. We observed an increasing trend in the relative importance of the stomatal pathway during the morning hours and synchronous steep drops of mixing ratios of OCS (amplitude in the range of 60–100 ppt and O3 (amplitude in the range of 15–30 ppb after sunrise and before the break up of the nocturnal boundary layer. The uptake of OCS by plants was also characterized from vertical profiles. However, the time window for calculation of the ecosystem relative

  14. Bio-orthogonal "click-and-release" donation of caged carbonyl sulfide (COS) and hydrogen sulfide (H2S). (United States)

    Steiger, Andrea K; Yang, Yang; Royzen, Maksim; Pluth, Michael D


    Hydrogen sulfide (H 2 S) is an important biomolecule with high therapeutic potential. Here we leverage the inverse-electron demand Diels-Alder (IEDDA) click reaction between a thiocarbamate-functionalized trans-cyclooctene and a tetrazine to deliver carbonyl sulfide (COS), which is quickly converted to H 2 S by the uniquitous enzyme carbonic anhydrase (CA), thus providing a new strategy for bio-orthogonal COS/H 2 S donation.

  15. Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector (United States)

    Johnson, James E.; Bates, Timothy S.


    Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

  16. Instrument for Airborne Measurement of Carbonyl Sulfide, Phase II (United States)

    National Aeronautics and Space Administration — In this Phase II SBIR program, Southwest Sciences will continue the development of small, low power instrumentation for real-time direct measurement of carbonyl...

  17. Kinetics of the gas-phase reaction between hydroxyl and carbonyl sulfide over the temperature range 300-517 K (United States)

    Leu, M.-T.; Smith, R. H.


    By use of a discharge-flow resonance-fluorescence method the rate constant for the title reaction has been measured at five temperatures in the range 300-520 K. The Arrhenius expression is k(OH + OCS) = (1.3 + or - 0.3) x 10 to the -12th exp/-(2300 + or - 100)/T/ cu cm/s. Mass spectrometry has been used to detect the product HS and to collect some information about its reactivity. This study has carefully avoided the pitfalls associated with possible photolysis of reactants and complications due to H2S impurity in carbonyl sulfide that may have marred previous studies. This study has confirmed that the rate constant for this reaction is so much lower than the value originally used in computer modeling of the upper and lower atmosphere that conclusions about the relative importance of photolysis of OCS and of the reaction OH + OCS in the stratosphere must now be reassessed. The reaction OH + OCS has little significance for atmospheric chemistry.

  18. Microwave spectrum, dipole moment, and internal dynamics of the methyl fluoride-carbonyl sulfide weakly bound complex. (United States)

    Serafin, Michal M; Peebles, Sean A


    Rotational spectra for the normal and four isotopically substituted species of the 1:1 complex between methyl fluoride (H3CF) and carbonyl sulfide (OCS) have been measured using Fourier-transform microwave spectroscopy in the 5-16 GHz frequency region. The observed spectra fit well to a semirigid Watson Hamiltonian, and an analysis of the rotational constants has allowed a structure to be determined for this complex. The dipole moment vectors of the H3CF and OCS monomers are aligned approximately antiparallel with a C...C separation of 3.75(3) A and with an ab plane of symmetry. The values of the Pcc planar moments were found to be considerably different from the expected rigid values for all isotopologues. An estimate of approximately 14.5(50) cm-1 for the internal rotation barrier of the CH3 group with respect to the framework of the complex has been made using the Pcc values for the H3CF-OCS and D3CF-OCS isotopic species. Two structures, very close in energy and approximately related by a 60 degrees rotation about the C3 axis of the methyl fluoride, were identified by ab initio calculations at the MP2/6-311++G(2d,2p) level and provide reasonable agreement with the experimental rotational constants and dipole moment components.

  19. Sulfur isotopic fractionation of carbonyl sulfide during degradation by soil bacteria and enzyme (United States)

    Kamezaki, Kazuki; Hattori, Shohei; Ogawa, Takahiro; Toyoda, Sakae; Kato, Hiromi; Katayama, Yoko; Yoshida, Naohiro


    Carbonyl sulfide (COS) is an atmospheric trace gas that possess great potential for tracer of carbon cycle (Campbell et al., 2008). COS is taken up by vegetation during photosynthesis like absorption of carbon dioxide but COS can not emit by respiration of vegetation, suggesting possible tracer for gross primary production. However, some studies show the COS-derived GPP is larger than the estimates by using carbon dioxide flux because COS flux by photolysis and soil flux are not distinguished (e.g. Asaf et al., 2013). Isotope analysis is a useful tool to trace sources and transformations of trace gases. Recently our group developed a promising new analytical method for measuring the stable sulfur isotopic compositions of COS using nanomole level samples: the direct isotopic analytical technique of on-line gas chromatography-isotope ratio mass spectrometry (GC-IRMS) using fragmentation ions S+ enabling us to easily analyze sulfur isotopes in COS (Hattori et al., 2015). Soil is thought to be important as both a source and a sink of COS in the troposphere. In particular, soil has been reported as a large environmental sink for atmospheric COS. Bacteria isolated from various soils actively degrade COS, with various enzymes such as carbonic anhydrase and COSase (Ogawa et al., 2013) involved in COS degradation. However, the mechanism and the magnitude of bacterial contribution in terms of a sink for atmospheric COS is still uncertain. Therefore, it is important to quantitatively evaluate this contribution using COS sulfur isotope analysis. We present isotopic fractionation constants for COS by laboratory incubation experiments during degradation by soil bacteria and COSase. Incubation experiments were conducted using strains belonging to the genera Mycobacterium, Williamsia, Cupriavidus, and Thiobacillus, isolated from natural soil or activated sludge and enzyme purified from a bacteria. As a result, the isotopic compositions of OCS were increased during degradation of

  20. Canopy uptake dominates nighttime carbonyl sulfide fluxes in a boreal forest

    NARCIS (Netherlands)

    Kooijmans, Linda MJ; Maseyk, Kadmiel; Seibt, Ulli; Sun, Wu; Vesala, Timo; Mammarella, Ivan; Kolari, Pasi; Aalto, Juho; Franchin, Alessandro; Vecchi, Roberta; Valli, Gianluigi; Chen, Huilin


    Nighttime vegetative uptake of carbonyl sulfide (COS) can exist due to the incomplete closure of stomata and the light independence of the enzyme carbonic anhydrase, which complicates the use of COS as a tracer for gross primary productivity (GPP). In this study we derived night-time COS fluxes in a

  1. Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland

    NARCIS (Netherlands)

    Sun, Wu; Kooijmans, Linda M. J.; Maseyk, Kadmiel; Chen, Huilin; Mammarella, Ivan; Vesala, Timo; Levula, Janne; Keskinen, Helmi; Seibt, Ulli


    Soil is a major contributor to the biosphere-atmosphere exchange of carbonyl sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify terrestrial photosynthesis based on the coupled leaf uptake of COS and CO2, but such use requires separating soil COS flux, which is unrelated

  2. Ionization of oriented carbonyl sulfide molecules by intense circularly polarized laser pulses

    DEFF Research Database (Denmark)

    Dimitrovski, Darko; Abu-Samha, Mahmoud; Madsen, Lars Bojer


    We present combined experimental and theoretical results on strong-field ionization of oriented carbonyl sulfide molecules by circularly polarized laser pulses. The obtained molecular frame photoelectron angular distributions show pronounced asymmetries perpendicular to the direction...... of the molecular electric dipole moment. These findings are explained by a tunneling model invoking the laser-induced Stark shifts associated with the dipoles and polarizabilities of the molecule and its unrelaxed cation. The focus of the present article is to understand the strong-field ionization of one......-dimensionally-oriented polar molecules, in particular asymmetries in the emission direction of the photoelectrons. In the following article [Phys. Rev. A 83, 023406 (2011)] the focus is to understand strong-field ionization from three-dimensionally-oriented asymmetric top molecules, in particular the suppression of electron...

  3. Neurotoxicity of carbonyl sulfide in F344 rats following inhalation exposure for up to 12 weeks

    International Nuclear Information System (INIS)

    Morgan, Daniel L.; Little, Peter B.; Herr, David W.; Moser, Virginia C.; Collins, Bradley; Herbert, Ronald; Johnson, G. Allan; Maronpot, Robert R.; Harry, G. Jean; Sills, Robert C.


    Carbonyl sulfide (COS), a high-priority Clean Air Act chemical, was evaluated for neurotoxicity in short-term studies. F344 rats were exposed to 75-600 ppm COS 6 h per day, 5 days per week for up to 12 weeks. In rats exposed to 500 or 600 ppm for up to 4 days, malacia and microgliosis were detected in numerous neuroanatomical regions of the brain by conventional optical microscopy and magnetic resonance microscopy (MRM). After a 2-week exposure to 400 ppm, rats were evaluated using a functional observational battery. Slight gait abnormality was detected in 50% of the rats and hypotonia was present in all rats exposed to COS. Decreases in motor activity, and forelimb and hindlimb grip strength were also detected. In rats exposed to 400 ppm for 12 weeks, predominant lesions were in the parietal cortex area 1 (necrosis) and posterior colliculus (neuronal loss, microgliosis, hemorrhage), and occasional necrosis was present in the putamen, thalamus, and anterior olivary nucleus. Carbonyl sulfide specifically targeted the auditory system including the olivary nucleus, nucleus of the lateral lemniscus, and posterior colliculus. Consistent with these findings were alterations in the amplitude of the brainstem auditory evoked responses (BAER) for peaks N 3 , P 4 , N 4 , and N 5 that represented changes in auditory transmission between the anterior olivary nucleus to the medial geniculate nucleus in animals after exposure for 2 weeks to 400 ppm COS. A concentration-related decrease in cytochrome oxidase activity was detected in the posterior colliculus and parietal cortex of exposed rats as early as 3 weeks. Cytochrome oxidase activity was significantly decreased at COS concentrations that did not cause detectable lesions, suggesting that disruption of the mitochondrial respiratory chain may precede these brain lesions. Our studies demonstrate that this environmental air contaminant has the potential to cause a wide spectrum of brain lesions that are dependent on the degree

  4. Review of the toxicology of carbonyl sulfide, a new grain fumigant. (United States)

    Bartholomaeus, Andrew R; Haritos, Victoria S


    Carbonyl sulfide (COS) is a new grain fumigant which has been developed to replace methyl bromide, being phased out due to its ozone depletion properties, and to supplement phosphine gas which is experiencing increased insect resistance. Treatment of commodities with COS, a highly effective fumigant, results in residues that are near or indistinguishable to natural background levels of this compound. COS is a naturally occurring gas, being the predominant sulfur moiety in the atmosphere, occurs naturally in food and is a normal by-product of mammalian aerobic metabolism. COS has low acute inhalational toxicity but with a steep dose response curve; COS is neither genotoxic nor a developmental toxicant but does reversibly impair male fertility. Prolonged, repeated exposure to COS is likely to present similar neurotoxicity hazards to that of the structurally and toxicologically related compound carbon disulfide. Although the occupational risks presented by COS as a fumigant of bulk grain are significant, these are, as they have been for a considerable time for phosphine and methyl bromide, manageable by good occupational safety practices. Consideration may need to be given to scrubbing of ventilated COS and its breakdown product hydrogen sulfide, at the completion of fumigation to minimise worker and bystander exposure. In terms of classical regulatory toxicology studies, the available database for COS is deficient in many aspects and registration in most jurisdictions will depend on sound scientific argument built upon the totality of the existing scientific data as there are strong arguments supporting the registration of this compound.

  5. Relationships between carbonyl sulfide (COS) and CO2 during leaf gas exchange. (United States)

    Stimler, Keren; Montzka, Stephen A; Berry, Joseph A; Rudich, Yinon; Yakir, Dan


    *Carbonyl sulfide (COS) exchange in C(3) leaves is linked to that of CO(2), providing a basis for the use of COS as a powerful tracer of gross CO(2) fluxes between plants and the atmosphere, a critical element in understanding the response of the land biosphere to global change. *Here, we carried out controlled leaf-scale gas-exchange measurements of COS and CO(2) in representative C(3) plants under a range of light intensities, relative humidities and temperatures, CO(2) and COS concentrations, and following abscisic acid treatments. *No 'respiration-like' emission of COS or detectable compensation point, and no cross-inhibition effects between COS and CO(2) were observed. The mean ratio of COS to CO(2) assimilation flux rates, A(s)/A(c), was c. 1.4 pmol micromol(-1) and the leaf relative uptake (assimilation normalized to ambient concentrations, (A(s)/A(c))(C(a)(c)/C(a)(s))) was 1.6-1.7 across species and conditions, with significant deviations under certain conditions. Stomatal conductance was enhanced by increasing COS, which was possibly mediated by hydrogen sulfide (H(2)S) produced from COS hydrolysis, and a correlation was observed between A(s) and leaf discrimination against C(18)OO. *The results provide systematic and quantitative information necessary for the use of COS in photosynthesis and carbon-cycle research on the physiological to global scales.

  6. Ultrasensitive Analyzer for Realtime, In-Situ Airborne and Terrestrial Measurements of OCS, CO2, and CO Project (United States)

    National Aeronautics and Space Administration — In this SBIR effort, Los Gatos Research (LGR) will employ its patented mid-infrared Off-Axis ICOS technique to develop a compact carbonyl sulfide (OCS), carbon...

  7. Ultrasensitive Analyzer for Realtime, In-Situ Airborne and Terrestrial Measurements of OCS, CO2, and CO, Phase II (United States)

    National Aeronautics and Space Administration — In this SBIR effort, Los Gatos Research (LGR) will employ its patented mid-infrared Off-Axis ICOS technique to develop a compact carbonyl sulfide (OCS), carbon...

  8. The flux of carbonyl sulfide and carbon disulfide between the atmosphere and a spruce forest

    Directory of Open Access Journals (Sweden)

    X. Xu


    Full Text Available Turbulent fluxes of carbonyl sulfide (COS and carbon disulfide (CS2 were measured over a spruce forest in Central Germany using the relaxed eddy accumulation (REA technique. A REA sampler was developed and validated using simultaneous measurements of CO2 fluxes by REA and by eddy correlation. REA measurements were conducted during six campaigns covering spring, summer, and fall between 1997 and 1999. Both uptake and emission of COS and CS2 by the forest were observed, with deposition occurring mainly during the sunlit period and emission mainly during the dark period. On the average, however, the forest acts as a sink for both gases. The average fluxes for COS and CS2 are  -93 ± 11.7 pmol m-2 s-1 and  -18 ± 7.6 pmol m-2 s-1, respectively. The fluxes of both gases appear to be correlated to photosynthetically active radiation and to the CO2 and chem{H_2O} fluxes, supporting the idea that the air-vegetation exchange of both gases is controlled by stomata. An uptake ratio COS/CO2 of 10 ± 1.7 pmol m mol-1 has been derived from the regression line for the correlation between the COS and CO2 fluxes. This uptake ratio, if representative for the global terrestrial net primary production, would correspond to a sink of 2.3 ± 0.5 Tg COS yr-1.

  9. Towards the understanding of biogeochemical processes involved in the release of carbonyl sulfide (COS) from soil (United States)

    Behrendt, Thomas; Catao, Elisa; Bunk, Rüdiger; Yi, Zhigang; Greule, Markus; Keppler, Frank; Kesselmeier, Jürgen; Trumbore, Susan


    Carbonyl sulfide (COS) is present in the atmosphere in low mixing ratio ( 500ppt). It is relevant in climate change through the effect in aerosol formation. Soils can act as source of COS, e.g. by microbial degradation of thiocyanate from plant material. On the other side it is known that COS can be consumed via various enzymatic pathways. Assuming that biogenic processes dominate over chemical reactions we extracted nucleic acids and performed amplicon sequencing for bacteria (16S rRNA) and fungi (ITS region) from a mid-latitude agricultural maize soil which was previously incubated under ambient COS and COS fumigation ( 1000ppt). The mixing ratios of COS have been measured online from soil samples in a dynamic chamber system under laboratory conditions by an integrated cavity output spectroscopy (IOCS) analyzer (Los Gatos Research Inc., USA). Additionally stable carbon isotope values (δ13C values) of COS were measured using a pre-concentration method and stable isotope ratio mass spectrometry (IRMS). Under low COS mixing ratio ( 50ppt) δ13C +4.7 ‰ for spruce forest ( 23°C), and -24.4‰ for mid-latitude cornfield ( 22°C), respectively. Linking gas release rates of (COS, CO2, CO, NO) to isotopic signatures of COS and molecular results might allow us to indicate bacterial s-compound degradation related to the higher activity of β-Proteobacteria and of the family Acetobacteraceae from the α-Proteobacteria phylum, potentially involved with the hydrolysis of thiocyanate in the soil releasing COS. Furthermore, our study reports the first COS data for rainforest and desert soils which are in the order of 0.5 pmol gdw-1 h-1 and 2 pmol gdw-1 h-1, respectively.

  10. Observations of the uptake of carbonyl sulfide (COS by trees under elevated atmospheric carbon dioxide concentrations

    Directory of Open Access Journals (Sweden)

    L. Sandoval-Soto


    Full Text Available Global change forces ecosystems to adapt to elevated atmospheric concentrations of carbon dioxide (CO2. We understand that carbonyl sulfide (COS, a trace gas which is involved in building up the stratospheric sulfate aerosol layer, is taken up by vegetation with the same triad of the enzymes which are metabolizing CO2, i.e. ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco, phosphoenolpyruvate carboxylase (PEP-Co and carbonic anhydrase (CA. Therefore, we discuss a physiological/biochemical acclimation of these enzymes affecting the sink strength of vegetation for COS. We investigated the acclimation of two European tree species, Fagus sylvatica and Quercus ilex, grown inside chambers under elevated CO2, and determined the exchange characteristics and the content of CA after a 1–2 yr period of acclimation from 350 ppm to 800 ppm CO2. We demonstrate that a compensation point, by definition, does not exist. Instead, we propose to discuss a point of uptake affinity (PUA. The results indicate that such a PUA, the CA activity and the deposition velocities may change and may cause a decrease of the COS uptake by plant ecosystems, at least as long as the enzyme acclimation to CO2 is not surpassed by an increase of atmospheric COS. As a consequence, the atmospheric COS level may rise causing an increase of the radiative forcing in the troposphere. However, this increase is counterbalanced by the stronger input of this trace gas into the stratosphere causing a stronger energy reflection by the stratospheric sulfur aerosol into space (Brühl et al., 2012. These data are very preliminary but may trigger a discussion on COS uptake acclimation to foster measurements with modern analytical instruments.

  11. Soil-atmosphere carbonyl sulfide (COS) exchange in a tropical rainforest at La Selva, Costa Rica (United States)

    Sun, W.; Maseyk, K. S.; Juarez, S.; Lett, C.; Seibt, U. H.


    Carbonyl sulfide (COS) has recently been proposed as a promising tracer for partitioning ecosystem carbon assimilation due to the close analogy between leaf uptake processes of COS and CO2. This emerging framework requires accurate characterization of the source and sink components of COS, including soil fluxes. Here we present the first direct, continuous observations of soil COS fluxes for 4 months at a tropical rainforest, La Selva Biological Station, Costa Rica. Three soil plots with contrasting water content were selected for chamber measurements. Our observations confirmed that soils are principally COS sinks, with daily mean COS fluxes averaged across all chambers ranging from -3 to 0 pmol m-2 s-1. When compared with net ecosystem COS uptake which peaks around -30 pmol m-2 s-1, their contributions should be considered in ecosystem COS balance. We did not find a temperature optimum, but soil COS uptake slightly increased with soil temperature, indicating biotic control on soil COS fluxes. Diurnal cycles of COS fluxes were observed during drying out periods after rain. The diel periodicity of COS fluxes was probably obscured by frequent raining at the site. Diffusional control of soil COS fluxes is shown from increasing soil COS uptake at lower soil water-filled pore space. These confirm that soil COS fluxes are mediated both by soil physical and biological factors. Using a depth-resolved diffusion-reaction model with data-driven enzyme activity parameterization, we simulated the COS fluxes from measured soil environmental variables, consistent with observations. This modeling scheme is useful for separating soil COS fluxes from net ecosystem COS fluxes, which lends support to the emergent COS-based approach of carbon flux partitioning.

  12. Sources and sinks of carbonyl sulfide in an agricultural field in the Southern Great Plains (United States)

    Maseyk, Kadmiel; Berry, Joseph A.; Billesbach, Dave; Campbell, John Elliott; Torn, Margaret S.; Zahniser, Mark; Seibt, Ulli


    Net photosynthesis is the largest single flux in the global carbon cycle, but controls over its variability are poorly understood because there is no direct way of measuring it at the ecosystem scale. We report observations of ecosystem carbonyl sulfide (COS) and CO2 fluxes that resolve key gaps in an emerging framework for using concurrent COS and CO2 measurements to quantify terrestrial gross primary productivity. At a wheat field in Oklahoma we found that in the peak growing season the flux-weighted leaf relative uptake of COS and CO2 during photosynthesis was 1.3, at the lower end of values from laboratory studies, and varied systematically with light. Due to nocturnal stomatal conductance, COS uptake by vegetation continued at night, contributing a large fraction (29%) of daily net ecosystem COS fluxes. In comparison, the contribution of soil fluxes was small (1–6%) during the peak growing season. Upland soils are usually considered sinks of COS. In contrast, the well-aerated soil at the site switched from COS uptake to emissions at a soil temperature of around 15 °C. We observed COS production from the roots of wheat and other species and COS uptake by root-free soil up to a soil temperature of around 25 °C. Our dataset demonstrates that vegetation uptake is the dominant ecosystem COS flux in the peak growing season, providing support of COS as an independent tracer of terrestrial photosynthesis. However, the observation that ecosystems may become a COS source at high temperature needs to be considered in global modeling studies. PMID:24927594

  13. Carbonyl sulfide (COS) as a tracer for canopy photosynthesis, transpiration and stomatal conductance: potential and limitations. (United States)

    Wohlfahrt, Georg; Brilli, Federico; Hörtnagl, Lukas; Xu, Xiaobin; Bingemer, Heinz; Hansel, Armin; Loreto, Francesco


    The theoretical basis for the link between the leaf exchange of carbonyl sulfide (COS), carbon dioxide (CO(2)) and water vapour (H(2)O) and the assumptions that need to be made in order to use COS as a tracer for canopy net photosynthesis, transpiration and stomatal conductance, are reviewed. The ratios of COS to CO(2) and H(2)O deposition velocities used to this end are shown to vary with the ratio of the internal to ambient CO(2) and H(2)O mole fractions and the relative limitations by boundary layer, stomatal and internal conductance for COS. It is suggested that these deposition velocity ratios exhibit considerable variability, a finding that challenges current parameterizations, which treat these as vegetation-specific constants. COS is shown to represent a better tracer for CO(2) than H(2)O. Using COS as a tracer for stomatal conductance is hampered by our present poor understanding of the leaf internal conductance to COS. Estimating canopy level CO(2) and H(2)O fluxes requires disentangling leaf COS exchange from other ecosystem sources/sinks of COS. We conclude that future priorities for COS research should be to improve the quantitative understanding of the variability in the ratios of COS to CO(2) and H(2)O deposition velocities and the controlling factors, and to develop operational methods for disentangling ecosystem COS exchange into contributions by leaves and other sources/sinks. To this end, integrated studies, which concurrently quantify the ecosystem-scale CO(2), H(2)O and COS exchange and the corresponding component fluxes, are urgently needed. © 2011 Blackwell Publishing Ltd.

  14. State-to-state photodissociation of carbonyl sulfide (ν2=0,1|JlM). II. The effect of initial bending on coherence of S(1D2) polarization

    International Nuclear Information System (INIS)

    Brom, Alrik J. van den; Rakitzis, T. Peter; Janssen, Maurice H. M.


    Photodissociation studies using ion imaging are reported, measuring the coherence of the polarization of the S( 1 D 2 ) fragment from the photolysis of single-quantum state-selected carbonyl sulfide (OCS) at 223 and 230 nm. A hexapole state-selector focuses a molecular beam of OCS parent molecules in the ground state (ν 2 =0 vertical bar JM=10) or in the first excited bending state (ν 2 =1 vertical bar JlM=111). At 230 nm photolysis the Im[a 1 (1p arallel ,perpendicular )] moment for the fast S( 1 D 2 ) channel increases by about 50% when the initial OCS parent state changes from the vibrationless ground state to the first excited bending state. No dependence on the initial bending state is found for photolysis at 223 nm. We observe separate rings in the slow channel of the velocity distribution of S( 1 D 2 ) correlating to single CO(J) rotational states. The additional available energy for photolysis at 223 nm is found to be channeled mostly into the CO(J) rotational motion. An improved value for the OC-S bond energy D 0 =4.292 eV is reported

  15. Gridded anthropogenic emissions inventory and atmospheric transport of carbonyl sulfide in the U.S.: U.S. Anthropogenic COS Source and Transport

    Energy Technology Data Exchange (ETDEWEB)

    Zumkehr, Andrew [Sierra Nevada Research Institute, University of California, Merced California USA; Hilton, Timothy W. [Sierra Nevada Research Institute, University of California, Merced California USA; Whelan, Mary [Sierra Nevada Research Institute, University of California, Merced California USA; Smith, Steve [Joint Global Change Research Institute, PNNL, College Park Maryland USA; Campbell, J. Elliott [Sierra Nevada Research Institute, University of California, Merced California USA


    Carbonyl sulfide (COS or OCS), the most abundant sulfur containing gas in the troposphere, has recently emerged as a potentially important atmospheric tracer for the carbon cycle. Atmospheric inverse modeling studies may be able to use existing tower, airborne, and satellite observations of COS to infer information about photosynthesis. However, such analysis relies on gridded anthropogenic COS source estimates that are largely based on industry activity data from over three decades ago. Here we use updated emission factor data and industry activity data to develop a gridded inventory with a 0.1 degree resolution for the U.S. domain. The inventory includes the primary anthropogenic COS sources including direct emissions from the coal and aluminum industries as well as indirect sources from industrial carbon disulfide emissions. Compared to the previously published inventory, we found that the total anthropogenic source (direct and indirect) is 47% smaller. Using this new gridded inventory to drive the STEM/WRF atmospheric transport model, we found that the anthropogenic contribution to COS variation in the troposphere is small relative to the biosphere influence, which is encouraging of carbon cycle applications in this region. Additional anthropogenic sectors with highly uncertain emission factors require further field measurements.

  16. Soil atmosphere exchange of carbonyl sulfide (COS regulated by diffusivity depending on water-filled pore space

    Directory of Open Access Journals (Sweden)

    H. Van Diest


    Full Text Available The exchange of carbonyl sulfide (COS between soil and the atmosphere was investigated for three arable soils from Germany, China and Finland and one forest soil from Siberia for parameterization in the relation to ambient carbonyl sulfide (COS concentration, soil water content (WC and air temperature. All investigated soils acted as sinks for COS. A clear and distinct uptake optimum was found for the German, Chinese, Finnish and Siberian soils at 11.5%, 9%, 11.5%, and 9% soil WC, respectively, indicating that the soil WC acts as an important biological and physical parameter for characterizing the exchange of COS between soils and the atmosphere. Different optima of deposition velocities (Vd as observed for the Chinese, Finnish and Siberian boreal soil types in relation to their soil WC, aligned at 19% in relation to the water-filled pore space (WFPS, indicating the dominating role of gas diffusion. This interpretation was supported by the linear correlation between Vd and bulk density. We suggest that the uptake of COS depends on the diffusivity dominated by WFPS, a parameter depending on soil WC, soil structure and porosity of the soil.

  17. Infrared spectra of two isomers of protonated carbonyl sulfide (HOCS+and HSCO+) and t-HOCS in solid para-hydrogen. (United States)

    Tsuge, Masashi; Lee, Yuan-Pern


    We report infrared (IR) spectra of HOCS + , HSCO + , t-HOCS, and other species produced on electron bombardment of a mixture of carbonyl sulfide (OCS) and para-hydrogen (p-H 2 ) during deposition at 3.2 K. After maintenance of the matrix in darkness for 15 h, the intensities of absorption features of HOCS + at 2945.9 (ν 1 ), 1875.3 (ν 2 ), and 1041.9 (ν 3 ) cm -1 and those of HSCO + at 2506.9 (ν 1 ) and 2074.2 (ν 2 ) cm -1 decreased through neutralization with trapped electrons. Lines observed at 3563.4, 1394.8, and 1199.0 cm -1 , which decreased slightly in intensity after maintenance in darkness and were nearly depleted after irradiation at 373 nm, are assigned to a t-HOCS radical. The corresponding spectra of their 13 C- and D-isotopologues were observed. The IR spectra of HSCO + and t-HOCS and those of modes ν 2 and ν 3 of HOCS + are new. The assignments were made according to the expected chemical behavior and a comparison of experimental and calculated wavenumbers and 13 C- and D-isotopic shifts. The wavenumber of the OH stretching mode (2945.9 cm -1 ) of HOCS + in solid p-H 2 is significantly red-shifted from that (3435.16 cm -1 ) reported for gaseous HOCS + ; this shift is attributed to partial sharing of a proton between OCS and H 2 . The corresponding p-H 2 induced shift is small in HSCO + because of a much weaker interaction between HSCO + and H 2 .


    Because of the amount of carbonyl sulfide (COS) emissions and the lack of toxicological data, COS was listed in the Clean Air Act of 1990 as a Hazardous Air Pollutant. In 1999 COS was nominated by the US EPA to the National Toxicology Program for additional toxicological investig...

  19. Measurements of atmospheric carbonyl sulfide during the NASA Chemical Instrumentation Test and Evaluation Project: Implications for the global COS budget (United States)

    Johnson, James E.; Bandy, Alan R.; Thornton, Donald C.; Bates, Timothy S.


    Atmospheric carbonyl sulfide COS concentrations were measured by three analytical systems during the Chemical Instrumentation Test and Evaluation (CITE 3) project. The three systems all used cryogenic sample preconcentration and gas chromatographic (GC) separation but differed in the method of detection. The FPD system used a flame photometric detector, the MS system used a mass selective detector, and the ECD-S system used a fluorinating catalyst followed by an electron capture detector. With the FPD system, we found a mean COS concentration of 510 ppt over the North Atlantic and 442 ppt over the Tropical Atlantic. With the ECD-S system, we found a mean COS concentration of 489 ppt over the North Atlantic and 419 ppt over the Tropical Atlantic. All three systems registered a latitudinal gradient in atmospheric COS of between 1.6 and 2.0 ppt per degree of latitude, with increasing COS concentrations northward which was similar to the gradient measured by Bingemer et al. (1990). It is difficult to reconcile the measured latitudinal concentration gradient with present theories of the global COS budget since the largest sink of COS is thought to be a flux to land plants, most of which are in the northern hemisphere.

  20. Association between Carbonyl Sulfide Uptake and 18Δ during Gas Exchange in C3 and C4 Leaves1[OA (United States)

    Stimler, Keren; Berry, Joseph A.; Montzka, Steve A.; Yakir, Dan


    Carbonyl sulfide (COS) and C18OO exchange by leaves provide potentially powerful tracers of biosphere-atmosphere CO2 exchange, and both are assumed to depend on carbonic anhydrase (CA) activity and conductance along the diffusive pathway in leaves. We investigated these links using C3 and C4 plants, hypothesizing that the rates of COS and C18OO exchange by leaves respond in parallel to environmental and biological drivers. Using CA-deficient antisense lines of C4 and C3 plants, COS uptake was essentially eliminated and discrimination against C18OO exchange (18Δ) greatly reduced, demonstrating CA’s key role in both processes. 18Δ showed a positive linear correlation with leaf relative uptake (LRU; ratio of COS to CO2 assimilation rates, As/Ac, normalized to their respective ambient concentrations), which reflected the effects of stomatal conductance on both COS and C18OO exchange. Unexpectedly, a decoupling between As and 18Δ was observed in comparing C4 and C3 plants, with a large decrease in 18Δ but no parallel reduction in As in the former. This could be explained by C4 plants having higher COS concentrations at the CA site (maintaining high As with reduced CA) and a high phosphoenolpyruvate carboxylase/CA activity ratio (reducing 18O exchange efficiency between CO2 and water, but not As). Similar As but higher Ac in C4 versus C3 plants resulted in lower LRU values in the former (1.16 ± 0.20 and 1.82 ± 0.18 for C4 and C3, respectively). LRU was, however, relatively constant in both plant types across a wide range of conditions, except low light (<191 μmol photon m−2 s−1). PMID:21715674

  1. Association between carbonyl sulfide uptake and (18)Δ during gas exchange in C(3) and C(4) leaves. (United States)

    Stimler, Keren; Berry, Joseph A; Montzka, Steve A; Yakir, Dan


    Carbonyl sulfide (COS) and C(18)OO exchange by leaves provide potentially powerful tracers of biosphere-atmosphere CO(2) exchange, and both are assumed to depend on carbonic anhydrase (CA) activity and conductance along the diffusive pathway in leaves. We investigated these links using C(3) and C(4) plants, hypothesizing that the rates of COS and C(18)OO exchange by leaves respond in parallel to environmental and biological drivers. Using CA-deficient antisense lines of C(4) and C(3) plants, COS uptake was essentially eliminated and discrimination against C(18)OO exchange ((18)Δ) greatly reduced, demonstrating CA's key role in both processes. (18)Δ showed a positive linear correlation with leaf relative uptake (LRU; ratio of COS to CO(2) assimilation rates, A(s)/A(c), normalized to their respective ambient concentrations), which reflected the effects of stomatal conductance on both COS and C(18)OO exchange. Unexpectedly, a decoupling between A(s) and (18)Δ was observed in comparing C(4) and C(3) plants, with a large decrease in (18)Δ but no parallel reduction in A(s) in the former. This could be explained by C(4) plants having higher COS concentrations at the CA site (maintaining high A(s) with reduced CA) and a high phosphoenolpyruvate carboxylase/CA activity ratio (reducing (18)O exchange efficiency between CO(2) and water, but not A(s)). Similar A(s) but higher A(c) in C(4) versus C(3) plants resulted in lower LRU values in the former (1.16 ± 0.20 and 1.82 ± 0.18 for C(4) and C(3), respectively). LRU was, however, relatively constant in both plant types across a wide range of conditions, except low light (<191 μmol photon m(-2) s(-1)).

  2. Soil fluxes of carbonyl sulfide (COS), carbon monoxide, and carbon dioxide in a boreal forest in southern Finland (United States)

    Sun, Wu; Kooijmans, Linda M. J.; Maseyk, Kadmiel; Chen, Huilin; Mammarella, Ivan; Vesala, Timo; Levula, Janne; Keskinen, Helmi; Seibt, Ulli


    Soil is a major contributor to the biosphere-atmosphere exchange of carbonyl sulfide (COS) and carbon monoxide (CO). COS is a tracer with which to quantify terrestrial photosynthesis based on the coupled leaf uptake of COS and CO2, but such use requires separating soil COS flux, which is unrelated to photosynthesis, from ecosystem COS uptake. For CO, soil is a significant natural sink that influences the tropospheric CO budget. In the boreal forest, magnitudes and variabilities of soil COS and CO fluxes remain poorly understood. We measured hourly soil fluxes of COS, CO, and CO2 over the 2015 late growing season (July to November) in a Scots pine forest in Hyytiälä, Finland. The soil acted as a net sink of COS and CO, with average uptake rates around 3 pmol m-2 s-1 for COS and 1 nmol m-2 s-1 for CO. Soil respiration showed seasonal dynamics controlled by soil temperature, peaking at around 4 µmol m-2 s-1 in late August and September and dropping to 1-2 µmol m-2 s-1 in October. In contrast, seasonal variations of COS and CO fluxes were weak and mainly driven by soil moisture changes through diffusion limitation. COS and CO fluxes did not appear to respond to temperature variation, although they both correlated well with soil respiration in specific temperature bins. However, COS : CO2 and CO : CO2 flux ratios increased with temperature, suggesting possible shifts in active COS- and CO-consuming microbial groups. Our results show that soil COS and CO fluxes do not have strong variations over the late growing season in this boreal forest and can be represented with the fluxes during the photosynthetically most active period. Well-characterized and relatively invariant soil COS fluxes strengthen the case for using COS as a photosynthetic tracer in boreal forests.

  3. The influence of vapor pressure deficit (VPD) on the use of carbonyl sulfide (COS) as a photosynthetic tracer (United States)

    Sun, W.; Maseyk, K. S.; Lett, C.; Seibt, U.


    Using carbonyl sulfide (COS) as a tracer to derive gross primary productivity (GPP) estimates requires knowledge of the relationship between leaf COS and CO2 uptake, which is typically embodied in a parameter called leaf relative uptake (LRU) ratio, defined as the concentration normalized COS:CO2 flux ratio. Previous laboratory and field studies have found light as the key environmental driver of LRU due to differential light responses of COS and CO2 uptake imposed by stomatal regulation. But the influences on LRU from other environmental drivers, particularly vapor pressure deficit (VPD) that affects stomatal conductance, remain elusive. Here we show that VPD is an important determinant of the COS-CO2 uptake relationship in a water-stressed ecosystem. We measured leaf COS and CO2 fluxes from a coast live oak with automated leaf chambers in spring 2013 in a southern Californian woodland. In this semiarid ecosystem, both leaf COS and CO2 uptake responded to VPD and showed a midday depression caused by reduced stomatal conductance. Above a moderate light level ( 500 µmol m-2 s-1), COS uptake decreased with light, whereas CO2 uptake saturated. As a result of the VPD-limited COS uptake, LRU value became smaller than 1.0 at high light (> 1000 µmol m-2 s-1), strongly deviating from previous laboratory values that converge to 1.6. Hence, failure to consider VPD influence may result in overestimated LRU value and underestimated CO2 uptake in this ecosystem. Using a coupled photosynthesis-stomatal conductance model, we show that the VPD control on LRU is in accordance with the response of stomatal conductance to VPD. Our results highlight that incorporating the VPD effect into the prediction of LRU value is crucial to the implementation of COS-based photosynthesis estimates in semiarid ecosystems.

  4. Sources and sinks of carbonyl sulfide in a mountain grassland and relationships to the carbon dioxide exchange (United States)

    Spielmann, Felix M.; Kitz, Florian; Hammerle, Albin; Gerdel, Katharina; Wohlfahrt, Georg


    The trace gas carbonyl sulfide (COS) has been proposed as a tracer for canopy gross primary production (GPP), canopy transpiration and stomatal conductance of plant canopies in the last few years. COS enters the plant leaf through the stomata and diffuses through the intercellular space, the cell wall, the plasma membrane and the cytosol like CO2. It is then catalyzed by the enzyme carbonic anhydrase (CA) in a one-way reaction to H2S and CO2. This one-way flux into the leaf makes COS a promising tracer for the GPP. However there is growing evidence, that plant leaves aren't the only contributors to the ecosystem flux of COS. Therefor the COS uptake of soil microorganisms also containing CA and abiotic COS production might have to be accounted for when using COS as a tracer at the ecosystem scale. The overarching objective of this study was to quantify the relationship between the ecosystem-scale exchange of COS, CO2 and H2O and thus to test for the potential of COS to be used as a tracer for the plant canopy CO2 and H2O exchange. More specifically we aimed at quantifying the contribution of the soil to the ecosystem-scale COS exchange in order to understand complications that may arise due to a non-negligible soil COS exchange. In May 2015 we set up our quantum cascade laser (QCL) (Aerodyne Research Inc., MA, USA) at a temperate mountain grassland in Stubai Valley close to the village of Neustift, Austria. Our site lies at the valley bottom and is an intensively managed mountain grassland, which is cut 3-4 times a year. With the QCL we were able to measure concurrently the concentrations of COS, CO2, H2O (and CO) at a frequency of 10 Hz with minimal noise. This allowed us to conduct ecosystem-scale eddy covariance measurements. The eddy covariance flux measurements revealed that the COS uptake continues at night, which we confirmed was not caused by soil microorganisms, as the soil exchange was close to neutral during nighttime. Instead, the nocturnal COS uptake

  5. A new mechanistic framework to predict OCS fluxes from soils (United States)

    Ogée, Jérôme; Sauze, Joana; Kesselmeier, Jürgen; Genty, Bernard; Van Diest, Heidi; Launois, Thomas; Wingate, Lisa


    Estimates of photosynthetic and respiratory fluxes at large scales are needed to improve our predictions of the current and future global CO2 cycle. Carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere and has been proposed as a new tracer of photosynthetic gross primary productivity (GPP), as the uptake of OCS from the atmosphere is dominated by the activity of carbonic anhydrase (CA), an enzyme abundant in leaves that also catalyses CO2 hydration during photosynthesis. However soils also exchange OCS with the atmosphere, which complicates the retrieval of GPP from atmospheric budgets. Indeed soils can take up large amounts of OCS from the atmosphere as soil microorganisms also contain CA, and OCS emissions from soils have been reported in agricultural fields or anoxic soils. To date no mechanistic framework exists to describe this exchange of OCS between soils and the atmosphere, but empirical results, once upscaled to the global scale, indicate that OCS consumption by soils dominates OCS emission and its contribution to the atmospheric budget is large, at about one third of the OCS uptake by vegetation, also with a large uncertainty. Here, we propose a new mechanistic model of the exchange of OCS between soils and the atmosphere that builds on our knowledge of soil CA activity from CO2 oxygen isotopes. In this model the OCS soil budget is described by a first-order reaction-diffusion-production equation, assuming that the hydrolysis of OCS by CA is total and irreversible. Using this model we are able to explain the observed presence of an optimum temperature for soil OCS uptake and show how this optimum can shift to cooler temperatures in the presence of soil OCS emission. Our model can also explain the observed optimum with soil moisture content previously described in the literature as a result of diffusional constraints on OCS hydrolysis. These diffusional constraints are also responsible for the response of OCS uptake to soil weight and

  6. Methanol absorption characteristics for the removal of H2S (hydrogen sulfide), COS (carbonyl sulfide) and CO2 (carbon dioxide) in a pilot-scale biomass-to-liquid process

    International Nuclear Information System (INIS)

    Seo, Myung Won; Yun, Young Min; Cho, Won Chul; Ra, Ho Won; Yoon, Sang Jun; Lee, Jae Goo; Kim, Yong Ku; Kim, Jae Ho; Lee, See Hoon; Eom, Won Hyun; Lee, Uen Do; Lee, Sang Bong


    The BTL (biomass-to-liquid) process is an attractive process that produces liquid biofuels from biomass. The FT (Fisher–Tropsch) process is used to produce synfuels such as diesel and gasoline from gasified biomass. However, the H 2 S (hydrogen sulfide), COS (carbonyl sulfide) and CO 2 (carbon dioxide) in the syngas that are produced from the biomass gasifiers cause a decrease of the conversion efficiency and deactivates the catalyst that is used in the FT process. To remove the acid gases, a pilot-scale methanol absorption tower producing diesel at a rate of 1 BPD (barrel per day) was developed, and the removal characteristics of the acid gases were determined. A total operation time of 500 h was achieved after several campaigns. The average syngas flow rate at the inlet of methanol absorption tower ranged from 300 to 800 L/min. The methanol absorption tower efficiently removed H 2 S from 30 ppmV to less than 1 ppmV and COS from 2 ppmV to less than 1 ppmV with a removal of CO 2 from 20% to 5%. The outlet gas composition adhered to the guidelines for FT reactors. No remaining sulfurous components were found, and the tar component was analyzed in the spent methanol after long-term operations. - Highlights: • The gas cleaning system in a pilot-scale BTL (biomass-to-liquid) process is reported. • Although methanol absorption tower is conventional process, its application to BTL process is attempted. • The methanol absorption tower efficiently removed H 2 S, COS and CO 2 in the syngas. • The sulfurous and tar components in the methanol are analyzed

  7. A coupled model of the global cycles of carbonyl sulfide and CO2: A possible new window on the carbon cycle (United States)

    Berry, Joe; Wolf, Adam; Campbell, J. Elliott; Baker, Ian; Blake, Nicola; Blake, Don; Denning, A. Scott; Kawa, S. Randy; Montzka, Stephen A.; Seibt, Ulrike; Stimler, Keren; Yakir, Dan; Zhu, Zhengxin


    Carbonyl sulfide (COS) is an atmospheric trace gas that participates in some key reactions of the carbon cycle and thus holds great promise for studies of carbon cycle processes. Global monitoring networks and atmospheric sampling programs provide concurrent data on COS and CO2 concentrations in the free troposphere and atmospheric boundary layer over vegetated areas. Here we present a modeling framework for interpreting these data and illustrate what COS measurements might tell us about carbon cycle processes. We implemented mechanistic and empirical descriptions of leaf and soil COS uptake into a global carbon cycle model (SiB 3) to obtain new estimates of the COS land flux. We then introduced these revised boundary conditions to an atmospheric transport model (Parameterized Chemical Transport Model) to simulate the variations in the concentration of COS and CO2 in the global atmosphere. To balance the threefold increase in the global vegetation sink relative to the previous baseline estimate, we propose a new ocean COS source. Using a simple inversion approach, we optimized the latitudinal distribution of this ocean source and found that it is concentrated in the tropics. The new model is capable of reproducing the seasonal variation in atmospheric concentration at most background atmospheric sites. The model also reproduces the observed large vertical gradients in COS between the boundary layer and free troposphere. Using a simulation experiment, we demonstrate that comparing drawdown of CO2 with COS could provide additional constraints on differential responses of photosynthesis and respiration to environmental forcing. The separation of these two distinct processes is essential to understand the carbon cycle components for improved prediction of future responses of the terrestrial biosphere to changing environmental conditions.

  8. Combination Bands of the Nonpolar OCS Dimer Involving Intermolecular Modes (United States)

    Rezaei, M.; Oliaee, J. Norooz; Moazzen-Ahmadi, N.; McKellar, A. R. W.


    Spectra of the nonpolar carbonyl sulfide in the region of the OCS ν_1 fundamental band were observed in a supersonic slit-jet apparatus. The expansion gas was probed using radiation from a tunable diode laser employed in a rapid-scan signal averaging mode. Three bands centered at 2085.906, 2103.504, and 2114.979 cm-1 were observed and anlysed. The rotational assignment and fitting of the bands were made by fixing the lower state parameters to those for the ground state of nonpolar (OCS)_2, thus confirming that they were indeed combination bands of the of the most stable isomer of OCS dimer. The band centered at 2085.906 cm-1 is a combination of the forbidden A_g intramolecular mode plus the geared bend intermolecular mode and that centered at 2114.979 cm-1 is a combination of the allowed B_u intramolecular mode plus the intermolecular van der Waals stretch. The combination at 2103.504 cm-1 can be assigned as a band whose upper state involves four quanta of the intramolecular bend or the B_u intramolecular mode plus two quanta of the intermolecular torsional mode. Isotopic work is needed to conclusively identify the vibrational assignment of this band. Our experimental frequencies for the geared bend and van der Waals modes are in good agreement with a recent high level ab initio calculation by Brown et al. J. Brown, Xiao-Gang Wang, T. Carrington Jr. and Richard Dawes, Journal of Chemical Physics, submitted.


    Hoover, T.B.


    An improved process is presented for the deposition of nickel coatings by the thermal decomposition of nickel carbonyl vapor. The improvement consists in incorporating a small amount of hydrogen sulfide gas in the nickel carbonyl plating gas. It is postulated that the hydrogen sulfide functions as a catalyst. i

  10. Seasonal carbon fluxes for an old-growth temperate forest inferred from carbonyl sulphide (United States)

    Rastogi, Bharat; Jiang, Yueyang; Berkelhammer, Maxwell; Wharton, Sonia; Noone, David; Still, Christopher


    Characterizing and quantifying the processes that control terrestrial ecosystem exchanges of carbon and water are critical for understanding how forested ecosystems respond to a changing climate. A small but increasing number of studies has identified carbonyl sulfide (OCS) as a potential tracer of canopy photosynthesis and stomatal function. Here we present seasonal fluxes of OCS from a 60m tall old-growth temperate forest. An off-axis integrated cavity output spectroscopy analyzer (Los Gatos Research Inc.) was deployed at the Wind River Experimental Forest in Washington (45.8205°N, 121.9519°W) in 2014 and 2015. GPP (Gross Primary Production) is inferred from OCS fluxes and compared with estimates derived from measurements of NEE (Net Ecosystem Exchange) from eddy flux data as well as GPP predictions using a process based model. Our findings seek to resolve scientific questions regarding ecosystem carbon exchange from tall old growth forests, which have a complicated vertical leaf area structure, high above ground biomass and amount and aerial cover of epiphytic vegetation. Estimates of canopy conductance calculated using tower flux data are also combined with measurements of stable isotopologues of CO2 to infer emergent ecosystem properties such as canopy ci/ca and water use efficiency.

  11. Measurement of OCS, CO2, CO and H2O aboard NASA's WB-57 High Altitude Platform Using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) (United States)

    Leen, J. B.; Owano, T. G.; Du, X.; Gardner, A.; Gupta, M.


    Carbonyl sulfide (OCS) is the most abundant sulfur gas in the atmosphere and has been implicated in controlling the sulfur budget and aerosol loading of the stratosphere. In the troposphere, OCS is irreversibly consumed during photosynthesis and may serve as a tracer for gross primary production (GPP). Its primary sources are ocean outgassing, industrial processes, and biomass burning. Its primary sinks are vegetation and soils. Despite the importance of OCS in atmospheric processes, the OCS atmospheric budget is poorly determined and has high uncertainty. OCS is typically monitored using either canisters analyzed by gas chromatography or integrated atmospheric column measurements. Improved in-situ terrestrial flux and airborne measurements are required to constrain the OCS budget and further elucidate its role in stratospheric aerosol formation and as a tracer for biogenic volatile organics and photosynthesis. Los Gatos Research has developed a flight capable mid-infrared Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) analyzer to simultaneously quantify OCS, CO2, CO, and H2O in ambient air at up to 2 Hz. The prototype was tested on diluted, certified samples and found to be precise (OCS, CO2, CO, and H2O to better than ±4 ppt, ±0.2 ppm, ±0.31 ppb, and ±3.7 ppm respectively, 1s in 1 sec) and linear (R2 > 0.9997 for all gases) over a wide dynamic range (OCS, CO2, CO, and H2O ranging from 0.2 - 70 ppb, 500 - 3000 ppm, 150 - 480 ppb, and 7000 - 21000 ppm respectively). Cross-interference measurements showed no appreciable change in measured OCS concentration with variations in CO2 (500 - 3500 ppm) or CO. We report on high altitude measurements made aboard NASA's WB-57 research aircraft. Two research flights were conducted from Houston, TX. The concentration of OCS, CO2, CO, and H2O were continuously recorded from sea level to approximately 60,000 feet. The concentration of OCS was observed to increase with altitude through the troposphere due to the

  12. The ultraviolet spectrum of OCS from first principles

    DEFF Research Database (Denmark)

    Schmidt, Johan Albrecht; Johnson, Matthew Stanley; McBane, G.C.


    Global three dimensional potential energy surfaces and transition dipole moment functions are calculated for the lowest singlet and triplet states of carbonyl sulfide at the multireference configuration interaction level of theory. The first ultraviolet absorption band is then studied by means of...

  13. OCS in He droplets

    Energy Technology Data Exchange (ETDEWEB)

    Grebenev, V.


    Phenomenon of superfluidity of para-hydrogen (pH{sub 2}){sub 1-17} and helium {sup 4}He{sub 1-7000} systems doped with an OCS chromophore molecule was investigated in this work. The study of such systems became possible after the development of the depletion spectroscopy technique in helium droplets. The droplets can be easily created and doped with up to 100 particles such as OCS, para-hydrogen or ortho-hydrogen molecules and {sup 4}He atoms. The measured infrared depletion spectra give the information about the temperature of the droplets and their aggregate state. The depletion spectrum of OCS in pure {sup 4}He droplets was comprehensively studied. The rovibrational OCS spectrum shows well resolved narrow lines. The spectrum is shifted to the red relative to the corresponding gas phase spectrum and the rotational constant of OCS in {sup 4}He droplet is three times smaller than that for free molecule. Different models of OCS rotation in the helium environment were discussed. It was shown that the shapes of the rovibrational lines are defined mainly by inhomogeneous broadening due to the droplet size distribution. The sub-rotational structure of the OCS rovibrational lines was revealed in microwave-infrared double resonance experiments. This structure arises due to the interaction of the OCS with the He environment. However, the information obtained in the experiments was not enough to understand the nature of this interaction. (orig.)

  14. Photodissociation of OCS: Deviations between theory and experiment, and the importance of higher order correlation effects

    International Nuclear Information System (INIS)

    Schmidt, J. A.; Olsen, J. M. H.


    The photodissociation of carbonyl sulfide (OCS) was investigated theoretically in a series of studies by Schmidt and co-workers. Initial studies [J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 136, 131101 (2012); J. A. Schmidt, M. S. Johnson, G. C. McBane, and R. Schinke, J. Chem. Phys. 137, 054313 (2012)] found photodissociation in the first UV-band to occur mainly by excitation of the 2 1 A ′ (A) excited state. However, in a later study [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] it was found that a significant fraction of photodissociation must occur by excitation of 1 1 A ″ (B) excited state to explain the product angular distribution. The branching between excitation of the A and B excited states is determined by the magnitude of the transition dipole moment vectors in the Franck-Condon region. This study examines the sensitivity of these quantities to changes in the employed electronic structure methodology. This study benchmarks the methodology employed in previous studies against highly correlated electronic structure methods (CC3 and MRAQCC) and provide evidence in support of the picture of the OCS photodissociation process presented in [G. C. McBane, J. A. Schmidt, M. S. Johnson, and R. Schinke, J. Chem. Phys. 138, 094314 (2013)] showing that excitation of A and B electronic states both contribute significantly to the first UV absorption band of OCS. In addition, this study presents evidence in support of the assertion that the A state potential energy surface employed in previous studies underestimates the energy at highly bent geometries (γ ∼ 70°) leading to overestimated rotational energy in the product CO

  15. Protein carbonylation in plants

    DEFF Research Database (Denmark)

    Møller, Ian Max; Havelund, Jesper; Rogowska-Wrzesinska, Adelina


    This chapter provides an overview of the current knowledge on protein carbonylation in plants and its role in plant physiology. It starts with a brief outline of the turnover and production sites of reactive oxygen species (ROS) in plants and the causes of protein carbonylation. This is followed...... by a description of the methods used to study protein carbonylation in plants, which is also very brief as the methods are similar to those used in studies on animals. The chapter also focuses on protein carbonylation in plants in general and in mitochondria and in seeds in particular, as case stories where...

