Unraveling multiple phases of sulfur cycling during the alteration of ancient ultramafic oceanic lithosphere

Science.gov (United States)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Johnston, David T.

2018-02-01

Ultramafic-hosted hydrothermal systems - characterized by ongoing serpentinization reactions - exert an important influence on the global sulfur cycle. Extensive water-rock interaction causes elemental exchange between seawater and the oceanic lithosphere, effectively removing sulfate from seawater through both abiogenic and biogenic processes. Here, we use bulk rock multiple sulfur isotope signatures (32S, 33S, 34S) and in situ sulfide analyses together with petrographic observations to track the sulfur cycling processes and the hydrothermal evolution of ancient peridotite-hosted hydrothermal systems. We investigate serpentinized peridotites from the Northern Apennine ophiolite in Italy and the Santa Elena ophiolite in Costa Rica and compare those with the Iberian Margin (Ocean Drilling Program (ODP) Leg 149 and 173) and the 15°20‧N Fracture Zone along the Mid-Atlantic Ridge (ODP Leg 209). In situ measurements of sulfides in the Northern Apennine serpentinites preserve a large range in δ34Ssulfide of -33.8 to +13.3‰ with significant heterogeneities within single sulfide grains and depending on mineralogy. Detailed mineralogical investigation and comparison with bulk rock Δ33Ssulfide and in situ δ34Ssulfide data implies a thermal evolution of the system from high temperatures (∼350 °C) that allowed thermochemical sulfate reduction and input of hydrothermal sulfide to lower temperatures (rock associated with detachment faulting along a mid-ocean ridge spreading center. The Santa Elena peridotites preserve distinct signatures for fluid circulation at high temperatures with both closed system thermochemical sulfate reduction and input of mafic-derived sulfur. In addition, the peridotites provide strong evidence that low Ca2+ concentrations in peridotite-hosted systems can limit sulfate removal during anhydrite precipitation at temperatures above 150 °C. This may play a central role for the availability of sulfate to microbial communities within these

Radiolytic degradation of chlorinated hydrocarbons in water

Energy Technology Data Exchange (ETDEWEB)

Wu, Xing-Zheng; Yamamoto, Takeshi [Fukui Univ., Faculty of Engineering, Dept. of Materials Science and Engineering, Fukui (Japan); Hatashita, Masanori [The Wakasa Wan Energy Research Center, Research Dept., Tsuruga, Fukui (Japan)

2002-11-01

Radiolytic degradation of chlorinated hydrocarbons (chloroform, trichloroethylene, and tetrachloroethylene) in water was carried out. Water solutions of the chlorinated hydrocarbons with different concentrations were irradiated with {gamma} rays. Concentrations of methane, ethane, CO, CO{sub 2}, H{sub 2}, and O{sub 2} after the irradiation were determined by gas chromatography. Concentration of chloride ion in the irradiated sample was determined by ion chromatography. Experimental results show that radiolytic degradation of the chlorinated hydrocarbon increased with the radiation dose. Methane, ethane, CO{sub 2}, H{sub 2}, and Cl{sup -} concentrations increased with the radiation dose and the sample concentration. On the other hand, O{sub 2} concentration decreased with the radiation dose and the sample concentration. When sample concentration was high, dissolved oxygen might be not enough for converting most of the C atoms in the sample into CO{sub 2}. This resulted in a low decomposition ratio. Addition of H{sub 2}O{sub 2} as an oxygen resource could increase the decomposition ratio greatly. Furthermore, gas chromatography-mass spectroscopy was applied to identify some intermediates of the radiolytic dehalogenation. Radiolytic degradation mechanisms are also discussed. (author)

Hydrogen production using the sulfur-iodine cycle coupled to a VHTR: An overview

International Nuclear Information System (INIS)

Vitart, X.; Le Duigou, A.; Carles, P.

2006-01-01

The sulfur-iodine thermo-chemical cycle is considered to be one of the most promising routes for massive hydrogen production, using high temperature heat from a Generation IV VHTR. We propose here a brief overview of the main questions raised by this cycle, along with the general lines of French CEA's program

Radiolytic hydrogen production in the subseafloor basaltic aquifer

Directory of Open Access Journals (Sweden)

Mary E Dzaugis

2016-02-01

Full Text Available Hydrogen (H2 is produced in geological settings by dissociation of water due to radiation from radioactive decay of naturally occurring uranium (238U, 235U, thorium (232Th and potassium (40K. To quantify the potential significance of radiolytic H2 as an electron donor for microbes within the South Pacific subseafloor basaltic aquifer, we use radionuclide concentrations of 43 basalt samples from IODP Expedition 329 to calculate radiolytic H2 production rates in basement fractures. The samples are from three sites with very different basement ages and a wide range of alteration types. U, Th and K concentrations vary by up to an order of magnitude from sample to sample at each site. Comparison of our samples to each other and to the results of previous studies of unaltered East Pacific Rise basalt suggests that significant variations in radionuclide concentrations are due to differences in initial (unaltered basalt concentrations (which can vary between eruptive events and post-emplacement alteration. In our samples, there is no clear relationship between alteration type and calculated radiolytic yields. Local maxima in U, Th, and K produce hotspots of H2 production, causing calculated radiolytic rates to differ by up to a factor of 80 from sample to sample. Fracture width also greatly influences H2 production, where microfractures are hotspots for radiolytic H2 production. For example, H2 production rates normalized to water volume are 190 times higher in 1 μm wide fractures than in fractures that are 10 cm wide. To assess the importance of water radiolysis for microbial communities in subseafloor basaltic aquifers, we compare electron transfer rates from radiolysis to rates from iron oxidation in subseafloor basalt. Radiolysis appears likely to be a more important electron donor source than iron oxidation in old (>10 Ma basement basalt. Radiolytic H2 production in the volume of water adjacent to a square cm of the most radioactive SPG basalt may

A Cryptic Sulfur Cycle in Oxygen-Minimum-Zone Waters off the Chilean Coast

Science.gov (United States)

Canfield, Don E.; Stewart, Frank J.; Thamdrup, Bo; De Brabandere, Loreto; Dalsgaard, Tage; Delong, Edward F.; Revsbech, Niels Peter; Ulloa, Osvaldo

2010-12-01

Nitrogen cycling is normally thought to dominate the biogeochemistry and microbial ecology of oxygen-minimum zones in marine environments. Through a combination of molecular techniques and process rate measurements, we showed that both sulfate reduction and sulfide oxidation contribute to energy flux and elemental cycling in oxygen-free waters off the coast of northern Chile. These processes may have been overlooked because in nature, the sulfide produced by sulfate reduction immediately oxidizes back to sulfate. This cryptic sulfur cycle is linked to anammox and other nitrogen cycling processes, suggesting that it may influence biogeochemical cycling in the global ocean.

Bacterial sulfur cycle shapes microbial communities in surface sediments of an ultramafic hydrothermal vent field

DEFF Research Database (Denmark)

Schauer, Regina; Røy, Hans; Augustin, Nico

2011-01-01

RNA sequence analysis, was characterized by the capability to metabolize sulfur components. High sulfate reduction rates as well as sulfide depleted in (34)S further confirmed the importance of the biogeochemical sulfur cycle. In contrast, methane was found to be of minor relevance for microbial life in mat......, these sediments were investigated in order to determine biogeochemical processes and key organisms relevant for primary production. Temperature profiling at two mat-covered sites showed a conductive heating of the sediments. Elemental sulfur was detected in the overlying mat and metal-sulfides in the upper...

Improved method for minimizing sulfur loss in analysis of particulate organic sulfur.

Science.gov (United States)

Park, Ki-Tae; Lee, Kitack; Shin, Kyoungsoon; Jeong, Hae Jin; Kim, Kwang Young

2014-02-04

The global sulfur cycle depends primarily on the metabolism of marine microorganisms, which release sulfur gas into the atmosphere and thus affect the redistribution of sulfur globally as well as the earth's climate system. To better quantify sulfur release from the ocean, analysis of the production and distribution of organic sulfur in the ocean is necessary. This report describes a wet-based method for accurate analysis of particulate organic sulfur (POS) in the marine environment. The proposed method overcomes the considerable loss of sulfur (up to 80%) that occurs during analysis using conventional methods involving drying. Use of the wet-based POS extraction procedure in conjunction with a sensitive sulfur analyzer enabled accurate measurements of cellular POS. Data obtained using this method will enable accurate assessment of how rapidly sulfur can transfer among pools. Such information will improve understanding of the role of POS in the oceanic sulfur cycle.

Active sulfur cycling by diverse mesophilic and thermophilic microorganisms in terrestrial mud volcanoes of Azerbaijan.

Science.gov (United States)

Green-Saxena, A; Feyzullayev, A; Hubert, C R J; Kallmeyer, J; Krueger, M; Sauer, P; Schulz, H-M; Orphan, V J

2012-12-01

Terrestrial mud volcanoes (TMVs) represent geochemically diverse habitats with varying sulfur sources and yet sulfur cycling in these environments remains largely unexplored. Here we characterized the sulfur-metabolizing microorganisms and activity in four TMVs in Azerbaijan. A combination of geochemical analyses, biological rate measurements and molecular diversity surveys (targeting metabolic genes aprA and dsrA and SSU ribosomal RNA) supported the presence of active sulfur-oxidizing and sulfate-reducing guilds in all four TMVs across a range of physiochemical conditions, with diversity of these guilds being unique to each TMV. The TMVs varied in potential sulfate reduction rates (SRR) by up to four orders of magnitude with highest SRR observed in sediments where in situ sulfate concentrations were highest. Maximum temperatures at which SRR were measured was 60°C in two TMVs. Corresponding with these trends in SRR, members of the potentially thermophilic, spore-forming, Desulfotomaculum were detected in these TMVs by targeted 16S rRNA analysis. Additional sulfate-reducing bacterial lineages included members of the Desulfobacteraceae and Desulfobulbaceae detected by aprA and dsrA analyses and likely contributing to the mesophilic SRR measured. Phylotypes affiliated with sulfide-oxidizing Gamma- and Betaproteobacteria were abundant in aprA libraries from low sulfate TMVs, while the highest sulfate TMV harboured 16S rRNA phylotypes associated with sulfur-oxidizing Epsilonproteobacteria. Altogether, the biogeochemical and microbiological data indicate these unique terrestrial habitats support diverse active sulfur-cycling microorganisms reflecting the in situ geochemical environment. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

Energy generation and the sulfur-carbon cycles: Final technical report for period March 1981 thru February 1985

International Nuclear Information System (INIS)

Zeikus, J.G.

1987-05-01

The aim of this research was to understand the role of anaerobic bacteria in natural and man-influenced carbon cycles in nature. The major goal was to elucidate how sulfur metabolism influenced organic decomposition in aquatic sediments. The research compared these processes in two different anaerobic ecosystems: the sulfate-depleted sediments of Lake Mendota, Wisconsin and the sulfate-saturated sediments of Great Salt Lake, Utah. The approach was both ecological and physiological, and employed both in situ characterization of carbon and sulfur metabolism with radiotracers and laboratory species isolation-characterization studies with pure and defined mixed cultures to demonstrate the prevalent environmental paths of carbon electrons, and sulfur during the anaerobic decomposition of organic matter. The significance of this research encompassed fundamental knowledge of the carbon sulfur cycles, applied knowledge on the microbial genesis of flammable gas and oil and extended knowledge on the diversity and metabolic activity of obligately anaerobic bacteria in nature. 13 refs

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Science.gov (United States)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-12-26

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Global warming potential of the sulfur-iodine process using life cycle assessment methodology

International Nuclear Information System (INIS)

Lattin, William C.; Utgikar, Vivek P.

2009-01-01

A life cycle assessment (LCA) of one proposed method of hydrogen production - thermochemical water-splitting using the sulfur-iodine cycle couple with a very high-temperature nuclear reactor - is presented in this paper. Thermochemical water-splitting theoretically offers a higher overall efficiency than high-temperature electrolysis of water because heat from the nuclear reactor is provided directly to the hydrogen generation process, instead of using the intermediate step of generating electricity. The primary heat source for the S-I cycle is an advanced nuclear reactor operating at temperatures corresponding to those required by the sulfur-iodine process. This LCA examines the environmental impact of the combined advanced nuclear and hydrogen generation plants and focuses on quantifying the emissions of carbon dioxide per kilogram of hydrogen produced. The results are presented in terms of global warming potential (GWP). The GWP of the system is 2500 g carbon dioxide-equivalent (CO 2 -eq) per kilogram of hydrogen produced. The GWP of this process is approximately one-sixth of that for hydrogen production by steam reforming of natural gas, and is comparable to producing hydrogen from wind- or hydro-electric conventional electrolysis. (author)

Radiolytic generation of gases in reactors

International Nuclear Information System (INIS)

Ramshesh, V.; Venkateswarlu, K.S.

1988-01-01

Water or heavy water is used in different circuits in a reactor. Their most common use is as a moderator and/or as a coolant. Light water is used at other places such as in end shield, calandria vault etc., In the process they are exposed to intense ionizing radiation and undergo radiolytic degradation. The molecular produts of radiolysis are hydrogen, hydrogen peroxide and oxygen. As is commonly known if hydrogen is formed beyond a certain level, in the presence of oxygen it may lead to combustion or even explosion. Thus one should comprehend the basic principles of radiolysis and see whether the concentration of these gases under various conditions can be worked out. This report attempts to analyse in depth the radiolytic generation of gases in reactor systems. (author). 3 tabs

Hierarchical N-Rich Carbon Sponge with Excellent Cycling Performance for Lithium-Sulfur Battery at High Rates.

Science.gov (United States)

Zhen, Mengmeng; Wang, Juan; Wang, Xin; Wang, Cheng

2018-04-17

Lithium-sulfur batteries (LSBs) are receiving extensive attention because of their high theoretical energy density. However, practical applications of LSBs are still hindered by their rapid capacity decay and short cycle life, especially at high rates. Herein, a highly N-doped (≈13.42 at %) hierarchical carbon sponge (HNCS) with strong chemical adsorption for lithium polysulfide is fabricated through a simple sol-gel route followed by carbonization. Upon using the HNCS as the sulfur host material in the cathode and an HNCS-coated separator, the battery delivers an excellent cycling stability with high specific capacities of 424 and 326 mA h g -1 and low capacity fading rates of 0.033 % and 0.030 % per cycle after 1000 cycles under high rates of 5 and 10 C, respectively, which are superior to those of other reported carbonaceous materials. These impressive cycling performances indicate that such a battery could promote the practical application prospects of LSBs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

Science.gov (United States)

Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

2017-05-23

Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

Radiolytic decomposition of dioxins in liquid wastes

International Nuclear Information System (INIS)

Zhao Changli; Taguchi, M.; Hirota, K.; Takigami, M.; Kojima, T.

2006-01-01

The dioxins including polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are some of the most toxic persistent organic pollutants. These chemicals have widely contaminated the air, water, and soil. They would accumulate in the living body through the food chains, leading to a serious public health hazard. In the present study, radiolytic decomposition of dioxins has been investigated in liquid wastes, including organic waste and waste-water. Dioxin-containing organic wastes are commonly generated in nonane or toluene. However, it was found that high radiation doses are required to completely decompose dioxins in the two solvents. The decomposition was more efficient in ethanol than in nonane or toluene. The addition of ethanol to toluene or nonane could achieve >90% decomposition of dioxins at the dose of 100 kGy. Thus, dioxin-containing organic wastes can be treated as regular organic wastes after addition of ethanol and subsequent γ-ray irradiation. On the other hand, radiolytic decomposition of dioxins easily occurred in pure-water than in waste-water, because the reaction species is largely scavenged by the dominant organic materials in waste-water. Dechlorination was not a major reaction pathway for the radiolysis of dioxin in water. In addition, radiolytic mechanism and dechlorinated pathways in liquid wastes were also discussed. (authors)

Radiolytic decomposition of 4-bromodiphenyl ether

International Nuclear Information System (INIS)

Tang Liang; Xu Gang; Wu Wenjing; Shi Wenyan; Liu Ning; Bai Yulei; Wu Minghong

2010-01-01

Polybrominated diphenyl ethers (PBDEs) spread widely in the environment are mainly removed by photochemical and anaerobic microbial degradation. In this paper, the decomposition of 4-bromodiphenyl ether (BDE -3), the PBDEs homologues, is investigated by electron beam irradiation of its ethanol/water solution (reduction system) and acetonitrile/water solution (oxidation system). The radiolytic products were determined by GC coupled with electron capture detector, and the reaction rate constant of e sol - in the reduction system was measured at 2.7 x 10 10 L · mol -1 · s -1 by pulsed radiolysis. The results show that the BDE-3 concentration affects strongly the decomposition ratio in the alkali solution, and the reduction system has a higher BDE-3 decomposition rate than the oxidation system. This indicates that the BDE-3 was reduced by effectively capturing e sol - in radiolytic process. (authors)

Conductive framework of inverse opal structure for sulfur cathode in lithium-sulfur batteries.

Science.gov (United States)

Jin, Lu; Huang, Xiaopeng; Zeng, Guobo; Wu, Hua; Morbidelli, Massimo

2016-09-07

As a promising cathode inheritor for lithium-ion batteries, the sulfur cathode exhibits very high theoretical volumetric capacity and energy density. In its practical applications, one has to solve the insulating properties of sulfur and the shuttle effect that deteriorates cycling stability. The state-of-the-art approaches are to confine sulfur in a conductive matrix. In this work, we utilize monodisperse polystyrene nanoparticles as sacrificial templates to build polypyrrole (PPy) framework of an inverse opal structure to accommodate (encapsulate) sulfur through a combined in situ polymerization and melting infiltration approach. In the design, the interconnected conductive PPy provides open channels for sulfur infiltration, improves electrical and ionic conductivity of the embedded sulfur, and reduces polysulfide dissolution in the electrolyte through physical and chemical adsorption. The flexibility of PPy and partial filling of the inverse opal structure endure possible expansion and deformation during long-term cycling. It is found that the long cycling stability of the cells using the prepared material as the cathode can be substantially improved. The result demonstrates the possibility of constructing a pure conductive polymer framework to accommodate insulate sulfur in ion battery applications.

Structure elucidation and toxicity analyses of the radiolytic products of aflatoxin B{sub 1} in methanol-water solution

Energy Technology Data Exchange (ETDEWEB)

Wang, Feng [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Graduate School of Chinese Academy of Agricultural Sciences, 12th Zhongguancun South Road, Hai Dian District, Beijing 100081 (China); Xie, Fang [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Xue, Xiaofeng [Bee Research Institute of Chinese Academy of Agricultural Sciences, 1st Xiangshan North Ditch, Hai Dian District, Beijing 100093 (China); Wang, Zhidong; Fan, Bei [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Ha, Yiming, E-mail: wxfay2011@hotmail.com [Institute of Agro-food Science and Technology of Chinese Academy of Agricultural Sciences, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China); Key Opening Laboratory of Agricultural Products Processing and Quality Control, Ministry of Agriculture, 2nd Yuanmingyuan West Road, Hai Dian District, Beijing 100193 (China)

2011-09-15

Highlights: {yields} Radiolytic products of aflatoxin B{sub 1} were produced under gamma irradiation. {yields} Seven key radiolytic products were structure-elucidated. {yields} Free-radical species in radiolytic solution resulted in the formation of products. {yields} Based on the structure-activity relationship analysis, the toxicity of radiolytic products was significantly reduced compared with that of AFB{sub 1}. {yields} The addition reaction on furan ring double bond was the reason for the reduced toxicity. - Abstract: The identification of the radiolytic products of mycotoxins is a key issue in the feasibility study of gamma ray radiation detoxification. Methanol-water solution (60:40, v/v) spiked with aflatoxin B{sub 1} (AFB{sub 1}; 20 mg L{sup -1}) was irradiated with Co{sup 60} gamma ray to generate radiolytic products. Liquid chromatography-quadruple time-of-flight mass spectrometry was applied to identify the radiolytic products of AFB{sub 1}. Accurate mass and proposed molecular formulas with a high-matching property of more than 20 radiolytic products were obtained. Seven key radiolytic products were proposed based on the molecular formulas and tandem mass spectrometry spectra. The analyses of toxicity and formation pathways were proposed based on the structure of the radiolytic products. The addition reaction caused by the free-radical species in the methanol-water solution resulted in the formation of most radiolytic products. Based on the structure-activity relationship analysis, the toxicity of radiolytic products was significantly reduced compared with that of AFB{sub 1} because of the addition reaction that occurred on the double bond in the terminal furan ring. For this reason, gamma irradiation is deemed an effective tool for the detoxification of AFB{sub 1}.

Strong Capillarity, Chemisorption, and Electrocatalytic Capability of Crisscrossed Nanostraws Enabled Flexible, High-Rate, and Long-Cycling Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Zhang, Wenjun; Wang, Lei; Hu, Yi; Zhu, Guoyin; Wang, Yanrong; Chen, Renpeng; Chen, Tao; Tie, Zuoxiu; Liu, Jie; Jin, Zhong

2018-05-22

The development of flexible lithium-sulfur (Li-S) batteries with high energy density and long cycling life are very appealing for the emerging flexible, portable, and wearable electronics. However, the progress on flexible Li-S batteries was limited by the poor flexibility and serious performance decay of existing sulfur composite cathodes. Herein, we report a freestanding and highly flexible sulfur host that can simultaneously meet the flexibility, stability, and capacity requirements of flexible Li-S batteries. The host consists of a crisscrossed network of carbon nanotubes reinforced CoS nanostraws (CNTs/CoS-NSs). The CNTs/CoS-NSs with large inner space and high conductivity enable high loading and efficient utilization of sulfur. The strong capillarity effect and chemisorption of CNTs/CoS-NSs to sulfur species were verified, which can efficiently suppress the shuttle effect and promote the redox kinetics of polysulfides. The sulfur-encapsulated CNTs/CoS-NSs (S@CNTs/CoS-NSs) cathode in Li-S batteries exhibits superior performance, including high discharge capacity, rate capability (1045 mAh g -1 at 0.5 C and 573 mAh g -1 at 5.0 C), and cycling stability. Intriguingly, the soft-packed Li-S batteries based on S@CNTs/CoS-NSs cathode show good flexibility and stability upon bending.

Insight into the loading temperature of sulfur on sulfur/carbon cathode in lithium-sulfur batteries

International Nuclear Information System (INIS)

Ye, Huan; Yin, Ya-Xia; Guo, Yu-Guo

2015-01-01

Highlights: • A cost-effective chemical activation method to prepare porous carbon nanospheres. • Carbon nanospheres with bimodal microporous structure show high specific area and large micropore volume. • The S/C composite cathodes with in-situformed S−C bond exhibit high sulfur activity with a reversible capacity of 1000 mA h g −1 . • S−C bond enables well confinement on sulfur and polysulfides. - Abstract: Lithium–sulfur batteries are highly desired because of their characteristics such as high energy density. However, the applications of Li-S batteries are limited because they exist dissolution of polysulfides into electrolytes. This study reports the preparation of sulfur cathodes by using bimodal microporous (0.5 nm and 0.8 nm to 2.0 nm) carbon spheres with high specific area (1992 m 2 g −1 ) and large micropore volume (1.2 g cm −1 ), as well as the encapsulation of polysulfides via formation of carbon–sulfur bonds in a sealed vacuum glass tube at high temperature. Given that sulfur and polysulfides are well confined by the S−C bond, the shuttle effect is effectively suppressed. The prepared S/C cathodes with a sulfur loading of up to 75% demonstrate high sulfur activity with reversible capacity of 1000 mA h g −1 at the current density of 0.1 A g −1 and good cycling stability (667 mA h g −1 after 100 cycles).

Sulfur cycling in contaminated aquifers: What can we learn from oxygen isotopes in sulfate? (Invited)

Science.gov (United States)

Knoeller, K.; Vogt, C.; Hoth, N.

2009-12-01

Bacterial reduction of dissolved sulfate (BSR) is a key process determining the natural attenuation in many contaminated aquifers. For example, in groundwater bodies affected by acid mine drainage (AMD) BSR reduces the contaminant load by producing alkalinity and facilitating a sustainable fixation of sulfur in the sediment. In aquifers contaminated with petroleum hydrocarbons sulfate may act as a terminal electron acceptor for the anaerobic oxidation of the organic contaminants to carbon dioxide and water. Due to the isotope selectivity of sulfate reducing bacteria, BSR shows the most pronounced isotope fractionation within the sulfur cycle. While sulfur displays a straightforward kinetic enrichment in the residual sulfate described by the enrichment factor epsilon (ɛ), the mechanism of oxygen isotope fractionation is still being discussed controversially. Nevertheless, it is agreed on that oxygen isotope exchange between ambient water and residual sulfate occurs during BSR in natural environments. With respect to this potential isotope exchange, the fractionation parameter theta (θ) is introduced instead of the kinetic enrichment factor epsilon (ɛ). The dual isotope system considering both sulfate-sulfur and sulfate-oxygen isotope fractionation and the respective fractionation parameters ɛ and θ provides an excellent tool for the recognition and quantification of BSR. Beyond that, the dual isotope approach may help identify and estimate interfering sulfur transformations such as re-oxidation and disproportionation processes which is especially vital for the understanding of the overall natural attenuation potential of the investigated aquifers. We present two examples from different field studies showing the benefits of applying the combination of sulfur and oxygen isotopes in dissolved sulfate to reveal the details of the sulfur cycle. The first case study is concerned with the evaluation of the potential for BSR in an AMD-affected aquifer close to an

Sulfur cathode integrated with multileveled carbon nanoflake-nanosphere networks for high-performance lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, S.H.; Wang, X.H.; Xia, X.H.; Wang, Y.D.; Wang, X.L.; Tu, J.P.

2017-01-01

Tailored design/construction of high-quality sulfur/carbon composite cathode is critical for development of advanced lithium-sulfur batteries. We report a powerful strategy for integrated fabrication of sulfur impregnated into three-dimensional (3D) multileveled carbon nanoflake-nanosphere networks (CNNNs) by means of sacrificial ZnO template plus glucose carbonization. The multileveled CNNNs are not only utilized as large-area host/backbone for sulfur forming an integrated S/CNNNs composite electrode, but also serve as multiple carbon blocking barriers (nanoflake infrastructure andnanosphere superstructure) to physically confine polysulfides at the cathode. The designedself-supported S/CNNNs composite cathodes exhibit superior electrochemical performances with high capacities (1395 mAh g −1 at 0.1C, and 769 mAh g −1 at 5.0C after 200 cycles) and noticeable cycling performance (81.6% retention after 200 cycles). Our results build a new bridge between sulfur and carbon networks with multiple blocking effects for polysulfides, and provide references for construction of other high-performance sulfur cathodes.

Polycarbonate radiolytic degradation and stabilization

International Nuclear Information System (INIS)

Araujo, E.S. de

1994-01-01

Polycarbonate Durolon, useful for medical supplies fabrication, is submitted to gamma radiation for sterilization purposes. Scissions in main chain occur, in carbonyl groups, producing molecular degradations and yellowness. The radiolytic stabilization is obtained through additive to the polymer. In this work some degradation and stabilization aspects are presented. (L.C.J.A.). 7 refs, 7 figs, 2 tabs

The significance of elemental sulfur dissolution in liquid electrolyte lithium sulfur batteries

NARCIS (Netherlands)

Harks, Peter Paul R.M.L.; Robledo, Carla B.; Verhallen, Tomas W.; Notten, Peter H.L.; Mulder, Fokko M.

2017-01-01

It is shown that the dissolution of elemental sulfur into, and its diffusion through, the electrolyte allows cycling of lithium–sulfur batteries in which the sulfur is initially far removed and electrically insulated from the current collector. These findings help to understand why liquid

Radiolytic degradation of sorbic acid in isolated systems

International Nuclear Information System (INIS)

Thakur, B.R.; Trehan, I.R.; Arya, S.S.

1990-01-01

Effect of Co(60) gamma-irradiation on stability of sorbic acid (SA) in solutions, dough and chapaties has been investigated. SA was highly susceptible to radiolytic degradation in aqueous systems. Rate of degradation decreased with rise in pH. Sugars, hydrocolloids except pectin, citric acid, lactic acid, malic acid, arginine and threonine, catalyzed degradation while oxalic acid, maleic acid, Cu2+, nitrite, nitrate and phthalate had protective effects. SA was more stable in alcohols and vegetable oils than in aqueous solutions. In wheat flour radiolytic degradation of SA was less at lower moisture. Relatively SA was more stable in chapaties than in dough. Gelatinization and addition of oil in dough reduced degradation of SA

Microbial Character Related Sulfur Cycle under Dynamic Environmental Factors Based on the Microbial Population Analysis in Sewerage System.

Science.gov (United States)

Dong, Qian; Shi, Hanchang; Liu, Yanchen

2017-01-01

The undesired sulfur cycle derived by microbial population can ultimately causes the serious problems of sewerage systems. However, the microbial community characters under dynamic environment factors in actual sewerage system is still not enough. This current study aimed to character the distributions and compositions of microbial communities that participate in the sulfur cycle under the dynamic environmental conditions in a local sewerage system. To accomplish this, microbial community compositions were assessed using 454 high-throughput sequencing (16S rDNA) combined with dsrB gene-based denaturing gradient gel electrophoresis. The results indicated that a higher diversity of microbial species was present at locations in sewers with high concentrations of H 2 S. Actinobacteria and Proteobacteria were dominant in the sewerage system, while Actinobacteria alone were dominant in regions with high concentrations of H 2 S. Specifically, the unique operational taxonomic units could aid to characterize the distinct microbial communities within a sewerage manhole. The proportion of sulfate-reducing bacteria, each sulfur-oxidizing bacteria (SOB) were strongly correlated with the liquid parameters (DO, ORP, COD, Sulfide, NH 3 -N), while the Mycobacterium and Acidophilic SOB (M&A) was strongly correlated with gaseous factors within the sewer, such as H 2 S, CH 4 , and CO. Identifying the distributions and proportions of critical microbial communities within sewerage systems could provide insights into how the microbial sulfur cycle is affected by the dynamic environmental conditions that exist in sewers and might be useful for explaining the potential sewerage problems.

Radiolytic production of chemical fuels in fusion reactor systems

Energy Technology Data Exchange (ETDEWEB)

Fish, J D

1977-06-01

Miley's energy flow diagram for fusion reactor systems is extended to include radiolytic production of chemical fuel. Systematic study of the economics and the overall efficiencies of fusion reactor systems leads to a criterion for evaluating the potential of radiolytic production of chemical fuel as a means of enhancing the performance of a fusion reactor system. The ecumenicity of the schema is demonstrated by application to (1) tokamaks, (2) mirror machines, (3) theta-pinch reactors, (4) laser-heated solenoids, and (5) inertially confined, laser-pellet devices. Pure fusion reactors as well as fusion-fission hybrids are considered.

Radiolytic production of chemical fuels in fusion reactor systems

International Nuclear Information System (INIS)

Fish, J.D.

1977-06-01

Miley's energy flow diagram for fusion reactor systems is extended to include radiolytic production of chemical fuel. Systematic study of the economics and the overall efficiencies of fusion reactor systems leads to a criterion for evaluating the potential of radiolytic production of chemical fuel as a means of enhancing the performance of a fusion reactor system. The ecumenicity of the schema is demonstrated by application to (1) tokamaks, (2) mirror machines, (3) theta-pinch reactors, (4) laser-heated solenoids, and (5) inertially confined, laser-pellet devices. Pure fusion reactors as well as fusion-fission hybrids are considered

Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand.

Science.gov (United States)

Hug, Katrin; Maher, William A; Stott, Matthew B; Krikowa, Frank; Foster, Simon; Moreau, John W

2014-01-01

Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid) resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand). Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic), and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur concentration reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

Enhanced Cycling Stability of Lithium–Sulfur batteries by Electrostatic-Interaction

International Nuclear Information System (INIS)

Ma, Zhaoling; Huang, Xiaobing; Jiang, Qianqian; Huo, Jia; Wang, Shuangyin

2015-01-01

Highlights: • Electrostatic interaction is utilized to hinder the shuttling of polysulfides. • Directly functionalizing SG can better prolong the cycle life of Li–S batteries. • SG/PDDA showed significantly improved capacity retention. - Abstract: Lithiums–sulfur battery is considered as one of the most promising energy storage devices to replace the current Li ion batteries because of its high theoretical capacity of 1675 mA h g −1 . However, the poor cycle stability hinders the further development of this battery system. In order to improve the stability of Li–S batteries, the diffusion of polysulfides from electrodes into electrolyte should be suppressed. Herein, we utilize a positively charged polyelectrolyte to functionalize the electrode materials with the aim to hamper the polysulfides dissolution via electrostatic interaction between strong positively charged polyelectrolyte and negatively charged polysulfides anion. The effect of the functionalization quantity of poly(diallyl dimethylammonium) chloride (PDDA) and functionalization sequence on cycling performances is investigated in detail. It is found that the sulfur–graphene composite (SG) directly functionalized with 10 times PDDA exhibited best cycling stability. At a discharge current density of 0.2 C, much higher capacity retention was realized on the functionalized electrodes than the unfunctionalized (81% vs. 47.3%) after 120 cycles. The as-observed results demonstrate that the electrostatic interaction can effectively prolong the cycling life of Li–S batteries, which provides a new promising strategy for improving the electrochemical performance of Li–S batteries.

Sulfur redox chemistry governs diurnal antimony and arsenic cycles at Champagne Pool, Waiotapu, New Zealand

Science.gov (United States)

Ullrich, Maria K.; Pope, James G.; Seward, Terry M.; Wilson, Nathaniel; Planer-Friedrich, Britta

2013-07-01

Champagne Pool, a sulfidic hot spring in New Zealand, exhibits distinct diurnal variations in antimony (Sb) and arsenic (As) concentrations, with daytime high and night-time low concentrations. To identify the underlying mobilization mechanisms, five sites along the drainage channel of Champagne Pool were sampled every 2 h during a 24 h period. Temporal variations in elemental concentrations and Sb, As, and sulfur (S) speciation were monitored in the discharging fluid. Total trace element concentrations in filtered and unfiltered samples were analyzed using ICP-MS, and Sb, As and S species were determined by IC-ICP-MS. Sulfur speciation in the drainage channel was dominated by thiosulfate and sulfide at night, while sulfate dominated during the day. The distinct diurnal changes suggest that the transformations are caused by phototrophic sulfur-oxidizing bacteria. These bacteria metabolize thiosulfate and sulfide in daylight to form sulfate and, as suggested by modeling with PhreeqC, elemental sulfur. Sulfide consumption during the day results in undersaturation of antimony sulfides, which triggers the additional release of dissolved Sb. For As, diurnal cycles were much more pronounced in speciation than in total concentrations, with di- and trithioarsenate forming at night due to excess sulfide, and monothioarsenate forming from arsenite and elemental sulfur during the day. Sulfur speciation was thus found to control Sb and As in terms of both solubility and speciation.

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

International Nuclear Information System (INIS)

Dong, Kang; Wang, Shengping; Zhang, Hanyu; Wu, Jinping

2013-01-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al 2 O 3 can provide surface area for the deposition of Li 2 S and Li 2 S 2 . ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g −1 , and the remaining capacity was 585 mAh g −1 after 50 cycles at 0.25 mA cm −2 . Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process

Simultaneous nitrogen and phosphorus removal in the sulfur cycle-associated Enhanced Biological Phosphorus Removal (EBPR) process.

Science.gov (United States)

Wu, Di; Ekama, George A; Wang, Hai-Guang; Wei, Li; Lu, Hui; Chui, Ho-Kwong; Liu, Wen-Tso; Brdjanovic, Damir; van Loosdrecht, Mark C M; Chen, Guang-Hao

2014-02-01

Hong Kong has practiced seawater toilet flushing since 1958, saving 750,000 m(3) of freshwater every day. A high sulfate-to-COD ratio (>1.25 mg SO4(2-)/mg COD) in the saline sewage resulting from this practice has enabled us to develop the Sulfate reduction, Autotrophic denitrification and Nitrification Integrated (SANI(®)) process with minimal sludge production and oxygen demand. Recently, the SANI(®) process has been expanded to include Enhanced Biological Phosphorus Removal (EBPR) in an alternating anaerobic/limited-oxygen (LOS-EBPR) aerobic sequencing batch reactor (SBR). This paper presents further development - an anaerobic/anoxic denitrifying sulfur cycle-associated EBPR, named as DS-EBPR, bioprocess in an alternating anaerobic/anoxic SBR for simultaneous removal of organics, nitrogen and phosphorus. The 211 day SBR operation confirmed the sulfur cycle-associated biological phosphorus uptake utilizing nitrate as electron acceptor. This new bioprocess cannot only reduce operation time but also enhance volumetric loading of SBR compared with the LOS-EBPR. The DS-EBPR process performed well at high temperatures of 30 °C and a high salinity of 20% seawater. A synergistic relationship may exist between sulfur cycle and biological phosphorus removal as the optimal ratio of P-release to SO4(2-)-reduction is close to 1.0 mg P/mg S. There were no conventional PAOs in the sludge. Copyright © 2013 Elsevier Ltd. All rights reserved.

Radiolytically-induced novel materials and their application to waste processing

International Nuclear Information System (INIS)

Massimo Bertino; Akira Tokuhiro; Tadashi Tokuhiro

2007-01-01

In the present NEER project we investigated two different types of gel materials with respect to potential applications in environmental remediation, including mixed waste generated from the nuclear fuel cycles. The materials under study were: (1) silica-polymer based aerogel composites into which specific metallic cations diffuse into and remain, and (2) polymer gels made of thermo-sensitive polymer networks, whose functional groups can be ''tailored'' to have a preferred affinity for specific cations, again diffusing into and remaining in the network under a volumetrically, contractive phase-transition. The molecular, diffusion of specific cations, including those of concern in low-level waste streams, into the gel materials studied here indicates that a scaled, engineered system can be designed so that it is passive; that is, minimal (human) intervention and risk would be involved in encapsulating LLW species. In addition, the gel materials hold potential significance in environmental remediation of and recovery of metallic cations identified in respective domains and physico-chemical processes. In brief, silica gels start as aqueous/liquid solutions of base catalyzed silica hydrogels and metal ions (targeted species), such as silver. The metal ions are reduced radiolytically and migrate through the solution to form clusters. Upon post-irradiation processing, aerogel monoliths, extremely lightweight but mechanically strong, that encapsulate the metals are produced. Interestingly the radiolytic or photonic source can be gamma-rays and/or other rays from ''artificial sources'', such as reactors, or ''inherent sources'' like those characterizing mixed waste. Polymer gels, in contrast exhibit thermally-induced volumetric contraction at 20-50 C by expelling water from the gels physical state. Further, some functional groups that capture di- or tri-valent cations from aqueous solutions can be incorporated into the polymer networks on synthesis, including by radiolytic

Radiolytically-induced novel materials and their application to waste processing

Energy Technology Data Exchange (ETDEWEB)

Massimo Bertino, Akira Tokuhiro, Tadashi Tokuhiro

2007-12-05

In the present NEER project we investigated two different types of gel materials with respect to potential applications in environmental remediation, including mixed waste generated from the nuclear fuel cycles. The materials under study were: (1) silica-polymer based aerogel composites into which specific metallic cations diffuse into and remain, and (2) polymer gels made of thermo-sensitive polymer networks, whose functional groups can be ''tailored'' to have a preferred affinity for specific cations, again diffusing into and remaining in the network under a volumetrically, contractive phase-transition. The molecular, diffusion of specific cations, including those of concern in low-level waste streams, into the gel materials studied here indicates that a scaled, engineered system can be designed so that it is passive; that is, minimal (human) intervention and risk would be involved in encapsulating LLW species. In addition, the gel materials hold potential significance in environmental remediation of and recovery of metallic cations identified in respective domains and physico-chemical processes. In brief, silica gels start as aqueous/liquid solutions of base catalyzed silica hydrogels and metal ions (targeted species), such as silver. The metal ions are reduced radiolytically and migrate through the solution to form clusters. Upon post-irradiation processing, aerogel monoliths, extremely lightweight but mechanically strong, that encapsulate the metals are produced. Interestingly the radiolytic or photonic source can be gamma-rays and/or other rays from ''artificial sources'', such as reactors, or ''inherent sources'' like those characterizing mixed waste. Polymer gels, in contrast exhibit thermally-induced volumetric contraction at 20-50 C by expelling water from the gels physical state. Further, some functional groups that capture di- or tri-valent cations from aqueous solutions can be incorporated

Isotopic insights into microbial sulfur cycling in oil reservoirs

Directory of Open Access Journals (Sweden)

Christopher G Hubbard

2014-09-01

Full Text Available Microbial sulfate reduction in oil reservoirs (biosouring is often associated with secondary oil production where seawater containing high sulfate concentrations (~28 mM is injected into a reservoir to maintain pressure and displace oil. The sulfide generated from biosouring can cause corrosion of infrastructure, health exposure risks, and higher production costs. Isotope monitoring is a promising approach for understanding microbial sulfur cycling in reservoirs, enabling early detection of biosouring, and understanding the impact of souring. Microbial sulfate reduction is known to result in large shifts in the sulfur and oxygen isotope compositions of the residual sulfate, which can be distinguished from other processes that may be occurring in oil reservoirs, such as precipitation of sulfate and sulfide minerals. Key to the success of this method is using the appropriate isotopic fractionation factors for the conditions and processes being monitored. For a set of batch incubation experiments using a mixed microbial culture with crude oil as the electron donor, we measured a sulfur fractionation factor for sulfate reduction of -30‰. We have incorporated this result into a simplified 1D reservoir reactive transport model to highlight how isotopes can help discriminate between biotic and abiotic processes affecting sulfate and sulfide concentrations. Modeling results suggest that monitoring sulfate isotopes can provide an early indication of souring for reservoirs with reactive iron minerals that can remove the produced sulfide, especially when sulfate reduction occurs in the mixing zone between formation waters containing elevated concentrations of volatile fatty acids and injection water containing elevated sulfate. In addition, we examine the role of reservoir thermal, geochemical, hydrological, operational and microbiological conditions in determining microbial souring dynamics and hence the anticipated isotopic signatures.

Global distribution of radiolytic H2 production in marine sediment and implications for subsurface life

Science.gov (United States)

Sauvage, J.; Flinders, A. F.; Spivack, A. J.; D'Hondt, S.

2017-12-01

We present the first global estimate of radiolytic H2production in marine sediment. Knowledge of microbial electron donor production rates is critical to understand the bioenergetics of Earth's subsurface ecosystems In marine sediment, radiolysis of water by radiation from naturally occurring radionuclides leads to production of reduced (H2) and oxidized (H2O2, O2) species. Water radiolysis is catalyzed by marine sediment. The magnitude of catalysis depends on sediment composition and radiation type. Deep-sea clay is especially effective at enhancing H2 yields, increasing yield by more than an order of magnitude relative to pure water. This previously unrecognized catalytic effect of geological materials on radiolytic H2 production is important for fueling microbial life in the subseafloor, especially in sediment with high catalytic power. Our estimate of radiolytic H2 production is based on spatially integrating a previously published model and uses (i) experimentally constrained radiolytic H2 yields for the principal marine sediment types, (ii) bulk sediment radioactive element content of sediment cores in three ocean basins (N. Atlantic, N. and S. Pacific), and global distributions of (iii) seafloor lithology, (iv) sediment porosity, and (v) sediment thickness. We calculate that global radiolytic H2 production in marine sediment is 1.6E+12 mol H2 yr-1. This production rate is small relative to the annual rate of photosynthetic organic-matter production in the surface ocean. The globally integrated ratio of radiolytic H2 production relative to photosynthetic primary production is 4.1E-4, based on electron equivalences. Although small relative to global photosynthetic biomass production, sediment-catalyzed production of radiolytic products is significant in the subseafloor. Our analysis of 9 sites in the N. Atlantic, N. and S. Pacific suggests that H2 is the primary microbial fuel in organic-poor sediment older than a few million years; at these sites, calculated

Old Faithful Model for Radiolytic Gas-Driven Cryovolcanism at Enceladus

Science.gov (United States)

Cooper, John F.; Cooper, Paul D.; Sittler, Edward; Sturner, Steven J.; Rymer, Abigail M.

2009-01-01

A new model is presented on how chemically driven cryovolcanism might contribute to episodic outgassing at the icy moon Enceladus and potentially elsewhere including Europa and Kuiper Belt Objects. Exposed water ices can become oxidized from radiolytic chemical alteration of near-surface water ice by space environment irradiation. In contact with primordially abundant reductants such as NH3, CH4, and other hydrocarbons, the product oxidants can react exothermically to produce volatile gases driving cryovolcanism via gas-piston forces on any subsurface liquid reservoirs. Radiolytic oxidants such as H2O2 and O2 can continuously accumulate deep in icy regoliths and be conveyed by rheological flows to subsurface chemical reaction zones over million-year time scales indicated by cratering ages for active regions of Enceladus and Europa. Surface blanketing with cryovolcanic plume ejecta would further accelerate regolith burial of radiolytic oxidants. Episodic heating from transient gravitational tides, radioisotope decay, impacts, or other geologic events might occasionally accelerate chemical reaction rates and ignite the exothermic release of cumulative radiolytic oxidant energy. The time history for the suggested "Old Faithful" model of radiolytic gas-driven cryovolcanism at Enceladus and elsewhere therefore consists of long periods of chemical energy accumulation punctuated by much briefer episodes of cryovolcanic activity. The most probable sequence for detection of activity in the current epoch is a long evolutionary phase of slow but continuous oxidant accumulation over billions of years followed by continuous but variable high activity over the past 10(exp 7)-10(exp 8) years. Detectable cryovolcanic activity could then later decline due to near-total oxidation of the rheologically accessible ice crust and depletion the accessible reductant abundances, as may have already occurred for Europa in the more intense radiation environment of Jupiter's magnetosphere

Identification of sulfur-cycle prokaryotes in a low-sulfate lake (Lake Pavin) using aprA and 16S rRNA gene markers.

Science.gov (United States)

Biderre-Petit, Corinne; Boucher, Delphine; Kuever, Jan; Alberic, Patrick; Jézéquel, Didier; Chebance, Brigitte; Borrel, Guillaume; Fonty, Gérard; Peyret, Pierre

2011-02-01

Geochemical researches at Lake Pavin, a low-sulfate-containing freshwater lake, suggest that the dominant biogeochemical processes are iron and sulfate reduction, and methanogenesis. Although the sulfur cycle is one of the main active element cycles in this lake, little is known about the sulfate-reducer and sulfur-oxidizing bacteria. The aim of this study was to assess the vertical distribution of these microbes and their diversities and to test the hypothesis suggesting that only few SRP populations are involved in dissimilatory sulfate reduction and that Epsilonproteobacteria are the likely key players in the oxidative phase of sulfur cycle by using a PCR aprA gene-based approach in comparison with a 16S rRNA gene-based analysis. The results support this hypothesis. Finally, this preliminary work points strongly the likelihood of novel metabolic processes upon the availability of sulfate and other electron acceptors.

Preparation and electrochemical performance of sulfur-alumina cathode material for lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Dong, Kang [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Wang, Shengping, E-mail: spwang@cug.edu.cn [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China); Zhang, Hanyu; Wu, Jinping [Faculty of Material Science and Chemistry, China University of Geosciences, 388 Lumo Road, 430074 Wuhan (China)

2013-06-01

Highlights: ► Micron-sized alumina was synthesized as adsorbent for lithium-sulfur batteries. ► Sulfur-alumina material was synthesized via crystallizing nucleation. ► The Al{sub 2}O{sub 3} can provide surface area for the deposition of Li{sub 2}S and Li{sub 2}S{sub 2}. ► The discharge capacity of the battery is improved during the first several cycles. - Abstract: Nano-sized sulfur particles exhibiting good adhesion with conducting acetylene black and alumina composite materials were synthesized by means of an evaporated solvent and a concentrated crystallization method for use as the cathodes of lithium-sulfur batteries. The composites were characterized and examined by X-ray diffraction, environmental scanning electron microscopy and electrochemical methods, such as cyclic voltammetry, electrical impedance spectroscopy and charge–discharge tests. Micron-sized flaky alumina was employed as an adsorbent for the cathode material. The initial discharge capacity of the cathode with the added alumina was 1171 mAh g{sup −1}, and the remaining capacity was 585 mAh g{sup −1} after 50 cycles at 0.25 mA cm{sup −2}. Compared with bare sulfur electrodes, the electrodes containing alumina showed an obviously superior cycle performance, confirming that alumina can contribute to reducing the dissolution of polysulfides into electrolytes during the sulfur charge–discharge process.