  16. OCS National Compendium

    Energy Technology Data Exchange (ETDEWEB)

    Gould, G.J.; Karpas, R.M.; Slitor, D.L.


    The Minerals Management Service's (MMS) Outer Continental Shelf Information Program (OCSIP) is responsible for making available to affected coastal States, local governments, and other interested parties data and information related to the Outer Continental Shelf (OCS) Oil and Gas Program. Since its establishment through Section 26 of the OCS Lands Act (OCSLA) Amendments of 1978, OCSIP has prepared regional summary reports, updates, and indexes on leasing, exploration, development, and production activities to fulfill the mandates of the OCSLA Amendments. The OCSIP receives many requests for out-of-print summary reports, updates, and indexes. The purpose of the OCS National Compendium is to consolidate these historical data and to present the data on an OCS-wide and regional scale. The single-volume approach allows the reader access to historical information and facilitates regional comparisons. The fold-out chart in the front of this publication provides the reader with a timeline (January 1988--November 1990) of events since publication of the last Compendium. Some of the events are directly related to the 5-year Oil and Gas Program, whereas others may or may not have an effect on the program. A predominantly graphic format is used in the report so that the large accumulation of data can be more readily comprehended. In some cases, it is not possible to update information through October 21, 1990, because of the nature of the data. For example, production data normally lags 3 months. 58 figs., 37 tabs.

  17. Reciprocal carbonyl-carbonyl interactions in small molecules and proteins. (United States)

    Rahim, Abdur; Saha, Pinaki; Jha, Kunal Kumar; Sukumar, Nagamani; Sarma, Bani Kanta


    Carbonyl-carbonyl n→π* interactions where a lone pair (n) of the oxygen atom of a carbonyl group is delocalized over the π* orbital of a nearby carbonyl group have attracted a lot of attention in recent years due to their ability to affect the 3D structure of small molecules, polyesters, peptides, and proteins. In this paper, we report the discovery of a "reciprocal" carbonyl-carbonyl interaction with substantial back and forth n→π* and π→π* electron delocalization between neighboring carbonyl groups. We have carried out experimental studies, analyses of crystallographic databases and theoretical calculations to show the presence of this interaction in both small molecules and proteins. In proteins, these interactions are primarily found in polyproline II (PPII) helices. As PPII are the most abundant secondary structures in unfolded proteins, we propose that these local interactions may have implications in protein folding.Carbonyl-carbonyl π* non covalent interactions affect the structure and stability of small molecules and proteins. Here, the authors carry out experimental studies, analyses of crystallographic databases and theoretical calculations to describe an additional type of carbonyl-carbonyl interaction.

  18. Carbonyl Sulfide Serves as Tattletale for Biosphere Signal (United States)

    Villalba, G.; Campbell, J. E.


    Currently, anthropogenic CO2 emissions over a geographic region can be calculated in several ways: 1) based on energy consumption using emission factors within city limits, 2) using 14CO2 as tracer for fossil CO2, and 3) subtracting the biosphere signal from observation (measured) CO2 data. In order to calculate the ecosystem CO2 emissions (respiration and photosynthesis), ecosystem models such as SiB, CASA, or others are used. However, it is not clear which is the best one to determine the ecosystem signal because they all give different results in terms of GPP. We first show simulations of biosphere CO2 given by SiB, CASA, and CAN-IBIS over central California. Each model gives different values of CO2 GPP. Using these values to determine fossil fuel CO2 contribution can give very different results. We suggest that COS can be used to determine which ecosystem model best represents the biosphere signal. Just like CO2, COS is taken up by photosynthesis but is not given off in respiration and can thus be used as a trace gas to estimate GPP. We begin with COS surface fluxes provided by SiB, CASA and CAN-IBIS for a 9km-resolution domain over the Bay Area of San Francisco and part of the San Joaquin Valley. Simulations using the atmospheric model WRF provide the meteorological data, which along with the COS fluxes, are used to run the transport model STEM over a 10-day period in March 2015. Simulations of COS mixing ratio based on the various surface flux models are compared to observed data available from several locations. The model that best represents COS uptake consequently also provides the most accurate simulation of CO2 biosphere signal, and is used to estimate fossil fuel CO2 emissions.

  19. Validation of protein carbonyl measurement

    DEFF Research Database (Denmark)

    Augustyniak, Edyta; Adam, Aisha; Wojdyla, Katarzyna


    protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5min of UV irradiation irrespective of method used. After irradiation for 15min, less oxidation was detected by half of the laboratories than after 5min...

  20. Alternating current electroluminescent properties of zinc sulfide powders


    Salimian, Alireza


    In order to investigate the alternating current electroluminescent properties of zinc sulfide powders the following experiments were conducted: synthesis of zinc sulfide phosphors (comprised of zinc, sulfur and copper dopant); thermal shocking of phosphor materials (sudden cooling, using liquid nitrogen, of phosphor particles heated up to 500oC) and analysis of their alternating current electroluminescent properties as well as studies of particle crystal structures by synchrotron and conventi...

  1. Femtosecond Fluorescence and Intersystem Crossing in Rhenium(I) Carbonyl-Bipyridine Complexes

    Czech Academy of Sciences Publication Activity Database

    Cannizzo, A.; Blanco-Rodríguez, A. M.; Nahhas, A. E.; Šebera, Jakub; Záliš, Stanislav; Vlček, Antonín; Chergui, M.


    Roč. 130, č. 28 (2008), s. 8967-8974 ISSN 0002-7863 R&D Projects: GA MŠk 1P05OC068 Institutional research plan: CEZ:AV0Z40400503 Keywords : rhenium(I) * carbonyl-bipyridine * intersystem crossing Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 8.091, year: 2008

  2. Diaroyl Tellurides: Synthesis, Structure and NBO Analysis of (2-MeOC6H4CO2Te – Comparison with Its Sulfur and Selenium Isologues. The First Observation of [MgBr][R(C=TeO] Salts

    Directory of Open Access Journals (Sweden)

    Fumio Ando


    Full Text Available A series of aromatic diacyl tellurides were prepared in moderate to good yields by the reactions of sodium orpotassium arenecarbotelluroates with acyl chlorides in acetonitrile. X-ray structure analyses and theoretical calculations of 2-methoxybenzoic anhydride and bis(2-methoxybenzoyl sulfide, selenide and telluride were carried out. The two 2-MeOC6H4CO moieties of bis(2-methoxybenzoyl telluride are nearly planar and the two methoxy oxygen atoms intramolecularly coordinate to the central tellurium atom from both side of C(11-Te(11-C(22 plane. In contrast, the oxygen and sulfur isologues (2-MeOC6H4CO2E (E = O, S, show that one of the two methoxy oxygen atoms contacts with the oxygen atom of the carbonyl group connected to the same benzene ring. The structure of di(2-methoxybenzoyl selenide which was obtained by MO calculation resembles that of tellurium isologues rather than the corresponding oxygen and sulfur isologues. The reactions of di(aroyl tellurides with Grignard reagents lead to the formation of tellurocarboxylato magnesium complexes [MgBr][R(C=TeO].

  3. Sulfide chemiluminescence detection (United States)

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


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

  4. Complex sulfides and thiosalts

    International Nuclear Information System (INIS)

    Uehlls, A.


    Different types of the structures of complex sulfides, thiosalts of alkali, alkaline earth, rare earth, transition and actinide metals are considered in the review of the papers published before 1980 and devoted to the crystal structure of complex sulfides

  5. Application of static and dynamic enclosures in determining DMS and OCS fluxes in Sphagnum peatlands (United States)

    Demello, William Zamboni; Hines, Mark E.


    A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and OCS between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic enclosure measurements with S-free air used as sweep gas. DMS emission rates determined by both methods were comparable between 5 and 500 nmol/m(sup -2)h(sup -1). The dynamic method provided positive OCS flux rates (emission) for measurements performed at sites containing Sphagnum. Conversely, data from the static method indicated that OCS was consumed from the atmosphere. Measurements using both techniques at a site devoid of vegetation showed that peat is a source of both DMS and OCS. Results suggested that OCS is produced in surface peat but it is taken up from the atmosphere by Sphagnum mosses. However, the net effect of both processes is that OCS uptake exceeds emission. The dynamic enclosure technique is adequate to measure rates of emissions of S gases which are produced in peatlands but not consumed, as long as attention is paid to the rate of sweep flow.

  6. Transition metal catalyzed carbonylation reactions carbonylative activation of C-X bonds

    CERN Document Server

    Beller, Matthias


    This book provides students and researchers in organic synthesis with a detailed discussion of carbonylation from the basics through to applications. It discusses the past, present and future of carbonylation reactions.

  7. Antitumor Allium Sulfides. (United States)

    Nohara, Toshihiro; Fujiwara, Yukio; El-Aasr, Mona; Ikeda, Tsuyoshi; Ono, Masateru; Nakano, Daisuke; Kinjo, Junei


    We examined the sulfides in onion (Allium cepa L.), Welsh onion (A. fistulosum L.), and garlic (A. sativum L.), and obtained three new thiolane-type sulfides (onionins A 1 -A 3 ) from onion; two new thiabicyclic-type sulfides (welsonins A 1 , A 2 ), together with onionins A 1 -A 3 , from Welsh onion; and six new acyclic-type sulfides (garlicnins L-1-L-4, E, and F), ten new thiolane-type sulfides (garlicnins A, B 1 -B 4 , C 1 -C 3 , K 1 , and K 2 ), and three new atypical cyclic-type sulfides (garlicnins G, I, and J) from garlic. Acetone extracts showed the potential of these sulfides in inhibiting the polarization of M2 activated macrophages that are capable of suppressing tumor-cell proliferation. The effect of the thiolane-type sulfide of a major component, onionin A 1 , on tumor progression and metastasis in both osteosarcoma and ovarian cancer-bearing mouse models was then examined. Tumor proliferation was depressed, and tumor metastasis was controlled by regulating macrophage activation. These results showed that onionin A 1 is an effective agent for controlling tumors in both in vitro and in vivo models, and that the antitumor effects observed in vivo are likely caused by reversing the antitumor immune system. Activation of the antitumor immune system by onionin A 1 might be an effective adjuvant therapy for patients with osteosarcoma, ovarian cancer and other malignant tumors. Based on these findings, pharmacological investigations will be conducted in the future to develop natural and healthy foods and anti-cancer agents that can prevent or combat disease.

  8. Convenient Reduction of Carbonyl Compounds to their ...

    African Journals Online (AJOL)

    Sodium borohydride (0.4–1.5 equivalents) in the presence of ammonium oxalate (0.2 equivalents) reduces varieties of organic carbonyl compounds such as aldehydes, ketones, acyloins, α-diketones and α,β-unsaturated carbonyl compounds to their corresponding alcohols. Reduction reactions were carried out in ...

  9. Titanocene sulfide chemistry

    Czech Academy of Sciences Publication Activity Database

    Horáček, Michal


    Roč. 314, MAY 2016 (2016), s. 83-102 ISSN 0010-8545 R&D Projects: GA ČR(CZ) GAP207/12/2368 Institutional support: RVO:61388955 Keywords : titanocene sulfide chemistry * photolysis * titanocene hydrosulfides Ti-(SH)n Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 13.324, year: 2016

  10. Protein Carbonylation and Adipocyte Mitochondrial Function* (United States)

    Curtis, Jessica M.; Hahn, Wendy S.; Stone, Matthew D.; Inda, Jacob J.; Droullard, David J.; Kuzmicic, Jovan P.; Donoghue, Margaret A.; Long, Eric K.; Armien, Anibal G.; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J.; Bernlohr, David A.


    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte. PMID:22822087

  11. Protein carbonylation and adipocyte mitochondrial function. (United States)

    Curtis, Jessica M; Hahn, Wendy S; Stone, Matthew D; Inda, Jacob J; Droullard, David J; Kuzmicic, Jovan P; Donoghue, Margaret A; Long, Eric K; Armien, Anibal G; Lavandero, Sergio; Arriaga, Edgar; Griffin, Timothy J; Bernlohr, David A


    Carbonylation is the covalent, non-reversible modification of the side chains of cysteine, histidine, and lysine residues by lipid peroxidation end products such as 4-hydroxy- and 4-oxononenal. In adipose tissue the effects of such modifications are associated with increased oxidative stress and metabolic dysregulation centered on mitochondrial energy metabolism. To address the role of protein carbonylation in the pathogenesis of mitochondrial dysfunction, quantitative proteomics was employed to identify specific targets of carbonylation in GSTA4-silenced or overexpressing 3T3-L1 adipocytes. GSTA4-silenced adipocytes displayed elevated carbonylation of several key mitochondrial proteins including the phosphate carrier protein, NADH dehydrogenase 1α subcomplexes 2 and 3, translocase of inner mitochondrial membrane 50, and valyl-tRNA synthetase. Elevated protein carbonylation is accompanied by diminished complex I activity, impaired respiration, increased superoxide production, and a reduction in membrane potential without changes in mitochondrial number, area, or density. Silencing of the phosphate carrier or NADH dehydrogenase 1α subcomplexes 2 or 3 in 3T3-L1 cells results in decreased basal and maximal respiration. These results suggest that protein carbonylation plays a major instigating role in cytokine-dependent mitochondrial dysfunction and may be linked to the development of insulin resistance in the adipocyte.

  12. Sulfidation kinetics of silver nanoparticles reacted with metal sulfides. (United States)

    Thalmann, Basilius; Voegelin, Andreas; Sinnet, Brian; Morgenroth, Eberhard; Kaegi, Ralf


    Recent studies have documented that the sulfidation of silver nanoparticles (Ag-NP), possibly released to the environment from consumer products, occurs in anoxic zones of urban wastewater systems and that sulfidized Ag-NP exhibit dramatically reduced toxic effects. However, whether Ag-NP sulfidation also occurs under oxic conditions in the absence of bisulfide has not been addressed, yet. In this study we, therefore, investigated whether metal sulfides that are more resistant toward oxidation than free sulfide, could enable the sulfidation of Ag-NP under oxic conditions. We reacted citrate-stabilized Ag-NP of different sizes (10-100 nm) with freshly precipitated and crystalline CuS and ZnS in oxygenated aqueous suspensions at pH 7.5. The extent of Ag-NP sulfidation was derived from the increase in dissolved Cu(2+) or Zn(2+) over time and linked with results from X-ray absorption spectroscopy (XAS) analysis of selected samples. The sulfidation of Ag-NP followed pseudo first-order kinetics, with rate coefficients increasing with decreasing Ag-NP diameter and increasing metal sulfide concentration and depending on the type (CuS and ZnS) and crystallinity of the reacting metal sulfide. Results from analytical electron microscopy revealed the formation of complex sulfidation patterns that seemed to follow preexisting subgrain boundaries in the pristine Ag-NP. The kinetics of Ag-NP sulfidation observed in this study in combination with reported ZnS and CuS concentrations and predicted Ag-NP concentrations in wastewater and urban surface waters indicate that even under oxic conditions and in the absence of free sulfide, Ag-NP can be transformed into Ag2S within a few hours to days by reaction with metal sulfides.

  13. Modelling the impact of soil Carbonic Anhydrase on the net ecosystem exchange of OCS at Harvard forest using the MuSICA model (United States)

    Launois, Thomas; Ogée, Jérôme; Commane, Roisin; Wehr, Rchard; Meredith, Laura; Munger, Bill; Nelson, David; Saleska, Scott; Wofsy, Steve; Zahniser, Mark; Wingate, Lisa


    The exchange of CO2 between the terrestrial biosphere and the atmosphere is driven by photosynthetic uptake and respiratory loss, two fluxes currently estimated with considerable uncertainty at large scales. Model predictions indicate that these biosphere fluxes will be modified in the future as CO2 concentrations and temperatures increase; however, it still unclear to what extent. To address this challenge there is a need for better constraints on land surface model parameterisations. Additional atmospheric tracers of large-scale CO2 fluxes have been identified as potential candidates for this task. In particular carbonyl sulphide (OCS) has been proposed as a complementary tracer of gross photosynthesis over land, since OCS uptake by plants is dominated by carbonic anhydrase (CA) activity, an enzyme abundant in leaves that catalyses CO2 hydration during photosynthesis. However, although the mass budget at the ecosystem is dominated by the flux of OCS into leaves, some OCS is also exchanged between the atmosphere and the soil and this component of the budget requires constraining. In this study, we adapted the process-based isotope-enabled model MuSICA (Multi-layer Simulator of the Interactions between a vegetation Canopy and the Atmosphere) to include the transport, reaction, diffusion and production of OCS within a forested ecosystem. This model was combined with 3 years (2011-2013) of in situ measurements of OCS atmospheric concentration profiles and fluxes at the Harvard Forest (Massachussets, USA) to test hypotheses on the mechanisms responsible for CA-driven uptake by leaves and soils as well as possible OCS emissions during litter decomposition. Model simulations over the three years captured well the impact of diurnally and seasonally varying environmental conditions on the net ecosystem OCS flux. A sensitivity analysis on soil CA activity and soil OCS emission rates was also performed to quantify their impact on the vertical profiles of OCS inside the

  14. Suicide with hydrogen sulfide. (United States)

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas


    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  15. Quantification of amine functional groups and their influence on OM/OC in the IMPROVE network (United States)

    Kamruzzaman, Mohammed; Takahama, Satoshi; Dillner, Ann M.


    Recently, we developed a method using FT-IR spectroscopy coupled with partial least squares (PLS) regression to measure the four most abundant organic functional groups, aliphatic C-H, alcohol OH, carboxylic acid OH and carbonyl C=O, in atmospheric particulate matter. These functional groups are summed to estimate organic matter (OM) while the carbon from the functional groups is summed to estimate organic carbon (OC). With this method, OM and OM/OC can be estimated for each sample rather than relying on one assumed value to convert OC measurements to OM. This study continues the development of the FT-IR and PLS method for estimating OM and OM/OC by including the amine functional group. Amines are ubiquitous in the atmosphere and come from motor vehicle exhaust, animal husbandry, biomass burning, and vegetation among other sources. In this study, calibration standards for amines are produced by aerosolizing individual amine compounds and collecting them on PTFE filters using an IMPROVE sampler, thereby mimicking the filter media and collection geometry of ambient standards. The moles of amine functional group on each standard and a narrow range of amine-specific wavenumbers in the FT-IR spectra (wavenumber range 1 550-1 500 cm-1) are used to develop a PLS calibration model. The PLS model is validated using three methods: prediction of a set of laboratory standards not included in the model, a peak height analysis and a PLS model with a broader wavenumber range. The model is then applied to the ambient samples collected throughout 2013 from 16 IMPROVE sites in the USA. Urban sites have higher amine concentrations than most rural sites, but amine functional groups account for a lower fraction of OM at urban sites. Amine concentrations, contributions to OM and seasonality vary by site and sample. Amine has a small impact on the annual average OM/OC for urban sites, but for some rural sites including amine in the OM/OC calculations increased OM/OC by 0.1 or more.

  16. Effect of Sodium Sulfide on Ni-Containing Carbon Monoxide Dehydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Jian Feng; Paul A. Lindahl


    OAK-B135 The structure of the active-site C-cluster in CO dehydrogenase from Carboxythermus hydrogenoformans includes a {mu}{sup 2}-sulfide ion bridged to the Ni and unique Fe, while the same cluster in enzymes from Rhodospirillum rubrum (CODH{sub Rr}) and Moorella thermoacetica (CODH{sub Mt}) lack this ion. This difference was investigated by exploring the effects of sodium sulfide on activity and spectral properties. Sulfide partially inhibited the CO oxidation activity of CODH{sub Rr} and generated a lag prior to steady-state. CODH{sub Mt} was inhibited similarly but without a lag. Adding sulfide to CODH{sub Mt} in the C{sub red1} state caused the g{sub av} = 1.82 EPR signal to decline and new features to appear, including one with g = 1.95, 1.85 and (1.70 or 1.62). Removing sulfide caused the g{sub av} = 1.82 signal to reappear and activity to recover. Sulfide did not affect the g{sub av} = 1.86 signal from the C{sub red2} state. A model was developed in which sulfide binds reversibly to C{sub red1}, inhibiting catalysis. Reducing this adduct causes sulfide to dissociate, C{sub red2} to develop, and activity to recover. Using this model, apparent K{sub I} values are 40 {+-} 10 nM for CODH{sub Rr} and 60 {+-} 30 {micro}M for CODH{sub Mt}. Effects of sulfide are analogous to those of other anions, including the substrate hydroxyl group, suggesting that these ions also bridge the Ni and unique Fe. This proposed arrangement raises the possibility that CO binding labilizes the bridging hydroxyl and increases its nucleophilic tendency towards attacking Ni-bound carbonyl.

  17. Carbonated soft drinks and carbonyl stress burden. (United States)

    Nakayama, Keisuke; Nakayama, Masaaki; Terawaki, Hiroyuki; Murata, Yaeko; Sato, Toshinobu; Kohno, Masahiro; Ito, Sadayoshi


    Carbonated soft drinks reportedly contain methylglyoxal (MG), which is strongly associated with human carbonyl stress. We sought to evaluate the effects of carbonated drink intake on human carbonyl stress. We measured MG levels in 4 commercial beverage brands, and evaluated the changes in plasma MG in healthy subjects following the intake of carbonated drinks. By 30 min after intake of samples containing high glucose and high MG, the levels of plasma MG, glucose, insulin and uric acid had increased significantly, and then returned to basal levels by 120 min. After intake of the low-calorie carbonated samples containing little MG, there were no increases in plasma MG. Our results suggest that glucose-containing carbonated soft drinks are associated with increases in not only glucose but also carbonyl burden.

  18. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Dezhao, Liu; Hansen, Michael Jørgen

    oxidizing bacteria but several fungal families including Trichocomaceae. A positive correlation was found between the presence of mold and sulfide uptake. However there have been no reports on fungi metabolizing hydrogen sulfide. We hypothesize that the mold increases the air exposed surface, enabling...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  19. Sulfide oxidation in a biofilter

    DEFF Research Database (Denmark)

    Pedersen, Claus Lunde; Liu, Dezhao; Hansen, Michael Jørgen


    oxidizing bacteria but several fungal families including Trichocomaceae. A positive correlation was found between the presence of mold and sulfide uptake. However there have been no reports on fungi metabolizing hydrogen sulfide. We hypothesize that the mold increases the air exposed surface, enabling...... higher hydrogen sulfide uptake followed by oxidation catalyzed by iron-containing enzymes such as cytochrome c oxidase in a process uncoupled from energy conservation....

  20. Theoretical study of molecular vibration and Application to linear triatomic molecules: case of OCS

    International Nuclear Information System (INIS)

    Andrianavalomahefa, A.


    Our aim is to give a theoretical approach to the calculation of vibrational energy levels of polyatomic molecules. By using matrix calculation, we have to solve an eigenvalue equation that gives normal vibration frequencies of the system. A basis change introduces normal coordinates of vibration, which diagonalize the Hamiltonian. The harmonic approximation gives a rough evaluation of parameters which describe the system. Then, we introduce nonlinear terms to take into account the anharmonicity of interatomic bounds. Morse oscillator gives good approximation for diatomic molecules. We consider cubic and quartic potential terms for polyatomic molecules. We treat the problem both in classical and quantum approach. The results thus obtained are applied to study longitudinal vibration of carbonyl sulfide. [fr

  1. Benzyllithiums bearing aldehyde carbonyl groups. A flash chemistry approach. (United States)

    Nagaki, Aiichiro; Tsuchihashi, Yuta; Haraki, Suguru; Yoshida, Jun-ichi


    Reductive lithiation of benzyl halides bearing aldehyde carbonyl groups followed by reaction with subsequently added electrophiles was successfully accomplished without affecting the carbonyl groups by taking advantage of short residence times in flow microreactors.

  2. Protein Carbonylation in Patients with Myelodysplastic Syndromes

    Czech Academy of Sciences Publication Activity Database

    Hlaváčková, A.; Štikarová, J.; Kotlín, R.; Chrastinová, L.; Šácha, Pavel; Májek, P.; Čermák, J.; Suttnar, J.; Dyr, J. E.


    Roč. 126, č. 23 (2015), s. 5232 ISSN 0006-4971. [Annual Meeting and Exposition of the American Society of Hematology /55./. 07.12.2013-10.12.2013, New Orleans] Institutional support: RVO:61388963 Keywords : protein carbonylation * myelodysplastic syndromes Subject RIV: CE - Biochemistry

  3. Polymethylhydrosiloxane reduction of carbonyl function catalysed by ...

    African Journals Online (AJOL)

    However, in the reduction of the substrate with two methoxy groups in close proximity (1,2-positions), the reaction necessitated a larger amount of the titanium catalyst and a longer reaction time to complete the reduction of the carbonyl function due to a likely complex formation of titanium tetrachloride with the methoxy ...

  4. Cyclometallated ruthenium (II) carbonyl complexes with 1 ...

    Indian Academy of Sciences (India)

    A facile method for the synthesis of a series of cyclometallated ruthenium(II) carbonyl complexes with 1-pyrenaldehyde 4-R-3-thiosemicarbazones (H2Ln where the two H's represent the dissociable thioamide and pyrenyl protons; R = H, Me and Ph) has been described. The characterization of the complexes having the ...

  5. Growth and characterization of semiconducting nickel sulfide nanocrystals from air-stable single-source metal organic precursors

    Directory of Open Access Journals (Sweden)

    Sohail Saeed


    Full Text Available Three symmetrical and unsymmetrical nickel(II complexes [cis-(C3H72NC(SNC(OC6H3(3,5-NO22]2Ni(II, [cis-(C4H92NC(SNC(OC6H3(3,5-NO22]2Ni(II, and [cis-(Hex(Me2NC(SNC(O C6H3(3,5-NO22]2Ni(II were synthesized and characterized by FTIR spectroscopy, elemental analysis, and mass spectrometry. These metal complexes have been used as single-source precursors for the preparation of semiconducting nickel sulfide nanocrystals. Rapid injection of metal complexes into oleylamine at 230°C, followed by immediate cooling, led to the formation of irregular-shaped 20–170-nm nickel sulfide nanocrystals. The deposited nickel sulfide nanocrystals were characterized by X-ray powder diffraction and transmission electron microscopy.

  6. Method for conversion of .beta.-hydroxy carbonyl compounds (United States)

    Lilga, Michael A.; White, James F.; Holladay, Johnathan E.; Zacher, Alan H.; Muzatko, Danielle S.; Orth, Rick J.


    A process is disclosed for conversion of salts of .beta.-hydroxy carbonyl compounds forming useful conversion products including, e.g., .alpha.,.beta.-unsaturated carbonyl compounds and/or salts of .alpha.,.beta.-unsaturated carbonyl compounds. Conversion products find use, e.g., as feedstock and/or end-use chemicals.

  7. Vapor-phase carbonylation of dimethoxymethane over H-Faujasite. (United States)

    Celik, Fuat E; Kim, Tae-Jin; Bell, Alexis T


    Carbonylation gets a phase lift: The usual liquid-phase, high-pressure processes for carbonylating formaldehydes are avoided in a novel vapor-phase reaction. Using an acid zeolite (Faujasite) at near-atmospheric pressure dimethoxymethane (DMM; the dimethyl acetal of formaldehyde; see scheme) is carbonylated to produce methyl methoxyacetate (MMAc). This approach provides a new route to ethylene glycol under mild conditions.

  8. Essential Factors in Removing Carbonyl Sulfide from Coal Gas with Lime and Limestone

    Czech Academy of Sciences Publication Activity Database

    Hartman, Miloslav; Svoboda, Karel; Trnka, Otakar


    Roč. 54, č. 5 (2000), s. 302-306 ISSN 0366-6352 R&D Projects: GA AV ČR IAA4072711; GA ČR GA203/98/0101 Institutional research plan: CEZ:AV0Z4072921 Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 0.154, year: 2000

  9. Methane and Carbonyl Sulfide Analysis of Siple Dome Ice Core Subsamples, Version 1 (United States)

    National Aeronautics and Space Administration — This data set is part of the West Antarctic Ice Sheet cores (WAISCORES) project, an NSF-funded project to understand the influence of the West Antarctic ice sheet on...

  10. Effects of carbonyl sulfide (COS) and carbonic anhydrase on stomatal conductance (United States)

    Yakir, D.; Stimler, K.; Berry, J. A.


    The potential use of COS as tracer of the gross, one-way, CO2 flux into plants is based on its co-diffusion with CO2 into leaves without outflux stimulated research on COS-CO2 interactions during leaf gas exchange. We carried out gas exchange measurements of COS and CO2 in 22 plant species representing deciduous and evergreen trees, grasses, and shrubs, under a range of light intensities and ambient COS concentrations, using mid IR laser spectroscopy. A narrow range in the normalized ratio of the net uptake rates of COS (As) and CO2 (Ac; As/Ac*[CO2]/[COS]) was observed, with a mean value of 1.61±0.26. These results reflect the dominance of stomatal conductance over both COS and CO2 uptake, imposing a relatively constant ratio between the two fluxes (except under low light conditions when CO2, but not COS, metabolism is light limited). A relatively constant ratio under common ambient conditions will facilitate the application of COS as a tracer of gross photosynthesis from leaf to global scales. However, its effect on stomatal conductance may require a special attention. Increasing COS concentrations between 250 and 2800 pmol mol-1 (enveloping atmospheric levels) seems to stimulate stomatal conductance. We examined the stimulation of conductance by COS in a range of species and show that there is a large variation with some species showing almost no response while others are highly responsive (up to doubling stomatal conductance). Using C3 and C4 plants with antisense lines abolishing carbonic anhydrase activity, we show that the activity of this enzyme is essential for both the uptake of COS and the enhancement of stomatal conductance by COS. Since carbonic anhydrase catalyzes the conversion of COS to CO2 and H2S it seems likely that the stomata are responding to H2S produced in the mesophyll. In all natural species examined the uptake of COS and CO2 were highly correlated, and there was no relationship between the sensitivity of stomata and the rate of COS uptake (or by inference H2S production). The basis for this variation in sensitivity is still to be determined. The studies reported here clearly implicate CA as a plausible source of H2S within the leaf, and probably provide the first demonstration of a possible alternative mechanism, independent of the production of HCO3-, whereby CA could function as a biosensor ("sensoenzyme") influencing stomatal conductance and, in turn, ecosystem-atmosphere fluxes of carbon, water and energy.

  11. Sulfide intrusion and detoxification in Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne


    Sulfide intrusion in seagrasses represents a global threat to seagrasses. In contrast seegrasses grow in hostile sediments, where they are constantly exposed to sulfide intrusion. Little is known about the strategies to survive sulfide intrusion, if there are detoxification mechanisms and sulfur...... indicating a possible role of sulfide in the sulfur nutrition beside the detoxification function. Our results suggest different adaptations of Z. marina to reduced sediments and sulfide intrusion ranging from bacterial and chemical reoxidation of sulfide to sulfate to incorporation of sulfide into organic...

  12. Organocatalytic Hydrophosphonylation Reaction of Carbonyl Groups. (United States)

    Herrera, Raquel P


    This revision is covering the limited examples reported for a pivotal strategy in the formation of C-P bonds such as the asymmetric organocatalytic hydrophosphonylation of carbonyl groups (Pudovik reaction). The scope and limitations, and the proposed mechanisms for the scarce different possibilities of asymmetric induction are also shown. The recent evolution and future trends of this undeveloped approach are commented. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Carbonyl Compounds Generated from Electronic Cigarettes

    Directory of Open Access Journals (Sweden)

    Kanae Bekki


    Full Text Available Electronic cigarettes (e-cigarettes are advertised as being safer than tobacco cigarettes products as the chemical compounds inhaled from e-cigarettes are believed to be fewer and less toxic than those from tobacco cigarettes. Therefore, continuous careful monitoring and risk management of e-cigarettes should be implemented, with the aim of protecting and promoting public health worldwide. Moreover, basic scientific data are required for the regulation of e-cigarette. To date, there have been reports of many hazardous chemical compounds generated from e-cigarettes, particularly carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, and glyoxal, which are often found in e-cigarette aerosols. These carbonyl compounds are incidentally generated by the oxidation of e-liquid (liquid in e-cigarette; glycerol and glycols when the liquid comes in contact with the heated nichrome wire. The compositions and concentrations of these compounds vary depending on the type of e-liquid and the battery voltage. In some cases, extremely high concentrations of these carbonyl compounds are generated, and may contribute to various health effects. Suppliers, risk management organizations, and users of e-cigarettes should be aware of this phenomenon.

  14. Prevention of sulfide oxidation in sulfide-rich waste rock (United States)

    Nyström, Elsa; Alakangas, Lena


    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  15. Apparatus for use in sulfide chemiluminescence detection (United States)

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


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

  16. Mechanochemical reduction of copper sulfide

    DEFF Research Database (Denmark)

    Balaz, P.; Takacs, L.; Jiang, Jianzhong


    The mechanochemical reduction of copper sulfide with iron was induced in a Fritsch P-6 planetary mill, using WC vial filled with argon and WC balls. Samples milled for specific intervals were analyzed by XRD and Mossbauer spectroscopy. Most of the reaction takes place during the first 10 min...... of milling and only FeS and Cu are found after 60 min. The main chemical process is accompanied by phase transformations of the sulfide phases as a result of milling. Djurleite partially transformed to chalcocite and a tetragonal copper sulfide phase before reduction. The cubic modification of FeS was formed...... first, transforming to hexagonal during the later stages of the process. The formation of off-stoichiometric phases and the release of some elemental sulfur by copper sulfide are also probable....

  17. CARIBIC observations of short-lived halocarbons and carbonyl sulphide over Asia (United States)

    Leedham, E.; Wisher, A.; Oram, D.; Baker, A. K.; Brenninkmeijer, C. A.


    The CARIBIC project (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container, aims to investigate the spatial and temporal distribution of a wide-range of compounds, including those of marine origin/influence, via ~monthly flights to collect in situ data and whole air samples aboard a commercial Lufthansa aircraft. CARIBIC measures up to an altitude of 12 km, allowing the influence of marine compounds on the upper troposphere/lower stratosphere (UTLS) to be explored. In particular, CARIBIC is a useful tool for exploring the impact of very short lived halocarbons (e.g. CH2Br2, CHBr3), whose impact on stratospheric ozone is dependent on convective uplift to the UTLS, a process which is not yet fully quantified. As part of the suite of CARIBIC measurements, whole air samples are analysed at the University of East Anglia (UEA) via gas chromatography mass spectrometry for carbonyl sulphide (OCS) and up to 40 halocarbons (accounting for virtually 100% of organic chlorine, bromine and iodine in the UTLS). Here we present an overview of short-lived halocarbons and OCS measured by CARIBIC. We focus on two regions of particular interest. (1) measurements made in 2012 over the tropical west Pacific to link with UEA measurements made during the SHIVA campaign. (2) measurements made during a collection of flights over India in 2008. Flights over India investigated the impact of monsoon circulation on the distribution of these compounds; for example, elevated concentrations of OCS were seen in CARIBIC samples taken over India during the summer monsoon (July - September). These flights, along with a wider range of flights over Asia (from Frankfurt to Guangzhou, Manila, Bangkok and Kuala Lumpur) can provide unique information on the influence of tropical convection and monsoon circulation on halocarbon and OCS transport within this region.

  18. Validation of protein carbonyl measurement: A multi-centre study

    Directory of Open Access Journals (Sweden)

    Edyta Augustyniak


    Full Text Available Protein carbonyls are widely analysed as a measure of protein oxidation. Several different methods exist for their determination. A previous study had described orders of magnitude variance that existed when protein carbonyls were analysed in a single laboratory by ELISA using different commercial kits. We have further explored the potential causes of variance in carbonyl analysis in a ring study. A soluble protein fraction was prepared from rat liver and exposed to 0, 5 and 15 min of UV irradiation. Lyophilised preparations were distributed to six different laboratories that routinely undertook protein carbonyl analysis across Europe. ELISA and Western blotting techniques detected an increase in protein carbonyl formation between 0 and 5 min of UV irradiation irrespective of method used. After irradiation for 15 min, less oxidation was detected by half of the laboratories than after 5 min irradiation. Three of the four ELISA carbonyl results fell within 95% confidence intervals. Likely errors in calculating absolute carbonyl values may be attributed to differences in standardisation. Out of up to 88 proteins identified as containing carbonyl groups after tryptic cleavage of irradiated and control liver proteins, only seven were common in all three liver preparations. Lysine and arginine residues modified by carbonyls are likely to be resistant to tryptic proteolysis. Use of a cocktail of proteases may increase the recovery of oxidised peptides. In conclusion, standardisation is critical for carbonyl analysis and heavily oxidised proteins may not be effectively analysed by any existing technique.

  19. Carbonyl Emissions from Gasoline and Diesel Motor Vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Destaillats, Hugo; Jakober, Chris A.; Robert, Michael A.; Riddle, Sarah G.; Destaillats, Hugo; Charles, M. Judith; Green, Peter G.; Kleeman, Michael J.


    Carbonyls from gasoline powered light-duty vehicles (LDVs) and heavy-duty diesel powered vehicles (HDDVs) operated on chassis dynamometers were measured using an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery, 4-fluorobenzaldehyde forcarbonyls and 6-fluoro-4-chromanone for>_C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 ? 2000 ?g/L fuel for LDVs and 1.8 - 27000 mu g/L fuel for HDDVs. Gas-phase species accounted for 81-95percent of the total carbonyls from LDVs and 86-88percent from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19percent of particulate organic carbon (POC) emissions from low-emission LDVs and 37percent of POC emissions from three-way catalyst equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9percent depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas- and particle-phase under the dilution factors of 126-584 used in the current study.

  20. On the differences between 1.5oC and 2oC of global warming (United States)

    King, A.


    The Paris Agreement of 2015 has resulted in a drive to limit global warming to 2oC with an aim for a lower 1.5oC target. It is therefore vital that we understand some of the differences we would expect between these two levels of global warming. My research uses coupled climate model projections to investigate where and for what variables we can differentiate between worlds of 1.5oC and 2oC global warming. I place a particular focus on climate extremes and population exposure to those extremes. I have found that there are perceptible benefits in limiting global warming to 1.5oC as opposed to 2oC through reduced frequency and intensity of heat extremes, both over land and in ocean areas where thermal stress on coral has resulted in bleaching. Differences in high and low precipitation extremes between the 1.5oC and 2oC global warming levels are projected for some regions. I have also examined how "scalable" changes from the 1.5oC to 2oC level are. In areas of the world such as Eastern China I find that changes in anthropogenic aerosol concentrations will influence the level of change projected at 1.5oC and 2oC, such that past warming is likely to be a poor indicator of future changes. Overall, my research finds clear benefits to limiting global warming to 1.5oC relative to higher levels.

  1. Infrared spectroscopy of solid hydrogen sulfide and deuterium sulfide. (United States)

    Fathe, Kristin; Holt, Jennifer S; Oxley, Susan P; Pursell, Christopher J


    The infrared spectra of solid hydrogen sulfide (H2S) and deuterium sulfide (D2S) were collected at very low temperatures. Vapor deposition of thin films at the lowest temperature of 10 K produced amorphous solids while deposition at 70 K yielded the crystalline phase III. Infrared interference fringe patterns produced by the films during deposition were used to determine the film thickness. Careful measurement of the integrated absorbance peaks, along with the film thickness, allowed determination of the integrated band intensities. This report represents the first complete presentation of the infrared spectra of the amorphous solids. Observations of peaks near 3.915 and 1.982 microm (ca. 2554 and 5045 cm(-1), respectively) may be helpful in the conclusive identification of solid hydrogen sulfide on the surface of Io, a moon of Jupiter.

  2. Hydrogen Sulfide Induced Carbon Dioxide Activation by Metal-Free Dual Catalysis. (United States)

    Kumar, Manoj; Francisco, Joseph S


    The role of metal free dual catalysis in the hydrogen sulfide (H2S)-induced activation of carbon dioxide (CO2) and subsequent decomposition of resulting monothiolcarbonic acid in the gas phase has been explored. The results suggest that substituted amines and monocarboxylic type organic or inorganic acids via dual activation mechanisms promote both activation and decomposition reactions, implying that the judicious selection of a dual catalyst is crucial to the efficient C-S bond formation via CO2 activation. Considering that our results also suggest a new mechanism for the formation of carbonyl sulfide from CO2 and H2S, these new insights may help in better understanding the coupling between the carbon and sulfur cycles in the atmospheres of Earth and Venus. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Oxidation process of cadmium sulfide

    International Nuclear Information System (INIS)

    Hashimoto, Koshiro; Toda, Yoshitomo; Sato, Takayori


    Complicated thermogravimetric curve was observed on oxidation process of cadmium sulfide precipitate in air. Phases of various oxidation stage were identified by X-ray diffraction method. Cadmium sulfide was first oxidized to cadmium oxide at 400 0 C, while the successive reaction with sulfur dioxide and oxygen gases gave rise to cadmium sulfate. The phases such as 2 CdS. CdSO 4 , Cd 3 SO 6 and β-CdSO 4 appeared during the oxidation process up to 1100 0 C, at which all the particles were converted into cadmium oxide at 1100 0 C. Cadmium sulfide kept in nitrogen gas above 700 0 C was directly converted into cadmium oxide when oxygen gas was introduced into the furnace. (auth.)

  4. 7 CFR 43.105 - Operating characteristics (OC) curves. (United States)


    ... 7 Agriculture 2 2010-01-01 2010-01-01 false Operating characteristics (OC) curves. 43.105 Section 43.105 Agriculture Regulations of the Department of Agriculture AGRICULTURAL MARKETING SERVICE... CONTAINER REGULATIONS STANDARDS FOR SAMPLING PLANS Sampling Plans § 43.105 Operating characteristics (OC...

  5. Status of the OCS Bragg-Spectrometer for SODART

    DEFF Research Database (Denmark)

    Wiebicke, H.J.; Halm, I.; Christensen, Finn Erland


    OCS, the Bragg spectrometer for the SODART X-ray telescope onboard the SPECTRUM-RONTGEN-GAMMA (SRG) satellite has been completed. Preliminary results of his performance are presented.......OCS, the Bragg spectrometer for the SODART X-ray telescope onboard the SPECTRUM-RONTGEN-GAMMA (SRG) satellite has been completed. Preliminary results of his performance are presented....

  6. Prediction of OCS Grades and Fitness Report Marks. (United States)

    Lau, Alan W.; And Others

    The report describes research designed to improve personnel decisions which the Navy must make relative to the input and output of Officer Candidate School (OCS). Officers making the first decision consider all relevant applications data in deciding on men to be accepted and rejected for entry into OCS; those making the second determine the best…

  7. Bifunctional dendrons for multiple carbohydrate presentation via carbonyl chemistry

    Directory of Open Access Journals (Sweden)

    Davide Bini


    Full Text Available The synthesis of new dendrons of the generations 0, 1 and 2 with a double bond at the focal point and a carbonyl group at the termini has been carried out. The carbonyl group has been exploited for the multivalent conjugation to a sample saccharide by reductive amination and alkoxyamine conjugation.

  8. Nanostructured metal sulfides for energy storage. (United States)

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu


    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  9. 30 CFR 250.604 - Hydrogen sulfide. (United States)


    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

  10. 30 CFR 250.808 - Hydrogen sulfide. (United States)


    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S...

  11. 30 CFR 250.504 - Hydrogen sulfide. (United States)


    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in...

  12. Autism and ADHD Symptoms in Patients with OCD: Are They Associated with Specific OC Symptom Dimensions or OC Symptom Severity? (United States)

    Anholt, Gideon E.; Cath, Danielle C.; van Oppen, Patricia; Eikelenboom, Merijn; Smit, Johannes H.; van Megen, Harold; van Balkom, Anton J. L. M.


    In obsessive-compulsive disorder (OCD), the relationship between autism spectrum disorders (ASD), attention-deficit/hyperactivity disorder (ADHD) symptom, and obsessive-compulsive (OC) symptom dimensions and severity has scarcely been studied. Therefore, 109 adult outpatients with primary OCD were compared to 87 healthy controls on OC, ADHD and…

  13. Carbonyl emissions in diesel and biodiesel exhaust (United States)

    Machado Corrêa, Sérgio; Arbilla, Graciela

    With the use of biodiesel in clear growth, it is important to quantify any potential emission benefits or liabilities of this fuel. Several researches are available concerning the regulated emissions of biodiesel/diesel blends, but there is a lack of information about non-regulated emissions. In a previous paper [Corrêa, S.M., Arbilla, G., 2006. Emissões de formaldeído e acetaldeído de misturas biodiesel/diesel. Periódico Tchê Química, 3, 54-68], the emissions of aromatic hydrocarbons were reported. In this work, seven carbonyl emissions (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, butyraldehyde, and benzaldehyde) were evaluated by a heavy-duty diesel engine fueled with pure diesel (D) and biodiesel blends (v/v) of 2% (B2), 5% (B5), 10% (B10), and 20% (B20). The tests were conducted using a six cylinder heavy-duty engine, typical of the Brazilian fleet of urban buses, in a steady-state condition under 1000, 1500, and 2000 rpm. The exhaust gases were diluted nearly 20 times and the carbonyls were sampled with SiO 2-C18 cartridges, impregnated with acid solution of 2,4-dinitrophenylhydrazine. The chemical analyses were performed by high performance liquid chromatography using UV detection. Using average values for the three modes of operation (1000, 1500, and 2000 rpm) benzaldehyde showed a reduction on the emission (-3.4% for B2, -5.3% for B5, -5.7% for B10, and -6.9% for B20) and all other carbonyls showed a significative increase: 2.6, 7.3, 17.6, and 35.5% for formaldehyde; 1.4, 2.5, 5.4, and 15.8% for acetaldehyde; 2.1, 5.4, 11.1, and 22.0% for acrolein+acetone; 0.8, 2.7, 4.6, and 10.0% for propionaldehyde; 3.3, 7.8, 16.0, and 26.0% for butyraldehyde.

  14. Carbonyl-Olefin Exchange Reaction: Present State and Outlook (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  15. Catalyst Initiation in the Oscillatory Carbonylation Reaction

    Directory of Open Access Journals (Sweden)

    Katarina Novakovic


    Full Text Available Palladium(II iodide is used as a catalyst in the phenylacetylene oxidative carbonylation reaction that has demonstrated oscillatory behaviour in both pH and heat of reaction. In an attempt to extract the reaction network responsible for the oscillatory nature of this reaction, the system was divided into smaller parts and they were studied. This paper focuses on understanding the reaction network responsible for the initial reactions of palladium(II iodide within this oscillatory reaction. The species researched include methanol, palladium(II iodide, potassium iodide, and carbon monoxide. Several chemical reactions were considered and applied in a modelling study. The study revealed the significant role played by traces of water contained in the standard HPLC grade methanol used.

  16. Sulfide intrusion and detoxification in seagrasses ecosystems

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne

    is known about the strategies of seagrasses to survive sulfide intrusion, their potential detoxification mechanisms and sulfur nutrition in general. By a global review of sulfide intrusion, coupled with a series of field studies and in situ experiments we elucidate sulfide intrusion and different...... not present in terrestrial plants at that level. Sulfide is not necessarily toxic but used as sulfur nutrition, presupposing healthy seagrass ecosystems that can support detoxification mechanisms. Presence or absence of those mechanisms determines susceptibility of seagrass ecosystems to sediment sulfide...

  17. Spectroscopic studies of OCS-doped 4He clusters with 9-72 helium atoms: observation of broad oscillations in the rotational moment of inertia. (United States)

    McKellar, A R W; Xu, Yunjie; Jäger, Wolfgang


    High-resolution spectra of HeN-OCS clusters with N up to 39 in the microwave region and up to 72 in the infrared region were observed with apparatus-limited line widths of about 15 kHz and 0.001 cm(-1), respectively. The cold (approximately 0.2 K) clusters were produced in pulsed supersonic jet expansions of very dilute OCS + He mixtures and probed using a microwave Fourier transform spectrometer or a tunable infrared diode laser spectrometer. Consistent analyses of the microwave and infrared data yield band origins for the carbonyl stretching vibration, together with rotational parameters for the ground and excited vibrational states. The rotational constant, B, passes through a minimum at N = 9 and then rises as the He atoms uncouple from the OCS rotational motion as a result of superfluid effects. There are broad unexpected oscillations in B, with maxima at N = 24 and 47 and minima at N = 36 and 62. The change in B upon vibrational excitation, which is negative for the OCS molecule, converges to positive values for N > 15. These results help to bridge the gap between individual molecules and bulk matter with atom-by-atom resolution over a significant range of cluster sizes.

  18. High throughput assay for evaluation of reactive carbonyl scavenging capacity

    Directory of Open Access Journals (Sweden)

    N. Vidal


    Full Text Available Many carbonyl species from either lipid peroxidation or glycoxidation are extremely reactive and can disrupt the function of proteins and enzymes. 4-hydroxynonenal and methylglyoxal are the most abundant and toxic lipid-derived reactive carbonyl species. The presence of these toxics leads to carbonyl stress and cause a significant amount of macromolecular damages in several diseases. Much evidence indicates trapping of reactive carbonyl intermediates may be a useful strategy for inhibiting or decreasing carbonyl stress-associated pathologies. There is no rapid and convenient analytical method available for the assessment of direct carbonyl scavenging capacity, and a very limited number of carbonyl scavengers have been identified to date, their therapeutic potential being highlighted only recently. In this context, we have developed a new and rapid sensitive fluorimetric method for the assessment of reactive carbonyl scavengers without involvement glycoxidation systems. Efficacy of various thiol- and non-thiol-carbonyl scavenger pharmacophores was tested both using this screening assay adapted to 96-well microplates and in cultured cells. The scavenging effects on the formation of Advanced Glycation End-product of Bovine Serum Albumin formed with methylglyoxal, 4-hydroxynonenal and glucose-glycated as molecular models were also examined. Low molecular mass thiols with an α-amino-β-mercaptoethane structure showed the highest degree of inhibitory activity toward both α,β-unsaturated aldehydes and dicarbonyls. Cysteine and cysteamine have the best scavenging ability toward methylglyoxal. WR-1065 which is currently approved for clinical use as a protective agent against radiation and renal toxicity was identified as the best inhibitor of 4-hydroxynonenal.

  19. The O.C.: Our Guide to ALA in Anaheim (United States)

    Hardstark, Georgia


    For those who grew up in Orange County (O.C.), Disneyland is the metaphoric morsel of food that gets stuck between the teeth of someone one does not like. While D-land is a must-see for millions of visitors each year, there is much more to Anaheim. Although O.C. is portrayed on numerous reality TV shows as a mecca for rich white people with…

  20. 16th Carbonyl Metabolism Meeting: from enzymology to genomics

    Directory of Open Access Journals (Sweden)

    Maser Edmund


    Full Text Available Abstract The 16th International Meeting on the Enzymology and Molecular Biology of Carbonyl Metabolism, Castle of Ploen (Schleswig-Holstein, Germany, July 10–15, 2012, covered all aspects of NAD(P-dependent oxido-reductases that are involved in the general metabolism of xenobiotic and physiological carbonyl compounds. Starting 30 years ago with enzyme purification, structure elucidation and enzyme kinetics, the Carbonyl Society members have meanwhile established internationally recognized enzyme nomenclature systems and now consider aspects of enzyme genomics and enzyme evolution along with their roles in diseases. The 16th international meeting included lectures from international speakers from all over the world.

  1. Efficiency of Carbonyl Iron in Prevention of Anaemia in Piglets

    Directory of Open Access Journals (Sweden)

    M. Svoboda


    Full Text Available The aim of this study was to evaluate efficiency of elemental iron preparation in the form of carbonyl iron in prevention of iron deficiency in piglets. The piglets in group I (n = 14 were given 210 mg of carbonyl iron orally at the age of 3 days. The piglets in group II (n = 15 received 210 mg of carbonyl iron orally on days 3 and 9. In group III (n = 14 the piglets were injected i.m. with 200 mg Fe3+ as iron dextran. Fourteen days after birth, haemoglobin concentration in group I started to decrease and the piglets developed anaemia. In group II, at the age of 28 days, Hb dropped below 80 g/l and the piglets developed anaemia. Under conditions of this trial, the oral administration of carbonyl iron did not prevent development of iron deficiency in piglets.

  2. Targeting Reactive Carbonyl Species with Natural Sequestering Agents

    Directory of Open Access Journals (Sweden)

    Sung Won Hwang


    Full Text Available Reactive carbonyl species generated by the oxidation of polyunsaturated fatty acids and sugars are highly reactive due to their electrophilic nature, and are able to easily react with the nucleophilic sites of proteins as well as DNA causing cellular dysfunction. Levels of reactive carbonyl species and their reaction products have been reported to be elevated in various chronic diseases, including metabolic disorders and neurodegenerative diseases. In an effort to identify sequestering agents for reactive carbonyl species, various analytical techniques such as spectrophotometry, high performance liquid chromatography, western blot, and mass spectrometry have been utilized. In particular, recent advances using a novel high resolution mass spectrometry approach allows screening of complex mixtures such as natural products for their sequestering ability of reactive carbonyl species. To overcome the limited bioavailability and bioefficacy of natural products, new techniques using nanoparticles and nanocarriers may offer a new attractive strategy for increased in vivo utilization and targeted delivery of bioactives.

  3. Aerobic Oxidation of Alcohols to Carbonyl Compounds Catalyzed by ...

    Indian Academy of Sciences (India)

    hydroxyphthalimide. 1. Introduction. The selective oxidation of alcohols to the corresponding carbonyl compounds is one of the most important reac- tions in organic synthesis and fine chemical industries.1. Numerous methods have been developed for the ...

  4. Carbonyl-Olefin Exchange Reaction and Related Chemistry (United States)

    Jossifov, Christo; Kalinova, Radostina

    A new carbon—carbon double bond forming reaction (carbonyl olefin exchange reaction) mediated by transition metal catalytic systems has been discovered. The catalytic systems used (transition metal halides or oxohalides alone or in combination with Lewis acids) are active only in the case when the two reacting groups are in one molecules and are conjugated. In addition these systems accelerate other reactions which run simultaneously with the carbonyl olefin metathesis rendering a detailed investigation of the process very complicated.

  5. Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs). (United States)

    Cao, Kai; Murshid, Nimer; Wang, Xiaosong


    Synthesis of main-chain metal carbonyl organometallic macromolecules (MCMCOMs) is difficult, mainly due to the instability of metal carbonyl complexes. Despite its challenge a number of MCMCOMs has been prepared by strategically using organometallic, organic, and polymer synthetic chemistry. Main contributions to this research field were reported by the groups of Tyler, Pannell, and Wang and are briefly summarized in this article. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Carbonyl species characteristics during the evaporation of essential oils (United States)

    Chiang, Hsiu-Mei; Chiu, Hua-Hsien; Lai, Yen-Ming; Chen, Ching-Yen; Chiang, Hung-Lung


    Carbonyls emitted from essential oils can affect the air quality when they are used in indoors, especially under poor ventilation conditions. Lavender, lemon, rose, rosemary, and tea tree oils were selected as typical and popular essential oils to investigate in terms of composition, thermal characteristics and fifteen carbonyl constituents. Based on thermogravimetric (TG) analysis, the activation energy was 7.6-8.3 kcal mol -1, the reaction order was in the range of 0.6-0.7 and the frequency factor was 360-2838 min -1. Formaldehyde, acetaldehyde, acetone, and propionaldehyde were the dominant carbonyl compounds, and their concentrations were 0.034-0.170 ppm. The emission factors of carbonyl compounds were 2.10-3.70 mg g -1, and acetone, propionaldehyde, acetaldehyde, and formaldehyde accounted for a high portion of the emission factor of carbonyl compounds in essential oil exhaust. Some unhealthy carbonyl species such as formaldehyde and valeraldehyde, were measured at low-temperature during the vaporization of essential oils, indicating a potential effect on indoor air quality and human health.

  7. Sulfidation behavior of Fe20Cr alloys

    International Nuclear Information System (INIS)

    Pillis, Marina Fuser


    Alloys for use in high temperature environments rely on the formation of an oxide layer for their protection. Normally, these protective oxides are Cr 2 O 3 , Al 2 O 3 and, some times, SiO 2 . Many industrial gaseous environments contain sulfur. Sulfides, formed in the presence of sulfur are thermodynamically less stable, have lower melting points and deviate much more stoichiometrically, compared to the corresponding oxides. The mechanism of sulfidation of various metals is as yet not clear, in spite of the concerted efforts during the last decade. To help address this situation, the sulfidation behavior of Fe20Cr has been studied as a function of compositional modifications and surface state of the alloy. The alloys Fe20Cr, Fe20Cr0.7Y, Fe20Cr5Al and Fe20Cr5Al0.6Y were prepared and three sets of sulfidation tests were carried out. In the first set, the alloys were sulfidized at 700 deg C and 800 deg C for 10h. In the second set, the alloys were pre-oxidized at 1000 deg C and then sulfidized at 800 deg C for up to 45h. In the third set of tests, the initial stages of sulfidation of the alloys was studied. All the tests were carried out in a thermobalance, in flowing H 2 /2%H 2 S, and the sulfidation behavior determined as mass change per unit area. Scanning electron microscopy coupled to energy dispersive spectroscopy and X-ray diffraction analysis were used to characterize the reaction products. The addition of Y and Al increased sulfidation resistance of Fe20Cr. The addition of Y altered the species that diffused predominantly during sulfide growth. It changed from predominant cationic diffusion to predominant anionic diffusion. The addition of Al caused an even greater increase in sulfidation resistance of Fe20Cr, with the parabolic rate constant decreasing by three orders of magnitude. Y addition to the FeCrAl alloy did not cause any appreciable alteration in sulfidation resistance. Pre-oxidation of the FeCrAl and FeCrAlY alloys resulted in an extended

  8. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate. (United States)

    Heshmat, Mojgan; Privalov, Timofei


    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Determination of Carbonyl Compounds in Exhaled Cigarette Smoke

    Directory of Open Access Journals (Sweden)

    Moldoveanu S


    Full Text Available This paper presents the findings on a quantitative evaluation of carbonyl levels in exhaled cigarette smoke from human subjects. The cigarettes evaluated include products with 5.0 mg ‘tar’, 10.6 mg ‘tar’ and 16.2 mg ‘tar’, where ‘tar’ is defined as the weight of total wet particulate matter (TPM minus the weight of nicotine and water, and the cigarettes are smoked following U.S. Federal Trade Commission (FTC recommendations. The measured levels of carbonyls in the exhaled smoke were compared with calculated yields of carbonyls in the inhaled smoke and a retention efficiency was obtained. The number of human subjects included a total of ten smokers for the 10.6 mg ‘tar’, five for the 16.2 mg ‘tar’, and five for the 5.0 mg ‘tar’ product, each subject smoking three cigarettes. The analyzed carbonyl compounds included several aldehydes (formaldehyde, acetaldehyde, acrolein, propionaldehyde, crotonaldehyde and n-butyraldehyde, and two ketones (acetone and 2-butanone. The smoke collection from the human subjects was vacuum assisted. Exhaled smoke was collected on Cambridge pads pretreated with a solution of dinitrophenylhydrazine (DNPH followed by high performance liquid chromatography (HPLC analysis of the dinitrophenylhydrazones of the carbonyl compounds. The cigarette butts from the smokers were collected and analyzed for nicotine. The nicotine levels for the cigarette butts from the smokers were used to calculate the level of carbonyls in the inhaled smoke, based on calibration curves. These were generated separately by analyzing the carbonyls in smoke and the nicotine in the cigarette butts obtained by machine smoking under different puffing regimes. The comparison of the level of carbonyl compounds in exhaled smoke with that from the inhaled smoke showed high retention of all the carbonyls. The retention of aldehydes was above 95% for all three different ‘tar’ levels cigarettes. The ketones were retained with a

  10. Characterization of upgraded fast pyrolysis oak oil distillate fractions from sulfided and non-sulfided catalytic hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Olarte, Mariefel V.; Padmaperuma, Asanga B.; Ferrell, Jack R.; Christensen, Earl D.; Hallen, Richard T.; Lucke, Richard B.; Burton, Sarah D.; Lemmon, Teresa L.; Swita, Marie S.; Fioroni, Gina; Elliott, Douglas C.; Drennan, Corinne


    Catalytic hydroprocessing of pyrolysis oils from biomass produces hydrocarbons that can be considered for liquid fuel production. This process requires removal of oxygen and cracking of the heavier molecular weight bio-oil constituents into smaller fragments at high temperatures and pressures under hydrogen. A comprehensive understanding of product oils is useful to optimize cost versus degree of deoxygenation. Additionally, a better understanding of the chemical composition of the distillate fractions can open up other uses of upgraded oils for potentially higher-value chemical streams. We present in this paper the characterization data for five well-defined distillate fractions of two hydroprocessed oils with different oxygen levels: a low oxygen content (LOC, 1.8% O, wet basis) oil and a medium oxygen content (MOC, 6.4% O, wet basis) oil. Elemental analysis and 13C NMR results suggest that the distillate fractions become more aromatic/unsaturated as they become heavier. Our results also show that the use of sulfided catalysts directly affects the S content of the lightest distillate fraction. Carbonyl and carboxylic groups were found in the MOC light fractions, while phenols were present in the heavier fractions for both MOC and LOC. PIONA analysis of the light LOC fraction shows a predominance of paraffins with a minor amount of olefins. These results can be used to direct future research on refinery integration and production of value-added product from specific upgraded oil streams.

  11. Emissions of carbonyl compounds from various cookstoves in China

    International Nuclear Information System (INIS)

    Zhang, J.; Smith, K.R.; Univ. of California, Berkeley, CA


    This paper presents a new database of carbonyl emission factors for commonly used cookstoves in China. The emission factors, reported both on a fuel-mass basis (mg/kg) and on a defined cooking-task basis (mg/task), were determined using a carbon balance approach for 22 types of fuel/stove combinations. These include various stoves using different species of crop residues and wood, kerosene, and several types of coals and gases. The results show that all the tested cookstoves produced formaldehyde and acetaldehyde and that the vast majority of the biomass stoves produced additional carbonyl compounds such as acetone, acrolein, propionaldehyde, crotonaldehyde, 2-butanone, isobutyraldehyde, butyraldehyde, isovaleraldehyde, valeraldehyde, hexaldehyde, benzaldehyde, o-tolualdehyde, m,p-tolualdehyde, and 2,4-dimethylbenzaldehyde. Carbonyls other than formaldehyde and acetaldehyde, however, were rarely generated by burning coal, coal gas, and natural gas. Kerosene and LPG stoves generated more carbonyl compounds than coal, coal gas, and natural gas stoves, but less than biomass stoves. Indoor levels of carbonyl compounds for typical village houses during cooking hours, estimated using a mass balance model and the measured emission factors, can be high enough to cause acute health effects documented for formaldehyde exposure, depending upon house parameters and individuals' susceptibility

  12. Sulfide toxicity kinetics of a uasb reactor

    Directory of Open Access Journals (Sweden)

    D. R. Paula Jr.


    Full Text Available The effect of sulfide toxicity on kinetic parameters of anaerobic organic matter removal in a UASB (up-flow anaerobic sludge blanket reactor is presented. Two lab-scale UASB reactors (10.5 L were operated continuously during 12 months. The reactors were fed with synthetic wastes prepared daily using glucose, ammonium acetate, methanol and nutrient solution. One of the reactors also received increasing concentrations of sodium sulfide. For both reactors, the flow rate of 16 L.d-1 was held constant throughout the experiment, corresponding to a hydraulic retention time of 15.6 hours. The classic model for non-competitive sulfide inhibition was applied to the experimental data for determining the overall kinetic parameter of specific substrate utilization (q and the sulfide inhibition coefficient (Ki. The application of the kinetic parameters determined allows prediction of methanogenesis inhibition and thus the adoption of operating parameters to minimize sulfide toxicity in UASB reactors.

  13. A cautionary tale of interpreting O-C diagrams

    DEFF Research Database (Denmark)

    Skarka, M.; Liska, J.; Dreveny, R.


    We present a comprehensive study of Z CVn, an RR Lyrae star that shows long-term cyclic variations of its pulsation period. A possible explanation suggested from the shape of the O-C diagram is the light travel-time effect, which we thoroughly examine. We used original photometric and spectroscop...

  14. 75 FR 71734 - Outer Continental Shelf (OCS), Scientific Committee (SC) (United States)


    ... program covers a wide range of field and laboratory studies in biology, chemistry, and physical oceanography, as well as studies of the social and economic impacts of OCS energy and marine minerals... Environmental Studies Program (ESP) and environmental aspects of the offshore energy and marine minerals...

  15. 77 FR 18260 - Outer Continental Shelf (OCS), Alaska OCS Region, Cook Inlet Planning Area, Proposed Oil and Gas... (United States)


    ... Federal OCS offshore area has been limited in the past decade, recently there has been renewed interest in..., both offshore and onshore. This RFI seeks to determine the level of industry interest in a possible...-gathering step is important to ensure that all pertinent information is assessed in determining whether to...

  16. Magnetorheological Fluids with Carbonyl and Water Atomized Iron Powders (United States)

    Bombard, Antonio J. F.; Teodoro, João Victor R.

    Our aim in this work was to propose the use of a ternary blend of two carbonyl iron powder CIP, mixed with water atomized iron powder (WAIP), to reduce the off-state viscosity, without prejudice of MRF performance in terms of yield stress and torque output. The idea of mix water atomized iron powder with carbonyl iron powder is not new. The US Pat. # 5,900,184 by Weiss et al. (1999) describes that a binary blend, half-to-half, can reduces the viscosity of MRF in the absence of magnetic field, and increase the torque output under field.

  17. Sulfide Intrusion and Detoxification in the Seagrass Zostera marina

    DEFF Research Database (Denmark)

    Hasler-Sheetal, Harald; Holmer, Marianne


    Gaseous sulfide intrusion into seagrasses growing in sulfidic sediments causes little or no harm to the plant, indicating the presence of an unknown sulfide tolerance or detoxification mechanism. We assessed such mechanism in the seagrass Zostera marina in the laboratory and in the field...... as sulfate throughout the plant. We conclude that avoidance of sulfide exposure by reoxidation of sulfide in the rhizosphere or aerenchyma and tolerance of sulfide intrusion by incorporation of sulfur in the plant are likely major survival strategies of seagrasses in sulfidic sediments....

  18. One-pot desymmetrizing hydroformylation/carbonyl ene cyclization process: straightforward access to highly functionalized cyclohexanols. (United States)

    Bigot, Aurélien; Breuninger, Daniel; Breit, Bernhard


    Rapid access to highly functionalized alkylidene cyclohexanols through a one-pot desymmetrizing hydroformylation/carbonyl ene cyclization starting from simple bisalkenylcarbinols is reported. Mechanistic insight into the carbonyl ene reaction is given, highlighting the importance of hyperconjugative substituent effects.

  19. Comparing forward and inverse models to estimate the seasonal variation of hemisphere-integrated fluxes of carbonyl sulfide

    Directory of Open Access Journals (Sweden)

    A. J. Kettle


    Full Text Available A simple inverse model is proposed to deduce hemisphere-integrated COS flux based on published time series of total column COS. The global atmosphere is divided into two boxes representing the Northern and Southern Hemispheres, and the total column COS data from several stations are used to calculate hemispheric COS loadings. The integrated flux within each hemisphere is calculated as a linear combination of a steady-state solution and time-varying perturbation. The nature of the time-varying perturbation is deduced using two different approaches: an analytic solution based on a cosine function that was fitted to the original total column COS measurement time series and a Simplex optimization with no underlying assumption about the functional form of the total column time series. The results suggest that there is a steady-state COS flux from the Northern to the Southern Hemisphere. There is a seasonal variation superimposed on this flux that in the Southern Hemisphere has a maximum rate of COS input into the atmosphere around January and a maximum rate of COS removal from the atmosphere around August--September. In the Northern Hemisphere, the maximum rate of COS input into the atmosphere is around May--June, and the maximum rate of COS removal is either August or January, depending on which station in the Northern Hemisphere is considered. The results of the inverse model are compared with the outcome of a forward approach on the temporal and spatial variation of the dominant global sources and sinks published earlier. In general, the deduced hemisphere-integrated flux estimates showed good agreement with the database estimates, though it remains uncertain whether COS removal from the atmosphere in the Northern Hemisphere is dominated by plant and soil uptake in the boreal summer or by oceanic uptake in boreal winter.

  20. Measurements of atmospheric carbonyl sulfide during the NASA Chemical Instrumentation Test and Evaluation Project: Implications for the global COS budget (United States)

    Johnson, James E.; Bandy, Alan R.; Thornton, Donald C.; Bates, Timothy S.


    Atmospheric COS concentrations were measured by three analytical systems during the Chemical Instrumentation Test and Evaluation (CITE 3) project. The three systems all used cryogenic sample preconcentration and gas chromatographic (GC) separation but differed in the method of detection. The FPD system used a flame photometric detector, the MS system used a mass selective detector, and the ECD-S system used a fluorinating catalyst followed by an electron capture detector. With the FPD system, we found a mean COS concentration of 510 ppt over the North Atlantic and 442 ppt over the Tropical Atlantic. With the ECD-S system, we found a mean COS concentration of 489 ppt over the North Atlantic and 419 ppt over the Tropical Atlantic. All three systems registered a latitudinal gradient in atmospheric COS of between 1.6 and 2.0 ppt per degree of latitude, with increasing COS concentrations northward which was similar to the gradient measured by Bingemer et al. (1990). It is difficult to reconcile the measured latitudinal concentration gradient with present theories of the global COS budget since the largest sink of COS is thought to be a flux to land plants, most of which are in the northern hemisphere.

  1. Deactivation mechanism of the simultaneous removal of carbonyl ...

    Indian Academy of Sciences (India)

    KAI LI


    Nov 10, 2017 ... REGULAR ARTICLE. Deactivation mechanism of the simultaneous removal of carbonyl sulphide and carbon disulphide over Fe–Cu–Ni/MCSAC catalysts. KAI LIa, XIN SONGa, CHI WANGb, YI MEIb, XIN SUNa and PING NINGa,∗. aFaculty of Environmental Science and Engineering, Kunming University of ...

  2. Electromagnetic properties of carbonyl iron and their microwave ...

    Indian Academy of Sciences (India)


    Abstract. The complex permittivity, permeability and microwave-absorbing properties of rubber composites filled with carbonyl iron are measured at frequencies from 2–18 GHz. The results indicate that the reflection loss peak shifts towards low frequency region with increasing layer thickness or increasing weight concentra-.

  3. Electromagnetic properties of carbonyl iron and their microwave ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 33; Issue 5. Electromagnetic properties of carbonyl iron and their microwave absorbing characterization as filler in silicone rubber. Yuping Duan ... These results show that the composites possess good microwave absorbing ability in both low- and highfrequency bands.

  4. cyclo-addition reaction of triplet carbonyl compounds to substituted ...

    Indian Academy of Sciences (India)

    Abstract. Regioselectivity of the photochemical [2 + 2] cyclo-addition of triplet carbonyl compounds with a series of ground state electron-rich and electron-poor alkenes, the Paterno-Büchi reaction, is studied. Activation barriers for the first step of the triplet reaction are computed in the case of the O-attack. Next, the observed ...

  5. Sampling And Analysis Of Carbonyl In Laboratory Atmospheres ...

    African Journals Online (AJOL)

    A sampling and analytical method has been developed for carbonyl concentrations in different laboratory atmospheres at the faculty of Science Bayero University; Kano, Nigeria using cold oximation followed by titrimetric finish. The analysis was carried out between 008 and 1800 hrs from from October 2002 to June 2003.

  6. Hyperfine coupling constants in muonium adducts of the carbonyl bond

    International Nuclear Information System (INIS)

    Cox, S.F.J.; Scott, C.A.; Geeson, D.A.; Rhodes, C.J.; Symons, M.C.R.; Roduner, E.


    A representative series is studied of organic radicals formed by the effective addition of muonium to the carbonyl oxygen atom of aldehydes, ketones, esters and amides. Low values of the muon-electron hyperfine coupling are measured which are particularly sensitive to radical structure and dynamics. The systematics of these values are discussed in terms of the opposing contributions of conjugation and hyperconjugation. (orig.)

  7. Selective Oxidative Carbonylation of Aniline to Diphenylurea with Ionic Liquids

    DEFF Research Database (Denmark)

    Zahrtmann, Nanette; Claver, Carmen; Godard, Cyril


    A catalytic system for the selective oxidative carbonylation of aniline to diphenylurea based on Pd complexes in combination with imidazolium ionic liquids is presented. Both oxidants, Pd complexes and ionic liquids affect the activity of the reaction while the choice of oxidant determines...

  8. Olefination of carbonyl compounds: modern and classical methods

    Energy Technology Data Exchange (ETDEWEB)

    Korotchenko, V N; Nenajdenko, Valentine G; Balenkova, Elizabeth S [Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow (Russian Federation); Shastin, Aleksey V [Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region (Russian Federation)


    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  9. Olefination of carbonyl compounds: modern and classical methods (United States)

    Korotchenko, V. N.; Nenajdenko, Valentine G.; Balenkova, Elizabeth S.; Shastin, Aleksey V.


    The published data on the methods for alkene synthesis by olefination of carbonyl compounds are generalised and systematised. The main attention is given to the use of transition metals and organoelement compounds. The review covers the data on both classical and newly developed methods that are little known to chemists at large.

  10. Frustrated Lewis pairs-assisted reduction of carbonyl compounds

    DEFF Research Database (Denmark)

    Marek, Ales; Pedersen, Martin Holst Friborg


    An alternative and robust method for the reduction of carbonyl groups by frustrated Lewis pairs (FLPs) is reported in this paper. With its very mild reaction conditions, good to excellent yields, absolute regioselectivity and the non-metallic character of the reagent, it provides an excellent too...

  11. Electrochemical Synthesis and Characterization of Zinc Sulfide Nanoparticles


    M. Rahimi-Nasarabadi


    Electrosynthesis process has been used for preparation of zinc sulfide nanoparticles. Zinc sulfide nanoparticles in different size and shapes were electrodeposited by electrolysis of zinc plate as anode in sodium sulfide solution. Effects of several reaction variables, such as electrolysis voltage, sulfide ion concentration as reactant, stirring rate of electrolyte solution and temperature on particle size of prepared zinc sulfide were investigated. The significance of these parameters in tun...

  12. Platinum Metals in Magmatic Sulfide Ores (United States)

    Naldrett, A. J.; Duke, J. M.


    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example.

  13. Crossett Hydrogen Sulfide Air Sampling Report (United States)

    This report summarizes the results of the EPA’s hydrogen sulfide air monitoring conducted along Georgia Pacific’s wastewater treatment system and in surrounding Crossett, AR, neighborhoods in 2017.

  14. Degradation of carbonyl hydroperoxides in the atmosphere and in combustion

    KAUST Repository

    Xing, Lili


    Oxygenates with carbonyl and hydroperoxy functional groups are important intermediates that are generated during the autooxidation of organic compounds in the atmosphere and during the autoignition of transport fuels. In the troposphere, the degradation of carbonyl hydroperoxides leads to low-vapor-pressure polyfunctional species that be taken into in cloud and fog droplets or to the formation of secondary organic aerosols (SOAs). In combustion, the fate of carbonyl hydroperoxides is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the carbonyl hydroperoxides is reac-tion with OH radicals, for which kinetics data are experimentally unavailable. Here, we study 4-hydroperoxy-2-pentanone (CH3C(=O)CH2CH(OOH)CH3) as a model compound to clarify the kinetics of OH reactions with carbonyl hydroperoxides, in par-ticular H-atom abstraction and OH addition reactions. With a combination of electronic structure calculations, we determine previ-ously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunnel-ing (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in atmospheric and combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for the addition reaction are computed using system-specific quantum RRK theory. The calculated temperature range is 298-2400 K, and the pressure range is 0.01–100 atm. The accu-rate thermodynamic and kinetics data determined in this work are indispensable in the global modeling of SOAs in atmospheric science and in the detailed understanding and prediction of ignition properties of hydrocarbons

  15. Cesium Carbonate-Catalyzed α-Phenylchalcogenation of Carbonyl Compounds with Diphenyl Dichalcogenide

    Directory of Open Access Journals (Sweden)

    Yutaka Nishiyama


    Full Text Available It was found that cesium carbonate has a unique catalytic ability on the reaction of carbonyl compounds with diphenyl diselenide to give the corresponding α-phenylseleno carbonyl compounds in moderate to good yields. Similarly, the α-phenylthiolation of carbonyl compounds with diphenyl disulfide was promoted by the cesium carbonate catalyst.

  16. Low pressure carbonylation of benzyl chloride = Die carbonylierung von benzylchlorid bei niedrigen drücken

    NARCIS (Netherlands)

    Luggenhorst, H.J.; Westerterp, K.R.


    For carbonylations, metal carbonyls, particularly cobalt and iron carbonyls, are often used as catalysts. These reactions take place under rather drastic reaction conditions, e.g. 200–300 °C and 60–100 MPa. In some patents it is stated that similar reactions using the same catalysts can also be

  17. Optimized biotin-hydrazide enrichment and mass spectrometry analysis of peptide carbonyls

    DEFF Research Database (Denmark)

    Havelund, Jesper F.; Wojdyla, K; Jensen, O. N.

    Irreversible cell damage through protein carbonylation is the result of reaction with reactive oxygen species (ROS) and has been coupled to many diseases. The precise molecular consequences of protein carbonylation, however, are still not clear. The localization of the carbonylated amino acid is ...

  18. Sulfide as a soil phytotoxin - A review

    Directory of Open Access Journals (Sweden)

    Leon P M Lamers


    Full Text Available In wetland soils and underwater sediments of marine, brackish and freshwater systems, the strong phytotoxin sulfide may accumulate as a result of microbial reduction of sulfate during anaerobiosis, its level depending on prevailing edaphic conditions. In this review, we compare an extensive body of literature on phytotoxic effects of this reduced sulfur compound in different ecosystem types, and review the effects of sulfide at multiple ecosystem levels: the ecophysiological functioning of individual plants, plant-microbe associations, and community effects including competition and facilitation interactions. Recent publications on multi-species interactions in the rhizosphere show even more complex mechanisms explaining sulfide resistance. It is concluded that sulfide is a potent phytotoxin, profoundly affecting plant fitness and ecosystem functioning in the full range of wetland types including coastal systems, and at several levels. Traditional toxicity testing including hydroponic approaches generally neglect rhizospheric effects, which makes it difficult to extrapolate results to real ecosystem processes. To explain the differential effects of sulfide at the different organizational levels, profound knowledge about the biogeochemical, plant physiological and ecological rhizosphere processes is vital. This information is even more important, as anthropogenic inputs of sulfur into freshwater ecosystems and organic loads into freshwater and marine systems are still much higher than natural levels, and are steeply increasing in Asia. In addition, higher temperatures as a result of global climate change may lead to higher sulfide production rates in shallow waters.

  19. Air-water transfer of hydrogen sulfide

    DEFF Research Database (Denmark)

    Yongsiri, C.; Vollertsen, J.; Rasmussen, M. R.


    The emissions process of hydrogen sulfide was studied to quantify air–water transfer of hydrogen sulfide in sewer networks. Hydrogen sulfide transfer across the air–water interface was investigated at different turbulence levels (expressed in terms of the Froude number) and pH using batch...... experiments. By means of the overall mass–transfer coefficient (KLa), the transfer coefficient of hydrogen sulfide (KLaH2S), referring to total sulfide, was correlated to that of oxygen (KLaO2) (i.e., the reaeration coefficient). Results demonstrate that both turbulence and pH in the water phase play...... a significant role for KLaH2S. An exponential expression is a suitable representation for the relationship between KLaH2S and the Froude number at all pH values studied (4.5 to 8.0). Because of the dissociation of hydrogen sulfide, KLaH2S increased with decreasing pH at a constant turbulence level. Relative...

  20. Accumulation of carbonyls accelerates the formation of pentosidine, an advanced glycation end product: carbonyl stress in uremia. (United States)

    Miyata, T; Ueda, Y; Yamada, Y; Izuhara, Y; Wada, T; Jadoul, M; Saito, A; Kurokawa, K; van Ypersele de Strihou, C


    Advanced glycation end product (AGE) formation is related to hyperglycemia in diabetes but not in uremia, because plasma AGE levels do not differ between diabetic and nondiabetic hemodialysis patients. The mechanism of this phenomenon remains elusive. Previously, it was suggested that elevation of AGE levels in uremia might result from the accumulation of unknown AGE precursors. The present study evaluates the in vitro generation of pentosidine, a well identified AGE structure. Plasma samples from healthy subjects and nondiabetic hemodialysis patients were incubated under air for several weeks. Pentosidine levels were determined at intervals by HPLC assay. Pentosidine rose to a much larger extent in uremic than in control plasma. Pentosidine yield, i.e., the change in pentosidine level between 0 and 4 wk divided by 28 d, averaged 0.172 nmol/ml per d in uremic versus 0.072 nmol/ml per d in control plasma (P aminoguanidine and OPB-9195, which inhibit the Maillard reaction, lowered pentosidine yield in both uremic and control plasma. When ultrafiltrated plasma was exposed to 2,4-dinitrophenylhydrazine, the yield of hydrazones, formed by interaction with carbonyl groups, was markedly higher in uremic than in control plasma. These observations strongly suggest that the pentosidine precursors accumulated in uremic plasma are carbonyl compounds. These precursors are unrelated to glucose or ascorbic acid, whose concentration is either normal or lowered in uremic plasma. They are also unrelated to 3-deoxyglucosone, a glucose-derived dicarbonyl compound whose level is raised in uremic plasma: Its addition to normal plasma fails to increase pentosidine yield. This study reports an elevated level of reactive carbonyl compounds ("carbonyl stress") in uremic plasma. Most have a lower than 5000 Da molecular weight and are thus partly removed by hemodialysis. Their effect on pentosidine generation can be inhibited by aminoguanidine or OPB-9195. Carbonyl stress might contribute to

  1. Sulfide response analysis for sulfide control using a pS electrode in sulfate reducing bioreactors

    NARCIS (Netherlands)

    Villa Gomez, D.K.; Cassidy, J.; Keesman, K.J.; Sampaio, R.M.; Lens, P.N.L.


    Step changes in the organic loading rate (OLR) through variations in the influent chemical oxygen demand (CODin) concentration or in the hydraulic retention time (HRT) at constant COD/SO4 2- ratio (0.67) were applied to create sulfide responses for the design of a sulfide control in sulfate reducing

  2. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort


    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  3. La estrategia del océano azul para emprendedores

    Directory of Open Access Journals (Sweden)

    Tula Mendoza Farro


    Full Text Available Los emprendedores deben tener presente que no siempre la planeación garantiza el logro de los objetivos, sin embargo sin planes es difícil alcanzar metas (1. Alfred Chandler J. define que “la estrategia es la determinación de los objetivos y planes a largo plazo de la empresa, las acciones a emprender y la asignación de recursos necesarios para lograr esto...” (2. Michael Porter sostiene que “la empresa sin estrategia está dispuesta a intentar cualquier cosa” (3. C.K. Prahalad dice que “si queremos escapar de la atracción gravitacional del pasado tenemos que ser capaces de replantear nuestras propias ortodoxias. Debemos volver a generar nuestras estrategias esenciales y replantear nuestras creencias fundamentales sobre cómo vamos a competir” (4. Peter Drucker, en tanto, considera que “la estrategia de la organización es la respuesta a dos preguntas: ¿qué es nuestro negocio? y ¿qué debería ser?” (5. Las concepciones de estrategia en la empresa son diversas, pero todas coinciden en la enorme trascendencia que tiene para la gestión empresarial. Los modelos de estrategia, del mismo modo esencial para la gestión, también son distintos, pero suelen variar en función de la búsqueda de mejores resultados. Un emergente y expectante modelo es hoy la estrategia del océano azul, que alienta la innovación en la apertura de mercados y deja de lado la competencia como modelo estratégico. La estrategia del océano azul, formulada por W. Chan Kim y Renée Mauborgne en su gran best seller del mismo nombre (6, sostiene que las empresas si quieren ser exitosas pueden hacerlo explorando nuevos mercados, nuevas oportunidades y a través de la innovación en valor (innovación con utilidad, precio y costo, sin preocuparse en la competencia. Es un modelo de “no competencia”, de búsqueda de nuevas oportunidades, de intactos escenarios, de aguas tranquilas e inexploradas que simbolizan el océano azul, y que precisamente es una

  4. Anchoring selenido-carbonyl ruthenium clusters to functionalized silica xerogels

    International Nuclear Information System (INIS)

    Cauzzi, Daniele; Graiff, Claudia; Pattacini, Roberto; Predieri, Giovanni; Tiripicchio, Antonio


    Silica Xerogels containing carbonyl Ru 3 Se 2 nido clusters were prepared in three different ways. The simple dispersion of [Ru 3 (μ 3 -Se) 2 (CO) 7 (PPh 3 ) 2 ] via sol gel process produces an inhomogeneous material; by contrast, homogeneous xerogels were obtained by reaction of [Ru 3 (μ 3 -Se) 2 (CO) 8 (PPh 3 )] with functionalized xerogels containing grafted diphenylphosphine moieties and by reaction of [Ru 3 (CO) 12 ] with a xerogel containing grafted phosphine-selenide groups. The reaction between [Ru 3 (CO) 12 ] and dodecyl diphenylphosphine selenide led to the formation of four selenido carbonyl clusters, which are soluble in hydrocarbon solvents and can be deposited as thin films from their solution by slow evaporation. (author)

  5. Role of Carbonyl Modifications on Aging-Associated Protein Aggregation (United States)

    Tanase, Maya; Urbanska, Aleksandra M.; Zolla, Valerio; Clement, Cristina C.; Huang, Liling; Morozova, Kateryna; Follo, Carlo; Goldberg, Michael; Roda, Barbara; Reschiglian, Pierluigi; Santambrogio, Laura


    Protein aggregation is a common biological phenomenon, observed in different physiological and pathological conditions. Decreased protein solubility and a tendency to aggregate is also observed during physiological aging but the causes are currently unknown. Herein we performed a biophysical separation of aging-related high molecular weight aggregates, isolated from the bone marrow and splenic cells of aging mice and followed by biochemical and mass spectrometric analysis. The analysis indicated that compared to younger mice an increase in protein post-translational carbonylation was observed. The causative role of these modifications in inducing protein misfolding and aggregation was determined by inducing carbonyl stress in young mice, which recapitulated the increased protein aggregation observed in old mice. Altogether our analysis indicates that oxidative stress-related post-translational modifications accumulate in the aging proteome and are responsible for increased protein aggregation and altered cell proteostasis.

  6. Hydrogenation of coal liquid utilizing a metal carbonyl catalyst (United States)

    Feder, Harold M.; Rathke, Jerome W.


    Coal liquid having a dissolved transition metal, catalyst as a carbonyl complex such as Co.sub.2 (CO.sub.8) is hydrogenated with hydrogen gas or a hydrogen donor. A dissociating solvent contacts the coal liquid during hydrogenation to form an immiscible liquid mixture at a high carbon monoxide pressure. The dissociating solvent, e.g. ethylene glycol, is of moderate coordinating ability, while sufficiently polar to solvate the transition metal as a complex cation along with a transition metal, carbonyl anion in solution at a decreased carbon monoxide pressure. The carbon monoxide pressure is reduced and the liquids are separated to recover the hydrogenated coal liquid as product. The dissociating solvent with the catalyst in ionized form is recycled to the hydrogenation step at the elevated carbon monoxide pressure for reforming the catalyst complex within fresh coal liquid.

  7. Synthetic and mechanistic aspects of titanium-mediated carbonyl olefinations

    Energy Technology Data Exchange (ETDEWEB)

    Petasis, N.A.; Staszewski, J.P.; Hu, Yong-Han; Lu, Shao-Po [Univ. of Southern California, Los Angeles, CA (United States)


    A new method for the olefination of carbonyl compounds with dimethyl titanocene, and other related bishydrocarbyl titanocene derivatives has been recently developed in the author`s laboratories. This process is experimentally convenient and works with various types of carbonyl compounds, including aldehydes, ketones, esters, lactones, carbonates, anhydrides, amides, imides, lactams, thioesters, selenoesters, and acylsilanes. More recent studies have focused on the scope and utility of this reaction, including mechanistic studies and synthetic applications. In addition to varying the reaction conditions, the authors have examined several mixed titanocene derivatives and have found ways for carrying out this type of olefination at room temperature, such as the use of tris(trimethylsilyl) titanacyclobutene. The authors have also employed this reaction in the modification of carbohydrates and cyclobutenediones. This olefination was also followed-up with subsequent transformations to produce carbocycles and heterocycles, including tetrahydrofurans and tetrahydropyrans.

  8. A three-membered ring approach to carbonyl olefination. (United States)

    Niyomchon, Supaporn; Oppedisano, Alberto; Aillard, Paul; Maulide, Nuno


    The carbon-carbon double bond, with its diverse and multifaceted reactivity, occupies a prominent position in organic synthesis. Although a variety of simple alkenes are readily available, the mild and chemoselective introduction of a unit of unsaturation into a functionalized organic molecule remains an ongoing area of research, and the olefination of carbonyl compounds is a cornerstone of such approaches. Here we show the direct olefination of hydrazones via the intermediacy of three-membered ring species generated by addition of sulfoxonium ylides, departing from the general dogma of alkenes synthesis from carbonyls. Moreover, the mild reaction conditions and operational simplicity of the transformation render the methodology appealing from a practical point of view.

  9. The reaction of sulfhydryl groups with carbonyl compounds. (United States)

    Włodek, L


    The sulfhydryl groups of L-cysteine and reduced glutathione (GSH) react nonenzymatically with formaldehyde (F), acrolein (Al), acetaldehyde (AA), malondialdehyde (DAM), pyruvate (P), oxoglutarate (oxo-G) and glucose (G) to form thiazolidine derivatives. These reactions show different velocities and the adducts formed show different stabilities. The equilibrium constants K, as well as the rate constants kr for the reverse reaction, show considerable variation. The carbonyls reveal higher reactivity with sulfhydryl group of L-Cys than with those of GSH, and the stability of the adducts is higher than that of GSH. Al, F and AA react more rapidly with both thiol compounds than the other carbonyls, but the adducts are less stable. The sulfhydryl groups level of bovine serum albumin as well as those of high- and low-molecular thiols of human plasma is reduced in the presence of Al, F or DAM.

  10. Metal Carbonyl-Hydrosilane Reactions and Hydrosilation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Cutler, A. R.


    Manganese carbonyl complexes serve as hydrosilation precatalysts for selectively transforming a carbonyl group into a siloxy methylene or a fully reduced methylene group. Substrates of interest include (1) aldehydes, ketones, carboxylic acids, silyl esters, and esters, and (2) their organometallic acyl counterparts. Three relevant catalytic reactions are shown. Two types of manganese precatalysts have been reported: (a) alkyl and acyl complexes (L)(C0){sub 4}MnR [L = CO, PPh{sub 3}; R = COCH{sub 3}, COPh, CH{sub 3}] and (b) halides (CO){sub 5}MnX and [(CO){sub 4}MnX]{sub 2} (X = Br, I). The former promote hydrosilation and deoxygenation catalysis; the latter promote dehydrogenative silation of alcohols and carboxylic acids as well as hydrosilation and deoxygenation of some metallocarboxylic acid derivatives. In every case studied, these Mn precatalysts are far more reactive or selective than traditional Rh(I) precatalysts.

  11. Sulfurization of Dissolved Organic Matter Increases Hg-Sulfide-Dissolved Organic Matter Bioavailability to a Hg-Methylating Bacterium. (United States)

    Graham, Andrew M; Cameron-Burr, Keaton T; Hajic, Hayley A; Lee, Connie; Msekela, Deborah; Gilmour, Cynthia C


    Reactions of dissolved organic matter (DOM) with aqueous sulfide (termed sulfurization) in anoxic environments can substantially increase DOM's reduced sulfur functional group content. Sulfurization may affect DOM-trace metal interactions, including complexation and metal-containing particle precipitation, aggregation, and dissolution. Using a diverse suite of DOM samples, we found that susceptibility to additional sulfur incorporation via reaction with aqueous sulfide increased with increasing DOM aromatic-, carbonyl-, and carboxyl-C content. The role of DOM sulfurization in enhancing Hg bioavailability for microbial methylation was evaluated under conditions typical of Hg methylation environments (μM sulfide concentrations and low Hg-to-DOM molar ratios). Under the conditions of predicted metacinnabar supersaturation, microbial Hg methylation increased with increasing DOM sulfurization, likely reflecting either effective inhibition of metacinnabar growth and aggregation or the formation of Hg(II)-DOM thiol complexes with high bioavailability. Remarkably, Hg methylation efficiencies with the most sulfurized DOM samples were similar (>85% of total Hg methylated) to that observed in the presence of l-cysteine, a ligand facilitating rapid Hg(II) biouptake and methylation. This suggests that complexes of Hg(II) with DOM thiols have similar bioavailability to Hg(II) complexes with low-molecular-weight thiols. Overall, our results are a demonstration of the importance of DOM sulfurization to trace metal and metalloid (especially mercury) fate in the environment. DOM sulfurization likely represents another link between anthropogenic sulfate enrichment and MeHg production in the environment.

  12. Nucleophilic tetrafluoroethylation of carbonyl compounds with fluorinated sulfones

    Czech Academy of Sciences Publication Activity Database

    Václavík, Jiří; Chernykh, Yana; Jurásek, Bronislav; Beier, Petr


    Roč. 169, Jan (2015), s. 24-31 ISSN 0022-1139 R&D Projects: GA ČR GAP207/11/0421 Grant - others:GA MŠk(CZ) ED3.2.00/08.0144; GA MŠk(CZ) LM2010005 Institutional support: RVO:61388963 Keywords : fluorine * tetrafluoroethylation * sulfones * nucleophilic addition * carbonyl compounds Subject RIV: CC - Organic Chemistry Impact factor: 2.213, year: 2015

  13. Magnetophoretic manipulation in microsystem using carbonyl iron-polydimethylsiloxane microstructures


    Faivre, Magalie; Gelszinnis, Renaud; Degouttes, Jérôme; Terrier, Nicolas; Rivière, Charlotte; Ferrigno, Rosaria; Deman, Anne-Laure


    This paper reports the use of a recent composite material, noted hereafter i-PDMS, made of carbonyl iron microparticles mixed in a PolyDiMethylSiloxane (PDMS) matrix, for magnetophoretic functions such as capture and separation of magnetic species. We demonstrated that this composite which combine the advantages of both components, can locally generate high gradients of magnetic field when placed between two permanent magnets. After evaluating the magnetic susceptibility of the material as a ...

  14. Iron(III)-catalysed carbonyl-olefin metathesis (United States)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.


    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  15. Vacuolating encephalitis in mice infected by human coronavirus OC43

    International Nuclear Information System (INIS)

    Jacomy, Helene; Talbot, Pierre J.


    Involvement of viruses in human neurodegenerative diseases and the underlying pathologic mechanisms remain generally unclear. Human respiratory coronaviruses (HCoV) can infect neural cells, persist in human brain, and activate myelin-reactive T cells. As a means of understanding the human infection, we characterized in vivo the neurotropic and neuroinvasive properties of HCoV-OC43 through the development of an experimental animal model. Virus inoculation of 21-day postnatal C57BL/6 and BALB/c mice led to a generalized infection of the whole CNS, demonstrating HCoV-OC43 neuroinvasiveness and neurovirulence. This acute infection targeted neurons, which underwent vacuolation and degeneration while infected regions presented strong microglial reactivity and inflammatory reactions. Damage to the CNS was not immunologically mediated and microglial reactivity was instead a consequence of direct virus-mediated neuronal injury. Although this acute encephalitis appears generally similar to that induced by murine coronaviruses, an important difference rests in the prominent spongiform-like degeneration that could trigger neuropathology in surviving animals

  16. UV absorption cross-sections of selected sulfur-containing compounds at temperatures up to 500°C

    DEFF Research Database (Denmark)

    Grosch, Helge; Fateev, Alexander; Clausen, Sønnik


    The temperature dependence of the ultraviolet absorption cross-sections of three different sulfur containing compounds, hydrogen sulfide (H2S), carbon disulfide (CS2) and carbonyl sulfide (OCS), are presented between 200nm and 360nm at a resolution of 0.018nm. The absorption cross-sections for ea...

  17. The new ret process for hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Nakamura, S.; Onishi, H.


    It was developed for gas streams from rayon production containing either 4500 ppM hydrogen sulfide and 5 ppM carbon disulfide or 900 ppM hydrogen sulfide and 16 ppM carbon disulfide (average values). The process consists of absorption towers, alkali scrubbers for the recovery of carbon disulfide, and an oxidation reactor. The process is catalyzed by an organic iron complex catalyst. For the removal of 1 kg hydrogen sulfide, the process uses 130 g sodium hydroxide, catalyst (20 yen), 2.5 kw-hr electricity, 15 kg steam (3 kg in winter), 2 cu m cooling water (1 cu m in winter), and 8 l. fresh water. The recovered sulfur (99%) is 99.9% pure. Eight litres of 0.03 kg COD wastewater are also produced. The process equipment is described. Flow diagrams, graph, and tables.

  18. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Xiaobing, E-mail: [Department of Chemistry, University of York, Heslington, York, YO10 5DD (United Kingdom); Lewis, Alastair C., E-mail: [National Centre for Atmospheric Science, University of York, Heslington, York, YO10 5DD (United Kingdom)


    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 {mu}g cigarette{sup -1} ({mu}g cig{sup -1}) and the particulate carbonyl emissions varied in the range of 23-127 {mu}g cig{sup -1}. Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 {mu}g cig{sup -1} gaseous and 141 {mu}g cig{sup -1} particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: {yields} Carbonyl

  19. Carbonyl compounds in gas and particle phases of mainstream cigarette smoke

    International Nuclear Information System (INIS)

    Pang, Xiaobing; Lewis, Alastair C.


    Carbonyl compounds (carbonyls) are important constituents of cigarette smoke and some are toxic and may be carcinogenic or mutagenic to humans. In this study carbonyl emissions in the gas and particle phases of mainstream cigarette smoke were assessed by GC-MS with pentafluorophenyl hydrazine (PFPH) derivatization. Seven brands of cigarettes and one brand of cigar common in the UK market and having differing nicotine, tar and carbon monoxide yields were investigated. Sixteen carbonyl components were identified in gaseous emissions and twenty in the particle phase. In the gaseous emissions, acetaldehyde presented as the predominant species, followed by formaldehyde, 2-propenal, and pentanal. In the particulate emissions, 1-hydroxy-2-propanone was the most abundant followed by formaldehyde, benzaldehyde, and 2,5-dimethylbenzaldehyde. Significant differences were found in carbonyl emissions among the brands of cigarettes. The gaseous carbonyl emissions varied in the range of 216-405 μg cigarette -1 (μg cig -1 ) and the particulate carbonyl emissions varied in the range of 23-127 μg cig -1 . Positive correlations were found between the total emission of carbonyls, tar yield and carbon monoxide yield. Similar gas/particle (G/P) partitioning ratios of carbonyls were found among all cigarettes, which implies that G/P partitions of carbonyls in smoke mainly depend on the physical properties of the carbonyls. The gaseous carbonyl emissions were enhanced by 40% to 130% when some of the water, accounting for 8-12% of cigarettes in mass, was removed from the tobacco. Non-filtered cigarettes showed significantly higher carbonyl emissions compared to their filtered equivalents. Carbonyl particulate accounted for 11-19% by mass of total particulate matter from tobacco smoke. The cigar generated 806 μg cig -1 gaseous and 141 μg cig -1 particulate carbonyls, which is 2-4 times greater than the cigarettes. - Highlights: → Carbonyl emission factors in both gas (16 species) and

  20. Interresidue carbonyl-carbonyl polarization transfer experiments in uniformly 13C, 15N-labeled peptides and proteins (United States)

    Janik, Rafal; Ritz, Emily; Gravelle, Andrew; Shi, Lichi; Peng, Xiaohu; Ladizhansky, Vladimir


    In this work, we demonstrate that Homonuclear Rotary Resonance Recoupling (HORROR) can be used to reintroduce carbonyl-carbonyl interresidue dipolar interactions and to achieve efficient polarization transfer between carbonyl atoms in uniformly 13C, 15N-labeled peptides and proteins. We show that the HORROR condition is anisotropically broadened and overall shifted to higher radio frequency intensities because of the CSA effects. These effects are analyzed theoretically using Average Hamiltonian Theory. At spinning frequencies used in this study, 22 kHz, this broadening is experimentally found to be on the order of a kilohertz at a proton field of 600 MHz. To match HORROR condition over all powder orientations, variable amplitude radio frequency (RF) fields are required, and efficient direct transfers on the order of 20-30% can be straightforwardly established. Two- and three-dimensional chemical shift correlation experiments establishing long-range interresidue connectivities (e.g., (N[i]-CO[i - 2])) are demonstrated on the model peptide N-acetyl-valine-leucine, and on the third immunoglobulin binding domain of protein G. Possible future developments are discussed.

  1. Determination of Carbonyl Functional Groups in Bio-oils by Potentiometric Titration: The Faix Method. (United States)

    Black, Stuart; Ferrell, Jack R


    Carbonyl compounds present in bio-oils are known to be responsible for bio-oil property changes upon storage and during upgrading. Specifically, carbonyls cause an increase in viscosity (often referred to as 'aging') during storage of bio-oils. As such, carbonyl content has previously been used as a method of tracking bio-oil aging and condensation reactions with less variability than viscosity measurements. Additionally, carbonyls are also responsible for coke formation in bio-oil upgrading processes. Given the importance of carbonyls in bio-oils, accurate analytical methods for their quantification are very important for the bio-oil community. Potentiometric titration methods based on carbonyl oximation have long been used for the determination of carbonyl content in pyrolysis bio-oils. Here, we present a modification of the traditional carbonyl oximation procedures that results in less reaction time, smaller sample size, higher precision, and more accurate carbonyl determinations. While traditional carbonyl oximation methods occur at room temperature, the Faix method presented here occurs at an elevated temperature of 80 °C.

  2. Ambient levels of carbonyl compounds and their sources in Guangzhou, China (United States)

    Feng, Yanli; Wen, Sheng; Chen, Yingjun; Wang, Xinming; Lü, Huixiong; Bi, Xinhui; Sheng, Guoying; Fu, Jiamo

    Ambient levels of carbonyl compounds and their possible sources, vehicular exhaust and cooking exhaust, were studied at seven places in Guangzhou, including five districts (a residential area, an industrial area, a botanical garden, a downtown area and a semi-rural area), a bus station and a restaurant during the period of June-September 2003. Nineteen carbonyl compounds were identified in the ambient air, of which acetone was the most abundant carbonyl, followed by formaldehyde and acetaldehyde. Only little changes were found in carbonyl concentration levels in the five different districts because of their dispersion and mixture in the atmosphere in summer. The lower correlations between the carbonyls' concentrations might result from the mixture of carbonyls derived from different sources, including strong photochemical reactions at noon in summer. Formaldehyde and acetaldehyde were the main carbonyls in bus station, while straight-chain carbonyls were comparatively abundant in cooking exhaust. Besides vehicular exhaust, cooking might be another major source of carbonyl compounds in Guangzhou City, especially for high molecular weight carbonyls.

  3. Refractory sulfides as IR window materials (United States)

    White, William B.


    The development of sulfide materials as infrared-transmitting optical ceramics is limited by intrinsic optical properties, thermomechanical properties, and considerations of chemical stability. Screening procedures with respect to band gap, electronic absorption, chemical stability, and refractory character reduced the set of all sulfides to about a dozen structural families. Systematic relationships were developed between crystal chemistry and phonon absorption edge, vibrational modes frequencies, and coefficient of thermal expansion which allow possible ranges of properties to be estimated. It is concluded that improved materials are possible but that radically improved new materials are unlikely.

  4. Iron-sulfide crystals in probe deposits

    DEFF Research Database (Denmark)

    Laursen, Karin; Frandsen, Flemming


    Iron-sulfides were observed in deposits collected on a probe inserted at the top of the furnace of a coal-fired power station in Denmark. The chemical composition of the iron-sulfides is equivalent to pyrrhotite (FeS). The pyrrhotites are present as crystals and, based on the shape of the crystals......, it was deduced that they were not deposited but instead grew within the deposit. The presence of unburned char particles within the deposits supports the concept that a reducing environment existed in the deposits. Two processes are proposed for explaining the existence of pyrrhotite crystals within a deposit...

  5. Membrane for hydrogen recovery from streams containing hydrogen sulfide (United States)

    Agarwal, Pradeep K.


    A membrane for hydrogen recovery from streams containing hydrogen sulfide is provided. The membrane comprises a substrate, a hydrogen permeable first membrane layer deposited on the substrate, and a second membrane layer deposited on the first layer. The second layer contains sulfides of transition metals and positioned on the on a feed side of the hydrogen sulfide stream. The present invention also includes a method for the direct decomposition of hydrogen sulfide to hydrogen and sulfur.

  6. Use of biogenic sulfide for ZnS precipitation

    NARCIS (Netherlands)

    Esposito, G.; Veeken, A.; Weijma, J.; Lens, P.N.L.


    A 600 ml continuously stirred tank reactor was used to assess the performance of a zinc sulfide precipitation process using a biogenic sulfide solution (the effluent of a sulfate-reducing bioreactor) as sulfide source. In all experiments, a proportional-integral (PI) control algorithm was used to

  7. A physiologically based kinetic model for bacterial sulfide oxidation

    NARCIS (Netherlands)

    Klok, J.B.M.; Graaff, de C.M.; Bosch, van den P.L.F.; Boelee, N.C.; Keesman, K.J.; Janssen, A.J.H.


    In the biotechnological process for hydrogen sulfide removal from gas streams, a variety of oxidation products can be formed. Under natron-alkaline conditions, sulfide is oxidized by haloalkaliphilic sulfide oxidizing bacteria via flavocytochrome c oxidoreductase. From previous studies, it was

  8. 40 CFR 425.03 - Sulfide analytical methods and applicability. (United States)


    ... § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration method... ferricyanide titration method for the determination of sulfide in wastewaters discharged by plants operating in... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Sulfide analytical methods and...

  9. La Terre sous l'Océan


    Vanney, Jean-René


    Parmi les acquisitions actuelles en matière de géomorphologie océanique, trois voies prometteuses sont choisies en guise d'introduction à ce numéro thématique qui lui est consacré : 1) l'agencement et l'énergie des reliefs en fonction de la vitesse de création et destruction crustale (céléro-dépendance) ; 2) le démantèlement des grands versants par des processus gravitaires de grande ampleur ; 3) le conditionnement interactif de l'environnement global. La seconde partie reconstitue trois séri...

  10. Immunoscintigraphy of ovarian carcinoma using OC 125 monoclonal antibody

    International Nuclear Information System (INIS)

    Park, Sang Yoon


    Immunoscintigraphy (ISG) with I-131 labeled OC 125 F (ab')2 fragments was studied in 7 patients for primary diagnosis and follow up of ovarian cancer. Total body planar photoscans with a scintillation camera were performed three to seven days after antibody application and results were compared with operation and/or computed tomography (CT) examination. By the region of interest technique, the tumor to background ratio was calaulated in vivo. Results are as follows. 1) The sensitivity of ISG and CT for detection of 14 tumor sites which were confirmed with histopathology were 100 % and 57.1 % and the sensitivity for the detection of omental metastasis were 100 % and 20 % respectively. 2) There were no correlation between the serum CA 125 levels and tumor to background antibody uptake ratio. 3) Tumor to background antibody uptake ratio were progressively increased from day 3 to day 7. (author)

  11. Conformational behavior of CH3OC(O)SX (X = CN and SCN) pseudohalide congeners. A combined experimental and theoretical study. (United States)

    Torrico-Vallejos, Sonia; Erben, Mauricio F; Ge, Mao-Fa; Willner, Helge; Della Védova, Carlos O


    Pure methoxycarbonylsulfenyl cyanide, CH(3)OC(O)SCN (I), and methoxycarbonylsulfenyl thiocyanate, CH(3)OC(O)SSCN (II), were prepared by reacting liquid CH(3)OC(O)SCl with either AgCN or AgSCN, respectively. Compounds I and II were characterized by (1)H NMR, CG-MS, and vibrational (FTIR and FT-Raman) techniques. The conformational properties have been studied by using vibrational spectroscopy [infrared (gaseous, liquid, and Ar matrix isolated), Raman (liquid) spectroscopy] together with quantum chemical calculations at the B3LYP and MP2 methods with the extended 6-311++G** and aug-cc-pVTZ basis sets. Compound I exhibits a conformational equilibrium at room temperature having the most stable form C(s) symmetry with a synperiplanar (syn) orientation of the carbonyl double bond (C=O) with respect to both the CH(3)O- and -SCN groups (syn-syn). Several bands assigned to a second conformer have been observed in the IR matrix spectra. This rotamer presents an antiperiplanar orientation of the thiocyanate group (syn-anti). Evaluating the equilibrium compositions at different temperatures by quenching the gas phase mixtures as Ar matrices allowed us to determine the conformational enthalpy difference DeltaH(0) = H(0)((syn-anti)) - H(0)((syn-syn)) = 0.80(18) kcal mol(-1). A similar conformational behavior has been determined for compound II. Thermodynamic properties were also computed at the high-level G2MP2 and G3 model chemistry methods. The importance of mesomeric (resonance) and anomeric (hyperconjugation) electronic interaction in the conformational behavior is evaluated by using the NBO approach for both species.