Hydrogen production system based on high temperature gas cooled reactor energy using the sulfur-iodine (SI) thermochemical water splitting cycle

International Nuclear Information System (INIS)

Garcia, L.; Gonzalez, D.

2011-01-01

Hydrogen production from water using nuclear energy offers one of the most attractive zero-emission energy strategies and the only one that is practical on a substantial scale. Recently, strong interest is seen in hydrogen production using heat of a high-temperature gas-cooled reactor. The high-temperature characteristics of the modular helium reactor (MHR) make it a strong candidate for producing hydrogen using thermochemical or high-temperature electrolysis (HTE) processes. Eventually it could be also employ a high-temperature gas-cooled reactor (HTGR), which is particularly attractive because it has unique capability, among potential future generation nuclear power options, to produce high-temperature heat ideally suited for nuclear-heated hydrogen production. Using heat from nuclear reactors to drive a sulfur-iodine (SI) thermochemical hydrogen production process has been interest of many laboratories in the world. One of the promising approaches to produce large quantity of hydrogen in an efficient way using the nuclear energy is the sulfur-iodine (SI) thermochemical water splitting cycle. Among the thermochemical cycles, the sulfur iodine process remains a very promising solution in matter of efficiency and cost. This work provides a pre-conceptual design description of a SI-Based H2-Nuclear Reactor plant. Software based on chemical process simulation (CPS) was used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. (Author)

Integration of photovoltaic and concentrated solar thermal technologies for H2 production by the hybrid sulfur cycle

Science.gov (United States)

Liberatore, Raffaele; Ferrara, Mariarosaria; Lanchi, Michela; Turchetti, Luca

2017-06-01

It is widely agreed that hydrogen used as energy carrier and/or storage media may significantly contribute in the reduction of emissions, especially if produced by renewable energy sources. The Hybrid Sulfur (HyS) cycle is considered as one of the most promising processes to produce hydrogen through the water-splitting process. The FP7 project SOL2HY2 (Solar to Hydrogen Hybrid Cycles) investigates innovative material and process solutions for the use of solar heat and power in the HyS process. A significant part of the SOL2HY2 project is devoted to the analysis and optimization of the integration of the solar and chemical (hydrogen production) plants. In this context, this work investigates the possibility to integrate different solar technologies, namely photovoltaic, solar central receiver and solar troughs, to optimize their use in the HyS cycle for a green hydrogen production, both in the open and closed process configurations. The analysis carried out accounts for different combinations of geographical location and plant sizing criteria. The use of a sulfur burner, which can serve both as thermal backup and SO2 source for the open cycle, is also considered.

Layered sulfur/PEDOT:PSS nano composite electrodes for lithium sulfur cell applications

Science.gov (United States)

Anilkumar, K. M.; Jinisha, B.; Manoj, M.; Pradeep, V. S.; Jayalekshmi, S.

2018-06-01

Lithium-Sulfur (Li-S) cells are emerging as the next generation energy storage devices owing to their impressive electrochemical properties with high theoretical specific capacity of 1675 mAh/g. Lack of electronic conductivity of sulfur, its volume expansion during high lithium intake and the shuttling effect due to the formation of soluble polysulfides are the main limitations, delaying the commercialization of this technology. To address these challenges, in the present work, the conducting polymer PEDOT:PSS is used as the covering matrix over the sulfur particles to improve their Li storage properties. The sulfur/PEDOT:PSS nanocomposite is synthesised using the hydrothermal process and its formation with the polymer coating over sulfur nanoparticles is established from the XRD, Raman spectroscopy, FE-SEM and TEM studies. The electrochemical studies show that the cells assembled using the sulfur/PEDOT:PSS nanocomposite as the cathode, with the components taken in the weight ratio of 9:1, offer a reversible capacity of 1191 mAh g-1 at 0.1C rate. These cells display stable electrochemical capacities over 200 cycles at gradually increasing current rates. The polymer layer facilitates electronic conduction and suppresses the polysulfide formation and the volume expansion of sulfur. A reversible capacity of 664 mAh g-1 is observed after 200 cycles at 1C rate with the capacity retention of 75 % of the initial stable capacity. The highlight of the present work is the possibility to achieve high discharge capacities at high C rates and the retention of a good percentage of the initial capacity over 200 cycles, for these Li-S cells.

Polonium in Florida groundwater and its possible relationship to the sulfur cycle and bacteria

International Nuclear Information System (INIS)

Harada, K.; Burnett, W.C.; LaRock, P.A.; Cowart, J.B.

1989-01-01

The last radioactive member of the 238 U natural decay-series, 210 Po is normally considered a very particle-reactive isotope. Analysis of most natural waters shows that 210 Po is present at very low activities, usually even lower than its insoluble precursor, 210 Pb. The authors have recently discovered, however, that 210 Po exists at very high concentrations in groundwaters of some shallow aquifers in west central Florida. These waters tend to be fairly acidic (pH 222 Rn. Detailed study of one well with extraordinary levels of 210 Po (∼ 1000 dpm/l) indicates that: (1) 210 Po in this water is in great excess of radioactive equilibrium with its predecessors 210 Pb and 210 Bi; (2) most Po in this water exists in a form which does not coprecipitate with an iron hydroxide scavenge; and (3) the conversion of soluble (0.2 μm filter) to particulate Po occurs over a time scale of a few days during sulfide oxidation. The authors suspect that Po cycling in this environment is related to the sulfur cycle and may, therefore, be influenced by sulfur bacteria

Nanostructured sulfur cathodes

KAUST Repository

Yang, Yuan

2013-01-01

Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes. © 2013 The Royal Society of Chemistry.

Experimental studies on optimal process of the iodine-sulfur cycle for nuclear hydrogen production

Energy Technology Data Exchange (ETDEWEB)

Yoon, Ho Joon

2010-02-15

For nuclear hydrogen production, we selected Iodine-Sulfur (I-S) cycle as the most promising one by screening process among 115 thermo-chemical water splitting technologies. We developed a thermo-physical model for the hydrogen-iodide (HI) VLE and decomposition behavior in the iodine-sulfur (IS) cycle to improve the conventional I-S cycle suggested by GA. Neumann's modified NRTL model was improved by correcting an unphysical assumption for the non-randomness parameter, and using the two-step equilibrium approach for the HI decomposition modeling. However, the parameters of the model were decided through regression with the 271 sets of existing experimental data: the accuracy of the model should be improved by more experimental data over all operating ranges, especially, in the high temperature and high pressure regions. To obtain the data of those regions, an autoclave for high temperature and high pressure was designed and manufactured. Various materials and surface coating technologies were investigated for preventing corrosion from acids. However, we have currently failed to overcome the corrosion problems with highly corrosive acids at a high temperature and high pressure. We experimentally validated that azeotropic constraint between acid and H{sub 2}O undermined the total efficiency of the I-S cycle. As mentioned above, the conventional I-S cycle suffers from low thermal efficiency and highly corrosive streams. To alleviate these problems, we have proposed the optimal operating conditions for the Bunsen reaction and devised a new KAIST flowsheet that produces highly enriched HI through spontaneous L-L phase separation and simple flash processes under low pressure. A series of phase separation experiments were performed to validate the new flowsheet and extend its feasibility. When the molar ratio of I{sub 2}/H{sub 2}SO{sub 4} in the feed increased from 2 to 4, the molar ratio of HI/(HI+H{sub 2}O) in the HI{sub x} phase improved from 0.157 to 0.22, which

Experimental studies on optimal process of the iodine-sulfur cycle for nuclear hydrogen production

International Nuclear Information System (INIS)

Yoon, Ho Joon

2010-02-01

For nuclear hydrogen production, we selected Iodine-Sulfur (I-S) cycle as the most promising one by screening process among 115 thermo-chemical water splitting technologies. We developed a thermo-physical model for the hydrogen-iodide (HI) VLE and decomposition behavior in the iodine-sulfur (IS) cycle to improve the conventional I-S cycle suggested by GA. Neumann's modified NRTL model was improved by correcting an unphysical assumption for the non-randomness parameter, and using the two-step equilibrium approach for the HI decomposition modeling. However, the parameters of the model were decided through regression with the 271 sets of existing experimental data: the accuracy of the model should be improved by more experimental data over all operating ranges, especially, in the high temperature and high pressure regions. To obtain the data of those regions, an autoclave for high temperature and high pressure was designed and manufactured. Various materials and surface coating technologies were investigated for preventing corrosion from acids. However, we have currently failed to overcome the corrosion problems with highly corrosive acids at a high temperature and high pressure. We experimentally validated that azeotropic constraint between acid and H 2 O undermined the total efficiency of the I-S cycle. As mentioned above, the conventional I-S cycle suffers from low thermal efficiency and highly corrosive streams. To alleviate these problems, we have proposed the optimal operating conditions for the Bunsen reaction and devised a new KAIST flowsheet that produces highly enriched HI through spontaneous L-L phase separation and simple flash processes under low pressure. A series of phase separation experiments were performed to validate the new flowsheet and extend its feasibility. When the molar ratio of I 2 /H 2 SO 4 in the feed increased from 2 to 4, the molar ratio of HI/(HI+H 2 O) in the HI x phase improved from 0.157 to 0.22, which is high enough to generate

Photolytic and radiolytic destruction of natural polycyclic mycotoxins

International Nuclear Information System (INIS)

Mammadov, Kh. F

2011-01-01

Full text: The kinetics of degradation of natural polycyclic toxins in grains and dried fruits under the influence of UV-light and ionizing radiation 60 C and the probability of radiolytic detoxication of these products has been studied for the first time

Local radiolytic effectiveness of Auger electrons of iodine-125 in benzene-iodine solutions

International Nuclear Information System (INIS)

Uenak, P.; Uenak, T.

1987-01-01

High radiotoxicity of iodine-125 has been mainly attributed to the local radiolytic effects of Auger electrons on biological systems. In the present study, experimental and theoretical results are compared. The agreement between the experimental and theoretical results explains that the energy absorption of iodine aggregates has an important role in the radiolytic effectiveness of Auger electrons and iodine-125 in benzene-iodine solutions. (author) 18 refs.; 3 figs

Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery

International Nuclear Information System (INIS)

Bao, Weizhai; Zhang, Zhian; Qu, Yaohui; Zhou, Chengkun; Wang, Xiwen; Li, Jie

2014-01-01

Highlights: • Metal organic framework @ reduced graphene oxide was applied for sulfur cathode. • MIL-101(Cr)@rGO/S composites are synthesized by a facile two-step liquid method. • Cycling stability of MIL-101(Cr)@rGO/S sulfur cathode was improved. -- Abstract: Mesoporous metal organic framework @ reduced graphene oxide (MIL-101(Cr)@rGO) materials have been used as a host material to prepare the multi-composite sulfur cathode through a facile and effective two-step liquid phase method successfully, which is different from the simple MIL-101(Cr)/S mixed preparation method. The successful reduced graphene oxide coating in the MIL-101(Cr)@rGO improve the electronic conductivity of meso-MOFs effectively. The discharge capacity and capacity retention rate of MIL-101(Cr)@rGO/S composite sulfur cathode are as high as 650 mAh g −1 and 66.6% at the 50th cycle at the current density of 335 mA g −1 . While the discharge capacity and capacity retention rate of MIL-101(Cr)/S mixed sulfur cathode is 458 mAh g −1 and 37.3%. Test results indicate that the MIL-101(Cr)@rGO is a promising host material for the sulfur cathode in the lithium–sulfur battery applications

Chemical and radiolytical solvent degradation in the Purex process

International Nuclear Information System (INIS)

Stieglitz, L.; Becker, R.

1985-01-01

The state of the art of chemical and radiolytical solvent degradation is described. For the hydrolysis of tributylphosphate TBP->HDBP->H 2 MBP->H 3 PO 4 values are given for the individual constants in a temperature range from 23 to 90 0 C. Radiolytic yields were measured for HDBP as 80 mg/Wh, for H 2 MBP as 2 mg/Wh, and for H 3 PO 4 as 5 mg/Wh. Experimental results on the degradation products of the diluent are summarized and their influence on the process is discussed. Long chain acid phosphates and acid TBP oligomeres were identified as responsible for the retention of fission products. Techniques such as polarography, infrared spectrometry and electrolytic conductometry are applied to estimate concentrations of degradation products down to 10 -5 mol/l. (orig.) [de

Radiolytic oxidation of UO{sub 2} pellets doped with alpha-emitters ({sup 238/239}Pu)

Energy Technology Data Exchange (ETDEWEB)

Muzeau, B. [Commissariat a l' Energie Atomique, Rhone Valley Research Center DTCD/SECM/LMPA, BP 17 171, 30207 Bagnols-sur-Ceze Cedex (France); Jegou, C. [Commissariat a l' Energie Atomique, Rhone Valley Research Center DTCD/SECM/LMPA, BP 17 171, 30207 Bagnols-sur-Ceze Cedex (France)], E-mail: christophe.jegou@cea.fr; Delaunay, F. [Commissariat a l' Energie Atomique, Valduc Research Center, 21120 Is-sur-Tille (France); Broudic, V. [Commissariat a l' Energie Atomique, Rhone Valley Research Center DTCD/SECM/LMPA, BP 17 171, 30207 Bagnols-sur-Ceze Cedex (France); Brevet, A. [Commissariat a l' Energie Atomique, Valduc Research Center, 21120 Is-sur-Tille (France); Catalette, H. [Electricite de France, Les Renardieres Research Center, Route de Sens Ecuelles, 77250 Moret-sur-Loing (France); Simoni, E. [Institut de Physique Nucleaire, Bat. 100, 91406 Orsay Cedex (France); Corbel, C. [Laboratoire des Solides Irradies, UMR 7642-CNRS-CEA-Ecole Polytechnique, Ecole Polytechnique, 91128 Palaiseau Cedex (France)

2009-01-07

To assess the impact of alpha radiolysis of water on the oxidative dissolution of UO{sub 2} under anoxic conditions, two series of plutonium-doped samples (specific alpha activity 385 and 18 MBqg{sub UO{sub 2}}{sup -1}) were fabricated, characterized and leached in water of varying complexity (pure water, carbonated water, dissolved hydrogen). Given the very high reactivity of these samples in the presence of air and in order to minimize any prior surface oxidation, a strict experimental protocol was developed based on high-temperature annealing in Ar + 4% H{sub 2} with preleaching cycles. Failure to follow this protocol prevents absolute quantification of oxidation of the UO{sub 2} surface by water radiolysis in solutions. Preoxidation of the pellet surface can lead to uranium release in solution that is dependent on the alpha particle flux, revealing initial oxidation by radiolysis in air including potential traces of water. This makes difficult the accurate quantification of the radiolytic oxidation in water solutions. Controlling the initial surface condition of the samples finally allowed us to demonstrate that radiolytic oxidation in water-saturated media is governed by several threshold effects for which the main parameters are the sample alpha activity and the hydrogen concentration.

Physiology and application of sulfur-reducing microorganisms from acidic environments

NARCIS (Netherlands)

Florentino, Anna Patrícya

2017-01-01

Sulfur cycle is one of the main geochemical cycles on Earth. Oxidation and reduction reactions of sulfur are mostly biotic and performed by microorganisms. In anaerobic conditions – marine and some freshwater systems, dissimilatory sulfur- and sulfate-reducing bacteria and archaea are key players

Identification of radiolytic products from N-nitrosodimethylamine and N-nitrosopyrrolidine by gas chromatography and mass spectrometry

International Nuclear Information System (INIS)

Ahn, H.-J.; Lee, C.-H.; Kim, J.-H.; Han, S.-B.; Jo, Cheorun; Kim, Sung; Byun, M.-W.

2004-01-01

The radiolytic products of N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) dissolved in dichloromethane (DCM) were identified after gamma irradiation. The UV spectra of NDMA and NPYR indicated that irradiation reduced the typical peak of NDMA at 258 nm and NPYR at 260 nm.The major radiolytic components identified in irradiated NDMA were ethyl acetate and 2-dimethyl propanol. The irradiated NPYR dissolved in DCM and produced 2-butanone and 2-methyl-6-propyl piperidine as the major radiolytic components. 2-Methyl-6-propyl piperidine was the component detected in the greatest concentration in irradiated NPYR

Sulfur impregnated in tunable porous N-doped carbon as sulfur cathode: effect of pore size distribution

International Nuclear Information System (INIS)

Wang, Sha; Zhao, Zhenxia; Xu, Hui; Deng, Yuanfu; Li, Zhong; Chen, Guohua

2015-01-01

Highlights: •Effects of pore size were investigated on electrochemistry for S cathode. •Activation energy of sulfur desorption from the PDA-C was estimated. •Strong interaction was formed between sulfur and porous N-doped carbon. •PDA-C@S showed good cycling performance of 608 mA h g −1 at 2 C over 300 cycles. •PDA-C@S showed good rate stability and high rate capacity. -- Abstract: A novel porous N-doped carbon microsphere (polymer-dopamine derived carbon, PDA-C) with high specific surface area was synthesized as sulfur host for high performance of lithium-sulfur batteries. We used KOH to adjust the pore size and surface area of the PDA-C materials, and then impregnated sulfur into the PDA-C samples by vapor-melting diffusion method. Effects of pore size of the PDA-C samples on the electrochemical performance of the PDA-C@sulfur cathodes were systematically investigated. Raman spectra indicated an enhanced trend of the degree of graphitization of the PDA-C samples with increasing calcination temperature. The surface area of the PDA-C samples increases with amount of the KOH in the pore-creating process. The graphitized porous N-doped carbon provides the high electronic conductive network. Meanwhile, the PDA-C with high surface area and uniform micropores ensures a high interaction toward sulfur as well as the high dispersion of nanoscale sulfur layer on it. The microporous PDA-C@S cathode material exhibits the excellent high rate discharge capability (636 mA h g −1 at 2.0 C) and good low/high-rate cycling stability (893 mA h g −1 (0.5 C) and 608 mA h g −1 (2.0 C) over 100 and 300 cycles). Cyclic voltammogram curves and electrochemical impedance plots show that both the impedance and polarization of the cells increase with decreasing pore size

Micro-Spherical Sulfur/Graphene Oxide Composite via Spray Drying for High Performance Lithium Sulfur Batteries

Science.gov (United States)

Tian, Yuan; Sun, Zhenghao; Zhang, Yongguang; Yin, Fuxing

2018-01-01

An efficient, industry-accepted spray drying method was used to synthesize micro-spherical sulfur/graphene oxide (S/GO) composites as cathode materials within lithium sulfur batteries. The as-designed wrapping of the sulfur-nanoparticles, with wrinkled GO composites, was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The unique morphological design of this material enabled superior discharge capacity and cycling performance, demonstrating a high initial discharge capacity of 1400 mAh g−1 at 0.1 C. The discharge capacity remained at 828 mAh g−1 after 150 cycles. The superior electrochemical performance indicates that the S/GO composite improves electrical conductivity and alleviates the shuttle effect. This study represents the first time such a facile spray drying method has been adopted for lithium sulfur batteries and used in the fabrication of S/GO composites. PMID:29346303

Chemical and radiolytical solvent degradation in the Purex process

Energy Technology Data Exchange (ETDEWEB)

Stieglitz, L; Becker, R

1985-01-01

The state of the art of chemical and radiolytical solvent degradation is described. For the hydrolysis of tributylphosphate TBP->HDBP->H/sub 2/MBP->H/sub 3/PO/sub 4/ values are given for the individual constants in a temperature range from 23 to 90/sup 0/C. Radiolytic yields were measured for HDBP as 80 mg/Wh, for H/sub 2/MBP as 2 mg/Wh, and for H/sub 3/PO/sub 4/ as 5 mg/Wh. Experimental results on the degradation products of the diluent are summarized and their influence on the process is discussed. Long chain acid phosphates and acid TBP oligomeres were identified as responsible for the retention of fission products. Techniques such as polarography, infrared spectrometry and electrolytic conductometry are applied to estimate concentrations of degradation products down to 10/sup -5/ mol/l.

Sulfurized carbon: a class of cathode materials for high performance lithium/sulfur batteries

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2013-12-01

Full Text Available Liquid electrolyte lithium/sulfur (Li/S batteries cannot come into practical applications because of many problems such as low energy efficiency, short cycle life, and fast self-discharge. All these problems are related to the dissolution of lithium polysulfide, a series of sulfur reduction intermediates, in the liquid electrolyte, and resulting parasitic reactions with the Li anode. Covalently binding sulfur onto carbon surface is a solution to completely eliminate the dissolution of lithium polysulfide and make the Li/S battery viable for practical applications. This can be achieved by replacing elemental sulfur with sulfurized carbon as the cathode material. This article reviews the current efforts on this subject and discusses the syntheses, electrochemical properties, and prospects of the sulfurized carbon as a cathode material in the rechargeable Li/S batteries.

Anaerobic sulfide-oxidation in marine colorless sulfur-oxidizing bacteria

Digital Repository Service at National Institute of Oceanography (India)

LokaBharathi, P.A.; Nair, S.; Chandramohan, D.

Colorless sulfur-oxidizing bacteria are ubiquitous in Indian waters and have the ability to oxidize sulfide under anaerobic conditions. These bacteria can not only mediate the sulfur cycle oxidatively but also the nitrogen cycle reductively without...

Superior supercapacitors based on nitrogen and sulfur co-doped hierarchical porous carbon: Excellent rate capability and cycle stability

Science.gov (United States)

Zhang, Deyi; Han, Mei; Wang, Bing; Li, Yubing; Lei, Longyan; Wang, Kunjie; Wang, Yi; Zhang, Liang; Feng, Huixia

2017-08-01

Vastly improving the charge storage capability of supercapacitors without sacrificing their high power density and cycle performance would bring bright application prospect. Herein, we report a nitrogen and sulfur co-doped hierarchical porous carbon (NSHPC) with very superior capacitance performance fabricated by KOH activation of nitrogen and sulfur co-doped ordered mesoporous carbon (NSOMC). A high electrochemical double-layer (EDL) capacitance of 351 F g-1 was observed for the reported NSHPC electrodes, and the capacitance remains at 288 F g-1 even under a large current density of 20 A g-1. Besides the high specific capacitance and outstanding rate capability, symmetrical supercapacitor cell based on the NSHPC electrodes also exhibits an excellent cycling performance with 95.61% capacitance retention after 5000 times charge/discharge cycles. The large surface area caused by KOH activation (2056 m2 g-1) and high utilized surface area owing to the ideal micro/mesopores ratio (2.88), large micropores diameter (1.38 nm) and short opened micropores structure as well as the enhanced surface wettability induced by N and S heteroatoms doping and improved conductivity induced by KOH activation was found to be responsible for the very superior capacitance performance.

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium-sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-06-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium-sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium-sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium-sulfur cells display discharge capacity of 945 mAh g-1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g-1 at 0.1 C and 730 mAh g-1 at 5 C.

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-01-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium–sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium–sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium–sulfur cells display discharge capacity of 945 mAh g−1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g−1 at 0.1 C and 730 mAh g−1 at 5 C. PMID:26065407

Iron release from ferritin and lipid peroxidation by radiolytically generated reducing radicals

International Nuclear Information System (INIS)

Reif, D.W.; Schubert, J.; Aust, S.D.

1988-01-01

Iron is involved in the formation of oxidants capable of damaging membranes, protein, and DNA. Using 137 Cs gamma radiation, we investigated the release of iron from ferritin and concomitant lipid peroxidation by radiolytically generated reducing radicals, superoxide and the carbon dioxide anion radical. Both radicals released iron from ferritin with similar efficiencies and iron mobilization from ferritin required an iron chelator. Radiolytically generated superoxide anion resulted in peroxidation of phospholipid liposomes as measured by malondialdehyde formation only when ferritin was included as an iron source and the released iron was found to be chelated by the phospholipid liposomes

A model to estimate volume change due to radiolytic gas bubbles and thermal expansion in solution reactors

International Nuclear Information System (INIS)

Souto, F.J.; Heger, A.S.

2001-01-01

To investigate the effects of radiolytic gas bubbles and thermal expansion on the steady-state operation of solution reactors at the power level required for the production of medical isotopes, a calculational model has been developed. To validate this model, including its principal hypotheses, specific experiments at the Los Alamos National Laboratory SHEBA uranyl fluoride solution reactor were conducted. The following sections describe radiolytic gas generation in solution reactors, the equations to estimate the fuel solution volume change due to radiolytic gas bubbles and thermal expansion, the experiments conducted at SHEBA, and the comparison of experimental results and model calculations. (author)

Determination of non-volatile radiolytic compounds in ethylene co-vinyl alcohol

International Nuclear Information System (INIS)

Kothapalli, A.; Sadler, G.

2003-01-01

The use of ionizing radiation on food contact polymers is increasing due to the critical role of the package in holding or containing the irradiated foods [Food Add. Contam. 18(6) (2001) 475]. Irradiation benefits the food if properly applied and the food is pre-packaged prior to irradiation to protect it from subsequent recontamination. The United States Food and Drug Administration (USFDA) has approved the use of ionizing radiation within the dosage range of 0-60 kGy on limited films since the 1960s [USFDA 21CFR 179.45]. The obstacle in the way of approval of additional polymers is that FDA fears that these materials may undergo changes during irradiation producing toxic radiolytic fragments. Ethylene co-vinyl alcohol (EVOH), which is often used in food applications, is not approved by the FDA for pre-packaged irradiated foods. The present work examines the non-volatile radiolytic compounds, which may be formed due to exposure to gamma irradiation at the dosage levels of 3 and 10 kGy versus a non-radiated control. Irradiated EVOH is subjected to extraction with 95:5 ethanol and water (by volume) as the food simulating solvent (FSS) for a period of 10 days at 40 deg. C, which models the amount of radiolytic compound a food would extract in 1 year [USFDA Chemistry Requirement for Food Contact Notification]. The FSS is then analyzed for the presence of non-volatile compounds using advanced liquid chromatographic techniques. The chromatograms obtained from different dosages show that non-volatile radiolytic compounds are not formed in EVOH and it would, therefore be in compliance with safety demands of USFDA [Available at: http://www.cfsan.fda.gov/~dms/opa-guid.htmlref and http://www.access.gpo.gov/nara/cfr/cfr-table-search.htmlpage1

Determination of non-volatile radiolytic compounds in ethylene co-vinyl alcohol

Science.gov (United States)

Kothapalli, A.; Sadler, G.

2003-08-01

The use of ionizing radiation on food contact polymers is increasing due to the critical role of the package in holding or containing the irradiated foods [Food Add. Contam. 18(6) (2001) 475]. Irradiation benefits the food if properly applied and the food is pre-packaged prior to irradiation to protect it from subsequent recontamination. The United States Food and Drug Administration (USFDA) has approved the use of ionizing radiation within the dosage range of 0-60 kGy on limited films since the 1960s [USFDA 21CFR 179.45]. The obstacle in the way of approval of additional polymers is that FDA fears that these materials may undergo changes during irradiation producing toxic radiolytic fragments. Ethylene co-vinyl alcohol (EVOH), which is often used in food applications, is not approved by the FDA for pre-packaged irradiated foods. The present work examines the non-volatile radiolytic compounds, which may be formed due to exposure to gamma irradiation at the dosage levels of 3 and 10 kGy versus a non-radiated control. Irradiated EVOH is subjected to extraction with 95:5 ethanol and water (by volume) as the food simulating solvent (FSS) for a period of 10 days at 40 °C, which models the amount of radiolytic compound a food would extract in 1 year [USFDA Chemistry Requirement for Food Contact Notification]. The FSS is then analyzed for the presence of non-volatile compounds using advanced liquid chromatographic techniques. The chromatograms obtained from different dosages show that non-volatile radiolytic compounds are not formed in EVOH and it would, therefore be in compliance with safety demands of USFDA [Available at: http://www.cfsan.fda.gov/~dms/opa-guid.html#ref and http://www.access.gpo.gov/nara/cfr/cfr-table-search.html#page1].

Effect of sulfur removal on Al2O3 scale adhesion

Science.gov (United States)

Smialek, James L.

1991-03-01

If the role of reactive element dopants in producing A12O3 scale adhesion on NiCrAl alloys is to getter sulfur and prevent interfacial segregation, then eliminating sulfur from undoped alloys should also produce adherence. Four experiments successfully produced scale adhesion by sulfur removal alone. (1) Repeated oxidation and polishing of a pure NiCrAl alloy lowered the sulfur content from 10 to 2 parts per million by weight (ppmw), presumably by removing the segregated interfacial layer after each cycle. Total scale spallation changed to total retention after 13 such cycles, with no changes in the scale or interfacial morphology. (2) Thinner samples became adherent after fewer oxidation polishing cycles because of a more limited supply of sulfur. (3) Spalling in subsequent cyclic oxidation tests of samples from experiment (1) was a direct function of the initial sulfur content. (4) Desulfurization to 0.1 ppmw levels was accomplished by annealing melt-spun foil in 1 arm H2. These foils produced oxidation weight change curves for 500 1-hour cycles at 1100 °C similar to those for Y- or Zr-doped NiCrAl. The transition between adherent and nonadherent behavior was modeled in terms of sulfur flux, sulfur content, and sulfur segregation.

A dual coaxial nanocable sulfur composite for high-rate lithium-sulfur batteries.

Science.gov (United States)

Li, Zhen; Yuan, Lixia; Yi, Ziqi; Liu, Yang; Xin, Ying; Zhang, Zhaoliang; Huang, Yunhui

2014-01-01

Lithium-sulfur batteries have great potential for some high energy applications such as in electric vehicles and smart grids due to their high capacity, natural abundance, low cost and environmental friendliness. But they suffer from rapid capacity decay and poor rate capability. The problems are mainly related to the dissolution of the intermediate polysulfides in the electrolyte, and to the poor conductivity of sulfur and the discharge products. In this work, we propose a novel dual coaxial nanocable sulfur composite fabricated with multi-walled nanotubes (MWCNT), nitrogen-doped porous carbon (NPC) and polyethylene glycol (PEG), i.e. MWCNTs@S/NPC@PEG nanocable, as a cathode material for Li-S batteries. In such a coaxial structure, the middle N-doped carbon with hierarchical porous structure provides a nanosized capsule to contain and hold the sulfur particles; the inner MWCNTs and the outer PEG layer can further ensure the fast electronic transport and prevent the dissolution of the polysulfides into the electrolyte, respectively. The as-designed MWCNT@S/NPC@PEG composite shows good cycling stability and excellent rate capability. The capacity is retained at 527 mA h g(-1) at 1 C after 100 cycles, and 791 mA h g(-1) at 0.5 C and 551 mA h g(-1) at 2 C after 50 cycles. Especially, the high-rate capability is outstanding with 400 mA h g(-1) at 5 C.

Interactive effects of vertical mixing, solar radiation and microbial activity on oceanic dimethylated sulfur cycling

OpenAIRE

Galí Tàpias, Martí

2012-01-01

The production and subsequent emission of volatile compounds is one of the numerous ways by which microbial plankton participate in the cycling of elements and influence the Earth's climate. Dimethylsulfide (DMS), produced by enzymatic decomposition of the algal intracellular compound dimethylsulfoniopropionate (DMSP), is the more abundant organic volatile in the upper ocean. Its global emission amounts ca. 28 Tg S per year, and represents the main biogenic source of sulfur to the troposphere...

NATO Advanced Research Workshop on The Biogeochemical Cycling of Sulfur and Nitrogen in the Remote Atmosphere

CERN Document Server

Charlson, Robert; Andreae, Meinrat; Rodhe, Henning

1985-01-01

Viewed from space, the Earth appears as a globe without a beginning or an end. Encompassing the globe is the atmosphere with its three phases-­ gaseous, liquid, and solid--moving in directions influenced by sunlight, gravity, and rotation. The chemical compositions of these phases are determined by biogeochemical cycles. Over the past hundred years, the processes governing the rates and reactions in the atmospheric biogeochemical cycles have typically been studied in regions where scientists lived. Hence, as time has gone by, the advances in our knowledge of atmospheric chemical cycles in remote areas have lagged substantially behind those for more populated areas. Not only are the data less abundant, they are also scattered. Therefore, we felt a workshop would be an excellent mechanism to assess the state­ of-knowledge of the atmospheric cycles of sulfur and nitrogen in remote areas and to make recommendations for future research. Thus, a NATO Advanced Research Workshop '~he Biogeochemical Cycling of Sulfu...

Sulfur turnover and emissions during storage of cattle slurry

DEFF Research Database (Denmark)

Eriksen, Jørgen; Andersen, Astrid J; Poulsen, Henrik Vestergaard

2012-01-01

Slurry acidification using sulfuric acid reduces ammonia emissions but also affects sulfur (S) cycling. Emission of sulfur is a source of malodor and reduces the sulfur fertilizer value of the slurry. We investigated the effect of sulfate and methionine amendments, alone or in combination...

Microbial contributions to coupled arsenic and sulfur cycling in the acid-sulfide hot spring Champagne Pool, New Zealand

Directory of Open Access Journals (Sweden)

Katrin eHug

2014-11-01

Full Text Available Acid-sulfide hot springs are analogs of early Earth geothermal systems where microbial metal(loid resistance likely first evolved. Arsenic is a metalloid enriched in the acid-sulfide hot spring Champagne Pool (Waiotapu, New Zealand. Arsenic speciation in Champagne Pool follows reaction paths not yet fully understood with respect to biotic contributions and coupling to biogeochemical sulfur cycling. Here we present quantitative arsenic speciation from Champagne Pool, finding arsenite dominant in the pool, rim and outflow channel (55-75% total arsenic, and dithio- and trithioarsenates ubiquitously present as 18-25% total arsenic. In the outflow channel, dimethylmonothioarsenate comprised ≤9% total arsenic, while on the outflow terrace thioarsenates were present at 55% total arsenic. We also quantified sulfide, thiosulfate, sulfate and elemental sulfur, finding sulfide and sulfate as major species in the pool and outflow terrace, respectively. Elemental sulfur reached a maximum at the terrace. Phylogenetic analysis of 16S rRNA genes from metagenomic sequencing revealed the dominance of Sulfurihydrogenibium at all sites and an increased archaeal population at the rim and outflow channel. Several phylotypes were found closely related to known sulfur- and sulfide-oxidizers, as well as sulfur- and sulfate-reducers. Bioinformatic analysis revealed genes underpinning sulfur redox transformations, consistent with sulfur speciation data, and illustrating a microbial role in sulfur-dependent transformation of arsenite to thioarsenate. Metagenomic analysis also revealed genes encoding for arsenate reductase at all sites, reflecting the ubiquity of thioarsenate and a need for microbial arsenate resistance despite anoxic conditions. Absence of the arsenite oxidase gene, aio, at all sites suggests prioritization of arsenite detoxification over coupling to energy conservation. Finally, detection of methyl arsenic in the outflow channel, in conjunction with

Sandwich-like graphene-mesoporous carbon as sulfur host for enhanced lithium-sulfur batteries

Science.gov (United States)

Tian, Ting; Li, Bin; Zhu, Mengqi; Liu, Jianhua; Li, Songmei

2017-10-01

Graphene-mesoporous carbon/sulfur composites (G-MPC/S) were constructed by melt-infiltration of sulfur into graphene-mesoporous carbon which was synthesized by soft template method. The SEM and BET results of the graphene-mesoporous carbon show that the as-prepared sandwich-like G-MPC composites with a unique microporous-mesoporous structure had a high specific surface area of 554.164 m2 · g-1 and an average pore size of about 13 nm. The XRD analysis presents the existence of orthorhombic sulfur in the G-MPC/S composite, which indicates the complete infiltration of sulfur into the pores of the G-MPC. When the graphene-mesoporous carbon/surfur composites (G-MPC/S) with 53.9 wt.% sulfur loading were used as the cathode for lithium-sulfur (Li-S) batteries, it exhibited an outstanding electrochemical performance including excellent initial discharge specific capacity of 1393 mAh · g-1 at 0.1 °C, high cycle stability (731 mAh · g-1 at 200 cycles) and good rate performance (1038 mAh · g-1, 770 mAh · g-1, 518 mAh · g-1 and 377 mAh · g-1 at 0.1 °C, 0.2 °C, 0.5 °C and 1 °C, respectively), which suggested the important role of the G-MPC composite in providing more electrons and ions channels, in addition, the shuttle effect caused by the dissolved polysulfide was also suppressed.

Structural and behavioral characteristics of radiolytically synthesized polyacrylic acid–polyacrylonitrile copolymeric hydrogels

International Nuclear Information System (INIS)

Bera, Anuradha; Misra, R.K.; Singh, Shailendra K.

2013-01-01

Copolymeric hydrogels of polyacrylic acid (PAA) – polyacrylonitrile (PAN) was radiolytically synthesized from their respective monomers with trimethyloltrimethacrylate (TMPTMA) as the crosslinker wherein both polymerization and crosslinking could be achieved in a single step reaction using 60 Co γ-radiation under varying doses and dose rates. The formation of the hydrogels was confirmed by their FT-IR analysis, while their thermal degradation patterns were investigated through thermogravimetric analysis in both the dry and swelled state. The water sorption studies showed rapid swelling behavior of these hydrogels, where swelling (%EWC) was found to be strongly dependent on the ratio of the two monomers in the hydrogels and the swelling kinetics dependent on the dose rates of hydrogel synthesis. These radiolytically synthesized hydrogels responded to electrical stimulus both in terms of the bending speed as well as bending angle under an applied voltage. The nature of the deformation was reversible and can be controlled through switching the voltage on and off. - Highlights: • Polyacrylic acid – polyacrilonitrile copolymeric hydrogel has been radiolytically synthesized. • Trimethyloltrimethacrylate (TMPTMA) used as crosslinker. • Hydrogel has been characterized and tested for electroresponsive character. • Bending angles and bending speed were found dependent upon applied voltage

Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

2015-01-01

Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

Bimetallic catalysts for HI decomposition in the iodine-sulfur thermochemical cycle

International Nuclear Information System (INIS)

Wang Laijun; Hu Songzhi; Xu Lufei; Li Daocai; Han Qi; Chen Songzhe; Zhang Ping; Xu Jingming

2014-01-01

Among the different kinds of thermochemical water-splitting cycles, the iodine-sulfur (IS) cycle has attracted more and more interest because it is one of the promising candidates for economical and massive hydrogen production. However, there still exist some science and technical problems to be solved before industrialization of the IS process. One such problem is the catalytic decomposition of hydrogen iodide. Although the active carbon supported platinum has been verified to present the excellent performance for HI decomposition, it is very expensive and easy to agglomerate under the harsh condition. In order to decrease the cost and increase the stability of the catalysts for HI decomposition, a series of bimetallic catalysts were prepared and studied at INET. This paper summarized our present research advances on the bimetallic catalysts (Pt-Pd, Pd-Ir and Pt-Ir) for HI decomposition. In the course of the study, the physical properties, structure, and morphology of the catalysts were characterized by specific surface area, X-ray diffractometer; and transmission electron microscopy, respectively. The catalytic activity for HI decomposition was investigated in a fixed bed reactor under atmospheric pressure. The results show that due to the higher activity and better stability, the active carbon supported bimetallic catalyst is more potential candidate than mono metallic Pt catalyst for HI decomposition in the IS thermochemical cycle. (author)

Bioleaching of metals from soils or sediments using the microbial sulfur cycle

NARCIS (Netherlands)

Tichy, R.

1998-01-01

Reduced inorganic sulfur species like elemental sulfur or sulfide are sensitive to changes in oxidative environments. Generally, inorganic reduced sulfur exists in natural environments in a solid phase, whereas its oxidation leads to sulfur solubilization and a production of acidity. This

Role of sulfur redox cycling on arsenic mobilization in aquifers of Datong Basin, northern China

International Nuclear Information System (INIS)

Pi, Kunfu; Wang, Yanxin; Xie, Xianjun; Ma, Teng; Su, Chunli; Liu, Yaqing

2017-01-01

Sulfur redox cycling potentially exerts important influences on arsenic (As) fate in shallow groundwater systems. Hydrochemical and sediment geochemical analysis combined with thermodynamic modeling study were conducted at Datong Basin to elaborate the effects of sulfur redox cycling on As speciation and mobilization under a strongly reducing environment. Dissolved As and sulfide concentration in 32 groundwater samples with depths of 19–40 m below the land surface varied from 8 to 2700 μg/L and from <5 to 490 μg/L, respectively, while dissolved Fe(II) was relatively low ranging from <20 to 280 μg/L. The apparent co-increase in dissolved sulfide and As concentration, especially for samples with As content larger than 500 μg/L, indicates that sulfidogenesis may significantly contribute to the mobilization of As via sulfide-induced reduction of both As-bearing Fe(III) oxide minerals and As(V). Thermodynamic calculations indicate that groundwater As might be also thiolated in the presence of high-level sulfide, particularly to a large extent for As(V) speciation, instead of sequestration by As-sulfide precipitates. Results of sequential extraction and scanning electron microscopy array on sediments indicate the presence of Fe(II) sulfide mineral phases and an appreciable amount of co-existent As in the sediments, suggesting the precipitation of Fe(II) sulfides can restrict the build-up of dissolved Fe(II) and sequester As from groundwater, but not strongly enough, thereby lowering down As to a moderate level of about 500 μg/L. Thus, redox processes involving As, S and Fe species under sulfidic conditions as observed in Datong Basin not only facilitate the enrichment of As(III) species and As(V) potentially existing as thiolated species, but also the depletion of Fe(II) concentration in groundwater due to Fe(II) sulfide formation. - Highlights: • Effects of sulfur redox cycling on As enrichment were clarified in Datong. • Co-increase in aqueous As and

The impact of the Cretaceous-Paleogene (K-Pg) mass extinction event on the global sulfur cycle: Evidence from Seymour Island, Antarctica

Science.gov (United States)

Witts, James D.; Newton, Robert J.; Mills, Benjamin J. W.; Wignall, Paul B.; Bottrell, Simon H.; Hall, Joanna L. O.; Francis, Jane E.; Alistair Crame, J.

2018-06-01

The Cretaceous-Paleogene (K-Pg) mass extinction event 66 million years ago led to large changes to the global carbon cycle, primarily via a decrease in primary or export productivity of the oceans. However, the effects of this event and longer-term environmental changes during the Late Cretaceous on the global sulfur cycle are not well understood. We report new carbonate associated sulfate (CAS) sulfur isotope data derived from marine macrofossil shell material from a highly expanded high latitude Maastrichtian to Danian (69-65.5 Ma) succession located on Seymour Island, Antarctica. These data represent the highest resolution seawater sulfate record ever generated for this time interval, and are broadly in agreement with previous low-resolution estimates for the latest Cretaceous and Paleocene. A vigorous assessment of CAS preservation using sulfate oxygen, carbonate carbon and oxygen isotopes and trace element data, suggests factors affecting preservation of primary seawater CAS isotopes in ancient biogenic samples are complex, and not necessarily linked to the preservation of original carbonate mineralogy or chemistry. Primary data indicate a generally stable sulfur cycle in the early-mid Maastrichtian (69 Ma), with some fluctuations that could be related to increased pyrite burial during the 'mid-Maastrichtian Event'. This is followed by an enigmatic +4‰ increase in δ34SCAS during the late Maastrichtian (68-66 Ma), culminating in a peak in values in the immediate aftermath of the K-Pg extinction which may be related to temporary development of oceanic anoxia in the aftermath of the Chicxulub bolide impact. There is no evidence of the direct influence of Deccan volcanism on the seawater sulfate isotopic record during the late Maastrichtian, nor of a direct influence by the Chicxulub impact itself. During the early Paleocene (magnetochron C29R) a prominent negative excursion in seawater δ34S of 3-4‰ suggests that a global decline in organic carbon burial

Honeycomb-like Nitrogen and Sulfur Dual-Doped Hierarchical Porous Biomass-Derived Carbon for Lithium-Sulfur Batteries.

Science.gov (United States)

Chen, Manfang; Jiang, Shouxin; Huang, Cheng; Wang, Xianyou; Cai, Siyu; Xiang, Kaixiong; Zhang, Yapeng; Xue, Jiaxi

2017-04-22

Honeycomb-like nitrogen and sulfur dual-doped hierarchical porous biomass-derived carbon/sulfur composites (NSHPC/S) are successfully fabricated for high energy density lithium-sulfur batteries. The effects of nitrogen, sulfur dual-doping on the structures and properties of the NSHPC/S composites are investigated in detail by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and charge/discharge tests. The results show that N, S dual-doping not only introduces strong chemical adsorption and provides more active sites but also significantly enhances the electronic conductivity and hydrophilic properties of hierarchical porous biomass-derived carbon, thereby significantly enhancing the utilization of sulfur and immobilizing the notorious polysulfide shuttle effect. Especially, the as-synthesized NSHPC-7/S exhibits high initial discharge capacity of 1204 mA h g -1 at 1.0 C and large reversible capacity of 952 mA h g -1 after 300 cycles at 0.5 C with an ultralow capacity fading rate of 0.08 % per cycle even at high sulfur content (85 wt %) and high active material areal mass loading (2.8 mg cm -2 ) for the application of high energy density Li-S batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene derived carbon confined sulfur cathodes for lithium-sulfur batteries: Electrochemical impedance studies

International Nuclear Information System (INIS)

Ganesan, Aswathi; Varzi, Alberto; Passerini, Stefano; Shaijumon, Manikoth M.

2016-01-01

Highlights: • Graphene-derived carbon (GDC) with distinctive porosity characteristics are prepared. • Effect of micro-/mesoporosity of GDC for improved Li-S battery performance is studied. • Impedance studies reveal insights into Li-S redox reactions and capacity fading phenomena. - Abstract: Sulfur nanocomposites are prepared by using graphene derived carbon (GDC), with controlled porosity characteristics, as confining matrix and are studied as efficient cathodes for lithium-sulfur (Li-S) batteries. To understand the effect of micro-/mesoporosity in porous carbon for the effective encapsulation of sulfur and polysulfides towards improved Li-S battery performance, two different GDC samples with controlled porosity characteristics, one with predominantly micropores (GDC-1) and a surface area of 1970 m 2 g −1 and the other with a surface area of 3239 m 2 g −1 , having more or less equal contribution of micro- and mesopores (GDC-2), are used to synthesize nanocomposite sulfur electrodes following melt diffusion process. Electrochemical studies are carried out by using cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy (EIS). EIS spectra collected at different depth of discharge (DOD) in the first cycle as well as upon cycling give valuable insights into the Li-S redox reactions and capacity fading phenomena in these electrodes. The impedance response of GDC-S electrodes suggests a detrimental effect of the mesopores, where insoluble reaction products can easily accumulate, resulting in the loss of active material leading to capacity fading of Li-S cells.

Improved Cyclability of Liquid Electrolyte Lithium/Sulfur Batteries by Optimizing Electrolyte/Sulfur Ratio

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2012-12-01

Full Text Available A liquid electrolyte lithium/sulfur (Li/S cell is a liquid electrochemical system. In discharge, sulfur is first reduced to highly soluble Li2S8, which dissolves into the organic electrolyte and serves as the liquid cathode. In solution, lithium polysulfide (PS undergoes a series of complicated disproportionations, whose chemical equilibriums vary with the PS concentration and affect the cell’s performance. Since the PS concentration relates to a certain electrolyte/sulfur (E/S ratio, there is an optimized E/S ratio for the cyclability of each Li/S cell system. In this work, we study the optimized E/S ratio by measuring the cycling performance of Li/S cells, and propose an empirical method for determination of the optimized E/S ratio. By employing an electrolyte of 0.25 m LiSO3CF3-0.25 m LiNO3 dissolved in a 1:1 (wt:wt mixture of dimethyl ether (DME and 1,3-dioxolane (DOL in an optimized E/S ratio, we show that the Li/S cell with a cathode containing 72% sulfur and 2 mg cm−2 sulfur loading is able to retain a specific capacity of 780 mAh g−1 after 100 cycles at 0.5 mA cm−2 between 1.7 V and 2.8 V.