  12. JSpOC Mission System Application Development Environment (United States)

    Luce, R.; Reele, P.; Sabol, C.; Zetocha, P.; Echeverry, J.; Kim, R.; Golf, B.


    The Joint Space Operations Center (JSpOC) Mission System (JMS) is the program of record tasked with replacing the legacy Space Defense Operations Center (SPADOC) and Astrodynamics Support Workstation (ASW) capabilities by the end of FY2015 as well as providing additional Space Situational Awareness (SSA) and Command and Control (C2) capabilities post-FY2015. To meet the legacy replacement goal, the JMS program is maturing a government Service Oriented Architecture (SOA) infrastructure that supports the integration of mission applications while acquiring mature industry and government mission applications. Future capabilities required by the JSpOC after 2015 will require development of new applications and procedures as well as the exploitation of new SSA data sources. To support the post FY2015 efforts, the JMS program is partnering with the Air Force Research Laboratory (AFRL) to build a JMS application development environment. The purpose of this environment is to: 1) empower the research & development community, through access to relevant tools and data, to accelerate technology development, 2) allow the JMS program to communicate user capability priorities and requirements to the developer community, 3) provide the JMS program with access to state-of-the-art research, development, and computing capabilities, and 4) support market research efforts by identifying outstanding performers that are available to shepherd into the formal transition process. The application development environment will consist of both unclassified and classified environments that can be accessed over common networks (including the Internet) to provide software developers, scientists, and engineers everything they need (e.g., building block JMS services, modeling and simulation tools, relevant test scenarios, documentation, data sources, user priorities/requirements, and SOA integration tools) to develop and test mission applications. The developed applications will be exercised in these

  13. Microaeration reduces hydrogen sulfide in biogas (United States)

    Although there are a variety of biological and chemical treatments for removal of hydrogen sulfide (H2S) from biogas, all require some level of chemical or water inputs and maintenance. In practice, managing biogas H2S remains a significant challenge for agricultural digesters where labor and opera...


    The fate of arsenic in the environment is fundamentally linked to its speciation. Arsenic in aerobic environments is predominantly arsenate, however under reducing conditions arsenite species dominate. In anoxic or sulfidic environments thioarsenite ((As(OH)x(SH)yz-) species alon...

  15. Microbial Fuel Cells for Sulfide Removal

    NARCIS (Netherlands)

    Rabaey, K.; Sompel, van de S.; Maignien, L.; Boon, N.; Aelterman, P.; Clauwaert, P.; Schamphelaire, de L.; The Pham, H.; Vermeulen, J.; Verhaege, M.; Lens, P.N.L.; Verstraete, W.


    Thus far, microbial fuel cells (MFCs) have been used to convert carbon-based substrates to electricity. However, sulfur compounds are ubiquitously present in organic waste and wastewater. In this study, a MFC with a hexacyanoferrate cathodic electrolyte was used to convert dissolved sulfide to

  16. Support Effect in Hydrodesulfurization over Ruthenium Sulfide

    Czech Academy of Sciences Publication Activity Database

    Gulková, Daniela; Kaluža, Luděk; Vít, Zdeněk; Zdražil, Miroslav


    Roč. 51, č. 2 (2009), s. 146-149 ISSN 1337-7027 R&D Projects: GA ČR GA104/06/0705 Institutional research plan: CEZ:AV0Z40720504 Keywords : ruthenium sulfide * hydrodesulfurization * support effect Subject RIV: CC - Organic Chemistry

  17. Mitochondrial Sulfide Quinone Oxidoreductase Prevents Activation of the Unfolded Protein Response in Hydrogen Sulfide*


    Horsman, Joseph W.; Miller, Dana L.


    Hydrogen sulfide (H2S) is an endogenously produced gaseous molecule with important roles in cellular signaling. In mammals, exogenous H2S improves survival of ischemia/reperfusion. We have previously shown that exposure to H2S increases the lifespan and thermotolerance in Caenorhabditis elegans, and improves protein homeostasis in low oxygen. The mitochondrial SQRD-1 (sulfide quinone oxidoreductase) protein is a highly conserved enzyme involved in H2S metabolism. SQRD-1 is generally considere...

  18. Carbonyl Compounds Produced by Vaporizing Cannabis Oil Thinning Agents. (United States)

    Troutt, William D; DiDonato, Matthew D


    Cannabis use has increased in the United States, particularly the use of vaporized cannabis oil, which is often mixed with thinning agents for use in vaporizing devices. E-cigarette research shows that heated thinning agents produce potentially harmful carbonyls; however, similar studies have not been conducted (1) with agents that are commonly used in the cannabis industry and (2) at temperatures that are appropriate for cannabis oil vaporization. The goal of this study was to determine whether thinning agents used in the cannabis industry produce potentially harmful carbonyls when heated to a temperature that is appropriate for cannabis oil vaporization. Four thinning agents (propylene glycol [PG], vegetable glycerin [VG], polyethylene glycol 400 [PEG 400], and medium chain triglycerides [MCT]) were heated to 230°C and the resulting vapors were tested for acetaldehyde, acrolein, and formaldehyde. Each agent was tested three times. Testing was conducted in a smoking laboratory. Carbonyl levels were measured in micrograms per puff block. Analyses showed that PEG 400 produced significantly higher levels of acetaldehyde and formaldehyde than PG, MCT, and VG. Formaldehyde production was also significantly greater in PG compared with MCT and VG. Acrolein production did not differ significantly across the agents. PG and PEG 400 produced high levels of acetaldehyde and formaldehyde when heated to 230°C. Formaldehyde production from PEG 400 isolate was particularly high, with one inhalation accounting for 1.12% of the daily exposure limit, nearly the same exposure as smoking one cigarette. Because PG and PEG 400 are often mixed with cannabis oil, individuals who vaporize cannabis oil products may risk exposure to harmful formaldehyde levels. Although more research is needed, consumers and policy makers should consider these potential health effects before use and when drafting cannabis-related legislation.

  19. Determination of Carbonyl Compounds in Cigarette Mainstream Smoke. The CORESTA 2010 Collaborative Study and Recommended Method

    Directory of Open Access Journals (Sweden)

    Intorp M


    Full Text Available A recommended method has been developed and published by CORESTA, applicable to the quantification of selected carbonyl compounds (acetaldehyde, formaldehyde, acetone, acrolein, methyl ethyl ketone, crotonaldehyde, propionaldehyde and butyraldehyde in cigarette mainstream smoke. The method involved smoke collection in impinger traps, derivatisation of carbonyls with 2,4-dinitrophenylhydrazine (DNPH, separation of carbonyl hydrazones by reversed phase high performance liquid chromatography and detection by ultra violet or diode array.

  20. Platinum and Palladium Exsolution Textures in Quenched Sulfide Melts (United States)

    Reo, G.; Frank, M. R.; Loocke, M. P.; Macey, C. J.


    Magmatic sulfide ore deposits account for over 80% of the world's platinum group element (PGE) reserves. Layered mafic intrusions (LMIs), a type of magmatic sulfide ore deposit, contain alternating layers of silicate and sulfide mineralization that are thought to have coexisted as an immiscible silicate + sulfide melt pair. Platinum and palladium, the most common PGEs found in LMIs, heavily favor the sulfide melt. Nernst partition coefficients for Pt (D = wt% of Pt in sulfide/wt% of Pt in silicate) range from 102 to 109. This study examined the Pt- and Pd-bearing phases that formed from the quenched sulfide melts to better constrain the PGE-rich sulfide layers of LMIs system. Experiments were conducted with a basalt melt, sulfide melt, and Pt-Pd metal in a vertical tube furnace at 1100°C and 1 atm and with oxygen fugacity buffered to QFM (quartz-fayalite-magnetite). Following the experiments, run products containing both sulfide and silicate glasses (quenched melts) were analyzed by a Shimadzu EPMA-1720HT Electron Probe Microanalyzer. The focus here is on the quenched Fe-rich sulfides whereas data on the partitioning of Pt and Pd between the coexisting silicate and sulfide melts will be presented in the future. The sulfide samples were imaged in back-scattering mode and major and trace element concentrations of separate metal-rich phases in the sulfide matrix were ascertained through wavelength-dispersive x-ray spectroscopy. Three discernable PGE-rich phases were found to have exsolved from the sulfide matrix upon quenching of the sulfide melt. All of these phases had Fe and S of 21-24 and 16-22 wt.%, respectively. An irregularly shaped Pd- and Cu-rich sulfide phase ( 36 and 14 wt.%, respectively) makes up the majority of the exsolution product. A separate Pd- and Ni-rich phase ( 22 and 14 wt%, respectively) can be found as grains or rims adjacent to the exsolved Pd- and Cu-rich phase. A third Pd- and Pt-rich phase ( 26 and 18 wt.%, respectively) exhibits a

  1. Preparation and magnetorheological characteristics of polymer coated carbonyl iron suspensions

    International Nuclear Information System (INIS)

    Choi, J.S.; Park, B.J.; Cho, M.S.; Choi, H.J.


    Core-shell structured magnetic carbonyl iron (CI)-poly(methyl methacrylate) (PMMA) particles were fabricated via CI-seeded dispersion polymerization method, in order to enhance dispersion stability of their magnetorheological (MR) fluid when dispersed in mineral oil. The rheological properties of MR fluid with core-shell structured magnetic particles were then measured via a rotational rheometer with a magnetic field generator. It was found that the synthesized core-shell structured encapsulated CI particles possess better dispersion stability in suspending oil than bare CI particle suspension, due to the density reduction of the particles

  2. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.


    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak Cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetoacetonitrile. Three different types of samples (rural, urban, petrol emission) were successfully analyzed. (Author) 12 refs

  3. Determination of carbonyl compounds in air by HPLC

    International Nuclear Information System (INIS)

    Garcia, S.; Perez, R.M.; Campos, A.; Gonzalez, D.


    A method for the determination of seven carbonyl compounds in air is presented. The procedure involve sampling of air by a Sep-Pak cartridge impregnated with 2,4-dinitrophenylhydrazine. Elution was done with 3 mL of acetonitrile and the eluate was diluted to 5 mL. The analysis was done by HPLC with UV detection and external standard method quantification. It has been achieved relative standard deviations about 5% and detection limits of 80 ng/cartridge for formaldehyde, acetaldehyde and acetone+acrolein. Three different types of samples (rural, urban, petrol emission) were successfully analyzed

  4. A Carbonyl Compound-Based Flexible Cathode with Superior Rate Performance and Cyclic Stability for Flexible Lithium-Ion Batteries. (United States)

    Amin, Kamran; Meng, Qinghai; Ahmad, Aziz; Cheng, Meng; Zhang, Miao; Mao, Lijuan; Lu, Kun; Wei, Zhixiang


    A sulfur-linked carbonyl-based poly(2,5-dihydroxyl-1,4-benzoquinonyl sulfide) (PDHBQS) compound is synthesized and used as cathode material for lithium-ion batteries (LIBs). Flexible binder-free composite cathode with single-wall carbon nanotubes (PDHBQS-SWCNTs) is then fabricated through vacuum filtration method with SWCNTs. Electrochemical measurements show that PDHBQS-SWCNTs cathode can deliver a discharge capacity of 182 mA h g -1 (0.9 mA h cm -2 ) at a current rate of 50 mA g -1 and a potential window of 1.5 V-3.5 V. The cathode delivers a capacity of 75 mA h g -1 (0.47 mA h cm -2 ) at 5000 mA g -1 , which confirms its good rate performance at high current density. PDHBQS-SWCNTs flexible cathode retains 89% of its initial capacity at 250 mA g -1 after 500 charge-discharge cycles. Furthermore, large-area (28 cm 2 ) flexible batteries based on PDHBQS-SWCNTs cathode and lithium foils anode are also assembled. The flexible battery shows good electrochemical activities with continuous bending, which retains 88% of its initial discharge capacity after 2000 bending cycles. The significant capacity, high rate performance, superior cyclic performance, and good flexibility make this material a promising candidate for a future application of flexible LIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Carbonylated plasma proteins as potential biomarkers of obesity induced type 2 diabetes mellitus. (United States)

    Bollineni, Ravi Chand; Fedorova, Maria; Blüher, Matthias; Hoffmann, Ralf


    Protein carbonylation is a common nonenzymatic oxidative post-translational modification, which is often considered as biomarker of oxidative stress. Recent evidence links protein carbonylation also to obesity and type 2 diabetes mellitus (T2DM), though the protein targets of carbonylation in human plasma have not been identified. In this study, we profiled carbonylated proteins in plasma samples obtained from lean individuals and obese patients with or without T2DM. The plasma samples were digested with trypsin, carbonyl groups were derivatized with O-(biotinylcarbazoylmethyl)hydroxylamine, enriched by avidin affinity chromatography, and analyzed by RPC-MS/MS. Signals of potentially modified peptides were targeted in a second LC-MS/MS analysis to retrieve the peptide sequence and the modified residues. A total of 158 unique carbonylated proteins were identified, of which 52 were detected in plasma samples of all three groups. Interestingly, 36 carbonylated proteins were detected only in obese patients with T2DM, whereas 18 were detected in both nondiabetic groups. The carbonylated proteins originated mostly from liver, plasma, platelet, and endothelium. Functionally, they were mainly involved in cell adhesion, signaling, angiogenesis, and cytoskeletal remodeling. Among the identified carbonylated proteins were several candidates, such as VEGFR-2, MMP-1, argin, MKK4, and compliment C5, already connected before to diabetes, obesity and metabolic diseases.

  6. A biotin enrichment strategy identifies novel carbonylated amino acids in proteins from human plasma

    DEFF Research Database (Denmark)

    Havelund, Jesper F; Wojdyla, Katarzyna Iwona; Davies, Michael J


    preparation and chromatography. For the first time MS/MS data analysis utilising diagnostic biotin fragment ions is used to pinpoint sites of biotin labelling and improve the confidence of carbonyl peptide assignments. We identified a total of 125 carbonylated residues in bovine serum albumin after extensive...... at the protein level and help to understand how carbonylation affects protein structure and function. The challenge for future research is to identify the type and nature of oxidised residues to gain a deeper understanding of the mechanism(s) governing carbonylation in cells and organisms and assess their role...

  7. Ruthenium(ii)-catalyzed olefination via carbonyl reductive cross-coupling. (United States)

    Wei, Wei; Dai, Xi-Jie; Wang, Haining; Li, Chenchen; Yang, Xiaobo; Li, Chao-Jun


    Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO t Bu and bidentate phosphine dmpe is vital to this transformation.

  8. Thermal-Conductivity Studies of Macro-porous Polymer-Derived SiOC Ceramics (United States)

    Qiu, L.; Li, Y. M.; Zheng, X. H.; Zhu, J.; Tang, D. W.; Wu, J. Q.; Xu, C. H.


    A three-dimensional reticular macro-porous SiOC ceramics structure, made of spherical agglomerates, has been thermally characterized using a freestanding sensor-based method. The effective thermal conductivity of the macro-porous SiOC ceramics, including the effects of voids, is found to be to at room temperature, comparable with that of alumina aerogel or carbon aerogel. These results suggest that SiOC ceramics hold great promise as a thermal insulation material for use at high temperatures. The measured results further reveal that the effective thermal conductivity is limited by the low solid-phase volume fraction for the SiOC series processed at the same conditions. For SiOC ceramics processed under different pyrolysis temperatures, the contact condition between neighboring particles in the SiOC networks is another key factor influencing the effective thermal conductivity.

  9. Oxidation and Precipitation of Sulfide in Sewer Networks

    DEFF Research Database (Denmark)

    Nielsen, A. H.

    (Fe(II)) and precipitated subsequently with dissolved sulfide as ferrous sulfide (FeS). The ferrous sulfide precipitation was relatively fast, but not immediate. Despite the very low solubility of ferrous sulfide, initially present iron did not react completely with sulfide. This observation...... were studied in both wastewater and biofilms. Particular emphasis was on the importance of iron in the sulfur cycle. Iron is typically among the dominant metals in wastewater. The experiments showed that, ferric iron (Fe(III)) that was added to anaerobic wastewater was rapidly reduced to ferrous iron...... was probably explained by the presence of ligands in the wastewater, which reacted with the iron. The biofilm experiments showed that sulfide accumulated along with several metals in anaerobic biofilms as the result of metal sulfide precipitation. Particularly, zinc and cupper were important...

  10. Electrochemical Synthesis and Characterization of Zinc Sulfide Nanoparticles

    Directory of Open Access Journals (Sweden)

    M. Rahimi-Nasarabadi


    Full Text Available Electrosynthesis process has been used for preparation of zinc sulfide nanoparticles. Zinc sulfide nanoparticles in different size and shapes were electrodeposited by electrolysis of zinc plate as anode in sodium sulfide solution. Effects of several reaction variables, such as electrolysis voltage, sulfide ion concentration as reactant, stirring rate of electrolyte solution and temperature on particle size of prepared zinc sulfide were investigated. The significance of these parameters in tuning the size of zinc sulfide particles was quantitatively evaluated by analysis of variance (ANOVA. Also, optimum conditions for synthesis of zinc sulfide nanoparticles via electrosynthesis reaction were proposed. The structure and composition of prepared nanoparticles under optimum condition was characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, transmission electron microscopy (TEM, and UV-Vis spectrophotometry techniques.

  11. Hydrocracking of Calophyllum inophyllum Oil With Non-sulfide CoMo Catalysts

    Directory of Open Access Journals (Sweden)

    Rismawati Rasyid


    Full Text Available This research was aimed to convert Calophyllum inophyllum kernel oil into liquid fuel through hydro-cracking process using non-sulfide CoMo catalysts. The experiment was carried out in a pressurized re-actor operated at temperature and pressure up to 350 oC and 30 bar, respectively. The CoMo catalysts used in the experiment were prepared by 10 wt.% loading of cobalt and molybdenum solutions over various supports, i.e. γ-Al2O3, SiO2, and γ-Al2O3-SiO2 through impregnation method. It is figured out from the experiment that non-sulfide CoMo based catalysts have functioned well in the hydrocracking conversion of Calophyllum inophyllum kernel oil into fuels, such as gasoline, kerosene, and gasoil. The CoMo/γ-Al2O3 catalyst resulted higher conversion than CoMo/SiO2 and CoMo/γ-Al2O3-SiO2. The fuel yields were 25.63% gasoline, 17.31% kerosene, and 38.59% gasoil. The fuels obtained in this research do not contain sulfur compounds so that they can be categorized as environmentally friendly fuels. © 2015 BCREC UNDIP. All rights reservedReceived: 24th March 2014; Revised: 25th November 2014; Accepted: 26th November 2014How to Cite: Rasyid, R., Prihartantyo, A., Mahfud, M., Roesyadi, A. (2015. Hydrocracking of Calophyllum inophyllum Oil With Non-sulfide CoMo Catalysts. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 61-69. (doi:10.9767/bcrec.10.1.6597.61-69Permalink/DOI:

  12. trans-Di-μ-carbonyl-bis{carbonyl[η5-2,3,4,5-tetramethyl-1-(5-methyl-2-furylcyclopentadienyl]ruthenium(I}(Ru—Ru

    Directory of Open Access Journals (Sweden)

    Jin Lin


    Full Text Available In the crystal structure of the title compound, [Ru2(C14H17O2(CO4], each RuI atom is connected to one end-on and two bridging carbonyl groups and one cyclopentadienyl ring. The two Ru atoms are connected into binuclear complexes via two bridging carbonyl groups, forming four-membered rings which are located on centres of inversion. The Ru—Ru distance of 2.7483 (11 Å corresponds to a single bond. The two carbonyl groups in these binuclear complexes are trans-oriented.

  13. Cadmium zinc sulfide by solution growth (United States)

    Chen, Wen S.


    A process for depositing thin layers of a II-VI compound cadmium zinc sulfide (CdZnS) by an aqueous solution growth technique with quality suitable for high efficiency photovoltaic or other devices which can benefit from the band edge shift resulting from the inclusion of Zn in the sulfide. A first solution comprising CdCl.sub.2 2.5H.sub.2 O, NH.sub.4 Cl, NH.sub.4 OH and ZnCl.sub.2, and a second solution comprising thiourea ((NH.sub.2).sub.2 CS) are combined and placed in a deposition cell, along with a substrate to form a thin i.e. 10 nm film of CdZnS on the substrate. This process can be sequentially repeated with to achieve deposition of independent multiple layers having different Zn concentrations.

  14. Iron-sulfide redox flow batteries (United States)

    Xia, Guan-Guang; Yang, Zhenguo; Li, Liyu; Kim, Soowhan; Liu, Jun; Graff, Gordon L


    Iron-sulfide redox flow battery (RFB) systems can be advantageous for energy storage, particularly when the electrolytes have pH values greater than 6. Such systems can exhibit excellent energy conversion efficiency and stability and can utilize low-cost materials that are relatively safer and more environmentally friendly. One example of an iron-sulfide RFB is characterized by a positive electrolyte that comprises Fe(III) and/or Fe(II) in a positive electrolyte supporting solution, a negative electrolyte that comprises S.sup.2- and/or S in a negative electrolyte supporting solution, and a membrane, or a separator, that separates the positive electrolyte and electrode from the negative electrolyte and electrode.

  15. Layered metal sulfides capture uranium from seawater. (United States)

    Manos, Manolis J; Kanatzidis, Mercouri G


    Uranium is the main source for nuclear energy but also one of the most toxic heavy metals. The current methods for uranium removal from water present limitations, such as narrow pH operating range, limited tolerance to high salt concentrations, or/and high cost. We show here that a layered sulfide ion exchanger K(2)MnSn(2)S(6) (KMS-1) overcomes these limitations and is exceptionally capable in selectively and rapidly sequestering high (ppm) as well as trace (ppb) quantities of UO(2)(2+) under a variety of conditions, including seawater. KMS-1 can efficiently absorb the naturally occurring U traces in seawater samples. The results presented here reveal the exceptional potential of sulfide-based ion-exchangers for remediating of uranium-containing wastes and groundwater and for extracting uranium from the sea.

  16. Ferrocene sulfonates as electrocatalysts for sulfide detection

    International Nuclear Information System (INIS)

    Lawrence, Nathan S.; Tustin, Gary J.; Faulkner, Michael; Jones, Timothy G.J.


    The electrochemical characterization of both the mono- and di-substituted forms of ferrocene sulfonate are given. The results show both species produce voltammograms consistent with quasi-irreversible diffusion controlled redox reactions. The FcSO 3 - species was found to be easier to oxidize than its Fc(SO 3 ) 2 2- counterpart, due to the electron withdrawing affect of the sulfonate group on the Fe centre. In the presence of sulfide, the voltammetric response of FcSO 3 - is shown to be consistent with the occurrence of an electrocatalytic EC' reaction. This analytical response was utilized as a means of determining sulfide and was found to be linear over the concentration 0.02-1 mM with a limit of detection of 14 μM

  17. Preparation and microwave shielding property of silver-coated carbonyl iron powder

    International Nuclear Information System (INIS)

    Cao, Xiao Guo; Ren, Hao; Zhang, Hai Yan


    Highlights: • The silver-coated carbonyl iron powder is prepared by the electroless plating process. • The silver-coated carbonyl iron powder is a new kind of conductive filler. • The reflection and absorption dominate the shielding mechanism of the prepared powder. • Increasing the thickness of electroconductive adhesive will increase the SE. - Abstract: Electroless silver coating of carbonyl iron powder is demonstrated in the present investigation. The carbonyl iron powders are characterized by scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction analysis (XRD) before and after the coating process. The relatively uniform and continuous silver coating is obtained under the given coating conditions. In this paper, the electromagnetic interference (EMI) shielding mechanism of the silver-coated carbonyl iron powder is suggested. The reflection of silver coating and absorption of carbonyl iron powder dominate the shielding mechanism of the silver-coated carbonyl iron powder. The silver-coated carbonyl iron powders are used as conductive filler in electroconductive adhesive for electromagnetic interference shielding applications. The effect of the thickness of electroconductive adhesive on the shielding effectiveness (SE) is investigated. The results indicate that the SE increases obviously with the increase of the thickness of electroconductive adhesive. The SE of the electroconductive adhesive with 0.35 mm thickness is above 38 dB across the tested frequency range

  18. Quantification of airborne fossil and biomass carbonylic carbon by combined radiocarbon and liquid chromatography mass spectrometry (United States)

    Larsen, B. R.; Tudos, A.; Slanina, J.; Van der Borg, K.; Kotzias, D.

    Airborne carbonyl compounds have been sampled at three European semi-remote to semi-urban test sites for radiocarbon ( 14C) analysis. The used methodology included collection on 2,4-dinitrophenylhydrazine coated silica gel cartridges, chromatographic isolation of the formed hydrazones, combustion into CO 2, reduction into graphite followed by accelerator mass spectrometry. In combination with this, liquid chromatography coupled to atmospheric pressure chemical ionisation mass spectrometry was used for chemical speciation of the collected carbonyls. At all sites the carbonyls were found to be of a mixed biogenic/anthropogenic origin. The determining factor for the proportion of fossil (anthropogenic) carbon in the samples was the vicinity of urban sources for carbonyls and their photochemical precursors. At meteorological conditions, which gave the test sites semi-rural/semi-remote characteristics the samples contained an average of 24% (range: 10-34%) of fossil carbonylic carbon. When air masses were transported from urban areas to the test-sites significantly higher proportions of fossil carbonylic carbon were determined with a maximum of 61%. Principal component analysis on this limited data set indicated that a low fossil proportion of carbonylic carbon is associated with high proportions of acetaldehyde, acetone, pentanone and acrolein. Until further radicarbon studies are carried out the conclusion remains that for the carbonyl compounds measured European background levels are of a predominant biogenic origin.

  19. Iron(III)-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis. (United States)

    Saá, Carlos


    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Protein carbonyl content: a novel biomarker for aging in HIV/AIDS patients

    Directory of Open Access Journals (Sweden)

    Vaishali Kolgiri


    Conclusions: Carbonyl content may has a role as a biomarker for detecting oxidative DNA damage induced ART toxicity and/or accelerated aging in HIV/AIDS patients. Larger studies are warranted to elucidate the role of carbonyl content as a biomarker for premature aging in HIV/AIDS patients.

  1. Comparison of carbonyl compounds emissions from diesel engine fueled with biodiesel and diesel (United States)

    He, Chao; Ge, Yunshan; Tan, Jianwei; You, Kewei; Han, Xunkun; Wang, Junfang; You, Qiuwen; Shah, Asad Naeem

    The characteristics of carbonyl compounds emissions were investigated on a direct injection, turbocharged diesel engine fueled with pure biodiesel derived from soybean oil. The gas-phase carbonyls were collected by 2,4-dinitrophenylhydrazine (DNPH)-coated silica cartridges from diluted exhaust and analyzed by HPLC with UV detector. A commercial standard mixture including 14 carbonyl compounds was used for quantitative analysis. The experimental results indicate that biodiesel-fueled engine almost has triple carbonyls emissions of diesel-fueled engine. The weighted carbonyls emission of 8-mode test cycle of biodiesel is 90.8 mg (kW h) -1 and that of diesel is 30.7 mg (kW h) -1. The formaldehyde is the most abundant compound of carbonyls for both biodiesel and diesel, taking part for 46.2% and 62.7% respectively. The next most significant compounds are acetaldehyde, acrolein and acetone for both fuels. The engine fueled with biodiesel emits a comparatively high content of propionaldehyde and methacrolein. Biodiesel, as an alternative fuel, has lower specific reactivity (SR) caused by carbonyls compared with diesel. When fueled with biodiesel, carbonyl compounds make more contribution to total hydrocarbon emission.

  2. One-pot Reductive Amination of Carbonyl Compounds with NaBH4 ...

    Indian Academy of Sciences (India)

    product. Another problem during reductive amination of carbonyl compounds with primary amines is over- alkylation and direct reduction of carbonyl compound to the corresponding alcohol. In these cases, formation and isolation of the imines which followed by reduction can avoid the problem, but the need to isolate imines.

  3. Various communications concerning sulfigran (sodium sulfide)

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, H.; Montfort, F.; Wickert; Horn; Junkermann; Wissel, K.; Pier, M.


    Most of these communications concerned the problems experienced by Poelitz when its regular supplier of Sulfigran (sodium sulfide), the I.G. Farbenindustrie plant at Luverkusen, had to shut down for repairs and Poelitz had to get an impure form of Sulfigran mixture (a crude melt of ore) from other suppliers, including the I.G. Farbenindustrie plant at Wolfen (Bitterfeld). Various problems arose in the transition, including the fact that the mixture supplied was not ground finely enough for the coal-paste-preparing machinery at Poelitz to handle without damage. An analysis of one sample of the raw melt mixture gave 68.8% sodium sulfide, 12.0% carbon, 1.5% hydrogen, 1.6% silicon dioxide, 1.8% iron, 1.0% aluminum, 0.6% calcium, traces of magnesium and sulfate, and 15.4% water-insoluble. An analysis for another sample showed about 1.8% less sodium sulfide, 1.5% more silicon dioxide, 0.7% less iron, 0.5% less aluminum, 0.6% more calcium, etc., than the previous analysis. Finally one of the communications was a letter in which Ludwigshafen responded favorably to Poelitz's question about whether it would be advantageous to add Sulfigran directly to the first oven of a hydrogenation chamber instead of grinding it with the coal paste. Ludwigshafen said that in some experiments it had observed deposits at places where Sulfigran and coal paste encountered each other in preheater tubes. The deposits consisted of sodium sulfide and iron compounds. 3 tables.

  4. Hydrogen sulfide prodrugs—a review

    Directory of Open Access Journals (Sweden)

    Yueqin Zheng


    Full Text Available Hydrogen sulfide (H2S is recognized as one of three gasotransmitters together with nitric oxide (NO and carbon monoxide (CO. As a signaling molecule, H2S plays an important role in physiology and shows great potential in pharmaceutical applications. Along this line, there is a need for the development of H2S prodrugs for various reasons. In this review, we summarize different H2S prodrugs, their chemical properties, and some of their potential therapeutic applications.

  5. Single-layer transition metal sulfide catalysts (United States)

    Thoma, Steven G [Albuquerque, NM


    Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

  6. Sulfide Precipitation in Wastewater at Short Timescales

    DEFF Research Database (Denmark)

    Kiilerich, Bruno; van de Ven, Wilbert; Nielsen, Asbjørn Haaning


    that this is not the case for sulfide precipitation by ferric iron. Instead, the reaction time was found to be on a timescale where it must be considered when performing end-of-pipe treatment. For real wastewaters at pH 7, a stoichiometric ratio around 14 mol Fe(II) (mol S(−II))−1 was obtained after 1.5 s, while the ratio...

  7. Kinetics of reversible reductive carbonylation of heme in human cystathionine β-synthase. (United States)

    Carballal, Sebastián; Cuevasanta, Ernesto; Marmisolle, Inés; Kabil, Omer; Gherasim, Carmen; Ballou, David P; Banerjee, Ruma; Alvarez, Beatriz


    Cystathionine β-synthase (CBS) catalyzes the condensation of homocysteine with serine or cysteine to form cystathionine and water or hydrogen sulfide (H2S), respectively. In addition to pyridoxal phosphate, human CBS has a heme cofactor with cysteine and histidine as ligands. While Fe(III)-CBS is inert to exogenous ligands, Fe(II)-CBS can be reversibly inhibited by carbon monoxide (CO) and reoxidized by O2 to yield superoxide radical. In this study, we have examined the kinetics of Fe(II)CO-CBS formation and reoxidation. Reduction of Fe(III)-CBS by dithionite showed a square root dependence on concentration, indicating that the reductant species was the sulfur dioxide radical anion (SO2(•-)) that exists in rapid equilibrium with S2O4(2-). Formation of Fe(II)CO-CBS from Fe(II)-CBS and 1 mM CO occurred with a rate constant of (3.1 ± 0.4) × 10(-3) s(-1) (pH 7.4, 25 °C). The reaction of Fe(III)-CBS with the reduced form of the flavoprotein methionine synthase reductase in the presence of CO and NADPH resulted in its reduction and carbonylation to form Fe(II)CO-CBS. Fe(II)-CBS was formed as an intermediate with a rate constant of (9.3 ± 2.5) × 10(2) M(-1) s(-1). Reoxidation of Fe(II)CO-CBS by O2 was multiphasic. The major phase showed a hyperbolic dependence on O2 concentration. Although H2S is a product of the CBS reaction and a potential heme ligand, we did not find evidence of an effect of exogenous H2S on activity or heme binding. Reversible reduction of CBS by a physiologically relevant oxidoreductase is consistent with a regulatory role for the heme and could constitute a mechanism for cross talk among the CO, H2S, and superoxide signaling pathways.

  8. Reactions of rhodium(I) carbonyl chloride with olefins

    International Nuclear Information System (INIS)

    Varshavskii, Yu.S.; Kiseleva, N.V.; Cherkasova, T.G.; Buzina, N.A.; Bresler, L.S.


    The reactions of [Rh(CO) 2 Cl] 2 (Y 0 ) with cyclooctene and several other olefins (1-heptene, 1-hexene, ethylene, and cyclohexene) have been studied by IR and 13 C NMR spectroscopy. The main reaction products are the binuclear complexes Rh 2 L(CO) 3 Cl 2 (Y 1 ) and [RhL(CO)Cl] 2 (Y 2 ), where L denotes the olefin. The extent of replacement of the carbonyl groups depends on the nature of the olefin and the conditions under which the reaction is carried out (the L:Rh ratio and the removal of CO from the reaction sphere). The liquid olefins form the following series according to their ability to replace the carbonyl groups: C 8 H 14 > C 7 H 14 , C 6 H 12 > C 6 H 10 . In the presence of an excess of C 8 H 14 , Y 2 disproportionates with the formation of a dicarbonyl product, which presumably corresponds to the formula Rh(C 8 H 14 ) 2 (CO) 2 Cl (a pentacoordinate complex with a trigonal-bipyramidal structure). The 13 C signal in the NMR spectrum of a solution of Y 2 in C 8 H 14 is a singlet with σ( 13 C) 180.3 ppm, which is an indication of the rapid exchange of the carbonyl groups. Rapid exchange of the CO ligands is also observed in solutions of Y 0 in the olefins (with the exception of C 6 H 10 ). For example, the 13 C signal in the spectrum of a solution of Y 0 in C 8 H 14 is a singlet with σ( 13 C) 179.8 ppm. The spectrum of Y 0 in C 6 H 10 is a doublet with σ( 13 C) = 178.5 ppm and 1 J(CRh) = 76.3 Hz. A scheme for the interaction of Y 0 with olefins based on the conception of the trans antagonism of π-acceptor ligands has been proposed

  9. Development of an automatic sampling device for the continuous measurement of atmospheric carbonyls compounds

    International Nuclear Information System (INIS)

    Perraud, V.


    Two sampling strategies were studied to develop an automatic instrument for the continuous measurement of atmospheric carbonyl compounds. Because of its specificity towards carbonyls compounds, sampling by using a transfer of gaseous phase in a liquid phase associated with a simultaneous chemical derivatization of the trapped compounds was first studied. However, this method do not allow a quantitative sampling of all studied carbonyl compounds, nor a continuous measurement in the field. To overcome the difficulties, a second strategy was investigated: the cryogenic adsorption onto solid adsorbent followed by thermodesorption and a direct analysis by GC/MS. Collection efficiency using different solid adsorbents was found greater than 95% for carbonyl compounds consisting of 1 to 7 carbons. This work is a successful first step towards the realization of the automatic sampling device for a continuous measurement of atmospheric carbonyls compounds. (author)

  10. Protein carbonylation and metal-catalyzed protein oxidation in a cellular perspective

    DEFF Research Database (Denmark)

    Møller, Ian Max; Rogowska-Wrzesinska, Adelina; Rao, Shyama Prasad


    Proteins can become oxidatively modified in many different ways, either by direct oxidation of amino acid side chains and protein backbone or indirectly by conjugation with oxidation products of polyunsaturated fatty acids and carbohydrates. While reversible oxidative modifications are thought...... to be relevant in physiological processes, irreversible oxidative modifications are known to contribute to cellular damage and disease. The most well-studied irreversible protein oxidation is carbonylation. In this work we first examine how protein carbonylation occurs via metal-catalyzed oxidation (MCO) in vivo...... and in vitro with an emphasis on cellular metal ion homeostasis and metal binding. We then review proteomic methods currently used for identifying carbonylated proteins and their sites of modification. Finally, we discuss the identified carbonylated proteins and the pattern of carbonylation sites in relation...

  11. [Size distributions of organic carbon (OC) and elemental carbon (EC) in Shanghai atmospheric particles]. (United States)

    Wang, Guang-Hua; Wei, Nan-Nan; Liu, Wei; Lin, Jun; Fan, Xue-Bo; Yao, Jian; Geng, Yan-Hong; Li, Yu-Lan; Li, Yan


    Size distributions of organic carbon (OC), elemental carbon (EC) and secondary organic carbon (SOC) in atmospheric particles with size range from 7.20 microm, collected in Jiading District, Shanghai were determined. For estimating size distribution of SOC in these atmospheric particles, a method of determining (OC/EC)(pri) in atmospheric particles with different sizes was discussed and developed, with which SOC was estimated. According to the correlation between OC and EC, main sources of the particles were also estimated roughly. The size distributions of OC and SOC showed a bi-modal with peaks in the particles with size of 3.0 microm, respectively. EC showed both of a bi-modal and tri-modal. Compared with OC, EC was preferably enriched in particles with size of 3.00 microm) accounted for 41.4% and 43.5% of corresponding OC. Size distributions of OC, EC and SOC showed time-dependence. The correlation between OC and EC showed that the main contribution to atmospheric particles in Jiading District derived from light petrol vehicles exhaust.

  12. Determination of the dipole moment of OCS with a microwave absorption cavity

    NARCIS (Netherlands)

    Dijkerman, H.A.; Ruitenberg, G.

    The electric dipole moment of OCS has been measured with a resonance cavity as a Stark absorption cell. The result: μOCS = 0.7149 ± 0.0003. Debye agrees well with the dipole moment data obtained with an electric resonance beam experiment.

  13. 46 CFR 35.20-40 - Maneuvering characteristics-T/OC. (United States)


    ... 46 Shipping 1 2010-10-01 2010-10-01 false Maneuvering characteristics-T/OC. 35.20-40 Section 35.20-40 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY TANK VESSELS OPERATIONS Navigation § 35.20-40 Maneuvering characteristics—T/OC. For each ocean and coastwise tankship of 1,600 gross tons or...

  14. Definition of the Semisubmersible Floating System for Phase II of OC4

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, A.; Jonkman, J.; Masciola, M.; Song, H.; Goupee, A.; Coulling, A.; Luan, C.


    Phase II of the Offshore Code Comparison Collaboration Continuation (OC4) project involved modeling of a semisubmersible floating offshore wind system as shown below. This report documents the specifications of the floating system, which were needed by the OC4 participants for building aero-hydro-servo-elastic models.

  15. OCLI-023, a Novel Pyrimidine Compound, Suppresses Osteoclastogenesis In Vitro and Alveolar Bone Resorption In Vivo.

    Directory of Open Access Journals (Sweden)

    Hye Jung Ihn

    Full Text Available An abnormal increase in osteoclast differentiation and activation results in various bone-resorptive diseases, including periodontitis, rheumatoid arthritis, and osteoporosis. Chemical compounds containing pyrimidine ring have been shown to regulate a variety of biological processes. Therefore, in order to identify an antiresorptive agent, we synthesized a series of pyrimidine ring-containing chemical compounds, and found that OCLI-023 suppressed the differentiation and activation of osteoclasts in vitro. OCLI-023 directly inhibited receptor activator of nuclear factor-κB ligand (RANKL-induced differentiation of bone marrow macrophages into osteoclasts, without a cytotoxic response. OCLI-023 also downregulated the RANKL-induced mRNA expression of osteoclast markers as well as inhibited the formation of actin rings and resorption pits. OCLI-023 attenuated the RANKL-induced activation of c-Jun N-terminal kinase and nuclear factor kappa-light-chain-enhancer of activated B cell signaling pathways. In a mouse model of periodontitis, ligature induced an increase of distance between cementoenamel junction (CEJ and alveolar bone crest (ABC in the second molar, and OCLI-023 significantly reduced it. Histological analysis showed ligature-induced increase of osteoclast numbers was also significantly reduced by OCLI-023. These data demonstrated the inhibitory effect of OCLI-023 on osteoclast differentiation and activity of osteoclasts in vitro, as well as on ligature-induced bone loss in vivo, and OCLI-023 can be proposed as a novel anti-resorptive compound.

  16. Definition of the Floating System for Phase IV of OC3

    Energy Technology Data Exchange (ETDEWEB)

    Jonkman, J.


    Phase IV of the IEA Annex XXIII Offshore Code Comparison Collaboration (OC3) involves the modeling of an offshore floating wind turbine. This report documents the specifications of the floating system, which are needed by the OC3 participants for building aero-hydro-servo-elastic models.

  17. Improvement of coverage and utilization of EmOC services in southwestern Bangladesh. (United States)

    Islam, M T; Hossain, M M; Islam, M A; Haque, Y A


    The Government of Bangladesh has implemented safe motherhood programs throughout the country supported by the United Nations Children's Fund (UNICEF) and United Nations Population Fund (UNFPA) aimed at reducing maternal morbidity and mortality. The objective of this study is to assess the effect of the interventions on the UN emergency obstetric care (EmOC) process indicators in Khulna division, Bangladesh. Of the 71 government health facilities in Khulna division, 32 were providing comprehensive and 20 were providing basic EmOC services. Another 4 facilities were providing comprehensive or basic EmOC services during the first three-quarters but became non-functional during the last quarter. EmOC data, from January to December 2002, were collected from all these 56 facilities to determine the levels of EmOC process indicators relative to the UN guidelines and compared with baseline data from 1998 to 1999. There were 1.04 and 0.64 comprehensive and basic EmOC facilities respectively per 500,000 population. When compared with the baseline data, the coverage of comprehensive EmOC services was substantially increased from 0.23 to 1.04 per 500,000 population, which achieves the minimum UN standards but the coverage of basic EmOC services remained the same. The data also showed that, compared with the baseline survey, the proportion of births at the EmOC facilities increased 119% from 5.3% to 11.7% (pEmOC after the interventions, there was significant improvement in all the EmOC process indicators in Khulna division. However, most of the process indicators are still far from the minimum recommended UN standards. Efforts should continue to keep the EmOC facilities functional 24/7 while increasing the number of basic EmOC facilities, and improving utilization of services to reach the minimum UN standards. Community mobilization should be directed to understand the danger signs and utilization of services at functional facilities when necessary. Further research to identify

  18. A method of detecting carbonyl compounds in tree leaves in China. (United States)

    Huang, Juan; Feng, Yanli; Fu, Jiamo; Sheng, Guoying


    Carbonyl compounds have been paid more and more attention because some carbonyl species have been proven to be carcinogenic or a risk for human health. Plant leaves are both an important emission source and an important sink of carbonyl compounds. But the research on carbonyl compounds from plant leaves is very scarce. In order to make an approach to the emission mechanism of plant leaves, a new method was established to extract carbonyl compounds from fresh plant leaves. The procedure combining derivatization with ultrasonication was developed for the fast extraction of carbonyl compounds from tree leaves. Fresh leaves (trees, i.e., camphor tree (Cinnamomum camphora), sweet olive (Osmanthus fragrans), cedar (Cedrus deodara), and dawn redwood (Metasequoia glyptostroboides), were selected and extracted by this method. Seven carbonyl compounds, including formaldehyde, acetaldehyde, acetone, acrolein, p-tolualdehyde, m/o-tolualdehyde, and hexaldehyde were determined and quantified. The most common carbonyl species of the four tree leaves were formaldehyde, acrolein, and m/o-tolualdehyde. They accounted for 67.3% in cedar, 50.8% in sweet olive, 45.8% in dawn redwood, and 44.6% in camphor tree, respectively. Camphor tree had the highest leaf level of m/o-tolualdehyde with 15.0 +/- 3.4 microg g(-1)(fresh leaf weight), which indicated that camphor tree may be a bioindicator of the level of tolualdehyde or xylene in the atmosphere. By analyzing carbonyl compounds from different tree leaves, it is not only helpful for further studying the relationship between sink and emission of carbonyls from plants, but also helpful for exploring optimum plant population in urban greening.

  19. SILP catalysis in gas-phase hydroformylation and carbonylation

    Energy Technology Data Exchange (ETDEWEB)

    Riisager, A.; Fehrmann, R. [Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Haumann, M.; Wasserscheid, P. [Univ. Erlangen-Nuernberg (Germany). Lehrstuhl fuer Chemische Reaktionstechnik


    Supported ionic liquid phase (SILP) catalysts are new materials consisting of an ionic liquid-metal catalyst solution highly dispersed on a porous support. The use of a non-volatile, ionic liquid catalyst phase in SILP catalysts results in a stable heterogeneous-type material with selectivity and efficiency like homogeneous catalysts. The silica-supported SILP Rh-bisphosphine hydroformylation catalyst exhibited good activities and excellent selectivities in gas phase hydroformylation with stability exceeding 700 hours time-on-stream. Spectroscopic and kinetic data confirmed the homogeneous nature of the catalyst. In the Rh- SILP catalysed carbonylation of methanol the formation of undesired by-products could be suppressed by variation of residence time and gas pressure. (orig.)

  20. Microaeration for hydrogen sulfide removal in UASB reactor. (United States)

    Krayzelova, Lucie; Bartacek, Jan; Kolesarova, Nina; Jenicek, Pavel


    The removal of hydrogen sulfide from biogas by microaeration was studied in Up-flow Anaerobic Sludge Blanket (UASB) reactors treating synthetic brewery wastewater. A fully anaerobic UASB reactor served as a control while air was dosed into a microaerobic UASB reactor (UMSB). After a year of operation, sulfur balance was described in both reactors. In UASB, sulfur was mainly presented in the effluent as sulfide (49%) and in biogas as hydrogen sulfide (34%). In UMSB, 74% of sulfur was detected in the effluent (41% being sulfide and 33% being elemental sulfur), 10% accumulated in headspace as elemental sulfur and 9% escaped in biogas as hydrogen sulfide. The efficiency of hydrogen sulfide removal in UMSB was on average 73%. Microaeration did not cause any decrease in COD removal or methanogenic activity in UMSB and the elemental sulfur produced by microaeration did not accumulate in granular sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

  1. Anti-Amoebic Properties of Carbonyl Thiourea Derivatives

    Directory of Open Access Journals (Sweden)

    Maizatul Akma Ibrahim


    Full Text Available Thiourea derivatives display a broad spectrum of applications in chemistry, various industries, medicines and various other fields. Recently, different thiourea derivatives have been synthesized and explored for their anti-microbial properties. In this study, four carbonyl thiourea derivatives were synthesized and characterized, and then further tested for their anti-amoebic properties on two potential pathogenic species of Acanthamoeba, namely A. castellanii (CCAP 1501/2A and A. polyphaga (CCAP 1501/3A. The results indicate that these newly-synthesized thiourea derivatives are active against both Acanthamoeba species. The IC50 values obtained were in the range of 2.39–8.77 µg·mL‑1 (9.47–30.46 µM for A. castellanii and 3.74–9.30 µg·mL‑1 (14.84–31.91 µM for A. polyphaga. Observations on the amoeba morphology indicated that the compounds caused the reduction of the amoeba size, shortening of their acanthopodia structures, and gave no distinct vacuolar and nuclear structures in the amoeba cells. Meanwhile, fluorescence microscopic observation using acridine orange and propidium iodide (AOPI staining revealed that the synthesized compounds induced compromised-membrane in the amoeba cells. The results of this study proved that these new carbonyl thiourea derivatives, especially compounds M1 and M2 provide potent cytotoxic properties toward pathogenic Acanthamoeba to suggest that they can be developed as new anti-amoebic agents for the treatment of Acanthamoeba keratitis.

  2. [Measuring workplace climate: reliability and validity of the 12-item Organizational Climate Scale (OCS-12)]. (United States)

    Fukui, Satoe; Haratani, Takashi; Toshima, Yutaka; Shima, Satoru; Takahashi, Masaya; Nakata, Akinori; Fukasawa, Kenji; Ohba, Sayo; Sato, Emi; Hirota, Yasuko


    In order to investigate the reliability and validity of the short version of the 30-item Organizational Climate Scale (OCS-30; Toshima and Matsuda, 1992, 1995), a self-administered questionnaire was conducted in a sample of 819 employees of two medium-sized private companies in Japan by using the OCS-30, the Generic Job Stress Questionnaire (GJSQ), and the 12-item General Health Questionnaire (GHQ-12). The OCS has two subscales, i.e., the Tradition Scale (TS) and the Organizational Environment Scale (OES). The organizational climate perceived by each worker can be grouped into four categories based on the subscale scores: low TS and high OES (Active), high TS and high OES (Governed), low TS and low OES (Disorganized), and high TS and low OES (Reluctant). Principal component analysis for the OCS-30 was submitted (varimax rotation, the number of factors = 2), and 6 items for each factor, with factor loadings greater than 0.50, were selected for the short version, which constituted the 12-item Organizational Climate Scale (OCS-12). Cronbach's alpha reliability coefficients of the two subscales of the OCS-12 were acceptable; 0.63 for the TS and 0.71 for the OES. Both two subscales of the OCS-12 were significantly correlated with the GHQ-12 and many subscales of the GJSQ, which indicated the good constructive validity of the OCS-12. Among 4 types of organizational climate categorized by the OCS-12, the "Active" group showed the lowest job stress scores. It is suggested that the OCS-12 could be a reliable and valid instrument for assessing workers' perception of workplace climate.

  3. Thermal Properties of SiOC Glasses and Glass Ceramics at Elevated Temperatures. (United States)

    Stabler, Christina; Reitz, Andreas; Stein, Peter; Albert, Barbara; Riedel, Ralf; Ionescu, Emanuel


    In the present study, the effect of the chemical and phase composition on the thermal properties of silicon oxide carbides (SiOC) has been investigated. Dense monolithic SiOC materials with various carbon contents were prepared and characterized with respect to their thermal expansion, as well as thermal conductivity. SiOC glass has been shown to exhibit low thermal expansion (e.g., ca. 3.2 × 10 -6 K -1 for a SiOC sample free of segregated carbon) and thermal conductivity (ca. 1.5 W/(m∙K)). Furthermore, it has been observed that the phase separation, which typically occurs in SiOC exposed to temperatures beyond 1000-1200 °C, leads to a decrease of the thermal expansion (i.e., to 1.83 × 10 -6 K -1 for the sample above); whereas the thermal conductivity increases upon phase separation (i.e., to ca. 1.7 W/(m∙K) for the sample mentioned above). Upon adjusting the amount of segregated carbon content in SiOC, its thermal expansion can be tuned; thus, SiOC glass ceramics with carbon contents larger than 10-15 vol % exhibit similar coefficients of thermal expansion to that of the SiOC glass. Increasing the carbon and SiC content in the studied SiOC glass ceramics leads to an increase in their thermal conductivity: SiOC with relatively large carbon and silicon carbides (SiC) volume fractions (i.e., 12-15 and 20-30 vol %, respectively) were shown to possess thermal conductivities in the range from 1.8 to 2.7 W/(m∙K).

  4. Modeling Sulfides, pH and Hydrogen Sulfide Gas in the Sewers of San Francisco

    DEFF Research Database (Denmark)

    Vollertsen, Jes; Revilla, Nohemy; Hvitved-Jacobsen, Thorkild


    An extensive measuring campaign targeted on sewer odor problems was undertaken in San Francisco. It was assessed whether a conceptual sewer process model could reproduce the measured concentrations of total sulfide in the wastewater and H2S gas in the sewer atmosphere, and to which degree...... (WATS) sewer process concept, which never had been calibrated to such an extensive dataset. The study showed that the model was capable of reproducing the general levels of wastewater sulfide, wastewater pH, and sewer H2S gas. It could also reproduce the general variability of these parameters, albeit...

  5. Recent findings on sinks for sulfide in gravity sewer networks

    DEFF Research Database (Denmark)

    Nielsen, Asbjørn Haaning; Hvitved-Jacobsen, Thorkild; Vollertsen, Jes


    Sulfide buildup in sewer networks is associated with several problems, including health impacts, corrosion of sewer structures and odor nuisance. In recent years, significant advances in the knowledge of the major processes governing sulfide buildup in sewer networks have been made. This paper...... summarizes this newly obtained knowledge and emphasizes important implications of the findings. Model simulations of the in-sewer processes important for the sulfur cycle showed that sulfide oxidation in the wetted biofilm is typically the most important sink for dissolved sulfide in gravity sewers. However...

  6. The multidrug transporter MATE1 sequesters OCs within an intracellular compartment that has no influence on OC secretion in renal proximal tubules. (United States)

    Martínez-Guerrero, L J; Evans, K K; Dantzler, W H; Wright, S H


    Secretion of organic cations (OCs) across renal proximal tubules (RPTs) involves basolateral OC transporter (OCT)2-mediated uptake from the blood followed by apical multidrug and toxin extruder (MATE)1/2-mediated efflux into the tubule filtrate. Whereas OCT2 supports electrogenic OC uniport, MATE is an OC/H(+) exchanger. As assessed by epifluorescence microscopy, cultured Chinese hamster ovary (CHO) cells that stably expressed human MATE1 accumulated the fluorescent OC N,N,N-trimethyl-2-[methyl(7-nitrobenzo[c][l,2,5]oxadiazol-4-yl)amino]ethanaminium (NBD-MTMA) in the cytoplasm and in a smaller, punctate compartment; accumulation in human OCT2-expressing cells was largely restricted to the cytoplasm. A second intracellular compartment was also evident in the multicompartmental kinetics of efflux of the prototypic OC [(3)H]1-methyl-4-phenylpyridinium (MPP) from MATE1-expressing CHO cells. Punctate accumulation of NBD-MTMA was markedly reduced by coexposure of MATE1-expressing cells with 5 μM bafilomycin (BAF), an inhibitor of V-type H(+)-ATPase, and accumulation of [(3)H]MPP and [(3)H]NBD-MTMA was reduced by >30% by coexposure with 5 μM BAF. BAF had no effect on the initial rate of MATE1-mediated uptake of NBD-MTMA, suggesting that the influence of BAF was a secondary effect involving inhibition of V-type H(+)-ATPase. The accumulation of [(3)H]MPP by isolated single nonperfused rabbit RPTs was also reduced >30% by coexposure to 5 μM BAF, suggesting that the native expression in RPTs of MATE protein within endosomes can increase steady-state OC accumulation. However, the rate of [(3)H]MPP secretion by isolated single perfused rabbit RPTs was not affected by 5 μM BAF, suggesting that vesicles loaded with OCs(+) are not likely to recycle into the apical plasma membrane at a rate sufficient to provide a parallel pathway for OC secretion. Copyright © 2016 the American Physiological Society.

  7. Catalase as a sulfide-sulfur oxido-reductase: An ancient (and modern?) regulator of reactive sulfur species (RSS). (United States)

    Olson, Kenneth R; Gao, Yan; DeLeon, Eric R; Arif, Maaz; Arif, Faihaan; Arora, Nitin; Straub, Karl D


    Catalase is well-known as an antioxidant dismutating H 2 O 2 to O 2 and H 2 O. However, catalases evolved when metabolism was largely sulfur-based, long before O 2 and reactive oxygen species (ROS) became abundant, suggesting catalase metabolizes reactive sulfide species (RSS). Here we examine catalase metabolism of H 2 S n , the sulfur analog of H 2 O 2 , hydrogen sulfide (H 2 S) and other sulfur-bearing molecules using H 2 S-specific amperometric electrodes and fluorophores to measure polysulfides (H 2 S n ; SSP4) and ROS (dichlorofluorescein, DCF). Catalase eliminated H 2 S n , but did not anaerobically generate H 2 S, the expected product of dismutation. Instead, catalase concentration- and oxygen-dependently metabolized H 2 S and in so doing acted as a sulfide oxidase with a P 50 of 20mmHg. H 2 O 2 had little effect on catalase-mediated H 2 S metabolism but in the presence of the catalase inhibitor, sodium azide (Az), H 2 O 2 rapidly and efficiently expedited H 2 S metabolism in both normoxia and hypoxia suggesting H 2 O 2 is an effective electron acceptor in this reaction. Unexpectedly, catalase concentration-dependently generated H 2 S from dithiothreitol (DTT) in both normoxia and hypoxia, concomitantly oxidizing H 2 S in the presence of O 2 . H 2 S production from DTT was inhibited by carbon monoxide and augmented by NADPH suggesting that catalase heme-iron is the catalytic site and that NADPH provides reducing equivalents. Catalase also generated H 2 S from garlic oil, diallyltrisulfide, thioredoxin and sulfur dioxide, but not from sulfite, metabisulfite, carbonyl sulfide, cysteine, cystine, glutathione or oxidized glutathione. Oxidase activity was also present in catalase from Aspergillus niger. These results show that catalase can act as either a sulfide oxidase or sulfur reductase and they suggest that these activities likely played a prominent role in sulfur metabolism during evolution and may continue do so in modern cells as well. This also appears

  8. Catalase as a sulfide-sulfur oxido-reductase: An ancient (and modern? regulator of reactive sulfur species (RSS

    Directory of Open Access Journals (Sweden)

    Kenneth R. Olson


    Full Text Available Catalase is well-known as an antioxidant dismutating H2O2 to O2 and H2O. However, catalases evolved when metabolism was largely sulfur-based, long before O2 and reactive oxygen species (ROS became abundant, suggesting catalase metabolizes reactive sulfide species (RSS. Here we examine catalase metabolism of H2Sn, the sulfur analog of H2O2, hydrogen sulfide (H2S and other sulfur-bearing molecules using H2S-specific amperometric electrodes and fluorophores to measure polysulfides (H2Sn; SSP4 and ROS (dichlorofluorescein, DCF. Catalase eliminated H2Sn, but did not anaerobically generate H2S, the expected product of dismutation. Instead, catalase concentration- and oxygen-dependently metabolized H2S and in so doing acted as a sulfide oxidase with a P50 of 20 mmHg. H2O2 had little effect on catalase-mediated H2S metabolism but in the presence of the catalase inhibitor, sodium azide (Az, H2O2 rapidly and efficiently expedited H2S metabolism in both normoxia and hypoxia suggesting H2O2 is an effective electron acceptor in this reaction. Unexpectedly, catalase concentration-dependently generated H2S from dithiothreitol (DTT in both normoxia and hypoxia, concomitantly oxidizing H2S in the presence of O2. H2S production from DTT was inhibited by carbon monoxide and augmented by NADPH suggesting that catalase heme-iron is the catalytic site and that NADPH provides reducing equivalents. Catalase also generated H2S from garlic oil, diallyltrisulfide, thioredoxin and sulfur dioxide, but not from sulfite, metabisulfite, carbonyl sulfide, cysteine, cystine, glutathione or oxidized glutathione. Oxidase activity was also present in catalase from Aspergillus niger. These results show that catalase can act as either a sulfide oxidase or sulfur reductase and they suggest that these activities likely played a prominent role in sulfur metabolism during evolution and may continue do so in modern cells as well. This also appears to be the first observation of catalase

  9. Carbon steel protection in G.S. (Girlder sulfide) plants. Iron sulfide scales formation conditions. Pt. 1

    International Nuclear Information System (INIS)

    Bruzzoni, P.; Burkart, A.L.; Garavaglia, R.N.


    An ASTM A 516 degree 60 carbon steel superficial protection technique submitted to a hydrogen-water sulfide corrosive medium at 2 MPa of pressure and 40-125 deg C forming on itself an iron sulfide layer was tested. Studies on pH influence, temperature, passivating mean characteristics and exposure time as well as the mechanical resistance of sulfide layers to erosion are included. (Author) [es

  10. 76 FR 64022 - Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting (United States)


    ... Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting AGENCY: Environmental Protection Agency (EPA). ACTION: Lifting of Administrative Stay for Hydrogen Sulfide. SUMMARY: EPA is announcing... (EPCRA) section 313 toxic chemical release reporting requirements for hydrogen sulfide (Chemical...

  11. Protein carbonylation sites in bovine raw milk and processed milk products. (United States)

    Milkovska-Stamenova, Sanja; Mnatsakanyan, Ruzanna; Hoffmann, Ralf


    During thermal treatment of milk, proteins are oxidized, which may reduce the nutritional value of milk, abolish protein functions supporting human health, especially important for newborns, and yield potentially harmful products. The side chains of several amino acids can be oxidized to reactive carbonyls, which are often used to monitor oxidative stress in organisms. Here we mapped protein carbonylation sites in raw milk and different brands of pasteurized, ultra high temperature (UHT) treated milk, and infant formulas (IFs) after digesting the precipitated proteins with trypsin. Reactive carbonyls were derivatized with O-(biotinylcarbazoylmethyl)hydroxylamine to enrich the modified peptides by avidin-biotin affinity chromatography and analyze them by nanoRP-UPLC-ESI-MS. Overall, 53 unique carbonylated peptides (37 carbonylation sites, 15 proteins) were identified. Most carbonyls were derived from dicarbonyls (mainly glyoxal). The number of carbonylation sites increased with the harsher processing from raw milk (4) to pasteurized (16) and UHT milk (16) and to IF (24). Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Paraquat exposure and Sod2 knockdown have dissimilar impacts on the Drosophila melanogaster carbonylated protein proteome (United States)

    Narayanasamy, Suresh K.; Simpson, David C.; Martin, Ian; Grotewiel, Mike; Gronert, Scott


    Exposure to Paraquat and RNA interference knockdown of Mn or mitochondrial superoxide dismutase (Sod2) are known to result in significant lifespan reduction, locomotor dysfunction, and mitochondrial degeneration in Drosophila melanogaster. Both perturbations increase the flux of the progenitor ROS, superoxide, but the molecular underpinnings of the resulting phenotypes are poorly understood. Improved understanding of such processes could lead to advances in the treatment of numerous age-related disorders. Superoxide toxicity can act through protein carbonylation. Analysis of carbonylated proteins is attractive since carbonyl groups are not present in the twenty canonical amino acids and are amenable to labeling and enrichment strategies. Here, carbonylated proteins were labeled with biotin hydrazide and enriched on streptavidin beads. On-bead digestion was used to release carbonylated protein peptides, with relative abundance ratios versus controls obtained using the iTRAQ MS-based proteomics approach. Western blotting and biotin quantitation assay approaches were also investigated. By both western blotting and proteomics, Paraquat exposure, but not Sod2 knockdown, resulted in increased carbonylated protein relative abundance. For Paraquat exposure versus control, the median carbonylated protein relative abundance ratio (1.53) determined using MS-based proteomics was in good agreement with that obtained using a commercial biotin quantitation kit (1.36). PMID:25091824

  13. Characteristics of carbonyls: Concentrations and source strengths for indoor and outdoor residential microenvironments in China (United States)

    Wang, B.; Lee, S. C.; Ho, K. F.

    Indoor and outdoor carbonyl concentrations were measured simultaneously in 12 urban dwellings in Beijing, Shanghai, Guangzhou, and Xi'an, China in summer (from July to September in 2004) and winter (from December 2004 to February 2005). Formaldehyde was the most abundant indoor carbonyls species, while formaldehyde, acetaldehyde and acetone were found to be the most abundant outdoor carbonyls species. The average formaldehyde concentrations in summer indoor air varied widely between cities, ranging from a low of 19.3 μg m -3 in Xi'an to a high of 92.8 μg m -3 in Beijing. The results showed that the dwellings with tobacco smoke, incense burning or poor ventilation had significantly higher indoor concentrations of certain carbonyls. It was noticed that although one half of the dwellings in this study installed with low emission building materials or furniture, the carbonyls levels were still significantly high. It was also noted that in winter both the indoor and outdoor acetone concentrations in two dwellings in Guangzhou were significantly high, which were mainly caused by the usage of acetone as industrial solvent in many paint manufacturing and other industries located around Guangzhou and relatively longer lifetime of acetone for removal by photolysis and OH reaction than other carbonyls species. The indoor carbonyls levels in Chinese dwellings were higher than that in dwellings in the other countries. The levels of indoor and ambient carbonyls showed great seasonal differences. Six carbonyls species were carried out the estimation of indoor source strengths. Formaldehyde had the largest indoor source strength, with an average of 5.25 mg h -1 in summer and 1.98 mg h -1 in winter, respectively. However, propionaldehyde, crotonaldehyde and benzaldehyde had the weakest indoor sources.

  14. Sulfidation behavior of rhenium and cobalt-rhenium alloys

    International Nuclear Information System (INIS)

    Shiring, R.; Douglass, D.L.


    The sulfidation behavior of Re and three Co-Re alloys, 15, 30, and 45 w/o, was studied over the temperature range 700--800 C at sulfur pressures of 10 -4 and 10 -2 atm. The kinetics of sulfidation followed the parabolic rate law and the activation energies for all alloys were similar to that of pure cobalt. A positive rate dependency on sulfur pressure was observed and Pt markers were located at the metal-scale interface, both observations clearly suggesting that outward cation diffusion through a P-type sulfide scale occurred. Two dominant sulfides, Co 9 S 8 and ReS 2 , formed. Weight gains decreased for a given set of conditions with increasing rhenium content. An order of magnitude decrease in the sulfidation rate occurred as the rhenium content increased from 15 to 45 w/o. Preferential sulfidation of cobalt initially occurred, causing a rhenium-enriched zone to form in the substrate beneath the cobalt-sulfide scale. The initial sulfide to form was Co 3 S 4 , but, subsequently, Co 9 S 8 became the dominant sulfide, forming beneath the outer Co 3 S 4 layer. ReS 2 formed at lower cobalt levels. Pure Re was also studied, the sulfidation rate being about 10 4 times slower than that of cobalt. The decreasing rate of sulfidation with increasing Re content is attributed primarily to slower cobalt diffusion outward through the Re-enriched substrate, a phenomenon similar to that observed by C. Wagner for the oxidation of Ni-Pt alloys

  15. Mechanisms of TL for production of the 230 {sup o}C peak in natural sodalite

    Energy Technology Data Exchange (ETDEWEB)

    Cano, Nilo F., E-mail: nilocano@dfn.if.usp.b [Institute of Physics, University of Sao Paulo, Rua do Matao, Travessa R, 187, CEP 05508-090, Sao Paulo (Brazil); Professional School of Physics, University of San Agustin of Arequipa, Av. Independencia S/N, Arequipa (Peru); Blak, Ana R. [Institute of Physics, University of Sao Paulo, Rua do Matao, Travessa R, 187, CEP 05508-090, Sao Paulo (Brazil); Ayala-Arenas, Jorge S. [Professional School of Physics, University of San Agustin of Arequipa, Av. Independencia S/N, Arequipa (Peru); Watanabe, Shigueo [Institute of Physics, University of Sao Paulo, Rua do Matao, Travessa R, 187, CEP 05508-090, Sao Paulo (Brazil)


    The thermoluminescence (TL) peak in natural sodalite near 230 {sup o}C, which appears only after submitted to thermal treatments and to gamma irradiation, has been studied in parallel with electron paramagnetic resonance (EPR) spectrum appearing under the same procedure. This study revealed a full correlation between the 230 {sup o}C TL peak and the eleven hyperfine lines from EPR spectrum. In both case, the centers disappear at the same temperature and are restored after gamma irradiation. A complete model for the 230 {sup o}C TL peak is presented and discussed. In addition to the correlation and TL model, specific characteristics of the TL peaks are described.

  16. Millimeter-Wave Transmittance and Reflectance Measurement on Pure and Diluted Carbonyl Iron (United States)

    Korolev, Konstantin; Chen, Shu; Li, Zijing; Afsar, Mohammed


    Transmittance and reflectance measurements on highly absorbing carbonyl iron materials over a broad millimeter-wave frequency range have been performed. Frequency dependence of the complex dielectric permittivity of carbonyl iron diluted composite and pure powdered materials have been determined in the millimeter waves for the first time. The measurements have been employed using a free-space quasi-optical millimeter-wave spectrometer equipped with a set of high power backward wave oscillators as sources of coherent radiation, tunable in the range from 30 -- 120 GHz. Significant transmission zone of the millimeter-wave radiation at frequency around 60 GHz has been observed in transmittance spectra for the carbonyl iron materials.

  17. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis. (United States)

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping


    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Visible Light-Induced Carbonylation Reactions with Organic Dyes as the Photosensitizers. (United States)

    Peng, Jin-Bao; Qi, Xinxin; Wu, Xiao-Feng


    Dyes can CO do it: Organic dyes and pigments are usually applied in textile dyeing, which can be dated back to the Neolithic period. Interestingly, the possibility to use organic dyes as photoredox catalysts has also been noticed by organic chemists and applied in organic synthesis. Carbonylation reactions as a powerful procedure in carbonyl-containing compound preparation have also been studied. In this manuscript, the recent achievements in using organic dyes as visible-light sensitizers in carbonylation chemistry are summarized and discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Cadmium Sulfide Nanoparticles Synthesized by Microwave Heating for Hybrid Solar Cell Applications

    Directory of Open Access Journals (Sweden)

    Claudia Martínez-Alonso


    Full Text Available Cadmium sulfide nanoparticles (CdS-n are excellent electron acceptor for hybrid solar cell applications. However, the particle size and properties of the CdS-n products depend largely on the synthesis methodologies. In this work, CdS-n were synthetized by microwave heating using thioacetamide (TA or thiourea (TU as sulfur sources. The obtained CdS-n(TA showed a random distribution of hexagonal particles and contained TA residues. The latter could originate the charge carrier recombination process and cause a low photovoltage (Voc, 0.3 V in the hybrid solar cells formed by the inorganic particles and poly(3-hexylthiophene (P3HT. Under similar synthesis conditions, in contrast, CdS-n synthesized with TU consisted of spherical particles with similar size and contained carbonyl groups at their surface. CdS-n(TU could be well dispersed in the nonpolar P3HT solution, leading to a Voc of about 0.6–0.8 V in the resulting CdS-n(TU : P3HT solar cells. The results of this work suggest that the reactant sources in microwave methods can affect the physicochemical properties of the obtained inorganic semiconductor nanoparticles, which finally influenced the photovoltaic performance of related hybrid solar cells.

  20. Technetium behavior in sulfide and ferrous iron solutions

    International Nuclear Information System (INIS)

    Lee, S.Y.; Bondietti, E.A.


    Pertechnetate oxyanion ( 99 TcO 4- ), a potentially mobile species in leachate from a breached radioactive waste repository, was removed from a brine solution by precipitation with sulfide, iron, and ferrous sulfide at environmental pH's. Maghemite (ν-Fe 2 O 3 ) and geothite (α-FeOOH) were the dominant minerals in the precipitate obtained from the TcO 4- -ferrous iron reaction. The observation of small particle size and poor crystallinity of the minerals formed in the presence of Tc suggested that the Tc was incorporated into the mineral structure after reduction to a lower valence state. Amorphous ferrous sulfide, an initial phase precipitating in the TcO 4- -ferrous iron-sulfide reaction, was transformed to goethite and hematite (α-Fe 2 O 3 ) on aging. The black precipitate obtained from the TcO 4- -sulfide reaction was poorly crystallized technetium sulfide (Tc 2 S 7 ) which was insoluble in both acid and alkaline solution in the absence of strong oxidents. The results suggested that ferrous- and/or sulfide-bearing groundwaters and minerals in host rocks or backfill barriers could reduce the mobility of Tc through the formation of less-soluble Tc-bearing iron and/or sulfide minerals

  1. Petroleum sulfides, sulfoxides, and sulfones used as extragents

    International Nuclear Information System (INIS)

    Nikitin, Yu.E.; Lyapina, N.K.; Murinov, Yu.I.


    Possibilities of using petroleum sulfides, sulfoxides and sulfones for extraction and separation of wide range of elements are considered. It is shown that petroleum sulfides appear to be effective and selective extractants in extraction and separation of noble metals (Ru, Au, Pt, etc.). Petroleum sulfoxides are promising for solvent extraction of transition metals, actinides, rare earths etc

  2. Effect of Soluble Sulfide on the Activity of Luminescent Bacteria

    Directory of Open Access Journals (Sweden)

    Feng Wang


    Full Text Available Sulfide is an important water pollutant widely found in industrial waste water that has attracted much attention. S2−, as a weak acidic anion, is easy hydrolyzed to HS and H2S in aqueous solution. In this study, biological tests were performed to establish the toxicity of sulfide solutions on luminescent bacteria. Considering the sulfide solution was contained three substances—S2−, HS and H2S—the toxicity test was performed at different pH values to investigate which form of sulfide increased light emission and which reduced light emission. It was shown that the EC50 values were close at pH 7.4, 8.0 and 9.0 which were higher than pH 5 and 10. The light emission and sulfide concentrations displayed an inverse exponential dose-response relationship within a certain concentration range at pH 5, 6.5 and 10. The same phenomenon occurred for the high concentration of sulfide at pH 7.4, 8 and 9, in which the concentration of sulfide was HS >> H2S > S2−. An opposite hormesis-effect appeared at the low concentrations of sulfide.

  3. Hydrogen sulfide: from brain to gut. (United States)

    Kimura, Hideo


    Three hundred years have passed since the first description of the toxicity of hydrogen sulfide (H(2)S). Three papers in 1989 and 1990 described relatively high concentrations of sulfide in the brain. In 1996 we demonstrated that cystathionine beta-synthase (CBS) is a H(2)S producing enzyme in the brain and that H(2)S enhances the activity of NMDA receptors and facilitates the induction of hippocampal long-term potentiation (LTP), a synaptic model of memory. In the following year, we demonstrated that another H(2)S producing enzyme, cystathionine gamma-lyase is in the thoracic aorta, portal vein, and the ileum, and that H(2)S relaxes these tissues. Based on these observations we proposed H(2)S as a neuromodulator as well as a smooth muscle relaxant. We recently demonstrated that the third H(2)S-producing enzyme, 3-mercaptopyruvate sulfurtransferase (3MST) along with cysteine aminotransferase (CAT) produces H(2)S in the brain as well as in vascular endothelium. Various functions in many tissues have been proposed. H(2)S protects neurons and cardiac muscle from oxidative stress. H(2)S has pro- and anti-inflammatory effects, nociceptive effects, the regulatory function of insulin release, and is even involved in longevity. Recent progress in the studies of physiological functions of H(2)S in neurons and smooth muscle was described.

  4. Sulindac Sulfide, but Not Sulindac Sulfone, Inhibits Colorectal Cancer Growth

    Directory of Open Access Journals (Sweden)

    Christopher S. Williams


    Full Text Available Sulindac sulfide, a metabolite of the nonsteroidal antiinflammatory drug (NSAID sulindac sulfoxide, is effective at reducing tumor burden in both familial adenomatous polyposis patients and in animals with colorectal cancer. Another sulindac sulfoxide metabolite, sulindac sulfone, has been reported to have antitumor properties without inhibiting cyclooxygenase activity. Here we report the effect of sulindac sulfone treatment on the growth of colorectal carcinoma cells. We observed that sulindac sulfide or sulfone treatment of HCA-7 cells led to inhibition of prostaglandin E2 production. Both sulindac sulfide and sulfone inhibited HCA-7 and HCT-116 cell growth in vitro. Sulindac sulfone had no effect on the growth of either HCA-7 or HCT-116 xenografts, whereas the sulfide derivative inhibited HCA-7 growth in vivo. Both sulindac sulfide and sulfone inhibited colon carcinoma cell growth and prostaglandin production in vitro, but sulindac sulfone had no effect on the growth of colon cancer cell xenografts in nude mice.

  5. Hierarchical Architecturing for Layered Thermoelectric Sulfides and Chalcogenides (United States)

    Jood, Priyanka; Ohta, Michihiro


    Sulfides are promising candidates for environment-friendly and cost-effective thermoelectric materials. In this article, we review the recent progress in all-length-scale hierarchical architecturing for sulfides and chalcogenides, highlighting the key strategies used to enhance their thermoelectric performance. We primarily focus on TiS2-based layered sulfides, misfit layered sulfides, homologous chalcogenides, accordion-like layered Sn chalcogenides, and thermoelectric minerals. CS2 sulfurization is an appropriate method for preparing sulfide thermoelectric materials. At the atomic scale, the intercalation of guest atoms/layers into host crystal layers, crystal-structural evolution enabled by the homologous series, and low-energy atomic vibration effectively scatter phonons, resulting in a reduced lattice thermal conductivity. At the nanoscale, stacking faults further reduce the lattice thermal conductivity. At the microscale, the highly oriented microtexture allows high carrier mobility in the in-plane direction, leading to a high thermoelectric power factor. PMID:28787992

  6. Influence of Water Salinity on Air Purification from Hydrogen Sulfide

    Directory of Open Access Journals (Sweden)

    Leybovych L.I.


    Full Text Available Mathematical modeling of «sliding» water drop motion in the air flow was performed in software package FlowVision. The result of mathematical modeling of water motion in a droplet with diameter 100 microns at the «sliding» velocity of 15 m/s is shown. It is established that hydrogen sulfide oxidation occurs at the surface of phases contact. The schematic diagram of the experimental setup for studying air purification from hydrogen sulfide is shown. The results of the experimental research of hydrogen sulfide oxidation by tap and distilled water are presented. The dependence determining the share of hydrogen sulfide oxidized at the surface of phases contact from the dimensionless initial concentration of hydrogen sulfide in the air has been obtained.

  7. Geological Sulfur Isotopes Indicate Elevated OCS in the Archean Atmosphere, Solving the Faint Young Sun Paradox

    DEFF Research Database (Denmark)

    Ueno, Yuichiro; Johnson, Matthew Stanley; Danielache, Sebastian Oscar


    Distributions of sulfur isotopes in geological samples would provide a record of atmospheric composition if the mechanism producing the isotope effects could be described quantitatively. We determined the UV absorption spectra of 32SO2, 33SO2, and 34SO2 and use them to interpret the geological...... record. The calculated isotopic fractionation factors for SO2 photolysis give mass independent distributions that are highly sensitive to the atmospheric concentrations of O2, O3, CO2, H2O, CS2, NH3, N2O, H2S, OCS, and SO2 itself. Various UV-shielding scenarios are considered and we conclude...... that the negative 33S observed in the Archean sulfate deposits can only be explained by OCS shielding. Of relevant Archean gases, OCS has the unique ability to prevent SO2 photolysis by sunlight at >202 nm. Scenarios run using a photochemical box model show that ppm levels of OCS will accumulate in a CO...

  8. Photodecomposition of Molybdenum andTungsten Carbonyl Complexes

    Directory of Open Access Journals (Sweden)

    Thamer A. Alwani


    Full Text Available The photodecomposition of four different colored organometallic molybdenum and tungsten carbonyl complexes, i.e. [Mo(CO52LA] (complex I, [(Mo(CO3(bipy2LB] (complex II, [(W(CO3(tmen2LB] (complex III and [Mo(CO2LC]2 (complex I V where LA 2-phenyl-1,3-indandionebis(2-methyl anilines, LB 2-phenyl-1,3-indandione bis (4-hydroxy anilines and LCbis (2-hydroxo-benzalydine benzidine ion have been performed at 365 nm in chloroform at 25 °C under oxygen atmosphere. The absorbance spectrum of these complexes has been recorded with the time of irradiation in order to examine the kinetics of photodecomposition. The rate of the photodecomposition process was investigated and the relative values of the rate constants of dissociation (Kd for the first-order reaction are tabulated. The apparent rate constant of photodecomposition was found to be (8.33-11.50 × 10-5 s-1.

  9. 78 FR 59968 - Potential Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Oregon... (United States)


    ...; MMAA104000] Potential Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Oregon... BOEM by Principle Power, Inc. (Principle Power) to acquire an OCS commercial wind lease; (2) solicit... from Principle Power for a commercial wind lease on the OCS offshore Oregon. Principle [[Page 59969...

  10. 77 FR 47877 - Potential Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Maine... (United States)


    ... Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Maine; Request for Interest... Request for a Commercial OCS Wind Lease, Request for Interest, and Request for Public Comment SUMMARY: The... (Statoil NA) to acquire an OCS wind lease; (2) solicit public input regarding the proposal, its potential...

  11. 76 FR 70156 - Proposed 5-Year Outer Continental Shelf (OCS) Oil and Gas Leasing Program for 2012-2017 (United States)


    ... Shelf (OCS) Oil and Gas Leasing Program for 2012-2017 AGENCY: Bureau of Ocean Energy Management... the availability of and requests comments on the Proposed 5-Year OCS Oil and Gas Leasing Program for..., including the public, to assist in the preparation of a 5-Year OCS Oil and Gas Leasing Program for 2012-2017...

  12. Fluorescent hydrazides for the high-performance liquid chromatographic determination of biological carbonyls. (United States)

    Anderson, J M


    Methods for the determination of carbonyl compounds of biological origin by high-performance liquid chromatography were improved by the use of new fluorescent derivatizing agents. Eight fluorescent hydrazides were either synthesized or obtained commercially and compared to dansyl hydrazine (1-dimethylaminonaphthalene-5-sulfonylohydrazide). Four of the compounds yielded carbonyl hydrazones with a higher relative fluorescence quantum yield than dansyl hydrazine in acetonitrile:water mixtures. Darpsyl hydrazide [(3-phenylpyrazoline-1-yl)-4-phenylsulfonylohydrazide] and apmayl hydrazide [N-(2-aminophenyl-6-methylbenzthiazole)-acetylohydrazide] both yielded an increase of greater than 20-fold in sensitivity over dansyl hydrazine in determinations of abscisic acid and jasmonic acid from plant tissues. Different hydrazides and derivatizing conditions were found to be optimum for the determination of different carbonyl compounds. Also, a simple method for precolumn purification of the hydrazones of acidic carbonyls was developed to remove contaminants arising during derivatization and from the tissue source.

  13. Magnetic carbonyl iron suspension with organoclay additive and its magnetorheological properties

    CSIR Research Space (South Africa)

    Hato, MJ


    Full Text Available Soft magnetic carbonyl iron (CI) based magnetorheological (MR) fluids containing three different loadings of submicron-sized organoclay were prepared. The MR characteristics were measured via rotational and oscillatory tests, in which the flow...

  14. Protective mechanisms of Cucumis sativus in diabetes-related models of oxidative stress and carbonyl stress

    Directory of Open Access Journals (Sweden)

    Himan Heidari


    Conclusion: It can be concluded that C. sativus has protective effects in diabetes complications and can be considered a safe and suitable candidate for decreasing the oxidative stress and carbonyl stress that is typically observed in diabetes mellitus.

  15. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Schindler, Matthias, E-mail:; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander


    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO{sub 2} and reduced to graphite to determine {sup 14}C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  16. Comparison of sampling methods for radiocarbon dating of carbonyls in air samples via accelerator mass spectrometry (United States)

    Schindler, Matthias; Kretschmer, Wolfgang; Scharf, Andreas; Tschekalinskij, Alexander


    Three new methods to sample and prepare various carbonyl compounds for radiocarbon measurements were developed and tested. Two of these procedures utilized the Strecker synthetic method to form amino acids from carbonyl compounds with either sodium cyanide or trimethylsilyl cyanide. The third procedure used semicarbazide to form crystalline carbazones with the carbonyl compounds. The resulting amino acids and semicarbazones were then separated and purified using thin layer chromatography. The separated compounds were then combusted to CO2 and reduced to graphite to determine 14C content by accelerator mass spectrometry (AMS). All of these methods were also compared with the standard carbonyl compound sampling method wherein a compound is derivatized with 2,4-dinitrophenylhydrazine and then separated by high-performance liquid chromatography (HPLC).

  17. Reaction or organomagnesium compounds of the adamantane series with carbonyl compounds

    International Nuclear Information System (INIS)

    Yurchenko, A.G.; Fedorenko, T.V.


    In the transformations of organomagnesium compounds of the adamantane series involving aldehydes, ketones, esters, and acid chlorides the nature of the reaction products and their yields are determined by the steric hindrances at the reaction centers of the organomagnesium and carbonyl compounds and by the ease of homolysis of the C-H bonds of the carbonyl reagent. The retardation of the faster addition of the Grignard reagent at the carbonyl group as a result of steric hindrances permits homolytic removal of a hydrogen atom from the carbonyl compound by the adamantyl radical. The PMR spectra were measured on a Tesla BS-487C spectrometer at 80 MHz in carbon tetrachloride with the substances at concentrations of 5-20% and with TMS as internal standard. The IR spectra were obtained in carbon tetrachloride on a UR-10 spectrophotometer

  18. Structure and Bonding in Binuclear Metal Carbonyls. Classical Paradigms vs. Insights from Modern Theoretical Calculations

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert


    Roč. 1053, SI (2015), s. 195-213 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : binuclear metal carbonyls * DAFH analysis * 18-electron rule Subject RIV: CC - Organic Chemistry Impact factor: 1.403, year: 2015

  19. Efficient and selective α-bromination of carbonyl compounds with N-bromosuccinimide under microwave

    KAUST Repository

    Guan, Xiao-Yu


    A highly efficient method for the synthesis of α-halocarbonyl compounds has been achieved via selective monobromination of aromatic and aliphatic carbonyl compounds with N-bromosuccinimide catalyzed by p-toluenesulfonic acid under microwave irradiation within 30 min.

  20. Analysis of the premitting processes associated with exploration of Federal OCS leases. Final report

    Energy Technology Data Exchange (ETDEWEB)


    Under contract to the Office of Leasing Policy Development (LPDO), Jack Faucett Associates is currently undertaking the description and analysis of the Outer Continental Shelf (OCS) regulatory process to determine the nature of time delays that affect OCS production of oil and gas. This report represents the results of the first phase of research under this contract, the description and analysis of regulatory activity associated with exploration activities on the Federal OCS. Volume 1 contains the following three sections: (1) study results; (2) Federal regulatory activities during exploration of Federal OCS leases which involved the US Geological Survey, Environmental Protection Agency, US Coast Guard, Corps of Engineers, and National Ocean and Atmospheric Administration; and (3) state regulatory activities during exploration of Federal OCS leases of Alaska, California, Louisiana, Massachusetts, New Jersey, North Carolina, and Texas. Volume II contains appendices of US Geological Survey, Environmental Protection Agency, Coast Guard, Corps of Engineers, the Coastal Zone Management Act, and Alaska. The major causes of delay in the regulatory process governing exploration was summarized in four broad categories: (1) the long and tedious process associated with the Environmental Protection Agency's implementation of the National Pollutant Discharge Elimination System Permit; (2) the lack of mandated time periods for the completion of individual activities in the permitting process; (3) the lack of overall coordination of OCS exploratory regulation; and (4) the inexperience of states, the Federal government and industry relating to the appropriate level of regulation for first-time lease sale areas.

  1. A Review of Graphite Irradiation Creep Data from the "OC-Series" of Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Davies, Mark A. [MARAD Co. Ltd., Washington, DC (United States); Burchell, Timothy D. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)


    The OC-Series graphite irradiation creep experiments were conducted in the early 1970s in the Oak Ridge Research Reactor (ORR) at ORNL. The OC Series consisted of 5 experiments, Capsules 1, 3 and 5 were irradiated at 900°C and Capsules 2 and 4 were irradiated at 600°C. Each capsule contained four columns of specimens, two loaded in compression and two un-loaded. The loaded columns had specimens of different diameter to generate two stress levels, 13.8 MPa and 20.7 MPa. Some of the data from these experiments were presented in extended abstracts at a Carbon Conference (Kennedy et al, 1977: Kennedy and Eatherly, 1979). The data presented some challenges to the accepted approach to irradiation induced creep in graphite adopted in the UK, specifically lateral creep strain behaviour and the effect of irradiation induced creep strain on material properties, e.g. CTE and Poisson’s Ratio. A recent review of irradiation induced creep (Davies & Bradford, 2004) included an anlaysis of the available OC-series data (Mobasheran, 1990) and led to a request to ORNL for an examination of the original OC-Series dataset. An initial search of the ORNL archive revealed additional data from the OC-Series experiment including previously unknown irradiation annealing experiments. This report presents a re-analysis of the available data from the OC-Series archive.

  2. 1,2,3-Triazoles from carbonyl azides and alkynes: filling the gap. (United States)

    Haldón, Estela; Álvarez, Eleuterio; Nicasio, M Carmen; Pérez, Pedro J


    Electron deficient azides are challenging substrates in CuAAC reactions. Particularly, when N-carbonyl azides are applied the formation of N-carbonyl triazoles has not yet been observed. We report herein the first example of this class of reaction, with a copper-based system that efficiently enables the synthesis of N-carbamoyl 1,2,3-triazoles by [3+2] cycloaddition of N-carbamoyl azides and alkynes.

  3. Chemoselective Reduction and Alkylation of Carbonyl Functions Using Phosphonium Salts as an in Situ Protecting Groups. (United States)

    Ohta, Reiya; Fujioka, Hiromichi


    Recent progress in the chemoselective reduction and alkylation of carbonyl functions using our in situ protection method is described. Methods that enable reversal or control of the reactivity of a carbonyl functional group are potentially useful. They open up new areas of synthetic organic chemistry and change the concept of retrosynthesis because they remove the need for complicated protection/deprotection sequences. In this account, we discuss the strategy and applications of our in situ protection method using phosphonium salts.

  4. Functionalization of 6-Nitrobenzo[1,3]dioxole with Carbonyl Compounds via TDAE methodology

    Directory of Open Access Journals (Sweden)

    Patrice Vanelle


    Full Text Available We report herein the synthesis of substituted 2-(6-nitrobenzo[1,3]dioxol-5-yl-1- aryl ethanols and 2-(6-nitrobenzo[1,3]dioxol-5-yl-propionic acid ethyl esters from the reaction of 5-chloromethyl-6-nitrobenzo[1,3]dioxole with various aromatic carbonyl and α- carbonyl ester derivatives using the tetrakis(dimethylaminoethylene (TDAE methodology.

  5. Diastereo- and Enantioselective Iridium Catalyzed Carbonyl (α-Cyclopropyl)allylation via Transfer Hydrogenation. (United States)

    Tsutsumi, Ryosuke; Hong, Suckchang; Krische, Michael J


    The first examples of diastereo- and enantioselective carbonyl α-(cyclopropyl)allylation are reported. Under the conditions of iridium catalyzed transfer hydrogenation using the chiral precatalyst (R)-Ir-I modified by SEGPHOS, carbonyl α-(cyclopropyl)allylation may be achieved with equal facility from alcohol or aldehyde oxidation levels. This methodology provides a conduit to hitherto inaccessible inaccessible enantiomerically enriched cyclopropane-containing architectures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Organocatalyzed α-Sulfenylation of carbonyl compounds using N-formly/Acyl Sulfenmides

    Energy Technology Data Exchange (ETDEWEB)

    Noh, Hyeon Wan; Lee, Chan; Jang, Hye Young [Dept. of Energy Systems Research, Ajou University, Suwon (Korea, Republic of)


    α-Sulfenylation of aldehydes and ketones using N-formyl and N-acyl sulfenamides, prepared by Cu-catalyzed aerobic coupling of amides and thiols, was achieved in the presence of cyclic secondary amine⋅HCl catalysts. To obtain various sulfur-functionalized carbonyl compounds, sulfenamides containing aromatic and aliphatic organosulfur were investigated. As carbonyl compounds, cyclic and acyclic ketones, 1,3-dicarbonyl compounds, and aldehydes were investigated, affording the desired α-sulfenylation products in good yields.

  7. Cytoprotective Effects of Pumpkin (Cucurbita Moschata) Fruit Extract against Oxidative Stress and Carbonyl Stress. (United States)

    Shayesteh, Reyhaneh; Kamalinejad, Mohammad; Adiban, Hasan; Kardan, Azin; Keyhanfar, Fariborz; Eskandari, Mohammad Reza


    Background Diabetes mellitus is a chronic endocrine disorder that is associated with significant mortality and morbidity due to microvascular and macrovascular complications. Diabetes complications accompanied with oxidative stress and carbonyl stress in different organs of human body because of the increased generation of free radicals and impaired antioxidant defense systems. In the meantime, reactive oxygen species (ROS) and reactive carbonyl species (RCS) have key mediatory roles in the development and progression of diabetes complications. Therapeutic strategies have recently focused on preventing such diabetes-related abnormalities using different natural and chemical compounds. Pumpkin ( Cucurbita moschata ) is one of the most important vegetables in the world with a broad-range of pharmacological activities such as antihyperglycemic effect. Methods In the present study, the cytoprotective effects of aqueous extract of C. moschata fruit on hepatocyte cytotoxicity induced by cumene hydroperoxide (oxidative stress model) or glyoxal (carbonylation model) were investigated using freshly isolated rat hepatocytes. Results The extract of C. moschata (50 μg/ml) excellently prevented oxidative and carbonyl stress markers, including hepatocyte lysis, ROS production, lipid peroxidation, glutathione depletion, mitochondrial membrane potential collapse, lysosomal damage, and cellular proteolysis. In addition, protein carbonylation was prevented by C. moschata in glyoxal-induced carbonyl stress. Conclusion It can be concluded that C. moschata has cytoprotective effects in oxidative stress and carbonyl stress models and this valuable vegetable can be considered as a suitable herbal product for the prevention of toxic subsequent of oxidative stress and carbonyl stress seen in chronic hyperglycemia. © Georg Thieme Verlag KG Stuttgart · New York.

  8. Study of interaction products of chromium, molybdenum and tungsten carbonyls with ethanolamines

    Energy Technology Data Exchange (ETDEWEB)

    Mozgin, S.V.; Felin, M.G.; Subbotina, N.A.; Spitsyn, V.I. (Moskovskij Gosudarstvennyj Univ. (USSR))


    The interaction of the 6th group metal carbonyls with mono-, di-, and triethanolamines was investigated. It was established that chromium, molybdenum and tungsten carbonyls could react with ethanolamines. Complex compounds of the mentioned metals that had been separated after carrying out those reactions were characterized by chemical analysis data. Properties of the produced complexes were studied by methods of UV, visible and IR spectroscopy, thermomagnetic and thermal analyses and their structure is proposed.

  9. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines. (United States)

    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew J


    Palladium(II)-catalyzed C-H carbonylation reactions of methylene C-H bonds in secondary aliphatic amines lead to the formation of trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C-H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields for the β-lactam products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

    International Nuclear Information System (INIS)

    Fedoseev, I.V.; Solov'ev, N.V.


    Researches in the field of platinum metal coordination compounds, where nitrogen enters as a ligand in coordination sphere of metal, are discussed. Results of experiments on the ammonia synthesis during the CO+N 2 mixture passing through alkali solution containing mixture of carbonyl clusters of rhodium, ruthenium and iridium at atmospheric pressure are given. Technique of the experiment and steps of assumed reactions of nitrogen fixation by Rh, Ir and Ru carbonyl clusters are demonstrated [ru

  11. Plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids


    Sedlačík, M.; Pavlínek, V.; Lehocký, M.; Mráček, A.; Grulich, O.; Švrčinová, P. (Petra); Filip, P. (Petr); Vesel, A.


    The aim of this paper is to document suitability of plasma-treated carbonyl iron particles as a dispersed phase in magnetorheological fluids. Surface-modified carbonyl iron particles were prepared via their exposure to 50% argon and 50% octafluorocyclobutane plasma. The X-ray photoelectron spectroscopy was used for analysis of chemical bonding states in the surface layer. Plasma-treated particles were adopted for a dispersed phase in magnetorheological (MR) fluids, and the MR behaviour was in...

  12. Carbon steel protection in G.S. (Girlder sulfide) plants. Pressure influence on iron sulfide scales formation. Pt. 5

    International Nuclear Information System (INIS)

    Delfino, C.A.; Lires, O.A.; Rojo, E.A.


    In order to protect carbon steel towers and piping of Girlder sulfide (G.S.) experimental heavy water plants against corrosion produced by the action of aqueous solutions of hydrogen sulfide, a method, previously published, was developed. Carbon steel, exposed to saturated aqueous solutions of hydrogen sulfide, forms iron sulfide scales. In oxygen free solutions evolution of corrosion follows the sequence: mackinawite → cubic ferrous sulfide → troilite → pyrrotite → pyrite. Scales formed by pyrrotite-pyrite or pyrite are the most protective layers (these are obtained at 130 deg C, 2MPa, for periods of 14 days). Experiments, at 125 deg C and periods of 10-25 days, were performed in two different ways: 1- constant pressure operations at 0.5 and 1.1 MPa. 2- variable pressure operation between 0.3-1 MPa. In all cases pyrrotite-pyrite scales were obtained. (Author) [es

  13. Oxidative Stress and Carbonyl Lesions in Ulcerative Colitis and Associated Colorectal Cancer

    Directory of Open Access Journals (Sweden)

    Zhiqi Wang


    Full Text Available Oxidative stress has long been known as a pathogenic factor of ulcerative colitis (UC and colitis-associated colorectal cancer (CAC, but the effects of secondary carbonyl lesions receive less emphasis. In inflammatory conditions, reactive oxygen species (ROS, such as superoxide anion free radical (O2∙-, hydrogen peroxide (H2O2, and hydroxyl radical (HO∙, are produced at high levels and accumulated to cause oxidative stress (OS. In oxidative status, accumulated ROS can cause protein dysfunction and DNA damage, leading to gene mutations and cell death. Accumulated ROS could also act as chemical messengers to activate signaling pathways, such as NF-κB and p38 MAPK, to affect cell proliferation, differentiation, and apoptosis. More importantly, electrophilic carbonyl compounds produced by lipid peroxidation may function as secondary pathogenic factors, causing further protein and membrane lesions. This may in turn exaggerate oxidative stress, forming a vicious cycle. Electrophilic carbonyls could also cause DNA mutations and breaks, driving malignant progression of UC. The secondary lesions caused by carbonyl compounds may be exceptionally important in the case of host carbonyl defensive system deficit, such as aldo-keto reductase 1B10 deficiency. This review article updates the current understanding of oxidative stress and carbonyl lesions in the development and progression of UC and CAC.

  14. A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer

    Energy Technology Data Exchange (ETDEWEB)

    Grannas, A.M.; Shepson, P.B.; Guimbaud, C. [Purdue Univ., West Lafayette, IN (US). Dept. of Earth and Atmospheric Sciences] [and others


    Experiments were conducted during the ALERT 2000 field campaign aimed at understanding the role of air-snow interactions in carbonyl compound chemistry and the associated ozone depletion in the atmospheric boundary layer. Under sunlit conditions, we find that formaldehyde, acetaldehyde and acetone exhibit a significant diel cycle with average ambient air concentrations of 166, 53 and 385 ppt, respectively. A box model of Arctic surface layer chemistry was used to understand the diel behavior of carbonyl compound concentrations at Alert, Nunavut, Canada, with a focus on the chemical and physical processes that affect carbonyl compounds. Results of the study showed that the measured carbonyl compound concentrations can only be simulated when a radiation-dependent snowpack source term (possibly photochemistry) and a temperature-dependent sink (physical uptake on snow grains) of carbonyl compounds were added to the model. We are able to simulate the concentration and amplitude of the observed diel cycle, but not the phase of the cycle. These results help confirm the importance of snowpack chemistry and physical processes with respect to carbonyl compound concentrations in the Arctic surface boundary layer, and reveal weakness in the details of our understanding. (Author)

  15. Role of protein-bound carbonyl groups in the formation of advanced glycation endproducts. (United States)

    Liggins, J; Furth, A J


    Several mechanisms have been postulated for the formation of advanced glycation endproducts (AGEs) from glycated proteins; they all feature protein-bound carbonyl intermediates. Using 2,4-dinitrophenylhydrazine (DNPH), we have detected these intermediates on bovine serum albumin, lysozyme and beta-lactoglobulin after in vitro glycation by glucose or fructose. Carbonyls were formed in parallel with AGE-fluorophores, via oxidative Maillard reactions. Neither Amadori nor Heyns products contributed to the DNPH reaction. Fluorophore and carbonyl yields were much enhanced in lipid-associated proteins, but both groups could also be detected in lipid-free proteins. When pre-glycated proteins were incubated in the absence of free sugar, carbonyl groups were rapidly lost in a first-order reaction, while fluorescence continued to develop beyond the 21 days of incubation. Another unexpected finding was that not all carbonyl groups were blocked by aminoguanidine, although there was complete inhibition of reactions leading to AGE-fluorescence. It is suggested that carbonyls acting as fluorophore precursors react readily with aminoguanidine, while others are resistant to this hydrazine, possibly because they are involved in ring closure. Factors influencing the relative rates of acyclisation and hydrazone formation are discussed, together with possible implications for antiglycation therapy.

  16. Characteristics of carbonyl compounds in public vehicles of Beijing city: Concentrations, sources, and personal exposures (United States)

    Pang, Xiaobing; Mu, Yujing

    The characteristics of carbonyl compounds (carbonyls) including concentrations, major sources, and personal exposure were investigated for 29 vehicles including taxi, bus and subway in Beijing. It was found that the taxis (Xiali, TA) and buses (Huanghe, BA) fueled by gasoline with longer service years had the higher indoor carbonyl levels (178±42.7 and 188±31.6 μg m -3) while subways energized by electricity without exhaust and the jingwa buses (BB) driven in the suburb had the lower levels with total concentrations of 98.5±26.3 and 92.1±20.3 μg m -3, respectively. Outdoor carbonyls of taxi cars and buses were nearly at the same level with their total concentrations varying from 80 to 110 μg m -3. The level of outdoor subways carbonyls was equal with the ambient air levels. Exhaust leakage, indoor material emissions, photochemical formation, and infiltration of outdoor air were considered to be the major sources to in-vehicle carbonyls. Personal exposures and cancer risk to formaldehyde and acetaldehyde were calculated for professional bus and taxi drivers, respectively. Taxi drivers had the highest cancer risk with personal exposure to formaldehyde and acetaldehyde of 212 and 243 μg day -1, respectively. The public concern should pay considerable attention to professional drivers' health.


    Directory of Open Access Journals (Sweden)



    Full Text Available Iron deficiency anemia is the most common and important public health problem all over the world in the risk group of antenatal women. Research is going on to improve the iron status of the pregnant women with different forms of iron available. In this regard, Carbonyl Iron is showing promising results in improving the red cell mass with better compliance. 120 antenatal women were recruited in this study. The study comprised of 6weeks for each patient. They were given Carbonyl Iron 100 mg/day and FeS04 100gm/day . Before and after treatment all the baseline and specific investigations were one. Results were tabulated, comparison and significance were tested by unpaired student ’s’ test and their 'p' value was calculated. Results were shown graphically also. Carbonyl Iron showed improvement in hemoglobin, PCV and better than ferrous Sulphate (P <0.001. Incidence of side effects were less with Carbonyl Iron than Ferrous Sulphate, better compliance was seen with Carbonyl Iron. In conclusion, the present study s howed that Carbonyl Iron had better efficacy and safety in the management of Iron deficiency anemia in antenatal women than ferrous Sulphate

  18. Predicting personal exposure to airborne carbonyls using residential measurements and time/activity data (United States)

    Liu, Weili; Zhang, Junfeng (Jim); Korn, Leo R.; Zhang, Lin; Weisel, Clifford P.; Turpin, Barbara; Morandi, Maria; Stock, Tom; Colome, Steve

    As a part of the Relationships of Indoor, Outdoor, and Personal Air (RIOPA) study, 48 h integrated residential indoor, outdoor, and personal exposure concentrations of 10 carbonyls were simultaneously measured in 234 homes selected from three US cities using the Passive Aldehydes and Ketones Samplers (PAKS). In this paper, we examine the feasibility of using residential indoor concentrations to predict personal exposures to carbonyls. Based on paired t-tests, the means of indoor concentrations were not different from those of personal exposure concentrations for eight out of the 10 measured carbonyls, indicating indoor carbonyls concentrations, in general, well predicted the central tendency of personal exposure concentrations. In a linear regression model, indoor concentrations explained 47%, 55%, and 65% of personal exposure variance for formaldehyde, acetaldehyde, and hexaldehyde, respectively. The predictability of indoor concentrations on cross-individual variability in personal exposure for the other carbonyls was poorer, explainingexposure concentrations. It was found that activities related to driving a vehicle and performing yard work had significant impacts on personal exposures to a few carbonyls.

  19. A new agent for derivatizing carbonyl species used to investigate limonene ozonolysis (United States)

    Wells, J. R.; Ham, Jason E.


    A new method for derivatizing carbonyl compounds is presented. The conversion of a series of dicarbonyls to oximes in aqueous solution and from gas-phase sampling was achieved using O-tert-butylhydroxylamine hydrochloride (TBOX). Some advantages of using this derivatization agent include: aqueous reactions, lower molecular weight oximes, and shortened oxime-formation reaction time. Additionally, the TBOX derivatization technique was used to investigate the carbonyl reaction products from limonene ozonolysis. With ozone (O3) as the limiting reagent, four carbonyl compounds were detected: 7-hydroxy-6-oxo-3-(prop-1-en-2-yl)heptanal; 3-Isopropenyl-6-oxoheptanal (IPOH), 3-acetyl-6-oxoheptanal (3A6O) and one carbonyl of unknown structure. Using cyclohexane as a hydroxyl (OHrad) radical scavenger, the relative yields (peak area) of the unknown carbonyl, IPOH, and 3A6O were reduced indicating the influence secondary OH radicals have on limonene ozonolysis products. The relative yield of the hydroxy-dicarbonyl based on the chromatogram was unchanged suggesting it is only made by the limonene + O3 reaction. The detection of 3A6O using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

  20. Amorphous molybdenum sulfides as hydrogen evolution catalysts. (United States)

    Morales-Guio, Carlos G; Hu, Xile


    Providing energy for a population projected to reach 9 billion people within the middle of this century is one of the most pressing societal issues. Burning fossil fuels at a rate and scale that satisfy our near-term demand will irreversibly damage the living environment. Among the various sources of alternative and CO2-emission-free energies, the sun is the only source that is capable of providing enough energy for the whole world. Sunlight energy, however, is intermittent and requires an efficient storage mechanism. Sunlight-driven water splitting to make hydrogen is widely considered as one of the most attractive methods for solar energy storage. Water splitting needs a hydrogen evolution catalyst to accelerate the rate of hydrogen production and to lower the energy loss in this process. Precious metals such as Pt are superior catalysts, but they are too expensive and scarce for large-scale applications. In this Account, we summarize our recent research on the preparation, characterization, and application of amorphous molybdenum sulfide catalysts for the hydrogen evolution reaction. The catalysts can be synthesized by electrochemical deposition under ambient conditions from readily available and inexpensive precursors. The catalytic activity is among the highest for nonprecious catalysts. For example, at a loading of 0.2 mg/cm(2), the optimal catalyst delivers a current density of 10 mA/cm(2) at an overpotential of 160 mV. The growth mechanism of the electrochemically deposited film catalysts was revealed by an electrochemical quartz microcrystal balance study. While different electrochemical deposition methods produce films with different initial compositions, the active catalysts are the same and are identified as a "MoS(2+x)" species. The activity of the film catalysts can be further promoted by divalent Fe, Co, and Ni ions, and the origins of the promotional effects have been probed. Highly active amorphous molybdenum sulfide particles can also be prepared

  1. Protein carbonylation, protein aggregation and neuronal cell death in a murine model of multiple sclerosis (United States)

    Dasgupta, Anushka

    Many studies have suggested that oxidative stress plays an important role in the pathophysiology of both multiple sclerosis (MS) and its animal model experimental autoimmune encephalomyelitis (EAE). Yet, the mechanism by which oxidative stress leads to tissue damage in these disorders is unclear. Recent work from our laboratory has revealed that protein carbonylation, a major oxidative modification caused by severe and/or chronic oxidative stress conditions, is elevated in MS and EAE. Furthermore, protein carbonylation has been shown to alter protein structure leading to misfolding/aggregation. These findings prompted me to hypothesize that carbonylated proteins, formed as a consequence of oxidative stress and/or decreased proteasomal activity, promote protein aggregation to mediate neuronal apoptosis in vitro and in EAE. To test this novel hypothesis, I first characterized protein carbonylation, protein aggregation and apoptosis along the spinal cord during the course of myelin-oligodendrocyte glycoprotein (MOG)35-55 peptide-induced EAE in C57BL/6 mice [Chapter 2]. The results show that carbonylated proteins accumulate throughout the course of the disease, albeit by different mechanisms: increased oxidative stress in acute EAE and decreased proteasomal activity in chronic EAE. I discovered not only that there is a temporal correlation between protein carbonylation and apoptosis but also that carbonyl levels are significantly higher in apoptotic cells. A high number of juxta-nuclear and cytoplasmic protein aggregates containing the majority of the oxidized proteins are also present during the course of EAE, which seems to be due to reduced autophagy. In chapter 3, I show that when gluthathione levels are reduced to those in EAE spinal cord, both neuron-like PC12 (nPC12) cells and primary neuronal cultures accumulate carbonylated proteins and undergo cell death (both by necrosis and apoptosis). Immunocytochemical and biochemical studies also revealed a temporal

  2. Occupational exposure to hydrogen sulfide: management of hydrogen sulfide exposure victims (Preprint No. SA-5)

    International Nuclear Information System (INIS)

    Srivastava, P.P.