A Li+-conductive microporous carbon–sulfur composite for Li-S batteries

International Nuclear Information System (INIS)

Zhang, Wenhua; Qiao, Dan; Pan, Jiaxin; Cao, Yuliang; Yang, Hanxi; Ai, Xinping

2013-01-01

Highlights: ► A carbon–sulfur composite was prepared by vaporizing sulfur into the nanopores of Li + -conductive carbon microspheres. ► The redox reaction of S 8 molecules embedded in the nanopores of carbon microspheres proceeds through a solid–solid mechanism at the S/C interfaces. ► The carbon–sulfur composite exhibits a stable cycling performance and a superior high coulombic efficiency of 100%. - Abstract: In this paper, we propose a new strategy to develop high performance sulfur electrode by impregnating sulfur into the micropores of a Li + -insertable carbon matrix with the simultaneous use of a carbonate electrolyte, which does not dissolve polysulfides, to restrain the solution of the reaction intermediates of sulfur. To proof this concept, we prepared a Li + -insertable microporous carbon–sulfur composite by vaporizing sulfur into the micropores of the nanofiber-wired carbon microspheres. The experimental results demonstrate that, in the carbonate electrolyte of 1 M LiPF 6 /PC-EC-DEC, such S/C composite electrode exhibits not only stable cycling performance with a reversible capacity of 720 mAh g −1 after 100 cycles, but also superior high coulombic efficiency of ∼100% upon extended cycling (except the first three cycles). The structural and electrochemical analysis indicates that the improved electrochemical behaviors of the S/C composite arise from a new reaction mechanism, in which Li + ions and electrons transport through the carbon matrix into the interior of the cathode and then react with the embedded sulfur in the S/C solid–solid interfaces, avoiding the solution of the intermediates into the bulk electrolyte. More significantly, the structural design and working mechanism of such a sulfur cathode could be extended to a variety of poorly conductive and easily soluble redox-active materials for battery applications.

A general survey of the potential and the main issues associated with the sulfur-iodine thermochemical cycle for hydrogen production using nuclear heat

International Nuclear Information System (INIS)

Vitart, Xavier; Carles, Philippe; Anzieu, Pascal

2008-01-01

The thermochemical sulfur-iodine cycle is studied by CEA with the objective of massive hydrogen production using nuclear heat at high temperature. The challenge is to acquire by the end of 2008 the necessary decision elements, based on a scientific and validated approach, to choose the most promising way to produce hydrogen using a generation IV nuclear reactor. Amongst the thermochemical cycles, the sulfur-iodine process remains a very promising solution in matter of efficiency and cost, versus its main competitor, conventional electrolysis. The sulfur-iodine cycle is a very versatile process, which allows lot of variants for each section which can be adjusted in synergy in order to optimise the whole process. The main part of CEA's program is devoted to the study of the basic processes: new thermodynamics data acquisition, optimisation of water and iodine quantity, optimisation of temperature and pressure in each unit of the flow-sheet and survey of innovative solutions (membrane separations for instance). This program also includes optimisation of a detailed flow-sheet and studies for a hydrogen production plant (design, scale, first evaluations of safety issues and technico-economic questions). This program interacts strongly with other teams, in the framework of international collaborations (Europe, USA for instance). (author)

A general survey of the potential and the main issues associated with the sulfur-iodine thermochemical cycle for hydrogen production using nuclear heat

International Nuclear Information System (INIS)

Vitart, X.; Carles, P.; Anzieu, P.

2008-01-01

The thermochemical sulfur-iodine cycle is studied by CEA with the objective of massive hydrogen production using nuclear heat at high temperature. The challenge is to acquire by the end of 2008 the necessary decision elements, based on a scientific and validated approach, to choose the most promising way to produce hydrogen using a generation IV nuclear reactor. Amongst the thermochemical cycles, the sulfur-iodine process remains a very promising solution in matter of efficiency and cost, versus its main competitor, conventional electrolysis. The sulfur-iodine cycle is a very versatile process, which allows lot of variants for each section which can be adjusted in synergy in order to optimise the whole process. The main part of CEA's program is devoted to the study of the basic processes: new thermodynamics data acquisition, optimisation of water and iodine quantity, optimisation of temperature and pressure in each unit of the flow-sheet and survey of innovative solutions (membrane separations for instance). This program also includes optimisation of a detailed flow-sheet and studies for a hydrogen production plant (design, scale, first evaluations of safety issues and technico-economic questions). This program interacts strongly with other teams, in the framework of international collaborations (Europe, USA for instance). (authors)

Decoupling of Neoarchean sulfur sources recorded in Algoma-type banded iron formation

Science.gov (United States)

Diekrup, David; Hannington, Mark D.; Strauss, Harald; Ginley, Stephen J.

2018-05-01

Neoarchean Algoma-type banded iron formations (BIFs) are widely viewed as direct chemical precipitates from proximal volcanic-hydrothermal vents. However, a systematic multiple sulfur isotope study of oxide-facies BIF from a type locality in the ca. 2.74 Ga Temagami greenstone belt reveals mainly bacterial turnover of atmospheric elemental sulfur in the host basin rather than deposition of hydrothermally cycled seawater sulfate or sulfur from direct volcanic input. Trace amounts of chromium reducible sulfur that were extracted for quadruple sulfur isotope (32S-33S-34S-36S) analysis record the previously known mass-independent fractionation of volcanic SO2 in the Archean atmosphere (S-MIF) and biological sulfur cycling but only minor contributions from juvenile sulfur, despite the proximity of volcanic sources. We show that the dominant bacterial metabolisms were iron reduction and sulfur disproportionation, and not sulfate reduction, consistent with limited availability of organic matter and the abundant ferric iron deposited as Fe(OH)3. That sulfur contained in the BIF was not a direct volcanic-hydrothermal input, as expected, changes the view of an important archive of the Neoarchean sulfur cycle in which the available sulfur pools were strongly decoupled and only species produced photochemically under anoxic atmospheric conditions were deposited in the BIF-forming environment.

Simulation of global sulfate distribution and the influence of effective cloud drop radii with a coupled photochemistry-sulfur cycle model

NARCIS (Netherlands)

Roelofs, G.J.; Lelieveld, J.; Ganzeveld, L.N.

1998-01-01

A sulfur cycle model is coupled to a global chemistry-climate model. The simulated surface sulfate concentrations are generally within a factor of 2 of observed concentrations, and display a realistic seasonality for most background locations. However, the model tends to underestimate sulfate and

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

Science.gov (United States)

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

2013-11-01

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

Radiolytic gas generation in salt cake technical task plan

International Nuclear Information System (INIS)

Walker, D.D.; Crawford, C.L.; Bibler, N.E.

1993-01-01

High-level radioactive wastes are stored in large, steel tanks in the Savannah River Site Tank Farms. The liquid levels in these tanks are monitored to detect leakage of waste out of tanks or leakage of liquids into the tanks. Recent unexplained level fluctuations in high-level waste (HLW) tanks have caused High Level Waste Engineering (HLWE) to develop a program to better understand tank level behavior. Interim Waste Technology (IWT) has been requested by HLWE to obtain data which will lead to a better understanding of the radiolytic generations of gases in salt cake. The task described below will provide data from laboratory experiments with simulated wastes which can be used in tank level fluctuation modeling. The following experimental programs have been formulated to meet the task requirements of the customer: (A) determine whether radiolytically generated gas bubbles can be trapped in salt cake; (B) determine the composition of gases produced by radiolysis; (C) determine the yield of radiolysis gases as a function of radiation dose; (D) determine bubble distribution

Radiolytic reactions in the coolant of helium cooled reactors

International Nuclear Information System (INIS)

Tingey, G.L.; Morgan, W.C.

1975-01-01

The success of helium cooled reactors is dependent upon the ability to prevent significant reaction between the coolant and the other components in the reactor primary circuit. Since the thermal reaction of graphite with oxidizing gases is rapid at temperatures of interest, the thermal reactions are limited primarily by the concentration of impurity gases in the helium coolant. On the other hand, the rates of radiolytic reactions in helium are shown to be independent of reactive gas concentration until that concentration reaches a very low level. Calculated steady-state concentrations of reactive species in the reactor coolant and core burnoff rates are presented for current U. S. designed, helium cooled reactors. Since precise base data are not currently available for radiolytic rates of some reactions and thermal reaction rate data are often variable, the accuracy of the predicted gas composition is being compared with the actual gas compositions measured during startup tests of the Fort Saint Vrain high temperature gas-cooled reactor. The current status of these confirmatory tests is discussed. 12 references

The role of iron-sulfides on cycling of organic carbon in the St Lawrence River system: Evidence of sulfur-promoted carbon sequestration?

Science.gov (United States)

Balind, K.; Barber, A.; Gélinas, Y.

2017-12-01

The biogeochemical cycle of sulfur is intimately linked with that of carbon, as well as with that of iron through the formation of iron-sulfur complexes. Iron-sulfide minerals such as mackinawite (FeS) and greigite (Fe3S4) form below the oxic/anoxic redox boundary in marine and lacustrine sediments and soils. Reactive iron species, abundant in surface sediments, can undergo reductive dissolution leading to the formation of soluble Fe(II) which can then precipitate in the form of iron sulfur species. While sedimentary iron-oxides have been thoroughly explored in terms of their ability to sorb and sequester organic carbon (OC) (Lalonde et al.; 2012), the role of FeS in the long-term preservation of OC remains undefined. In this study, we present depth profiles for carbon, iron, and sulfur in the aqueous-phase, along with data from sequential extractions of sulfur speciation in the solid-phase collected from sediment cores from the St Lawrence River and estuarine system, demonstrating the transition from fresh to saltwater sediments. Additionally, we present synthetic iron sulfur sorption experiments using both model and natural organic molecules in order to assess the importance of FeS in sedimentary carbon storage.

Radiolytic stabilization of industrial poly(methyl methacrylate)

International Nuclear Information System (INIS)

Aquino, Katia Aparecida da Silva

2005-03-01

Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterilisable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its physical properties. Therefore, radiolytic stabilization of PMMA is important for to become it commercially radio sterilisable. In this work we investigated the radiolytic stabilization of PMMA by using HALS (Hindered Amine Light Stabilizer) additive, commercially used for photo and thermo oxidative stabilization of polymers. The investigation of the radiation-induced main chain scissions was carried out by viscometric method. The additive added to the polymer system at 0.3 % w/w promotes a molecular radioprotection of 61%. That means a reduction of G value (scissions/100 eV) from 2.6 to 1.0. In addition, the glassy transition temperature (Tg) of PMMA (no additive), significantly changed by radiation, does not change when PMMA (with additive) is irradiated. TGA analysis showed that the additive promotes thermal stability to the system, increasing decomposition temperature of PMMA. Spectroscopy analysis, FT-IR and RMN ( 1 H), showed that the radioprotector additive added to the system does not change the PMMA structure. Analysis on mechanical (tensile strength and elongation at break) and optical (yellowness index and refractive index) properties showed a good influence of the additive on polymer system. (author)

Diversity of sulfur-cycle prokaryotes in freshwater lake sediments investigated using aprA as the functional marker gene.

Science.gov (United States)

Watanabe, Tomohiro; Kojima, Hisaya; Takano, Yoshinori; Fukui, Manabu

2013-09-01

The diversity of sulfate-reducing prokaryotes (SRPs) and sulfur-oxidizing prokaryotes (SOPs) in freshwater lake ecosystems was investigated by cloning and sequencing of the aprA gene, which encodes for a key enzyme in dissimilatory sulfate reduction and sulfur oxidation. To understand their diversity better, the spatial distribution of aprA genes was investigated in sediments collected from six geographically distant lakes in Antarctica and Japan, including a hypersaline lake for comparison. The microbial community compositions of freshwater sediments and a hypersaline sediment showed notable differences. The clones affiliated with Desulfobacteraceae and Desulfobulbaceae were frequently detected in all freshwater lake sediments. The SOP community was mainly composed of four major phylogenetic groups. One of them formed a monophyletic cluster with a sulfur-oxidizing betaproteobacterium, Sulfuricella denitrificans, but the others were not assigned to specific genera. In addition, the AprA sequences, which were not clearly affiliated to either SRP or SOP lineages, dominated the libraries from four freshwater lake sediments. The results showed the wide distribution of some sulfur-cycle prokaryotes across geographical distances and supported the idea that metabolic flexibility is an important feature for SRP survival in low-sulfate environments. Copyright © 2013 Elsevier GmbH. All rights reserved.

An assessment of post-LOCA radiolytic generation of hydrogen in reactor containment of Indian PHWRs

International Nuclear Information System (INIS)

Bose, H.; Shah, G.C.; Dutta, S.

2002-01-01

Full text: An event-wise assessment has been carried out for the 220 MWe Indian PHWRs of standardized design, to estimate the post-LOCA release of radiolytic hydrogen inside reactor containment, in absence of steam-zirconium reaction. The assessment is based on (i) the dissolved hydrogen concentration build-up in water corresponding to the decaying gamma dose profile and (ii) the rate of concentration dependent mass-transfer of hydrogen from water to gas-space. It is observed that the total radiolytic hydrogen released is about three times less than that obtained by the conventional method of calculation which assumes the radiolytic yield of hydrogen to be equal to the primary yield G(H 2 ) = 0.44 molecules per 100 eV. It is also seen that a major part (∼90 %) of the total release is due to the spillage of fission product irradiated suppression pool water flowing through the core, followed by moderator and suppression pool surface releases respectively

Sulfur isotopic analysis of carbonyl sulfide and its application for biogeochemical cycles

Science.gov (United States)

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

2016-04-01

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

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium-sulfur batteries.

Science.gov (United States)

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen David

2016-10-20

Lithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles.

Reduced graphene oxide encapsulated sulfur spheres for the lithium-sulfur battery cathode

Directory of Open Access Journals (Sweden)

Feiyan Liu

Full Text Available Reduced graphene oxide (rGO encapsulated sulfur spheres for the Li-S batteries were prepared via the redox reaction between sodium polysulfide. XRD spectra showed that the diffraction peak of graphite oxide (GO at 10° disappeared, while the relatively weak diffraction peak at 27° belongs to graphene emerged. FT-IR spectra showed that the vibrations of the functional groups of GO, such as 3603 cm−1, 1723 cm−1and 1619 cm−1 which contributed from OH, COC and CO respectively, disappeared when compared to the spectra of GSC. SEM observations indicated that the optimum experimental condition followed as: mass ratio of GO and S was 1:1, 10% NaOH was used to adjust the pH. EDX analysis showed that the sulfur content reached at 68.8% of the composite material. The resultant electric resistance was nearly less than GO’s resistance in three orders of magnitude under same condition. Further electrochemical performance tests showed a coulombic efficiency was 96% from the first cycle capacity was 827 mAh g−1, to 388 mAh g−1 in the 100 cycles. This study carries substantial significance to the development of Li-S battery cathode materials. Keywords: Lithium-sulfur battery, Graphene, Sulfur spheres, Cathode material

Preparation and enhanced electrochemical properties of nano-sulfur/poly(pyrrole-co-aniline) cathode material for lithium/sulfur batteries

International Nuclear Information System (INIS)

Qiu Linlin; Zhang Shichao; Zhang Lan; Sun, Mingming; Wang Weikun

2010-01-01

Poly(pyrrole-co-aniline) (PPyA) copolymer nanofibers were prepared by chemical oxidation method with cetyltrimethyl ammonium chloride (CTAC) as template, and the nano-sulfur/poly(pyrrole-co-aniline) (S/PPyA) composite material in lithium batteries was achieved via co-heating the mixture of PPyA and sublimed sulfur at 160 deg. C for 24 h. The component and structure of the materials were characterized by FTIR, Raman, XRD, and SEM. PPyA with nanofiber network structure was employed as a conductive matrix, adsorbing agent and firm reaction chamber for the sulfur cathode materials. The nano-dispersed composite exhibited a specific capacity up to 1285 mAh g -1 in the initial cycle and remained 866 mAh g -1 after 40 cycles.

Emissions of toxic pollutants from compressed natural gas and low sulfur diesel-fueled heavy-duty transit buses tested over multiple driving cycles.

Science.gov (United States)

Kado, Norman Y; Okamoto, Robert A; Kuzmicky, Paul A; Kobayashi, Reiko; Ayala, Alberto; Gebel, Michael E; Rieger, Paul L; Maddox, Christine; Zafonte, Leo

2005-10-01

The number of heavy-duty vehicles using alternative fuels such as compressed natural gas (CNG) and new low-sulfur diesel fuel formulations and equipped with after-treatment devices are projected to increase. However, few peer-reviewed studies have characterized the emissions of particulate matter (PM) and other toxic compounds from these vehicles. In this study, chemical and biological analyses were used to characterize the identifiable toxic air pollutants emitted from both CNG and low-sulfur-diesel-fueled heavy-duty transit buses tested on a chassis dynamometer over three transient driving cycles and a steady-state cruise condition. The CNG bus had no after-treatment, and the diesel bus was tested first equipped with an oxidation catalyst (OC) and then with a catalyzed diesel particulate filter (DPF). Emissions were analyzed for PM, volatile organic compounds (VOCs; determined on-site), polycyclic aromatic hydrocarbons (PAHs), and mutagenic activity. The 2000 model year CNG-fueled vehicle had the highest emissions of 1,3-butadiene, benzene, and carbonyls (e.g., formaldehyde) of the three vehicle configurations tested in this study. The 1998 model year diesel bus equipped with an OC and fueled with low-sulfur diesel had the highest emission rates of PM and PAHs. The highest specific mutagenic activities (revertants/microg PM, or potency) and the highest mutagen emission rates (revertants/mi) were from the CNG bus in strain TA98 tested over the New York Bus (NYB) driving cycle. The 1998 model year diesel bus with DPF had the lowest VOCs, PAH, and mutagenic activity emission. In general, the NYB driving cycle had the highest emission rates (g/mi), and the Urban Dynamometer Driving Schedule (UDDS) had the lowest emission rates for all toxics tested over the three transient test cycles investigated. Also, transient emissions were, in general, higher than steady-state emissions. The emissions of toxic compounds from an in-use CNG transit bus (without an oxidation

Sulfur cathodes with hydrogen reduced titanium dioxide inverse opal structure.

Science.gov (United States)

Liang, Zheng; Zheng, Guangyuan; Li, Weiyang; Seh, Zhi Wei; Yao, Hongbin; Yan, Kai; Kong, Desheng; Cui, Yi

2014-05-27

Sulfur is a cathode material for lithium-ion batteries with a high specific capacity of 1675 mAh/g. The rapid capacity fading, however, presents a significant challenge for the practical application of sulfur cathodes. Two major approaches that have been developed to improve the sulfur cathode performance include (a) fabricating nanostructured conductive matrix to physically encapsulate sulfur and (b) engineering chemical modification to enhance binding with polysulfides and, thus, to reduce their dissolution. Here, we report a three-dimensional (3D) electrode structure to achieve both sulfur physical encapsulation and polysulfides binding simultaneously. The electrode is based on hydrogen reduced TiO2 with an inverse opal structure that is highly conductive and robust toward electrochemical cycling. The relatively enclosed 3D structure provides an ideal architecture for sulfur and polysulfides confinement. The openings at the top surface allow sulfur infusion into the inverse opal structure. In addition, chemical tuning of the TiO2 composition through hydrogen reduction was shown to enhance the specific capacity and cyclability of the cathode. With such TiO2 encapsulated sulfur structure, the sulfur cathode could deliver a high specific capacity of ∼1100 mAh/g in the beginning, with a reversible capacity of ∼890 mAh/g after 200 cycles of charge/discharge at a C/5 rate. The Coulombic efficiency was also maintained at around 99.5% during cycling. The results showed that inverse opal structure of hydrogen reduced TiO2 represents an effective strategy in improving lithium sulfur batteries performance.

One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

International Nuclear Information System (INIS)

Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu; Hu, Pengfei; Zhao, Bing

2015-01-01

Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g −1 after 50 cycles at 100 mA g −1 . • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g −1 after 50 cycles at a current density of 100 mA g −1 and reversible capacity of 517.9 mA h g −1 at 1 A g −1 . The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems

Removal of sulfur from process streams

International Nuclear Information System (INIS)

Brignac, D.G.

1984-01-01

A process wherein water is added to a non-reactive gas stream, preferably a hydrogen or hydrogen-containing gas stream, sufficient to raise the water level thereof to from about 0.2 percent to about 50 percent, based on the total volume of the process gas stream, and the said moist gas stream is contacted, at elevated temperature, with a particulate mass of a sulfur-bearing metal alumina spinel characterized by the formula MAl 2 O 4 , wherein M is chromium, iron, cobalt, nickel, copper, cadmium, mercury, or zinc to desorb sulfur thereon. In the sulfur sorption cycle, due to the simultaneous adsorption of water and sulfur, the useful life of the metal alumina spinel for sulfur adsorption can be extended, and the sorbent made more easily regenerable after contact with a sulfur-bearing gas stream, notably sulfur-bearing wet hydrogen or wet hydrogen-rich gas streams

Sulfur nanocrystals anchored graphene composite with highly improved electrochemical performance for lithium-sulfur batteries

Science.gov (United States)

Zhang, Jun; Dong, Zimin; Wang, Xiuli; Zhao, Xuyang; Tu, Jiangping; Su, Qingmei; Du, Gaohui

2014-12-01

Two kinds of graphene-sulfur composites with 50 wt% of sulfur are prepared using hydrothermal method and thermal mixing, respectively. Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectra mapping show that sulfur nanocrystals with size of ∼5 nm dispersed on graphene sheets homogeneously for the sample prepared by hydrothermal method (NanoS@G). While for the thermal mixed graphene-sulfur composite (S-G mixture), sulfur shows larger and uneven size (50-200 nm). X-ray Photoelectron Spectra (XPS) reveals the strong chemical bonding between the sulfur nanocrystals and graphene. Comparing with the S-G mixture, the NanoS@G composite shows highly improved electrochemical performance as cathode for lithium-sulfur (Li-S) battery. The NanoS@G composite delivers an initial capacity of 1400 mAh g-1 with the sulfur utilization of 83.7% at a current density of 335 mA g-1. The capacity keeps above 720 mAh g-1 over 100 cycles. The strong adherence of the sulfur nanocrystals on graphene immobilizes sulfur and polysulfides species and suppressed the "shuttle effect", resulting higher coulombic efficiency and better capacity retention. Electrochemical impedance also suggests that the strong bonding enabled rapid electronic/ionic transport and improved electrochemical kinetics, therefore good rate capability is obtained. These results demonstrate that the NanoS@G composite is a very promising candidate for high-performance Li-S batteries.

A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

Science.gov (United States)

Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

2016-12-01

Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

In-situ sulfuration synthesis of sandwiched spherical tin sulfide/sulfur-doped graphene composite with ultra-low sulfur content

Science.gov (United States)

Zhao, Bing; Yang, Yaqing; Wang, Zhixuan; Huang, Shoushuang; Wang, Yanyan; Wang, Shanshan; Chen, Zhiwen; Jiang, Yong

2018-02-01

SnS is widely studied as anode materials since of its superior structural stability and physicochemical property comparing with other Sn-based composites. Nevertheless, the inconvenience of phase morphology control and excessive consumption of sulfur sources during synthesis hinder the scalable application of SnS nanocomposites. Herein, we report a facile in-situ sulfuration strategy to synthesize sandwiched spherical SnS/sulfur-doped graphene (SnS/S-SG) composite. An ultra-low sulfur content with approximately stoichiometric ratio of Sn:S can effectively promote the sulfuration reaction of SnO2 to SnS and simultaneous sulfur-doping of graphene. The as-prepared SnS/S-SG composite shows a three-dimensional interconnected spherical structure as a whole, in which SnS nanoparticles are sandwiched between the multilayers of graphene sheets forming a hollow sphere. The sandwiched sphere structure and high S doping amount can improve the binding force between SnS and graphene, as well as the structural stability and electrical conductivity of the composite. Thus, a high reversibility of conversion reaction, promising specific capacity (772 mAh g-1 after 100 cycles at 0.1 C) and excellent rate performance (705 and 411 mAh g-1 at 1 C and 10 C, respectively) are exhibited in the SnS/S-SG electrode, which are much higher than that of the SnS/spherical graphene synthesized by traditional post-sulfuration method.

Advanced Sulfur Cathode Enabled by Highly Crumpled Nitrogen-Doped Graphene Sheets for High-Energy-Density Lithium-Sulfur Batteries.

Science.gov (United States)

Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Wang, Donghai

2016-02-10

Herein, we report a synthesis of highly crumpled nitrogen-doped graphene sheets with ultrahigh pore volume (5.4 cm(3)/g) via a simple thermally induced expansion strategy in absence of any templates. The wrinkled graphene sheets are interwoven rather than stacked, enabling rich nitrogen-containing active sites. Benefiting from the unique pore structure and nitrogen-doping induced strong polysulfide adsorption ability, lithium-sulfur battery cells using these wrinkled graphene sheets as both sulfur host and interlayer achieved a high capacity of ∼1000 mAh/g and exceptional cycling stability even at high sulfur content (≥80 wt %) and sulfur loading (5 mg sulfur/cm(2)). The high specific capacity together with the high sulfur loading push the areal capacity of sulfur cathodes to ∼5 mAh/cm(2), which is outstanding compared to other recently developed sulfur cathodes and ideal for practical applications.

Biomimetic Ant-Nest Electrode Structures for High Sulfur Ratio Lithium-Sulfur Batteries.

Science.gov (United States)

Ai, Guo; Dai, Yiling; Mao, Wenfeng; Zhao, Hui; Fu, Yanbao; Song, Xiangyun; En, Yunfei; Battaglia, Vincent S; Srinivasan, Venkat; Liu, Gao

2016-09-14

The lithium-sulfur (Li-S) rechargeable battery has the benefit of high gravimetric energy density and low cost. Significant research currently focuses on increasing the sulfur loading and sulfur/inactive-materials ratio, to improve life and capacity. Inspired by nature's ant-nest structure, this research results in a novel Li-S electrode that is designed to meet both goals. With only three simple manufacturing-friendly steps, which include slurry ball-milling, doctor-blade-based laminate casting, and the use of the sacrificial method with water to dissolve away table salt, the ant-nest design has been successfully recreated in an Li-S electrode. The efficient capabilities of the ant-nest structure are adopted to facilitate fast ion transportation, sustain polysulfide dissolution, and assist efficient precipitation. High cycling stability in the Li-S batteries, for practical applications, has been achieved with up to 3 mg·cm(-2) sulfur loading. Li-S electrodes with up to a 85% sulfur ratio have also been achieved for the efficient design of this novel ant-nest structure.

Room-Temperature, Ambient-Pressure Chemical Synthesis of Amine-Functionalized Hierarchical Carbon-Sulfur Composites for Lithium-Sulfur Battery Cathodes.

Science.gov (United States)

Chae, Changju; Kim, Jinmin; Kim, Ju Young; Ji, Seulgi; Lee, Sun Sook; Kang, Yongku; Choi, Youngmin; Suk, Jungdon; Jeong, Sunho

2018-02-07

Recently, the achievement of newly designed carbon-sulfur composite materials has attracted a tremendous amount of attention as high-performance cathode materials for lithium-sulfur batteries. To date, sulfur materials have been generally synthesized by a sublimation technique in sealed containers. This is a well-developed technique for the synthesizing of well-ordered sulfur materials, but it is limited when used to scale up synthetic procedures for practical applications. In this study, we suggest an easily scalable, room-temperature/ambient-pressure chemical pathway for the synthesis of highly functioning cathode materials using electrostatically assembled, amine-terminated carbon materials. It is demonstrated that stable cycling performance outcomes are achievable with a capacity of 730 mAhg -1 at a current density of 1 C with good cycling stability by a virtue of the characteristic chemical/physical properties (a high conductivity for efficient charge conduction and the presence of a number of amine groups that can interact with sulfur atoms during electrochemical reactions) of composite materials. The critical roles of conductive carbon moieties and amine functional groups inside composite materials are clarified with combinatorial analyses by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy.

Comparative analysis of the mechanisms of sulfur anion oxidation and reduction by dsr operon to maintain environmental sulfur balance.

Science.gov (United States)

Ghosh, Semanti; Bagchi, Angshuman

2015-12-01

Sulfur metabolism is one of the oldest known redox geochemical cycles in our atmosphere. These redox processes utilize different sulfur anions and the reactions are performed by the gene products of dsr operon from phylogenetically diverse sets of microorganisms. The operon is involved in the maintenance of environmental sulfur balance. Interestingly, the dsr operon is found to be present in both sulfur anion oxidizing and reducing microorganisms and in both types of organisms DsrAB protein complex plays a vital role. Though there are various reports regarding the genetics of dsr operon there are practically no reports dealing with the structural aspects of sulfur metabolism by dsr operon. In our present study, we tried to compare the mechanisms of sulfur anion oxidation and reduction by Allochromatium vinosum and Desulfovibrio vulgaris respectively through DsrAB protein complex. We analyzed the modes of bindings of sulfur anions to the DsrAB protein complex and observed that for sulfur anion oxidizers, sulfide and thiosulfate are the best substrates whereas for reducers sulfate and sulfite have the best binding abilities. We analyzed the binding interaction pattern of the DsrA and DsrB proteins while forming the DsrAB protein complexes in Desulfovibrio vulgaris and Allochromatium vinosum. To our knowledge this is the first report that analyzes the differences in binding patterns of sulfur substrates with DsrAB protein from these two microorganisms. This study would therefore be essential to predict the biochemical mechanism of sulfur anion oxidation and reduction by these two microorganisms i.e., Desulfovibrio vulgaris (sulfur anion reducer) and Allochromatium vinosum (sulfur anion oxidizer). Our observations also highlight the mechanism of sulfur geochemical cycle which has important implications in future study of sulfur metabolism as it has a huge application in waste remediation and production of industrial bio-products viz. vitamins, bio-polyesters and bio

Radiolytic decomposition of pesticide carbendazim in waters and wastes for environmental protection

International Nuclear Information System (INIS)

Bojanowska-Czajka, A.; Drzewicz, P.; Meczynska, S.; Kruszewski, M.; Zimek, Z.; Nichipor, H.; Galezowska, A.; Nalecz-Jawecki, G.; Trojanowicz, M.; Warsaw University, Warsaw

2011-01-01

The radiolytic degradation of widely used fungicide, carbendazim, in synthetic aqueous solutions and industrial wastewater was investigated employing γ-irradiation. The effect of the absorbed dose, initial concentration and pH of irradiated solution on the effectiveness of carbendazim decomposition were investigated. Decomposition of carbendazim in 100 μM concentration in synthetic aqueous solutions required irradiation with 600 Gy dose. The aqueous solutions of carbendazim have been irradiated in different conditions, where particular active radical species from water radiolysis predominate. The obtained data have been compared with the kinetic modeling. The reversed-phase high-performance liquid chromatography was used for the determination of carbendazim and its radiolytic decomposition products in irradiated solutions. The changes of toxicity of irradiated solutions were examined with different test organisms and human leukemia cells. (author)

A Polysulfide-Infiltrated Carbon Cloth Cathode for High-Performance Flexible Lithium–Sulfur Batteries

Directory of Open Access Journals (Sweden)

Ji-Yoon Song

2018-02-01

Full Text Available For practical application of lithium–sulfur batteries (LSBs, it is crucial to develop sulfur cathodes with high areal capacity and cycle stability in a simple and inexpensive manner. In this study, a carbon cloth infiltrated with a sulfur-containing electrolyte solution (CC-S was utilized as an additive-free, flexible, high-sulfur-loading cathode. A freestanding carbon cloth performed double duty as a current collector and a sulfur-supporting/trapping material. The active material in the form of Li2S6 dissolved in a 1 M LiTFSI-DOL/DME solution was simply infiltrated into the carbon cloth (CC during cell fabrication, and its optimal loading amount was found to be in a range between 2 and 10 mg/cm2 via electrochemical characterization. It was found that the interwoven carbon microfibers retained structural integrity against volume expansion/contraction and that the embedded uniform micropores enabled a high loading and an efficient trapping of sulfur species during cycling. The LSB coin cell employing the CC-S electrode with an areal sulfur loading of 6 mg/cm2 exhibited a high areal capacity of 4.3 and 3.2 mAh/cm2 at C/10 for 145 cycles and C/3 for 200 cycles, respectively, with minor capacity loss (<0.03%/cycle. More importantly, such high performance could also be realized in flexible pouch cells with dimensions of 2 cm × 6 cm before and after 300 bending cycles. Simple and inexpensive preparation of sulfur cathodes using CC-S electrodes, therefore, has great potential for the manufacture of high-performance flexible LSBs.

Atomic Iron Catalysis of Polysulfide Conversion in Lithium-Sulfur Batteries.

Science.gov (United States)

Liu, Zhenzhen; Zhou, Lei; Ge, Qi; Chen, Renjie; Ni, Mei; Utetiwabo, Wellars; Zhang, Xiaoling; Yang, Wen

2018-06-13

Lithium-sulfur batteries have been regarded as promising candidates for energy storage because of their high energy density and low cost. It is a main challenge to develop long-term cycling stability battery. Here, a catalytic strategy is presented to accelerate reversible transformation of sulfur and its discharge products in lithium-sulfur batteries. This is achieved with single-atomic iron active sites in porous nitrogen-doped carbon, prepared by polymerizing and carbonizing diphenylamine in the presence of iron phthalocyanine and a hard template. The Fe-PNC/S composite electrode exhibited a high discharge capacity (427 mAh g -1 ) at a 0.1 C rate after 300 cycles with the Columbic efficiency of above 95.6%. Besides, the electrode delivers much higher capacity of 557.4 mAh g -1 at 0.5 C over 300 cycles. Importantly, the Fe-PCN/S has a smaller phase nucleation overpotential of polysulfides than nitrogen-doped carbon alone for the formation of nanoscale of Li 2 S as revealed by ex situ SEM, which enhance lithium-ion diffusion in Li 2 S, and therefore a high rate performance and remarkable cycle life of Li-sulfur batteries were achieved. Our strategy paves a new way for polysulfide conversion with atomic iron catalysis to exploit high-performance lithium-sulfur batteries.

The impact of radiolytic yield on the calculated ECP in PWR primary coolant circuits

International Nuclear Information System (INIS)

Urquidi-Macdonald, Mirna; Pitt, Jonathan; Macdonald, Digby D.

2007-01-01

A code, PWR-ECP, comprising chemistry, radiolysis, and mixed potential models has been developed to calculate radiolytic species concentrations and the corrosion potential of structural components at closely spaced points around the primary coolant circuits of pressurized water reactors (PWRs). The pH(T) of the coolant is calculated at each point of the primary-loop using a chemistry model for the B(OH) 3 + LiOH system. Although the chemistry/radiolysis/mixed potential code has the ability to calculate the transient reactor response, only the reactor steady state condition (normal operation) is discussed in this paper. The radiolysis model is a modified version of the code previously developed by Macdonald and coworkers to model the radiochemistry and corrosion properties of boiling water reactor primary coolant circuits. In the present work, the PWR-ECP code is used to explore the sensitivity of the calculated electrochemical corrosion potential (ECP) to the set of radiolytic yield data adopted; in this case, one set had been developed from ambient temperature experiments and another set reported elevated temperatures data. The calculations show that the calculated ECP is sensitive to the adopted values for the radiolytic yields

Modeling of Radiolytic Degradation of Cefaclor by Ionizing Energy

International Nuclear Information System (INIS)

Yu, Seungho; Choi, Dongkyu; Lee, Myunjoo

2008-01-01

Recently, many researches have been conducted on the treatments of antibiotics found in groundwater, surface water, and wastewater. Ingerslev et al. showed that antibiotics under aerobic and anaerobic conditions were not readily biodegradable. Advanced oxidation processes (AOPs) have been suggested in recent years as a suitable alternative for the removal of refractory organic compounds found in a variety of environment. AOPs by using free radicals such as the hydroxyl radical (·OH) include ozone, ozone/UV, TiO 2 photo catalysis, fenton's reaction, H 2 O 2 /UV, H 2 O 2 /O 3 and ionizing radiation. Herein are reported the results of the radiolytic degradation of cefaclor. This study focused on the use of gamma radiation as an AOP for the complete mineralization of antibiotics. Among the many kinds of antibiotics, the target antibiotic in this study was cefaclor, which a β lactam antibiotic widely used for the medical treatment of microbial infective diseases. The objectives of this study were: 1) to investigate the decomposition and mineralization of cefaclor using gamma irradiation; 2) to study the decomposition kinetics of cefaclor; and 3) to simulate radiolytic decomposition of cefaclor with experimentally measured kinetic parameters

A composite of hollow carbon nanospheres and sulfur-rich polymers for lithium-sulfur batteries

Science.gov (United States)

Zeng, Shao-Zhong; Yao, Yuechao; Zeng, Xierong; He, Qianjun; Zheng, Xianfeng; Chen, Shuangshuang; Tu, Wenxuan; Zou, Jizhao

2017-07-01

Lithium-sulfur batteries are the most promising candidates for future high-energy applications because of the unparalleled capacity of sulfur (1675 mAh g-1). However, lithium-sulfur batteries have limited cycle life and rate capability due to the dissolution of polysulfides and the extremely low electronic conductivity of sulfur. To solve these issues, various porous carbons including hollow carbon nanospheres (HCNs) have been used for improving the conductivity. However, these methods still suffer from polysulfides dissolution/loss owing to their weak physical adsorption to polysulfides. Herein, we introduced a covalent grafting route to composite the HCNs and the vulcanized trithiocyanuric acid (TTCA). The composite exhibits a high loading of the vulcanized TTCA by the HCNs with high surface area and large pore volume, and covalent bonds to sulfur, effectively depressing the dissolution of polysulfides. The first discharge capacity of the composite reaches 1430 mAh g-1 at 0.1 C and 1227 mAh g-1 at 0.2 C.

Analysis and optimal process development of the iodine-Sulfur cycle for nuclear hydrogen production

International Nuclear Information System (INIS)

Lee, Byung Jin

2009-02-01

Hydrogen is expected to be a main energy vector for the future society. Among many thermo-chemical water splitting technologies for mass production of hydrogen, Iodine-Sulfur (I-S) cycle is considered to be the most promising one. Originated in the 1980s by General Atomics in the United States, the I-S cycle utilizes high temperature heat from energy sources such as nuclear reactors. Despite its high viability relative to many other options, lots of technical challenges need to be resolved until it can practically contribute to the mass production of hydrogen. In the present work, based on the experimental data available from previous works and discussions collected through the literature survey, the optimal operating conditions were proposed for the Bunsen reaction, considering the key concerns of the I-S cycle: i.e., the liquid-liquid (L-L) phase separation performance, the water distributions between the sulfuric acid and poly-hydroiodic acid (HI x ) phases, the side reactions, and the operating cost due to the excess iodine and water. All the available experimental data were combined together, and a series of parametric studies were done to find out any trends among parameters. The optimal operating point is determined as 4 mol of excess iodine and 11 mol of excess water in the stoichiometry at temperature of 330K, while the allowable window ranges between 4∼6 mol for excess iodine, 11∼13 moles for excess water, and 330∼350K for temperature. As for the distribution of excess water after the Bunsen reaction and L-L phase separation, 5 mol moves to the sulfuric acid phase and 6∼8 mol to the HI x phase. By controlling the operation within this window, it should be possible to avoid the side reaction and iodine solidification, to increase the HI concentration well above the azeotrope in the HI x section, and to minimize the operating cost caused by the excess iodine and water. With the optimized Bunsen reaction process to yield an over-azeotropic HI liquid

One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Hu, Pengfei [Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444 (China); Zhao, Bing, E-mail: bzhao@shu.edu.cn [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)

2015-10-05

Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g{sup −1} after 50 cycles at 100 mA g{sup −1}. • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g{sup −1} after 50 cycles at a current density of 100 mA g{sup −1} and reversible capacity of 517.9 mA h g{sup −1} at 1 A g{sup −1}. The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems.

LC-MS analysis in the e-beam and gamma radiolysis of metoprolol tartrate in aqueous solution: Structure elucidation and formation mechanism of radiolytic products

Energy Technology Data Exchange (ETDEWEB)

Slegers, Catherine [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium)]. E-mail: catherine.slegers@skynet.be; Maquille, Aubert [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium); Deridder, Veronique [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium); Sonveaux, Etienne [Unite de Chimie Pharmaceutique et de Radiopharmacie, Universite Catholique de Louvain, Brussels (Belgium); Habib Jiwan, Jean-Louis [Laboratoire de Spectrometrie de Masse, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Tilquin, Bernard [Unite d' Analyse Chimique et Physico-chimique des Medicaments, Universite Catholique de Louvain, CHAM 72.30, Avenue E. Mounier, 72, B-1200, Brussels (Belgium)

2006-09-15

E-beam and gamma products from the radiolysis of aqueous solutions of ({+-})-metoprolol tartrate, saturated in nitrogen, are analyzed by HPLC with on-line mass and UV detectors. The structures of 10 radiolytic products common to e-beam and gamma irradiations are elucidated by comparing their fragmentation pattern to that of ({+-})-metoprolol. Two of the radiolytic products are also metabolites. Different routes for the formation of the radiolytic products are proposed.

The importance of variables and parameters in radiolytic chemical kinetics modeling

International Nuclear Information System (INIS)

Piepho, M.G.; Turner, P.J.; Reimus, P.W.

1989-01-01

Many of the pertinent radiochemical reactions are not completely understood, and most of the associated rate constants are poorly characterized. To help identify the important radiochemical reactions, rate constants, species, and environmental conditions, an importance theory code, SWATS (Sensitivitiy With Adjoint Theory-Sparse version)-LOOPCHEM, has been developed for the radiolytic chemical kinetics model in the radiolysis code LOOPCHEM. The LOOPCHEM code calculates the concentrations of various species in a radiolytic field over time. The SWATS-LOOPCHEM code efficiently calculates: the importance (relative to a defined response of interest) of each species concentration over time, the sensitivity of each parameter of interest, and the importance of each equation in the radiolysis model. The calculated results will be used to guide future experimental and modeling work for determining the importance of radiolysis on waste package performance. A demonstration (the importance of selected concentrations and the sensitivities of selected parameters) of the SWATS-LOOPCHEM code is provided for illustrative purposes

Influence of radiolytic products on the chemistry of uranium VI in brines

International Nuclear Information System (INIS)

Lucchini, J-F.; Reed, D.T.; Borkowski, M.; Rafalski, A.; Conca, J.

2004-01-01

In the near field of a salt repository of nuclear waste, ionizing radiations can strongly affect the chemistry of concentrated saline solutions. Radiolysis can locally modify the redox conditions, speciation, solubility and mobility of the actinide compounds. In the case of uranium VI, radiolytic products can not only reduce U(VI), but also react with uranium species. The net effect on the speciation of uranyl depends on the relative kinetics of the reactions and the buildup of molecular products in brine solutions. The most important molecular products in brines are expected to be hypochlorite ion, hypochlorous acid and hydrogen peroxide. Although U(VI) is expected not to be significantly affected by radiolysis, the combined effects of the major molecular radiolytic products on the chemistry of U(VI) in brines have not been experimentally established previously. (authors)

Identity of major sulfur-cycle prokaryotes in freshwater lake ecosystems revealed by a comprehensive phylogenetic study of the dissimilatory adenylylsulfate reductase.

Science.gov (United States)

Watanabe, Tomohiro; Kojima, Hisaya; Fukui, Manabu

2016-11-08

Adenylylsulfate reductase is a heterodimeric complex of two subunits, AprB and AprA, and is a key enzyme in dissimilatory sulfate reduction and sulfur oxidation. Common use of aprA as a functional marker gene has revealed the diversity of sulfur-cycle prokaryotes in diverse environments. In this study, we established a comprehensive sequence set of apr genes and employed it to reanalyze apr phylogeny, evaluate the coverage of a widely used primer set (AprA-1-FW/AprA-5-RV), and categorize environmental aprA sequences. Phylogenetic tree construction revealed new members of Apr lineage II and several previously unrecognized lateral gene transfer events. Using the established phylogenetic tree, we classified all previously reported aprA sequences amplified from freshwater lakes with the primer pair AprA-1-FW/AprA-5-RV in addition to the aprA sequences newly retrieved from freshwater lakes; the obtained results were complemented by 16S rRNA clone library analysis. Apr-based classifications of some of operational taxonomic units were supported by 16S rRNA-based analysis. This study updates our knowledge on the phylogeny of aprBA and shows the identities of several sulfur-cycle bacteria, which could not be classified to a known taxa until now. The established apr sequence set is publicly available and can be applied to assign environmental sequences to known lineages.

Radiolytic alteration of biopolymers in the Mulga Rock (Australia) uranium deposit

International Nuclear Information System (INIS)

Jaraula, Caroline M.B.; Schwark, Lorenz; Moreau, Xavier; Pickel, Walter; Bagas, Leon; Grice, Kliti

2015-01-01

Highlights: • Bulk kerogen compositions indicate land plant sources for organic matter in the uranium deposit. • Radiolysis led to cleavage of straight long chain forming medium chain length n-alkyl moieties. • Secondary and tertiary reactions with OH − radicals promoted the formation of alkanones. • “Radiolytic molecular markers” imply molecular markers resulting from radiolytic cracking. • A mechanism is proposed for the production of n-alkanes and n-alkanones. - Abstract: We investigated the effect of ionizing radiation on organic matter (OM) in the carbonaceous uranium (U) mineralization at the Mulga Rock deposit, Western Australia. Samples were collected from mineralized layers between 53 and 58.5 m depths in the Ambassador prospect, containing <5300 ppm U. Uranium bears a close spatial relationship with OM, mostly finely interspersed in the attrinite matrix and via enrichments within liptinitic phytoclasts (mainly sporinite and liptodetrinite). Geochemical analyses were conducted to: (i) identify the natural sources of molecular markers, (ii) recognize relationships between molecular markers and U concentrations and (iii) detect radiolysis effects on molecular marker distributions. Carbon to nitrogen ratios between 82 and 153, and Rock–Eval pyrolysis yields of 316–577 mg hydrocarbon/g TOC (HI) and 70–102 mg CO 2 /g TOC (OI) indicate a predominantly lipid-rich terrigenous plant OM source deposited in a complex shallow swampy wetland or lacustrine environment. Saturated hydrocarbon and ketone fractions reveal molecular distributions co-varying with U concentration. In samples with <1700 ppm U concentrations, long-chain n-alkanes and alkanones (C 27 –C 31 ) reveal an odd/even carbon preference indicative of extant lipids. Samples with ⩾1700 ppm concentrations contain intermediate-length n-alkanes and alkanones, bearing a keto-group in position 2–10, with no carbon number preference. Such changes in molecular distributions are

Radiolytic oxidation

International Nuclear Information System (INIS)

Burns, W.G.; Ewart, F.T.; Hobley, J.; Smith, A.J.; Walters, W.S.; Williams, S.J.

1991-01-01

Work under the Radiolytic Oxidation Contract from 1986 until April 1989 is reported. The effects of alpha- and gamma-irradiation on the chemistries of plutonium, neptunium and technetium, under conditions representative of the near fields of intermediate and high level waste repositories, were investigated. Gamma-radiolysis of Np (IV) results in oxidation in solutions below pH 12. Solutions of Tc (VII) are reduced to Tc (IV) by gamma-irradiation in contact with blast furnace slag/ordinary Portland cement under an inert atmosphere but not when in contact with pulverized fuel ash/ordinary Portland cement. Tc (IV) is shown to be susceptible to oxidation by the products of the alpha-radiolysis of water. The results of 'overall effects' experiments, which combined representative components of typical ILW or HLW near fields, supported these observations and also showed enhanced plutonium concentrations in alpha-irradiated, HLW simulations. Mathematical models of the behaviour of plutonium and neptunium during gamma-radiolysis have been developed and indicate that oxidation to Pu (VI) is possible at dose rates typical of those expected for HLW. Simulations at ILW dose rates have indicated some effect upon the speciation of neptunium. Laboratory studies of the gamma-irradiation of Np (IV) in bentonite-equilibrated water have also been modelled. Computer code used: PHREEQE, 8 Figs.; 48 Tabs.; 38 refs

LC-MS analysis in the e-beam and gamma radiolysis of metoprolol tartrate in aqueous solution: Structure elucidation and formation mechanism of radiolytic products

International Nuclear Information System (INIS)

Slegers, Catherine; Maquille, Aubert; Deridder, Veronique; Sonveaux, Etienne; Habib Jiwan, Jean-Louis; Tilquin, Bernard

2006-01-01

E-beam and gamma products from the radiolysis of aqueous solutions of (±)-metoprolol tartrate, saturated in nitrogen, are analyzed by HPLC with on-line mass and UV detectors. The structures of 10 radiolytic products common to e-beam and gamma irradiations are elucidated by comparing their fragmentation pattern to that of (±)-metoprolol. Two of the radiolytic products are also metabolites. Different routes for the formation of the radiolytic products are proposed

Novel separation process of gaseous mixture of SO2 and O2 with ionic liquid for hydrogen production in thermochemical sulfur-iodine water splitting cycle

International Nuclear Information System (INIS)

Kim, Chang Soo; Gong, Gyeong Taek; Yoo, Kye Sang; Kim, Honggon; Lee, Byoung Gwon; Ahn, Byoung Sung; Jung, Kwang Deog; Lee, Ki Yong; Song, Kwang Ho

2007-01-01

Sulfur-Iodine cycle is the most promising thermochemical cycle for water splitting to produce hydrogen which can replace the fossil fuels in the future. As a sub-cycle in the thermochemical Sulfur-Iodine water splitting cycle, sulfuric acid (H 2 SO 4 ) decomposes into oxygen (O 2 ) and sulfur dioxide (SO 2 ) which should be separated for the recycle of SO 2 into the sulfuric acid generation reaction (Bunsen Reaction). In this study, absorption and desorption process of SO 2 by ionic liquid which is useful for the recycle of SO 2 into sulfuric acid generation reaction after sulfuric acid decomposition in the thermochemical Sulfur-Iodine cycle is investigated. At first, the operability as an absorbent for the SO 2 absorption and desorption at high temperature without the volatilization of absorbents which is not suitable for the recycle of absorbent-free SO 2 after the absorption process. The temperature range of operability is determined by TGA and DTA analysis. Most of ionic liquids investigated are applicable at high temperature desorption without volatility around 300 deg. C except [BMIm] Cl, and [BMIm] OAc which show the decomposition of ionic liquids. To evaluate the capability of SO 2 absorption, each ionic liquid is located in the absorption tube and gaseous SO 2 is bubbled into the ionic liquid. During the bubbling, the weight of the system is measured and converted into the absorbed SO 2 amount at each temperature controlled by the heater. Saturated amounts of absorbed SO 2 by ionic liquids at 50 deg. C are presented. The effect of anions for the SO 2 absorption capability is shown in the order of Cl, OAc, MeSO 3 , BF 4 , MeSO 4 , PF 6 , and HSO 4 when they are combined with [BMIm] cation. [BMIm]Cl has the largest amount of SO 2 absorbed which can be the most promising absorbent; however, from the point of operability at high temperature which includes desorption process, [BMIm]Cl is vulnerable to high temperature around 250 deg. C based on the TGA

ADVANCED SULFUR CONTROL CONCEPTS

Energy Technology Data Exchange (ETDEWEB)

Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael; Jeffrey W. Portzer

2003-01-01

Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).

Polyaniline-Coated Activated Carbon Aerogel/Sulfur Composite for High-performance Lithium-Sulfur Battery

Science.gov (United States)

Tang, Zhiwei; Jiang, Jinglin; Liu, Shaohong; Chen, Luyi; Liu, Ruliang; Zheng, Bingna; Fu, Ruowen; Wu, Dingcai

2017-12-01

An activated carbon aerogel (ACA-500) with high surface area (1765 m2 g-1), pore volume (2.04 cm3 g-1), and hierarchical porous nanonetwork structure is prepared through direct activation of organic aerogel (RC-500) with a low potassium hydroxide ratio (1:1). Based on this substrate, a polyaniline (PANi)-coated activated carbon aerogel/sulfur (ACA-500-S@PANi) composite is prepared via a simple two-step procedure, including melt-infiltration of sublimed sulfur into ACA-500, followed by an in situ polymerization of aniline on the surface of ACA-500-S composite. The obtained ACA-500-S@PANi composite delivers a high reversible capacity up to 1208 mAh g-1 at 0.2C and maintains 542 mAh g-1 even at a high rate (3C). Furthermore, this composite exhibits a discharge capacity of 926 mAh g-1 at the initial cycle and 615 mAh g-1 after 700 cycles at 1C rate, revealing an extremely low capacity decay rate (0.48‰ per cycle). The excellent electrochemical performance of ACA-500-S@PANi can be attributed to the synergistic effect of hierarchical porous nanonetwork structure and PANi coating. Activated carbon aerogels with high surface area and unique three-dimensional (3D) interconnected hierarchical porous structure offer an efficient conductive network for sulfur, and a highly conductive PANi-coating layer further enhances conductivity of the electrode and prevents the dissolution of polysulfide species.

Gamma radiolytic degradation of 4-chlorophenol determination of degraded products with HPLC and GC-MS

International Nuclear Information System (INIS)

Butt, S.B.; Masood, M.N.

2007-01-01

Contamination by chlorophenols of surface water and groundwater is an emerging issue in environmental science and engineering. After their usage as pesticide, herbicide and disinfectant, these organic compounds subsequently enter the aquatic environment through a number of routes. Some of the chlorophenols are slightly biodegradable, while others are more persistent and mobile in the aquatic environment especially chlorophenols. Gamma radiolytic degradation is one of advance oxidation process that has been thought to be one of the promising treatments to deal with this problem. This radiolytic study was carried out in methanolic 4-CP (4-chlorophenol) samples. Among several factors effecting radiolytic degradation of 4-CP, dose and concentration are important that were evaluated under atmospheric conditions. A degradation yield (G -value) for 4- CP of 0.38 and 1.35 was achieved in 20 and 100 mg/dm/sup 3/ solution. It was observed that degradation yield decreases with increasing 4-CP concentration. Gamma radiolysis produce free radicals in solvent which further react with 4-CP molecules to generate different products. The identification of degradation products was proposed using HPLC and GC-MS. (author)

Atmospheric sulfur and climate changes: a modelling study at mid and high-southern latitudes

International Nuclear Information System (INIS)

Castebrunet, H.

2007-09-01

The mid and high-southern latitudes are still marginally affected by anthropogenic sulfur emissions. They are the only regions in the world where the natural cycle of the atmospheric sulfur may still be observed. Sulfur aerosols are well-known for their radiative impact, and thus interact with climate. Climate can in turn affect atmospheric sulfur sources, distribution and chemistry. Antarctic ice cores provide information on the evolution of climate and sulfur deposition at the surface of the ice sheet at glacial-interglacial time scales. The aim of this thesis is to develop and use modeling towards a better understanding of the atmospheric sulfur cycle in antarctic and sub-antarctic regions. Ice core data are used to validate model results under glacial climate conditions. An Atmospheric General Circulation Model (AGCM) coupled to a sulfur chemistry module is used: the LMD-ZTSulfur model, version 4. An update of both the physical and chemical parts of the model. The model was first performed. The impact of there changes on modelled sulfur cycle are evaluated for modern climate. Further, boundary conditions are adapted to simulate the atmospheric circulation and sulfur cycle at the Last Glacial Maximum, approximately 20,000 years ago. In the model, sulfur is found to be highly sensitive to antarctic sea-ice coverage, which is still poorly known during the ice age. An original dataset of ice-age sea-ice coverage was developed. Its impact on the oceanic emissions of dimethyl sulfide, main precursor of sulfur aerosols at high-southern latitudes, is discussed. Using the same oceanic sulfur reservoirs as for present day climate, the model broadly reproduces the glacial deposits of sulfur aerosols on the Antarctic plateau, suggesting little impact of climate on oceanic sulfur production in the Antarctic region. Sensitivity tests were carried out to draw an up-to-date status of major uncertainties and difficulties facing future progress in understanding atmospheric

Is overprotection of the sulfur cathode good for Li-S batteries?

Science.gov (United States)

Gao, Tian; Shao, Jie; Li, Xingxing; Zhu, Guobin; Lu, Qiujian; Han, Yuyao; Qu, Qunting; Zheng, Honghe

2015-08-11

How to restrain the dissolution of polysulfides from the sulfur cathode is the current research focus of Li-S batteries. Here, we find that moderate dissolution of polysulfides is of great importance for high-efficiency and stable discharge/charge cycling. Both overprotection and inadequate protection of the sulfur cathode are unfavorable for the cycling of Li-S batteries.

Radiolytic Syntheses of Nanoparticles and Inorganic-Polymer Hybrid Microgels

International Nuclear Information System (INIS)

Chen, Q.; Shi, J.; Zhao, R.; Shen, X.

2010-01-01

In the second year of the project, we have gotten progress mainly in two directions. Firstly, for the first time, Prussian blue (PB) nanoparticles (NPs) were successfully synthesized by the partly radiolytic reduction of Fe3+ and Fe(CN)63 in the presence of poly(N-vinyl pyrrolidine) (PVP) under N2 atmospheres at room temperature. With the increase of the concentration of PVP, the size and the size distribution of the synthesized quasi-spherical PB NPs decreased obviously, leading to a hypsochromic shift on their peak position of the characteristic absorption. In the experiment, we further found that the smaller ones have a larger capacity to Cs+, suggesting that the application of PB NPs in curing thallotoxicosis may decrease the usage of PB for the patient to great extent. Secondly, through a series of preliminary experiments, we got a clear picture about the one-step radiolytic preparation of inorganic-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by surfactant-free emulsion polymerization. Besides, unpurified N-carbamothioylmethacrylamide was synthesized via the methacrylation of thiourea. These created favorable conditions for the one-step synthesis of metal sulfide-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by -irradiation and surfactant-free emulsion polymerization. (author)

Radiolytic Syntheses of Nanoparticles and Inorganic-Polymer Hybrid Microgels

Energy Technology Data Exchange (ETDEWEB)

Chen, Q.; Shi, J.; Zhao, R.; Shen, X., E-mail: qdchen@pku.edu.cn [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, No. 5, Yiheyuan Load, Haidian District Beijing 100871 (China)

2010-07-01

In the second year of the project, we have gotten progress mainly in two directions. Firstly, for the first time, Prussian blue (PB) nanoparticles (NPs) were successfully synthesized by the partly radiolytic reduction of Fe3+ and Fe(CN)63 in the presence of poly(N-vinyl pyrrolidine) (PVP) under N2 atmospheres at room temperature. With the increase of the concentration of PVP, the size and the size distribution of the synthesized quasi-spherical PB NPs decreased obviously, leading to a hypsochromic shift on their peak position of the characteristic absorption. In the experiment, we further found that the smaller ones have a larger capacity to Cs+, suggesting that the application of PB NPs in curing thallotoxicosis may decrease the usage of PB for the patient to great extent. Secondly, through a series of preliminary experiments, we got a clear picture about the one-step radiolytic preparation of inorganic-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by surfactant-free emulsion polymerization. Besides, unpurified N-carbamothioylmethacrylamide was synthesized via the methacrylation of thiourea. These created favorable conditions for the one-step synthesis of metal sulfide-poly(methacrylic acid-co-methyl methacrylate) hybrid microgels by -irradiation and surfactant-free emulsion polymerization. (author)

Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

International Nuclear Information System (INIS)

Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

1983-01-01

A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH 4 CN, CH 3 CN, and C 2 H 4 CN, that had received multikilogray doses of 60 Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

The Conceptual Design of an Integrated Nuclearhydrogen Production Plant Using the Sulfur Cycle Water Decomposition System

Science.gov (United States)

Farbman, G. H.

1976-01-01

A hydrogen production plant was designed based on a hybrid electrolytic-thermochemical process for decomposing water. The sulfur cycle water decomposition system is driven by a very high temperature nuclear reactor that provides 1,283 K helium working gas. The plant is sized to approximately ten million standard cubic meters per day of electrolytically pure hydrogen and has an overall thermal efficiently of 45.2 percent. The economics of the plant were evaluated using ground rules which include a 1974 cost basis without escalation, financing structure and other economic factors. Taking into account capital, operation, maintenance and nuclear fuel cycle costs, the cost of product hydrogen was calculated at $5.96/std cu m for utility financing. These values are significantly lower than hydrogen costs from conventional water electrolysis plants and competitive with hydrogen from coal gasification plants.

Sandwich-Type Nitrogen and Sulfur Codoped Graphene-Backboned Porous Carbon Coated Separator for High Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Chen, Feng; Ma, Lulu; Ren, Jiangang; Luo, Xinyu; Liu, Bibo; Zhou, Xiangyang

2018-03-26

Lithium-sulfur (Li-S) batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg -1 . However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC) to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m² g -1 ), high pore volume (1.78 cm³ g -1 ), good conductivity, and in situ nitrogen (1.86 at %) and sulfur (5.26 at %) co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li⁺ ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g -1 at 0.2 C), excellent rate capability (596.6 mAh g -1 at 5 C), and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle). Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm -2 (70 wt. % sulfur), the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g -1 , which is quite beneficial to commercialized applications.

Stabilized sulfur as cathodes for room temperature sodium-ion batteries.

Energy Technology Data Exchange (ETDEWEB)

Xu, Yunhua [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yang [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies; Zhu, Yujie [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Zheng, Shiyou [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yihang [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Luo, Chao [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Gaskell, Karen [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Eichhorn, Bryan [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Wang, Chunsheng [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering

2013-05-01

Sodium-sulfur batteries, offering high capacity and low cost, are promising alternative to lithium-ion batteries for large-scale energy storage applications. The conventional sodium-sulfur batteries, operating at a high temperature of 300–350°C in a molten state, could lead to severe safety problems. However, the room temperature sodium-sulfur batteries using common organic liuid electrolytes still face a significant challenge due to the dissolution of intermediate sodium polysulfides. For this study, we developed room temperatue sodium-sulfur batteries using a unique porous carbon/sulfur (C/S) composite cathode, which was synthesized by infusing sulfur vapor into porous carbon sphere particles at a high temperatrure of 600°C. The porous C/S composites delivered a reversible capacity of ~860 mAh/g and retained 83% after 300 cycles. The Coulombic efficiency of as high as 97% was observed over 300 cycles. The superior electrochemical performance is attrbuted to the super sulfur stability as evidenced by its lower sensitivity to probe beam irradiation in TEM, XPS and Raman charaterization and high evaperation temperature in TGA. The results make it promising for large-scale grid energy storage and electric vehicles.

Observation of Radiolytic Field Alteration of the Uranyl Cation in Bicarbonate Solution

Energy Technology Data Exchange (ETDEWEB)

Snow, Lanee A.; McNamara, Bruce K.; Sinkov, Sergey I.; Cho, Herman M.; Friese, Judah I.

2006-12-01

In previous work we demonstrated that radiolysis of uranyl tris carbonate in near neutral pH to alkaline carbonate solutions, could be followed by 13C NMR. Radiolysis of the complex produced novel uranyl peroxo carbonate solution state species, whose structures depended on the pH and radiolytic dose rate. In this work, we investigate speciation of the uranyl carbonate trimer which is predominant in bicarbonate solution near pH 5.9. We observe radiolytically derived speciation to different mixed peroxy carbonate species than seen in the higher pH solutions. Auto radiolysis of uranium (VI) carbonate solutions between pH 5.9 and 7.2 is shown to alter the uranium speciation over relatively short periods of time and was followed by 13C NMR and visible spectrophotometry, using dissolved 233(UO2)3(CO3)6 6- both as the radiolysis source (D= 14.9 Gy/hr) and as a trap for the newly formed hydrogen peroxide. Direct addition of hydrogen peroxide to solutions of the uranyl-carbonate trimer is shown to reproduce the 13 C NMR signatures of the complexe(s) formed by radiolysis, but additionally a variety of new complexes are revealed. Ratios of H2O2/trimer < 1.5 produced a uranyl peroxo carbonate adduct, that is shown to be common to the radiolytically produced species. Ratios of H2O2/ trimer >1 resulted in formation of stable higher order peroxo carbonate complexes. The 13C NMR signatures and visible spectra of these complexes are described here. Rigorous characterization of the species is an ongoing effort.

Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

International Nuclear Information System (INIS)

Kao, Yu-Hsuan; Wang, Sheng-Wei; Liu, Chen-Wuing; Wang, Pei-Ling; Wang, Chung-Ho; Maji, Sanjoy Kumar

2011-01-01

Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using δ 34 S [SO 4 ] and δ 18 O [SO 4 ] sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of 34 S [SO 4 ] and 18 O [SO 4 ] present in Type A, caused by microbial-mediated reduction of sulfate, and high 18 O enrichment factor (ε [SO 4 -H 2 O] ), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high δ 18 O [SO 4 ] and low δ 34 S [SO 4 ] values under mildly reducing conditions. Base on 18 O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O 2 , caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: → Seawater intrusion and elevated As are the main issues of groundwater in Taiwan. → Sulfur and oxygen isotopes of sulfate were analyzed to evaluate the As mobility. → Reductive dissolution of Fe minerals and

Sulfur bacteria in wastewater stabilization ponds periodically affected by the 'red-water' phenomenon

NARCIS (Netherlands)

Belila, A.; Abbas, B.; Fazaa, I.; Saidi, N.; Snoussi, M.; Hassen, A.; Muyzer, G.

2013-01-01

Several wastewater stabilization ponds (WSP) in Tunisia suffer periodically from the ‘red-water’ phenomenon due to blooming of purple sulfur bacteria, indicating that sulfur cycle is one of the main element cycles in these ponds. In this study, we investigated the microbial diversity of the El

Modelling of Radiolytical Proceses in Polystyrenic Structures

International Nuclear Information System (INIS)

Postolache, C.

2006-01-01

The behavior of polystyrene, poly α-methylstyrene and poly β-methylstyrene structures in ionizing fields was analyzed using computational methods. In this study, the primary radiolytic effect was evaluated using a free radical mechanism. Molecular structures were built and geometrical optimized using quantum-chemical methods. Binding energies for different quantum states and peripheral orbitals distribution were determined. Based on obtained results it was proposed an evaluation model of radiolytical processes in polymers in solid phase. Suggested model suppose to distinguish the dominant processes by binding energies values analysis and LUMO peripheral orbital distribution. Computed binding energies analysis of energetically optimized molecular structures in ionized state (charge +1, multiplicity 2) reveals a high similitude of obtained binding energies for ionized states. The same similitude was observed also in case of total binding energies for neutral state (charge 0, multiplicity 1). Analyzed molecular structures can be associated with ionized molecule state right after one electron capture. This fact suggests that the determined stage of radiolitical fragmentation act is intermediate state of ionized molecule. This molecule captured one electron but it had no necessary time for atoms rearrangement in the molecule for new quantum state. This supposition is in accordance with literature, the time period between excitation act and fragmentation act being lower than 10 - 15 seconds. Based on realized model could be explained the behavior differences of polymeric structures in ionizing radiation field. Preferential fracture of main chains in fragmentation poly α-methylstirene can be explained in accordance with proposed model by C-C from main C bonding energies decreasing in the neighboring of quaternary C

Sulfur pollution: an environmental study of Welland, Ontario

Science.gov (United States)

Michael R. Moss

1977-01-01

The distribution of sulfur as an environmental pollutant is analysed in the vicinity of Welland, Ontario. A biogeochemical-cycle approach enables areas of excess accumulation to be compared among all linked ecosystem components. Although the patterns of distribution are similar, the amounts of sulfur accumulated in different ecosystems, grassland and woodland, show...

Identification of radiolytic products from N-nitrosodimethylamine and N-nitrosopyrrolidine by gas chromatography and mass spectrometry[Gamma irradiation; N-Nitrosodimethylamine; N-Nitrosopyrrolidine; Radiolysis

Energy Technology Data Exchange (ETDEWEB)

Ahn, H -J; Lee, C -H; Kim, J -H; Han, S -B; Jo, Cheorun; Kim, Sung; Byun, M -W

2004-01-01

The radiolytic products of N-nitrosodimethylamine (NDMA) and N-nitrosopyrrolidine (NPYR) dissolved in dichloromethane (DCM) were identified after gamma irradiation. The UV spectra of NDMA and NPYR indicated that irradiation reduced the typical peak of NDMA at 258 nm and NPYR at 260 nm.The major radiolytic components identified in irradiated NDMA were ethyl acetate and 2-dimethyl propanol. The irradiated NPYR dissolved in DCM and produced 2-butanone and 2-methyl-6-propyl piperidine as the major radiolytic components. 2-Methyl-6-propyl piperidine was the component detected in the greatest concentration in irradiated NPYR.

Sandwich-Type Nitrogen and Sulfur Codoped Graphene-Backboned Porous Carbon Coated Separator for High Performance Lithium-Sulfur Batteries

Science.gov (United States)

Chen, Feng; Ma, Lulu; Ren, Jiangang; Luo, Xinyu; Liu, Bibo; Zhou, Xiangyang

2018-01-01

Lithium-sulfur (Li-S) batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg−1. However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC) to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m2 g−1), high pore volume (1.78 cm3 g−1), good conductivity, and in situ nitrogen (1.86 at %) and sulfur (5.26 at %) co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li+ ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g−1 at 0.2 C), excellent rate capability (596.6 mAh g−1 at 5 C), and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle). Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm−2 (70 wt. % sulfur), the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g−1, which is quite beneficial to commercialized applications. PMID:29587467

Sandwich-Type Nitrogen and Sulfur Codoped Graphene-Backboned Porous Carbon Coated Separator for High Performance Lithium-Sulfur Batteries

Directory of Open Access Journals (Sweden)

Feng Chen

2018-03-01

Full Text Available Lithium-sulfur (Li-S batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg−1. However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m2 g−1, high pore volume (1.78 cm3 g−1, good conductivity, and in situ nitrogen (1.86 at % and sulfur (5.26 at % co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li+ ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g−1 at 0.2 C, excellent rate capability (596.6 mAh g−1 at 5 C, and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle. Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm−2 (70 wt. % sulfur, the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g−1, which is quite beneficial to commercialized applications.

Lithium battery using sulfur infiltrated in three-dimensional flower-like hierarchical porous carbon electrode

Energy Technology Data Exchange (ETDEWEB)

Moreno, Noelia; Caballero, Alvaro [Dpto.Química Inorgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica, Universidad de Córdoba, Campus de Rabanales (Spain); Morales, Julián, E-mail: iq1mopaj@uco.es [Dpto.Química Inorgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica, Universidad de Córdoba, Campus de Rabanales (Spain); Agostini, Marco [Department of Chemistry, SapienzaUniversity, P.zzale Aldo Moro 5, 00185, Rome (Italy); Hassoun, Jusef, E-mail: jusef.hassoun@unife.it [Università di Ferrara, Dipartimento di Scienze Chimiche e Farmaceutiche, Via Fossato di Mortara 17, Ferrara (Italy)

2016-09-01

Three dimensional, flower-like hierarchical porous carbon (FPC) and its CO{sub 2}-activation (AFPC) are reported as sulfur-hosting matrixes in Li/S battery. The composites are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherms as well as by galvanostatic cycling and electrochemical impedance spectroscopy (EIS) in lithium-cell. Both samples show well defined micrometric morphology and a sulfur content as high as 66% expected to reflect into rather high practical energy density of the electrode in lithium-sulfur battery. The lithium sulfur cell using the FPC-S composite exhibits at 25 °C a moderate cycling stability with delivered capacity ranging from 1000 to about 610 mAh g{sup −1} upon 50 cycles at 100 mA g{sup −1}. The AFPC-S composite reveals increased cycling stability and delivers a capacity ranging from 1000 to 680 mAh g{sup −1}. Improved capacity is achieved by slightly increasing the temperature, as demonstrated by cycling the FPC-S at 35 °C using a current as high as 500 mA g{sup −1}. The excellent rate capability of the electrode is associated to the carbon texture and morphology that significantly lower the cell resistance, as indeed demonstrated by EIS measurement upon cycling. - Highlights: • Sulfur electrode basing on activated, flower-like hierarchical porous carbon is reported. • Defined micrometric morphology and a sulfur content as high as 66% are obtained. • Lithium sulfur cell using the composite exhibits remarkable performances. • A specific capacity of about 1000 mAh g{sup −1} is obtained at high current rate. • The resulting Li/S battery has relevant energy content.

Macroporous Activated Carbon Derived from Rapeseed Shell for Lithium–Sulfur Batteries

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Mingbo Zheng

2017-10-01

Full Text Available Lithium–sulfur batteries have drawn considerable attention because of their extremely high energy density. Activated carbon (AC is an ideal matrix for sulfur because of its high specific surface area, large pore volume, small-size nanopores, and simple preparation. In this work, through KOH activation, AC materials with different porous structure parameters were prepared using waste rapeseed shells as precursors. Effects of KOH amount, activated temperature, and activated time on pore structure parameters of ACs were studied. AC sample with optimal pore structure parameters was investigated as sulfur host materials. Applied in lithium–sulfur batteries, the AC/S composite (60 wt % sulfur exhibited a high specific capacity of 1065 mAh g−1 at 200 mA g−1 and a good capacity retention of 49% after 1000 cycles at 1600 mA g−1. The key factor for good cycling stability involves the restraining effect of small-sized nanopores of the AC framework on the diffusion of polysulfides to bulk electrolyte and the loss of the active material sulfur. Results demonstrated that AC materials derived from rapeseed shells are promising materials for sulfur loading.

Some information needs for air quality modeling. [Environmental effects of sulfur compounds

Energy Technology Data Exchange (ETDEWEB)

Hill, F B

1975-09-01

The following topics were considered at the workshop: perturbation of the natural sulfur cycle by human activity; ecosystem responses to a given environmental dose of sulfur compounds; movement of sulfur compounds within the atmosphere; air quality models; contribution of biogenic sulfur compounds to atmospheric burden of sulfur; production of acid rain from sulfur dioxide; meteorological processes; and rates of oxidation of SO/sub 2/ via direct photo-oxidation, oxidation resulting from photo-induced free radical chemistry, and catalytic oxidation in cloud droplets and on dry particles. (HLW)

A model-based insight into the coupling of nitrogen and sulfur cycles in a coastal upwelling system

DEFF Research Database (Denmark)

Muchamad, Al Azhar; Canfield, Donald Eugene; Fennel, Katja

2014-01-01

is masked, however, by rapid sulfide oxidation, most likely through nitrate reduction. Thus, the cryptic sulfur cycle links with the nitrogen cycle in OMZ settings. Here, we model the physical-chemical water column structure and the observed process rates as driven by formation and sinking of organic...... heterotrophic nitrate reduction and sulfate reduction are responsible for 47% and 36%, respectively, of organic remineralization in a 150 m deep zone below mixed layer. Anammox contributes to 61% of the fixed nitrogen lost to N2 gas, while the rest of the loss is through canonical denitrification...... as a combination of organic matter oxidation by nitrite reduction and sulfide-driven denitrification. Mineralization coupled to heterotrophic nitrate reduction supplies ~48% of the ammonium required by anammox. Due to active sulfate reduction, model results suggest that sulfide-driven denitrification contributes...

Sulfur bacteria in wastewater stabilization ponds periodically affected by the ‘red-water’ phenomenon

NARCIS (Netherlands)

Belila, A.; Abbas, B.; Fazaa, I.; Saidi, N.; Snoussi, M.; Hassen, A.; Muyzer, G.

2012-01-01

Several wastewater stabilization ponds (WSP) in Tunisia suffer periodically from the ‘red-water’ phenomenon due to blooming of purple sulfur bacteria, indicating that sulfur cycle is one of the main element cycles in these ponds. In this study, we investigated the microbial diversity of the El

Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

Science.gov (United States)

Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

2016-01-13

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Organic sulfur metabolisms in hydrothermal environments.

Science.gov (United States)

Rogers, Karyn L; Schulte, Mitchell D

2012-07-01

Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. While biotic and abiotic cycling of organic sulfur compounds has been well documented in low-temperature anaerobic environments, cycling of organic sulfur in hydrothermal environments has received less attention. Recently published thermodynamic data have been used to estimate aqueous alkyl thiol and sulfide activities in deep-sea hydrothermal systems. Here we use geochemical mixing models to predict fluid compositions that result from mixing end-member hydrothermal fluid from the East Pacific Rise with bottom seawater. These fluid compositions are combined with estimates of methanethiol and dimethylsulfide activities to evaluate energy yields for potential organic sulfur-based metabolisms under hydrothermal conditions. Aerobic respiration has the highest energy yields (over -240 kJ/mol e⁻) at lower temperature; however, oxygen is unlikely to persist at high temperatures, restricting aerobic respiration to mesophilic communities. Nitrite reduction to N₂ has the highest energy yields at higher temperatures (greater than ∼40 °C). Nitrate and nitrite reduction to ammonium also yield significant energy (up to -70 kJ/mol e⁻). Much lower, but still feasible energy yields are calculated for sulfate reduction, disproportionation, and reduction with H₂. Organic compound family and the activity of methanethiol and dimethylsulfide were less important than metabolic strategy in determining overall energy yields. All metabolic strategies considered were exergonic within some portion of the mixing regime suggesting that organic sulfur-based metabolisms may be prevalent within deep-sea hydrothermal vent microbial communities. © 2012 Blackwell Publishing Ltd.

Three-Dimensionally Hierarchical Graphene Based Aerogel Encapsulated Sulfur as Cathode for Lithium/Sulfur Batteries

Science.gov (United States)

Li, Haipeng; Sun, Liancheng; Wang, Zhuo; Zhang, Yongguang; Tan, Taizhe; Wang, Gongkai

2018-01-01

A simple and effective method was developed to obtain the electrode for lithium/sulfur (Li/S) batteries with high specific capacity and cycling durability via adopting an interconnected sulfur/activated carbon/graphene (reduced graphene oxide) aerogel (S/AC/GA) cathode architecture. The AC/GA composite with a well-defined interconnected conductive network was prepared by a reduction-induced self-assembly process, which allows for obtaining compact and porous structures. During this process, reduced graphene oxide (RGO) was formed, and due to the presence of oxygen-containing functional groups on its surface, it not only improves the electronic conductivity of the cathode but also effectively inhibits the polysulfides dissolution and shuttle. The introduced activated carbon allowed for lateral and vertical connection between individual graphene sheets, completing the formation of a stable three-dimensionally (3D) interconnected graphene framework. Moreover, a high specific surface area and 3D interconnected porous structure efficiently hosts a higher amount of active sulfur material, about 65 wt %. The designed S/AC/GA composite electrodes deliver an initial capacity of 1159 mAh g−1 at 0.1 C and can retain a capacity of 765 mAh g−1 after 100 cycles in potential range from 1 V to 3 V. PMID:29373525

Three-Dimensionally Hierarchical Graphene Based Aerogel Encapsulated Sulfur as Cathode for Lithium/Sulfur Batteries

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Haipeng Li

2018-01-01

Full Text Available A simple and effective method was developed to obtain the electrode for lithium/sulfur (Li/S batteries with high specific capacity and cycling durability via adopting an interconnected sulfur/activated carbon/graphene (reduced graphene oxide aerogel (S/AC/GA cathode architecture. The AC/GA composite with a well-defined interconnected conductive network was prepared by a reduction-induced self-assembly process, which allows for obtaining compact and porous structures. During this process, reduced graphene oxide (RGO was formed, and due to the presence of oxygen-containing functional groups on its surface, it not only improves the electronic conductivity of the cathode but also effectively inhibits the polysulfides dissolution and shuttle. The introduced activated carbon allowed for lateral and vertical connection between individual graphene sheets, completing the formation of a stable three-dimensionally (3D interconnected graphene framework. Moreover, a high specific surface area and 3D interconnected porous structure efficiently hosts a higher amount of active sulfur material, about 65 wt %. The designed S/AC/GA composite electrodes deliver an initial capacity of 1159 mAh g−1 at 0.1 C and can retain a capacity of 765 mAh g−1 after 100 cycles in potential range from 1 V to 3 V.

Studies on radiolysis of amino acids, (3)

International Nuclear Information System (INIS)

Oku, Tadatake

1978-01-01

For the purpose of investigating the radiolysis of amino acids and the safeness to radiation, the radiolytic mechanism and radio-sensitivity of sulfur-containing amino acids in aqueous solution in the presence of air or in the atmosphere of nitrogen were studied. Aqueous solutions of L-methionine, cysteine (both 1mM) and L-cystine (0.3mM) were irradiated with γ-ray of 60 Co at the dose of 4.2 - 2,640 x 10 3 rad. The amino acids and the radiolytic products were determined with an amino acid analyzer. The volatile sulfur compounds formed from γ-irradiated methionine were estimated by a flame photometric detector-gas chromatograph. From the results obtained, G values of the radiolysis of sulfur-containing amino acids and the products were calculated, and the radiolytic mechanisms of methionine, cysteine and cystine were proposed. The radio-sensitivity of sulfur-containing amino acids was shown as follows: cysteine (C3-SH) > methionine (C5, -SCH 3 ) > cystine (C 6 , -S-S-). Off-flavor development from γ-irradiated methionine when oxidizing agent was added was less than that when reducing agent was added. (Kobatake, H.)

Functional Differentiation of Three Pores for Effective Sulfur Confinement in Li-S Battery.

Science.gov (United States)

Wang, Qian; Yang, Minghui; Wang, Zhen-Bo; Li, Chao; Gu, Da-Ming

2018-03-01

Shuttle effect of the dissolved intermediates is regarded as the primary cause that leads to fast capacity degradation of Li-S battery. Herein, a microporous carbon-coated sulfur composite with novel rambutan shape (R-S@MPC) is synthesized from microporous carbon-coated rambutan-like zinc sulfide (R-ZnS@MPC), via an in situ oxidation process. The R-ZnS is employed as both template and sulfur precursor. The carbon frame of R-S@MPC composite possesses three kinds of pores that are distinctly separated from each other in space and are endowed with the exclusive functions. The central macropore serves as buffer pool to accommodate the dissolved lithium polysulfides (LPSs) and volumetric variation during cycling. The marginal straight-through mesoporous, connected with the central macropore, takes the responsibility of sulfur storage. The micropores, evenly distributed in the outer carbon shell of the as-synthesized R-S@MPC, enable the blockage of LPSs. These pores are expected to perform their respective single function, and collaborate synergistically to suppress the sulfur loss. Therefore, it delivers an outstanding cycling stability, decay rate of 0.013% cycle -1 after 500 cycles at 1 C, when the sulfur loading is kept at 4 mg cm -2 . © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation on thiosulfate-involved organics and nitrogen removal by a sulfur cycle-based biological wastewater treatment process.

Science.gov (United States)

Qian, Jin; Lu, Hui; Cui, Yanxiang; Wei, Li; Liu, Rulong; Chen, Guang-Hao

2015-02-01

Thiosulfate, as an intermediate of biological sulfate/sulfite reduction, can significantly improve nitrogen removal potential in a biological sulfur cycle-based process, namely the Sulfate reduction-Autotrophic denitrification-Nitrification Integrated (SANI(®)) process. However, the related thiosulfate bio-activities coupled with organics and nitrogen removal in wastewater treatment lacked detailed examinations and reports. In this study, S2O3(2-) transformation during biological SO4(2-)/SO3(2-) co-reduction coupled with organics removal as well as S2O3(2-) oxidation coupled with chemolithotrophic denitrification were extensively evaluated under different experimental conditions. Thiosulfate is produced from the co-reduction of sulfate and sulfite through biological pathway at an optimum pH of 7.5 for organics removal. And the produced S2O3(2-) may disproportionate to sulfide and sulfate during both biological S2O3(2-) reduction and oxidation most possibly carried out by Desulfovibrio-like species. Dosing the same amount of nitrate, pH was found to be the more direct factor influencing the denitritation activity than free nitrous acid (FNA) and the optimal pH for denitratation (7.0) and denitritation (8.0) activities were different. Spiking organics significantly improved both denitratation and denitritation activities while minimizing sulfide inhibition of NO3(-) reduction during thiosulfate-based denitrification. These findings in this study can improve the understanding of mechanisms of thiosulfate on organics and nitrogen removal in biological sulfur cycle-based wastewater treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Preparation of sulfur/multiple pore size porous carbon composite via gas-phase loading method for lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, Long-Yan; Chen, Yan-Xiao; Guo, Xiao-Dong; Zhong, Ben-He; Zhong, Yan-Jun

2014-01-01

A porous carbon with multiple pore size distribution was synthesized, and regarded as a carrier to obtain the sulfur/carbon (S/C) composite via a gas-phase loading method. We proposed this novel gas-phase loading method by using a specially designed fluid-bed reactor to encapsulate and sequester gas-phase sulfur molecules into the porous carbon in current study. The nitrogen Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) characterizations were investigated on both the porous carbon and the sulfur/carbon composite. The results show that the gas-phase loading method contributes to the combination of sulfur molecules and matrix porous carbon. Furthermore, the sulfur/multiple pore size distribution carbon composite based on the gas-phase loading method demonstrate an excellent electrochemical property. The initial specific discharge capacity is 795.0 mAh g −1 at 800 mA g −1 , with a capacity retention of 86.3% after 100 cycles

Dominance of sulfur-fueled iron oxide reduction in low-sulfate freshwater sediments.

Science.gov (United States)

Hansel, Colleen M; Lentini, Chris J; Tang, Yuanzhi; Johnston, David T; Wankel, Scott D; Jardine, Philip M

2015-11-01

A central tenant in microbial biogeochemistry is that microbial metabolisms follow a predictable sequence of terminal electron acceptors based on the energetic yield for the reaction. It is thereby oftentimes assumed that microbial respiration of ferric iron outcompetes sulfate in all but high-sulfate systems, and thus sulfide has little influence on freshwater or terrestrial iron cycling. Observations of sulfate reduction in low-sulfate environments have been attributed to the presumed presence of highly crystalline iron oxides allowing sulfate reduction to be more energetically favored. Here we identified the iron-reducing processes under low-sulfate conditions within columns containing freshwater sediments amended with structurally diverse iron oxides and fermentation products that fuel anaerobic respiration. We show that despite low sulfate concentrations and regardless of iron oxide substrate (ferrihydrite, Al-ferrihydrite, goethite, hematite), sulfidization was a dominant pathway in iron reduction. This process was mediated by (re)cycling of sulfur upon reaction of sulfide and iron oxides to support continued sulfur-based respiration--a cryptic sulfur cycle involving generation and consumption of sulfur intermediates. Although canonical iron respiration was not observed in the sediments amended with the more crystalline iron oxides, iron respiration did become dominant in the presence of ferrihydrite once sulfate was consumed. Thus, despite more favorable energetics, ferrihydrite reduction did not precede sulfate reduction and instead an inverse redox zonation was observed. These findings indicate that sulfur (re)cycling is a dominant force in iron cycling even in low-sulfate systems and in a manner difficult to predict using the classical thermodynamic ladder.

Changes in porosity of graphite caused by radiolytic gasification by carbon dioxide

International Nuclear Information System (INIS)

Murdie, Neil; Edwards, I.A.S.; Marsh, Harry

1986-01-01

Methods have been developed to study porosity in nuclear grade graphite. The changes induced during the radiolytic gasification of graphite in carbon dioxide have been investigated. Porosity in radiolytically gasified graphite (0-22.8% wt. loss) was examined by optical microscopy and scanning electron microscopy (SEM). Each sample was vacuum impregnated with a slow-setting resin containing a fluorescent dye. Optical microscopy was used to study pores >2 μm 2 c.s.a. A semi-automatic image analysis system linked to the optical microscope enabled pore parameter data including cross-sectional areas, perimeters, Feret's diameters and shape factors, to be collected. The results showed that radiolytic gasification produced a large increase in the number of pores 2 c.s.a. New open pores 2 c.s.a. were developed by gasification of existing open porosity into the closed porosity ( 2 c.s.a.) within the binder-coke. Open pores, 2-100 μm 2 c.s.a., which were gasified within the coarse-grained mosaics of the binder-coke. In the gasification process to 22.8% wt. loss, the apparent open pore volume increased from 6.6 to 33.8% and the apparent closed pore volumes decreased from approx. 3% to 0.1%. The increase in apparent open porosity from 6.6% (virgin) to 33.8% resulted from gasification within original open porosity and by the opening and development of closed porosity. There was no evidence for creation of porosity from within the 'bulk' graphite, it being developed from existing fine porosity. The structure of pores > 100 μm 2 c.s.a. showed no change because of the inhibition of oxidation by deposition of carbonaceous species from the CH 4 inhibitor. Such species diffuse to the pore wall and are sacrificially oxidised. (author)

The complex reaction sequence of the thermal and radiolytic degradation of polyvinyl chloride

International Nuclear Information System (INIS)

Reichert, W.

1983-03-01

The degradation of PVC-foils was been tested by thermal and radiolytic stress in N 2 - and O 2 -atmosphere. Additionally was determined the influence of plasticizers, Fe-, Zn- and Cu-stearates and other additives, which partially are known as stabilizators. Complex mechanisms of degradation are proposed, which were deduced from the HCl-elimination, consumption of oxygen and the shift of the molmass by the scission and crosslinking of main chains both for PVC as combination of PVC with additives. The mechanism corresponds to other known experimental results, too. It was shown, that the radiolytical degradation caused by radicals, which initiate a radical chain mechanism, if the temperature is higher than the glass temperature (Tg). The thermical degradation in a N 2 -atmosphere was explained by an ionic complex mechanism. At the presence of oxygen the ionic mechanism was superimposed by a radical chain mechanism following the oxidation of polyene structures. (author)

MicroRNA-210 regulates mitochondrial free radical response to hypoxia and krebs cycle in cancer cells by targeting iron sulfur cluster protein ISCU.

Directory of Open Access Journals (Sweden)

Elena Favaro

2010-04-01

Full Text Available Hypoxia in cancers results in the upregulation of hypoxia inducible factor 1 (HIF-1 and a microRNA, hsa-miR-210 (miR-210 which is associated with a poor prognosis.In human cancer cell lines and tumours, we found that miR-210 targets the mitochondrial iron sulfur scaffold protein ISCU, required for assembly of iron-sulfur clusters, cofactors for key enzymes involved in the Krebs cycle, electron transport, and iron metabolism. Down regulation of ISCU was the major cause of induction of reactive oxygen species (ROS in hypoxia. ISCU suppression reduced mitochondrial complex 1 activity and aconitase activity, caused a shift to glycolysis in normoxia and enhanced cell survival. Cancers with low ISCU had a worse prognosis.Induction of these major hallmarks of cancer show that a single microRNA, miR-210, mediates a new mechanism of adaptation to hypoxia, by regulating mitochondrial function via iron-sulfur cluster metabolism and free radical generation.

Biogeochemical cycling of arsenic in coastal salinized aquifers: Evidence from sulfur isotope study

Energy Technology Data Exchange (ETDEWEB)

Kao, Yu-Hsuan [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Sheng-Wei [Agricultural Engineering Research Center, Chungli 320, Taiwan, ROC (China); Liu, Chen-Wuing, E-mail: lcw@gwater.agec.ntu.edu.tw [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Pei-Ling [Institute of Oceanography, National Taiwan University, Taipei 106, Taiwan, ROC (China); Wang, Chung-Ho [Institute of Earth Sciences, Academia Sinica, Taipei 115, Taiwan, ROC (China); Maji, Sanjoy Kumar [Department of Bioenvironmental Systems Engineering, National Taiwan University, Taipei 106, Taiwan, ROC (China)

2011-10-15

Arsenic (As) contamination of groundwater, accompanied by critical salinization, occurs in the southwestern coastal area of Taiwan. Statistical analyses and geochemical calculations indicate that a possible source of aqueous arsenic is the reductive dissolution of As-bearing iron oxyhydroxides. There are few reports of the influence of sulfate-sulfide redox cycling on arsenic mobility in brackish groundwater. We evaluated the contribution of sulfate reduction and sulfide re-oxidation on As enrichment using {delta}{sup 34}S{sub [SO{sub 4]}} and {delta}{sup 18}O{sub [SO{sub 4]}} sulfur isotopic analyses of groundwater. Fifty-three groundwater samples were divided into groups of high-As content and salinized (Type A), low-As and non-salinized (Type B), and high-As and non-salinized (Type C) groundwaters, based on hydro-geochemical analysis. The relatively high enrichment of {sup 34}S{sub [SO{sub 4]}} and {sup 18}O{sub [SO{sub 4]}} present in Type A, caused by microbial-mediated reduction of sulfate, and high {sup 18}O enrichment factor ({epsilon}{sub [SO{sub 4-H{sub 2O]}}}), suggests that sulfur disproportionation is an important process during the reductive dissolution of As-containing iron oxyhydroxides. Limited co-precipitation of ion-sulfide increased the rate of As liberation under anaerobic conditions. In contrast to this, Type B and Type C groundwater samples showed high {delta}{sup 18}O{sub [SO{sub 4]}} and low {delta}{sup 34}S{sub [SO{sub 4]}} values under mildly reducing conditions. Base on {sup 18}O mass balance calculations, the oxide sources of sulfate are from infiltrated atmospheric O{sub 2}, caused by additional recharge of dissolved oxygen and sulfide re-oxidation. The anthropogenic influence of extensive pumping also promotes atmospheric oxygen entry into aquifers, altering redox conditions, and increasing the rate of As release into groundwater. - Highlights: {yields} Seawater intrusion and elevated As are the main issues of groundwater in Taiwan

Nitrogen-doped graphene nanosheets/sulfur composite as lithium–sulfur batteries cathode

Energy Technology Data Exchange (ETDEWEB)

Hao, Yong [Department of Mechanical and Materials Engineering, Florida International University, 10555 W. Flagler Street, Miami, FL 33174 (United States); Li, Xifei; Sun, Xueliang [Nanomaterials and Energy Lab, Department of Mechanical and Materials Engineering, Western University, London, Ontario N6A 5B9 (Canada); Energy and Materials Engineering Centre, College of Physics and Materials Science, Tianjin Normal University, Tianjin 300387 (China); Wang, Chunlei, E-mail: wangc@fiu.edu [Department of Mechanical and Materials Engineering, Florida International University, 10555 W. Flagler Street, Miami, FL 33174 (United States)

2016-11-15

Highlights: • NGNSs are synthesized with amino-N and pyridine-N-oxide groups. • NGNSs provide a matrix with high surface area and conductivity. • N groups facilitate immobilization of polysulfides for Li–S batteries. - Abstract: Lithium–sulfur batteries have been receiving unprecedented attentions in recent years due to their exceptional high theoretical capacity and energy density, low cost and environmental friendliness. Yet their practical applications are still hindered by short cycle life, low efficiency and poor conductivity which are mainly caused by the insulating nature of sulfur and dissolution of polysulfides. Here, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs was employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g{sup −1} and a reversible capacity of 319.3 mAh g{sup −1} at 0.1 C with good recoverable rate capability.

Sulfur Cycling in an Iron Oxide-Dominated, Dynamic Marine Depositional System: The Argentine Continental Margin

Directory of Open Access Journals (Sweden)

Natascha Riedinger

2017-05-01

Full Text Available The interplay between sediment deposition patterns, organic matter type and the quantity and quality of reactive mineral phases determines the accumulation, speciation, and isotope composition of pore water and solid phase sulfur constituents in marine sediments. Here, we present the sulfur geochemistry of siliciclastic sediments from two sites along the Argentine continental slope—a system characterized by dynamic deposition and reworking, which result in non-steady state conditions. The two investigated sites have different depositional histories but have in common that reactive iron phases are abundant and that organic matter is refractory—conditions that result in low organoclastic sulfate reduction rates (SRR. Deposition of reworked, isotopically light pyrite and sulfurized organic matter appear to be important contributors to the sulfur inventory, with only minor addition of pyrite from organoclastic sulfate reduction above the sulfate-methane transition (SMT. Pore-water sulfide is limited to a narrow zone at the SMT. The core of that zone is dominated by pyrite accumulation. Iron monosulfide and elemental sulfur accumulate above and below this zone. Iron monosulfide precipitation is driven by the reaction of low amounts of hydrogen sulfide with ferrous iron and is in competition with the oxidation of sulfide by iron (oxyhydroxides to form elemental sulfur. The intervals marked by precipitation of intermediate sulfur phases at the margin of the zone with free sulfide are bordered by two distinct peaks in total organic sulfur (TOS. Organic matter sulfurization appears to precede pyrite formation in the iron-dominated margins of the sulfide zone, potentially linked to the presence of polysulfides formed by reaction between dissolved sulfide and elemental sulfur. Thus, SMTs can be hotspots for organic matter sulfurization in sulfide-limited, reactive iron-rich marine sedimentary systems. Furthermore, existence of elemental sulfur and iron

Oxidation of inorganic sulfur compounds in acidophilic prokaryotes

Energy Technology Data Exchange (ETDEWEB)

Rohwerder, T.; Sand, W. [Universitaet Duisburg-Essen, Biofilm Centre, Aquatic Biotechnology, Duisburg (Germany)

2007-07-15

The oxidation of reduced inorganic sulfur compounds to sulfuric acid is of great importance for biohydrometallurgical technologies as well as the formation of acidic (below pH 3) and often heavy metal-contaminated environments. The use of elemental sulfur as an electron donor is the predominant energy-yielding process in acidic natural sulfur-rich biotopes but also at mining sites containing sulfidic ores. Contrary to its significant role in the global sulfur cycle and its biotechnological importance, the microbial fundamentals of acidophilic sulfur oxidation are only incompletely understood. Besides giving an overview of sulfur-oxidizing acidophiles, this review describes the so far known enzymatic reactions related to elemental sulfur oxidation in acidophilic bacteria and archaea. Although generally similar reactions are employed in both prokaryotic groups, the stoichiometry of the key enzymes is different. Bacteria oxidize elemental sulfur by a sulfur dioxygenase to sulfite whereas in archaea, a sulfur oxygenase reductase is used forming equal amounts of sulfide and sulfite. In both cases, the activation mechanism of elemental sulfur is not known but highly reactive linear sulfur forms are assumed to be the actual substrate. Inhibition as well as promotion of these biochemical steps is highly relevant in bioleaching operations. An efficient oxidation can prevent the formation of passivating sulfur layers. In other cases, a specific inhibition of sulfur biooxidation may be beneficial for reducing cooling and neutralization costs. In conclusion, the demand for a better knowledge of the biochemistry of sulfur-oxidizing acidophiles is underlined. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

A multi-electron redox mediator for redox-targeting lithium-sulfur flow batteries

Science.gov (United States)

Li, Guochun; Yang, Liuqing; Jiang, Xi; Zhang, Tianran; Lin, Haibin; Yao, Qiaofeng; Lee, Jim Yang

2018-02-01

The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g-1DMTS (1.66 A h L-1), which decreases to 59 mAh g-1DMTS (0.75 A h L-1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g-1sulfur (3.83 A h L-1), for which 1030.9 mAh g-1sulfur (3.23 A h L-1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.