    National Institute of Occupational Safety and Health, U.S.A. has listed 73 industries with potential exposure to hydrogen sulphide. Though the toxicity of hydrogen sulfide is known to mankind since the beginning of seventeenth century the exact mode of its toxicity and effective therapeutic regimen remains unclear as yet. This paper presents current thoughts on the toxicity of this substance and a discussion on the role of various antidotes used in H 2 S poisoning. (autho r)

  3. Azo dye decolorization assisted by chemical and biogenic sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Prato-Garcia, Dorian [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa de San José 2055, San Luis Potosí 78216 (Mexico); Buitrón, Germán, E-mail: [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico)


    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection.

  4. Synthesis and characterization of metal sulfide clusters for toxicological studies. (United States)

    Bowles, L C; Bell, Russell A; Ernste, Michael J; Kramer, James R; Manolopoulos, Helen; Ogden, Nancy


    Zinc sulfide clusters were synthesized and characterized at low micromolar concentrations to assess the effect of metal-sulfide ligands on metal toxicity to aquatic organisms in oxic environments. Recommended preparation times are greater than 2 h initial reaction of equimolar sodium sulfide and zinc nitrate, followed by oxic aeration for 3 d. Ionic strength, pH, and anoxic stabilization time were found to be relatively unimportant in controlling the final yield. Adsorptive losses of zinc sulfide (ZnS) clusters to surfaces, however, were significant for a variety of vessel materials and membrane filters. Ionic strength and pH were found to be important factors controlling the extent of adsorptive losses with minimal loss for pHs greater than 9 and for soft waters. The Ag(I), Cu(II), and Hg(II) as metal sulfides completely suppress the analysis of sulfide, whereas Pb(II), Mn(II), and Co(II) partially suppress the analysis of sulfide by the methylene blue technique. Ultraviolet and fluorescence spectra are shown for synthesized ZnS clusters.

  5. Sulfidation behavior and mechanism of zinc silicate roasted with pyrite (United States)

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


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

  6. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Daria L. [Department of Chemistry, Yale University, 225; Beltrán-Suito, Rodrigo [Department of Chemistry, Yale University, 225; Thomsen, Julianne M. [Department of Chemistry, Yale University, 225; Hashmi, Sara M. [Department of Chemical and Environmental; Materna, Kelly L. [Department of Chemistry, Yale University, 225; Sheehan, Stafford W. [Catalytic Innovations LLC, 70 Crandall; Mercado, Brandon Q. [Department of Chemistry, Yale University, 225; Brudvig, Gary W. [Department of Chemistry, Yale University, 225; Crabtree, Robert H. [Department of Chemistry, Yale University, 225


    This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.

  7. Sulfidic vapor phase catalysts, especially tungsten sulfide, in industrial coal hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Pier, M.


    The historical development of high-pressure processes of the I. G. Farbenindustrie, from ammonia through methanol and gasoline, and the special case of gasoline production with a fixed-bed catalyst (tungsten sulfide) were discussed. The preparation, properties, and uses of this versatile catalyst were discussed, but it was emphasized that with the sotrmy development of the process, a condition which still existed at the time of this report, and with a great number of practical problems to solve, no extensive study of basic facts had ben possible. This tungsten sulfide catalyst was an especially active vapor-phase catalyst which operated at lower temperatures than the molybdenum catalysts formerly used. It also permitted higher thruputs, even with the oils from bituminous coal that were difficult to split. For certain uses, such as the improvement of the antiknock properties or the saving in tungsten, it was strongly diluted. Studies on using up sulfur in the tungsten sulfide catalyst were in progress at this time and showed there was practically no reduction of it under the conditions of hydrogenation under pressure as long as the raw material contained sulfur.

  8. Size Effect Studies of the Creep Behaviour of 20MnMoNi55 at Temperatures from 700 {sup o}C to 900 {sup o}C

    Energy Technology Data Exchange (ETDEWEB)

    Krompholz, K.; Groth, E.; Kalkhof, D


    One of the objectives of the REVISA project (REactor Vessel Integrity in Severe Accidents) is to assess size and scale effects in plastic flow and failure. This includes an experimental programme devoted to characterising the influence of specimen size, strain rate, and strain gradients at various temperatures. One of the materials selected was the forged reactor pressure vessel material 20 MnMoNi 55, material number 1.6310 (heat number 69906). Among others, a size effect study of the creep response of this material was performed, using geometrically similar smooth specimens with 5 mm and 20 mm diameter. The tests were done under constant load in an inert atmosphere at 700 {sup o}C, 800 {sup o}C, and 900 {sup o}C, close to and within the phase transformation regime. The mechanical stresses varied from 10 MPa to 30 MPa, depending on temperature. Prior to creep testing the temperature and time dependence of scale oxidation as well as the temperature regime of the phase transformation was determined. The creep tests were supplemented by metallographical investigations.The test results are presented in form of creep curves strain versus time from which characteristic creep data were determined as a function of the stress level at given temperatures. The characteristic data are the times to 5% and 15% strain and to rupture, the secondary (minimum) creep rate, the elongation at fracture within the gauge length, the type of fracture and the area reduction after fracture. From metallographical investigations the austenitic phase contents at different temperatures could be estimated. From these data also the parameters of the regression calculation (e.g. Norton's creep law) were obtained. The evaluation revealed that the creep curves and characteristic data are size dependent of varying degree, depending on the stress and temperature level, but the size influence cannot be related to corrosion or orientation effects or to macroscopic heterogeneity (position effect) of

  9. On the pelletizing of sulfide molybdenite concentrate

    International Nuclear Information System (INIS)

    Palant, A.A.


    Investigation results are discussed on the process of pelletizing with the use of various binders (water, syrup, sulfite-alcoholic residue and bentonite) for flotation sulfide molybdenite concentrate (∼84 % MoS 2 ) of the Mongolian deposit. It is established that with the use of syrup rather strong pellets (>300 g/p) of desired size (2-3 mm) can be obtained at a binder flowrate of 1 kg per 100 kg of concentrate. The main advantage of using syrup instead of bentonite lies in the fact that in this instance no depletion of a molybdenum calcine obtained by oxidizing roasting of raw ore takes place due to syrup complete burning out. This affects positively subsequent hydrometallurgical conversion because of decreasing molybdenum losses with waste cakes [ru

  10. Modulated structure calculated for superconducting hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Majumdar, Arnab; Tse, John S.; Yao, Yansun [Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, SK (Canada)


    Compression of hydrogen sulfide using first principles metadynamics and molecular dynamics calculations revealed a modulated structure with high proton mobility which exhibits a diffraction pattern matching well with experiment. The structure consists of a sublattice of rectangular meandering SH{sup -} chains and molecular-like H{sub 3}S{sup +} stacked alternately in tetragonal and cubic slabs forming a long-period modulation. The novel structure offers a new perspective on the possible origin of the superconductivity at very high temperatures in which the conducting electrons in the SH chains are perturbed by the fluxional motions of the H{sub 3}S resulting in strong electron-phonon coupling. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Organometallic and Bioorganometallic Chemistry - Ferrocene and Metal Carbonyls

    Directory of Open Access Journals (Sweden)

    Čakić Semenčić, M.


    Full Text Available Organometallic chemistry deals with compounds containing metal-carbon bonds. Basic organometallics derived from the s- and p-block metals (containing solely σ-bonds were understood earlier, while organometallic chemistry of the d- and f-block has developed much more recently. These compounds are characterized by three types of M-C bonds (σ, π and δand their structures are impossible to deduce by chemical means alone; fundamental advances had to await the development of X-ray diffraction, as well as IR- and NMR-spectroscopy. On the other hand, elucidation of the structure of e. g. vitamin B12 and ferrocene (discovered in 1951 contributed to progress in these instrumental analytical methods, influencing further phenomenal success of transition-metal organometallic chemistry in the second half of the twentieth century. The most thoroughly explored fields of application of organometallics were in the area of catalysis, asymmetric synthesis, olefin metathesis, as well as organic synthesis and access to new materials and polymers.The most usual ligands bound to d- and f-metals are carbon monoxide, phosphines, alkyls, carbenes and arenes, and in this review the bonding patterns in the metal carbonyls and ferrocene are elaborated. The common characteristics of these two classes are two-component bonds. The CO-M bonds include (i donation from ligand HOMO to vacant M d-orbitals (σ-bond, and (ii back-donation from the filled M d-orbitals in the ligand LUMO (π-bond. Similar (but much more complicated ferrocene contains delocalized bonds consisting of electron donation from Cp to Fe (σ-bonds- and π-bonding and δ-back-bonding from metal to Cp. In such a way ferrocene, i. e. (η5-Cp2Fe contains 18 bonding electrons giving to this compound "superaromatic" properties in the sense of stability and electrophilic substitution. In contrast to benzenoid aromatic compounds reactions in two Cp-rings can occur giving homo- and heteroannularly mono-, two-… per

  12. Benchmarking of protein carbonylation analysis in Caenorhabditis elegans: specific considerations and general advice. (United States)

    Pyr Dit Ruys, S; Bonzom, J-M; Frelon, S


    Oxidative stress has been extensively studied due to its correlation with cellular disorders and aging. In proteins, one biomarker of oxidative stress is the presence of carbonyl groups, such as aldehyde and ketone, in specific amino acid side chains such as lysine, proline, arginine and threonine, so-called protein carbonylation (PC). PC study is now a growing field in general and medical science since PC accumulation is associated with various pathologies and disorders. At present, enzyme-linked immunosorbent assays (ELISA) seem to be the most robust method of quantifying the presence of carbonyl groups in proteins, despite having some recognised caveats. In parallel, gel-based approaches present cross-comparison difficulties, along with other technical problems. As generic PC analyses still suffer from poor homogeneity, leading to cross-data analysis difficulties and poor results overlap, the need for harmonisation in the field of carbonyl detection is now widely accepted. This study aims to highlight some of the technical challenges in proteomic gel-based multiplexing experiments when dealing with PC in difficult samples like those from Caenorhabditis elegans, from protein extraction to carbonyl detection. We demonstrate that some critical technical parameters, such as labelling time, probe concentration, and total and carbonylated protein recovery rates, should be re-addressed in a sample-specific way. We also defined a procedure to cost-effectively adapt CyDye™-hydrazide-based protocols to specific samples, especially when the experimental interest is focused on studying differences between stimulating conditions with a maximised signal-to-noise ratio. Moreover, we have improved an already-existing powerful solubilisation buffer, making it potentially useful for hard-to-solubilise protein pellets. Lastly, the depicted methodology exemplifies a simple way of normalising carbonyl-related signal to total protein in SDS-PAGE multiplexing experiments. Within

  13. 75 FR 8889 - Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting (United States)


    ... Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting AGENCY: Environmental Protection... for hydrogen sulfide (Chemical Abstracts Service Number (CAS No.) 7783-06-4). Hydrogen sulfide was... requirements for hydrogen sulfide in order to evaluate issues brought to the Agency's attention after...

  14. Thermoelectric properties of non-stoichiometric lanthanum sulfides

    International Nuclear Information System (INIS)

    Shapiro, E.; Danielson, L.R.


    The lanthanum sulfides are promising candidate materials for high-efficiency thermoelectric applications at temperatures up to 1300 0 C. The nonstoichiometric lanthanum sulfides (LaS /SUB x/ , where 1.33 2 //rho/ can be chosen. The thermal conductivity remains approximately constant with stoichiometry, so a material with an optimum value of α 2 //rho/ should possess the optimum figure-of-merit. Data for the Seebeck coefficient and electrical resistivity of non-stoichiometric lanthanum sulfides is presented, together with structural properties of these materials

  15. Sulfide Oxidation in the Anoxic Black-Sea Chemocline

    DEFF Research Database (Denmark)



    per day, occurred in anoxic water at the top of the sulfide zone concurrent with the highest rates of dark CO2 assimilation. The main soluble oxidized products of sulfide were thiosulfate (68-82%) and sulfate. Indirect evidence was presented for the formation of elemental sulfur which accumulated...... that the measured H2S oxidation rates were 4-fold higher than could be explained by the downward flux of organic carbon and too high to balance the availability of electron acceptors such as oxidized iron or manganese. A nitrate maximum at the lower boundary of the O2 zone did not extend down to the sulfide zone....

  16. Iron sulfide corrosion in the 700 atm. liquid phase preheater

    Energy Technology Data Exchange (ETDEWEB)

    Donath, E.; Nonnenmacher, H.


    Equilibrium calculations gave lower bounds on partial pressure of hydrogen sulfide within a 500 atm. hydrogen gas stream, below which no corrosion of the steel tube walls would occur. AT 450/sup 0/C the lower bound was 0.5 atm., whereas at 500/sup 0/C the lower bound was 0.8 atm. However, in most plants, the hydrogen sulfide partial pressure exceeded values, so corrosion by formation of iron sulfide did usually occur. It was estimated that the corrosion reaction rate at 500/sup 0/C was about twice what it was at 450/sup 0/C.

  17. Conspicuous veils formed by vibrioid bacteria on sulfidic marine sediment

    DEFF Research Database (Denmark)

    Thar, Roland Matthias; Kühl, Michael


    We describe the morphology and behavior of a hitherto unknown bacterial species that forms conspicuous veils (typical dimensions, 30 by 30 mm) on sulfidic marine sediment. The new bacteria were enriched on complex sulfidic medium within a benthic gradient chamber in oxygen-sulfide countergradients......, but the bacteria have so far not been isolated in pure culture, and a detailed characterization of their metabolism is still lacking. The bacteria are colorless, gram-negative, and vibrioid-shaped (1.3- to 2.5- by 4- to 10-µm) cells that multiply by binary division and contain several spherical inclusions of poly...

  18. Use of sulfide-containing liquors for removing mercury from flue gases (United States)

    Nolan, Paul S.; Downs, William; Bailey, Ralph T.; Vecci, Stanley J.


    A method and apparatus for reducing and removing mercury in industrial gases, such as a flue gas, produced by the combustion of fossil fuels, such as coal, adds sulfide ions to the flue gas as it passes through a scrubber. Ideally, the source of these sulfide ions may include at least one of: sulfidic waste water, kraft caustic liquor, kraft carbonate liquor, potassium sulfide, sodium sulfide, and thioacetamide. The sulfide ion source is introduced into the scrubbing liquor as an aqueous sulfide species. The scrubber may be either a wet or dry scrubber for flue gas desulfurization systems.

  19. Micro-aeration for hydrogen sulfide removal from biogas (United States)

    Duangmanee, Thanapong

    The presence of sulfur compounds (e.g. protein, sulfate, thiosulfate, sulfite, etc.) in the feed stream generates highly corrosive and odorous hydrogen sulfide during anaerobic digestion. The high sulfide level in the biogas stream is not only poisonous to many novel metal catalysts employed in thermo-catalytic processes but also reduces the quality of methane to produce renewable energy. This study used an innovative, low-maintenance, low-cost biological sulfide removal technology to remove sulfides simultaneously from both gas and liquid phase. ORP (Oxidation-Reduction-Potential) was used as the controlling parameter to precisely regulate air injection to the sulfide oxidizing unit (SOU). The microaeration technique provided just enough oxygen to partially oxidize sulfides to elemental sulfur without inhibiting methanogenesis. The SOU was equipped with a diffuser at the bottom for the dispersion of sulfide-laden biogas and injected air throughout the column. The SOU can be operated as a standalone unit or coupled with an anaerobic digester to simultaneously remove sulfide from the biogas and effluent. The integrated system was capable of reducing hydrogen sulfide in biogas from 2,450 to less than 2 ppmV with minimal sulfate production at the highest available sulfide loading rate of 0.24 kg/m3-day. More than 98% of sulfide removed was recovered as elemental sulfur. However, the standalone SOU was able to operate at high hydrogen sulfide loading of 1.46 kg/m 3-day at inlet sulfide concentration of 3000 ppmV and reduce the off-gas hydrogen sulfide concentrations to less than 10 ppmV. The experiment also revealed that the ORP controlled aeration was sensitive enough to prevent oxygen overdosing (dampening effect) during unexpected surges of aeration. Using generalized linear regression, a model predicting output H2S concentration based on input H2S concentrations, SOU medium heights, and biogas flow rates, was derived. With 95% confidence, output H2S concentration

  20. Proteomic identification of carbonylated proteins in F344 rat hippocampus after 1-bromopropane exposure

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Zhenlie [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Department of Toxicology, Guangdong Prevention and Treatment Center for Occupational Diseases, Guangzhou 510‐300 (China); Ichihara, Sahoko [Graduate School of Regional Innovation Studies, Mie University, Tsu 514‐8507 (Japan); Oikawa, Shinji [Department of Environmental and Molecular Medicine, Mie University Graduate School of Medicine, Mie 514‐8507 (Japan); Chang, Jie; Zhang, Lingyi; Subramanian, Kaviarasan; Mohideen, Sahabudeen Sheik [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan); Ichihara, Gaku, E-mail: [Department of Occupational and Environmental Health, Nagoya University Graduate School of Medicine, Nagoya 466‐8550 (Japan)


    1-Bromopropane (1-BP) is neurotoxic in both experimental animals and humans. Previous proteomic analysis of rat hippocampus implicated alteration of protein expression in oxidative stress, suggesting that oxidative stress plays a role in 1-BP-induced neurotoxicity. To understand this role at the protein level, we exposed male F344 rats to 1-BP at 0, 400, or 1000 ppm for 8 h/day for 1 week or 4 weeks by inhalation and quantitated changes in hippocampal protein carbonyl using a protein carbonyl assay, two-dimensional gel electrophoresis (2-DE), immunoblotting, and matrix-assisted laser-desorption ionization time-of-flight mass spectrometry (MALDI-TOF-TOF/MS). Hippocampal reactive oxygen species and protein carbonyl were significantly increased, demonstrating 1-BP-associated induction of oxidative stress and protein damage. MALDI-TOF-TOF/MS identified 10 individual proteins with increased carbonyl modification (p < 0.05; fold-change ≥ 1.5). The identified proteins were involved in diverse biological processes including glycolysis, ATP production, tyrosine catabolism, GTP binding, guanine degradation, and neuronal metabolism of dopamine. Hippocampal triosephosphate isomerase (TPI) activity was significantly reduced and negatively correlated with TPI carbonylation (p < 0.001; r = 0.83). Advanced glycation end-product (AGE) levels were significantly elevated both in the hippocampus and plasma, and hippocampal AGEs correlated negatively with TPI activity (p < 0.001; r = 0.71). In conclusion, 1-BP-induced neurotoxicity in the rat hippocampus seems to involve oxidative damage of cellular proteins, decreased TPI activity, and elevated AGEs. -- Highlights: ► 1-BP increases hippocampal ROS levels and hippocampal and plasma protein carbonyls. ► 1-BP increases TPI carbonylation and decreases TPI activity in the hippocampus. ► 1-BP increases hippocampal and plasma AGE levels.

  1. Potential impacts of OCS oil and gas activities on fisheries. Volume 2. Annotated bibliography for OCS oil and gas impact studies. Final report

    International Nuclear Information System (INIS)

    Tear, L.M.


    The volume is the second of two volumes to the final report, Potential Impacts of OCS Oil and Gas Activities on Fisheries. The volume presents an annotated bibliography of published and grey literature related to OCS oil and gas activity impacts of finfish and shellfish in marine and estuaring waters. The studies presented in the bibliography include those related to the following pollutants or impact-causing activities: Rig/reef effects, Drilling discharges (muds or cuttings), Oil (petroleum hydrocarbons), Trace metals, Produced water, Habitat alteration, Debris, Rig placement (avoidance), Pipelines, and Socioeconomic effects. The studies are listed alphabetically by the primary author's last name. An index is provided to help the reader identify studies related to a specific impact

  2. Portable Cathode-Air Vapor-Feed Electrochemical Medical Oxygen Concentrator (OC) (United States)

    Balasubramanian, Ashwin


    Missions on the International Space Station and future space exploration will present significant challenges to crew health care capabilities, particularly in the efficient utilization of onboard oxygen resources. Exploration vehicles will require lightweight, compact, and portable oxygen concentrators that can provide medical-grade oxygen from the ambient cabin air. Current pressure-swing adsorption OCs are heavy and bulky, require significant start-up periods, operate in narrow temperature ranges, and require a liquid water feed. Lynntech, Inc., has developed an electrochemical OC that operates with a cathode-air vapor feed, eliminating the need for a bulky onboard water supply. Lynntech's OC is smaller and lighter than conventional pressure-swing OCs, is capable of instant start-up, and operates over a temperature range of 5-80 C. Accomplished through a unique nanocomposite proton exchange membrane and catalyst technology, the unit delivers 4 standard liters per minute of humidified oxygen at 60 percent concentration. The technology enables both ambient-pressure operating devices for portable applications and pressurized (up to 3,600 psi) OC devices for stationary applications.

  3. The Hydraulic Project Włocławek: Design, Studies, Construction and Operation

    Directory of Open Access Journals (Sweden)

    Wojciech Majewski


    Full Text Available The Hydraulic Project Włocławek was commissioned in 1970 as the first barrage of the Lower Vistula Cascade (LVC. The purpose of the LVC was to create an important source of hydro-energy and inland navigation route connecting central Poland with the port city of Gdańsk. Along the Lower Vistula (LV important cities and industrial centres are located. The Włocławek project still remains the only barrage on the LV thus creating a number of problems. The paper presents the basic hydrological and hydraulic data for the Vistula river, and describes the Włocławek project, hydraulic model investigations conducted in the design phase, the construction of the project and the main problems, attendant on its use, including the winter flood of 1982 in the upper part of the Włocławek reservoir. The paper ends with conclusions on project construction and exploitation. The next barrage downstream from Włocławek is proposed.

  4. Co-settling of Chromite and Sulfide Melt Droplets and Trace Element Partitioning between Sulfide and Silicate Melts (United States)

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


    Gravitational settling of immiscible, dense sulfide melt droplets together with other cumulate phases such as chromite, combined with downward percolation of these droplets through a cumulate pile, is thought to be one of the possible processes leading to the formation of PGE rich sulfide deposits in layered mafic intrusions. Furthermore some chromitite seams in the Merensky Reef (Bushveld Complex) are considered to be acting as a filter or barrier for further downward percolation of sulfide melts into footwall layers. To investigate the feasibility of such mechanical processes and to study the partitioning behavior of 50 elements including transition metals and REEs (but not PGEs) between a silicate and a sulfide melt, two separate series of high temperature (1250-1380 °C) centrifuge-assisted experiments at 1000 g, 0.4-0.6 GPa were conducted. A synthetic silicate glass with a composition representative of the parental magma of the Bushveld Complex (~ 55 wt% SiO2) was mixed with pure FeS powder. For the first series of experiments, 15 or 25 wt% natural chromite with average grain sizes of ~ 5 or 31 μm were added to a mixture of silicate glass and FeS (10 wt%) adding 1 wt% water. For the second series, a mixture of the same glass and FeS was doped with 50 trace elements. These mixtures were first statically equilibrated and then centrifuged. In the first experimental series, sulfide melt droplets settled together with, but did not segregate from chromite grains even after centrifugation at 1000 g for 12 hours. A change in initial chromite grain size and proportions didn't have any effect on segregation. Without chromite, the starting mixture resulted in the formation of large sulfide melt pools together with finer droplets still disseminated through the silicate glass and both at the bottom of the capsule. The incomplete segregation of sulfide melt is interpreted as being due to high interfacial energies between sulfide and silicate melts/crystals which hinder

  5. Damage of Metal Structures Under the Action of Hydrogen Sulfide Containing Environments (United States)

    Kushnarenko, V. M.; Uzyakov, R. N.; Repyakh, V. S.


    The effect of hydrogen sulfide containing environments, stress-strain states, stress concentration and external actions on the hydrogen sulfide cracking of steels is considered. Examples of typical and atypical action of hydrogen sulfide containing environments on carbon and stainless steels are presented. The factors responsible for hydrogen sulfide cracking are determined. Recommendations are given on design and production of equipment contacting hydrogen sulfide environments.

  6. Rh(I)-catalyzed CO gas-free carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids using formaldehyde. (United States)

    Morimoto, Tsumoru; Yamasaki, Kae; Hirano, Akihisa; Tsutsumi, Ken; Kagawa, Natsuko; Kakiuchi, Kiyomi; Harada, Yasuyuki; Fukumoto, Yoshiya; Chatani, Naoto; Nishioka, Takanori


    The rhodium(I)-catalyzed reaction of alkynes with 2-bromophenylboronic acids in the presence of paraformaldehyde resulted in a CO gas-free carbonylative cyclization, yielding indenone derivatives. [RhCl(BINAP)](2) and [RhCl(cod)](2) were responsible for the decarbonylation of formaldehyde and the subsequent carbonylation of alkynes with 2-haloboronic acids, respectively, leading to efficient whole carbonylation. Sterically bulky and electron-withdrawing groups on unsymmetrically substituted alkynes favored the alpha-position of indenones.

  7. Assessing pollution in a Mediterranean lagoon using acid volatile sulfides and estimations of simultaneously extracted metals. (United States)

    Zaaboub, Noureddine; Helali, Mohamed Amine; Martins, Maria Virgínia Alves; Ennouri, Rym; Béjaoui, Béchir; da Silva, Eduardo Ferreira; El Bour, Monia; Aleya, Lotfi


    Bizerte Lagoon is a southern Mediterranean semi-enclosed lagoon with a maximum depth of 12 m. After assessing sediment quality, the authors report on the physicochemical characteristics of the lagoon's surface sediment using SEM (simultaneously extracted metals) and AVS (acid volatile sulfides) as proxies. Biogeochemical tools are used to investigate the environmental disturbance at the water-sediment interface by means of SEM and AVS to seek conclusions concerning the study area's pollution status. Results confirm accumulation of trace elements in sediment. The use of the SEM-AVS model with organic matter in sediment (ƒOC) confirms possible bioavailability of accumulated trace elements, especially Zn, in the southern part of the lagoon, with organic matter playing an important role in SEM excess correction to affirm a nontoxic total metal sediment state. Individual trace element toxicity is dependent on the bioavailable fraction of SEM Metal on sediment, as is the influence of lagoon inflow from southern water sources on element bioavailability. Appropriate management strategies are highly recommended to mitigate any potential harmful effects on health from this heavy-metal-based pollution.

  8. Desulfurizing Difluorination Reaction of Benzyl Sulfides Using IF5


    Fukuhara, Tadahito; Hara, Shoji


    A desulfurizing difluorination reaction of benzyl sulfides having a functional group such as an ester, a ketone, a nitrile, or an amide was performed by a reaction with IF5. Consequently, gem-difluoro compounds could be obtained selectively.

  9. Ambient gas-particle partitioning of atmospheric carbonyl at an urban site in Beijing (United States)

    Shen, H.; Chen, Z.


    Carbonyls are important oxidation intermediates of hydrocarbons and major carcinogenic and genotoxic compounds in urban areas. While their health and climate impacts are primarily associated with their gas-particle conversion such as oligomers and brown carbon formation in particle phase, however, observations of their actual ambient gas-particle partitioning are sparse. In this study, the Sep-Pak DNPH-Silica Gel Cartridges and a four-channel particle sampler were used to collect carbonyls in gaseous and particle (PM2.5) phases simultaneously. Six carbonyls (formaldehyde, acetaldehyde, acetone, propionaldehyde and two dicarbonyls, glyoxal and methylglyoxal) of the ten observed in gas phase (plus butyraldehyde, methacrolein, methyl vinyl ketone, benzaldehyde) were detected in ambient particles. The measured gas/particle (G/P) partitioning coefficients (Kp,field) of the six carbonyls were calculated and compared to their predicted G/P partitioning coefficients (Kp,theor) based on the absorptive partitioning theory. The values of Kp,field are 105-106 times higher than Kp,theor and the Kp,field of the measured total carbonyls were determined to be as high as (0.3-11)×10-4 m3 µg-1, indicating that small carbonyls were much easier to enter the particle phase than previously expected and their distribution between gas and particles varied greatly with environmental conditions. The measured Kp,CHOCHO > Kp,CH3COCHO > Kp,CH3CH3CHO > Kp,CH3CHO ≈ Kp,HCHO > Kp,CH3COCH3, suggesting that the aldehyde group, to some extent, is more likely to promote the carbonyl compounds into particle phase than ketone group and methyl group. The variation trends of the measured G/P partitioning coefficients were very consistent and significantly correlated, and did not reflect the different salting effect for glyoxal and methylglyoxal ("salting-in" for glyoxal and "salting-out" for methylglyoxal), which indicated that the factors affecting the gas-particle partitioning of carbonyls in the

  10. Advanced zirconia-coated carbonyl-iron particles for acidic magnetorheological finishing of chemical-vapor-deposited ZnS and other IR materials (United States)

    Salzman, S.; Giannechini, L. J.; Romanofsky, H. J.; Golini, N.; Taylor, B.; Jacobs, S. D.; Lambropoulos, J. C.


    We present a modified version of zirconia-coated carbonyl-iron (CI) particles that were invented at the University of Rochester in 2008. The amount of zirconia on the coating is increased to further protect the iron particles from corrosion when introduced to an acidic environment. Five low-pH, magnetorheological (MR) fluids were made with five acids: acetic, hydrochloric, nitric, phosphoric, and hydrofluoric. All fluids were based on the modified zirconia-coated CI particles. Off-line viscosity and pH stability were measured for all acidic MR fluids to determine the ideal fluid composition for acidic MR finishing of chemical-vapor-deposited (CVD) zinc sulfide (ZnS) and other infrared (IR) optical materials, such as hot-isostatic-pressed (HIP) ZnS, CVD zinc selenide (ZnSe), and magnesium fluoride (MgF2). Results show significant reduction in surface artifacts (millimeter-size, pebble-like structures on the finished surface) for several standard-grade CVD ZnS substrates and good surface roughness for the non-CVD MgF2 substrate when MR finished with our advanced acidic MR fluid.

  11. Determination of Hydrogen Sulfide in Fermentation Broths Containing SO21 (United States)

    Acree, T. E.; Sonoff, Elisabeth P.; Splittstoesser, D. F.


    A procedure for the determination of hydrogen sulfide in fermentation broths containing up to 100 μg of SO2 per ml is described. The method involves the sparging of H2S from the broth into a cadmium hydroxide absorption solution, the formation of methylene blue from the absorbed sulfide, and the measuring of this color spectrophotometrically. The use of cadmium hydroxide instead of zinc acetate, the common absorbent, substantially reduced the interference of SO2 with the analysis. PMID:5111300


    Directory of Open Access Journals (Sweden)

    Yu. P. Sedlukho


    Full Text Available The paper considers problems and features of biochemical removal of hydrogen sulfide from ground water. The analysis of existing methods for purification of ground water from hydrogen sulfide has been given in the paper. The paper has established shortcomings of physical and chemical purification of ground water. While using aeration methods for removal of hydrogen sulfide formation of colloidal sulfur that gives muddiness and opalescence to water occurs due to partial chemical air oxidation. In addition to this violation of sulfide-carbonate equilibrium taking place in the process of aeration due to desorption of H2S and CO2, often leads to clogging of degasifier nozzles with formed CaCO3 that causes serious operational problems. Chemical methods require relatively large flow of complex reagent facilities, storage facilities and transportation costs.In terms of hydrogen sulfide ground water purification the greatest interest is given to the biochemical method. Factors deterring widespread application of the biochemical method is its insufficient previous investigation and necessity to execute special research in order to determine optimal process parameters while purifying groundwater of a particular water supply source. Biochemical methods for oxidation of sulfur compounds are based on natural biological processes that ensure natural sulfur cycle. S. Vinogradsky has established a two-stage mechanism for oxidation of hydrogen sulfide with sulfur bacteria (Beggiatoa. The first stage presupposes oxidation of hydrogen sulphide to elemental sulfur which is accumulating in the cytoplasm in the form of globules. During the second stage sulfur bacteria begin to oxidize intracellular sulfur to sulfuric acid due to shortage of hydrogen sulfide.The paper provides the results of technological tests of large-scale pilot plants for biochemical purification of groundwater from hydrogen sulfide in semi-industrial conditions. Dependences of water quality

  13. Structural Properties of Zinc Sulfide Polymer Nanocomposite with Alginate


    A.M. Mieshkov; T.O. Berestok; L.F. Sukhodub; А.S. Оpanasyuk


    The comparison of structural and substructural characteristics of pure zinc sulfide and biopolymer based on ZnS composite with alginate was held by scanning electron microscopy, diffraction and X-ray fluorescence spectrometry. Films and nanostructures of zinc sulfide were obtained by chemical bath deposition from an aqueous solution of zinc nitrate, sodium alginate and tiaourea at 90 °C and synthesis time of 30-120 min. It is established that growth occurs through the formation of condensate ...

  14. Impacts of Outer Continental Shelf (OCS) development on recreation and tourism. Volume 3. Detailed methodology

    Energy Technology Data Exchange (ETDEWEB)


    The final report for the project is presented in five volumes. This volume, Detailed Methodology Review, presents a discussion of the methods considered and used to estimate the impacts of Outer Continental Shelf (OCS) oil and gas development on coastal recreation in California. The purpose is to provide the Minerals Management Service with data and methods to improve their ability to analyze the socio-economic impacts of OCS development. Chapter II provides a review of previous attempts to evaluate the effects of OCS development and of oil spills on coastal recreation. The review also discusses the strengths and weaknesses of different approaches and presents the rationale for the methodology selection made. Chapter III presents a detailed discussion of the methods actually used in the study. The volume contains the bibliography for the entire study.

  15. Impacts of Outer Continental Shelf (OCS) development on recreation and tourism. Volume 1. Executive summary

    Energy Technology Data Exchange (ETDEWEB)


    The study was intended to provide the Mineral Management Service (MMS) with an analytical tool to evaluate possible economic impacts from Outer Continental Shelf (OCS) development. In particular, the study was designed to provide MMS staff who work on lease sale Energy Impact Statements with an objective technique for estimating the impacts to coastal communities from events that might occur as a result of lease sales: oil spills, onshore construction, and construction of platforms offshore. The project had several specific objectives: (1) provide profiles of 1982 socio-economic conditions in coastal communities, including an analysis of the relative importance of the tourist industry in each coastal county; (2) develop a methodology for determining the effects of OCS development on coastal recreation; and recommend mitigation measure that may reduce the negative effect of OCS development on coastal recreation using gravity and economic effects models.

  16. Proteomic evaluation of myofibrillar carbonylation in chilled fish mince and its inhibition by catechin. (United States)

    Pazos, Manuel; Maestre, Rodrigo; Gallardo, José M; Medina, Isabel


    The present study investigates the susceptibility of individual myofibrillar proteins from mackerel (Scomber scombrus) mince to undergo carbonylation reactions during chilled storage, and the antioxidant capacity of (+)-catechin to prevent oxidative processes of proteins. The carbonylation of each particular protein was quantified by combining the labelling of protein carbonyls by fluorescein-5-thiosemicarbazide (FTSC) with 1-D or 2-D gel electrophoresis. Alpha skeletal actin, glycogen phosphorylase, unnamed protein product (UNP) similar to enolase, pyruvate kinase, isoforms of creatine kinase, aldolase A and an isoform of glyceraldehyde 3-phosphate dehydrogenase (G3PDH) showed elevated oxidation in chilled non-supplemented mince. Myosin heavy chain (MHC) was not carbonylated in chilled muscle, but an extensive MHC degradation was observed in those samples. The supplementation of catechin reduced protein oxidation and lipid oxidation in a concentration-dependent manner: control>25>100≈200ppm. Therefore, the highest catechin concentrations (100 and 200ppm) exhibited the strongest antioxidant activity. Catechin (200ppm) reduced significantly carbonylation of protein spots identified as glycogen phosphorylase, pyruvate kinase muscle isozyme, isoforms of creatine kinase. Conversely, catechin was ineffective to inhibit the oxidation of actin and UNP similar to enolase. These results draw attention to the inefficiency of catechin to prevent actin oxidation, in contrast to the extremely high efficiency of catechin in inhibiting oxidation of lipids and other proteins. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. The effect of humidity on peak value of HEMA carbonyl absorbance band

    Directory of Open Access Journals (Sweden)

    Adioro Soetojo


    Full Text Available Bond strength between 2-Hydroxyethyl methacrylate HEMA-based dentin bonding agent and dentin collagen had proved by presence of the chemical interaction. This union involved the carbonyl group on HEMA resin with amino group on dentin collagen following produce an amide chain. However, this bond strength influence by humidity condition of dentin collagen and HEMA resin. The aim of this study is to measure the effect of humidity on peak value of the HEMA carbonyl absorbance band. The bond strength between by HEMA bonding agent and dentine collagen was analyzed in different humidity, e.g. in 60%, 70%, 80%, and 90% humidity. Control experiment was done in ambient room humidity that is 65%. Chemical bond that formed between HEMA and dentine collagen was carried out by mixing pure HEMA with bovine type-I collagen which had been stored in different humidity. The esther carbonyl group of HEMA will react with the amino group of collagen, produced an amide bonding, which is observed by measuring the IR spectrum absorbance of the esther carbonyl group of HEMA in KBr method. The decrease of the carbonyl group absorbance indicates the more chemical bonds formed. By measuring the absorbance of C=O esther in different humidity, it showed that the greatest number of chemical bonds resulted when the experiment was done in 70% humidity condition.

  18. Enhanced antioxidation and microwave absorbing properties of SiO2-coated flaky carbonyl iron particles (United States)

    Zhou, Yingying; Xie, Hui; Zhou, Wancheng; Ren, Zhaowen


    SiO2 was successfully coated on the surface of flaky carbonyl iron particles using a chemical bath deposition method in the presence of 3-aminopropyl triethoxysilane (APTES). The morphologies, composition, valence states of elements, as well as antioxidation and electromagnetic properties of the samples were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetric (TG) and microwave network analyzer. TG curve shows the obvious weight gain of carbonyl iron was deferred to 360 °C after SiO2-coated, which can be ascribed to the exits of SiO2 overlayer. Compared with the raw carbonyl iron, SiO2-coated sample shows good wave absorption performance due to its impedance matching. The electromagnetic properties of raw and SiO2-coated carbonyl iron particles were characterized in X band before and after heat treatment at 250 °C for 10 h. It was established that SiO2-coated carbonyl iron demonstrate good thermal stability, indicating SiO2-coating is useful in the usage of microwave absorbers operating at temperature up to 250 °C.

  19. Enhanced microwave absorption in ZnO/carbonyl iron nano-composites by coating dielectric material

    International Nuclear Information System (INIS)

    Zhou Chang; Fang Qingqing; Yan Fangliang; Wang Weina; Wu Keyue; Liu Yanmei; Lv Qingrong; Zhang Hanming; Zhang Qiping; Li Jinguang; Ding Qiongqiong


    The microwave absorption properties of zinc oxide/carbonyl iron composite nanoparticles fabricated by high energy ball milling were studied at 0–20 GHz. Experiments showed that ZnO as a kind of dielectric material coating carbonyl iron particles made the bandwidth of reflection loss (RL)<−5 dB expanding to the low frequency, and enhanced absorption effect obviously. For a 3 mm thickness absorber of ZnO/carbonyl iron after 30 h milling, the values of RL<−5 dB and RL<−8 dB were obtained in the frequency range from 7.0 GHz to 17.8 GHz and from 9.8 dB to 14.9 dB, respectively, and its strongest RL peak was −29.34 dB at 13.59 GHz. The magnetic loss of carbonyl iron particles and the dielectric loss of ZnO particles were the main mechanisms of microwave absorption for the composites. - Highlights: ► We fabricated zinc oxide/carbonyl iron composites by high energy ball milling. ► ZnO dielectric property increased absorption effect and absorption bandwidth. ► Absorbing frequence of composites is expanding to low frequency direction. ► The craft of high energy ball milling is easy to realize commerce production.

  20. Formation of carbonyl groups on cellulose during ozone treatment of pulp: consequences for pulp bleaching. (United States)

    Pouyet, Frédéric; Chirat, Christine; Potthast, Antje; Lachenal, Dominique


    The formation of carbonyl groups during the ozone treatment (Z) of eucalyptus (Eucalyptus grandis and Eucalyptus urophylla hybrid) kraft pulps and their behaviors during subsequent alkaline stages were investigated by the CCOA method with carbazole-9-carboxylic acid [2-(2-aminooxethoxy)-ethoxy] amide (CCOA) as the carbonyl-selective fluorescence label. Several pulp samples with or without lignin and hexenuronic acids (hexA) were used to elucidate the effects of these components when present in unbleached kraft pulp. Both hexA and lignin increased the formation of carbonyl groups on cellulose and hemicellulose during ozonation. It was concluded that radicals are likely formed when ozone reacts with either lignin or hexA. These carbonyl groups were involved in cellulose depolymerization during subsequent alkaline extraction stages with sodium hydroxide (E) and alkaline hydrogen peroxide (P, in ZEP or ZP). Their numbers decreased after E but increased during P when H2O2 was not stabilized enough. Several ways to minimize the occurrence of carbonyl group formation are suggested. Copyright © 2014. Published by Elsevier Ltd.

  1. Brand variation in oxidant production in mainstream cigarette smoke: Carbonyls and free radicals. (United States)

    Reilly, Samantha M; Goel, Reema; Trushin, Neil; Elias, Ryan J; Foulds, Jonathan; Muscat, Joshua; Liao, Jason; Richie, John P


    Oxidative stress/damage resulting from exposure to cigarette smoke plays a critical role in the development of tobacco-caused diseases. Carbonyls and free radicals are two major classes of oxidants in tobacco smoke. There is little information on the combined delivery of these oxidants across different cigarette brands; thus, we set out to measure and compare their levels in mainstream smoke from popular US cigarettes. Mainstream smoke from 28 different cigarette brands produced by smoking (FTC protocol) was analyzed for five important, abundant carbonyls, and levels were compared to previously determined free radical for the same brands. Overall, there were large variations (3- to 6-fold) in carbonyl levels across brands with total carbonyl levels ranging from 275 to 804 μg/cigarette, which persisted even after adjusting for ventilation. Individual carbonyl levels were highly correlated with each other (r 2 : 0.40-0.95, P brand and the resulting difference in oxidant burden could potentially lead to differences in disease risk. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Low frequency vapour phase infrared spectra of metal carbonyls, derivatives of the type xmn (CO)/sub 5/ (where X=Br, Cl, H, D, Ch/sub 3/, Cd/sub 3/ Cf/sub 3/)

    International Nuclear Information System (INIS)

    Mehmood, Z.


    Many vibrations which occur in the far-infrared region of spectrum are similar to the types of vibrations found in other regions of the spectrum. They fall in the far-infrared because the atomic masses are large and/or the forces resisting the deformation are small. Most of the vibrations of metal carbonyls fall into this category and hence they give a good example of what can be expected A number of metal carbonyls ego BrMn(CO)/sub 5/, CIMn(CO)/sub 5/, HMn(CO)/sub 5/, DMn(CO)/sub 5/, CH/sub 3/Mn(CO)/sub 5/, CD/sub 3/Mn(CO)/sub 5/ and CF/sub 3/Mn(CO)/sub 5/ have been studied in the vapour phase for first time and it is now possible to discuss the general nature of the vibration in this region. The metal- CO stretching frequencies are found between 350 and 475 cm/sup -1/ The metal-C-O bending frequencies are more scattered and fall between 275 and 650 cm/sup -1/ depending in part upon the phase of motion. The OC-M-CO bending modes occur between 50 and 150 cm/sup -1/. Other vibrations are founds in this region when one or more CO group are replaced by groups in which heavy atoms are attached to the metal. Factor which shifts the positions of the frequencies, such as mass or charge on the metal carbonyl moiety, will be discussed. (author)

  3. Sulfide oxidation in fluidized bed bioreactor using nylon support material. (United States)

    Midha, Varsha; Jha, M K; Dey, Apurba


    A continuous fluidized bed bioreactor (FBBR) with nylon support particles was used to treat synthetic sulfide wastewater at different hydraulic retention time of 25, 50 and 75 min and upflow velocity of 14, 17 and 20 m/hr. The effects of upflow velocity, hydraulic retention time and reactor operation time on sulfide oxidation rate were studied using statistical model. Mixed culture obtained from the activated sludge, taken from tannery effluent treatment plant, was used as a source for microorganisms. The diameter and density of the nylon particles were 2-3 mm and 1140 kg/m3, respectively. Experiments were carried out in the reactor at a temperature of (30 +/- 2) degrees C, at a fixed bed height of 16 cm after the formation of biofilm on the surface of support particles. Biofilm thickness reached (42 +/- 3) microm after 15 days from reactor start-up. The sulfide oxidation, sulfate and sulfur formation is examined at all hydraulic retention times and upflow velocities. The results indicated that almost 90%-92% sulfide oxidation was achieved at all hydraulic retention times. Statistical model could explain 94% of the variability and analysis of variance showed that upflow velocity and hydraulic retention time slightly affected the sulfide oxidation rate. The highest sulfide oxidation of 92% with 70% sulfur was obtained at hydraulic retention time of 75 min and upflow velocity of 14 m/hr.

  4. Simultaneous removal of sulfide, nitrate and acetate: Kinetic modeling. (United States)

    Wang, Aijie; Liu, Chunshuang; Ren, Nanqi; Han, Hongjun; Lee, Duujong


    Biological removal of sulfide, nitrate and chemical oxygen demand (COD) simultaneously from industrial wastewaters to elementary sulfur (S(0)), N(2), and CO(2), or named the denitrifying sulfide (DSR) process, is a cost effective and environmentally friendly treatment process for high strength sulfide and nitrate laden organic wastewater. Kinetic model for the DSR process was established for the first time on the basis of Activated Sludge Model No. 1 (ASM1). The DSR experiments were conducted at influent sulfide concentrations of 200-800 mg/L, whose results calibrate the model parameters. The model correlates well with the DSR process dynamics. By introducing the switch function and the inhibition function, the competition between autotrophic and heterotrophic denitrifiers is quantitatively described and the degree of inhibition of sulfide on heterotrophic denitrifiers is realized. The model output indicates that the DSR reactor can work well at 0.51000 mg/L influent sulfide, however, the DSR system will break down. Copyright 2010 Elsevier B.V. All rights reserved.

  5. Bioavailability and stability of mercury sulfide in Armuchee (USA) soil

    International Nuclear Information System (INIS)

    Han, Fengxiang; Shiyab, Safwan; Su, Yi; Monts, David L.; Waggoner, Charles A.; Matta, Frank B.


    Because of the adverse effects of elemental mercury and mercury compounds upon human health, the U.S. Department of Energy (DOE) is engaged in an on-going effort to monitor and remediate mercury-contaminated DOE sites. In order to more cost effectively implement those extensive remediation efforts, it is necessary to obtain an improved understanding of the role that mercury and mercury compounds play in the ecosystem. We have conducted pilot scale experiments to study the bioavailability of mercury sulfide in an Armuchee (eastern US ) soil. The effects of plants and incubation time on chemical stability and bioavailability of HgS under simulated conditions of the ecosystem have been examined, as has the dynamics of the dissolution of mercury sulfide by various extractants. The results show that mercury sulfide in contaminated Armuchee soil was still to some extent bioavailable to plants. After planting, soil mercury sulfide is more easily dissolved by both 4 M and 12 M nitric acid than pure mercury sulfide reagent. Dissolution kinetics of soil mercury sulfide and pure chemical reagent by nitric acid are different. Mercury release by EDTA from HgS-contaminated soil increased with time of reaction and soil mercury level. Chelating chemicals increase the solubility and bioavailability of mercury in HgS-contaminated soil. (authors)

  6. Laser cleaning of sulfide scale on compressor impeller blade

    International Nuclear Information System (INIS)

    Tang, Q.H.; Zhou, D.; Wang, Y.L.; Liu, G.F.


    Highlights: • The effects of sulfide layers and fluence values on the mechanism of laser cleaning were experimentally established. • The specimen surface with sulfide scale becomes slightly smoother than that before laser cleaning. • The mechanism of laser cleaning the sulfide scale of stainless steel is spallation without oxidization. • It would avoid chemical waste and dust pollution using a fiber laser instead of using nitric acids or sandblasting. - Abstract: Sulfide scale on the surface of a compressor impeller blade can considerably reduce the impeller performance and its service life. To prepare for subsequent remanufacturing, such as plasma spraying, it needs to be removed completely. In the corrosion process on an FV(520)B stainless steel, sulfide scale is divided into two layers because of different outward diffusion rates of Cr, Ni and Fe. In this paper, the cleaning threshold values of the upper and inner layers and the damage threshold value of the substrate were investigated using a pulsed fiber laser. To obtain experimental evidence, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and 3D surface profilometry were employed to investigate the two kinds of sulfide layers on specimens before, during, and after laser cleaning.

  7. Geological Sulfur Isotopes Indicate Elevated OCS in the Archean Atmosphere, Solving the Faint Young Sun Paradox

    DEFF Research Database (Denmark)

    Ueno, Yuichiro; Johnson, Matthew Stanley; Danielache, Sebastian Oscar


    Distributions of sulfur isotopes in geological samples would provide a record of atmospheric composition if the mechanism producing the isotope effects could be described quantitatively. We determined the UV absorption spectra of 32SO2, 33SO2, and 34SO2 and use them to interpret the geological re......-rich, reducing Archean atmosphere. The radiative forcing, due to this level of OCS, is able to resolve the faint young sun paradox. Further, the decline of atmospheric OCS may have caused the late Archean glaciation....

  8. Effect of carbonyl iron particles composition on the physical characteristics of MR grease

    Energy Technology Data Exchange (ETDEWEB)

    Mohamad, Norzilawati, E-mail:; Mazlan, Saiful Amri, E-mail: [Vehicle System Engineering, Malaysia – Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra (Jalan Semarak), Kuala Lumpur, 54000 (Malaysia); Ubaidillah, E-mail: [Vehicle System Engineering, Malaysia – Japan International Institute of Technology, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra (Jalan Semarak), Kuala Lumpur, 54000 (Malaysia); Mechanical Engineering Department, Faculty of Engineering, Universitas Sebelas Maret, Jl. Ir. Sutami 36A, Kentingan, Surakarta, 57126, Central Java, Surakarta (Indonesia)


    Magnetorheological (MR) grease is an extension of the study of magnetorheological materials. The MR grease can help to reduce the particles sedimentation problem occurred in the MR fluids. Within this study, an effort has been taken to investigate the effect of different weight compositions of carbonyl iron particles on the physical and chemical characteristics of the MR grease under off-state condition (no magnetic field). The MR grease is prepared by mixing carbonyl iron particles having a size range of 1 to 10 µm with commercial NPC Highrex HD-3 grease. Characterizations of MR grease are investigated using Vibrating Sample Magnetometer (VSM), Environmental Scanning Electron Microscopy (ESEM), Differential Scanning Calorimeter (DSC) and rheometer. The dependency of carbonyl iron particles weight towards the magnetic properties of MR grease and other characterizations are investigated.

  9. Measurements of ambient hydrocarbons and carbonyls in the Pearl River Delta (PRD), China (United States)

    Yuan, Bin; Chen, Wentai; Shao, Min; Wang, Ming; Lu, Sihua; Wang, Bin; Liu, Ying; Chang, Chih-Chung; Wang, Boguang


    Measurements of 47 hydrocarbons and 3 carbonyls were performed at six sites in July 2006 and in October-November 2008 in Pearl River Delta (PRD), China. The distribution of volatile organic compound (VOC) concentrations and compositions at different sites revealed photochemical losses of hydrocarbons and secondary formation of carbonyls. Carbonyls were shown to be an important contributor to OH loss rates and ozone formation potentials. Correlations between VOCs were used to identify the sources of VOC species. Liquefied petroleum gas (LPG) is an important contributor in Guangzhou. Vehicle emissions were the dominant sources of C4-C5 alkenes (except isoprene), whereas industrial and/or solvent use accounted for a significant fraction of aromatic concentrations. Ethylbenzene/m, p-xylene ratios accurately described ozone formation at all sites except a site located upwind of Guangzhou in 2008.

  10. Influence of the Dielectric Medium on the Carbonyl Infrared Absorption Peak of Acetylferrocene

    Directory of Open Access Journals (Sweden)

    F. López-Linares


    Full Text Available The solvent effect on the position of the carbonyl vibrational stretching ofacetylferrocene in aprotic media was studied in this work. The solvent-induced shifts in thisorganometallic compound were interpreted in terms of the alternative reaction field model(SCRF-MO proposed by Kolling. In contrast to the established trends for carbonyl groupsin organic systems, the results suggest that the continuum models for the reaction field arenot adequate and that the influence of dipolarity-polarizability described by aninhomogeneous coupling function θ (ε L(n 2 that assumes optical dielectric saturation isresponsible for the carbonyl band shift and, there is empirical evidence that the effect offield-induced intermolecular interaction on band shift, interpreted in terms of the van derWaals forces from the solvent, have a important contribution to this phenomena.

  11. Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes. (United States)

    Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo


    Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Temporal variation of carbonyl compound concentrations at a semi-rural site in Denmark

    DEFF Research Database (Denmark)

    Christensen, C.S.; Skov, H.; Nielsen, T.


    .9 ppbv for acetone, For the set of carbonyl compounds, concentrations were found to be highly correlated, though only during daytime, The weak correlations observed during nighttime are believed to be caused by the dry deposition of especially formaldehyde, During periods with low photochemical activity......The atmospheric concentrations of formaldehyde, acetaldehyde and acetone were measured by the DNPH-technique at the semi-rural site Lille Valby, Denmark (55 degrees N) between May-July 1995, The average concentrations were observed to be 1.2 ppbv for formaldehyde, 0.8 ppbv for acetaldehyde and 1...... the carbonyl compounds also correlated with SO2 and the levels of carbonyl compounds were mainly controlled by meteorological parameters. The highest concentration levels were coincident with episodes of long-range transport from central Europe. A pronounced diurnal profile similar to those observed for PAN...