Long-Life Lithium-Sulfur Battery Derived from Nori-Based Nitrogen and Oxygen Dual-Doped 3D Hierarchical Biochar.

Science.gov (United States)

Wu, Xian; Fan, Lishuang; Wang, Maoxu; Cheng, Junhan; Wu, Hexian; Guan, Bin; Zhang, Naiqing; Sun, Kening

2017-06-07

Due to restrictions on the low conductivity of sulfur and soluble polysulfides during discharge, lithium sulfur batteries are unsuitable for further large scale applications. The current carbon based cathodes suffer from poor cycle stability and high cost. Recently, heteroatom doped carbons have been considered as a settlement to enhance the performance of lithium sulfur batteries. With this strategy, we report the low cost activated nori based N,O-doped 3D hierarchical carbon material (ANC) as a sulfur host. The N,O dual-doped ANC reveals an elevated electrochemical performance, which exhibits not only a good rate performance over 5 C, but also a high sulfur content of 81.2%. Further importantly, the ANC represents an excellent cycling stability, the cathode reserves a capacity of 618 mAh/g at 2 C after 1000 cycles, which shows a 0.022% capacity decay per cycle.

A model for void-induced back reaction between radiolytic products in NaCl

NARCIS (Netherlands)

Turkin, A.A.; Dubinko, V.I.; Vainshtein, D.I.; Hartog, H.W. den

A kinetic model is formulated for the chemical reaction between radiolytic sodium colloids and gas bubbles, which are brought into contact with each other during the exposure to ionising radiation by the growing voids. The reaction starts with the evaporation of Na atoms into the void due to the

Gas chromatographic measurement of the radiolytic products of irradiated pork

International Nuclear Information System (INIS)

Zhou Yingcai; Wang Xiuying; Xu Peishu; Yuan Bihuai

1988-01-01

The radiolytic products of irradiated pork were isolated, analyzed and identified by the techniques of vacuum distillation, GC-MS. The higher boiling point compounds in fat were collected by cold-finger and its lower boiling point compounds were recovered on a short precolumn packed with alumina, and the volatiles of lean pork were collected on a short column packed with TCEP/Chromosovb. Some experimental conditions were studied. 49 compounds were identified. These compounds include hydrocarbons and sulphides etc. (author)

Modeling and observational constraints on the sulfur cycle in the marine troposphere: a focus on reactive halogens and multiphase chemistry

Science.gov (United States)

Chen, Q.; Breider, T.; Schmidt, J.; Sherwen, T.; Evans, M. J.; Xie, Z.; Quinn, P.; Bates, T. S.; Alexander, B.

2017-12-01

The radiative forcing from marine boundary layer clouds is still highly uncertain, which partly stems from our poor understanding of cloud condensation nuclei (CCN) formation. The oxidation of dimethyl sulfide (DMS) and subsequent chemical evolution of its products (e.g. DMSO) are key processes in CCN formation, but are generally very simplified in large-scale models. Recent research has pointed out the importance of reactive halogens (e.g. BrO and Cl) and multiphase chemistry in the tropospheric sulfur cycle. In this study, we implement a series of sulfur oxidation mechanisms into the GEOS-Chem global chemical transport model, involving both gas-phase and multiphase oxidation of DMS, DMSO, MSIA and MSA, to improve our understanding of the sulfur cycle in the marine troposphere. DMS observations from six locations around the globe and MSA/nssSO42- ratio observations from two ship cruises covering a wide range of latitudes and longitudes are used to assess the model. Preliminary results reveal the important role of BrO for DMS oxidation at high latitudes (up to 50% over Southern Ocean). Oxidation of DMS by Cl radicals is small in the model (within 10% in the marine troposphere), probably due to an underrepresentation of Cl sources. Multiphase chemistry (e.g. oxidation by OH and O3 in cloud droplets) is not important for DMS oxidation but is critical for DMSO oxidation and MSA production and removal. In our model, about half of the DMSO is oxidized in clouds, leading to the formation of MSIA, which is further oxidized to form MSA. Overall, with the addition of reactive halogens and multiphase chemistry, the model is able to better reproduce observations of seasonal variations of DMS and MSA/nssSO42- ratios.

A dynamic study on the sulfuric acid distillation column for VHTR-assisted hydrogen production systems

International Nuclear Information System (INIS)

Youngjoon, Shin; Heesung, Shin; Jiwoon, Jang; Kiyoung, Lee; Jonghwa, Chang

2007-01-01

The sulfur-iodine (SI) cycle and the Westinghouse sulfur hybrid cycle coupled to a very high temperature gas-cooled reactor (VHTR) are well known as a feasible technology to produce hydrogen. The concentration of the sulfuric acid solution and its decomposition are essential parts in both cycles. In this paper, the thermophysical properties which are the boiling point, latent heat, and the partial pressures of water, sulfuric acid, and sulfur trioxide have been correlated as a function of the sulfuric acid concentration for the H 2 SO 4 and H 2 O binary chemical system, based on the data in Perry's chemical engineers' hand-book and other experimental data. By using these thermophysical correlations, a dynamic analysis of a sulfuric acid distillation column has been performed to establish the column design requirements and its optimum operation condition. From the results of the dynamic analysis, an optimized column system is anticipated for a distillation column equipped with 2 ideal plates and a second plate feeding system from the bottom plate. The effects of the hold-up of the re-boiler and the reflux ratio from the top product stream on the elapsing time when the system progresses toward a steady state have been analyzed. (authors)

Influence of radiolytic degradation products from organic phase

International Nuclear Information System (INIS)

Azevedo, H.L.P. de.

1980-01-01

The influence of primary and secondary degradation products from TBP - dodecane on zirconium extraction is studied. The presence of radiolytical degradation at organic phase, in systems of initial concentration of HNO 3 1 and 4M, and absorbed γ radiation doses from 0,5 to 4,5 Wh/l, lead to an increase of zirconium extraction, being the HDBP the main product of degradation responsable by this effect. The influence of secondary degradation products is significative in systems of HNO 3 1M initial concentration. The formation of precipitator in extractions of Zr in HNO 3 1M with irradiated TBP-dodecane was observed. (M.C.K.) [pt

Investigation of the hydrolytic and radiolytic degradation of HEH[EHP

International Nuclear Information System (INIS)

Peterman, Dean Richard; McDowell, Rocklan George; Zarzana, Christopher Andrew; Johnson, Kristyn Marie; Rowe, Salene Marie; Groenewold, Gary Steven

2016-01-01

The extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) is a component used in both the Advanced TALSPEAK and ALSEP solvent extraction processes. The most likely compound formed via hydrolytic or radiolytic degradation of HEH[EHP] would be the phosphonic acid 2-ethylhexylphosphonic acid (H2EHP) that is formed by cleavage of the P-O-R bond. Thus far, attempts to detect H2EHP by gas chromatography or mass spectrometry have not been successful. The inability to detect this proposed degradation product in analytical samples is likely due to inadequate analysis techniques, lack of H2EHP production, further decomposition of H2EHP forming products not detectable by the employed analytical techniques, or a combination of all of the above scenarios. In order to address this problem, commercially available alkylphosphonic acids were acquired and used as surrogates for H2EHP in the gas chromatography and mass spectrometry analysis of samples. Once the ability to detect alkylphosphonic acid compounds was confirmed, these analytical techniques were used to confirm the production of H2EHP in samples of HEH[EHP] exposed to nitric acid and nitric acid plus gamma radiation. This report provides a brief summary of results and serves as documentation of the completion the level four milestone M4FT-16IN030102025 “Investigate the hydrolytic and radiolytic degradation of HEH[EHP]”.

Anode Improvement in Rechargeable Lithium-Sulfur Batteries.

Science.gov (United States)

Tao, Tao; Lu, Shengguo; Fan, Ye; Lei, Weiwei; Huang, Shaoming; Chen, Ying

2017-12-01

Owing to their theoretical energy density of 2600 Wh kg -1 , lithium-sulfur batteries represent a promising future energy storage device to power electric vehicles. However, the practical applications of lithium-sulfur batteries suffer from poor cycle life and low Coulombic efficiency, which is attributed, in part, to the polysulfide shuttle and Li dendrite formation. Suppressing Li dendrite growth, blocking the unfavorable reaction between soluble polysulfides and Li, and improving the safety of Li-S batteries have become very important for the development of high-performance lithium sulfur batteries. A comprehensive review of various strategies is presented for enhancing the stability of the anode of lithium sulfur batteries, including inserting an interlayer, modifying the separator and electrolytes, employing artificial protection layers, and alternative anodes to replace the Li metal anode. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfur K-edge absorption spectroscopy on selected biological systems

International Nuclear Information System (INIS)

Lichtenberg, Henning

2008-07-01

Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H 2 S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

A MnO2/Graphene Oxide/Multi-Walled Carbon Nanotubes-Sulfur Composite with Dual-Efficient Polysulfide Adsorption for Improving Lithium-Sulfur Batteries.

Science.gov (United States)

Li, Yong; Ye, Daixin; Liu, Wen; Shi, Bin; Guo, Rui; Zhao, Hongbin; Pei, Haijuan; Xu, Jiaqiang; Xie, Jingying

2016-10-26

Lithium-sulfur batteries can potentially be used as a chemical power source because of their high energy density. However, the sulfur cathode has several shortcomings, including fast capacity attenuation, poor electrochemical activity, and low Coulombic efficiency. Herein, multi-walled carbon nanotubes (CNTs), graphene oxide (GO), and manganese dioxide are introduced to the sulfur cathode. A MnO 2 /GO/CNTs-S composite with a unique three-dimensional (3D) architecture was synthesized by a one-pot chemical method and heat treatment approach. In this structure, the innermost CNTs work as a conducting additive and backbone to form a conducting network. The MnO 2 /GO nanosheets anchored on the sidewalls of CNTs have a dual-efficient absorption capability for polysulfide intermediates as well as afford adequate space for sulfur loading. The outmost nanosized sulfur particles are well-distributed on the surface of the MnO 2 /GO nanosheets and provide a short transmission path for Li + and the electrons. The sulfur content in the MnO 2 /GO/CNTs-S composite is as high as 80 wt %, and the as-designed MnO 2 /GO/CNTs-S cathode displays excellent comprehensive performance. The initial specific capacities are up to 1500, 1300, 1150, 1048, and 960 mAh g -1 at discharging rates of 0.05, 0.1, 0.2, 0.5, and 1 C, respectively. Moreover, the composite cathode shows a good cycle performance: the specific capacity remains at 963.5 mAh g -1 at 0.2 C after 100 cycles when the area density of sulfur is 2.8 mg cm -2 .

Chloride-Reinforced Carbon Nanofiber Host as Effective Polysulfide Traps in Lithium-Sulfur Batteries.

Science.gov (United States)

Fan, Lei; Zhuang, Houlong L; Zhang, Kaihang; Cooper, Valentino R; Li, Qi; Lu, Yingying

2016-12-01

Lithium-sulfur (Li-S) battery is one of the most promising alternatives for the current state-of-the-art lithium-ion batteries due to its high theoretical energy density and low production cost from the use of sulfur. However, the commercialization of Li-S batteries has been so far limited to the cyclability and the retention of active sulfur materials. Using co-electrospinning and physical vapor deposition procedures, we created a class of chloride-carbon nanofiber composites, and studied their effectiveness on polysulfides sequestration. By trapping sulfur reduction products in the modified cathode through both chemical and physical confinements, these chloride-coated cathodes are shown to remarkably suppress the polysulfide dissolution and shuttling between lithium and sulfur electrodes. From adsorption experiments and theoretical calculations, it is shown that not only the sulfide-adsorption effect but also the diffusivity in the vicinity of these chlorides materials plays an important role on the reversibility of sulfur-based cathode upon repeated cycles. Balancing the adsorption and diffusion effects of these nonconductive materials could lead to the enhanced cycling performance of an Li-S cell. Electrochemical analyses over hundreds of cycles indicate that cells containing indium chloride-modified carbon nanofiber outperform cells with other halogenated salts, delivering an average specific capacity of above 1200 mAh g -1 at 0.2 C.

Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

International Nuclear Information System (INIS)

Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W.; Wang, L.M.

1997-07-01

Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m -1 , 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions

Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

Energy Technology Data Exchange (ETDEWEB)

Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W. [Argonne National Lab., IL (United States). Chemical Technology Div.; Wang, L.M. [Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Geology

1997-07-01

Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m{sup {minus}1}, 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions.

Porous-Shell Vanadium Nitride Nanobubbles with Ultrahigh Areal Sulfur Loading for High-Capacity and Long-Life Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Yuan, Hao; Zhang, Wenjun; Zhu, Guoyin; Wang, Yanrong; Hu, Yi; Zhao, Peiyang; Chen, Renpeng; Chen, Tao; Liu, Jie; Hu, Zheng; Jin, Zhong

2017-12-13

Lithium-sulfur (Li-S) batteries hold great promise for the applications of high energy density storage. However, the performances of Li-S batteries are restricted by the low electrical conductivity of sulfur and shuttle effect of intermediate polysulfides. Moreover, the areal loading weights of sulfur in previous studies are usually low (around 1-3 mg cm -2 ) and thus cannot fulfill the requirement for practical deployment. Herein, we report that porous-shell vanadium nitride nanobubbles (VN-NBs) can serve as an efficient sulfur host in Li-S batteries, exhibiting remarkable electrochemical performances even with ultrahigh areal sulfur loading weights (5.4-6.8 mg cm -2 ). The large inner space of VN-NBs can afford a high sulfur content and accommodate the volume expansion, and the high electrical conductivity of VN-NBs ensures the effective utilization and fast redox kinetics of polysulfides. Moreover, VN-NBs present strong chemical affinity/adsorption with polysulfides and thus can efficiently suppress the shuttle effect via both capillary confinement and chemical binding, and promote the fast conversion of polysulfides. Benefiting from the above merits, the Li-S batteries based on sulfur-filled VN-NBs cathodes with 5.4 mg cm -2 sulfur exhibit impressively high areal/specific capacity (5.81 mAh cm -2 ), superior rate capability (632 mAh g -1 at 5.0 C), and long cycling stability.

γ-radiolytical degradation of levofloxacin lactate and the activity of the byproducts

International Nuclear Information System (INIS)

Cao Dongmei; Zhang Xiaohong; Guan Yu; Zhu Wei; Zhang HaiQian

2010-01-01

Recently antibiotics wastewater in environment has induced the increment of bacterial resistance. This paper is to investigate the gamma radiolysis of wastewater containing 10 μg/mL levofloxacin lactate (LVF). It has been found that the antibiotic was removed more than 99% with 1 kGy under air while the G-value decreased with the dose increment.Five main degraded products (m/z 346, 330, 318, 302, 274) and the most probable radiolysis pathway were identified by liquid chromatography-mass spectrometry (LC-MS). Compared with the degradation under N 2 , the radiolytical mechanism was suggested.In the active assay, 2 μg/mL was the inhibitory concentration.Compared with the concentration of 4 μg/mL, the minimal inhibitory concentration (MIC), degraded products analysis can be suggested that the byproduct m/z 346 might have the anti-E. coli activity. It has been shown that 3 kGy is the appropriate dose for the radiolytical treatment of LVF. To sum up, the gamma radiation technique is an effective method for decomposing antibiotics, and it is necessary to take the activity of degraded products into consideration. (authors)

Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications.

Science.gov (United States)

Zhang, Bin; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Song, Shuqin; Chen, Guohua; Meng, Yuezhong

2014-08-13

Novel hierarchically porous carbon materials with very high surface areas, large pore volumes and high electron conductivities were prepared from silk cocoon by carbonization with KOH activation. The prepared novel porous carbon-encapsulated sulfur composites were fabricated by a simple melting process and used as cathodes for lithium sulfur batteries. Because of the large surface area and hierarchically porous structure of the carbon material, soluble polysulfide intermediates can be trapped within the cathode and the volume expansion can be alleviated effectively. Moreover, the electron transport properties of the carbon materials can provide an electron conductive network and promote the utilization rate of sulfur in cathode. The prepared carbon-sulfur composite exhibited a high specific capacity and excellent cycle stability. The results show a high initial discharge capacity of 1443 mAh g(-1) and retain 804 mAh g(-1) after 80 discharge/charge cycles at a rate of 0.5 C. A Coulombic efficiency retained up to 92% after 80 cycles. The prepared hierarchically porous carbon materials were proven to be an effective host matrix for sulfur encapsulation to improve the sulfur utilization rate and restrain the dissolution of polysulfides into lithium-sulfur battery electrolytes.

Sulfur metabolism in phototrophic sulfur bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Dahl, Christiane

2008-01-01

Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

Pyrite sulfur isotopes reveal glacial-interglacial environmental changes

Science.gov (United States)

Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina; Revillon, Sidonie; Houghton, Jennifer; Fike, David A.

2017-06-01

The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial-interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial-interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial-interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.

Radiolytic gas production in the alpha particle degradation of plastics

International Nuclear Information System (INIS)

Reed, D.T.; Hoh, J.; Emery, J.; Hobbs, D.

1992-01-01

Net gas generation due to alpha particle irradiation of polyethylene and polyvinyl chloride was investigated. Experiments were performed in an air environment at 30, 60, and 100 degree C. The predominant radiolytic degradation products of polyethylene were hydrogen and carbon dioxide with a wide variety of trace organic species noted. Irradiation of polyvinyl chloride resulted in the formation of HCl in addition to the products observed for polyethylene. For both plastic materials, a strong enhancement of net yields was noted at 100 degree C

MnO2-graphene nanosheets wrapped mesoporous carbon/sulfur composite for lithium-sulfur batteries

Science.gov (United States)

Li, Zhengzheng

2018-02-01

MnO2-graphene nanosheets wrapped mesoporous carbon/sulfur (MGN@MC/S) composite is successfully synthesized derived from metal-organic frameworks and investigated as cathode for lithium-ion batteries. Used as cathode, MGN@MC/S composite possesses electronic conductivity network for redox electron transfer and strong chemical bonding to lithium polysulfides, which enables low capacity loss to be achieved. MGN@MC/S cathodes exhibit high reversible capacity of 1475 mA h g-1 at 0.1 C and an ultra-low capacity fading of 0.042% per cycle at 1 C over 450 cycles.

Status of the INERI sulfur-iodine integrated-loop experiment

International Nuclear Information System (INIS)

Pickard, P.; Carles, Ph.; Buckingham, R.; Russ, B.; Besenbruch, G.

2007-01-01

The Sulfur-Iodine (S-I) thermochemical water-splitting cycle has been studied as a potential source of hydrogen on a large scale. Coupled to a nuclear reactor, an S-I hydrogen plant could efficiently produce hydrogen without greenhouse gas emissions. In the S-I cycle, iodine and sulfur dioxide are combined with water to create two immiscible acid phases - a light sulfuric acid phase, and a heavy hydriodic acid phase. The sulfuric acid phase is decomposed at temperatures near 850 C degrees, and the resulting sulfur dioxide is recycled back into the process. The hydriodic acid in the lower phase is separated from excess water and iodine, and is then decomposed into the product hydrogen and iodine. The water and iodine from these steps are also recycled. In an International Nuclear Energy Research Initiative (INERI) project supported by the US DOE Office of Nuclear Energy, Sandia National Labs (SNL) has teamed with Cea in France, and industrial partner General Atomics (GA) to construct and operate a closed-loop device for demonstration of hydrogen production by the S-I process. Previous work in Japan has demonstrated continuous closed-loop operation of the S-I cycle for up to one week using glass components at atmospheric pressure. This work will aim for operation under process conditions expected at the pilot plant-level and beyond pressures up to 20 bar using engineering materials of construction. Staff at Cea is responsible for the acid-generation step, known as the Bunsen reaction. SNL is handling the sulfuric acid decomposition step, and GA is providing equipment for decomposing hydriodic acid into the product hydrogen. All parties are assembling equipment at the GA site in San Diego, California. Operation of the closed-loop device is expected to commence in the second half of calendar year 2007. This paper will summarize project goals, work done to date, current status, and scheduled future work on the INERI S-I Integrated-Loop Experiment. (authors)

A highly efficient polysulfide mediator for lithium-sulfur batteries

Science.gov (United States)

Liang, Xiao; Hart, Connor; Pang, Quan; Garsuch, Arnd; Weiss, Thomas; Nazar, Linda F.

2015-01-01

The lithium-sulfur battery is receiving intense interest because its theoretical energy density exceeds that of lithium-ion batteries at much lower cost, but practical applications are still hindered by capacity decay caused by the polysulfide shuttle. Here we report a strategy to entrap polysulfides in the cathode that relies on a chemical process, whereby a host—manganese dioxide nanosheets serve as the prototype—reacts with initially formed lithium polysulfides to form surface-bound intermediates. These function as a redox shuttle to catenate and bind ‘higher’ polysulfides, and convert them on reduction to insoluble lithium sulfide via disproportionation. The sulfur/manganese dioxide nanosheet composite with 75 wt% sulfur exhibits a reversible capacity of 1,300 mA h g-1 at moderate rates and a fade rate over 2,000 cycles of 0.036%/cycle, among the best reported to date. We furthermore show that this mechanism extends to graphene oxide and suggest it can be employed more widely.

Simulated effects of sulfur deposition on nutrient cycling in class I wilderness areas

Science.gov (United States)

Katherine J. Elliott; James M. Vose; Jennifer D. Knoepp; Dale W. Johnson; William T. Swank; William Jackson

2008-01-01

As a consequence of human land use, population growth, and industrialization, wilderness and other natural areas can be threatened by air pollution, climate change, and exotic diseases or pests. Air pollution in the form of acidic deposition is comprised of sulfuric and nitric acids and ammonium derived from emissions of sulfur dioxide, nitrogen oxides, and ammonia....

Calculus of radiolytic products generation in water due to alpha radiation. Determination of the spent nuclear fuels matrix alteration rate Determination of velocity of spent fuel matrix

International Nuclear Information System (INIS)

Quinones, J.; Serrano, J.; Diaz Arocas, P.; Rodriguez Almazan, J. L.; Bruno, J.; Cera, E.; Merino, J.; Esteban, J. A.; Martinez-Esparza, A.

2000-01-01

The generation of radiolytic products as a result of alpha radiation in the surface of the spent fuel is a key process in order to understand how the it becomes degraded in repository conditions. The present work has established a radiolytic model based on a set of reactions involving fuel oxidation-dissolution and radiolytic products recombination. It also includes the decrease of the dose rates as the main alpha emitters decay away. Four cases, with varying parameters of the system, have been assessed. The results show a decrease in both the concentration of the radiolytic products in the gap water and the degradation of the fuel matrix. It has been estimated that in the period of the evaluation (10''6 years) up to 52% of the pellet is altered in the conservative cases, whereas only 11% is altered in the realistic cases. No significant differences were observed when the carbonates reactions were included in the system. (Author)

Peatland Acidobacteria with a dissimilatory sulfur metabolism.

Science.gov (United States)

Hausmann, Bela; Pelikan, Claus; Herbold, Craig W; Köstlbacher, Stephan; Albertsen, Mads; Eichorst, Stephanie A; Glavina Del Rio, Tijana; Huemer, Martin; Nielsen, Per H; Rattei, Thomas; Stingl, Ulrich; Tringe, Susannah G; Trojan, Daniela; Wentrup, Cecilia; Woebken, Dagmar; Pester, Michael; Loy, Alexander

2018-02-23

Sulfur-cycling microorganisms impact organic matter decomposition in wetlands and consequently greenhouse gas emissions from these globally relevant environments. However, their identities and physiological properties are largely unknown. By applying a functional metagenomics approach to an acidic peatland, we recovered draft genomes of seven novel Acidobacteria species with the potential for dissimilatory sulfite (dsrAB, dsrC, dsrD, dsrN, dsrT, dsrMKJOP) or sulfate respiration (sat, aprBA, qmoABC plus dsr genes). Surprisingly, the genomes also encoded DsrL, which so far was only found in sulfur-oxidizing microorganisms. Metatranscriptome analysis demonstrated expression of acidobacterial sulfur-metabolism genes in native peat soil and their upregulation in diverse anoxic microcosms. This indicated an active sulfate respiration pathway, which, however, might also operate in reverse for dissimilatory sulfur oxidation or disproportionation as proposed for the sulfur-oxidizing Desulfurivibrio alkaliphilus. Acidobacteria that only harbored genes for sulfite reduction additionally encoded enzymes that liberate sulfite from organosulfonates, which suggested organic sulfur compounds as complementary energy sources. Further metabolic potentials included polysaccharide hydrolysis and sugar utilization, aerobic respiration, several fermentative capabilities, and hydrogen oxidation. Our findings extend both, the known physiological and genetic properties of Acidobacteria and the known taxonomic diversity of microorganisms with a DsrAB-based sulfur metabolism, and highlight new fundamental niches for facultative anaerobic Acidobacteria in wetlands based on exploitation of inorganic and organic sulfur molecules for energy conservation.

Responses of Forest Ecosystems to Changing Sulfur Inputs

Science.gov (United States)

Dale W. Johnson; Myron J. Mitchell

1998-01-01

There was little information on sulfur (S) cycling in forests compared with that of other nutrients (especially N) until the past two decades. Interest in S nutrition and cycling in forests was heightened with the discovery of deficiencies in some unpolluted regions (Kelly and Lambert, 1972; Humphreys et al., 1975; Turner et al., 1977, 1980) and excesses associated...

Comparison of Optimal Thermodynamic Models of the Tricarboxylic Acid Cycle from Heterotrophs, Cyanobacteria, and Green Sulfur Bacteria

Energy Technology Data Exchange (ETDEWEB)

Thomas, Dennis G.; Jaramillo Riveri, Sebastian I.; Baxter, Douglas J.; Cannon, William R.

2014-12-15

We have applied a new stochastic simulation approach to predict the metabolite levels, energy flow, and material flux in the different oxidative TCA cycles found in E. coli and Synechococcus sp. PCC 7002, and in the reductive TCA cycle typical of chemolithoautotrophs and phototrophic green sulfur bacteria such as Chlorobaculum tepidum. The simulation approach is based on equations of state and employs an assumption similar to that used in transition state theory. The ability to evaluate the thermodynamics of metabolic pathways allows one to understand the relationship between coupling of energy and material gradients in the environment and the selforganization of stable biological systems, and it is shown that each cycle operates in the direction expected due to its environmental niche. The simulations predict changes in metabolite levels and flux in response to changes in cofactor concentrations that would be hard to predict without an elaborate model based on the law of mass action. In fact, we show that a thermodynamically unfavorable reaction can still have flux in the forward direction when it is part of a reaction network. The ability to predict metabolite levels, energy flow and material flux should be significant for understanding the dynamics of natural systems and for understanding principles for engineering organisms for production of specialty chemicals, such as biofuels.

Comparison of Optimal Thermodynamic Models of the Tricarboxylic Acid Cycle from Heterotrophs, Cyanobacteria, and Green Sulfur Bacteria.

Science.gov (United States)

Thomas, Dennis G; Jaramillo-Riveri, Sebastian; Baxter, Douglas J; Cannon, William R

2014-12-26

We have applied a new stochastic simulation approach to predict the metabolite levels, material flux, and thermodynamic profiles of the oxidative TCA cycles found in E. coli and Synechococcus sp. PCC 7002, and in the reductive TCA cycle typical of chemolithoautotrophs and phototrophic green sulfur bacteria such as Chlorobaculum tepidum. The simulation approach is based on modeling states using statistical thermodynamics and employs an assumption similar to that used in transition state theory. The ability to evaluate the thermodynamics of metabolic pathways allows one to understand the relationship between coupling of energy and material gradients in the environment and the self-organization of stable biological systems, and it is shown that each cycle operates in the direction expected due to its environmental niche. The simulations predict changes in metabolite levels and flux in response to changes in cofactor concentrations that would be hard to predict without an elaborate model based on the law of mass action. In fact, we show that a thermodynamically unfavorable reaction can still have flux in the forward direction when it is part of a reaction network. The ability to predict metabolite levels, energy flow, and material flux should be significant for understanding the dynamics of natural systems and for understanding principles for engineering organisms for production of specialty chemicals.

Nuclear Production of Hydrogen Using Thermochemical Water-Splitting Cycles

International Nuclear Information System (INIS)

Brown, L.C.; Besenbruch, G.E.; Schultz, K.R.; Marshall, A.C.; Showalter, S.K.; Pickard, P.S.; Funk, J.F.

2002-01-01

The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high-temperature heat from an advanced nuclear power station in a thermochemical water-splitting cycle. We carried out a detailed literature search to create a searchable database with 115 cycles and 822 references. We developed screening criteria to reduce the list to 25 cycles. We used detailed evaluation to select two cycles that appear most promising, the Adiabatic UT-3 cycle and the Sulfur-Iodine cycle. We have selected the Sulfur-Iodine thermochemical water-splitting cycle for further development. We then assessed the suitability of various nuclear reactor types to the production of hydrogen from water using the Sulfur-Iodine cycle. A basic requirement is to deliver heat to the process interface heat exchanger at temperatures up to 900 deg. C. We considered nine categories of reactors: pressurized water-cooled, boiling water-cooled, organic-cooled, alkali metal-cooled, heavy metal-cooled, gas-cooled, molten salt-cooled, liquid-core and gas-core reactors. We developed requirements and criteria to carry out the assessment, considering design, safety, operational, economic and development issues. This assessment process led to our choice of the helium gas-cooled reactor for coupling to the Sulfur-Iodine cycle. In continuing work, we are investigating the improvements that have been proposed to the Sulfur-Iodine cycle and will generate an integrated flowsheet describing a hydrogen production plant powered by a high-temperature helium gas-cooled nuclear reactor. This will allow us to size process equipment and calculate hydrogen production efficiency and capital cost, and to estimate the cost of the hydrogen produced as a function of nuclear reactor cost. (authors)

HYBRID SULFUR CYCLE FLOWSHEETS FOR HYDROGEN PRODUCTION USING HIGH-TEMPERATURE GAS-COOLED REACTORS

Energy Technology Data Exchange (ETDEWEB)

Gorensek, M.

2011-07-06

Two hybrid sulfur (HyS) cycle process flowsheets intended for use with high-temperature gas-cooled reactors (HTGRs) are presented. The flowsheets were developed for the Next Generation Nuclear Plant (NGNP) program, and couple a proton exchange membrane (PEM) electrolyzer for the SO2-depolarized electrolysis step with a silicon carbide bayonet reactor for the high-temperature decomposition step. One presumes an HTGR reactor outlet temperature (ROT) of 950 C, the other 750 C. Performance was improved (over earlier flowsheets) by assuming that use of a more acid-tolerant PEM, like acid-doped poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI), instead of Nafion{reg_sign}, would allow higher anolyte acid concentrations. Lower ROT was accommodated by adding a direct contact exchange/quench column upstream from the bayonet reactor and dropping the decomposition pressure. Aspen Plus was used to develop material and energy balances. A net thermal efficiency of 44.0% to 47.6%, higher heating value basis is projected for the 950 C case, dropping to 39.9% for the 750 C case.

Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO2 dynamic leaching experiments

International Nuclear Information System (INIS)

Merino, J.; Cera, E.; Bruno, J.; Quinones, J.; Casas, I.; Clarens, F.; Gimenez, J.; Pablo, J. de; Rovira, M.; Martinez-Esparza, A.

2005-01-01

Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO 2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO 2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO 2 , particularly the role of · OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions

Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries

KAUST Repository

Zheng, Guangyuan

2011-10-12

Sulfur has a high specific capacity of 1673 mAh/g as lithium battery cathodes, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a hollow carbon nanofiber-encapsulated sulfur cathode for effective trapping of polysulfides and demonstrate experimentally high specific capacity and excellent electrochemical cycling of the cells. The hollow carbon nanofiber arrays were fabricated using anodic aluminum oxide (AAO) templates, through thermal carbonization of polystyrene. The AAO template also facilitates sulfur infusion into the hollow fibers and prevents sulfur from coating onto the exterior carbon wall. The high aspect ratio of the carbon nanofibers provides an ideal structure for trapping polysulfides, and the thin carbon wall allows rapid transport of lithium ions. The small dimension of these nanofibers provides a large surface area per unit mass for Li2S deposition during cycling and reduces pulverization of electrode materials due to volumetric expansion. A high specific capacity of about 730 mAh/g was observed at C/5 rate after 150 cycles of charge/discharge. The introduction of LiNO3 additive to the electrolyte was shown to improve the Coulombic efficiency to over 99% at C/5. The results show that the hollow carbon nanofiber-encapsulated sulfur structure could be a promising cathode design for rechargeable Li/S batteries with high specific energy. © 2011 American Chemical Society.

Facile radiolytic synthesis of ruthenium nanoparticles on graphene oxide and carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Rojas, J.V., E-mail: jvrojas@vcu.edu [Mechanical and Nuclear Engineering Department, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia, 23284 (United States); Toro-Gonzalez, M.; Molina-Higgins, M.C. [Mechanical and Nuclear Engineering Department, Virginia Commonwealth University, 401 West Main Street, Richmond, Virginia, 23284 (United States); Castano, C.E., E-mail: cecastanolond@vcu.edu [Nanomaterials Core Characterization Facility, Chemical and Life Science Engineering Department, Virginia Commonwealth University, 601 West Main Street, Richmond, Virginia, 23284 (United States)

2016-03-15

Graphical abstract: - Highlights: • Facile radiolytic synthesis of Ru nanoparticles on graphene oxide and carbon nanotubes. • Homogeneously distributed Rh nanoparticles on supports are ∼2.5 nm in size. • Simultaneous reduction of graphene oxide and Ru ions occurs during the synthesis. • Ru-O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: Ruthenium nanoparticles on pristine (MWCNT) and functionalized carbon nanotubes (f-MWCNT), and graphene oxide have been prepared through a facile, single step radiolytic method at room temperature, and ambient pressure. This synthesis process relies on the interaction of high energy gamma rays from a {sup 60}Co source with the water in the aqueous solutions containing the Ru precursor, leading to the generation of highly reducing species that further reduce the Ru metal ions to zero valence state. Transmission electron microscopy and X-Ray diffraction revealed that the nanoparticles were homogeneously distributed on the surface of the supports with an average size of ∼2.5 nm. X-ray Photoelectron spectroscopy analysis showed that the interaction of the Ru nanoparticles with the supports occurred through oxygenated functionalities, creating metal-oxygen bonds. This method demonstrates to be a simple and clean approach to produce well dispersed nanoparticles on the aforementioned supports without the need of any hazardous chemical.

Facile radiolytic synthesis of ruthenium nanoparticles on graphene oxide and carbon nanotubes

International Nuclear Information System (INIS)

Rojas, J.V.; Toro-Gonzalez, M.; Molina-Higgins, M.C.; Castano, C.E.

2016-01-01

Graphical abstract: - Highlights: • Facile radiolytic synthesis of Ru nanoparticles on graphene oxide and carbon nanotubes. • Homogeneously distributed Rh nanoparticles on supports are ∼2.5 nm in size. • Simultaneous reduction of graphene oxide and Ru ions occurs during the synthesis. • Ru-O bonds evidenced the interaction of the nanoparticles with the support. - Abstract: Ruthenium nanoparticles on pristine (MWCNT) and functionalized carbon nanotubes (f-MWCNT), and graphene oxide have been prepared through a facile, single step radiolytic method at room temperature, and ambient pressure. This synthesis process relies on the interaction of high energy gamma rays from a "6"0Co source with the water in the aqueous solutions containing the Ru precursor, leading to the generation of highly reducing species that further reduce the Ru metal ions to zero valence state. Transmission electron microscopy and X-Ray diffraction revealed that the nanoparticles were homogeneously distributed on the surface of the supports with an average size of ∼2.5 nm. X-ray Photoelectron spectroscopy analysis showed that the interaction of the Ru nanoparticles with the supports occurred through oxygenated functionalities, creating metal-oxygen bonds. This method demonstrates to be a simple and clean approach to produce well dispersed nanoparticles on the aforementioned supports without the need of any hazardous chemical.

Radiolytic formation of organic iodides from organic compounds released from ripolin paint

International Nuclear Information System (INIS)

Attia, S.; Evans, G.J.

2002-01-01

The impact of a serious nuclear reactor accident is governed to a large extent by the possible release of airborne organic iodides to the environment. This research examines the identification and behavior of organic iodides formed in the containment due to the release of organic compounds from Ripolin paint, into the aqueous phase, following a nuclear reactor accident. A bench scale apparatus installed in the irradiation chamber of a Gammacell was used to analyze the formation of organic iodides. Iodo-organics, transferred to the gas phase above irradiated aqueous samples, were analyzed using a Thermal Desorption method coupled with gas chromatography and mass spectrometry. Detailed studies of the identity of the organic compounds released and the organic iodides formed were conducted. The effects of parameters such as irradiation dose were also examined. All the organic iodides formed, under radiolytic conditions, were identified as iodo-alkanes. The organic compounds that were released from the Ripolin paint, such as methyl isobutyl ketone, were found to decompose, by a series of reactions, to produce the organic iodides. The precursor organic compounds and the organic iodides formed were observed to consist of the same alkyl group. These results indicate that organic compounds released from surface paints directly influence the formation of radiolytic organic iodide. (author)

Effect of Nickel Coated Multi-Walled Carbon Nanotubes on Electrochemical Performance of Lithium-Sulfur Rechargeable Batteries.

Science.gov (United States)

Wu, Xiao; Yao, Shanshan; Hou, Jinli; Jing, Maoxiang; Qian, Xinye; Shen, Xiangqian; Xiang, Jun; Xi, Xiaoming

2017-04-01

Conventional lithium-sulfur batteries suffer from severe capacity fade, which is induced by low electron conductivity and high dissolution of intermediated polysulfides. Recent studies have shown the metal (Pt, Au, Ni) as electrocatalyst of lithium polysulfides and improved the performance for lithium sulfur batteries. In this work, we present the nickel coated multi-walled carbon nanotubes (Ni-MWNTs) as additive materials for elemental sulfur positive electrodes for lithium-sulfur rechargeable batteries. Compared with MWNTs, the obtained Ni-MWNTs/sulfur composite cathode demonstrate a reversible specific capacity approaching 545 mAh after 200 cycles at a rate of 0.5C as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact the MWNTs shows a vital role on polysulfides adsorption and nickel has a catalytic effect on the redox reactions during charge–discharge process. Meanwhile, the Ni-MWNTs is a good electric conductor for sulfur cathode.

Physicochemical properties and radiolytic degradation studies on tri-iso-amyl phosphate (TiAP)

Energy Technology Data Exchange (ETDEWEB)

Sreenivasulu, B.; Sivaraman, Nagarajan [Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu (India). Homi Bhabha National Inst.; Suresh, A.; Rajeswari, S.; Ramanathan, N.; Antony, M.P.; Joseph, M. [Indira Gandhi Centre for Atomic Research, Kalpakkam, Tamil Nadu (India). Chemistry Group

2017-06-01

The solvent composed of tri-iso-amyl phosphate (TiAP) in n-dodecane (n-DD) is regarded as a promising candidate for reprocessing of spent fuel. In this context, the radiolytic degradation of a solution of TiAP in n-dodecane was investigated by irradiating the solvent to various absorbed dose levels of γ-radiation. The neat extractant or a solution of extractant in n-dodecane was irradiated in the presence of nitric acid. Physicochemical properties such as density, viscosity and interfacial tension (IFT) were measured for unirradiated and irradiated solutions. The extent of degradation was determined by measuring the variation in extraction behavior of U(VI) and Pu(IV) with irradiated solvent systems. Uranium and plutonium retention with irradiated solvents was also measured. The distribution ratio of uranium and plutonium increased with increase in absorbed dose. Effect of alpha degradation was studied by plutonium retention as a function of time using 1.1 M TiAP/n-DD. Laser desorption/ionization mass spectrometric technique was employed to identify the possible radiolytic degradation products. Similar studies were also carried out with tri-n-butyl phosphate (TBP) based solvent system under identical experimental conditions and the results are compared.

Identification of the algal dimethyl sulfide-releasing enzyme: A missing link in the marine sulfur cycle

Science.gov (United States)

Alcolombri, Uria; Ben-Dor, Shifra; Feldmesser, Ester; Levin, Yishai; Tawfik, Dan S.; Vardi, Assaf

2015-06-01

Algal blooms produce large amounts of dimethyl sulfide (DMS), a volatile with a diverse signaling role in marine food webs that is emitted to the atmosphere, where it can affect cloud formation. The algal enzymes responsible for forming DMS from dimethylsulfoniopropionate (DMSP) remain unidentified despite their critical role in the global sulfur cycle. We identified and characterized Alma1, a DMSP lyase from the bloom-forming algae Emiliania huxleyi. Alma1 is a tetrameric, redox-sensitive enzyme of the aspartate racemase superfamily. Recombinant Alma1 exhibits biochemical features identical to the DMSP lyase in E. huxleyi, and DMS released by various E. huxleyi isolates correlates with their Alma1 levels. Sequence homology searches suggest that Alma1 represents a gene family present in major, globally distributed phytoplankton taxa and in other marine organisms.

Iron Sulfur and Molybdenum Cofactor Enzymes Regulate the Drosophila Life Cycle by Controlling Cell Metabolism

Science.gov (United States)

Marelja, Zvonimir; Leimkühler, Silke; Missirlis, Fanis

2018-01-01

Iron sulfur (Fe-S) clusters and the molybdenum cofactor (Moco) are present at enzyme sites, where the active metal facilitates electron transfer. Such enzyme systems are soluble in the mitochondrial matrix, cytosol and nucleus, or embedded in the inner mitochondrial membrane, but virtually absent from the cell secretory pathway. They are of ancient evolutionary origin supporting respiration, DNA replication, transcription, translation, the biosynthesis of steroids, heme, catabolism of purines, hydroxylation of xenobiotics, and cellular sulfur metabolism. Here, Fe-S cluster and Moco biosynthesis in Drosophila melanogaster is reviewed and the multiple biochemical and physiological functions of known Fe-S and Moco enzymes are described. We show that RNA interference of Mocs3 disrupts Moco biosynthesis and the circadian clock. Fe-S-dependent mitochondrial respiration is discussed in the context of germ line and somatic development, stem cell differentiation and aging. The subcellular compartmentalization of the Fe-S and Moco assembly machinery components and their connections to iron sensing mechanisms and intermediary metabolism are emphasized. A biochemically active Fe-S core complex of heterologously expressed fly Nfs1, Isd11, IscU, and human frataxin is presented. Based on the recent demonstration that copper displaces the Fe-S cluster of yeast and human ferredoxin, an explanation for why high dietary copper leads to cytoplasmic iron deficiency in flies is proposed. Another proposal that exosomes contribute to the transport of xanthine dehydrogenase from peripheral tissues to the eye pigment cells is put forward, where the Vps16a subunit of the HOPS complex may have a specialized role in concentrating this enzyme within pigment granules. Finally, we formulate a hypothesis that (i) mitochondrial superoxide mobilizes iron from the Fe-S clusters in aconitase and succinate dehydrogenase; (ii) increased iron transiently displaces manganese on superoxide dismutase, which

Iron Sulfur and Molybdenum Cofactor Enzymes Regulate the Drosophila Life Cycle by Controlling Cell Metabolism

Directory of Open Access Journals (Sweden)

Zvonimir Marelja

2018-02-01

Full Text Available Iron sulfur (Fe-S clusters and the molybdenum cofactor (Moco are present at enzyme sites, where the active metal facilitates electron transfer. Such enzyme systems are soluble in the mitochondrial matrix, cytosol and nucleus, or embedded in the inner mitochondrial membrane, but virtually absent from the cell secretory pathway. They are of ancient evolutionary origin supporting respiration, DNA replication, transcription, translation, the biosynthesis of steroids, heme, catabolism of purines, hydroxylation of xenobiotics, and cellular sulfur metabolism. Here, Fe-S cluster and Moco biosynthesis in Drosophila melanogaster is reviewed and the multiple biochemical and physiological functions of known Fe-S and Moco enzymes are described. We show that RNA interference of Mocs3 disrupts Moco biosynthesis and the circadian clock. Fe-S-dependent mitochondrial respiration is discussed in the context of germ line and somatic development, stem cell differentiation and aging. The subcellular compartmentalization of the Fe-S and Moco assembly machinery components and their connections to iron sensing mechanisms and intermediary metabolism are emphasized. A biochemically active Fe-S core complex of heterologously expressed fly Nfs1, Isd11, IscU, and human frataxin is presented. Based on the recent demonstration that copper displaces the Fe-S cluster of yeast and human ferredoxin, an explanation for why high dietary copper leads to cytoplasmic iron deficiency in flies is proposed. Another proposal that exosomes contribute to the transport of xanthine dehydrogenase from peripheral tissues to the eye pigment cells is put forward, where the Vps16a subunit of the HOPS complex may have a specialized role in concentrating this enzyme within pigment granules. Finally, we formulate a hypothesis that (i mitochondrial superoxide mobilizes iron from the Fe-S clusters in aconitase and succinate dehydrogenase; (ii increased iron transiently displaces manganese on superoxide

Radiolytic decomposition of organic C-14 released from TRU waste

International Nuclear Information System (INIS)

Kani, Yuko; Noshita, Kenji; Kawasaki, Toru; Nishimura, Tsutomu; Sakuragi, Tomofumi; Asano, Hidekazu

2007-01-01

It has been found that metallic TRU waste releases considerable portions of C-14 in the form of organic molecules such as lower molecular weight organic acids, alcohols and aldehydes. Due to the low sorption ability of organic C-14, it is important to clarify the long-term behavior of organic forms under waste disposal conditions. From investigations on radiolytic decomposition of organic carbon molecules into inorganic carbonic acid, it is expected that radiation from TRU waste will decompose organic C-14 into inorganic carbonic acid that has higher adsorption ability into the engineering barriers. Hence we have studied the decomposition behavior of organic C-14 by gamma irradiation experiments under simulated disposal conditions. The results showed that organic C-14 reacted with OH radicals formed by radiolysis of water, to produce inorganic carbonic acid. We introduced the concept of 'decomposition efficiency' which expresses the percentage of OH radicals consumed for the decomposition reaction of organic molecules in order to analyze the experimental results. We estimated the effect of radiolytic decomposition on the concentration of organic C-14 in the simulated conditions of the TRU disposal system using the decomposition efficiency, and found that the concentration of organic C-14 in the waste package will be lowered when the decomposition of organic C-14 by radiolysis was taken into account, in comparison with the concentration of organic C-14 without radiolysis. Our prediction suggested that some amount of organic C-14 can be expected to be transformed into the inorganic form in the waste package in an actual system. (authors)

Characterization of chemosynthetic microbial mats associated with intertidal hydrothermal sulfur vents in White Point, San Pedro, CA, USA

Directory of Open Access Journals (Sweden)

Priscilla J Miranda

2016-07-01

Full Text Available The shallow-sea hydrothermal vents at White Point (WP in Palos Verdes (PV on the southern California coast support microbial mats and provide easily accessed settings in which to study chemolithoautotrophic sulfur cycling. Previous studies have cultured sulfur-oxidizing bacteria from the WP mats; however, almost nothing is known about the in situ diversity and activity of the microorganisms in these habitats. We studied the diversity, micron-scale spatial associations and metabolic activity of the mat community via sequence analysis of 16S rRNA and aprA genes, Fluorescence in situ Hybridization (FISH microscopy and sulfate-reduction rate (SRR measurements. Sequence analysis revealed a diverse group of bacteria, dominated by sulfur cycling gamma-, epsilon- and deltaproteobacterial lineages such as Marithrix, Sulfurovum and Desulfuromusa. FISH microscopy suggests a close physical association between sulfur-oxidizing and sulfur-reducing genotypes, while radiotracer studies showed low, but detectable, SRR. Comparative 16S rRNA gene sequence analyses indicate the WP sulfur vent microbial mat community is similar, but distinct from other hydrothermal vent communities representing a range of biotopes and lithologic settings. These findings suggest a complete biological sulfur cycle is operating in the WP mat ecosystem mediated by diverse bacterial lineages, with some similarity with deep-sea hydrothermal vent communities.

Hybrid polyacrylamide/carbon coating on sulfur cathode for advanced lithium sulfur battery

International Nuclear Information System (INIS)

Li, Tao; Yuan, Yan; Hong, Bo; Cao, Huawei; Zhang, Kai; Lai, Yanqing; Liu, Yexiang; Huang, Zixin

2017-01-01

Commercialized conductive slurry consisting of polyacrylamide (PAM) and two kinds of carbon black was coated on the surface of sulfur cathode. The hybrid PAM/C coating not only physically blocks but also chemically anchors polysulfides within the cathode, confining their out-diffusion and shuttle. Besides, the flexible and highly-conductive coating layer buffers volume change of the cathode during discharge-charge process and reduces charge transfer resistance. A specific capacity of as high as ∼900 mAh g −1 after 300 cycles is demonstrated for the PAM/C coated cathode, which is a significant improvement of reversible capacity and cycle capability compared to uncoated or conventional PVDF/C coated cathode.

Electrochemical corrosion studies on a selected carbon steel for application in nuclear waste disposal containers: Influence of radiolytic products on corrosion in brines

International Nuclear Information System (INIS)

Farvaque-Bera, A.M.; Smailos, E.

1994-07-01

In previous corrosion studies, carbon steels were identified as promising materials for the manufacturing of long-lived high-level waste containers that could act as a radionuclide barrier in a rock-salt repository. In the present work, the influence of some important oxidizing radiolytic products generated in gamma irradiated brines on the electrochemical corrosion behaviour of the preselected fine-grained steel TStE 355 was studied. The steel was examined by potentiodynamic and potentiostatic polarization methods at 90 C in a disposal relevant NaCl-rich brine containing radiolytic products such as H 2 O 2 , ClO - , ClO 3 - and ClO 4 - at concentrations between 10 -4 and 10 -2 M/l. The significance of the radiolytic products to steel corrosion depends on their concentration at the metal-brine interface, which in turn, depends on many factors such as the dose rate, the amount of water present in the disposal area, the escape of gases (e.g. H 2 )

Time extrapolation of radiolytic degradation product kinetics: the case of polyurethane

International Nuclear Information System (INIS)

Dannoux, A.

2007-02-01

The prediction of the environmental impact of organic materials in nuclear waste geological storage needs knowledge of radiolytic degradation mechanisms and kinetics in aerobic and anaerobic conditions. In this framework, the effect of high doses (> MGy) and the variation of dose rate have to be considered. The material studied is a polyurethane composed of polyether soft segment and aromatic hard segments. Mechanisms were built on the analysis of material submitted to irradiations of simulation (high energy electrons and gamma radiation) by FTIR spectroscopy and gaseous and liquid degradation products by gas mass spectrometry and size exclusion chromatography. The electron paramagnetic resonance study of radical process and the determination of oxygen consumption and gas formation radiolytic yields allowed us to acquire kinetic data and to estimate dose rate and high doses effects. The polyurethane radio-oxidation mainly concerns soft segments and induced cross-linkings and production by scissions of oxidised compounds (esters, alcohols, carboxylic acids). The kinetic of radical termination is rapid and the dose rate effect is limited. After 10 MGy, branching and scission reactions are in equilibrium and low molecular weight products accumulate. At last, the degradation products release in water is influenced by the oxidation rate and the temperature. After 10 MGy, the soluble fraction is stabilised at 25%. The water soluble products identified by electro-spray ionisation mass spectrometry (alcohols, aldehydes, carboxylic acids) potentially formed complexes with radionuclides. (author)

Biomass-Derived Oxygen and Nitrogen Co-Doped Porous Carbon with Hierarchical Architecture as Sulfur Hosts for High-Performance Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

Yan Zhao

2017-11-01

Full Text Available In this work, a facile strategy to synthesize oxygen and nitrogen co-doped porous carbon (ONPC is reported by one-step pyrolysis of waste coffee grounds. As-prepared ONPC possesses highly rich micro/mesopores as well as abundant oxygen and nitrogen co-doping, which is applied to sulfur hosts as lithium/sulfur batteries’ appropriate cathodes. In battery testing, the sulfur/oxygen and nitrogen co-doped porous carbon (S/ONPC composite materials reveal a high initial capacity of 1150 mAh·g−1 as well as a reversible capacity of 613 mAh·g−1 after the 100th cycle at 0.2 C. Furthermore, when current density increases to 1 C, a discharge capacity of 331 mAh·g−1 is still attainable. Due to the hierarchical porous framework and oxygen/nitrogen co-doping, the S/ONPC composite exhibits a high utilization of sulfur and good electrochemical performance via the immobilization of the polysulfides through strong chemical binding.

Improving the Performance of Lithium–Sulfur Batteries by Conductive Polymer Coating

KAUST Repository

Yang, Yuan

2011-11-22

Rechargeable lithium-sulfur (Li-S) batteries hold great potential for next-generation high-performance energy storage systems because of their high theoretical specific energy, low materials cost, and environmental safety. One of the major obstacles for its commercialization is the rapid capacity fading due to polysulfide dissolution and uncontrolled redeposition. Various porous carbon structures have been used to improve the performance of Li-S batteries, as polysulfides could be trapped inside the carbon matrix. However, polysulfides still diffuse out for a prolonged time if there is no effective capping layer surrounding the carbon/sulfur particles. Here we explore the application of conducting polymer to minimize the diffusion of polysulfides out of the mesoporous carbon matrix by coating poly(3,4-ethylenedioxythiophene)- poly(styrene sulfonate) (PEDOT:PSS) onto mesoporous carbon/sulfur particles. After surface coating, coulomb efficiency of the sulfur electrode was improved from 93% to 97%, and capacity decay was reduced from 40%/100 cycles to 15%/100 cycles. Moreover, the discharge capacity with the polymer coating was ∼10% higher than the bare counterpart, with an initial discharge capacity of 1140 mAh/g and a stable discharge capacity of >600 mAh/g after 150 cycles at C/5 rate. We believe that this conductive polymer coating method represents an exciting direction for enhancing the device performance of Li-S batteries and can be applicable to other electrode materials in lithium ion batteries. © 2011 American Chemical Society.

Hydrolytic and radiolytic degradation of TBP in TBP.30% V/V-dodecane/UO2(NO3)2.HNO3.H2O systems

International Nuclear Information System (INIS)

Barreta, L.G.

1980-01-01

The hydrolytic and radiolytic degradation of TBP is investigated in systems of TBP 30% V/V-dodecane/H 2 O . HNO 3 . UO 2 (NO 3 ) 2 by gas chromatographic determination of HDBP. No direct relation between the concentration of HDBP formed and the quantity of HNO 3 extracted by the organic phase is observed in the studies of hydrolysis of TBP. The HDBP concentration is seen to increase non-linearly with the concentration of HNO 3 extracted by the organic phase. Radiolytic studies show that for doses greater than 1 Wh/l, the concentration of HDBP formed increases with the dose absorbed by the system. Whith doses smaller than 1 Wh/l and acid concentration greater than 2 M, two distinct patterns of behavior are observed. The concentration of HDBP as a function of the radiation dose absorbed by the system presents a minimum for uranyl nitrate concentrations smaller than 0.9 M; for uranyl nitrate concentrations greater than 1.3 M the concentration of radiolytic HDBP cannot be calculated because the concentration of the hydrolytic HDBP determined is greater than the sum of the experimental concentrations of hydrolytic and radiolytic HDBP. It is known that the dose absorbed by the process solutions during the reprocessing of light water reactor fuel elements is smaller than one Wh/l. Thus, dose rates between zero and one Wh/l should be studied for this system. (Author) [pt

Disproportionation of elemental sulfur by haloalkaliphilic bacteria from soda lakes.

Science.gov (United States)

Poser, Alexander; Lohmayer, Regina; Vogt, Carsten; Knoeller, Kay; Planer-Friedrich, Britta; Sorokin, Dimitry; Richnow, Hans-H; Finster, Kai

2013-11-01

Microbial disproportionation of elemental sulfur to sulfide and sulfate is a poorly characterized part of the anoxic sulfur cycle. So far, only a few bacterial strains have been described that can couple this reaction to cell growth. Continuous removal of the produced sulfide, for instance by oxidation and/or precipitation with metal ions such as iron, is essential to keep the reaction exergonic. Hitherto, the process has exclusively been reported for neutrophilic anaerobic bacteria. Here, we report for the first time disproportionation of elemental sulfur by three pure cultures of haloalkaliphilic bacteria isolated from soda lakes: the Deltaproteobacteria Desulfurivibrio alkaliphilus and Desulfurivibrio sp. AMeS2, and a member of the Clostridia, Dethiobacter alkaliphilus. All cultures grew in saline media at pH 10 by sulfur disproportionation in the absence of metals as sulfide scavengers. Our data indicate that polysulfides are the dominant sulfur species under highly alkaline conditions and that they might be disproportionated. Furthermore, we report the first organism (Dt. alkaliphilus) from the class Clostridia that is able to grow by sulfur disproportionation.

Interfacial Engineered Polyaniline/Sulfur-doped TiO2 Nanotube Arrays for Ultralong Cycle Lifetime Fiber-Shaped, Solid-State Supercapacitors.

Science.gov (United States)

Li, Chun; Wang, Zhuanpei; Li, Shengwen; Cheng, Jianli; Zhang, Yanning; Zhou, Jingwen; Yang, Dan; Tong, Dong-Ge; Wang, Bin

2018-05-04

Fiber-shaped supercapacitors (FSCs) have great potential in wearable electronics applications. However, the limited specific surface area and inadequate structural stability caused by the weak interfacial interactions of the electrodes result in relatively low specific capacitance and unsatisfactory cycle lifetime. Herein, solid-state FSCs with high energy density and ultralong cycle lifetime based on polyaniline (PANI)/sulfur-doped TiO2 nanotubes array (PANI/S-TiO2) are fabricated by interfacial engineering. The experimental results and ab initio calculations reveal that S doping can effectively promote the conductivity of titania nanotubes and increase the binding energy of PANI anchored on the electrode surface, leading to much stronger binding of PANI on the surface of the electrode and excellent electrode structure stability. As a result, the FSCs using the PANI/S-TiO2 electrodes deliver a high specific capacitance of 91.9 mF cm-2, a capacitance retention of 93.78% after 12,000 charge/discharge cycles, and an areal energy density of 3.2 µWh cm-2, respectively. Meanwhile, the all-solid-state FSC device retains its excellent flexibility and stable electrochemical capacitance even after bending 150 cycles. The enhanced performances of FSCs could be attributed to the large surface area, short ion diffusion path, high electrical conductivity and engineered interfacial interaction of the rationally designed electrodes.

Retention of radiolytic CO gas in irradiated pepper grains and irradiation detection of spices and dry grains with the level of stocked CO gas

International Nuclear Information System (INIS)

Furuta, M.; Dohmaru, T.; Katayama, T.; Toratani, H.; Takeda, A.

1995-01-01

The release of radiolytic CO gas from 60Co gamma-irradiated pepper seeds was unexpectedly slower than that of radiolytic H2 gas during a storage period after irradiation. These gases were retained in the grains and could be recovered by pulverization under gaslight condition. Using this procedure, 10-kGy-irradiated pepper grains could be distinguished from nonirradiated samples for more than 2 months by the level of CO and H2 gases. The patterns of CO change at 10, 20, and 30 kGy were similar, and the CO amounts were proportional to irradiation doses at any point of the storage period after irradiation. 60Co gamma-irradiated grains of allspice, cinnamon, cumin, polished rice, and wheat could be distinguished from nonirradiated ones by the level of retained CO gas even after 2 months of storage at room temperature. Thus, radiolytic CO gas could be an effective probe for rapid screening of irradiated pepper and dry grains

Pulse-radiolytic investigations of catechols and catecholamines

International Nuclear Information System (INIS)

Bors, W.; Saran, M.; Michel, C.; Lengfelder, E.; Fuchs, C.; Spoettl, R.

1975-01-01

Adrenaline (epinephrine), adrenochrome and C 4 -substituted catechol model compounds were pulse-irradiated in aqueous neutral and alkaline solutions. Transient spectra are reported after oxidizing adrenaline and reducing adrenochrome. All species appearing during the 20 msec interval after the pulse have been identified: the OH adduct with an absorption maximum at 300 to 310 nm, the semiquinone (at 245 nm), and adrenaline quinone (at 340 nm). The reaction of superoxide anions (O 2 - ) with adrenaline was less efficient, compared with OH radicals. A novel oxidation product, derived from the semiquinone and O 2 - , has been identified as the 4-hydroxy-3,6-dioxo derivate. The pulse-radiolytic reduction of adrenochrome by hydrated electrons (esub(aq) - ) yielded the semiquinone of adrenochrome (absorbing at 470 nm), which subsequently decayed by a second-order process. The dismutation products leucoadrenochrome (absorbing at 300 nm, pH 9.8) and the adrenochrome tautomer (absorbing at 375 nm) were unstable, forming a 5,6-dihydro-N-methyl indole and regenerating adrenochrome. (author)

Direct observation of lithium polysulfides in lithium-sulfur batteries using operando X-ray diffraction

Science.gov (United States)

Conder, Joanna; Bouchet, Renaud; Trabesinger, Sigita; Marino, Cyril; Gubler, Lorenz; Villevieille, Claire

2017-06-01

In the on going quest towards lithium-battery chemistries beyond the lithium-ion technology, the lithium-sulfur system is emerging as one of the most promising candidates. The major outstanding challenge on the route to commercialization is controlling the so-called polysulfide shuttle, which is responsible for the poor cycling efficiency of the current generation of lithium-sulfur batteries. However, the mechanistic understanding of the reactions underlying the polysulfide shuttle is still incomplete. Here we report the direct observation of lithium polysulfides in a lithium-sulfur cell during operation by means of operando X-ray diffraction. We identify signatures of polysulfides adsorbed on the surface of a glass-fibre separator and monitor their evolution during cycling. Furthermore, we demonstrate that the adsorption of the polysulfides onto SiO2 can be harnessed for buffering the polysulfide redox shuttle. The use of fumed silica as an electrolyte additive therefore significantly improves the specific charge and Coulombic efficiency of lithium-sulfur batteries.

Unusual radiolytic behavior of neptunium ions in aqueous bicarbonate solutions

International Nuclear Information System (INIS)

Shilov, V.P.; Gogolev, A.V.; Pikaev, A.K.

2000-01-01

Behavior of neptunium ions in carbonate and bicarbonate aqueous solutions saturated with air, oxygen or argon during gamma radiation ( 60 Co) by doses up to 3 kGy at dose rates 10 and 25 Gy/min was studied by the method of spectrophotometry. It is shown that in neptunium (5) bicarbonate solution nearly complete (95%) neptunium ion oxidation occurs under the effect of radiation, whereas no oxidation is observed in carbonate solution. Radiation-chemical yield of neptunium (5) oxidation and stationary concentration of neptunium (6) ions depend on concentration of bicarbonate-ions. Explanation to the results obtained is made from the viewpoint of potential radiolytic reactions [ru

Yolk-Shelled C@Fe3 O4 Nanoboxes as Efficient Sulfur Hosts for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

He, Jiarui; Luo, Liu; Chen, Yuanfu; Manthiram, Arumugam

2017-09-01

Owing to the high theoretical specific capacity (1675 mA h g -1 ) and low cost, lithium-sulfur (Li-S) batteries offer advantages for next-generation energy storage. However, the polysulfide dissolution and low electronic conductivity of sulfur cathodes limit the practical application of Li-S batteries. To address such issues, well-designed yolk-shelled carbon@Fe 3 O 4 (YSC@Fe 3 O 4 ) nanoboxes as highly efficient sulfur hosts for Li-S batteries are reported here. With both physical entrapment by carbon shells and strong chemical interaction with Fe 3 O 4 cores, this unique architecture immobilizes the active material and inhibits diffusion of the polysulfide intermediates. Moreover, due to their high conductivity, the carbon shells and the polar Fe 3 O 4 cores facilitate fast electron/ion transport and promote continuous reactivation of the active material during the charge/discharge process, resulting in improved electrochemical utilization and reversibility. With these merits, the S/YSC@Fe 3 O 4 cathodes support high sulfur content (80 wt%) and loading (5.5 mg cm -2 ) and deliver high specific capacity, excellent rate capacity, and long cycling stability. This work provides a new perspective to design a carbon/metal-oxide-based yolk-shelled framework as a high sulfur-loading host for advanced Li-S batteries with superior electrochemical properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfur based electrode materials for secondary batteries

Science.gov (United States)

Hao, Yong

Developing next generation secondary batteries has attracted much attention in recent years due to the increasing demand of high energy and high power density energy storage for portable electronics, electric vehicles and renewable sources of energy. This dissertation investigates sulfur based advanced electrode materials in Lithium/Sodium batteries. The electrochemical performances of the electrode materials have been enhanced due to their unique nano structures as well as the formation of novel composites. First, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs were employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g-1 and a reversible capacity of 319.3 mAh g-1 at 0.1C with good recoverable rate capability. Second, NGNS/S nanocomposites, synthesized using chemical reaction-deposition method and low temperature heat treatment, were further studied as active cathode materials for room temperature Na-S batteries. Both high loading composite with 86% gamma-S8 and low loading composite with 25% gamma-S8 have been electrochemically evaluated and compared with both NGNS and S control electrodes. It was found that low loading NGNS/S composite exhibited better electrochemical performance with specific capacity of 110 and 48 mAh g-1 at 0.1C at the 1st and 300th cycle, respectively. The Coulombic efficiency of 100% was obtained at the 300th cycle. Third, high purity rock-salt (RS), zinc-blende (ZB) and wurtzite (WZ) MnS nanocrystals with different morphologies were successfully synthesized via a facile solvothermal method. RS-, ZB- and WZ-MnS electrodes showed the capacities of 232.5 mAh g-1, 287.9 mAh g-1 and 79.8 mAh g-1 at the 600th cycle, respectively. ZB-MnS displayed the best performance in terms of specific capacity and cyclability. Interestingly, MnS electrodes

Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

Science.gov (United States)

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

2014-06-17

Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

Radiolytic gas generation in Salt Cake Quality Assurance Plan

International Nuclear Information System (INIS)

Walker, D.D.

1993-01-01

High-level radioactive wastes are stored in large, steel tanks in the Savannah River Site's Tank Farms. The liquid levels in these tanks are monitored to detect leakage of waste out of tanks or leakage of liquids into the tanks. Recent unexplained level fluctuations in high-level waste (HLW) tanks have caused High Level Waste Engineering (HLWE) to develop a program to better understand tank level behavioral Interim Waste Technology (IWT) has been requested by HLWE to obtain data which will lead to a better understanding of the radiolytic generation of gases in salt cake. A task plan has been written in response to this request. This document details the controls necessary to ensure the quality of the results of the activities described in the task plan

Degradation Mechanism of Poly(Ether-Urethane) Estane Induced by High Energy Radiation (III) : Radiolytic Gases and Water Soluble Products

International Nuclear Information System (INIS)

Dannoux, A.

2006-01-01

Within the framework of nuclear waste management, there is interest in the prediction of long-term behaviour of organic materials subjected to high energy radiation. Once organic waste has been stored, gases and low molecular products might be generated from materials irradiated by radionuclides. Long-term behaviour of organic material in nuclear waste has several common concerns with radiation ageing of polymers. But a more detailed description of the chemical evolution is needed for nuclear waste management. In a first approach, an extensive work on radiation ageing is used to identify the different processes encountered during the degradation of a polyurethane, including oxidation dose rate-effects and influence of dose on the oxidation mechanism. In a second approach, a study is performed to identify and quantify gases and possible production of water soluble chemical complexing agents which might enhance radionuclides migration away from the repository. In this work, we present results concerning the production of radiolytic gases and the formation of water soluble oligomers reached with leaching tests Films were made from a poly(ether-urethane) synthesized from methylene bis(p-phenyl isocyanate) (MDI) and poly(tetramethylene glycol) (PTMG) with 1,4 butanediol (BD) and were irradiated by high-energy electron beam to cover a wide doses range and by γ rays to determine the formation/consumption yields of gases. They were measured by mass spectrometry and gas-chromatography/mass spectrometry (GC/MS). The migration of water soluble oligomers in water was reached by measuring the weight loss versus leaching time. The identification of oligomers was performed by using a mass spectrometry with an electrospray ionisation interface (ESI-MS-MS). The analysis of radiolytic gases indicates the formation of H 2 , CO 2 and CO with respective radiolytic yields of 1, 0.5 and 0.3 molecule/100 eV. The consumption of O 2 is evaluated to 6 molecules/100 eV. For absorbed doses

Use of probabilistic safety analysis for design of emergency mitigation systems in hydrogen producer plant with sulfur-iodine technology, Section II: sulfuric acid decomposition

International Nuclear Information System (INIS)

Mendoza A, A.; Nelson E, P. F.; Francois L, J. L.

2009-10-01

Over the last decades, the need to reduce emissions of greenhouse gases has prompted the development of technologies for the production of clean fuels through the use of primary energy resources of zero emissions, as the heat of nuclear reactors of high temperature. Within these technologies, one of the most promising is the hydrogen production by sulfur-iodine cycle coupled to a high temperature reactor initially proposed by General Atomics. By their nature and because it will be large-scale plants, the development of these technologies from its present phase to its procurement and construction, will have to incorporate emergency mitigation systems in all its parts and interconnections to prevent undesired events that could put threaten the plant integrity and the nearby area. For the particular case of sulfur-iodine thermochemical cycle, most analysis have focused on hydrogen explosions and failures in the primary cooling systems. While these events are the most catastrophic, is that there are also many other events that even taking less direct consequences, could jeopardize the plant operation, the people safety of nearby communities and carry the same economic consequences. In this study we analyzed one of these events, which is the formation of a toxic cloud prompted by uncontrolled leakage of concentrated sulfuric acid in the second section of sulfur-iodine process of General Atomics. In this section, the sulfuric acid concentration is near to 90% in conditions of high temperature and positive pressure. Under these conditions the sulfuric acid and sulfur oxides from the reactor will form a toxic cloud that the have contact with the plant personnel could cause fatalities, or to reach a town would cause suffocation, respiratory problems and eye irritation. The methodology used for this study is the supported design in probabilistic safety analysis. Mitigation systems were postulated based on the isolation of a possible leak, the neutralization of a pond of

The impact of freeze-thawing on the friability of formed elemental sulfur

Energy Technology Data Exchange (ETDEWEB)

Clark, P.D.; Almond, P.

1995-10-01

Winter weather fluctuation tests were performed in a laboratory to determine the freeze-thaw effect on the particle size distribution and friability of sulfur samples of Polish Air Prills, Procor GX Granules, Petrosul, Sandvik Rotoform, and slate. Formed elemental sulfur is often stored outdoors and is subjected to temperature fluctuations which could potentially result in structural stress, particularly if the sulfur contained any moisture from rainwater or melting snow. Concern was expressed that sulfur stored under these conditions might have increased friability during shipping and handling. Results of stress level tests indicated that winter weather fluctuations did not effect the particle size distribution or friability of the samples. When sulfur samples were in contact with water for one month, there were was no significant change in overall friability. It was concluded that all premium product forms of solid elemental sulfur could be stored outdoors, even if subjected to freeze-thaw cycles. 4 tabs., 5 figs.

Radiolytic graphite oxidation revisited

International Nuclear Information System (INIS)

Minshall, P.C.; Sadler, I.A.; Wickham, A.J.

1996-01-01

The importance of radiolytic oxidation in graphite-moderated CO 2 -cooled reactors has long been recognised, especially in the Advanced Gas-Cooled Reactors where potential rates are higher because of the higher gas pressure and ratings than the earlier Magnox designs. In all such reactors, the rate of oxidation is partly inhibited by the CO produced in the reaction and, in the AGR, further reduced by the deliberate addition of CH 4 . Significant roles are also played by H 2 and H 2 O. This paper reviews briefly the mechanisms of these processes and the data on which they are based. However, operational experience has demonstrated that these basic principles are unsatisfactory in a number of respects. Gilsocarbon graphites produced by different manufacturers have demonstrated a significant difference in oxidation rate despite a similar specification and apparent equivalence in their pore size and distribution, considered to be the dominant influence on oxidation rate for a given coolant-gas composition. Separately, the inhibiting influence of CH 4 , which for many years had been considered to arise from the formation of a sacrificial deposit on the pore walls, cannot adequately be explained by the actual quantities of such deposits found in monitoring samples which frequently contain far less deposited carbon than do samples from Magnox reactors where the only source of such deposits is the CO. The paper also describes the current status of moderator weight-loss predictions for Magnox and AGR Moderators and the validation of the POGO and DIFFUSE6 codes respectively. 2 refs, 5 figs

Nitrogen/Sulfur-Codoped Carbon Materials from Chitosan for Supercapacitors

Science.gov (United States)

Li, Mei; Han, Xianlong; Chang, Xiaoqing; Yin, Wenchao; Ma, Jingyun

2016-08-01

d-Methionine and chitosan have been used for fabrication of nitrogen/sulfur-codoped carbon materials by a hydrothermal process followed by carbonization at 750°C for 3 h. The as-prepared carbon materials showed enhanced electrochemical performance, combining electrical double-layer capacitance with pseudocapacitance owing to the doping with sulfur and nitrogen. The specific capacitance of the obtained carbon material reached 135 F g-1 at current density of 1 A g-1, which is much higher than undoped chitosan (67 F g-1). The capacitance retention of the carbon material was almost 97.2% after 5000 cycles at current density of 1 A g-1. With such improved electrochemical performance, the nitrogen/sulfur-codoped carbon material may have promising potential for use in energy-storage electrodes of supercapacitors.

Large scale disposal of waste sulfur: From sulfide fuels to sulfate sequestration

International Nuclear Information System (INIS)

Rappold, T.A.; Lackner, K.S.

2010-01-01

Petroleum industries produce more byproduct sulfur than the market can absorb. As a consequence, most sulfur mines around the world have closed down, large stocks of yellow sulfur have piled up near remote operations, and growing amounts of toxic H 2 S are disposed of in the subsurface. Unless sulfur demand drastically increases or thorough disposal practices are developed, byproduct sulfur will persist as a chemical waste problem on the scale of 10 7 tons per year. We review industrial practices, salient sulfur chemistry, and the geochemical cycle to develop sulfur management concepts at the appropriate scale. We contend that the environmentally responsible disposal of sulfur would involve conversion to sulfuric acid followed by chemical neutralization with equivalent amounts of base, which common alkaline rocks can supply cheaply. The resulting sulfate salts are benign and suitable for brine injection underground or release to the ocean, where they would cause minimal disturbance to ecosystems. Sequestration costs can be recouped by taking advantage of the fuel-grade thermal energy released in the process of oxidizing reduced compounds and sequestering the products. Sulfate sequestration can eliminate stockpiles and avert the proliferation of enriched H 2 S stores underground while providing plenty of carbon-free energy to hydrocarbon processing.

Radiolytic products of irradiated authentic fatty acids and triacylglycerides

International Nuclear Information System (INIS)

Kim, K.-S.; Lee, Jeong-Min; Seo, Hye-Young; Kim, Jun-Hyoung; Song, Hyun-Pa; Byun, Myung-Woo; Kwon, Joong-Ho

2004-01-01

Radiolytic products of authentic fatty acids (palmitic, stearic, oleic, linoleic and linolenic acids) and triacylglycerides (tripalmitin, tristearin, triolein, trilinolein and trilinolenin) were determined. Concentrations of hydrocarbons from the saturated fatty acids were higher than the unsaturated fatty acids. Authentic fatty acids were mainly decomposed in the α-carbon position and C n-1 hydrocarbons occurred in higher than C n-2 hydrocarbons. Concentrations of 2-alkylcyclobutanones from the saturated fatty acids were lower than the unsaturated fatty acids. Concentrations of hydrocarbons from tripalmitin and tristearin were not a significant change compared with triolein, trilinolein and trilinolenin. For all triacylglycerides except triolein, C n-1 hydrocarbons were higher than C n-2 hydrocarbons. Radioproduction rates of 2-alkylcyclobutanones from tripalmitin and tristearin were higher than triolein, trilinolein and trilinolenin

Hydrogen radiolytic production in light and heavy water mixtures under conditions similar to LOCA (loss of coolant accidents)

International Nuclear Information System (INIS)

Garcia Rodenas, L.; Ali, S.P.; Liberman, S.J.

1987-01-01

H 2 , HD and D 2 radiolytic yield in heavy and light water mixtures has been determined to supply the necessary data which will allow to make a realistic estimation of the solution of such gas under LOCA conditions as a function of time. (Author)

Single-Cell Genome and Group-Specific dsrAB Sequencing Implicate Marine Members of the Class Dehalococcoidia (Phylum Chloroflexi) in Sulfur Cycling

DEFF Research Database (Denmark)

Wasmund, Kenneth; Cooper, Myriel; Schreiber, Lars

2016-01-01

The marine subsurface sediment biosphere is widely inhabited by bacteria affiliated with the class Dehalococcoidia (DEH), phylum Chloroflexi, and yet little is known regarding their metabolisms. In this report, genomic content from a single DEH cell (DEH-C11) with a 16S rRNA gene that was affilia......The marine subsurface sediment biosphere is widely inhabited by bacteria affiliated with the class Dehalococcoidia (DEH), phylum Chloroflexi, and yet little is known regarding their metabolisms. In this report, genomic content from a single DEH cell (DEH-C11) with a 16S rRNA gene...... that was affiliated with a diverse cluster of 16S rRNA gene sequences prevalent in marine sediments was obtained from sediments of Aarhus Bay, Denmark. The distinctive gene content of this cell suggests metabolic characteristics that differ from those of known DEH and Chloroflexi. The presence of genes encoding...... dissimilatory sulfite reductase (Dsr) suggests that DEH could respire oxidized sulfur compounds, although Chloroflexi have never been implicated in this mode of sulfur cycling. Using long-range PCR assays targeting DEH dsr loci, dsrAB genes were amplified and sequenced from various marine sediments. Many...

Toxicological potential of 2-alkylcyclobutanones--specific radiolytic products in irradiated fat-containing food--in bacteria and human cell lines

NARCIS (Netherlands)

Hartwig, A; Pelzer, A; Burnouf, D; Titéca, H; Delincée, H; Briviba, K; Soika, C; Hodapp, C; Raul, F; Miesch, M; Werner, D; Horvatovich, P; Marchioni, E

2007-01-01

Food irradiation has been considered as a safe processing technology to improve food safety and preservation, eliminating efficiently bacterial pathogens, parasites and insects. This study aims to characterize the toxicological potential of 2-alkylcyclobutanones (2-ACBs), radiolytic derivatives of

Levels of Sulfur as an Essential Nutrient Element in the Soil-Crop-Food System in Austria

Directory of Open Access Journals (Sweden)

Manfred Sager

2012-01-01

Full Text Available Total sulfur data of various agricultural and food items from the lab of the author, have been compiled to develop an understanding of sulfur levels and ecological cycling in Austria. As sulfur level is not an included factor among the quality criteria of soil and fertilizer composition, the database is rather small. Problems in analytical determinations of total sulfur, in particular digestions, are outlined. As a protein component, sulfur is enriched in matrices of animal origin, in particular in egg white. There is substantial excretion from animals and man via urine. Organic fertilizers (manures, composts might contribute significantly to the sulfur budget of soils, which is important for organic farming of crops with high sulfur needs. For soils, drainage is a main route of loss of soluble sulfate, thus pot experiments may yield unrealistic sulfur budgets.

Geology and stable isotope geochemistry of Paleoarchean sulfur. Formation, preservation and geobiology of ancient pyrite and barite

NARCIS (Netherlands)

Roerdink, D.L.|info:eu-repo/dai/nl/318834340

2013-01-01

Sulfur isotopes in ancient sulfate and sulfide minerals provide a comprehensive record of microbial processes involved in the early sulfur cycle on Earth. However, the interpretation of these isotopic signatures requires information on the geological context of such samples, because abiotic

A Facile Bottom-Up Approach to Construct Hybrid Flexible Cathode Scaffold for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Ghosh, Arnab; Manjunatha, Revanasiddappa; Kumar, Rajat; Mitra, Sagar

2016-12-14

Lithium-sulfur batteries mostly suffer from the low utilization of sulfur, poor cycle life, and low rate performances. The prime factors that affect the performance are enormous volume change of the electrode, soluble intermediate product formation, poor electronic and ionic conductivity of S, and end discharge products (i.e., Li 2 S 2 and Li 2 S). The attractive way to mitigate these challenges underlying in the fabrication of a sulfur nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic as well as electronic conductivity leading to a mechanically robust and mixed conductive (ionic and electronic conductive) sulfur electrode. Herein, we report a novel bottom-up approach to synthesize a unique freestanding, flexible cathode scaffold made of porous reduced graphene oxide, nanosized sulfur, and Mn 3 O 4 nanoparticles, and all are three-dimensionally interconnected to each other by hybrid polyaniline/sodium alginate (PANI-SA) matrix to serve individual purposes. A capacity of 1098 mAh g -1 is achieved against lithium after 200 cycles at a current rate of 2 A g -1 with 97.6% of initial capacity at a same current rate, suggesting the extreme stability and cycling performance of such electrode. Interestingly, with the higher current density of 5 A g -1 , the composite electrode exhibited an initial capacity of 1015 mA h g -1 and retained 71% of the original capacity after 500 cycles. The in situ Raman study confirms the polysulfide absorption capability of Mn 3 O 4 . This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance lithium-sulfur batteries and a strategy that can be used to develop flexible large power storage devices.

Chemical Immobilization Effect on Lithium Polysulfides for Lithium-Sulfur Batteries.

Science.gov (United States)

Li, Caixia; Xi, Zhucong; Guo, Dexiang; Chen, Xiangju; Yin, Longwei

2018-01-01

Despite great progress in lithium-sulfur batteries (LSBs), great obstacles still exist to achieve high loading content of sulfur and avoid the loss of active materials due to the dissolution of the intermediate polysulfide products in the electrolyte. Relationships between the intrinsic properties of nanostructured hosts and electrochemical performance of LSBs, especially, the chemical interaction effects on immobilizing polysulfides for LSB cathodes, are discussed in this Review. Moreover, the principle of rational microstructure design for LSB cathode materials with strong chemical interaction adsorbent effects on polysulfides, such as metallic compounds, metal particles, organic polymers, and heteroatom-doped carbon, is mainly described. According to the chemical immobilizing mechanism of polysulfide on LSB cathodes, three kinds of chemical immobilizing effects, including the strong chemical affinity between polar host and polar polysulfides, the chemical bonding effect between sulfur and the special function groups/atoms, and the catalytic effect on electrochemical reaction kinetics, are thoroughly reviewed. To improve the electrochemical performance and long cycling life-cycle stability of LSBs, possible solutions and strategies with respect to the rational design of the microstructure of LSB cathodes are comprehensively analyzed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of once-through hybrid sulfur process for nuclear hydrogen production

International Nuclear Information System (INIS)

Jung, Yong Hun

2010-02-01

Humanity has been facing major energy challenges such as the severe climate change, threat of energy security and global energy shortage especially for the developing world. Particularly, growing awareness of the global warming has led to efforts to develop the sustainable energy technologies for the harmony of the economy, social welfare and environment. Water-splitting nuclear hydrogen production is expected to help to resolve those challenges, when high energy efficiency and low cost for hydrogen production become possible. Once-through Hybrid Sulfur process (Ot-HyS), proposed in this work, produces hydrogen using the same SO 2 Depolarized water Electrolysis (SDE) process found in the original Hybrid Sulfur cycle (HyS) proposed by Westinghouse, which has the sulfuric acid decomposition (SAD) process using high temperature heat source in order to recover sulfur dioxide for the SDE process. But Ot-HyS eliminated this technical hurdle by replacing it with well-established sulfur combustion process to feed sulfur dioxide to the SDE process. Because Ot-HyS has less technical challenges, Ot-HyS is expected to advance the realization of the large-scale nuclear hydrogen production by feeding an initial nuclear hydrogen stock. Most of the elemental sulfur, at present, is supplied by desulfurization process for environmental reasons during the processing of natural gas and petroleum refining and expected to increase significantly. This recovered sulfur will be burned with oxygen in the sulfur combustion process so that produced sulfur dioxide could be supplied to the SDE process to produce hydrogen. Because the sulfur combustion is a highly exothermic reaction releasing 297 kJ/mol of combustion heat resulting in a large temperature rise, efficiency of the Ot-HyS is expected to be high by recovering this great amount of high grade excess heat with nuclear energy. Sulfuric acid, which is a byproduct of the SDE process, could be sent to the neighboring consumers with or even

In-test and post-test analyses of sodium-sulfur cells

Energy Technology Data Exchange (ETDEWEB)

Wada, Motoi; Kawamoto, Hiroyuki; Hatoh, Hisamitsu

1986-01-15

Cell life of sodium-sulfur cells is often determined by the degradation of the solid electrolyte. Solid electrolyte degradation will cause an increase of electrolyte resistivity, decrease of faradic efficiency, or even an electrolyte rupture which leads to a cell temperature rise due to direct reaction of reactants. Electrolyte degradation in actual sodium-sulfur cells is believed to be caused by the passage of sodium ion current across the solid electrolyte. The degree of degradation has been reported to be a function of amount of charge passed through the electrolyte, and the breakdown of the solid electrolyte was observed to occur above some threshold. For this reason, the concentration of sodium ion current density is to be avoided to prevent solid electrolyte from premature degradation and rupture, and the electrode structure for a sodium-sulfur cell should be determined with enough care to homogenize the current density distribution on the electrolyte. The longitudinal current density distribution of a sodium-sulfur cell was measured by attaching probing terminals on the electrode container. It was found that the current density distribution of a vertically supported cell was inhomogeneous due to the effect of gravity. This setup can be used as a way to locate the place where the first electrolyte cracking occurs. It was also found that the electrolyte cracking accompanies a fluctuation of cycling cell voltage that starts to appear several cycles before the noticeable break down of the electrolyte.

Facile synthesis of graphene oxide @ mesoporous carbon hybrid nanocomposites for lithium sulfur battery

International Nuclear Information System (INIS)

Bao, Weizhai; Zhang, Zhian; Chen, Wei; Zhou, Chengkun; Lai, Yanqing; Li, Jie

2014-01-01

Graphical abstract: - Highlights: • A novel design and synthesis of GO@Meso-C using GO@MOF-5 as precursor. • GO@Meso-C hybrid material as a host material was applied for sulfur cathode. • Electrochemical performances were improved in sulfur cathode using Go@Meso-C. - Abstract: We present a design and synthesis of a hierarchical architecture of graphene oxide @ mesoporous carbon (GO@Meso-C) using graphene oxide @ metal-organic framework hybrid materials (GO@MOF-5) as both the template and precursor. Active sulfur is encapsulated into the GO@Meso-C matrix prepared via carbonize GO@MOF-5 polyhedrons for high performance lithium sulfur battery. The initial and 100th cycle discharge capacity of GO@Meso-C/S sulfur cathode are as high as 1122 mAh g −1 and 820 mAh g −1 at a current rate of 0.2 C. The remarkably high special capacity and capacity retention rate indicate that the GO@Meso-C is a promising host material for the sulfur cathode in the lithium sulfur battery applications

Biologically produced sulfur

NARCIS (Netherlands)

Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

2003-01-01

Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are

Flexible three-dimensional electrodes of hollow carbon bead strings as graded sulfur reservoirs and the synergistic mechanism for lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Yang, Dan [College of Materials Science and Engineering, Sichuan University, Chengdu, 610064 (China); Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Ni, Wei, E-mail: niwei@iccas.ac.cn [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Cheng, Jianli; Wang, Zhuanpei; Wang, Ting; Guan, Qun [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Zhang, Yun, E-mail: y_zhang@scu.edu.cn [College of Materials Science and Engineering, Sichuan University, Chengdu, 610064 (China); Wu, Hao [College of Materials Science and Engineering, Sichuan University, Chengdu, 610064 (China); Li, Xiaodong [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China); Wang, Bin, E-mail: edward.bwang@gmail.com [Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang, 621900 (China)

2017-08-15

Graphical abstract: Flexible three-dimensional electrode comprised of stringed N-doped hollow carbon spheres shows a synergistic sulfur confinement mechanism and a higher energy/power density for the promising lithium-sulfur batteries compared with traditional electrodes. - Highlights: • Hollow carbon beads on string structure was first prepared. • Flexible 3D electrodes as graded reservoirs for polysulfides were conducted. • Synergistic effect for enhanced polysulfides storage was claimed. - Abstract: Three-dimensional (3D) flexible electrodes of stringed hollow nitrogen-doped (N-doped) carbon nanospheres as graded sulfur reservoirs and conductive frameworks were elaborately designed via a combination of the advantages of hollow structures, 3D electrodes and flexible devices. The as-prepared electrodes by a synergistic method of electrospinning, template sacrificing and activation for Li–S batteries without any binder or conductive additives but a 3D interconnected conductive network offered multiple transport paths for electrons and improved sulfur utilization and facilitated an easy access to Li{sup +} ingress/egress. With the increase of density of hollow carbon spheres in the strings, the self-supporting composite electrode reveals an enhanced synergistic mechanism for sulfur confinement and displays a better cycling stability and rate performance. It delivers a high initial specific capacity of 1422.6 mAh g{sup −1} at the current rate of 0.2C with the high sulfur content of 76 wt.%, and a much higher energy density of 754 Wh kg{sup −1} and power density of 1901 Wh kg{sup −1}, which greatly improve the energy/power density of traditional lithium–sulfur batteries and will be promising for further commercial applications.

Emissions of carbon, nitrogen, and sulfur from biomass burning in Nigeria

International Nuclear Information System (INIS)

Akeredolu, F.; Isichei, A.O.

1991-01-01

The atmospheric implications of the effects of burning of vegetation in Nigeria are discussed. The following topics are explored: the extent of biomass burning by geographical area; estimates of emission rates of carbon, nitrogen and sulfur; and the impact on biogeochemical cycling of elements. The results suggest that biomass burning generates a measurable impact on the cycling of carbon and nitrogen

Efficiency of the sulfur-iodine thermochemical water splitting process for hydrogen production based on ADS

International Nuclear Information System (INIS)

Gonzalez, D.; Garcia, L.; Garcia, C.; Garcia, L.; Brayner, C.

2013-01-01

The current hydrogel production is based on fossil fuels; they have a huge contribution to the atmosphere's pollution. thermochemical water splitting cycles don't present this issue because the required process heat is obtained from nuclear energy and therefore, the environmental impact is smaller than using conventional fuels. One of the promising approaches to produce large quantities of hydrogen in an efficient way using nuclear energy is the sulfur-iodine (S-I) thermochemical water splitting cycle. The nuclear source proposed in this paper is a pebble bed gas cooled transmutation facility. Pebble bed very high temperature advanced systems have great perspectives to assume the future nuclear energy. Software based on Chemical Process Simulation (CPS) can be used to simulate the thermochemical water splitting sulfur-iodine cycle for hydrogen production. In this paper, a model for analyzing the sulfur-iodine process sensibility is developed. Efficiency is also calculated and the influence of different parameters on this value. The behavior of the proposed model before different values of initial reactant's flow is analyzed. (Author)

Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

International Nuclear Information System (INIS)

Zheng, Jianming; Yan, Pengfei; Gu, Meng; Wagner, Michael J.; Hays, Kevin A.; Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

2015-01-01

Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness, and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species, which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li 2 S 2 /Li 2 S), which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

Energy Technology Data Exchange (ETDEWEB)

Zheng, Jianming; Yan, Pengfei; Gu, Meng [Pacific Northwest National Laboratory, Richland, WA (United States); Wagner, Michael J.; Hays, Kevin A. [The George Washington University, Washington, DC (United States); Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie, E-mail: jie.xiao@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States)

2015-05-26

Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness, and environmental friendliness of sulfur. However, there are still a number of technical challenges, such as low Coulombic efficiency and poor long-term cycle life, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species, which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) with highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li{sub 2}S{sub 2}/Li{sub 2}S), which limits the reversibility of the interfacial reactions and results in poor electrochemical performances. These findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.

A natural carbonized leaf as polysulfide diffusion inhibitor for high-performance lithium-sulfur battery cells.

Science.gov (United States)

Chung, Sheng-Heng; Manthiram, Arumugam

2014-06-01

Attracted by the unique tissue and functions of leaves, a natural carbonized leaf (CL) is presented as a polysulfide diffusion inhibitor in lithium-sulfur (Li-S) batteries. The CL that is covered on the pure sulfur cathode effectively suppresses the polysulfide shuttling mechanism and enables the use of pure sulfur as the cathode. A low charge resistance and a high discharge capacity of 1320 mA h g(-1) arise from the improved cell conductivity due to the innately integral conductive carbon network of the CL. The unique microstructure of CL leads to a high discharge/charge efficiency of >98 %, low capacity fade of 0.18 % per cycle, and good long-term cyclability over 150 cycles. The structural gradient and the micro/mesoporous adsorption sites of CL effectively intercept/trap the migrating polysulfides and facilitate their reutilization. The green CL polysulfide diffusion inhibitor thus offers a viable approach for developing high-performance lithium-sulfur batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk; Cho, Gyu-Bong; Cho, Kwon-Koo; Kim, Ki-Won [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical & Biological Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Wang, Guoxiu [School of Chemistry and Forensic Science, University of Technology Sydney, Sydney, NSW 2007 (Australia); Ahn, Jae-Pyeung [Advanced Analysis Center, Research Planning & Coordination Division, KIST, Seoul (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of)

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur content is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)

Radiolytic generation of chloro-organic compounds in transuranic and low-level radioactive waste

International Nuclear Information System (INIS)

Reed, D.T.; Armstrong, S.C.; Krause, T.R.

1993-01-01

The radiolytic degradation of chloro-plastics is being investigated to evaluate the formation of chlorinated volatile organic compounds in radioactive waste. These chlorinated VOCs, when their subsequent migration in the geosphere is considered, are potential sources of ground-water contamination. This contamination is an important consideration for transuranic waste repositories being proposed for the Waste Isolation Pilot Plant project and the several additional low-level radioactive waste sites being considered throughout the United States. The production of chlorinated volatile organic compounds due to the interaction of ionizing radiation with chloro-plastic materials has been well-established in both this work and past studies. This occurs as a result of gamma, beta, and alpha particle interactions with the plastic material. The assemblage of organic compounds generated depends on the type of plastic material, the type of ionizing radiation, the gaseous environment present and the irradiation temperature. In the authors' experiments, gas generation data were obtained by mounting representative plastics near (3 mm) an alpha particle source (Am-241 foil). This assembly was placed in an irradiation vessel which contained air, nitrogen, or a hydrogen/carbon dioxide mixture, at near-atmospheric pressures, to simulate the range of atmospheres likely to be encountered in the subsurface. The gas phase in the vessels are periodically sampled for net gas production. The gas phase concentrations are monitored over time to determine trends and calculate the radiolytic yield for the various gaseous products

Sulfur biogeochemistry of oil sands composite tailings

Energy Technology Data Exchange (ETDEWEB)

Warren, Lesley; Stephenson, Kate [Earth Sciences, McMaster University (Canada)], email: warrenl@mcmaster.ca; Penner, Tara [Syncrude Environmental Research (Canada)

2011-07-01

This paper discusses the sulfur biogeochemistry of oil sands composite tailings (CT). The Government of Alberta is accelerating reclamation activities on composite tailings. As a CT pilot reclamation operation, Syncrude is currently constructing the first freshwater fen. Minor unpredicted incidents with H2S gas released from the dewatering process associated with these reclamations have been reported. The objective of this study is to ascertain the connection between microbial activity and H2S generation within CT and to assess the sulfur biogeochemistry of untreated and treated (fen) CT over seasonal and annual timescales. The microbial geochemical interactions taking place are shown using a flow chart. CT is composed of gypsum, sand, clay and organics like naphthenic acids and bitumen. Sulfur and Fe cycling in mining systems and their microbial activities are presented. The chemistry and the processes involved within CT are also given along with the results. It can be said that the diverse Fe and S metabolizing microorganisms confirm the ecology involved in H2S dynamics.