  13. Subnanometer Thin β-Indium Sulfide Nanosheets. (United States)

    Acharya, Shinjita; Sarkar, Suresh; Pradhan, Narayan


    Nanosheets are a peculiar kind of nanomaterials that are grown two-dimensionally over a micrometer in length and a few nanometers in thickness. Wide varieties of inorganic semiconductor nanosheets are already reported, but controlling the crystal growth and tuning their thickness within few atomic layers have not been yet explored. We investigate here the parameters that determine the thickness and the formation mechanism of subnanometer thin (two atomic layers) cubic indium sulfide (In2S3) nanosheets. Using appropriate reaction condition, the growth kinetics is monitored by controlling the decomposition rate of the single source precursor of In2S3 as a function of nucleation temperature. The variation in the thickness of the nanosheets along the polar [111] direction has been correlated with the rate of evolved H2S gas, which in turn depends on the rate of the precursor decomposition. In addition, it has been observed that the thickness of the In2S3 nanosheets is related to the nucleation temperature.

  14. Thiosulfate leaching of gold from sulfide wastes

    Energy Technology Data Exchange (ETDEWEB)

    Block-Bolten, A.; Torma, A.E.


    The kinetics of gold extraction from lead-zinc sulfide flotation tailings by thiosulfate leachants has been investigated. The order of reaction as well as the overall reaction rate constant were, with respect to thiosulfate concentration, calculated to be n=0.75 and k=1.05 x 10/sup -6/ mol/sup 1/4/ dm/sup 5/4/ min/sup -1/. The apparent activation energy was found to be a/=48.53 kJ and the frequency factor A=7.5 x 10/sup 2/ mol dm/sup -3/ min/sup -1/. This activation energy value suggests chemical control of the reaction mechanism. Optimum leach temperature of 50/sup 0/C was established. Gold extractions as high as 99% have been realized in two step countercurrent leachings. Change in pH throughout the leaching process was found to be an excellent indicator for the progress of the extraction. A preliminary economic evaluation of the process is given.

  15. Fluorescence sensing system for seafloor massive sulfides (United States)

    Yamazaki, T.; Okanishi, D.; Nagano, H.; Nakatani, N.; Arai, R.


    Seafloor Massive Sulfides (SMS) including Au, Ag, Cu, Zn, Pb and some rare earth elements exist in exclusive economic zones (EEZ) of Pacific island countries and the ones in Japan’s EEZ are the largest and very much attractive. However, there are many problems to be solved for the development. The most important point is the location of ore dressing. If SMS were dressed in the water, energy and cost of transport would drastically decrease. Therefore, fundamental ore dressing method which is an optical measurement, fluorescence sensing system in water is studied. It seems to be able to apply to exploration and mining. No sun light means that ideal optical measurements are possible under artificial one in deep water. However, quite less studies have been done for the optical measurements because general sensing methods at deep water are sound and supersonic waves. Using a light system, the light attenuation and fluorescence characteristics in water are studied. From this study, it is revealed that fluorescence sensing system is applicable and useful for the development of SMS.

  16. The role of hydrogen sulfide in stroke

    Directory of Open Access Journals (Sweden)

    Yang Dou


    Full Text Available Stroke is a kind of acute cerebrovascular disease characterized by the focal lack of neurological function, including ischemic stroke and hemorrhagic stroke. As society ages rapidly, stroke has become the second leading cause of disability and death, and also become the main threat to human health and life. In recent years, findings from increasing animal and clinical trials have supplied scientific evidences for the treatment of stroke. Hydrogen sulfide (H 2 S, which has always been seen as a toxic gas, now has been thought to be the third gaseous signaling molecule following nitric oxide and carbon monoxide. Accumulating evidences indicate that H 2 S plays an important role in stroke. Given that its neuroprotective effect is dose-dependent, only when its concentration is relatively low, H 2 S can yield the neuroprotection, while high dose may lead to neurotoxicity. All these study results suggest that H 2 S may offer a new promising application for the therapy of stroke. Here, our review will present the role of H 2 S in stroke from its mechanism to animal and clinical studies.

  17. Hydrogen Sulfide and Endothelium-Dependent Vasorelaxation

    Directory of Open Access Journals (Sweden)

    Jerzy Bełtowski


    Full Text Available In addition to nitric oxide and carbon monoxide, hydrogen sulfide (H2S, synthesized enzymatically from l-cysteine or l-homocysteine, is the third gasotransmitter in mammals. Endogenous H2S is involved in the regulation of many physiological processes, including vascular tone. Although initially it was suggested that in the vascular wall H2S is synthesized only by smooth muscle cells and relaxes them by activating ATP-sensitive potassium channels, more recent studies indicate that H2S is synthesized in endothelial cells as well. Endothelial H2S production is stimulated by many factors, including acetylcholine, shear stress, adipose tissue hormone leptin, estrogens and plant flavonoids. In some vascular preparations H2S plays a role of endothelium-derived hyperpolarizing factor by activating small and intermediate-conductance calcium-activated potassium channels. Endothelial H2S signaling is up-regulated in some pathologies, such as obesity and cerebral ischemia-reperfusion. In addition, H2S activates endothelial NO synthase and inhibits cGMP degradation by phosphodiesterase 5 thus potentiating the effect of NO-cGMP pathway. Moreover, H2S-derived polysulfides directly activate protein kinase G. Finally, H2S interacts with NO to form nitroxyl (HNO—a potent vasorelaxant. H2S appears to play an important and multidimensional role in endothelium-dependent vasorelaxation.

  18. Luminescent sulfides of monovalent and trivalent cations

    International Nuclear Information System (INIS)


    The invention discloses a family of luminescent materials or phosphors having a rhombohedral crystal structure and consisting essentially of a mixed host sulfide of at least one monovalent host cation and at least one trivalent host cation, and containing, for each mole of phosphor, 0.0005 to 0.05 mole of at least one activating cation. The monovalent host cations may be Na, K or Rb and Cs. The trivalent host cations may be Gd, La, Lu, Sc and Y. The activating cations may be one or more of trivalent As, Bi, Ce, Dy, Er, Pr, Sb, Sm, Tb and Tm; divalent Lu, Mn, Pb and Sn; and monovalent Ag, Cu and Tl. The novel phosphors may be used in devices to convert electron-beam, ultraviolet or x-ray energy to light in the visible spectrum. Such energy conversion can be employed for example in fluoroscopic screens, and in viewing screens of cathode-ray tubes and other electron tubes

  19. Crystal structure of fac-tri-carbonyl-chlorido-bis-(4-hy-droxy-pyridine)-rhenium(I)-pyridin-4(1H)-one (1/1). (United States)

    Argibay-Otero, Saray; Carballo, Rosa; Vázquez-López, Ezequiel M


    The asymmetric unit of the title compound, [ReCl(C 5 H 5 NO) 2 (CO) 3 ]·C 5 H 5 NO, contains one mol-ecule of the complex fac -[ReCl(4-pyOH) 2 (CO) 3 ] (where 4-pyOH represents 4-hy-droxy-pyridine) and one mol-ecule of pyridin-4(1 H )-one (4-HpyO). In the mol-ecule of the complex, the Re atom is coordinated to two N atoms of the two 4-pyOH ligands, three carbonyl C atoms, in a facial configuration, and the Cl atom. The resulting geometry is slightly distorted octa-hedral. In the crystal structure, both fragments are associated by hydrogen bonds; two 4-HpyO mol-ecules bridge between two mol-ecules of the complex using the O=C group as acceptor for two different HO- groups of coordinated 4-pyOH from two neighbouring metal complexes. The resulting square arrangements are extented into infinite chains by hydrogen bonds involving the N-H groups of the 4-HpyO mol-ecule and the chloride ligands. The chains are further stabilized by π-stacking inter-actions.

  20. Comparison of Carbon XANES Spectra from an Iron Sulfide from Comet Wild 2 with an Iron Sulfide Interplanetary Dust Particle (United States)

    Wirick, S.; Flynn, G. J.; Keller, L. P.; Sanford, S. A.; Zolensky, M. E.; Messenger, Nakamura K.; Jacobsen, C.


    Among one of the first particles removed from the aerogel collector from the Stardust sample return mission was an approx. 5 micron sized iron sulfide. The majority of the spectra from 5 different sections of this particle suggests the presence of aliphatic compounds. Due to the heat of capture in the aerogel we initially assumed these aliphatic compounds were not cometary but after comparing these results to a heated iron sulfide interplanetary dust particle (IDP) we believe our initial interpretation of these spectra was not correct. It has been suggested that ice coating on iron sulfides leads to aqueous alteration in IDP clusters which can then lead to the formation of complex organic compounds from unprocessed organics in the IDPs similar to unprocessed organics found in comets [1]. Iron sulfides have been demonstrated to not only transform halogenated aliphatic hydrocarbons but also enhance the bonding of rubber to steel [2,3]. Bromfield and Coville (1997) demonstrated using Xray photoelectron spectroscopy that "the surface enhancement of segregated sulfur to the surface of sulfided precipitated iron catalysts facilitates the formation of a low-dimensional structure of extraordinary properties" [4]. It may be that the iron sulfide acts in some way to protect aliphatic compounds from alteration due to heat.

  1. Cryopreservation of bull semen is associated with carbonylation of sperm proteins. (United States)

    Mostek, Agnieszka; Dietrich, Mariola Aleksandra; Słowińska, Mariola; Ciereszko, Andrzej


    Artificial insemination with cryopreserved semen enables affordable, large-scale dissemination of gametes with superior genetics. However, cryopreservation can cause functional and structural damage to spermatozoa that is associated with reactive oxygen species (ROS) production, impairment of sperm motility and decreased fertilizing potential, but little attention has been paid to protein changes. The goal of this study was to investigate the oxidative modifications (measured as carbonylation level changes) of bull spermatozoa proteins triggered by the cryopreservation process. Flow cytometry and computer-assisted sperm analysis were used to evaluate changes in viability, ROS level and motility of spermatozoa. Western blotting, in conjunction with two-dimensional electrophoresis (2D-oxyblot) and matrix-assisted laser desorption/ionization time-of-flight/time-of-flight spectrometry, was employed to identify and quantify the specifically carbonylated spermatozoa proteins. Cryopreservation decreased motility and viability but increased the number of ROS-positive cells. We identified 11 proteins (ropporin-1, outer dense fiber protein 2, glutathione S-transferase, triosephosphate isomerase, capping protein beta 3 isoform, actin-related protein M1, actin-related protein T2, NADH dehydrogenase, isocitrate dehydrogenase, cilia- and flagella-associated protein 161, phosphatidylethanolamine-binding protein 4) showing differences in protein carbonylation in response to cryopreservation. The identified proteins are associated with cytoskeleton and flagella organization, detoxification and energy metabolism. Moreover, almost all of the identified carbonylated proteins are involved in capacitation. Our results indicate for the first time that cryopreservation induces oxidation of selected sperm proteins via carbonylation. We suggest that carbonylation of sperm proteins could be a direct result of oxidative stress and potentially lead to disturbances of capacitation

  2. Synthesis and Characterization of Group-6 Metal Carbonyl Complexes of Aroyl Hydrazone Derivatives


    Saleem, Mohd; Sharma, Mohita; Mahajan, Simpy; Sheikh, H. N.; Kalsotra, B. L.


    Carbonyl complexes of Chromium, molybdenum and tungsten of composition, [M(CO)4L-L], (where M= Cr, Mo or W and L-L= benzoic acid[1-(Furan-2-yl)methylene]hydrazide (BFMH), benzoic acid[(thiophene-2-yl)methylene]hydrazide (BTMH), benzoic acid[1-(thiophene-2-yl)ethylidene] hydrazide (BTEH), benzoic acid (phenylmethylene)hydrazide (BPMH) and benzoic acid[1-(anisol-3-yl)methylene] hydrazide (BAMH) are reported. These have been prepared by refluxing metal carbonyls and the ligands in 1:1molar ratio...

  3. First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation

    DEFF Research Database (Denmark)

    Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter


    A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.......A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)(2)I-2]-[BMIM]I -SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation....

  4. Polycyclic Aromatic Hydrocarbons via Iron(III)-Catalyzed Carbonyl-Olefin Metathesis. (United States)

    McAtee, Christopher C; Riehl, Paul S; Schindler, Corinna S


    Polycyclic aromatic hydrocarbons are important structural motifs in organic chemistry, pharmaceutical chemistry, and materials science. The development of a new synthetic strategy toward these compounds is described based on the design principle of iron(III)-catalyzed carbonyl-olefin metathesis reactions. This approach is characterized by its operational simplicity, high functional group compatibility, and regioselectivity while relying on FeCl 3 as an environmentally benign, earth-abundant metal catalyst. Experimental evidence for oxetanes as reactive intermediates in the catalytic carbonyl-olefin ring-closing metathesis has been obtained.

  5. Inactivation of cellular enzymes by carbonyls and protein-bound glycation/glycoxidation products

    DEFF Research Database (Denmark)

    Morgan, Philip E; Dean, Roger T; Davies, Michael Jonathan


    dismutase, or catalase dependent, suggesting that inhibition is not radical mediated. These effects are suggested to be due to direct adduction of the free- or protein-bound carbonyls with the target enzyme. Such an interpretation is supported by the detection of the loss of thiol groups on GAPDH...... and the detection of cross-linked materials on protein gels. Though direct comparison of the extent of inhibition induced by free versus protein-bound carbonyls was not possible, the significantly higher concentrations of the latter materials over the former in diabetic plasma and cells lead us to suggest...

  6. Impaired cardiac SIRT1 activity by carbonyl stress contributes to aging-related ischemic intolerance.

    Directory of Open Access Journals (Sweden)

    Chunhu Gu

    Full Text Available Reactive aldehydes can initiate protein oxidative damage which may contribute to heart senescence. Sirtuin 1 (SIRT1 is considered to be a potential interventional target for I/R injury management in the elderly. We hypothesized that aldehyde mediated carbonyl stress increases susceptibility of aged hearts to ischemia/reperfusion (I/R injury, and elucidate the underlying mechanisms with a focus on SIRT1. Male C57BL/6 young (4-6 mo and aged (22-24 mo mice were subjected to myocardial I/R. Cardiac aldehyde dehydrogenase (ALDH2, SIRT1 activity and protein carbonyls were assessed. Our data revealed that aged heart exhibited increased endogenous aldehyde/carbonyl stress due to impaired ALDH2 activity concomitant with blunted SIRT1 activity (P<0.05. Exogenous toxic aldehydes (4-HNE exposure in isolated cardiomyocyte verified that aldehyde-induced carbonyl modification on SIRT1 impaired SIRT1 activity leading to worse hypoxia/reoxygenation (H/R injury, which could all be rescued by Alda-1 (ALDH2 activator (all P<0.05. However, SIRT1 inhibitor blocked the protective effect of Alda-1 on H/R cardiomyocyte. Interestingly, myocardial I/R leads to higher carbonylation but lower activity of SIRT1 in aged hearts than that seen in young hearts (P<0.05. The application of Alda-1 significantly reduced the carbonylation on SIRT1 and markedly improved the tolerance to in vivo I/R injury in aged hearts, but failed to protect Sirt1(+/- knockout mice against myocardial I/R injury. This was verified by Alda-1 treatment improved postischemic contractile function recovery in ex vivo perfused aged but not in Sirt1(+/- hearts. Thus, aldehyde/carbonyl stress is accelerated in aging heart. These results provide a new insight that impaired cardiac SIRT1 activity by carbonyl stress plays a critical role in the increased susceptibility of aged heart to I/R injury. ALDH2 activation can restore this aging-related myocardial ischemic intolerance.

  7. Dithioacetals as an Entry to Titanium-Alkylidene Chemistry: A New and Efficient Carbonyl Olefination. (United States)

    Breit, Bernhard


    Wittig, Horner-Wadsworth-Emmons, Julia-Lythgoe, Tebbe, Grubbs, and Petasis-when it comes to carbonyl olefinations, these names are familiar to all chemistry students. In the future, the name Takeda will probably have to be added to this list. His recent work on the formation of titanium-alkylidene species from dithioacetals has provided organic chemists with a remarkable method for carbonyl olefination that is generally applicable under neutral to Lewis acidic conditions. © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  8. Selective Palladium(II)-Catalyzed Carbonylation of Methylene β-C-H Bonds in Aliphatic Amines.


    Cabrera-Pardo, Jaime R; Trowbridge, Aaron; Nappi, Manuel; Ozaki, Kyohei; Gaunt, Matthew James


    Pd(II)-catalyzed C–H carbonylation of methylene C–H bonds in secondary aliphatic amines leads to the formation trans-disubstituted β-lactams in excellent yields and selectivities. The generality of the C–H carbonylation process is aided by the action of xantphos-based ligands and is important in securing good yields of the β-lactam products. EPSRC (EP/100548X/1), ERC (ERC-STG-259711), Royal Society (Wolfson Award), Marie Curie Foundation and Herchel Smith Foundation.

  9. Modernized low pressure carbonylation methods in batch and flow employing common acids as a CO source. (United States)

    Brancour, Célia; Fukuyama, Takahide; Mukai, Yu; Skrydstrup, Troels; Ryu, Ilhyong


    Carbonylation reactions, such as Heck, Sonogashira, and radical carbonylations, were successfully carried out in a "two-chamber reactor" where carbon monoxide was produced ex situ by the Morgan reaction (dehydration of formic acid by sulfuric acid). By a subsequent application in a microflow system using a "tube-in-tube" reactor where gas-permeable Teflon AF2400 was used as the inner tube, it is demonstrated that formic acid/sulfuric acid can be employed concomitantly with an amine base such as triethylamine in the Heck aminocarbonylation of aryl iodide.

  10. Aqueous Catalytic Pauson-Khand-Type Reactions of Enynes with Formaldehyde: Transfer Carbonylation Involving an Aqueous Decarbonylation and a Micellar Carbonylation


    Fuji, Koji; Morimoto, Tsumoru; Tsutsumi, Ken; Kakiuchi, Kiyomi


    One rhodium(I) complex catalyzes two processes in an overall Pauson-Khand-type reaction of enynes such as 1 with formaldehyde in an aqueous medium to give bicyclic cyclopentenones such as 2 in excellent yields. The use of a water-soluble phosphane ligand in conjunction with a hydrophobic phosphane ligand in the presence of a surfactant promotes the decarbonylation of formaldehyde in the aqueous phase and the carbonylation of enynes in the micellar phase.

  11. Silver sulfide nanoparticle assembly obtained by reacting an assembled silver nanoparticle template with hydrogen sulfide gas. (United States)

    Chen, Rui; Nuhfer, Noel T; Moussa, Laura; Morris, Hannah R; Whitmore, Paul M


    A fast, simple procedure is described for obtaining an assembly of silver sulfide nanoparticles (Ag(2)S NPs) on a glass substrate through reaction of a template of an assembled layer of silver nanoparticles (Ag NPs) with hydrogen sulfide (H(2)S) gas. The Ag NP template was prepared by assembling a monolayer of spherical Ag NPs (mean diameter of 7.4 nm) on a polyethylenimine-treated glass substrate. Exposure to pure H(2)S for 10 min converted the Ag NPs of the template to Ag(2)S NPs. The resulting Ag(2)S NP assembly, which retains the template nanostructure and particle distribution, was characterized by optical absorption spectroscopy, atomic force microscopy, transmission electron microscopy (TEM), scanning high resolution TEM, energy dispersive x-ray spectroscopy and x-ray photoelectron spectroscopy. The Ag(2)S NPs have a crystal structure of monoclinic acanthite, and while they retained the spherical shape of the original Ag NPs, their mean particle size increased to 8.4 nm due to changes to the crystal structure when the Ag NPs are converted into Ag(2)S NPs. The measured optical absorption edge of the Ag(2)S NP assembly indicated an indirect interband transition with a band gap energy of 1.71 eV. The Ag(2)S NP assembly absorbed light with wavelengths below 725 nm, and the absorbance increased monotonically toward the UV region.

  12. Hydrogen sulfide can inhibit and enhance oxygenic photosynthesis in a cyanobacterium from sulfidic springs. (United States)

    Klatt, Judith M; Haas, Sebastian; Yilmaz, Pelin; de Beer, Dirk; Polerecky, Lubos


    We used microsensors to investigate the combinatory effect of hydrogen sulfide (H2 S) and light on oxygenic photosynthesis in biofilms formed by a cyanobacterium from sulfidic springs. We found that photosynthesis was both positively and negatively affected by H2 S: (i) H2 S accelerated the recovery of photosynthesis after prolonged exposure to darkness and anoxia. We suggest that this is possibly due to regulatory effects of H2 S on photosystem I components and/or on the Calvin cycle. (ii) H2 S concentrations of up to 210 μM temporarily enhanced the photosynthetic rates at low irradiance. Modelling showed that this enhancement is plausibly based on changes in the light-harvesting efficiency. (iii) Above a certain light-dependent concentration threshold H2 S also acted as an inhibitor. Intriguingly, this inhibition was not instant but occurred only after a specific time interval that decreased with increasing light intensity. That photosynthesis is most sensitive to inhibition at high light intensities suggests that H2 S inactivates an intermediate of the oxygen evolving complex that accumulates with increasing light intensity. We discuss the implications of these three effects of H2 S in the context of cyanobacterial photosynthesis under conditions with diurnally fluctuating light and H2 S concentrations, such as those occurring in microbial mats and biofilms. © 2015 Society for Applied Microbiology and John Wiley & Sons Ltd.

  13. Chemical and colloidal aspects of collectorless flotation behavior of sulfide and non-sulfide minerals. (United States)

    Aghazadeh, Sajjad; Mousavinezhad, Seyed Kamal; Gharabaghi, Mahdi


    Flotation has been widely used for separation of valuable minerals from gangues based on their surface characterizations and differences in hydrophobicity on mineral surfaces. As hydrophobicity of minerals widely differs from each other, their separation by flotation will become easier. Collectors are chemical materials which are supposed to make selectively valuable minerals hydrophobic. In addition, there are some minerals which based on their surface and structural features are intrinsically hydrophobic. However, their hydrophobicities are not strong enough to be floatable in the flotation cell without collectors such as sulfide minerals, coal, stibnite, and so forth. To float these minerals in a flotation cell, their hydrophobicity should be increased in specific conditions. Various parameters including pH, Eh, size distribution, mill types, mineral types, ore characterization, and type of reaction in flotation cells affect the hydrophobicity of minerals. Surface analysis results show that when sulfide minerals experience specific flotation conditions, the reactions on the surface of these minerals increase the amount of sulfur on the surface. These phenomenons improve the hydrophobicity of these minerals due to strong hydrophobic feature of sulfurs. Collectorless flotation reduces chemical material consumption amount, increases flotation selectivity (grade increases), and affects the equipment quantities; however, it can also have negative effects. Some minerals with poor surface floatability can be increased by adding some ions to the flotation system. Depressing undesirable minerals in flotation is another application of collectorless flotation.

  14. 76 FR 20367 - Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Off Delaware... (United States)


    ... No. BOEM-2011-0008] Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Off... determination that no competitive interest exists in acquiring a commercial wind lease in the area offshore... a Request for Interest (RFI) in the Federal Register on April 26, 2010 (75 FR 21653). Bluewater Wind...

  15. 76 FR 14681 - Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Massachusetts... (United States)


    ... No. BOEM-2010-0063] Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore..., Regulation and Enforcement (BOEMRE), Interior. ACTION: Request for Interest (RFI) in Commercial Wind Energy... (BOEMRE) is reopening the comment period on the RFI in Commercial Wind Energy Leasing Offshore...

  16. A four-dimensional compound-model morphed potential for the OC:HBr complex. (United States)

    Rivera-Rivera, Luis A; Lucchese, Robert R; Bevan, John W


    A parameterized compound-model morphed intermolecular potential energy surface has been generated for the dimer OC:HBr. This morphed potential is determined by fitting experimentally available gas phase spectroscopic data and found to have a global minimum with a well depth of 564(5) cm(-1) and linear (16)O(12)C-H(79)Br geometry having center of mass to center of mass distance R = 4.525(7) A. The linear isomers (12)C(16)O-H(79)Br and (16)O(12)C-(79)BrH are determined with a corresponding well depth of 273(7) and 269(2) cm(-1) having R = 4.35(4) and 4.24(3) A, respectively. This results in a DeltaE of 293(9) cm(-1) between the global potential energy minimum and the minima in the two higher energy isomers. The generated potential is compared with the corresponding OC:HCl morphed potential. Differences in the morphing parameters are attributed to different contributions to the interaction energy. It is found that the counterpoise method successfully corrected the basis set superposition error in OC:HCl, but was under corrected by 16(7)% in OC:HBr.

  17. 75 FR 82055 - Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Massachusetts... (United States)


    ... Nantucket and extending approximately 31 nm seaward, south to the 60 meter depth contour, then east... Smart from the Start OCS renewable energy initiative, which was announced by Secretary Ken Salazar on... Martha's Vineyard and Nantucket and extending approximately 31 nm seaward, south to the 60 meter depth...

  18. [Characteristics and sources apportionment of OC and EC in PM1.1 from Nanjing]. (United States)

    Jiang, Wen-juan; Guo, Zhao-bing; Liu, Feng-ling; Rui, Mao-ling; Shi, Lei; Zeng, Gang; Guo, Zi-yan


    The concentrations of OC and EC in PM1.1 collected from Nanshi (NS) and Nanhua (NH) in 2011 were analyzed using DRI Model 2001A Thermal Optical Carbon Analyzer. In addition, source apportionment was simultaneously evaluated. The results showed that the annual average concentrations of OC and EC in PM1.1 were 10. 10 μg x m(-3) and 2.52 μg x m(-3) in NS area, and 11.22 μg x m(-3) and 3.12 μg x m(-3) in NH area, respectively. This result indicated that OC and EC pollution in NH was more serious than that in NS area. Meanwhile, the concentrations of OC and EC in winter and spring were obviously higher compared to those in summer in these two sampling sites, which was mainly ascribed to the increased coal combustion and the unfavorable emission condition of air pollutants in summer and spring. We noted that the SOC/TOC value was the highest in summer and the lowest in winter. In addition, the SOC concentration was observed to show a positive correlation with ozone concentrations, which indicated that the photochemical reaction was a main way of SOC formation in autumn.

  19. Synthesis and Electrochemical Performance of SiOC-Carbon Nanotube Composite Coatings (United States)

    Bhandavat, Romil; Cologna, Marco; Raj, Rishi; Singh, Gurpreet


    Rechargeable battery anodes made from crystalline Si-based nanostructures have been shown to possess high experimental first cycle capacities (3000 mAh/g), but face challenges in sustaining these capacities beyond initial cycles mainly due to large volume expansion (400 percent) and chemical degradation (pulverization). Polymer-derived ceramic SiOC due to its high thermodynamic stability and nano domain structure could present a viable alternative. Additionally, functionalization of SiOC with carbon nanotubes could result in increased electronic and ionic conductivities in the ceramic. Here, we demonstrate synthesis and electrochemical characterization of SiOC-CNT composite coatings for use in Li-ion battery anode. Materials characterization performed using electron microscopy, Infrared (FT-IR), and X-ray photoelectron spectroscopy suggests non-covalent functionalization of CNT with oxygen moieties in SiOC. Sustained battery capacities of over 700 mAh/g and first cycle columbic efficiencies of about 75 percent were achieved. Future work will involve determination of lithium ion intercalation sites characterized by electron microscopy whereas cyclic voltammetry analysis will access the sequential change in anode chemistry.

  20. 76 FR 30184 - Outer Continental Shelf (OCS) Renewable Energy Program Interim Policy Leasing for Marine... (United States)


    .... These three blocks are located on the Atlantic OCS in the Official Protraction Diagram NG 17- 06..., deployment of small-scale ocean current devices, and operations of a deployment vessel on the potential... will be carried out during the EA process and will be completed before a final decision is made on...

  1. Laser-induced field-free alignment of the OCS molecule

    International Nuclear Information System (INIS)

    Loriot, V; Tzallas, P; Benis, E P; Hertz, E; Lavorel, B; Charalambidis, D; Faucher, O


    We investigate the dynamical alignment of jet-cooled OCS molecules induced by a short laser pulse. The alignment is measured through the orientational contribution of the optical Kerr effect using a second weak laser pulse as a probe. Maximum alignment is observed at conditions close to saturation of ionization. The results are analysed with a quantum mechanical model solving for the rotational dynamics

  2. 77 FR 75656 - Research Lease for Renewable Energy on the Outer Continental Shelf (OCS) Offshore Virginia... (United States)


    ... Lease for Renewable Energy on the Outer Continental Shelf (OCS) Offshore Virginia, Request for... obtain a lease under 30 CFR 585.238 for renewable energy research activities, including the siting of two... production of renewable energy within and around the Wind Energy Area (WEA) offshore Virginia, identified by...

  3. Infrared Spectroscopy of Two Isomers of the OCS-CS_{2} Complex (United States)

    Oliaee, J. N.; Dehghany, M.; Afshari, Mahin; Moazzen-Ahmadi, N.; McKellar, A. R. W.


    A second isomer of OCS-CS_{2} complex, with a nonplanar cross-shaped structure, has been studied for the first time by analysing an infrared band in the region of the OCS stretching vibration (2062 cm^{-1}). This isomer has C_{s} symmetry and the observed band consists of purely c-type rotational transitions. The ground state rotational parameters are found to be A=0.07306 cm^{-1}, B=0.03325 cm^{-1} and C=0.02879 cm^{-1}, in good agreement with a previous semi-empirical calculation. In addition, a hybrid band with a- and b-type rotational transitions has been assigned to be due to the known planar form of OCS-CS_{2}, as previously studied by microwave spectroscopy. The spectra were recorded using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. Calculations indicate that the planar isomer of OCS-CS_{2} is the lowest in energy, in contrast to CO_{2}-CS_{2} where the crossed form is believed to be the lowest. J. J. Newby, M. M. Serafin, R. A. Peebles and S. A. Peebles, Phys. Chem. Chem. Phys. 7, 487 (2005). C. C. Dutton, D. A. Dows, R. Eikey, S. Evans and R. A. Beaudet, J. Phys. Chem. A 102, 6904 (1998).

  4. The dominance of human coronavirus OC43 and NL63 infections in infants

    NARCIS (Netherlands)

    Dijkman, Ronald; Jebbink, Maarten F.; Gaunt, Eleanor; Rossen, John W. A.; Templeton, Kate E.; Kuijpers, Taco W.; van der Hoek, Lia


    Background: It is unknown to what extent the human coronaviruses (HCoVs) OC43, HKU1, 229E and NL63 infect healthy children. Frequencies of infections are only known for hospitalized children. Objectives: Comparing infection frequencies in children who have mild infections with frequencies in

  5. 77 FR 24734 - Outer Continental Shelf (OCS) Renewable Energy Program Leasing for Marine Hydrokinetic Technology... (United States)


    ... DEPARTMENT OF THE INTERIOR Bureau of Ocean Energy Management [Docket No. BOEM-2012-0011] Outer Continental Shelf (OCS) Renewable Energy Program Leasing for Marine Hydrokinetic Technology Testing Offshore... Leasing for Marine Hydrokinetic Technology Testing Offshore Florida EA'' to: Program Manager, Office of...

  6. 33 CFR 135.103 - Levy and payment of barrel fee on OCS oil. (United States)


    ... SECURITY (CONTINUED) MARINE POLLUTION FINANCIAL RESPONSIBILITY AND COMPENSATION OFFSHORE OIL POLLUTION COMPENSATION FUND Levy of Fees § 135.103 Levy and payment of barrel fee on OCS oil. (a) A fee of $.03 per... paragraph (a) of this section applies whenever the unobligated Fund balance is less than $200,000,000. (d...

  7. Fugitive hydrocarbon emissions from pacific OCS facilities. Volume 1. Final report

    International Nuclear Information System (INIS)


    In January 1989, the Minerals Management Service (MMS) conducted a study using the latest approved methods for emission screening and sampling solely on Outer Continental Shelf (OCS) oil and gas platforms in the Santa Barbara Channel in order to determine platform emission rates more representative of that region. The study was designed and reviewed throughout its conduct by a Quality Review Board (QRB) composed of air resource agencies and industry. Representatives from the Tri-county Air Pollution Control Districts and the MMS actively participated at these meetings. Some participants expressed concerns about some of the methods used and the study results. ABB's thorough responses to these questions and comments were submitted to all reviewers before the printing of the final report, and are contained in appendices of the study final report now available to the public. The results of the MMS study show that the average emission factors for the Pacific OCS oil and gas facilities measured in 1989 are 3.5 times lower than those Pacific OCS facilities sampled in the 1979 API/Rockwell study, and 7.8 times lower than the Gulf of Mexico OCS facilities sampled in the same 1979 study. Efforts to determine the quantitative effect of inspection and maintenance programs on controlling emissions were inconclusive

  8. OC3 -- Benchmark Exercise of Aero-Elastic Offshore Wind Turbine Codes: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Passon, P.; Kuhn, M.; Butterfield, S.; Jonkman, J.; Camp, T.; Larsen, T. J.


    This paper introduces the work content and status of the first international investigation and verification of aero-elastic codes for offshore wind turbines as performed by the "Offshore Code Comparison Collaboration" (OC3) within the "IEA Wind Annex XXIII -- Subtask 2".

  9. Synthesis, Deposition, and Microstructure Development of Thin Films Formed by Sulfidation and Selenization of Copper Zinc Tin Sulfide Nanocrystals (United States)

    Chernomordik, Boris David

    stoichiometric kesterite CZTS. The ~2 nm nanocrystals synthesized at 150 °C exhibit quantum confinement, with a band gap of 1.67 eV. Larger nanocrystals have the expected bulk CZTS band gap of 1.5 eV. Several micron thick films deposited by drop casting colloidal dispersions of ~40 nm CZTS nanocrystals were crack-free, while those cast using 5 nm nanocrystals had micron-scale cracks. We showed the applicability of these nanocrystal coatings for thin film solar cells by demonstrating a CZTS thin film solar cell using coatings annealed in a sulfur atmosphere. We conducted a systematic study of the factors controlling crystal growth and microstructure development during sulfidation annealing of films cast from colloidal dispersions of CZTS nanocrystals. The film microstructure is controlled by concurrent normal and abnormal grain growth. At 600 °C to 800 °C and low sulfur pressures (50 Torr), abnormal CZTS grains up to 10 microm in size grow on the surface of the CZTS nanocrystal film via transport of material from the nanocrystals to the abnormal grains. Meanwhile, the nanocrystals coarsen, sinter, and undergo normal grain growth. The driving force for abnormal grain growth is the reduction in total energy associated with the high surface area nanocrystals. The eventual coarsening of the CZTS nanocrystals reduces the driving force for abnormal crystal growth. Increasing the sulfur pressure by an order of magnitude to 500 Torr accelerates both normal and abnormal crystal growth though sufficient acceleration of the former eventually reduces the latter by reducing the driving force for abnormal grain growth. For example, at high temperatures (700-800 oC) and sulfur pressures (500 Torr) normal grains quickly grow to ~500 nm which significantly reduces abnormal grain growth. The use of soda lime glass as the substrate, instead of quartz, accelerates normal grain growth. Normal grains grow to ~500 nm at lower temperatures and sulfur pressures (i.e., 600 °C and 50 Torr) than those

  10. Aerobic sulfide production and cadmium precipitation by Escherichia coli expressing the Treponema denticola cysteine desulfhydrase gene. (United States)

    Wang, C L; Lum, A M; Ozuna, S C; Clark, D S; Keasling, J D


    The cysteine desulfhydrase gene of Treponema denticola was over-expressed in Escherichia coli to produce sulfide under aerobic conditions and to precipitate metal sulfide complexes on the cell wall. When grown in a defined salts medium supplemented with cadmium and cysteine, E. coli producing cysteine desulfhydrase secreted sulfide and removed nearly all of the cadmium from solution after 48 h. A control strain produced significantly less sulfide and removed significantly less cadmium. Measurement of acid-labile sulfide and energy dispersive X-ray spectroscopy indicated that cadmium was precipitated as cadmium sulfide. Without supplemental cysteine, both the E. coli producing cysteine desulfhydrase and the control E. coli demonstrated minimal cadmium removal.

  11. In situ visualization of carbonylation and its co-localization with proteins, lipids, DNA and RNA in Caenorhabditis elegans. (United States)

    Kuzmic, Mira; Javot, Hélène; Bonzom, Jean-Marc; Lecomte-Pradines, Catherine; Radman, Miroslav; Garnier-Laplace, Jacqueline; Frelon, Sandrine


    All key biological macromolecules are susceptible to carbonylation - an irreparable oxidative damage with deleterious biological consequences. Carbonyls in proteins, lipids and DNA from cell extracts have been used as a biomarker of oxidative stress and aging, but formation of insoluble aggregates by carbonylated proteins precludes quantification. Since carbonylated proteins correlate with and become a suspected cause of morbidity and mortality in some organisms, there is a need for their accurate quantification and localization. Using appropriate fluorescent probes, we have developed an in situ detection of total proteins, DNA, RNA, lipids and carbonyl groups at the level of the whole organism. In C. elegans, we found that after UV irradiation carbonylation co-localizes mainly with proteins and, to a lesser degree, with DNA, RNA and lipids. The method efficiency was illustrated by carbonylation induction assessment over 5 different UV doses. The procedure enables the monitoring of carbonylation in the nematode C. elegans during stress, aging and disease along its life cycle including the egg stage. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Synthesis of the [beta]-D-glucosyl ester of [carbonyl-[sup 13]C]-indole-3-acetic acid

    Energy Technology Data Exchange (ETDEWEB)

    Jakas, A.; Magnus, V. (Rudjer Boskovic Inst., Zagreb (Croatia)); Horvat, S.; Sandberg, G. (Swedish Univ. of Agricultural Sciences, Uppsala (Sweden))


    An efficient, operationally simple synthetic approach to 1-O-([carbonyl-[sup 13]C]-indole-3'-ylacetyl)-[beta]-D-glucopyranose is described. The synthesis was carried out by fusing a fully benzylated 1-O-glucosylpseudourea intermediate with [carbonyl-[sup 13]C]-indole-3-acetic acid, followed by hydrogenolytic removal of the protective groups. (Author).

  13. Environmental components of OCS policy committee recommendations regarding national oil spill prevention and response program

    International Nuclear Information System (INIS)

    Groat, C.G.; Thorman, J.


    The Exxon Valdez oil spill of March 24, 1989 resulted in thousands of pages of analytical reports assessing the environmental, organizational, legal, procedural, social, economic, and political aspects of the event. Even though the accident was a transportation incident, it had a major impact on the public and political perception of offshore oil operations. This caused the OCS Policy Committee, which advises the Secretary of the Interior and the Minerals Management Service on Outer Continental Shelf resource development and environmental matters, to undertake a review of the reports for the purpose of developing recommendations to the secretary for improvements in OCS operations that would insure maximum efforts to prevent spills and optimal ability to deal with any that occur. The Committee felt strongly that 'a credible national spill prevention and response program from both OCS and non-OCS oil spills in the marine environment is needed to create the political climate for a viable OCS program.' The report of the Committee described eight essential elements of this program; four of these focused on the environmental aspects of oil spills, calling for (1) adequate characterization of the marine and coastal environment, including both information and analysis, accessible to decision makers, (2) the capacity to restore economic and environmental resources as quickly as possible if damage occurs, (3) a mechanism for research on oil spill impacts, and (4) a meaningful role for all interested and responsible parties, including the public, in as many of these activities as possible, from spill prevention and contingency planning to environmental oversight of ongoing operations and participation in clean-up and restoration activities

  14. Variation in the OC locus of Acinetobacter baumannii genomes predicts extensive structural diversity in the lipooligosaccharide.

    Directory of Open Access Journals (Sweden)

    Johanna J Kenyon

    Full Text Available Lipooligosaccharide (LOS is a complex surface structure that is linked to many pathogenic properties of Acinetobacter baumannii. In A. baumannii, the genes responsible for the synthesis of the outer core (OC component of the LOS are located between ilvE and aspS. The content of the OC locus is usually variable within a species, and examination of 6 complete and 227 draft A. baumannii genome sequences available in GenBank non-redundant and Whole Genome Shotgun databases revealed nine distinct new types, OCL4-OCL12, in addition to the three known ones. The twelve gene clusters fell into two distinct groups, designated Group A and Group B, based on similarities in the genes present. OCL6 (Group B was unique in that it included genes for the synthesis of L-Rhamnosep. Genetic exchange of the different configurations between strains has occurred as some OC forms were found in several different sequence types (STs. OCL1 (Group A was the most widely distributed being present in 18 STs, and OCL6 was found in 16 STs. Variation within clones was also observed, with more than one OC locus type found in the two globally disseminated clones, GC1 and GC2, that include the majority of multiply antibiotic resistant isolates. OCL1 was the most abundant gene cluster in both GC1 and GC2 genomes but GC1 isolates also carried OCL2, OCL3 or OCL5, and OCL3 was also present in GC2. As replacement of the OC locus in the major global clones indicates the presence of sub-lineages, a PCR typing scheme was developed to rapidly distinguish Group A and Group B types, and to distinguish the specific forms found in GC1 and GC2 isolates.

  15. Electrical properties of seafloor massive sulfides (United States)

    Spagnoli, Giovanni; Hannington, Mark; Bairlein, Katharina; Hördt, Andreas; Jegen, Marion; Petersen, Sven; Laurila, Tea


    Seafloor massive sulfide (SMS) deposits are increasingly seen as important marine metal resources for the future. A growing number of industrialized nations are involved in the surveying and sampling of such deposits by drilling. Drill ships are expensive and their availability can be limited; seabed drill rigs are a cost-effective alternative and more suitable for obtaining cores for resource evaluation. In order to achieve the objectives of resource evaluations, details are required of the geological, mineralogical, and physical properties of the polymetallic deposits and their host rocks. Electrical properties of the deposits and their ore minerals are distinct from their unmineralized host rocks. Therefore, the use of electrical methods to detect SMS while drilling and recovering drill cores could decrease the costs and accelerate offshore operations by limiting the amount of drilling in unmineralized material. This paper presents new data regarding the electrical properties of SMS cores that can be used in that assessment. Frequency-dependent complex electrical resistivity in the frequency range between 0.002 and 100 Hz was examined in order to potentially discriminate between different types of fresh rocks, alteration and mineralization. Forty mini-cores of SMS and unmineralized host rocks were tested in the laboratory, originating from different tectonic settings such as the intermediate-spreading ridges of the Galapagos and Axial Seamount, and the Pacmanus back-arc basin. The results indicate that there is a clear potential to distinguish between mineralized and non-mineralized samples, with some evidence that even different types of mineralization can be discriminated. This could be achieved using resistivity magnitude alone with appropriate rig-mounted electrical sensors. Exploiting the frequency-dependent behavior of resistivity might amplify the differences and further improve the rock characterization.

  16. Synthesis of arsenic transition metal sulfides and metal arsenides

    Energy Technology Data Exchange (ETDEWEB)

    Singhal, G.H.; Brown, L.D.; Ryan, D.F. [Exxon Research & Development Labs, Baton Rouge, LA (United States)


    One of the chief problems in upgrading shale oil is the presence of inherent arsenic which is known to poison downstream catalysts. Highly dispersed transition metal sulfides formed in situ from the decomposition of dithiocarbamate (DTC) complexes of transition metals show excellent potential as dearsenation agents. The authors have studied the reaction of these sulfides with various arsenic compositions and characterized the metal arsenides and arsenic metal sulfides formed as well as the ease of their formation. Thus, the reaction of bis(butyldithiocarbamato)Ni, (NiBuDTC) with model compounds was very facile and gave NiAs, NiAsS, and NiAs2=xSx. In general the effectiveness of the sulfides for dearsenation followed the sequence Ni>Mo{much_gt}Co, while iron sulfides were totally ineffective. Based upon these results, tests were run in autoclaves (as well as a fixed-bed flow-through unit) with NiBuDTC and shale oil having 73 ppm inherent As. Under optimum conditions, dearsenation down to les than 1 ppm was obtained.

  17. Solubility and permeation of hydrogen sulfide in lipid membranes.

    Directory of Open Access Journals (Sweden)

    Ernesto Cuevasanta

    Full Text Available Hydrogen sulfide (H(2S is mainly known for its toxicity but has recently been shown to be produced endogenously in mammalian tissues and to be associated with physiological regulatory functions. To better understand the role of biomembranes in modulating its biological distribution and effects; we measured the partition coefficient of H(2S in models of biological membranes. The partition coefficients were found to be 2.1±0.2, 1.9±0.5 and 2.0±0.6 in n-octanol, hexane and dilauroylphosphatidylcholine liposome membranes relative to water, respectively (25°C. This two-fold higher concentration of H(2S in the membrane translates into a rapid membrane permeability, P(m = 3 cm s(-1. We used a mathematical model in three dimensions to gain insight into the diffusion of total sulfide in tissues. This model shows that the sphere of action of sulfide produced by a single cell expands to involve more than 200 neighboring cells, and that the resistance imposed by lipid membranes has a significant effect on the diffusional spread of sulfide at pH 7.4, increasing local concentrations. These results support the role of hydrogen sulfide as a paracrine signaling molecule and reveal advantageous pharmacokinetic properties for its therapeutic applications.

  18. Proteomic and carbonylation profile analysis of rat skeletal muscles following acute swimming exercise.

    Directory of Open Access Journals (Sweden)

    Francesca Magherini

    Full Text Available Previous studies by us and other groups characterized protein expression variation following long-term moderate training, whereas the effects of single bursts of exercise are less known. Making use of a proteomic approach, we investigated the effects of acute swimming exercise (ASE on protein expression and carbonylation patterns in two hind limb muscles: the Extensor Digitorum Longus (EDL and the Soleus, mostly composed of fast-twitch and slow-twitch fibres, respectively. Carbonylation is one of the most common oxidative modifications of proteins and a marker of oxidative stress. In fact, several studies suggest that physical activity and the consequent increase in oxygen consumption can lead to increase in reactive oxygen and nitrogen species (RONS production, hence the interest in examining the impact of RONS on skeletal muscle proteins following ASE. Results indicate that protein expression is unaffected by ASE in both muscle types. Unexpectedly, the protein carbonylation level was reduced following ASE. In particular, the analysis found 31 and 5 spots, in Soleus and EDL muscles respectively, whose carbonylation is reduced after ASE. Lipid peroxidation levels in Soleus were markedly reduced as well. Most of the decarbonylated proteins are involved either in the regulation of muscle contractions or in the regulation of energy metabolism. A number of hypotheses may be advanced to account for such results, which will be addressed in future studies.

  19. Additive role of attapulgite nanoclay on carbonyl iron-based magnetorheological suspension

    CSIR Research Space (South Africa)

    Chae, HS


    Full Text Available Attapulgite (ATP), a fibrous nanoclay mineral, was adopted as an additive in this study to improve the sedimentation problem of soft magnetic carbonyl iron (CI)-based magnetorheological (MR) fluids caused by the density mismatch between the CI...

  20. [pi] Backbonding in Carbonyl Complexes and Carbon-Oxygen Stretching Frequencies: A Molecular Modeling Exercise (United States)

    Montgomery, Craig D.


    An exercise is described that has illustrated the effect of various factors on [pi] backbonding to carbonyl ligands, where the students can view the molecular orbitals corresponding to the M-CO [pi] interaction as well as the competing interaction between the metal and co-ligands. The visual and hands-on nature of the modeling exercise has helped…

  1. Unsuitability of using the DNPH-coated solid sorbent cartridge for determination of airborne unsaturated carbonyls (United States)

    Ho, Steven Sai Hang; Ho, K. F.; Liu, W. D.; Lee, S. C.; Dai, W. T.; Cao, J. J.; Ip, H. S. S.


    Measurements of aldehydes and ketones are typically conducted by derivatization using sorbent cartridges coated with 2,4-dinitrophenylhydrazine (DNPH). The collected samples are eluted with acetonitrile and analyzed by high-pressure liquid chromatography coupled with an ultra-violet detector (HPLC/UV). This paper intends to examine artifacts about its suitability in identification of unsaturated carbonyls. Kinetic tests for acrolein, crotonaldehyde, methacrolein and methyl vinyl ketone (MVK) showed formations of carbonyl-DNP-hydrazone during sampling, which could further react with DNPH, resulting in undesired UV absorption products [e.g., carbonyl-DNP-hydrazone-DNPH (dimer) and 2(carbonyl-DNP-hydrazone)-DNPH (trimer)]. The dimerization and trimerization occurred for acrolein and MVK whereas only dimerization for crotonaldehyde and methacrolein. The polymerization products undoubtedly affect the integrity of the chromatogram, leading to misidentification and inaccurate quantification. Whether precautions taken during sampling and/or sample treatment could avoid or minimize this artifact has not been thoughtfully investigated. More often, such artifacts are usually overlooked by scientists when the data are reported.

  2. Ion solvation by channel carbonyls characterized by 17O solid-state NMR at 21 T. (United States)

    Hu, Jun; Chekmenev, Eduard Y; Gan, Zhehong; Gor'kov, Peter L; Saha, Saikat; Brey, William W; Cross, Timothy A


    Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts.

  3. Enantioselective α-Arylation of Carbonyls via Cu(I)-Bisoxazoline Catalysis (United States)

    Harvey, James S.; Simonovich, Scott P.; Jamison, Christopher R.; MacMillan, David W. C.


    The enantioselective α-arylation of both lactones and acyl oxazolidones has been accomplished using a combination of diaryliodonium salts and copper catalysis. These mild catalytic conditions provide a new strategy for the enantioselective construction and retention of enolizable α-carbonyl benzylic stereocenters, a valuable synthon for the production of medicinal agents. PMID:21848265

  4. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium. (United States)

    Wu, San; Li, Ying; Zhang, Songlin


    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions.

  5. Determination of protein carbonyls in plasma, cell extracts, tissue homogenates, isolated proteins

    DEFF Research Database (Denmark)

    Weber, Daniela; Davies, Michael J.; Grune, Tilman


    Protein oxidation is involved in regulatory physiological events as well as in damage to tissues and is thought to play a key role in the pathophysiology of diseases and in the aging process. Protein-bound carbonyls represent a marker of global protein oxidation, as they are generated by multiple...

  6. Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds (United States)

    A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

  7. Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds (United States)

    One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...


    Selective hydrogenation of a, a unsaturated carbonyls where molecules containing C=C and C=O double bonds has both practical importance for fine chemicals industry and theoretical significance. Various studies are reported to enhance the selective hydrogenation of C=O over group...

  9. One-pot Reductive Amination of Carbonyl Compounds with NaBH₄ ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 129; Issue 1. One-pot Reductive Amination of Carbonyl Compounds with NaBH₄-B(OSO₃H)₃/SiO₂ in Acetonitrile and in Solvent-free Condition. HOSEIN HAMADI SAMIRA JAVADI. Regular Article Volume 129 Issue 1 January 2017 pp 75-80 ...

  10. Anisotropic thermal motion in transition-metal carbonyls from experiments and ab initio theory. (United States)

    Deringer, Volker L; Wang, Ai; George, Janine; Dronskowski, Richard; Englert, Ulli


    The thermal motion of atoms in crystals is quantified by anisotropic displacement parameters (ADPs). Here we show that dispersion-corrected periodic density-functional theory can be used to compute accurate ADPs for transition metal carbonyls, which serve as model systems for crystalline organometallic and coordination compounds.

  11. Analysis of selected carbonyl oxidation products in wine by liquid chromatography with diode array detection. (United States)

    Elias, Ryan J; Laurie, V Felipe; Ebeler, Susan E; Wong, Jon W; Waterhouse, Andrew L


    A high performance liquid chromatography (HPLC) method for the detection and quantitation of acetaldehyde, glyceraldehyde, pyruvic acid, 2-ketoglutaric acid, and formaldehyde in wine, based on the formation of the 2,4-dinitrophenylhydrazones, is presented. These carbonyl compounds often result from the chemical oxidation of major wine components, and are known to affect flavor and color stability. Their analysis in wine is complicated due to their instability and their tendency to react reversibly with bisulfite to form alpha-hydroxysulfonates. Published methods that break down the sulfonates for the quantitation of total carbonyls in wine involve alkaline hydrolysis of sulfite-bound carbonyls, but we show, for the first time, that this alkaline treatment step significantly increases the concentration of carbonyls during analysis. A solution based on oxygen exclusion is described. The technique offers good specificity, reproducibility (%RSD 0.45-10.6), and limits of detection (1.29-7.53microgL(-1)). The method was successfully used to monitor concentration changes of these compounds in both white and red wines.

  12. Modular Approach for Novel Nanostructered Polycondensates Enabled by the Unique Selectivity of Carbonyl Biscaprolactam

    NARCIS (Netherlands)

    Loontjens, Ton


    New enabling chemistries have been developed to produce novel well-defined polymeric materials through the additions of small amounts of reactive functional compounds to standard polymers during regular processing steps. We found that carbonyl biscaprolactam and its derivatives couple polymer chains

  13. Cobalt-catalysed C-H carbonylative cyclisation of aliphatic amides. (United States)

    Williamson, Patrick; Galván, Alicia; Gaunt, Matthew J


    A cobalt-catalysed C-H carbonylation of aliphatic carboxamide derivatives is described, employing commercially available Co(ii)-salts in the presence of a silver oxidant. This operationally simple process utilises an atmospheric pressure of CO and generates a range of substituted succinimide products bearing diverse functional groups that can be successfully accessed via this methodology.

  14. NMR Studies of Structure-Reactivity Relationships in Carbonyl Reduction: A Collaborative Advanced Laboratory Experiment (United States)

    Marincean, Simona; Smith, Sheila R.; Fritz, Michael; Lee, Byung Joo; Rizk, Zeinab


    An upper-division laboratory project has been developed as a collaborative investigation of a reaction routinely taught in organic chemistry courses: the reduction of carbonyl compounds by borohydride reagents. Determination of several trends regarding structure-activity relationship was possible because each student contributed his or her results…

  15. Enantioselective gamma- and delta-Borylation of Unsaturated Carbonyl Derivatives: Synthesis, Mechanistic Insights, and Applications (United States)

    Hoang, Gia L.