Stable isotope phenotyping via cluster analysis of NanoSIMS data as a method for characterizing distinct microbial ecophysiologies and sulfur-cycling in the environment

Directory of Open Access Journals (Sweden)

Katherine S Dawson

2016-05-01

Full Text Available Stable isotope probing (SIP is a valuable tool for gaining insights into ecophysiology and biogeochemical cycling of environmental microbial communities by tracking isotopically labeled compounds into cellular macromolecules as well as into byproducts of respiration. SIP, in conjunction with nanoscale secondary ion mass spectrometry (NanoSIMS, allows for the visualization of isotope incorporation at the single cell level. In this manner, both active cells within a diverse population as well as heterogeneity in metabolism within a homogeneous population can be observed. The ecophysiological implications of these single cell stable isotope measurements are often limited to the taxonomic resolution of paired fluorescence in situ hybridization (FISH microscopy. Here we introduce a taxonomy-independent method using multi-isotope SIP and NanoSIMS for identifying and grouping phenotypically similar microbial cells by their chemical and isotopic fingerprint. This method was applied to SIP experiments in a sulfur-cycling biofilm collected from sulfidic intertidal vents amended with 13C-acetate, 15N-ammonium, and 33S-sulfate. Using a cluster analysis technique based on fuzzy c-means to group cells according to their isotope (13C/12C, 15N/14N, and 33S/32S and elemental ratio (C/CN and S/CN profiles, our analysis partitioned ~2200 cellular regions of interest (ROIs into 5 distinct groups. These isotope phenotype groupings are reflective of the variation in labeled substrate uptake by cells in a multispecies metabolic network dominated by Gamma- and Deltaproteobacteria. Populations independently grouped by isotope phenotype were subsequently compared with paired FISH data, demonstrating a single coherent deltaproteobacterial cluster and multiple gammaproteobacterial groups, highlighting the distinct ecophysiologies of spatially-associated microbes within the sulfur-cycling biofilm from White Point Beach, CA.

Cross-stacked carbon nanotube film as an additional built-in current collector and adsorption layer for high-performance lithium sulfur batteries.

Science.gov (United States)

Sun, Li; Kong, Weibang; Li, Mengya; Wu, Hengcai; Jiang, Kaili; Li, Qunqing; Zhang, Yihe; Wang, Jiaping; Fan, Shoushan

2016-02-19

Cross-stacked carbon nanotube (CNT) film is proposed as an additional built-in current collector and adsorption layer in sulfur cathodes for advanced lithium sulfur (Li-S) batteries. On one hand, the CNT film with high conductivity, microstructural rough surface, high flexibility and mechanical durability retains stable and direct electronic contact with the sulfur cathode materials, therefore decreasing internal resistivity and suppressing polarization of the cathode. On the other hand, the highly porous structure and the high surface area of the CNT film provide abundant adsorption points to support and confine sulfur cathode materials, alleviate their aggregation and promote high sulfur utilization. Moreover, the lightweight and compact structure of the CNT film adds no extra weight or volume to the sulfur cathode, benefitting the improvement of energy densities. Based on these characteristics, the sulfur cathode with a 100-layer cross-stacked CNT film presents excellent rate performances with capacities of 986, 922 and 874 mAh g(-1) at cycling rates of 0.2C, 0.5C and 1C for sulfur loading of 60 wt%, corresponding to an improvement of 52%, 109% and 146% compared to that without a CNT film. Promising cycling performances are also demonstrated, offering great potential for scaled-up production of sulfur cathodes for Li-S batteries.

Structural, optical and thermal properties of PVA/CdS nanocomposites synthesized by radiolytic method

International Nuclear Information System (INIS)

Kharazmi, Alireza; Saion, Elias; Faraji, Nastaran; Hussin, Roslina Mat; Yunus, W. Mahmood Mat

2014-01-01

Monodispersed spherical CdS nanoparticles stabilized in PVA solution were synthesized by the gamma radiolytic method and found the average particle size increased from 12 to 13 nm with the increment of dose from 10 to 40 kGy. The XRD results show that it has crystalline planes of cubic structure with crystal lattice parameter of 5.832 Å. The optical reflectance revealed a band-edge of CdS nanoparticles at about 475 nm and the reflectance wavelength red shifted with increasing dose due to increasing particle size. The thermal conductivity of CdS/PVA nanocomposites measured by the transient hot wire method that revealed a decrement of the thermal conductivity with an increase of dose caused by effect of radiation on crystallinity of the polymer structure. - Highlights: • CdS/PVA nanocomposite was synthesized by radiolytic method from 10 to 40 kGy doses. • The structure of nanocomposite and the effect of dose on structure were investigated by X-ray powder diffraction. • The morphology of nanoparticles and the effect of dose on nanoparticles were observed by transmission electron microscope. • The optical properties of nanocomposite and the effect of radiation were studied by UV–visible spectroscopy and fluorescence spectroscopy. • The thermal properties of nanocomposite and the effect of dose were investigated by the transient hot wire method

The radiolytic cracking decomposion of the plant cellulose materials and their chemcial properties

International Nuclear Information System (INIS)

Shou Hongxia

1987-01-01

Under the treatment with high energy radiation, plant cellulose materials undergo a series of changes in chemical and physical properties. This paper describes the chemical changes of water-soluble carbohydrate, easy-to-hydrolyse carbohydrate, hard-to-hydrolyse carbohydrate, amino acid and protein in rice straw after irradiation with 60 Co γ-ray. The content of water-soluble carbohydrate in rice straw can be increased significantly by such treatment. The combination treatment of irradiation and acid or alkali soaker can reduce the dose for the radiolytic cracking decomposition and produce a good effect

Performance Enhancement of a Sulfur/Carbon Cathode by Polydopamine as an Efficient Shell for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Zhang, Xuqing; Xie, Dong; Zhong, Yu; Wang, Donghuang; Wu, Jianbo; Wang, Xiuli; Xia, Xinhui; Gu, Changdong; Tu, Jiangping

2017-08-04

Lithium-sulfur batteries (LSBs) are considered to be among the most promising next-generation high-energy batteries. It is a consensus that improving the conductivity of sulfur cathodes and impeding the dissolution of lithium polysulfides are two key accesses to high-performance LSBs. Herein we report a sulfur/carbon black (S/C) cathode modified by self-polymerized polydopamine (pDA) with the assistance of polymerization treatment. The pDA acts as a novel and effective shell on the S/C cathode to stop the shuttle effect of polysulfides. By the synergistic effect of enhanced conductivity and multiple blocking effect for polysulfides, the S/C@pDA electrode exhibits improved electrochemical performances including large specific capacity (1135 mAh g -1 at 0.2 C), high rate capability (533 mAh g -1 at 5 C) and long cyclic life (965 mAh g -1 after 200 cycles). Our smart design strategy may promote the development of high-performance LSBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfur-Kβ /sub emission studies on sulfur-bearing heterocycles

International Nuclear Information System (INIS)

Phillips, D.R.; Andermann, G.G.; Fujiwara, F.

1986-01-01

Sulfur-K/β /sub x-ray fluorescence spectroscopy (XFS) has been used to study the electronic structure and bonding in sulfur-bearing heterocycles. XFS not only has the capability of experimentally measuring valence electron energies in molecular species, but can also provide intensity data which can help define the nature of the molecular orbitals defined by the electrons. This report discusses the feasibility of using XFS as an analytical tool for the determination of total and specific sulfur heterocycle content in samples. A variety of compounds were studied. These include thiophene, thiophene derivatives, tetranydrothiophene, several more complex saturated and unsaturated sulfur heterocycles, and heterocycles containing both sulfur and nitrogen. The sulfur-K/β /sub spectra were obtained using a double crystal spectrometer which provided an instrumental resolution of about 0.7 eV

How a gel polymer electrolyte affects performance of lithium/sulfur batteries

International Nuclear Information System (INIS)

Zhang, Sheng S.; Tran, Dat T.

2013-01-01

Highlights: •Conventional separator is coated with a 50PEO-50SiO 2 (wt.%) composite layer. •Composite coating increases tensile strength and electrolyte wettability. •Coated separator offers an alternative approach for making gel polymer Li/S battery. •Li/S battery takes benefits of gel polymer electrolyte at the expense of capacity. -- Abstract: Gel polymer electrolyte (GPE) and composite gel polymer electrolyte (CGPE) have been widely employed to improve the safety and cycling performance of rechargeable lithium and lithium-ion batteries. In order to determine whether this approach is applicable to lithium/sulfur (Li/S) battery, we examine the effect of CGPE on the cycling and storage performances of Li/S cells by comparing a 50PEO-50SiO 2 (wt.%) composite coated separator (C-separator) with a pristine separator (P-separator). Results show that the composite coating significantly enhances the wettability of liquid electrolyte on the separator and that resulting CGPE can tightly glue the separator and electrode together. In comparison with the P-separator, the C-separator offers Li/S cells similar capacity retention and rate capability; however it greatly affects the specific capacity of sulfur. The analysis on the impedance spectrum of a lithium polysulfide (PS) solution reveal that the reduction of sulfur specific capacity is due to the high viscosity of the CGPE and the strong adsorption of SiO 2 filler to the PS species, which trap PS species in the separator and hence reduce the utilization of sulfur active material. Therefore, the benefits of the GPE and CGPE to the Li/S batteries can be taken only at the expense of sulfur specific capacity

Multiple-heteroatom-containing sulfur compounds in a high sulfur coal

International Nuclear Information System (INIS)

Winans, R.E.; Neill, P.H.

1990-01-01

Flash vacuum pyrolysis of a high sulfur coal has been combined with high resolution mass spectrometry yielding information on aromatic sulfur compounds containing an additional heteroatom. Sulfur emission from coal utilization is a critical problem and in order to devise efficient methods for removing organic sulfur, it is important to know what types of molecules contain sulfur. A high sulfur Illinois No. 6 bituminous coal (Argonne Premium Coal Sample No. 3) was pyrolyzed on a platinum grid using a quartz probe inserted into a modified all glass heated inlet system and the products characterized by high resolution mass spectrometry (HRMS). A significant number of products were observed which contained both sulfur and an additional heteroatom. In some cases two additional heteroatoms were observed. These results are compared to those found in coal extracts and liquefaction products

New method for reduction of burning sulfur of coal

International Nuclear Information System (INIS)

Lyutskanov, L.; Dushanov, D.

1998-01-01

The coal pyrolysis is key phase in the the pyrolysis-combustion cycle as it provides char for combustor. The behaviour of sulfur compounds during coal pyrolysis depends on factors as rank of coal, quantity of sulfur and sulfur forms distribution in the coal, quantity and kind of mineral matter and the process conditions. The mineral content of coal may inhibit or catalyze the formation of volatile sulfur compounds. The pyrolysis itself is a mean of removing inorganic and organic sulfur but anyway a portion of it remains in the char while the other moves into the tar and gas. The aim of this study was to determine an optimal reduction of burning sulfur at the coal pyrolysis by varying parametric conditions. The pyrolysis of different kinds of coal has been studied. The samples with size particles o C at atmospheric pressure and with a heating rate of 6-50 o C min -1 . They were treated with exhaust gas and nitrogen at an addition of steam and air. The char obtained remains up to 10 min at the final temperature. The char samples cool without a contact with air. Two methods of desulfurization-pyrolysis were studied - using 9-vertical tubular reactor and 9-horizontal turning reactor. The results obtained show that at all samples there is a decrease of burning sulfur with maximal removal efficiency 83%. For example at a pyrolysis of Maritsa Iztok lignite coal the burning sulfur is only 16% in comparison with the control sample. The remained is 90% sulfate, 10% organic and pyrite traces when a mixture 'exhaust gas-water stream-air' was used. The method of desulfurization by pyrolysis could be applied at different kinds of coal and different conditions. Char obtained as a clean product can be used for generating electric power. This innovation is in a stage of patenting

Effect of radiolytic products on bacteria in a food system

International Nuclear Information System (INIS)

Dickson, J.S.; Maxcy, R.B.

1984-01-01

Inhibitory effects of radiolytic products were studied using Escherichia coli, Pediococcus cerevisiae, and two radiation-resistant microorganisms, an isolate of Moraxella-Acinetobacter and a Micrococcus sp. End Products of an irradiation dose of 300 Krads completely inhibited resistant organisms on an experimental medium with a very low concentration of nutrients. Plate count agar, with higher nutrient concentration, required 600 Krads to produce the same inhibition. On the same medium, radiation-sensitive organisms could tolerate products generated by a 1000 Krad dose. However, no inhibition could be detected when either Escherichia coli or Moraxella-Acinetobacter was incubated at 5 0 C on the surface of fresh meat irradiated to 1500 Krad. The effects of inhibitory products in culture media could be mitigated by the addition of catalase or sodium pyruvate. 19 references, 2 figures, 4 tables

Radiolytic and electron-transfer reactions in supercritical CO2

International Nuclear Information System (INIS)

Bartels, D. M.; Dimitrijevic, N. M.; Jonah, C. D.; Takahashi, K.

2000-01-01

Using supercritical fluids as solvents is useful for both practical and theoretical reasons. It has been proposed to use supercritical CO 2 as a solvent for synthesis because it eliminates the air pollution arising from other solvents. The properties of supercritical fluids can be easily varied with only modest changes in temperature and density, so they provide a way of testing theories of chemical reactions. It has also been proposed to use supercritical fluids for the treatment of hazardous mixed waste. For these reasons the authors have studied the production of radiolytic species in supercritical CO 2 and have measured their reactivity as a function of density. They have shown that the C 2 O 4 + is formed. They also have shown that the electron transfer reactions of dimethylaniline to C 2 O 4 + and CO 2 (e - ) to benzoquinone are diffusion controlled over a considerable density range

A three-dimensional cathode matrix with bi-confinement effect of polysulfide for lithium-sulfur battery

Science.gov (United States)

Song, Ren-Sheng; Wang, Bo; Ruan, Ting-Ting; Wang, Lei; Luo, Hao; Wang, Fei; Gao, Tian-Tian; Wang, Dian-Long

2018-01-01

Soluble polysulfide shuttling is still the main cause of restricting the development of lithium-sulfur (Li-S) battery. Here, we propose a novel three-dimensional reduced graphene oxide@sulfur/nitrogen-doped porous carbon polyhedron/carbon nanotubes (rGO@S/NCP/CNTs) composite with bi-confinement effect of polysulfide as an effective cathode material. In rGO@S/NCP/CNTs, NCP provides physical confinement for sulfur and soluble polysulfide by its abundant micropores and mesopores, while oxygen functional groups of rGO provide strong chemical confinement to soluble polysulfide. Additionally, CNTs with one-dimensional conductivity enable facile transport of electrons. Therefore, the resulting rGO@S/NCP/CNTs composite shows an obvious enhancement in cycling performance for Li-S battery, and reversible capacities up to 738 mAh g-1 and 660 mAh g-1 over 100 and 200 cycles are remained at 0.2 C rate.

A Comparison of Organic and Steam Rankine Cycle Power Systems for Waste Heat Recovery on Large Ships

Directory of Open Access Journals (Sweden)

Jesper Graa Andreasen

2017-04-01

Full Text Available This paper presents a comparison of the conventional dual pressure steam Rankine cycle process and the organic Rankine cycle process for marine engine waste heat recovery. The comparison was based on a container vessel, and results are presented for a high-sulfur (3 wt % and low-sulfur (0.5 wt % fuel case. The processes were compared based on their off-design performance for diesel engine loads in the range between 25% and 100%. The fluids considered in the organic Rankine cycle process were MM(hexamethyldisiloxane, toluene, n-pentane, i-pentane and c-pentane. The results of the comparison indicate that the net power output of the steam Rankine cycle process is higher at high engine loads, while the performance of the organic Rankine cycle units is higher at lower loads. Preliminary turbine design considerations suggest that higher turbine efficiencies can be obtained for the ORC unit turbines compared to the steam turbines. When the efficiency of the c-pentane turbine was allowed to be 10% points larger than the steam turbine efficiency, the organic Rankine cycle unit reaches higher net power outputs than the steam Rankine cycle unit at all engine loads for the low-sulfur fuel case. The net power production from the waste heat recovery units is generally higher for the low-sulfur fuel case. The steam Rankine cycle unit produces 18% more power at design compared to the high-sulfur fuel case, while the organic Rankine cycle unit using MM produces 33% more power.

ADVANCED SULFUR CONTROL CONCEPTS FOR HOT-GAS DESULFURIZATION TECHNOLOGY

Energy Technology Data Exchange (ETDEWEB)

A. LOPEZ ORTIZ; D.P. HARRISON; F.R. GROVES; J.D. WHITE; S. ZHANG; W.-N. HUANG; Y. ZENG

1998-10-31

a twenty-five-cycle test. The sorbent was exposed for 58 consecutive days to temperatures between 600°C and 800°C and gas atmospheres from highly reducing to highly oxidizing without measurable loss of sulfur capacity or reactivity. In the process analysis phase of this study, a two-stage desulfurization process using cerium sorbent with SO2 regeneration followed by zinc sorbent with dilute O2 regeneration was compared to a single-stage process using zinc sorbent and O2 regeneration with SO2 in the regeneration product gas converted to elemental sulfur using the direct sulfur recovery process (DSRP). Material and energy balances were calculated using the process simulation package PRO/II. Major process equipment was sized and a preliminary economic analysis completed. Sorbent replacement rate, which is determined by the multicycle sorbent durability, was found to be the most significant factor in both processes. For large replacement rates corresponding to average sorbent lifetimes of 250 cycles or less, the single-stage zinc sorbent process with DSRP was estimated to be less costly. However, the cost of the two-stage cerium sorbent process was more sensitive to sorbent replacement rate, and, as the required replacement rate decreased, the economics of the two-stage process improved. For small sorbent replacement rates corresponding to average sorbent lifetimes of 1000 cycles or more, the two-stage cerium process was estimated to be less costly. In the relatively wide middle range of sorbent replacement rates, the relative economics of the two processes depends on other factors such as the unit cost of sorbents, oxygen, nitrogen, and the relative capital costs.

Advanced sulfur control concepts for hot-gas desulfurization technology

International Nuclear Information System (INIS)

Lopez Ortiz, A.; Harrison, D.P.; Groves, F.R.; White, J.D.; Zhang, S.; Huang, W.N.; Zeng, Y.

1998-01-01

twenty-five-cycle test. The sorbent was exposed for 58 consecutive days to temperatures between 600C and 800C and gas atmospheres from highly reducing to highly oxidizing without measurable loss of sulfur capacity or reactivity. In the process analysis phase of this study, a two-stage desulfurization process using cerium sorbent with SO2 regeneration followed by zinc sorbent with dilute O2 regeneration was compared to a single-stage process using zinc sorbent and O2 regeneration with SO2 in the regeneration product gas converted to elemental sulfur using the direct sulfur recovery process (DSRP). Material and energy balances were calculated using the process simulation package PRO/II. Major process equipment was sized and a preliminary economic analysis completed. Sorbent replacement rate, which is determined by the multicycle sorbent durability, was found to be the most significant factor in both processes. For large replacement rates corresponding to average sorbent lifetimes of 250 cycles or less, the single-stage zinc sorbent process with DSRP was estimated to be less costly. However, the cost of the two-stage cerium sorbent process was more sensitive to sorbent replacement rate, and, as the required replacement rate decreased, the economics of the two-stage process improved. For small sorbent replacement rates corresponding to average sorbent lifetimes of 1000 cycles or more, the two-stage cerium process was estimated to be less costly. In the relatively wide middle range of sorbent replacement rates, the relative economics of the two processes depends on other factors such as the unit cost of sorbents, oxygen, nitrogen, and the relative capital costs

Time-dependent radiolytic yields at room temperature and temperature-dependent absorption spectra of the solvated electrons in polyols

International Nuclear Information System (INIS)

Lin Mingzhang; Mostafavi, M.; Lampre, I.; Muroya, Y.; Katsumura, Y.

2007-01-01

The molar extinction coefficients at the absorption maximum of the solvated electron spectrum have been evaluated to be 900, 970, and 1000 mol -1 ·m 2 for 1,2-ethanediol (12ED), 1,2-propanediol (12PD), and 1,3-propanediol (13PD), respectively. These values are two-third or three-fourth of the value usually reported in the published report. Picosecond pulse radiolysis studies have aided in depicting the radiolytic yield of the solvated electron in these solvents as a function of time from picosecond to microsecond. The radiolytic yield in these viscous solvents is found to be strongly different from that of the water solution. The temperature dependent absorption spectra of the solvated electron in 12ED, 12PD, and 13PD have been also investigated. In all the three solvents, the optical spectra shift to the red with increasing temperature. While the shape of the spectra does not change in 13PD, a widening on the blue side of the absorption band is observed in 12ED and 12PD at elevated temperatures. (authors)

Radiolytic stabilization of poly(hydroxybutyrate)

International Nuclear Information System (INIS)

Santos, Renata F.S.; Araujo, Elmo S.

2007-01-01

Poly(hydroxybutyrate), PHB, is a thermoplastic polyester synthesized by many types of bacteria. PHB is of special interest in the manufacture of medical devices sterilizable by gamma radiation, because of remarkable characteristics like its great biocompatibility and biodegradability. However, ionizing radiation causes main chain scissions of PHB followed by the reduction in its molar mass. Then, the purpose of this study was to investigate the radiolytic stabilization of the structure and properties of Brazilian PHB by commercial additives used in photo and thermo-oxidative stabilization of polymers. Initially, casting solvent films were prepared adding 0.5 wt% of five different additives to the polymer system. These films were irradiated at 25 kGy and investigated viscosity-average molar mass (Mv) changes in order to select the best stabilizer. Among the tested additives only one, antioxidant type, provided a good radiostabilization. New polymeric films were prepared with the antioxidant, whose concentrations (wt%) were 0.3, 0.5, 0.7 and 1.0. In this case, the samples were submitted to doses that varied from 15 to 50 kGy. Viscometric analysis was performed in order to assess the radiation-induced main chain scissions. The G value (scissions/100eV of energy transferred to the system) was also obtained by the viscosity technique. The most effective additive, added to the polymer system at 0.5 wt%, promotes a decrease of 8.6 to 1.5 in G value at a dose range of 0 - 35 kGy. In addition, (FT-IR, NMR-1H) spectroscopic analyses on polymer system were also performed. (author)

Sulfur isotope studies of biogenic sulfur emissions at Wallops Island, Virginia

International Nuclear Information System (INIS)

Hitchcock, D.R.; Black, M.S.; Herbst, R.P.

1978-03-01

This research attempted to determine whether it is possible to measure the stable sulfur isotope distributions of atmospheric particulate and gaseous sulphur, and to use this information together with measurements of the ambient levels of sulfur gases and particulate sulfate and sodium in testing certain hypotheses. Sulfur dioxide and particulate sulfur samples were collected at a coastal marine location and their delta (34)S values were determined. These data were used together with sodium concentrations to determine the presence of biogenic sulfur and the identity of the biological processes producing it. Excess (non-seasalt) sulfate levels ranged from 2 to 26 micrograms/cu m and SO2 from 1 to 9 ppb. Analyses of air mass origins and lead concentrations indicated that some anthropogenic contaminants were present on all days, but the isotope data revealed that most of the atmospheric sulfur originated locally from the metabolism of bacterial sulfate reducers on all days, and that the atmospheric reactions leading to the production of sulfate from this biogenic sulfur source are extremely rapid. Delta 34 S values of atmospheric sulfur dioxide correlated well with those of excess sulfate, and implied little or no sulfur isotope fractionation during the oxidation of sulfur gases to sulfate

Atmospheric sulfur and climate changes: a modelling study at mid and high-southern latitudes; Soufre atmospherique et changements climatiques: une etude de modelisation pour les moyennes et hautes latitudes Sud

Energy Technology Data Exchange (ETDEWEB)

Castebrunet, H

2007-09-15

The mid and high-southern latitudes are still marginally affected by anthropogenic sulfur emissions. They are the only regions in the world where the natural cycle of the atmospheric sulfur may still be observed. Sulfur aerosols are well-known for their radiative impact, and thus interact with climate. Climate can in turn affect atmospheric sulfur sources, distribution and chemistry. Antarctic ice cores provide information on the evolution of climate and sulfur deposition at the surface of the ice sheet at glacial-interglacial time scales. The aim of this thesis is to develop and use modeling towards a better understanding of the atmospheric sulfur cycle in antarctic and sub-antarctic regions. Ice core data are used to validate model results under glacial climate conditions. An Atmospheric General Circulation Model (AGCM) coupled to a sulfur chemistry module is used: the LMD-ZTSulfur model, version 4. An update of both the physical and chemical parts of the model. The model was first performed. The impact of there changes on modelled sulfur cycle are evaluated for modern climate. Further, boundary conditions are adapted to simulate the atmospheric circulation and sulfur cycle at the Last Glacial Maximum, approximately 20,000 years ago. In the model, sulfur is found to be highly sensitive to antarctic sea-ice coverage, which is still poorly known during the ice age. An original dataset of ice-age sea-ice coverage was developed. Its impact on the oceanic emissions of dimethyl sulfide, main precursor of sulfur aerosols at high-southern latitudes, is discussed. Using the same oceanic sulfur reservoirs as for present day climate, the model broadly reproduces the glacial deposits of sulfur aerosols on the Antarctic plateau, suggesting little impact of climate on oceanic sulfur production in the Antarctic region. Sensitivity tests were carried out to draw an up-to-date status of major uncertainties and difficulties facing future progress in understanding atmospheric

Effects of Electrospun Carbon Nanofibers’ Interlayers on High-Performance Lithium–Sulfur Batteries

Directory of Open Access Journals (Sweden)

Tianji Gao

2017-03-01

Full Text Available Two different interlayers were introduced in lithium–sulfur batteries to improve the cycling stability with sulfur loading as high as 80% of total mass of cathode. Melamine was recommended as a nitrogen-rich (N-rich amine component to synthesize a modified polyacrylic acid (MPAA. The electrospun MPAA was carbonized into N-rich carbon nanofibers, which were used as cathode interlayers, while carbon nanofibers from PAA without melamine was used as an anode interlayer. At the rate of 0.1 C, the initial discharge capacity with two interlayers was 983 mAh g−1, and faded down to 651 mAh g−1 after 100 cycles with the coulombic efficiency of 95.4%. At the rate of 1 C, the discharge capacity was kept to 380 mAh g−1 after 600 cycles with a coulombic efficiency of 98.8%. It apparently demonstrated that the cathode interlayer is extremely effective at shutting down the migration of polysulfide ions. The anode interlayer induced the lithium ions to form uniform lithium metal deposits confined on the fiber surface and in the bulk to strengthen the cycling stability of the lithium metal anode.

Sulfur-Containing Agrochemicals.

Science.gov (United States)

Devendar, Ponnam; Yang, Guang-Fu

2017-10-09

Modern agricultural chemistry has to support farmers by providing innovative agrochemicals. In this context, the introduction of sulfur atoms into an active ingredient is still an important tool in modulating the properties of new crop-protection compounds. More than 30% of today's agrochemicals contain at least one sulfur atom, mainly in fungicides, herbicides and insecticides. A number of recently developed sulfur-containing agrochemical candidates represent a novel class of chemical compounds with new modes of action, so we intend to highlight the emerging interest in commercially active sulfur-containing compounds. This chapter gives a comprehensive overview of selected leading sulfur-containing pesticidal chemical families namely: sulfonylureas, sulfonamides, sulfur-containing heterocyclics, thioureas, sulfides, sulfones, sulfoxides and sulfoximines. Also, the most suitable large-scale synthetic methods of the recently launched or provisionally approved sulfur-containing agrochemicals from respective chemical families have been highlighted.

Impact of different metal turbidities on radiolytic hydrogen generation in nuclear power plants

International Nuclear Information System (INIS)

Kumbhar, A.G.; Belapurkar, A.D.; Venkateswaran, G.; Kishore, K.

2005-01-01

Radiolytic hydrogen generation on γ irradiation of turbid solutions containing metal turbidities such as titanium, nickel, iron, chromium, copper, indium, and aluminium was studied. It is suggested that the chemical reactivity of the metal in the turbid solution with e aq -/H/OH produced by radiolysis of water interferes with the recombination reactions which destroy H 2 and H 2 O 2 , thus leading to higher yield of hydrogen. The rate of generation of hydrogen and the G(H 2 ) value is related to the reactivity of the metal ion/hydroxylated species with the free radicals. (orig.)

Hydrogen output from radiolytic split of water in the presence of some zeolites

International Nuclear Information System (INIS)

Cecal, A.; Colisnic, D.; Popa, K.; Paraschivescu, A.; Bilba, N.

2002-01-01

Radiolytic decomposition of water under the action of gamma rays in the presence of some zeolites such as ZSM-5, SAPO-5 and MOR was studied. The irradiation was performed using a gamma 60 Co source at an activity of 3 . 10 4 Ci and dose rate 8.3 KGy/h. The stable products of radiolysis as well as the other chemical species were identified by mass spectrometry. The calculated radiochemical yield decreased in order: H-ZSM-5 > Na-ZSM-5 > H-SAPO-5 > MOR and was higher in the presence of these catalysts than in their absence

Radiolytic stabilization of industrial poly(methyl methacrylate); Estabilizacao radiolitica do poli(metacrilato de metila) industrial

Energy Technology Data Exchange (ETDEWEB)

Aquino, Katia Aparecida da Silva

2005-03-15

Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterilisable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its physical properties. Therefore, radiolytic stabilization of PMMA is important for to become it commercially radio sterilisable. In this work we investigated the radiolytic stabilization of PMMA by using HALS (Hindered Amine Light Stabilizer) additive, commercially used for photo and thermo oxidative stabilization of polymers. The investigation of the radiation-induced main chain scissions was carried out by viscometric method. The additive added to the polymer system at 0.3 % w/w promotes a molecular radioprotection of 61%. That means a reduction of G value (scissions/100 eV) from 2.6 to 1.0. In addition, the glassy transition temperature (Tg) of PMMA (no additive), significantly changed by radiation, does not change when PMMA (with additive) is irradiated. TGA analysis showed that the additive promotes thermal stability to the system, increasing decomposition temperature of PMMA. Spectroscopy analysis, FT-IR and RMN ({sup 1}H), showed that the radioprotector additive added to the system does not change the PMMA structure. Analysis on mechanical (tensile strength and elongation at break) and optical (yellowness index and refractive index) properties showed a good influence of the additive on polymer system. (author)

Diesel Emission Control- Sulfur Effects (DECSE) Program- Phase II Summary Report: NOx Adsorber Catalysts; FINAL

International Nuclear Information System (INIS)

None

2000-01-01

The investigations performed in this project demonstrated the ability to develop a NO(sub x) regeneration strategy including both an improved lean/rich modulation cycle and rich engine calibration, which resulted in a high NO(sub x) conversion efficiency over a range of operating temperatures. A high-temperature cycle was developed to desulfurize the NO(sub x) absorber catalyst. The effectiveness of the desulfurization process was demonstrated on catalysts aged using two different sulfur level fuels. The major findings of this project are as follows: (1) The improved lean/rich engine calibration achieved as a part of this test project resulted in NO(sub x) conversion efficiencies exceeding 90% over a catalyst inlet operating temperature window of 300 C-450 C. This performance level was achieved while staying within the 4% fuel economy penalty target defined for the regeneration calibration. (2) The desulfurization procedure developed showed that six catalysts, which had been exposed to fuel sulfur levels of 3-, 16-, and 30-ppm for as long as 250 hours, could be recovered to greater than 85% NO(sub x) conversion efficiency over a catalyst inlet operating temperature window of 300 C-450 C, after a single desulfurization event. This performance level was achieved while staying within the 4% fuel economy penalty target defined for the regeneration calibration. (3) The desulfurization procedure developed has the potential to meet in-service engine operating conditions and provide acceptable driveability conditions. (4) Although aging with 78-ppm sulfur fuel reduced NO(sub x) conversion efficiency more than aging with 3-ppm sulfur fuel as a result of sulfur contamination, the desulfurization events restored the conversion efficiency to nearly the same level of performance. However, repeatedly exposing the catalyst to the desulfurization procedure developed in this program caused a continued decline in the catalyst's desulfurized performance. Additional work will be

Sulfur and Moisture Effects on Alumina Scale and TBC Spallation

Science.gov (United States)

Smialek, James L.

2007-01-01

It has been well established that a few ppmw sulfur impurity may segregate to the interface of thermally grown alumina scales and the underlying substrate, resulting in bond degradation and premature spallation. This has been shown for NiAl and NiCrAl-based alloys, bare single crystal superalloys, or coated superalloys. The role of reactive elements (especially Y) has been to getter the sulfur in the bulk and preclude interfacial segregation. Pt additions are also very beneficial, however a similar thermodynamic explanation does not apply. The purpose of the present discussion is to highlight some observations of these effects on Rene'142, Rene'N5, PWA1480, and PWA1484. For PWA1480, we have mapped cyclic oxidation and spallation in terms of potential sulfur interfacial layers and found that a cumulative amount of about one monolayer is sufficient to degrade long term adhesion. Depending on substrate thickness, optimum performance occurs if sulfur is reduced below about 0.2-0.5 ppmw. This is accomplished in the laboratory by hydrogen annealing or commercially by melt-fluxing. Excellent 1150 C cyclic oxidation is thus demonstrated for desulfurized Rene'142, Rene'N5, and PWA1484. Alternatively, a series of N5 alloys provided by GE-AE have shown that as little as 15 ppmw of Y dopant was effective in providing remarkable scale adhesion. In support of a Y-S gettering mechanism, hydrogen annealing was unable to desulfurize these alloys from their initial level of 5 ppmw S. This impurity and critical doping level corresponds closely to YS or Y2S3 stoichiometry. In many cases, Y-doped alloys or alloys with marginal sulfur levels exhibit an oxidative sensitivity to the ambient humidity called Moisture-Induced Delayed Spallation (MIDS). After substantial scale growth, coupled with damage from repeated cycling, cold samples may spall after a period of time, breathing on them, or immersing them in water. While stress corrosion arguments may apply, we propose that the underlying

[Sulfur dioxide limit standard and residues in Chinese medicinal materials].

Science.gov (United States)

Kang, Chuan-Zhi; Yang, Wan-Zhen; Mo, Ge; Zhou, Li; Jiang, Jing-Yi; Lv, Chao-Geng; Wang, Sheng; Zhou, Tao; Yang, Ye; Guo, Lan-Ping

2018-01-01

The traditional sulfur fumigation processing method has been widely used in the initial processing and storage of traditional Chinese medicinal materials due to its economy, efficiency, convenience, high operability and effect on mold and insect prevention. However, excessive sulfur fumigation of traditional Chinese medicinal materials would lead to the changes in chemical compositions, and even endanger human health. This study showed that traditional Chinese medicinal materials were sulfur fumigated directly after being harvested for quick drying, or fumigated after being weted in the storage process for preventing mold and insects. We found that the sulfur dioxide limits for traditional Chinese medicinal materials were stricter than those for foods. Based on the existing limit standards, we obtained the data of sulfur dioxide residues for 35 types of traditional Chinese medicinal materials in a total of 862 batches. According to the limit standard in the Chinese Pharmacopoeia (150， 400 mg·kg⁻¹), the average over-standard rate of sulfur dioxide was as high as 52.43%, but it was reduced to 29.47% if calculated based on the limit for vegetable additive standard (500 mg·kg⁻¹). Sulfur fumigation issue shall be considered correctly: sulfur dioxide is a type of low toxic substance and less dangerous than aflatoxin and other highly toxic substances, and a small amount of residue would not increase the toxicity of traditional Chinese medicinal materials. However, sulfur fumigation might change the content of chemical substances and affect the quality of traditional Chinese medicinal materials. Furthermore, the exposure hazards of toxic substances are comprehensively correlated with exposure cycle, exposure frequency, and application method. In conclusion, it is suggested to strengthen the studies on the limit standard of traditional Chinese medicinal materials, formulate practical and feasible limit standard for sulfur dioxide residues in traditional Chinese

Evolution of heavy ions (He{sup 2+}, H{sup +}) radiolytic yield of molecular hydrogen vs. ''Track-Segment'' LET values

Energy Technology Data Exchange (ETDEWEB)

Crumiere, Francis; Vandenborre, Johan; Blain, Guillaume; Fattahi, Massoud [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Haddad, Ferid [Nantes Univ., CNRS/IN2P3 (France). SUBATECH Unite Mixte de Recherche 6457; Cyclotron Arronax, Saint Herblain (France)

2017-08-01

Ionizing radiation's effects onto water molecules lead to the ionization and/or the excitation of them. Then, these phenomena are followed by the formation of radicals and molecular products. The linear energy transfer (LET), which defines the energy deposition density along the radiation length, is different according to the nature of ionizing particles. Thus, the values of radiolytic yields, defined as the number of radical and molecular products formed or consumed by unit of deposited energy, evolve according to this parameter. This work consists in following the evolution of radiolytic yield of molecular hydrogen and ferric ions according to the ''Track-Segment'' LET of ionizing particles (protons, helions). Concerning G(Fe{sup 3+}) values, it seems that the energy deposited into the Bragg peak does not play the main role for the Fe{sup 3+} radiolytic formation, whereas for the G(H{sub 2}) it is the case with a component around 40% of the Bragg peak in the dihydrogen production. Therefore, as main results of this work, for high energetic Helion and Proton beams, the G(Fe{sup 3+}) values, which can be used for further dosimetry studies for example during the α radiolysis experiments, and the primary g(H{sub 2}) values for the Track-Segment LET, which can be used to determine the dihydrogen production by α-emitters, are published.

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile

DEFF Research Database (Denmark)

Zopfi, Jakob; Michael E., Böttcher; Jørgensen, Bo Barker

2008-01-01

suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition...... of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations....

Radiolytic gas generation from cement-based waste hosts for DOE low-level radioactive wastes

International Nuclear Information System (INIS)

Dole, L.R.; Friedman, H.A.

1986-01-01

Using cement-based immobilization binders with simulated radioactive waste containing sulfate, nitrate, nitrite, phosphate, and fluoride anions, the gamma- and alpha-radiolytic gas generation factors (G/sub t/, molecules/100 eV) and gas compositions were measured on specimens of cured grouts. These tests studied the effects of; (1) waste composition; (2) the sample surface-to-volume ratio; (3) the waste slurry particle size; and (4) the water content of the waste host formula. The radiolysis test vessels were designed to minimize the ''dead'' volume and to simulate the configuration of waste packages

Once-through hybrid sulfur process for nuclear hydrogen production

International Nuclear Information System (INIS)

Jeong, Y. H.

2008-01-01

potential, the maximum efficiency is about 52 % under the conditions of 40% sulfur power plant efficiency and 60 w-% sulfuric acid concentration in electrolyzer The major factors that can affect the cycle efficiency are reducing the electrode over-potential Because the once-through process does not need a high temperature reactor for sulfuric acid decomposition, initial hydrogen feed for boosting the hydrogen economy can be provided by the currently available nuclear electricity which is carbon-free. After the initiation of the hydrogen economy, closed recycle of sulfuric acid using high temperature nuclear reactors can be pursued. Until the commercialization of closed nuclear hydrogen process, by using the once-through process, the initial hydrogen feed for the hydrogen economy can be provided by nuclear electricity. Fossil fuels provide 86% of total primary energy today. Considering the current energy mix, fossil fuels will inevitably play a major role and sulfur will flow out as a by product. The sulfur byproduct utilization for the nuclear hydrogen generation will make the transition to the hydrogen economy smooth. In addition, off-peak electricity can be converted into hydrogen by the once-through process and converted back to electricity for the peak load. Depending on the electrode potential and round trip efficiency, off-peak electricity can be stored very efficiently. (authors)

Experimental Evidence for Abiotic Sulfurization of Marine Dissolved Organic Matter

Directory of Open Access Journals (Sweden)

Anika M. Pohlabeln

2017-11-01

Full Text Available Dissolved organic sulfur (DOS is the largest pool of organic sulfur in the oceans, and as such it is an important component of the global sulfur cycle. DOS in the ocean is resistant against microbial degradation and turns over on a millennium time scale. However, sources and mechanisms behind its stability are largely unknown. Here, we hypothesize that in sulfate-reducing sediments sulfur is abiotically incorporated into dissolved organic matter (DOM and released to the ocean. We exposed natural seawater and the filtrate of a plankton culture to sulfidic conditions. Already after 1-h at 20°C, DOS concentrations had increased 4-fold in these experiments, and 14-fold after 4 weeks at 50°C, indicating that organic matter does not need long residence times in natural sulfidic environments to be affected by sulfurization. Molecular analysis via ultrahigh-resolution mass spectrometry showed that sulfur was covalently and unselectively bound to DOM. Experimentally produced and natural DOS from sediments were highly similar on a molecular and structural level. By combining our data with published benthic DOC fluxes we estimate that 30–200 Tg DOS are annually transported from anaerobic and sulfate reducing sediments to the oceans. Uncertainties in this first speculative assessment are large. However, this first attempt illustrates that benthic DOS flux is potentially one order of magnitude larger than that via rivers indicating that this could balance the estimated global net removal of refractory DOS.

Enhanced metabolic versatility of planktonic sulfur-oxidizing γ-proteobacteria in an oxygen-deficient coastal ecosystem

Directory of Open Access Journals (Sweden)

Alejandro A. Murillo

2014-07-01

Full Text Available Sulfur-oxidizing Gamma-proteobacteria are abundant in marine oxygen-deficient waters, and appear to play a key role in a previously unrecognized cryptic sulfur cycle. Metagenomic analyses of members of the uncultured SUP05 lineage in the Canadian seasonally anoxic fjord Saanich Inlet (SI, hydrothermal plumes in the Guaymas Basin (GB and single cell genomics analysis of two ARCTIC96BD-19 representatives from the South Atlantic Sub-Tropical Gyre (SASG have shown them to be metabolically versatile. However, SI and GB SUP05 bacteria seem to be obligate chemolithoautotrophs, whereas ARCTIC96BD-19 has the genetic potential for aerobic respiration. Here, we present results of a metagenomic analysis of sulfur-oxidizing Gamma-proteobacteria (GSO, closely related to the SUP05/ARCTIC96BD-19 clade, from a coastal ecosystem in the eastern South Pacific (ESP. This ecosystem experiences seasonal anoxia and accumulation of nitrite and ammonium at depth, with a corresponding increase in the abundance of GSO representatives. The ESP-GSOs appear to have a significantly different gene complement than those from Saanich Inlet, Guaymas Basin and SASG. Genomic analyses of de novo assembled contigs indicate the presence of a complete aerobic respiratory complex based on the cytochrome bc1 oxidase. Furthermore, they appear to encode a complete TCA cycle and several transporters for dissolved organic carbon species, suggesting a mixotrophic lifestyle. Thus, the success of sulfur-oxidizing Gamma-proteobacteria in oxygen-deficient marine ecosystems appears due not only to their previously recognized anaerobic metabolic versatility, but also to their capacity to function under aerobic conditions using different carbon sources. Finally, members of ESP-GSO cluster also have the genetic potential for reducing nitrate to ammonium based on the nirBD genes, and may therefore facilitate a tighter coupling of the nitrogen and sulfur cycles in oxygen-deficient waters.

Catalyst for the reduction of sulfur dioxide to elemental sulfur

Science.gov (United States)

Jin, Y.; Yu, Q.; Chang, S.G.

1996-02-27

The inventive catalysts allow for the reduction of sulfur dioxide to elemental sulfur in smokestack scrubber environments. The catalysts have a very high sulfur yield of over 90% and space velocity of 10,000 h{sup {minus}1}. They also have the capacity to convert waste gases generated during the initial conversion into elemental sulfur. The catalysts have inexpensive components, and are inexpensive to produce. The net impact of the invention is to make this technology practically available to industrial applications. 21 figs.

Modeling of a Large-Scale High Temperature Regenerative Sulfur Removal Process

DEFF Research Database (Denmark)

Konttinen, Jukka T.; Johnsson, Jan Erik

1999-01-01

model that does not account for bed hydrodynamics. The pilot-scale test run results, obtained in the test runs of the sulfur removal process with real coal gasifier gas, have been used for parameter estimation. The validity of the reactor model for commercial-scale design applications is discussed.......Regenerable mixed metal oxide sorbents are prime candidates for the removal of hydrogen sulfide from hot gasifier gas in the simplified integrated gasification combined cycle (IGCC) process. As part of the regenerative sulfur removal process development, reactor models are needed for scale......-up. Steady-state kinetic reactor models are needed for reactor sizing, and dynamic models can be used for process control design and operator training. The regenerative sulfur removal process to be studied in this paper consists of two side-by-side fluidized bed reactors operating at temperatures of 400...

A Nanoscale Study of Carbon and Nitrogen Fluxes in Mats of Purple Sulfur Bacteria: Implications for Carbon Cycling at the Surface of Coastal Sediments

Directory of Open Access Journals (Sweden)

Cédric Hubas

2017-10-01

Full Text Available Mass blooms of purple sulfur bacteria growing seasonally on green stranded macroalgae have a major impact on the microbial composition and functionality of intertidal mats. To explore the active anoxygenic phototrophic community in purple bacterial mats from the Roscoff Aber Bay (Brittany, France, we conducted a combined approach including molecular and high-resolution secondary ion mass spectrometry (NanoSIMS analyses. To investigate the dynamics of carbon and nitrogen assimilation activities, NanoSIMS was coupled with a stable isotope probing (SIP experiment and a compound specific isotope analysis (CSIA of fatty acid methyl ester (FAME. Sediment samples were incubated with 13C- and/or 15N-labeled acetate, pyruvate, bicarbonate and ammonium. NanoSIMS analysis of 13C - and 15N -incubated samples showed elevated incorporations of 13C - and 15N in the light and of 13C -acetate in the dark into dense populations of spherical cells that unambiguously dominated the mats. These results confirmed CSIA data that ranked vaccenic acid, an unambiguous marker of purple sulfur bacteria, as the most strongly enriched in the light after 13C -acetate amendment and indicated that acetate uptake, the most active in the mat, was not light-dependent. Analysis of DNA- and cDNA-derived pufM gene sequences revealed that Thiohalocapsa-related clones dominated both libraries and were the most photosynthetically active members of the mat samples. This study provides novel insights into the contribution of purple sulfur bacteria to the carbon cycle during their seasonal developments at the sediment surface in the intertidal zone.

High Capacitive Storage Performance of Sulfur and Nitrogen Codoped Mesoporous Graphene.

Science.gov (United States)

Ma, Xinlong; Gao, Daowei

2018-03-22

Mesoporous graphene is synthesized based on the chemical vapor deposition methodology by using heavy MgO flakes as substrates in a fluidized-bed reactor. Subsequently, sulfur and nitrogen coincorporation into graphene frameworks is realized by the reaction between carbon atoms and thiourea molecules. The as-obtained sulfur and nitrogen codoped mesoporous graphene (SNMG) exhibits remarkable capacitive energy-storage behavior, as a result of well-developed pore channels, in terms of that in a symmetric supercapacitor and lithium-ion hybrid capacitor (LIHC). The ultrahigh durability of the SNMG/SNMG symmetric supercapacitor is demonstrated by long-term cycling, for which no capacitance decay is found after 20 000 cycles. A LIHC constructed from commercial Li 4 Ti 5 O 12 (LTO) as the anode and SNMG as the cathode is capable of delivering much enhanced lithium-storage ability and better rate capability than that of activated carbon (AC)/LTO LIHC. Moreover, SNMG/LTO LIHC exhibits maximum energy and power densities of 86.2 Wh kg -1 and 7443 W kg -1 and maintains 87 % capacitance retention after 2000 cycles. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved Electrochemical Performance of Biomass-Derived Nanoporous Carbon/Sulfur Composites Cathode for Lithium-Sulfur Batteries by Nitrogen Doping

International Nuclear Information System (INIS)

Geng, Zhen; Xiao, Qiangfeng; Wang, Dabin; Yi, Guanghai; Xu, Zhigang; Li, Bing; Zhang, Cunman

2016-01-01

A two-step method with high-efficiency is developed to prepare nitrogen doped activated carbons (NACs) with high surface area and nitrogen content. Based on the method, series of NACs with similar surface area and pore texture but different nitrogen content and nitrogen group species are successfully prepared. The influence of nitrogen doping on electrochemical performance of carbon/sulfur composites cathode is studied deeply under the conditions of similar surface area and pore texture. It presents the directly experimental demonstration that both nitrogen content and nitrogen group species play crucial roles on electrochemical performance of carbon/sulfur composites cathode. NAC/sulfur composites show the much improved cycling performance, which is about 3.5 times as that of nitrogen free carbon. Improved electrochemical performance is due to synergistic effects between nitrogen content and effective nitrogen groups, which enables effective trapping of lithium polysulfides within carbon framework. Besides, it is found that oxygen groups exist in carbon materials obviously influence electrochemical performance of cathode, which could be ignored in most of studies. Based on above, it can be concluded that enhanced chemisorption to lithium polysulfides by functional groups modification is the effective route to improve the electrochemical performance of Li-S battery.