    Chiral boronic esters are valuable synthetic intermediates widely used in a variety of stereospecific transformations. Transition metal-catalyzed asymmetric hydroboration (CAHB) of alkenes is among the most popular methods for their preparation. Enantioselective hydroboration of activated alkenes (i.e., vinyl arene derivatives or conjugated carbonyl compounds) have been extensively studied by many research groups. We, on the other hand, are interested in enantioselective hydroboration of unactivated alkenes utilizing coordinating functional groups (e.g., carbonyl derivatives) to give functionalized, chiral boronic esters. While conjugate addition and C-H activation methodologies provide efficient alternatives to CAHB for enantioselective beta-borylation of carbonyl compounds, direct gamma- and delta-borylations were essentially unknown prior to our wok on CAHB. The gamma-borylated products were used for understanding stereochemical aspects of Suzuki-Miyaura cross-coupling reactions resulting in stereoretention and in contrast to similar beta-borylated carbonyl derivatives reported in literature. Some other selected transformations were carried out to construct a number of biologically relevant structural motifs, such as lignan precursors, 1,4-amino alcohols, gamma-amino acid derivatives, 5-substitued-gamma-lactone and lactam ring systems. In addition, collaborative experimental and computational studies of the enantioselective desymmetrization via CAHB gain a better understanding of the mechanistic pathways.

  16. Ruthenium(II) carbonyl compounds with the 4'-chloro-2,2':6',2''-terpyridine ligand. (United States)

    Tatikonda, Rajendhraprasad; Haukka, Matti


    Two ruthenium carbonyl complexes with the 4'-chloro-2,2':6',2''-terpyridine ligand (tpy-Cl, C 15 H 10 ClN 3 ), i.e. [RuCl(tpy-Cl)(CO) 2 ][RuCl 3 (CO) 3 ] (I) [systematic name: cis -di-carbonyl-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 3 N )ruthenium(II) fac -tricarbonyltri-chlorido-ruthenate(II)], and [RuCl 2 (tpy-Cl)(CO) 2 ] (II) [ cis -dicarbonyl- trans -di-chlorido(4'-chloro-2,2':6',2''-terpyridine-κ 2 N 1 , N 1' )ruthenium(II)], were synthesized and characterized by single-crystal X-ray diffraction. The Ru II atoms in both centrosymmetric structures (I) and (II) display similar, slightly distorted octa-hedral coordination spheres. The coordination sphere in the complex cation in compound (I) is defined by three N atoms of the tridentate tpy-Cl ligand, two carbonyl carbon atoms and one chlorido ligand; the charge is balanced by an octa-hedral [Ru(CO) 3 Cl 3 ] - counter-anion. In the neutral compound (II), the tpy-Cl ligand coordinates to the metal only through two of its N atoms. The coordination sphere of the Ru II atom is completed by two carbonyl and two chlorido ligands. In the crystal structures of both (I) and (II), weak C-H⋯Cl inter-actions are observed.

  17. Direct photolysis of carbonyl compounds dissolved in cloud and fog~droplets

    Directory of Open Access Journals (Sweden)

    S. A. Epstein


    Full Text Available Gas-phase photolysis is an important tropospheric sink for many carbonyl compounds; however the significance of direct photolysis of these compounds dissolved in cloud and fog droplets is uncertain. We develop a theoretical approach to assess the importance of aqueous photolysis for a series of carbonyls that possess carboxyl and hydroxyl functional groups by comparison with rates of other atmospheric processes. We use computationally and experimentally derived effective Henry's law constants, hydration equilibrium parameters, aqueous hydroxyl radical (OH rate constants, and optical extinction coefficients to identify types of compounds that will (or will not have competitive aqueous photolysis rates. We also present molecular dynamics simulations designed to estimate gas- and aqueous-phase extinction coefficients of unstudied atmospherically relevant compounds found in d-limonene and isoprene secondary organic aerosol. In addition, experiments designed to measure the photolysis rate of glyceraldehyde, an atmospherically relevant water-soluble organic compound, reveal that aqueous quantum yields are highly molecule-specific and cannot be extrapolated from measurements of structurally similar compounds. We find that only two out of the 92 carbonyl compounds investigated, pyruvic acid and acetoacetic acid, may have aqueous photolysis rates that exceed the rate of oxidation by dissolved OH. For almost all carbonyl compounds lacking α,β-conjugation that were investigated, atmospheric removal by direct photolysis in cloud and fog droplets can be neglected under typical atmospheric conditions.

  18. Effect of carotenoid structure on excited-state dynamics of carbonyl carotenoids

    Czech Academy of Sciences Publication Activity Database

    Chábera, P.; Fuciman, M.; Hříbek, P.; Polívka, Tomáš


    Roč. 11, - (2009), s. 8795-8703 ISSN 1463-9076 R&D Projects: GA AV ČR IAA608170604 Institutional research plan: CEZ:AV0Z50510513 Keywords : excited-state dynamics * carbonyl carotenoids * femtosecond spectroscopy Subject RIV: BO - Biophysics Impact factor: 4.116, year: 2009

  19. Effects of sulfide reduction on adsorption affinities of colloidal graphene oxide nanoparticles for phenanthrene and 1-naphthol. (United States)

    Wang, Fanfan; Wang, Fang; Zhu, Dongqiang; Chen, Wei


    The abiotic transformation of nanomaterials in the natural environment can significantly affect their fate,transport, and effects. We observed that the adsorption affinities of graphene oxide nanoparticles(GONPs) for both phenanthrene and 1-naphthol were profoundly enhanced in the presence of sulfide, an environmentally relevant reductant, with doses as low as 0.5 mM Na(2)S per 10 mg/L GONPs. For phenanthrene adsorption enhancement was predominantly caused by the increased surface hydrophobicity from Na(2)S treatment. For 1-naphthol, however, adsorption enhancement was caused mainly by the conversion of the epoxy/ether groups on the surface of graphene oxide (GO) to the phenolic hydroxyl and carbonyl groups, which allowed more significant H-bonding between 1-naphthol and GONPs. The findings of this study underline that abiotic transformation of GO not only affects the stability and mobility of GONPs, but also influences the adsorptive interactions between GONPs and environmental contaminants, and consequently, may increase the environmental risks of GONPs.

  20. 76 FR 4716 - Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Off Delaware, Notice of... (United States)


    ... No. BOEM-2010-0075] Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Off... commercial wind development on the OCS off Delaware and requests submission of indications of competitive... received two nominations of proposed lease areas: One from Bluewater Wind Delaware LLC (Bluewater) and...

  1. 78 FR 760 - Potential Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore New... (United States)


    ... Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore New York, Request for... York Power Authority (NYPA) to acquire an OCS wind lease; (2) solicit public input regarding the... Offshore Wind Collaborative,'' a public-private entity consisting of NYPA, the Long Island Power Authority...

  2. 75 FR 68824 - Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore Maryland-Request... (United States)


    ... No. BOEM-2010-0038] Commercial Leasing for Wind Power on the Outer Continental Shelf (OCS) Offshore..., Interior. ACTION: RFI in Commercial Wind Energy Leasing Offshore Maryland, and Invitation for Comments from... construction of a wind energy project(s) on the Outer Continental Shelf (OCS) offshore Maryland. The BOEMRE...

  3. 76 FR 30956 - Outer Continental Shelf, Alaska OCS Region, Chukchi Sea Planning Area, Oil and Gas Lease Sale 193 (United States)


    ... Point Hope et al., v. Salazar, No. 1:08-cv-00004-RRB (D. Alaska)]. The sale was conducted in February... Continental Shelf, Alaska OCS Region, Chukchi Sea Planning Area, Oil and Gas Lease Sale 193 AGENCY: Bureau of...: BOEMRE announces the availability of a Revised Draft SEIS, OCS Oil and Gas Lease Sale 193, Chukchi Sea...

  4. OC5 Project Phase Ib: Validation of Hydrodynamic Loading on a Fixed, Flexible Cylinder for Offshore Wind Applications

    DEFF Research Database (Denmark)

    Robertson, Amy N.; Wendt, Fabian; Jonkman, Jason M.


    This paper summarizes the findings from Phase Ib of the Offshore Code Comparison, Collaboration, Continued with Correlation (OC5) project. OC5 is a project run under the International Energy Agency (IEA) Wind Research Task 30, and is focused on validating the tools used for modelling offshore win...

  5. 75 FR 29996 - Review of MMS NEPA Policies, Practices, and Procedures for OCS Oil and Gas Exploration and... (United States)


    ... COUNCIL ON ENVIRONMENTAL QUALITY Review of MMS NEPA Policies, Practices, and Procedures for OCS... Environmental Policy Act (NEPA) policies, practices, and procedures for the Minerals Management Service (MMS) decisions for Outer Continental Shelf (OCS) oil and gas exploration and development. This review of MMS NEPA...

  6. 78 FR 9731 - Gulf of Mexico, Outer Continental Shelf (OCS), Central Planning Area (CPA) Oil and Gas Lease Sale... (United States)


    ... Bureau of Ocean Energy Management Gulf of Mexico, Outer Continental Shelf (OCS), Central Planning Area... OCS Oil and Gas Lease Sales: 2012-2017 Western Planning Area Lease Sales 229, 233, 238, 246, and 248; and Central Planning Area Lease Sales 227, 231, 235, 241, and 247; Final Environmental Impact...

  7. 78 FR 45557 - Gulf of Mexico, Outer Continental Shelf (OCS), Western Planning Area (WPA) Oil and Gas Lease Sale... (United States)


    ... WPA Lease Sale 233 on the Gulf of Mexico OCS Oil and Gas Lease Sales: 2013-2014; Western Planning Area Lease Sale 233, and Central Planning Area Lease Sale 231; Final Supplemental Environmental Impact... Bureau of Ocean Energy Management Gulf of Mexico, Outer Continental Shelf (OCS), Western Planning Area...

  8. 77 FR 68147 - Gulf of Mexico, Outer Continental Shelf (OCS), Western Planning Area (WPA), Oil and Gas Lease... (United States)


    ... OCS Oil and Gas Lease Sales: 2012-2017 Western Planning Area Lease Sales 229, 233, 238, 246, and 248, and Central Planning Area Lease Sales 227, 231, 235, 241, and 247 Final Environmental Impact Statement... Bureau of Ocean Energy Management Gulf of Mexico, Outer Continental Shelf (OCS), Western Planning Area...

  9. 77 FR 2991 - Gulf of Mexico (GOM), Outer Continental Shelf (OCS), Central Planning Area (CPA), Oil and Gas... (United States)


    ...: 2007-2012; Western Planning Area (WPA) Sales 204, 207, 210, 215, and 218; Central Planning Area (CPA... Bureau of Ocean Energy Management Gulf of Mexico (GOM), Outer Continental Shelf (OCS), Central Planning Area (CPA), Oil and Gas Lease Sale for the 2007-2012 5-Year OCS Program AGENCY: Bureau of Ocean Energy...

  10. 75 FR 16833 - Preliminary Revised 5-Year Outer Continental Shelf (OCS) Oil and Gas Leasing Program for 2007-2012 (United States)


    ... Continental Shelf (OCS) Oil and Gas Leasing Program for 2007-2012 AGENCY: Minerals Management Service... (MMS) requests comments on the Preliminary Revised 5-Year OCS Oil and Gas Leasing Program for 2007... to the leasing schedule that reflect his balancing of the potential for discovery of petroleum with...

  11. 78 FR 52562 - Outer Continental Shelf (OCS), Gulf of Mexico (GOM), Oil and Gas Lease Sales, Central Planning... (United States)


    ... Bureau of Ocean Energy Management Outer Continental Shelf (OCS), Gulf of Mexico (GOM), Oil and Gas Lease... socioeconomic analyses in the Gulf of Mexico OCS Oil and Gas Lease Sales: 2012-2017; Western Planning Area Lease... will focus on the potential environmental effects of oil and natural gas leasing, exploration...

  12. 77 FR 67394 - Gulf of Mexico (GOM), Outer Continental Shelf (OCS), Western Planning Area (WPA) Lease Sale 233... (United States)


    ... planning areas in the Gulf of Mexico OCS Oil and Gas Lease Sales: Western Planning Area Lease Sales 229... effects of oil and natural gas leasing, exploration, development, and production in the WPA and CPA. BOEM... Bureau of Ocean Energy Management Gulf of Mexico (GOM), Outer Continental Shelf (OCS), Western Planning...

  13. 78 FR 62660 - Outer Continental Shelf (OCS), Gulf of Mexico (GOM), Oil and Gas Lease Sales Eastern Planning... (United States)


    ... Bureau of Ocean Energy Management Outer Continental Shelf (OCS), Gulf of Mexico (GOM), Oil and Gas Lease... environmental effects of oil and natural gas leasing, exploration, development, and production in the EPA. The Final EIS incorporates by reference the analysis presented in the Gulf of Mexico OCS Oil and Gas Lease...

  14. Let's drink and be merry: The framing of alcohol in the prime time American youth series The OC

    NARCIS (Netherlands)

    Bulck, H. van den; Simons, N.; Gorp, B. van


    Objective: This study analyzed the framing of alcohol consumption in the American adolescent drama series The OC. Method: All 51 episodes of Seasons 1 and 2 of The OC were coded for visual and verbal references to beverage use on the level of the scene (n = 1,895) and on the level of the drinking

  15. Extraction of Nanosized Cobalt Sulfide from Spent Hydrocracking Catalyst

    Directory of Open Access Journals (Sweden)

    Samia A. Kosa


    Full Text Available The processes used for the extraction of metals (Co, Mo, and Al from spent hydrotreating catalysts were investigated in this study. A detailed mechanism of the metal extraction process is described. Additionally, a simulation study was performed to understand the sulfidizing mechanism. The suggested separation procedure was effective and achieved an extraction of approximately 80–90%. In addition, the sulfidization mechanism was identified. This sulfidizing process for Co was found to involve an intermediate, the structure of which was proposed. This proposed intermediate was confirmed through simulations. Moreover, the activities of the spent and the regenerated catalyst were examined in the cracking of toluene. The modification of the spent catalyst through the use of different iron oxide loadings improved the catalytic activity.

  16. Sulfide Catalysts Supported on Porous Aromatic Frameworks for Naphthalene Hydroprocessing

    Directory of Open Access Journals (Sweden)

    Eduard Karakhanov


    Full Text Available This paper describes the first example of using porous aromatic frameworks as supports for sulfide catalysts for the hydrogenation of aromatic hydrocarbons. The synthesis of bimetallic Ni-W and Ni-Mo sulfides was performed by in situ decomposition of [(n-Bu4N]2[Ni(MeS42] (Me = W, Mo complexes, supported on mesoporous aromatic framework with a diamond-like structure. It is shown that the highest naphthalene conversions were achieved in the case of additional sulfidation with sulfur. After the reaction, catalysts were characterized by X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The activity of synthesized catalysts has been studied using naphthalene as a model substrate. The materials used in this study were substantially active in hydrogenation and slightly in hydrocracking of naphthalene.

  17. Preparation of transition metal sulfide nanoparticles via hydrothermal route

    International Nuclear Information System (INIS)

    Fei-Ling, P.; Chin-Hua, C.; Sarani Zakaria; Tze-Khong, L.; Mohd Ambar Yarmo; Nay-Ming, H.


    Nano sized copper sulfide, iron sulfide and molybdenum sulfide were successfully synthesised via a simple hydrothermal method. Sodium thiosulfate pentahydrate (Na 2 S 2 O 3 ·5H 2 O) and hydroxylamine sulfate ((H 3 NO) 2 ·H 2 SO 4 ) were used as the starting materials and reacted with the transition metal source at 200 degree Celsius for 90 min. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and Fourier transform infrared spectroscopy (FTIR). Spherical shape CuS and FeS 2 nanoparticles with high crystallinity were successfully produced. The transmission electron micrographs revealed the well-dispersibility of the produced nanoparticles. Scanning electron micrograph showed the MoS 2 nanoparticles possessed a spherical shape with sheet-like structure covering on the outer surface of the particles. (author)

  18. Metal sulfide electrodes and energy storage devices thereof

    Energy Technology Data Exchange (ETDEWEB)

    Chiang, Yet-Ming; Woodford, William Henry; Li, Zheng; Carter, W. Craig


    The present invention generally relates to energy storage devices, and to metal sulfide energy storage devices in particular. Some aspects of the invention relate to energy storage devices comprising at least one flowable electrode, wherein the flowable electrode comprises an electroactive metal sulfide material suspended and/or dissolved in a carrier fluid. In some embodiments, the flowable electrode further comprises a plurality of electronically conductive particles suspended and/or dissolved in the carrier fluid, wherein the electronically conductive particles form a percolating conductive network. An energy storage device comprising a flowable electrode comprising a metal sulfide electroactive material and a percolating conductive network may advantageously exhibit, upon reversible cycling, higher energy densities and specific capacities than conventional energy storage devices.

  19. Separation of platinum metals by theirs extraction as sulfides

    International Nuclear Information System (INIS)

    Pilipenko, A.T.; Ryabushko, O.P.; Ty Van Mak


    Separation of platinum metals by means of their sediment in the form of sulfides with subsequent extraction is studied. The optimum conditions of metal sulfide extraction are determined, the metal output dependence from acidness and aqueous phase composition and also the organic solvent nature are investigated. Ruthenium concentration was determined photometrically. Ruthenium sulfide is extracted by butyl spirit from 1-4 normal hydrochloric acid. The maximum extraction grade of 63% is reached in 3.2-normal acid. When the mixture of acetic and hydrochloric acids (2:1) is used for decomposition of ruthenium tiosalts, the grade of ruthenium extraction by amyl spirit or the mixture of anyl and butyl spirits (1:1) constitutes 100%

  20. Riot control agents: the tear gases CN, CS and OC-a medical review. (United States)

    Schep, Leo J; Slaughter, R J; McBride, D I


    2-Chloroacetophenone (CN), o-chlorobenzylidene malonitrile (CS) and oleoresin capsicum (OC) are common riot control agents. While serious systemic effects are uncommon, exposure to high concentrations may lead to severe complications and even death. The aim of this narrative review is to summarise all main aspects of the riot control agents CN, CS and OC toxicology, including mechanisms of toxicity, clinical features and management. OVID MEDLINE and ISI Web of Science were searched for terms associated with CN, CS and OC toxicity in humans and those describing the mechanism of action, clinical features and treatment protocols. CN, CS and OC are effective lacrimating agents; evidence for toxicity, as measured by the threshold for irritation, is greatest for CN, followed by CS and OC. Typically, ocular and respiratory tract irritation occurs within 20-60 s of exposure. Ocular effects involve blepharospasm, photophobia, conjunctivitis and periorbital oedema. Following inhalation, effects may include a stinging or burning sensation in the nose, tight chest, sore throat, coughing, dyspnoea and difficulty breathing. Dermal outcomes are variable, more severe for CN and include dermal irritation, bulla formation and subcutaneous oedema. Removal from the contaminated area and fresh air is a priority. There is no antidote; treatment consists of thorough decontamination and symptom-directed supportive care. Ocular exposure requires thorough eye decontamination, an eye exam and appropriate pain management. Monitoring and support of respiratory function is important in patients with significant respiratory symptoms. Standard treatment protocols may be required with patients with pre-existing respiratory conditions. Dermal exposures may require systemic steroids for patients who develop delayed contact dermatitis. CN, CS and OC are effective riot control agents. In the majority of exposures, significant clinical effects are not anticipated. The irritant effects can be

  1. Circulating Protein Carbonyls, Antioxidant Enzymes and Related Trace Minerals among Preterms with Respiratory Distress Syndrome. (United States)

    Ahmed, Ahmed El-Abd; Abd-Elmawgood, Eman Ahmed; Hassan, Mohammed H


    Information about oxidative stress in preterms with Respiratory Distress Syndrome (RDS) is defective, so various researches in this area are required, which may open new roads in understanding the pathogenesis of the disease, hence provide additional helpful therapeutic approaches. To assess and compare the plasma level of protein carbonyls as a marker for oxidant status and the antioxidant enzymes; Superoxide Dismutase (SOD) and Glutathione Peroxidase (GPx) and the related trace minerals in the form of Copper (Cu), Zinc (Zn) and Selenium (Se) as markers for antioxidant status, in preterms with and without RDS. A hospital-based case-control study was conducted on fifty-seven preterm neonates (37 preterms with RDS and 20 preterms without RDS) admitted to neonatal intensive care unit of Qena University Hospitals after approval of the University Hospital Ethical Committee. Plasma protein carbonyls assay was done using commercially available ELISA assay kit. Plasma Cu, Zn, Se, erythrocyte SOD and GPx activities assays were done using commercially available colorimetric assay kits. Significant higher plasma levels of protein carbonyls and oxidant/antioxidants ratio (protein carbonyls/{SOD+GPx}) with significant lower plasma levels of Zn, Cu, Se, erythrocyte SOD and GPx activities were found in the preterms with RDS when compared with the preterms without RDS (p<0.001 for all measured markers for both groups). In terms of birth weights and gestational ages, they were negatively correlated with both plasma protein carbonyls and oxidant/antioxidants ratio and positively correlated with plasma copper, zinc, selenium, erythrocyte SOD and GPx activities in a statistically significant manner. Non-significant correlations were found between the measured oxidative stress markers and the severity of RDS. Oxidative stress may have a contributory role in the development of RDS among preterms. Lower birth weight and prematurity may increase the susceptibity to oxidative stress among

  2. Chaperone heat shock protein 90 mobilization and hydralazine cytoprotection against acrolein-induced carbonyl stress. (United States)

    Burcham, Philip C; Raso, Albert; Kaminskas, Lisa M


    Toxic carbonyls such as acrolein participate in many degenerative diseases. Although the nucleophilic vasodilatory drug hydralazine readily traps such species under "test-tube" conditions, whether these reactions adequately explain its efficacy in animal models of carbonyl-mediated disease is uncertain. We have previously shown that hydralazine attacks carbonyl-adducted proteins in an "adduct-trapping" reaction that appears to take precedence over direct "carbonyl-sequestering" reactions, but how this reaction conferred cytoprotection was unclear. This study explored the possibility that by increasing the bulkiness of acrolein-adducted proteins, adduct-trapping might alter the redistribution of chaperones to damaged cytoskeletal proteins that are known targets for acrolein. Using A549 lung adenocarcinoma cells, the levels of chaperones heat shock protein (Hsp) 40, Hsp70, Hsp90, and Hsp110 were measured in intermediate filament extracts prepared after a 3-h exposure to acrolein. Exposure to acrolein alone modestly increased the levels of all four chaperones. Coexposure to hydralazine (10-100 μM) strongly suppressed cell ATP loss while producing strong adduct-trapping in intermediate filaments. Most strikingly, hydralazine selectively boosted the levels of cytoskeletal-associated Hsp90, including a high-mass species that was sensitive to the Hsp90 inhibitor 17-N-allylamino-17-demethoxygeldanamycin. Biochemical fractionation of acrolein- and hydralazine-treated cells revealed that hydralazine likely promoted Hsp90 migration from cytosol into other subcellular compartments. A role for Hsp90 mobilization in cytoprotection was confirmed by the finding that brief heat shock treatment suppressed acute acrolein toxicity in A549 cells. Taken together, these findings suggest that by increasing the steric bulk of carbonyl-adducted proteins, adduct-trapping drugs trigger the intracellular mobilization of the key molecular chaperone Hsp90.

  3. Protein carbonyl content: a novel biomarker for aging in HIV/AIDS patients. (United States)

    Kolgiri, Vaishali; Patil, Vinayak Wamanrao

    The major complications of "treated" Human Immunodeficiency Virus (HIV) infection are cardiovascular disease, malignancy, renal disease, liver disease, bone disease, and perhaps neurological complications, which are phenomena of the normal aging process occurring at an earlier age in the HIV-infected population. The present study is aimed to explore protein carbonyl content as a biomarker for detecting oxidative DNA damage induced ART toxicity and/or accelerated aging in HIV/AIDS patients. To investigate the potential of carbonyl content as a biomarker for detecting oxidative Deoxyribonucleic acid (DNA) damage induced Antiretroviral Theraphy (ART) toxicity and/or accelerated aging in HIV/AIDS patients. In this case-control study a total 600 subjects were included. All subjects were randomly selected and grouped as HIV-negative (control group) (n=300), HIV-infected ART naive (n=100), HIV-infected on first line ART (n=100), and HIV-infected on second line ART (n=100). Seronegative control subjects were age- and sex-matched with the ART naive patients and the two other groups. Carbonyl protein was determined by the method described in Levine et al. DNA damage marker 8-OH-dG was determined using 8-hydroxy-2-deoxy Guanosine StressXpress ELA Kit by StressMarq Biosciences. Protein carbonyl content levels and oxidative DNA damage were significantly higher (paging in HIV/AIDS patients. Larger studies are warranted to elucidate the role of carbonyl content as a biomarker for premature aging in HIV/AIDS patients. Copyright © 2016 Sociedade Brasileira de Infectologia. Published by Elsevier Editora Ltda. All rights reserved.

  4. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix (United States)

    Osuntokun, Jejenija; Ajibade, Peter A.


    Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato-κS,S'-bis(N,N-dimethylthiourea-κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33-7.21 nm for ZnS and 4.95-7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.

  5. Morphology and thermal studies of zinc sulfide and cadmium sulfide nanoparticles in polyvinyl alcohol matrix

    Energy Technology Data Exchange (ETDEWEB)

    Osuntokun, Jejenija; Ajibade, Peter A., E-mail:


    Zn(II) and Cd(II) metal complexes of 1-cyano-1-carboethoxyethylene-2,2-dithiolato–κS,S’–bis (N,N-dimethylthiourea–κS) have been synthesized and characterized with analytical and spectroscopic techniques. The complexes were thermolysed in hexadecylamine at 200 °C to prepare ZnS and CdS nanoparticles. The nanoparticles were characterized with scanning electron microscope (SEM), transmission electron microscope (TEM), and powder X-ray diffraction (p-XRD). TEM images showed spherically shaped nanoparticles, whose sizes are in the range 4.33–7.21 nm for ZnS and 4.95–7.7 nm CdS respectively and XRD confirmed cubic crystalline phases for the nanoparticles. The optical band gap energy evaluated from the absorption spectra are 2.88 eV (430 nm) and 2.81 eV (440 nm) for the ZnS and CdS nanoparticles respectively. The as-prepared metal sulfide nanoparticles were further incorporated into polyvinyl alcohol (PVA) to give ZnS/PVA and CdS/PVA composites. The polymer nanocomposites were studied to investigate their morphology and thermal properties relative to the pure PVA. XRD diffractions indicated that the crystalline phases of the nanoparticles and the sizes in PVA matrices remained unaltered. Infra-red spectra studies revealed interactions between the PVA and the metal sulfide nanoparticles and TGA studies show that the ZnS/PVA and CdS/PVA nanocomposites exhibit better thermal stability than the pure PVA.


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

  7. Quantum cascade laser spectroscopy of OCS isotopologues in 4He nanodroplets: A test of adiabatic following for a heavy rotor (United States)

    Faulkner, Ty; Miller, Isaac; Raston, Paul L.


    We report high-resolution infrared spectra of OCS isotopologues embedded in helium nanodroplets that were recorded with a newly built spectrometer. For the normal isotopologue, we observed the relatively weak third bending overtone band, in addition to new high J transitions in the C-O stretching fundamental, which has previously been investigated by diode laser spectroscopy [S. Grebenev et al., J. Chem. Phys. 112, 4485 (2000)]. Similar to the gas phase, the overtone band is (only) 45 cm-1 higher in energy than the fundamental, and this leads to additional broadening due to rapid vibrational relaxation that is accompanied by the creation of real/virtual phonon excitations. We also observed spectra in the C-O stretching fundamental for several minor isotopologues of OCS, including 18OCS, O13CS, and OC33S, in addition to some new peaks for OC34S. A rovibrational analysis allowed for determination of the moment of inertia of helium (ΔIHe) that couples to the rotation of OCS for each isotopologue. In the context of the adiabatic following approximation, the helium density structure that follows the rotation of OCS should essentially remain unchanged between the isotopologues, i.e., there should be no dependence of ΔIHe on the gas phase moment of inertia of OCS (IG). While this behavior was expected for the "heavy" OCS rotor investigated here, we instead found an approximately linear 1:1 relation between ΔIHe and IG, which suggests partial breakdown of the adiabatic following approximation, making OCS the heaviest molecule for which evidence for this effect has been obtained.

  8. Handbook of Phase Transition Sulfides, Selenides and Tellurides, (United States)


    Cinnabar) ........ A-108 In2S3 (Indium Sulfide or 01-Indium Trisulfide) ...... A-113 MnS (Manganese Monosulfide) ... .... .. .......... A-116 - MnS2...1n2S 3 Indium Sulfide or Di-Indium Trisulflde In2S3 exists as cubic a-In 2S3 and tetragonal 0-In 2S3. Until recently, no detailed studies on the...structure and the vibrational properties of In2S3 have been reported. 0-In 2S3 is the stable room temperature phase. At 420°C there is a transition to c

  9. High conducting oxide--sulfide composite lithium superionic conductor

    Energy Technology Data Exchange (ETDEWEB)

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


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

  10. Experimental constraints on gold and silver solubility in iron sulfides

    International Nuclear Information System (INIS)

    Pal'yanova, Galina; Mikhlin, Yuri; Kokh, Konstantin; Karmanov, Nick; Seryotkin, Yurii


    Experiments were performed to determine crystallization of Fe,S-melts (pyriti≿ and troilitic with molar ratio S/Fe ratios of 2 and 1, respectively) containing traces of gold and silver at (Ag/Au) wt ratios varying from 10 to 0.1. The solid products were studied by optical microscopy, scanning electron microscopy, X-ray powder diffraction (XRD), microprobe analysis, and X-ray photoelectron spectroscopy (XPS) in order to reveal the concentration limits of “invisible” gold and silver in magmatic iron sulfides, and to determine the influence of sulfur on forms of precious metals in the Fe–S system with different Ag/Au ratios. Au–Ag phases do not form inclusions but instead concentrate on the grain boundaries in the synthetic pyrrhotite and troilite, while pyrite comprises micro- (1–5 μm) and macroinclusions of Au–Ag alloys and Au–Ag sulfides. In “pyriti≿” systems, the fineness of alloys increases from 650 to 970‰ and the composition of sulfides changes from acanthite (Ag 2 S) to uytenbogaardtite (Ag 3 AuS 2 ) and petrovskaite (AgAuS) as the Ag/Au ratio decreases. The concentrations of “invisible” precious metals revealed in troilite were 0.040 ± 0.013 wt.% Au and 0.079 ± 0.016 wt.% Ag. Measured concentrations in pyrite and pyrrhotite were <0.024 wt.% Au and <0.030 wt.% Ag. The surface layers of iron sulfides probed with XPS were enriched in the precious metals, and in silver relative to gold, especially in the systems with Fe/S = 1, probably, due to depletion of the metallic alloy surfaces with gold. Au- and Ag-bearing iron sulfides crystallized primarily from melts may be the source of redeposited phases in hydrothermal and hypergene processes. - Highlights: • The samples of Fe–S–Au–Ag system were synthesized. • Coupled solubility of gold and silver in iron sulfides was specified. • Ag–Au inclusions on surfaces of iron sulfides are likely to be enriched in silver. • Au–Ag sulfides can exist along with native gold in

  11. Thermal stability of semiconductor sulfide phases in air

    International Nuclear Information System (INIS)

    Tsiulyanv, I.I.; Lyalikova, K.Y.; Zhitar, V.F.


    This paper investigates the semiconductor sulfide phases Zn 3 In 2 S 6 , Zn 3 Ga 2 S 6 , and Zn 3 GaInS 6 , produced by chemical transport reactions in a sealed space. A typical derivatogram is shown. Up to 873 K no weight changes appear in the TG curve. As indium atoms are replaced by gallium atoms the kinetic oxidation parameters of the sulfide phases change regularly, and they correlate with the calculated heat of atomization, which characterizes bond strength. The dependence of the temperature of the start of oxidation on composition shows that zinc thiogallate is the most stable when heated in air

  12. Crystal structure of (OC5W(μ-dppeW(CO5

    Directory of Open Access Journals (Sweden)

    Hannah F. Drake


    Full Text Available The centrosymmetric title complex, [μ-ethane-1,2-diylbis(diphenylphosphane-κ2P:P′]bis[pentacarbonyltungsten(0], [W2(C26H24P2(CO10], consists of two W(CO5 moieties bridged by a bis(diphenylphosphanylethane (dppe ligand. The W0 atom has a slightly distorted octahedral coordination environment consisting of 5 carbonyl ligands and one P atom from the bridging dppe ligand with the nearest W0 atom 5.625 (5 Å away. The complex resides on a center of symmetry.

  13. Electrocatalysis of the hydrogen evolution reaction by thermally formed sulfides on steels


    Kumar, Prem T; Sathyanarayana, S


    The electrocatalytic activity was studied of sulfides, formed by thermal sulfidization of various com. available steels, for the cathodic evolution of H from sodium chloride. The effects of certain surface active anions on the H evolution reaction on these sulfidized steels were also studied. Sulfidization of C steels and Si steels increases their electrocatalytic activity with respect to cathodic H evolution and thereby reduces the over potential in sodium chloride solns. (typically about ...

  14. The solubility of iron sulfides and their role in mass transport in Girdler-Sulfide heavy water plants

    International Nuclear Information System (INIS)

    Tewari, P.H.; Wallace, G.; Campbell, A.B.


    The solubilities of several iron sulfides, mackinawite FeSsub((1-x)), troilite FeS, pyrrhotite Fesub((1-x))S (monoclinic and hexagonal), and pyrite FeS 2 have been determined in aqueous H 2 S solution at 0.1 MPa and 1.8 MPa H 2 S pressures between 25 deg and 125 deg C. The dependence of solubility on the pH of the medium has also been studied. It is concluded that since mackinawite is the most soluble of the iron sulfides, and has the highest dissolution rate and the steepest decline in solubility with temperature, its prolonged formation during plant operation should be avoided to minimize iron transport from lower to higher temperature areas in Girdler-Sulfide (G.S.) heavy water plants. This can be achieved by a preconditioning of carbon steel surfaces to convert mackinawite to pyrrhotite and pyrite

  15. Organochlorine Pesticides (OCs) and Polychlorinated Biphenyls (PCBs) in Tilapia zillii from Lake El-Manzala, Egypt

    International Nuclear Information System (INIS)

    El-Greisy, Zeinab Abdalbagi; Abdallah, A. Mohamed Ali


    A fresh water fish species, (Tilapia zillii) from Lake El-Manzala was analyzed for concentrations of several Organochlorine pesticides (OCs) and Polychlorine piphenyl's (PCBs) in liver, gonads, mesenteric fat, flesh and the digestive tract in mature fish during the breeding season. Polychlorinated piphenyls (PCBs) and Organochloripe pesticides (OCs) were calculated in (ng/g) dry weight (dw) in homogenized samples. The obtained results revealed differences in lipid content between these different organs. The females showed higher lipid content than males. There was significant positive correlation the lipid content and organochlorines and polychlorinated biphenyls (PCBs). The results come concomitant with the lipophilicity of studied compounds. However, the recoded concentration of these studied pollutants still does not exceed international hazardous levels. (author)

  16. Basic characteristics of the a-SiOC:H thin films prepared by PE CVD

    Czech Academy of Sciences Publication Activity Database

    Vaněk, J.; Čech, V.; Přikryl, R.; Zemek, Josef; Peřina, Vratislav


    Roč. 54, Suppl. C (2004), s. C937-C942 ISSN 0011-4626 R&D Projects: GA MŠk ME 597; GA MŠk OC 527.110; GA ČR GA104/03/0236 Institutional research plan: CEZ:AV0Z1010914 Keywords : vinyltriethoxysilane * thin film * PECVD Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.292, year: 2004

  17. Additional studies of competition and performance in OCS oil and gas sales, 1954-1975 (United States)

    Mead, Walter J.; Sorensen, Philip Edward


    Economic rent is commonly defined in economics as any payment to a factor of production in excess of the minimum necessary to engage it in production. In the case of OCS lands owned by the federal government, the minimum supply price necessary to induce the federal government to lease production rights would be the costs of establishing and administering lease contracts. Assuming, for the sake of simplicity, that these costs are small enough to be ignored in the analysis, all payments to the federal government for use of OCS lands are forms of economic rent. An ideal leasing system should transfer the full amount of economic rent implicit in OCS resources to the federal government. Whether such a complete transfer of economic rent occurs depends upon the conditions of competition in the market for OCS leases. The principal means for capturing economic rent under the bidding system employed by the federal government over the years 1954-1969 are the bonus paid by the highest bidder and a royalty payment which has historically been fixed at 16 2/3 percent of gross production value. Of less importance is an annual rental payment, usually about \\$3.00 per acre, which is paid as long as a tract under lease is not producing.In the sections which follow, major factors affecting the capture of economic rent by the federal government are discussed and data are presented which demonstrate the importance of the different means used. In computing the amounts of economic rent captured by the federal government, the discounted cash flow technique is employed. This requires selection of an appropriate discount rate, in contrast to the internal rate of return analysis used in Part I, above.

  18. Fracture response of SiOC based composites on dynamic loading

    Czech Academy of Sciences Publication Activity Database

    Halasová, Martina; Černý, Martin; Strachota, Adam; Chlup, Zdeněk; Dlouhý, Ivo


    Roč. 50, č. 11 (2015), s. 1547-1554 ISSN 0021-9983 R&D Projects: GA ČR GAP107/12/2445 Institutional support: RVO:68081723 ; RVO:61389013 ; RVO:67985891 Keywords : SiOC glass * basalt reinforcement * woven fabric * impact strength * energy consumption * fracture surface Subject RIV: JL - Materials Fatigue, Friction Mechanics; JH - Ceramics, Fire-Resistant Materials and Glass (USMH-B); CD - Macromolecular Chemistry (UMCH-V) Impact factor: 1.242, year: 2015

  19. A robust 43-GHz VCO in CMOS for OC-768 SONET applications

    NARCIS (Netherlands)

    van der Wel, A.P.; Gierkink, Sander L.J.; Gierink, Sander L.J.; Frye, Robert C.; Boccuzzi, Vito; Nauta, Bram

    In this paper, we present a 43-GHz LC-VCO in 0.13-μm CMOS for use in SONET OC-768 optical networks. A tuned output buffer is used to provide 1.3 Vp-p (single-ended) into a 90-fF capacitive load as is required when the VCO is used in typical clock and data recovery (CDR) circuits. Phase noise is -90


    NARCIS (Netherlands)



    The colorless sulfur bacterium Thiobacillus thioparus T5, isolated from a marine microbial mat, was grown in continuous culture under conditions ranging from sulfide limitation to oxygen limitation. Under sulfide-limiting conditions, sulfide was virtually completely oxidized to sulfate. Under

  1. Reliability of Electrochemical Techniques for Determining Corrosion Rates on Carbon Steel in Sulfide Media

    DEFF Research Database (Denmark)

    Hilbert, Lisbeth Rischel; Hemmingsen, T.; Nielsen, Lars Vendelbo


    Effects of film formation on carbon steel in hydrogen sulfide (H2S) media may corrupt corrosion rate monitoring by electrochemical techniques. Electrochemical data from H2S solutions, biological sulfide media, and natural sulfide containing geothermal water have been collected, and the process of...

  2. Sulfide-iron interactions in domestic wastewater from a gravity sewer

    NARCIS (Netherlands)

    Nielsen, A.H.; Lens, P.N.L.; Vollertsen, J.; Hvitved-Jacobsen, Th.


    Interactions between iron and sulfide in domestic wastewater from a gravity sewer were investigated with particular emphasis on redox cycling of iron and iron sulfide formation. The concentration ranges of iron and total sulfide in the experiments were 0.4-5.4 mg Fe L-1 and 0-5.1 mg S L-1,

  3. Is succession in wet calcareous dune slacks affected by free sulfide?

    NARCIS (Netherlands)

    Adema, EB; van Gemerden, H; Grootjans, AP; Adema, Erwin B.; Grootjans, Ab P.; Rapson, G.

    Consequences of sulfide toxicity on succession in wet calcareous dune slacks were investigated. Sulfide may exert an inhibitory effect on dune slack plants, but several pioneer species exhibit ROL (Radial Oxygen Loss) and thereby protect themselves against free sulfide. Under oxic conditions free

  4. Identifying the Prospective Area of Sulfide Groundwater within the Area of Palvantash Oil and Gas Deposit

    Directory of Open Access Journals (Sweden)

    M. R. Zhurayev


    Full Text Available This paper describes the methodology of prospecting for sulfide groundwater in the area of Palvantash oil fields. In result of study allowed determining the favorable conditions for the sulfide waters formation, and mapping the areas of different sulfide water concentration. The relatively permeable areas were established and the water borehole positions were recommended.

  5. 76 FR 69136 - Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting (United States)


    ... Hydrogen Sulfide; Community Right-to-Know Toxic Chemical Release Reporting AGENCY: Environmental Protection Agency (EPA). ACTION: Lifting of Administrative Stay for Hydrogen Sulfide; Correction. SUMMARY: The... Administrative Stay of the reporting requirements for hydrogen sulfide. The Office of the Federal Register...

  6. Surface functionalization of carbonyl iron with aluminum phosphate coating toward enhanced anti-oxidative ability and microwave absorption properties (United States)

    Duan, Wenju; Li, Xuandong; Wang, Ying; Qiang, Rong; Tian, Chunhua; Wang, Na; Han, Xijiang; Du, Yunchen


    Fe@AlPO4 core-shell composites with tunable AlPO4 content have been successfully prepared through in situ deposition of AlPO4 on the surface of carbonyl iron. The presence of the AlPO4 layer improves the anti-oxidative ability of the internal carbonyl iron, so that surface oxidation and magnetic degradation in these composites are significantly suppressed when compared with naked carbonyl iron. It is worth noting that the AlPO4 layer can affect the electromagnetic parameters of carbonyl iron, resulting in well-matched characteristic impedance. By optimizing the AlPO4 layer content, the Fe@AlPO4 composite can display excellent reflection loss characteristics, and qualified absorption in a very broad frequency range (2.4-18.0 GHz over -10 dB) can be achieved. The microwave absorption performance of the Fe@AlPO4 composite is indeed superior to pure carbonyl iron as well as many previously reported carbonyl iron-based composites. More importantly, the Fe@AlPO4 composite can maintain good microwave absorption properties after treatment at high temperature for long time periods. These results provide new insight into the fabrication of carbonyl iron-based composites with good microwave absorption and anti-oxidative properties that meet the requirements in practical applications.

  7. Trace hydrogen sulfide gas sensor based on tungsten sulfide membrane-coated thin-core fiber modal interferometer (United States)

    Deng, Dashen; Feng, Wenlin; Wei, Jianwei; Qin, Xiang; Chen, Rong


    A novel fiber-optic hydrogen sulfide sensor based on a thin-core Mach-Zehnder fiber modal interferometer (TMZFI) is demonstrated and fabricated. This in-line interferometer is composed of a short section of thin-core fiber sandwiched between two standard single mode fibers, and the fast response to hydrogen sulfide is achieved via the construction of tungsten sulfide film on the outside surface of the TMZFI using the dip-coating and calcination technique. The fabricated sensing nanofilm is characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) spectrometer, Fourier transform infrared (FTIR) and spectroscopic analysis technology, etc. Experimental results showed that the WS2 sensing film has a hexagonal structure with a compact and porous morphology. The XPS and FTIR indicate that the existence of two elements (W and S) is demonstrated. With the increasing concentration of hydrogen sulfide, the interference spectra appear blue shift. In addition, a high sensitivity of 18.37 pm/ppm and a good linear relationship are obtained within a measurement range from 0 to 80 ppm. In addition, there is an excellent selectivity for H2S, which has also been proved by the surface adsorption energy results of tungsten sulfide with four gases (H2S, N2, O2 and CO2) by using the density functional theory calculations. This interferometer has the advantages of simple structure, high sensitivity and easy manufacture, and could be used in the safety monitoring field of hydrogen sulfide gas.

  8. Red coloration by heat treatment of the coprecipitate of cadmium sulfide and mercury(II) sulfide prepared from the nitrates

    International Nuclear Information System (INIS)

    Nakahara, Fujiya


    The effects of starting salts on the color, particle size and crystal structure of mercury-cadmium-sulfide pigments were investigated. The coprecipitate (N-S) of cadmium sulfide and mercury (II) sulfide was prepared by adding sodium sulfide solution to a mixed cadmium-mercury (II) nitrate solution. The coprecipitate (C-S) of cadmium sulfide and mercury (II) sulfide was also prepared from the mixed solution of their chlorides by the same method as described above. The coprecipitated products were heat-treated (calcination or hydrothermal treatment) at 350 0 C for 2 hours and subsequent changes in powder properties of both products were compared from each other. The powder properties of N-S, C-S and their heat-treated products were investigated by spectral reflectance, electron microscopy, X-ray diffraction and specific surface area measurements. Sample (N-C) obtained by the calcination of N-S was brown, indicating no red coloration, but the calcined product (C-C) of C-S developed a red color. Cl - and hot water were found to be effective for the red color development of the pigment. The effectiveness was confirmed by calcining N-S in the presence of NaCl or by treating it hydrothermally. It was found that halides other than NaCl, (e.g., NH 4 Cl, KCl, KBr and KI), were also effective for the color development of the pigment. The red samples are solid solutions with a basically hexagonal CdS structure, and it appears that CdS takes up HgS without any apparent structural changes. The particle size of the red samples are larger than those of the non red samples. (author)

  9. Total hemispherical emissivity of pre-oxidized and un-oxidized Zr-2.5Nb pressure-tube materials at 600 {sup o}C to 1000 {sup o}C under vacuum

    Energy Technology Data Exchange (ETDEWEB)

    Fong, R.W.L.; Paine, M.; Nitheanandan, T., E-mail: [Canadian Nuclear Laboratories, Chalk River, Ontario (Canada)


    The emissivity of pre-oxidized and un-oxidized pressure-tube specimens has been measured at high temperatures under vacuum. The emissivity values of un-oxidized tube specimens decreased only slightly from 0.34 at 600 {sup o}C to 0.30 at 800 {sup o}C and changed gradually to 0.25 at 1000 {sup o}C. In comparison, the emissivity of pre-oxidized pressure-tube specimens decreased drastically from 0.70 at 600 {sup o}C to 0.35 at 800 {sup o}C, and gradually decreased to 0.25 at 1000 {sup o}C. The oxide layer of the pre-oxidized tube specimens dissolved into the metal matrix when heated to 700 {sup o}C and higher. Using these results, 2 linear correlations were obtained for emissivity with the oxide thickness measured by scanning electron microscopy and secondary ion mass spectroscopy analysis. (author)

  10. Tailored graphitized soot as reference material for EC/OC measurement validation

    Directory of Open Access Journals (Sweden)

    O. Popovicheva


    Full Text Available The lack of standard reference materials for calibrating, troubleshooting and intercomparing techniques that measure the composition of black carbon, commonly referred to as soot, has been a major obstacle that hinders improved understanding of how climate and health is impacted by this ubiquitous component of the atmosphere. A different approach is offered here as a means of constructing precisely controlled material with fractions of organic carbon (OC on the surface of elemental carbon (EC whose structure reflects that of the combustion produced particles found in the atmosphere. The proposed soot reference material (SRM uses EC as a basis substrate for surface coatings of organic compounds that are representative of the main classes of organics identified in the coverage of soot produced by fossil fuel burning. A number of methods are used to demonstrate the quality and stability of the reference EC and SRM. Comparison of the nominal fraction of OC deposited on the EC substrate with the fraction measured with thermal/optical analysis (TOA shows excellent agreement. Application of this type of reference material for evaluating the different methods of carbon analysis may help resolve differences that currently exist between comparable measurement techniques when trying to separate OC and EC from ambient samples.

  11. Studies of vibrational relaxation in OCS and CF4 by pulsed photoacoustic techniques

    International Nuclear Information System (INIS)

    Smith, N.J.G.; Davis, C.C.; Smith, I.W.M.


    We have used the pulsed photoacoustic technique to measure the effective collisional probabilities for relaxation of the lowest vibrational modes of OCS and CF 4 by several collision partners. The measured probabilities at 300 K are OCS by OCS: (3.7 +- 0.7) x 10 -4 ; He: (8.0 +- 0.3) x 10 -4 ; Ar: (0.96 +- 0.3) x 10 -4 ; H 2 : (12.0 +- 7.0) x 10 -4 ; D 2 : (12.9 +- 2.5) x 10 -4 ; N 2 : (2.5 +- 0.5) x 10 -4 ; CO: (3.0 +- 0.7) x 10 -4 ; CF 4 by CF 4 : (3.4 +- 0.2) x 10 -4 ; He: (8.6 +- 1.0) x 10 -4 ; Ar: (1.6 +- 0.2) x 10 -4 . We also consider in some detail the acoustic waves generated by cylindrically symmetric laser excitation of a weakly absorbing gas in a cylindrical tube and how the signals produced by a microphone in the tube wall reflect the V-R,T relaxation of the gas

  12. Uncertainty Analysis of OC5-DeepCwind Floating Semisubmersible Offshore Wind Test Campaign: Preprint

    Energy Technology Data Exchange (ETDEWEB)

    Robertson, Amy N [National Renewable Energy Laboratory (NREL), Golden, CO (United States)


    This paper examines how to assess the uncertainty levels for test measurements of the Offshore Code Comparison, Continued, with Correlation (OC5)-DeepCwind floating offshore wind system, examined within the OC5 project. The goal of the OC5 project was to validate the accuracy of ultimate and fatigue load estimates from a numerical model of the floating semisubmersible using data measured during scaled tank testing of the system under wind and wave loading. The examination of uncertainty was done after the test, and it was found that the limited amount of data available did not allow for an acceptable uncertainty assessment. Therefore, this paper instead qualitatively examines the sources of uncertainty associated with this test to start a discussion of how to assess uncertainty for these types of experiments and to summarize what should be done during future testing to acquire the information needed for a proper uncertainty assessment. Foremost, future validation campaigns should initiate numerical modeling before testing to guide the test campaign, which should include a rigorous assessment of uncertainty, and perform validation during testing to ensure that the tests address all of the validation needs.

  13. Radioimmunoscintigraphy and radioimmunotherapy with monoclonal antibodies (19-9/anti-CEA and OC 125)

    International Nuclear Information System (INIS)

    Baum, R.P.; Maul, F.D.; Senekowitsch, R.


    131 I labelled F (ab') 2 fragments of monoclonal antibodies to tumor-associated antigens (Ca 19-9/DEA and CA 125; specific activity: 55-111 MBq, mean injected activity 61 MBq) were administered to 116 patients for the radioimmunodetection of different malignant tumors (mainly colorectal (19-9/anti-CEA) and ovarian carcinomas (OC 125). Using planar scintigraphy and the second tracer isocontour technique (STIT) sensitivity was 83% and specificity 90% (n = 92 pts.) for the radioimmuno-cocktail 19-9/anti-CEA. In all patients examined with OC 125 retrospectively (n = 17 pts.) immunoscintigraphy was found to be positive. Up to now we have performed three radioimmunotherapies (once with 131 I-19-9/anti-CEA, 2.33 GBq (63mCi); twice with 131 I-OC 125, 3.70 GBq (100 mCi) and 4.63GBq (125 mCi) resulting in radiation doses to the tumor of about 20 Gy. Diagnostic application of radiolabelled monoclonal antibodies is encouraging. For therapeutic use many problems remain to be solved. (Author)

  14. Enantioselective Iridium Catalyzed Carbonyl Allylation from the Alcohol Oxidation Level via Transfer Hydrogenation: Minimizing Pre-Activation for Synthetic Efficiency (United States)

    Han, Soo Bong; Kim, In Su; Krische, Michael J.


    Existing methods for enantioselective carbonyl allylation, crotylation and tert-prenylation require stoichiometric generation of pre-metallated nucleophiles and often employ stoichiometric chiral modifiers. Under the conditions of transfer hydrogenation employing an ortho-cyclometallated iridium C,O-benzoate catalyst, enantioselective carbonyl allylations, crotylations and tert-prenylations are achieved in the absence of stoichiometric metallic reagents or stoichiometric chiral modifiers. Moreover, under transfer hydrogenation conditions, primary alcohols function dually as hydrogen donors and aldehyde precursors, enabling enantioselective carbonyl addition directly from the alcohol oxidation level. PMID:20024203

  15. 21 CFR 177.2490 - Polyphenylene sulfide resins. (United States)


    ... contact with food at temperatures up to and including normal baking and frying temperatures; provided that... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyphenylene sulfide resins. 177.2490 Section 177.2490 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED...

  16. An eco-friendly oxidation of sulfide compounds

    Indian Academy of Sciences (India)

    An improved green route has been developed for the oxidation of sulfide compounds. Albendazole is converted to ricobendazole or albendazole sulfone using H₂O₂ as an oxidant and H₂O as the solvent. High yields of the corresponding products were obtained by carrying out the reaction at room temperature.

  17. Micelle Mediated Trace Level Sulfide Quantification through Cloud Point Extraction

    Directory of Open Access Journals (Sweden)

    Samrat Devaramani


    Full Text Available A simple cloud point extraction protocol has been proposed for the quantification of sulfide at trace level. The method is based on the reduction of iron (III to iron (II by the sulfide and the subsequent complexation of metal ion with nitroso-R salt in alkaline medium. The resulting green-colored complex was extracted through cloud point formation using cationic surfactant, that is, cetylpyridinium chloride, and the obtained surfactant phase was homogenized by ethanol before its absorbance measurement at 710 nm. The reaction variables like metal ion, ligand, surfactant concentration, and medium pH on the cloud point extraction of the metal-ligand complex have been optimized. The interference effect of the common anions and cations was studied. The proposed method has been successfully applied to quantify the trace level sulfide in the leachate samples of the landfill and water samples from bore wells and ponds. The validity of the proposed method has been studied by spiking the samples with known quantities of sulfide as well as comparing with the results obtained by the standard method.

  18. Hydrogen sulfide : role in vascular physiology and pathology

    NARCIS (Netherlands)

    Holwerda, Kim M.; Karumanchi, S. Ananth; Lely, A. Titia

    Purpose of reviewHydrogen sulfide (H2S), a colorless gas that is endogenously generated in mammals from cysteine, has important biological functions. Within the vasculature it regulates vessel tone and outgrowth of new vessels. This review summarizes recent literature on H2S signaling in the

  19. Diuretic action of exogenous hydrogen sulfide in spontaneously ...

    African Journals Online (AJOL)

    Diuretic action of exogenous hydrogen sulfide in spontaneously hypertensive diabetic rats. F ud Din Ahmad, MA Sattar, HA Rathore, S Akhter, O Hui Jin, EJ Johns. Abstract. Purpose: To examine the hypothesis that in hypertensive diabetic rats hydrogen sulphide (H2S) reduces blood pressure through diuretic action in ...

  20. Luminescence in Sulfides: A Rich History and a Bright Future

    Directory of Open Access Journals (Sweden)

    Philippe F. Smet


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