Sulfur K-edge absorption spectroscopy on selected biological systems; Schwefel-K-Kanten-Absorptionsspektroskopie an ausgewaehlten biologischen Systemen

Energy Technology Data Exchange (ETDEWEB)

Lichtenberg, Henning

2008-07-15

Sulfur is an essential element in organisms. In this thesis investigations of sulfur compounds in selected biological systems by XANES (X-ray Absorption Near Edge Structure) spectroscopy are reported. XANES spectroscopy at the sulfur K-edge provides an excellent tool to gain information about the local environments of sulfur atoms in intact biological samples - no extraction processes are required. Spatially resolved measurements using a Kirkpatrick-Baez mirror focusing system were carried out to investigate the infection of wheat leaves by rust fungi. The results give information about changes in the sulfur metabolism of the host induced by the parasite and about the extension of the infection into visibly uninfected plant tissue. Furthermore, XANES spectra of microbial mats from sulfidic caves were measured. These mats are dominated by microbial groups involved in cycling sulfur. Additionally, the influence of sulfate deprivation and H{sub 2}S exposure on sulfur compounds in onion was investigated. To gain an insight into the thermal degradation of organic material the influence of roasting of sulfur compounds in coffee beans was studied. (orig.)

Novel nitrogen-doped hierarchically porous coralloid carbon materials as host matrixes for lithium–sulfur batteries

International Nuclear Information System (INIS)

Yang, Jing; Wang, Shuyuan; Ma, Zhipeng; Du, Zhiling; Li, Chunying; Song, Jianjun; Wang, Guiling; Shao, Guangjie

2015-01-01

Highlights: • Nitrogen-doped hierarchically porous coralloid carbon/sulfur composites were prepared • Nitrogen atoms were introduced to improve electrochemical properties • The intriguing structural features benefited discharge capacity and cycling stability - Abstract: Nitrogen-doped hierarchically porous coralloid carbon/sulfur composites (N-HPCC/S) served as attractive cathode materials for lithium–sulfur (Li–S) batteries were fabricated for the first time. The nitrogen-doped hierarchically porous coralloid carbon (N-HPCC) with an appropriate nitrogen content (1.29 wt%) was synthesized via a facile hydrothermal approach, combined with subsequent carbonization–activation. The N-HPCC/S composites prepared by a simple melt–diffusion method displayed an excellent electrochemical performance. With a high sulfur content (58 wt%) in the total electrode weight, the N-HPCC/S cathode delivered a high initial discharge capacity of 1626.8 mA h g −1 and remained high up to 1086.3 mA h g −1 after 50 cycles at 100 mA g −1 , which is about 1.86 times as that of activated carbon. Particularly, the reversible discharge capacity still maintained 607.2 mA h g −1 after 200 cycles even at a higher rate of 800 mA g −1 . The enhanced electrochemical performance was attributed to the synergetic effect between the intriguing hierarchically porous coralloid structure and appropriate nitrogen doping, which could effectively trap polysulfides, alleviate the volume expansion, enhance the electronic conductivity and improve the surface interaction between the carbon matrix and polysulfides

Dual-Functional Graphene Carbon as Polysulfide Trapper for High-Performance Lithium Sulfur Batteries.

Science.gov (United States)

Zhang, Linlin; Wan, Fang; Wang, Xinyu; Cao, Hongmei; Dai, Xi; Niu, Zhiqiang; Wang, Yijing; Chen, Jun

2018-02-14

The lithium sulfur (Li-S) battery has attracted much attention due to its high theoretical capacity and energy density. However, its cycling stability and rate performance urgently need to improve because of its shuttle effect. Herein, oxygen-doped carbon on the surface of reduced graphene oxide (labeled as ODC/rGO) was fabricated to modify the separators of Li-S batteries to limit the dissolution of the lithium polysulfides. The mesoporous structure in ODC/rGO can not only serve as the physical trapper, but also provide abundant channels for fast ion transfer, which is beneficial for effective confinement of the dissoluble intermediates and superior rate performance. Moreover, the oxygen-containing groups in ODC/rGO are able to act as chemical adsorption sites to immobilize the lithium polysulfides, suppressing their dissolution in electrolyte to enhance the utilization of sulfur cathode in Li-S batteries. As a result, because of the synergetic effects of physical adsorption and chemical interaction to immobilize the soluble polysulfides, the Li-S batteries with the ODC/rGO-coated separator exhibit excellent rate performance and good long-term cycling stability with 0.057% capacity decay per cycle at 1.0 C after 600 cycles.

Pulse and gamma radiolytic studies of Ag, Cd and mixed clusters in aqueous solutions of carboxymethyl cellulose and gelatin

International Nuclear Information System (INIS)

Kapoor, Sudhir; Gopinathan, C.

1996-01-01

Pulse and gamma radiolytic studies in aqueous solutions of Ag, Cd and mixed clusters were carried out in carboxymethylcellulose (CMC) or gelatin. The reaction rate of e aq - with Ag + is lower in the presence of CMC or gelatin and oligomeric clusters of silver, Cd and mixed clusters get stabilized in their presence. (author). 2 refs., 2 figs

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

Science.gov (United States)

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

2017-06-13

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

Radiolytic effect on the chemical state of iodine in aqueous solution

International Nuclear Information System (INIS)

Shiraishi, H.; Kimiya, T.; Ohmae, M.; Ishigure, K.

1988-01-01

The oxidation state of iodine dissolved in an aqueous solution is easily changed in the presence of radiation field. Hence, it is essential to take the radiolytic effect into account when one is to estimate chemical forms of iodine after being released into the containment under an LOCA condition. This paper summarizes results of γ-radiolysis experiments on aqueous solutions containing iodine species, which have been carried out to extend the previously reported study on the same system. Variation in iodine product distribution with time has been examined as before, utilizing a flow system under irradiation. Attention has been paid to the effect of oxygen, to that of an initial oxidation state of iodine, and to the influence of temperature. Some kinetic analysis on the system was also undertaken

Pulse radiolytic study of alpha-tocopherol radical mechanisms in ethanolic solution

International Nuclear Information System (INIS)

Jore, D.; Patterson, L.K.; Ferradini, C.

1986-01-01

Pulse radiolytic studies of alpha-tocopherol (alpha TH) oxidation-reduction processes were carried out with low doses (5 Gy) of high-energy electrons in O 2 -, N 2 -, and air-saturated ethanolic solutions. Depending on the concentration of oxygen in solution, two different radicals, A . and B ., were observed. The first, A ., was obtained under N 2 and results from alpha TH reaction with solvated electron (k alpha TH + e-solv = 3.4 X 10(8) mol-1 liter s-1) and with H 3 C-CH-OH, (R.) (k alpha TH + R. = 5 X 10(5) mol-1 liter s-1). B., observed under O 2 , is produced by alpha TH reaction with RO 2 . peroxyl radicals (k alpha TH + RO 2 . = 9.5 X 10(4) mol-1 liter s-1)

Sulfur-binding in recent environments: II. Speciation of sulfur and iron and implications for the occurrence of organo-sulfur compounds

Science.gov (United States)

Hartgers, Walter A.; Lòpez, Jordi F.; Sinninghe Damsté, Jaap S.; Reiss, Christine; Maxwell, James R.; Grimalt, Joan O.

1997-11-01

Speciation of iron and sulfur species was determined for two recent sediments (La Trinitat and Lake Cisó) which were deposited in environments with a high biological productivity and sulfate-reducing activity. In sediments from calcite ponds of La Trinitat an excess of reactive iron species (iron monosulfides, iron hydroxides) results in a depletion of reactive sulfur which is accompanied by a virtual absence of organo-sulfur compounds, both in low (LMW) and high molecular-weight (HMW) fractions. Small amounts of phytanyl and highly branched isoprenoid (HBI) thiophenes in the extract demonstrate that these molecules exhibit a higher reactivity towards reduced sulfur species as compared to detrital iron. Euxinic sediments from Lake Cisó are characterised by an excess of reduced sulfur species which can rapidly trap reactive iron. High concentrations of H 2S results in the formation of organo-sulfur compounds which were encountered in both LMW and HMW fractions. The major part of the organic sulfur is bound to the carbohydrate portion of woody tissues, whose presence was revealed by a specific alkylthiophene distribution in the flash pyrolysate and by Li/EtNH 2 desulfurisation of the kerogen which resulted in the solubilisation of the sulfur-enriched hemicellulose fraction. Relatively high amounts of sulfurised C 25 HBI compounds in the sediment extract of Lake Cisó reflect the incorporation of sulfur into algal derived organic matter upon early diagenesis. The combined approach of the speciation of iron and sulfur species and the molecular analysis of sedimentary fractions demonstrates that abiotic sulfur binding to organic matter occurs at the earliest stages of diagenesis under specific depositional conditions (anoxic, stratified water column) in which an excess of reduced sulfur species relative to the amount of reactive iron is a controlling factor.

FiveS rRNA sequences and fatty acid profiles of colourless sulfur-oxidising bacteria

Digital Repository Service at National Institute of Oceanography (India)

LokaBharathi, P.A.; Ortiz-conde, B.A.; Nair, S.; Chandramohan, D.; Colwell, R.R.

Colourless sulfur-oxidising bacteria have been encountered extensively in the oxygen minimum layers of the Arabian Sea. These oligotrophs have been known to mediate nitrogen cycle reductively even under autotrophic conditions. Some...

A combined theoretical and experimental study on the oxygenated graphitic carbon nitride as a promising sulfur host for lithium-sulfur batteries

Science.gov (United States)

He, Feng; Li, Kai; Yin, Cong; Ding, Yingchun; Tang, Hao; Wang, Ying; Wu, Zhijian

2018-01-01

To effectively restrain the dissolution of soluble polysulfides and fully utilize the active sulfur materials in lithium-sulfur (Li-S) batteries, host materials with unique compositions and porous structures have been pursued. Herein, we have investigated the mechanism of the excellent activity of oxygenated g-C3N4 for Li-S batteries from theoretical perspective, and the further experiment confirms that our O-g-C3N4-S cathode exhibits much better electrochemical performance compared with those in previous reports. Our DFT calculations reveal that the oxygenated material has better electrical conductivity and stronger adsorption ability with the Li2Sx species compared with the pristine g-C3N4 and other two-dimensional (2D) materials. Furthermore, we have confirmed experimentally that the O-g-C3N4-S composite cathode exhibits excellent electrochemical performance in Li-S batteries with high reversible discharge capacity of 1030 mAh g-1 after 100 cycles at 0.2 C, great rate capability with the discharge capacity of 364 mAh g-1 even at 5.0 C, and outstanding long-term cyclic stability with the discharge capacity of 465 mAh g-1 after 1000 cycles at 1.0 C (capacity decay was only 0.046% per cycle). Our results also suggest that theoretical study will play a significant role in predicting and screening novel materials with better performance.

Augmenting Sulfur Metabolism and Herbivore Defense in Arabidopsis by Bacterial Volatile Signaling

Directory of Open Access Journals (Sweden)

Mina eAziz

2016-04-01

Full Text Available Sulfur is an element necessary for the life cycle of higher plants. Its assimilation and reduction into essential biomolecules are pivotal factors determining a plant’s growth and vigor as well as resistance to environmental stress. While certain soil microbes can enhance ion solubility via chelating agents or oxidation, microbial regulation of plant-sulfur assimilation has not been reported. With an increasing understanding that soil microbes can activate growth and stress tolerance in plants via chemical signaling, the question arises as to whether such beneficial bacteria also regulate sulfur assimilation. Here we report a previously unidentified mechanism by which the growth-promoting rhizobacterium Bacillus amyloliquefaciens (GB03 transcriptionally activates genes responsible for sulfur assimilation, increasing sulfur uptake and accumulation in Arabidopsis. Transcripts encoding for sulfur-rich aliphatic and indolic glucosinolates are also GB03 induced. As a result, GB03-exposed plants with elevated glucosinolates exhibit greater protection against the generalist herbivore, Spodoptera exigua (beet armyworm. In contrast, a previously-characterized glucosinolate mutant compromised in the production of both aliphatic and indolic glucosinolates is also compromised in terms of GB03-induced protection against insect herbivory. As with in vitro studies, soil-grown plants show enhanced glucosinolate accumulation and protection against beet armyworm feeding with GB03 exposure. These results demonstrate the potential of microbes to enhance plant sulfur assimilation and emphasize the sophisticated integration of microbial signaling in plant defense.

PUMP DESIGN AND COMPUTATIONAL FLUID DYNAMIC ANALYSIS FOR HIGH TEMPERATURE SULFURIC ACID TRANSFER SYSTEM

Directory of Open Access Journals (Sweden)

JUNG-SIK CHOI

2014-06-01

Full Text Available In this study, we proposed a newly designed sulfuric acid transfer system for the sulfur-iodine (SI thermochemical cycle. The proposed sulfuric acid transfer system was evaluated using a computational fluid dynamics (CFD analysis for investigating thermodynamic/hydrodynamic characteristics and material properties. This analysis was conducted to obtain reliable continuous operation parameters; in particular, a thermal analysis was performed on the bellows box and bellows at amplitudes and various frequencies (0.1, 0.5, and 1.0 Hz. However, the high temperatures and strongly corrosive operating conditions of the current sulfuric acid system present challenges with respect to the structural materials of the transfer system. To resolve this issue, we designed a novel transfer system using polytetrafluoroethylene (PTFE, Teflon® as a bellows material for the transfer of sulfuric acid. We also carried out a CFD analysis of the design. The CFD results indicated that the maximum applicable temperature of PTFE is about 533 K (260 °C, even though its melting point is around 600 K. This result implies that the PTFE is a potential material for the sulfuric acid transfer system. The CFD simulations also confirmed that the sulfuric acid transfer system was designed properly for this particular investigation.

Interface polymerization synthesis of conductive polymer/graphite oxide@sulfur composites for high-rate lithium-sulfur batteries

International Nuclear Information System (INIS)

Wang, Xiwen; Zhang, Zhian; Yan, Xiaolin; Qu, Yaohui; Lai, Yanqing; Li, Jie

2015-01-01

Highlights: • A hybrid nanostructure that incorporate the merits of conductive polymer nanorods and graphite oxide sheets. • A novel approach based on interface polymerization for synthesizing CP/GO@S ternary composite. • CP/GO@S ternary composite cathode shows enhanced electrochemical properties compared with CP@S binary composite cathode. • PEDOT/GO@S composite is the material system that have best electrochemical performance in all CP/GO@S ternary composites. - Abstract: The novel ternary composites, conductive polymers (CPs)/graphene oxide (GO)@sulfur composites were successfully synthesized via a facile one-pot route and used as cathode materials for Li-S batteries The poly(3,4-ethylenedioxythiophene) (PEDOT)/GO and polyaniline (PANI)/GO composites were prepared by interface polymerization of monomers on the surface of GO sheets. Then sulfur was in-situ deposited on the CPs/GO composites in same solution. The component and structure of the composites were characterized by XPS, TGA, FTIR, SEM, TEM and electrochemical measurements. In this structure, the CPs nanostructures are believed to serve as a conductive matrix and an adsorbing agent, while the highly conductive GO will physically and chemically confine the sulfur and polysulfide within cathode. The PEDOT/GO@S composites with the sulfur content of 66.2 wt% exhibit a reversible discharge capacity of 800.2 mAh g −1 after 200 cycles at 0.5 C, which is much higher than that of PANI/GO@S composites (599.1 mAh g −1 ) and PANI@S (407.2 mAh g −1 ). Even at a high rate of 4 C, the PEDOT/GO@S composites still retain a high specific capacity of 632.4 mAh g −1

Method of removing and recovering elemental sulfur from highly reducing gas streams containing sulfur gases

Science.gov (United States)

Gangwal, Santosh K.; Nikolopoulos, Apostolos A.; Dorchak, Thomas P.; Dorchak, Mary Anne

2005-11-08

A method is provided for removal of sulfur gases and recovery of elemental sulfur from sulfur gas containing supply streams, such as syngas or coal gas, by contacting the supply stream with a catalyst, that is either an activated carbon or an oxide based catalyst, and an oxidant, such as sulfur dioxide, in a reaction medium such as molten sulfur, to convert the sulfur gases in the supply stream to elemental sulfur, and recovering the elemental sulfur by separation from the reaction medium.

Iron hexacyanide/cytochrome-C - intramolecular electron transfer and binding constants - (pulse radiolytic study). Progress report

International Nuclear Information System (INIS)

Ilan, Y.; Shafferman, A.

Internal oxidation and reduction rates of horse cytochrome-c in the complexes, CII.Fe/sup III/(CN) -3 6 and CIII.Fe/sup II/(CN) -4 6 , are 4.6.10 4 s -1 and 3.3.10 2 s -1 , respectively. The binding sites of the iron hexacyanide ions on either CII or CIII are kinetically almost indistinguishable; binding constants range from 0.87.10 3 to 2.10 3 M -1 . The present pulse radiolytic kinetic data are compared with that from N.M.R, T-jump and equilibrium dialysis studies

Dual functional MoS2/graphene interlayer as an efficient polysulfide barrier for advanced lithium-sulfur batteries

International Nuclear Information System (INIS)

Guo, Pengqian; Liu, Dequan; Liu, Zhengjiao; Shang, Xiaonan; Liu, Qiming; He, Deyan

2017-01-01

Highlights: •Dual functional MoS 2 /graphene interlayer was first used as an efficient polysulfide-trapping shield for lithium-sulfur batteries. •MoS 2 /graphene interlayer shows strong chemical interactions with LiPSs. •MoS 2 /graphene interlayer forms a 3D network to facilitate electron and ion transfer during the discharge-charge processes. •The resultant lithium-sulfur batteries exhibit a superior rate capacity and improved cycling capacity. -- Abstract: A dual functional interlayer consisted of composited two-dimensional MoS 2 and graphene has been developed as an efficient polysulfide barrier for lithium-sulfur batteries (LSBs). With such a configuration, LSBs show a superior rate capacity and improved cycling capacity. The excellent electrochemical performance can be attributed to the strong bonding interactions between the MoS 2 /graphene interlayer and the formed lithium polysulfides (LiPSs) as well as the good electrical conductivity of the MoS 2 /graphene composite. The MoS 2 /graphene interlayer can physically block LiPSs by the graphene nanosheets and chemically suppress the dissolution of LiPSs by the polar MoS 2 nanoflowers. Such a dual functional interlayer further provides a good contact with the surface of the sulfur cathode, acts as an upper current collector and greatly improves the sulfur utilization and the rate capability of LSBs.

Durability of incinerator ash waste encapsulated in modified sulfur cement

International Nuclear Information System (INIS)

Kalb, P.D.; Heiser, J.H. III; Pietrzak, R.; Colombo, P.

1991-01-01

Waste form stability under anticipated disposal conditions is an important consideration for ensuring continued isolation of contaminants from the accessible environment. Modified sulfur cement is a relatively new material and has only recently been applied as a binder for encapsulation of mixed wastes. Little data are available concerning its long-term durability. Therefore, a series of property evaluation tests for both binder and waste-binder combinations have been conducted to examine potential waste form performance under storage and disposal conditions. These tests include compressive strength, biodegradation, radiation stability, water immersion, thermal cycling, and leaching. Waste form compressive strength increased with ash waste loadings to 30.5 MPa at a maximum incinerator ash loading of 43 wt %. Biodegradation testing resulted in no visible microbial growth of either bacteria or fungi. Initial radiation stability testing did not reveal statistically significant deterioration in structural integrity. Results of 90 day water immersion tests were dependent on the type of ash tested. There were no statistically significant changes in compressive strength detected after completion of thermal cycle testing. Radionuclides from ash waste encapsulated in modified sulfur cement leached between 5 and 8 orders of magnitude slower than the leach index criterion established by the Nuclear Regulatory Commission (NRC) for low-level radioactive waste. Modified sulfur cement waste forms containing up to 43 wt % incinerator fly ash passed EPA Toxicity Characteristic Leaching Procedure (TCLP) criteria for lead and cadmium leachability. 11 refs., 2 figs., 5 tabs

Sulfur Removal by Adding Iron During the Digestion Process of High-sulfur Bauxite

Science.gov (United States)

Zhanwei, Liu; Hengwei, Yan; Wenhui, Ma; Keqiang, Xie; Dunyong, Li; Licong, Zheng; Pengfei, Li

2018-04-01

This paper proposes a novel approach to sulfur removal by adding iron during the digestion process. Iron can react with high-valence sulfur (S2O3 2-, SO3 2-, SO4 2-) to generate S2- at digestion temperature, and then S2- enter red mud in the form of Na3FeS3 to be removed. As iron dosage increases, high-valence sulfur concentration decreases, but the concentration of S2- increases; sulfur digestion rate decreases while sulfur content in red mud markedly increases; the alumina digestion rate, conversely, remains fairly stable. So sulfur can be removed completely by adding iron in digestion process, which provide a theoretical basis for the effective removal of sulfur in alumina production process.

Sulfur isotopes as a tracer for biogenic sulfate reduction in natural environments: A link between modern and ancient ecosystems. Geologica Ultraiectina (316)

NARCIS (Netherlands)

Stam, M.C.

2010-01-01

Sulfur isotopes have been widely used to trace the activity of sulfate reducing prokaryotes in modern and ancient geochemical settings and to estimate the role of this microbial metabolism in global sulfur cycling. Extensive pure culture data provide detailed insight into cellular mechanisms

Novel Radiolytic Rotenone Derivative, Rotenoisin B with Potent Anti-Carcinogenic Activity in Hepatic Cancer Cells

Directory of Open Access Journals (Sweden)

Srilatha Badaboina

2015-07-01

Full Text Available Rotenone, isolated from roots of derris plant, has been shown to possess various biological activities, which lead to attempting to develop a potent drug against several diseases. However, recent studies have demonstrated that rotenone has the potential to induce several adverse effects such as a neurodegenerative disease. Radiolytic transformation of the rotenone with gamma-irradiation created a new product, named rotenoisin B. The present work was designed to investigate the anticancer activity of rotenoisin B with low toxicity and its molecular mechanism in hepatic cancer cells compared to a parent compound, rotenone. Our results showed rotenoisin B inhibited hepatic cancer cells’ proliferation in a dose dependent manner and increased in apoptotic cells. Interestingly, rotenoisin B showed low toxic effects on normal cells compared to rotenone. Mitochondrial transmembrane potential has been decreased, which leads to cytochrome c release. Down regulation of anti-apoptotic Bcl-2 levels as well as the up regulation of proapoptotic Bax levels were observed. The cleaved PARP (poly ADP-ribose polymerase level increased as well. Moreover, phosphorylation of extracellular signal regulated kinase (ERK and p38 slightly up regulated and intracellular reactive oxygen species (ROS increased as well as cell cycle arrest predominantly at the G2/M phase observed. These results suggest that rotenoisin B might be a potent anticancer candidate similar to rotenone in hepatic cancer cells with low toxicity to normal cells even at high concentrations compared to rotenone.

Al2O3-coated porous separator for enhanced electrochemical performance of lithium sulfur batteries

International Nuclear Information System (INIS)

Zhang, Zhiyong; Lai, Yanqing; Zhang, Zhian; Zhang, Kai; Li, Jie

2014-01-01

Graphical abstract: Al2O3-coated separator with developed porous channels is prepared by coating Al2O3 polymer solution on routine separator. The batteries with Al2O3-coated separator exhibited a reversible capacity of as high as 593 mAh g-1 at the rate of 0.2 C after 50th charge/discharge cycle. The enhancement in the electrochemical performance could be attributed to the reduced charge transfer resistance after the introduction of Al2O3 coating layer. Besides, the Al2O3 coating layer, acting as a physical barrier for polysulfides, can effectively prevent polysulfides shuttling between the cathode and the anode. We believe that the Al2O3-coated separator is promising in the lithium sulfur battery applications. - Highlights: • Al 2 O 3 -coated separator is used as the separator of lithium sulfur battery. • The cell with Al 2 O 3 -coated separator exhibits excellent cycling stability and high rate capability. • Al 2 O 3 -coated separator is promising in the lithium sulfur battery applications. - Abstract: In this paper, Al 2 O 3 -coated separator with developed porous channels is prepared to improve the electrochemical performance of lithium sulfur batteries. It is demonstrated that the Al 2 O 3 -coating layer is quite effective in reducing shuttle effect and enhancing the stability of the sulfur electrode. The initial discharge capacity of the cell with Al 2 O 3 -coated separator can reach 967 mAh g −1 at the rate of 0.2 C. After 50th charge/discharge cycle, this cell can also deliver a reversible capacity of as high as 593.4 mAh g −1 . Significantly, the charge-transfer resistance of the electrode tends to be reducing after using Al 2 O 3 -coated separator. The improved cell performance is attributed to the porous architecture of the Al 2 O 3 -coating layer, which serves as an ion-conducting skeleton for trapping and depositing dissolved sulfur-containing active materials, as confirmed by scanning electron microscopy (SEM) and energy-dispersive X

Sulfur removal from low-sulfur gasoline and diesel fuel by metal-organic frameworks

Energy Technology Data Exchange (ETDEWEB)

Hagen, G.; Haemmerle, M.; Moos, R. [Functional Materials, University of Bayreuth, Bayreuth (Germany); Malkowsky, I.M.; Kiener, C. [BASF SE, Ludwigshafen (Germany); Achmann, S.

2010-02-15

Several materials in the class of metal-organic frameworks (MOF) were investigated to determine their sorption characteristics for sulfur compounds from fuels. The materials were tested using different model oils and common fuels such as low-sulfur gasoline or diesel fuel at room temperature and ambient pressure. Thiophene and tetrahydrothiophene (THT) were chosen as model substances. Total-sulfur concentrations in the model oils ranged from 30 mg/kg (S from thiophene) to 9 mg/kg (S from tetrahydrothiophene) as determined by elementary analysis. Initial sulfur contents of 8 mg/kg and 10 mg/kg were identified for low-sulfur gasoline and for diesel fuel, respectively, by analysis of the common liquid fuels. Most of the MOF materials examined were not suitable for use as sulfur adsorbers. However, a high efficiency for sulfur removal from fuels and model oils was noticed for a special copper-containing MOF (copper benzene-1,3,5-tricarboxylate, Cu-BTC-MOF). By use of this material, 78 wt % of the sulfur content was removed from thiophene containing model oils and an even higher decrease of up to 86 wt % was obtained for THT-based model oils. Moreover, the sulfur content of low-sulfur gasoline was reduced to 6.5 mg/kg, which represented a decrease of more than 22 %. The sulfur level in diesel fuel was reduced by an extent of 13 wt %. Time-resolved measurements demonstrated that the sulfur-sorption mainly occurs in the first 60 min after contact with the adsorbent, so that the total time span of the desulfurization process can be limited to 1 h. Therefore, this material seems to be highly suitable for sulfur reduction in commercial fuels in order to meet regulatory requirements and demands for automotive exhaust catalysis-systems or exhaust gas sensors. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

Oxidation of phosphine by sulfur or selenium involving a catalytic ...

Indian Academy of Sciences (India)

Administrator

P NMR spec- troscopy. Such interconversion with the participation of breaking of bridging copper-µ3-sulfur bond with the formation of new copper–phosphorous bond led to the development of a catalytic cycle using excess. PPh3 and S or Se as the reacting substrates. The turnover number for the oxidation of PPh3 by S ...

Investigation into the role of silica in lithium polysulfide adsorption for lithium sulfur battery

International Nuclear Information System (INIS)

Kim, Miso; Kang, Sung-Hwan; Manuel, James; Zhao, Xiaohui; Cho, Kwon Koo; Ahn, Jou Hyeon

2015-01-01

Highlights: • Amine functionalized silica nanoparticles (AFSN) were prepared. • Polysulfide adsorption studies were carried out with silica nanoparticles and AFSN. • Sulfur cathodes were prepared with SN and AFSN for Li–S batteries. • AFSN showed excellent polysulfide adsorption. - Abstract: A new type of sulfur electrodes with the ability for polysulfide adsorption was prepared by incorporating silica nanoparticles (SN) or amine functionalized silica nanoparticles (AFSN). AFSN was synthesized by a simple and cost-effective method. The functionalization and surface morphology of silica were confirmed with Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), respectively. Polysulfide adsorption studies were carried out using UV–vis spectrometer, which confirmed the excellent adsorption of polysulfides by AFSN. Interaction of polysulfides with SN or AFSN was studied using FTIR and FT-Raman spectroscopy. The effective polysulfide adsorption by SN and AFSN leads to good and stable cycle performance of lithium sulfur cells. The results show that the incorporation of SN or AFSN with sulfur is a promising method to prepare cathode material for lithium sulfur batteries

Plant Characteristics of an Integrated Solid Oxide Fuel Cell Cycle and a Steam Cycle

DEFF Research Database (Denmark)

Rokni, Masoud

2010-01-01

Plant characteristics of a system containing a solid oxide fuel cell (SOFC) cycle on the top of a Rankine cycle were investigated. Natural gas (NG) was used as the fuel for the plant. A desulfurization reactor removes the sulfur content in the fuel, while a pre-reformer broke down the heavier...... recovery steam generator (HRSG). The remaining energy of the off-gases was recycled back to the topping cycle for further utilization. Several parameter studies were carried out to investigate the sensitivity of the suggested plant. It was shown that the operation temperature of the desulfurization unit...

Determining total sulfur content in coal by MSC radiometric sulfur meter

Energy Technology Data Exchange (ETDEWEB)

Czerw, B; Sikora, T; Golebiowski, W

1976-01-01

The MSC radiometric sulfur meter is used to determine total sulfur content in brown and black coals. Sulfur content is determined by measuring intensity of radiation beam which has travelled through a coal sample with the optimum constant surface mass. Construction of the MSC, consisting of a measuring head and the electronic measuring system, is shown in a scheme. AM-241 (with activity of 50 mCi) is the source of radiation. Energy of 25.3 keV (tin disc) is selected as the optimum. The SSU-70 probe with NaJ/Tl crystal is the radiation detector. The black coal sample weighs 10 g and the brown coal sample weighs 18 g. Duration of sulfur determination is 10 min. Error of sulfur determination ranges from plus or minus 0.2% to 0.3%. The results of operational tests of MSC radiometric sulfur meters in black and brown coal mines are discussed. Accuracy of measurement is shown in 5 tables. (8 refs.)

Application of bacteria involved in the biological sulfur cycle for paper mill effluent purification

NARCIS (Netherlands)

Janssen, A.J.H.; Lens, P.N.L.; Stams, A.J.M.; Plugge, C.M.; Sorokin, D.Y.; Muyzer, G.; Dijkman, H.; Zessen, van E.; Luimes, F.J.T.; Buisman, C.J.N.

2009-01-01

In anaerobic wastewater treatment, the occurrence of biological sulfate reduction results in the formation of unwanted hydrogen sulfide, which is odorous, corrosive and toxic. In this paper, the role and application of bacteria in anaerobic and aerobic sulfur transformations are described and

Safety operation of chromatography column system with discharging hydrogen radiolytically generated

International Nuclear Information System (INIS)

Watanabe, S; Sano, Y.; Nomura, K.; Koma, Y.; Okamoto, Y.

2015-01-01

The extraction chromatography technology is one of the promising methods for the partitioning of minor actinides (Am and Cm) from spent nuclear fuels. In the extraction chromatography system, the accumulation of hydrogen gas in the chromatography column is suspected to lead to fire or explosion. In order to prevent hazardous accidents, it is necessary to evaluate behaviors of gas radiolytically generated inside the column. In this study, behaviors of gas inside the extraction chromatography column were investigated through experiments and Computation Fluid Dynamics (CFD) simulation. N_2 gas once accumulated as bubbles in the packed bed was hardly discharged by the flow of mobile phase. However, the CFD simulation and X-ray imaging on γ-ray irradiated column revealed that during operation the hydrogen gas generated in the column was dissolved into the mobile phase without accumulation and then discharged. (authors)

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Science.gov (United States)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li2Sx electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Genomic Insights into the Sulfur Metabolism of Phototrophic Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) utilize various combinations of sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for anaerobic photoautotrophic growth. Genome sequence data is currently available for 12 strains of GSB. We present here a genome-based survey of the distribution...... and phylogenies of genes involved in oxidation of sulfur compounds in these strains. Sulfide:quinone reductase, encoded by sqr, is the only known sulfur-oxidizing enzyme found in all strains. All sulfide-utilizing strains contain the dissimilatory sulfite reductase dsrABCEFHLNMKJOPT genes, which appear...... to be involved in elemental sulfur utilization. All thiosulfate-utilizing strains have an identical sox gene cluster (soxJXYZAKBW). The soxCD genes found in certain other thiosulfate-utilizing organisms like Paracoccus pantotrophus are absent from GSB. Genes encoding flavocytochrome c (fccAB), adenosine-5...

Capital cost: high and low sulfur coal plants-1200 MWe. [High sulfur coal

Energy Technology Data Exchange (ETDEWEB)

1977-01-01

This Commercial Electric Power Cost Study for 1200 MWe (Nominal) high and low sulfur coal plants consists of three volumes. The high sulfur coal plant is described in Volumes I and II, while Volume III describes the low sulfur coal plant. The design basis and cost estimate for the 1232 MWe high sulfur coal plant is presented in Volume I, and the drawings, equipment list and site description are contained in Volume II. The reference design includes a lime flue gas desulfurization system. A regenerative sulfur dioxide removal system using magnesium oxide is also presented as an alternate in Section 7 Volume II. The design basis, drawings and summary cost estimate for a 1243 MWe low sulfur coal plant are presented in Volume III. This information was developed by redesigning the high sulfur coal plant for burning low sulfur sub-bituminous coal. These coal plants utilize a mechanical draft (wet) cooling tower system for condenser heat removal. Costs of alternate cooling systems are provided in Report No. 7 in this series of studies of costs of commercial electrical power plants.

Characterization of desulfurization, denitrogenation and process sulfur transfer during hydropyrolysis of Chinese high sulfur coals

Energy Technology Data Exchange (ETDEWEB)

Sun Chenggong; Li Baoqing [Chinese Academy of Sciences, Taiyuan (China). State Key Lab. of Coal Conversion; Snape, C.E. [Strathclyde Univ., Glasgow (United Kingdom). Dept. of Pure and Applied Chemistry

1997-12-31

The process desulphurization and denitrogenation of Chinese high sulfur coals and the characteristics of sulfur transformation during non-catalytic hydropyrolysis were investigated by a 10 g fixed-bed reactor and a small-scaled reactor with online spectrometry respectively. It was indicated that more than 70% of the total sulfur of the two high sulfur coals and almost all pyritic sulfur are removed as H{sub 2}S, leaving the char and tar products with much less sulfur distribution. The liability of sulfur transformation to tar products is closely related to the thiophenic structure forms rather than sulfidic forms. At the same time, the formation of trace amount of sulfur dioxide indicates the presence of inherent sulfur oxidation reactions inside coal frame structures even under H{sub 2} pressure. (orig.)

Complexation of Cu2+, Ni2+ and UO22+ by radiolytic degradation products of bitumen

International Nuclear Information System (INIS)

Loon, L.R. Van; Kopajtic, Z.

1990-05-01

The radiolytic degradation of bitumen was studied under conditions which reflect those which will exist in the near field of a cementitious radioactive waste repository. The potential complexation capacity of the degradation products was studied and complexation experiments with Cu 2+ , Ni 2+ and UO 2 2+ were performed. In general 1:1 complexes with Cu 2+ , Ni 2+ and UO 2 2+ , with log K values of between 5.7 and 6.0 for Cu 2+ , 4.2 for Ni 2+ and 6.1 for UO 2 2+ , were produced at an ionic strength of 0.1 M. The composition of the bitumen water was analysed by GC-MS and IC. The major proportion of the bitumen degradation products in solution were monocarboxylic acids (acetic acid, formic acid, myric acid, stearic acid ...), dicarboxylic acids (oxalic acid, phthalic acid) and carbonates. The experimentally derived log K data are in good agreement with the literature and suggest that oxalate determines the speciation of Cu 2+ , Ni 2+ and UO 2 2+ in the bitumen water below pH=7. However, under the high pH conditions typical of the near field of a cementitious repository, competition with OH-ligands will be large and oxalate, therefore, will not play a significant role in the speciation of radionuclides. The main conclusion of the study is that the radiolytic degradation products of bitumen will have no influence on radionuclide speciation in a cementitious near field and, as such, need not to be considered in the appropriate safety assessment models. (author) 12 figs., 11 tabs., 31 refs

Radiolytic synthesis and electrocatalytic activity of bimetallic nanoaggregates grafted upon various electrodes

International Nuclear Information System (INIS)

Amblard, J.; Belloni, J.; Platzer, O.

1991-01-01

We show how to utilize the radiolytic pathway for grafting metal nanoaggregates upon anodes or cathodes involved in the chlorine-soda process, thus enhancing their electrochemical behaviour. In both cases important overpotentials are usually measured on unmodified electrodes. The electrocatalytic efficiency of bimetallic nanoparticles (such as Pt-Ru and Ni-Ru), once grafted onto bulk metal electrodes (Ti or Ni), has been investigated by measuring the overpotential for chlorine or hydrogen evolution, respectively. Experimental conditions are similar to those of the industrial process. A synergistic effect is shown when Pt and Ru are alloyed in a 2: 1 atomic ratio. Then the chlorine overpotential is minimum. Conversely, there is no synergy between Ni and Ru, although a minimum amount of Ru in Ru-Ni (50% atomic) ensures a very low hydrogen overpotential [fr

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

Energy Technology Data Exchange (ETDEWEB)

Xiao, Jie; Liu, Jun; Pan, Huilin; Henderson, Wesley A.

2018-04-24

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li₂S_x electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Surface-initiated growth of thin oxide coatings for Li-sulfur battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyu Tae; Black, Robert; Yim, Taeeun; Ji, Xiulei; Nazar, Linda F. [University of Waterloo, Department of Chemistry, Waterloo, ON (Canada)

2012-12-15

The concept of surface-initiated growth of oxides on functionalized carbons is introduced as a method to inhibit the dissolution of polysulfide ions in Li-S battery cathode materials. MO{sub x} (M: Si, V) thin layers are homogeneously coated on nanostructured carbon-sulfur composites. The coating significantly inhibits the dissolution of polysulfides on cycling, resulting in enhanced cycle performance and coulombic efficiency of the Li-S battery. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Contribution to the study of solvated electrons in water and alcohols and of radiolytic processes in organic carbonates by picosecond pulse radiolysis

International Nuclear Information System (INIS)

Torche, Faycal

2012-01-01

This work is part of the study area of the interaction of radiation with polar liquids. Using the picosecond electron accelerator ELYSE, studies were conducted using the techniques of pulse radiolysis combined with absorption spectrophotometry Time-resolved in the field of a picosecond. This work is divided into two separate chapters. The first study addresses the temporal variation of the radiolytic yield of solvated electron in water and simple alcohols. Due to original detection system mounted on the accelerator ELYSE, composed of a flash lamp specifically designed for the detection and a streak-camera used for the first time in absorption spectroscopy, it was possible to record the time-dependent radiolytic yields of the solvated electron from ten picoseconds to a few hundred nanoseconds. The scavenging of the electron solvated by methyl viologen, was utilized to reevaluate the molar extinction coefficient of the absorption spectrum of solvated electron in water and ethanol from isobestic points which corresponds to the intersection of the absorption spectra of solvated electron which disappears and methyl viologen which is formed during the reaction. The second chapter is devoted to the study of liquid organic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and propylene carbonate (PC). This family of carbonate which compose the electrolytes lithium batteries, has never been investigated by pulse radiolysis. The studies were focused on the PC in the light of these physicochemical characteristics, including its very high dielectric constant and its strong dipole moment of 4.9 D. The first results were obtained on aqueous solutions containing propylene carbonate to observe the reactions of reduction and oxidation of PC by radiolytic species of water (solvated electron and OH radicals). Then, after the identification (spectral and kinetic) of the species formed by interaction with the OH radical as the PC* radical resulting from the

Materials development for thermochemical cycles: sulfuric acid vaporizer. Semiannual technical report, October 1, 1977--March 31, 1978

International Nuclear Information System (INIS)

Krikorian, O.H.

1978-01-01

Installation of a sulfuric acid corrosion test facility has been completed and is described. The facility is to be used for testing of potential materials for containment and heat exchange of a sulfuric acid vaporizer at temperatures up to 725 0 K and boiling pressures of >20 atm (2 MPa). Materials that are ready for test are Duriron, Durichlor 51, single crystal Si, hot-pressed Si 3 N 4 (Noralide NC-132), and hot-pressed SiC (Crystar HD-435), and tests are expected to get underway in April pending Hazards Control approval

Self-assembled peptides for coating of active sulfur nanoparticles in lithium–sulfur battery

International Nuclear Information System (INIS)

Jewel, Yead; Yoo, Kisoo; Liu, Jin; Dutta, Prashanta

2016-01-01

Development of lithium–sulfur (Li–S) battery is hindered by poor cyclability due to the loss of sulfur, although Li–S battery can provide high energy density. Coating of sulfur nanoparticles can help maintain active sulfur in the cathode of Li–S battery, and hence increase the cyclability. Among myriad of coating materials, synthetic peptides are very attractive because of their spontaneous self-assembly as well as electrical conductive characteristics. In this study, we explored the use of various synthetic peptides as a coating material for sulfur nanoparticles. Atomistic simulations were carried out to identify optimal peptide structure and density for coating sulfur nanoparticles. Three different peptide models, poly-proline, poly(leucine–lysine) and poly-histidine, are selected for this study based on their peptide–peptide and peptide-sulfur interactions. Simulation results show that both poly-proline and poly(leucine–lysine) can form self-assembled coating on sulfur nanoparticles (2–20 nm) in pyrrolidinone, a commonly used solvent for cathode slurry. We also studied the structural integrity of these synthetic peptides in organic [dioxolane (DOL) and dimethoxyethane (DME)] electrolyte used in Li–S battery. Both peptides show stable structures in organic electrolyte (DOL/DME) used in Li–S battery. Furthermore, the dissolution of sulfur molecules in organic electrolyte is investigated in the absence and presence of these peptide coatings. It was found that only poly(leucine–lysine)-based peptide can most effectively suppress the sulfur loss in electrolyte, suggesting its potential applications in Li–S battery as a coating material.Graphical abstract

Sulfur-Iodine Integrated Lab Scale Experiment Development

Energy Technology Data Exchange (ETDEWEB)

Russ, Ben

2011-05-27

The sulfur-iodine (SI) cycle was deermined to be the best cycle for coupling to a high temperature reactor (HTR) because of its high efficiency and potential for further improvement. The Japanese Atomic Energy Agency (JAEA) has also selected the SI process for further development and has successfully completed bench-scale demonstrations of the SI process at atmospheric pressure. JEA also plans to proceed with pilot-scale demonstrations of the SI process and eventually plans to couple an SI demonstration plant to its High Temperature Test Reactor (HHTR). As part of an international NERI project, GA, SNL, and the Frech Commissariat L'Energie Atomique performed laboratory-scale demonstrations of the SI process at prototypical temperatures and pressures. This demonstration was performed at GA in San Diego, CA and concluded in April 2009.

Sulfur-Iodine Integrated Lab Scale Experiment Development

International Nuclear Information System (INIS)

Russ, Ben

2011-01-01

The sulfur-iodine (SI) cycle was determined to be the best cycle for coupling to a high temperature reactor (HTR) because of its high efficiency and potential for further improvement. The Japanese Atomic Energy Agency (JAEA) has also selected the SI process for further development and has successfully completed bench-scale demonstrations of the SI process at atmospheric pressure. JEA also plans to proceed with pilot-scale demonstrations of the SI process and eventually plans to couple an SI demonstration plant to its High Temperature Test Reactor (HHTR). As part of an international NERI project, GA, SNL, and the Frech Commissariat L'Energie Atomique performed laboratory-scale demonstrations of the SI process at prototypical temperatures and pressures. This demonstration was performed at GA in San Diego, CA and concluded in April 2009.

Microbial interactions involving sulfur bacteria : implications for the ecology and evolution of bacterial communities

NARCIS (Netherlands)

Overmann, J; van Gemerden, H

2000-01-01

A major goal of microbial ecology is the identification and characterization of those microorganisms which govern transformations in natural ecosystems. This review summarizes our present knowledge of microbial interactions in the natural sulfur cycle. Central to the discussion is the recent

Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.

2017-08-01

The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

Synthesis of a Flexible Freestanding Sulfur/Polyacrylonitrile/Graphene Oxide as the Cathode for Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

Huifen Peng

2018-04-01

Full Text Available Rechargeable lithium/sulfur (Li/S batteries have received quite significant attention over the years because of their high theoretical specific capacity (1672 mAh·g−1 and energy density (2600 mAh·g−1 which has led to more efforts for improvement in their electrochemical performance. Herein, the synthesis of a flexible freestanding sulfur/polyacrylonitrile/graphene oxide (S/PAN/GO as the cathode for Li/S batteries by simple method via vacuum filtration is reported. The S/PAN/GO hybrid binder-free electrode is considered as one of the most promising cathodes for Li/S batteries. Graphene oxide (GO slice structure provides effective ion conductivity channels and increases structural stability of the ternary system, resulting in excellent electrochemical properties of the freestanding S/PAN/GO cathode. Additionally, graphene oxide (GO membrane was able to minimize the polysulfides’ dissolution and their shuttle, which was attributed to the electrostatic interactions between the negatively-charged species and the oxygen functional groups on GO. Furthermore, these oxygen-containing functional groups including carboxyl, epoxide and hydroxyl groups provide active sites for coordination with inorganic materials (such as sulfur. It exhibits the initial reversible specific capacity of 1379 mAh·g−1 at a constant current rate of 0.2 C and maintains 1205 mAh·g−1 over 100 cycles (~87% retention. In addition, the freestanding S/PAN/GO cathode displays excellent coulombic efficiency (~100% and rate capability, delivering up to 685 mAh·g−1 capacity at 2 C.

Effect of different sulfur levels from various sources on brassica napus growth and soil sulfur fractions

International Nuclear Information System (INIS)

Khalid, R.; Khan, K.S.; Islam, M.; Yousaf, M.; Shabbir, G.

2012-01-01

A two year field study was conducted at two different locations in northern rain fed Punjab, Pakistan to assess the effect of different rates of sulfur application from various sources on soil sulfur fractions and growth of Brassica napus. The treatments included three sulfur sources i. e., single super phosphate, ammonium sulfate and gypsum each applied at five different rates (0, 10, 20, 30 and 40 kg S ha/sup -1/ ). Sulfur application had a significant positive effect on the growth and yield parameters of Brassica napus. Among the sulfur sources ammonium sulfate resulted in maximum increase in plant growth and yield parameters, followed by single super phosphate. Sulfur content and uptake by crop plants was significantly higher with ammonium sulfate application as compared to other two sulfur sources. Sulfur application also exerted a significant positive effect on different S fractions in the soils. On an average, 18.0% of the applied sulfur got incorporated into CaCl/sub 2/ extractable sulfur fraction, while 15.6% and 35.5% entered into adsorbed and organic sulfur fractions in the soils, respectively. The value cost ratio increased significantly by sulfur application up to 30 kg ha/sup -1/. Among sulfur sources, ammonium sulfate performed best giving the highest net return. (author)

The oceanic cycle and global atmospheric budget of carbonyl sulfide

Energy Technology Data Exchange (ETDEWEB)

Weiss, P.S.

1994-12-31

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.

A novel three-dimensional sulfur/graphene/carbon nanotube composite prepared by a hydrothermal co-assembling route as binder-free cathode for lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Yuan, Guanghui; Wang, Gang [Northwest University, National Key Laboratory of Photoelectric Technology and Functional Materials (Culture Base), National Photoelectric Technology and Functional Materials & Application International Cooperation Base, Physics Department, Institute of Photonics & Photon-Technology (China); Wang, Hui, E-mail: huiwang@nwu.edu.cn [Northwest University, Key Laboratory of Synthetic and Natural Functional Molecule Chemistry (Ministry of Education), College of Chemistry & Materials Science (China); Bai, Jintao, E-mail: jintaobai@sina.cn, E-mail: baijt@nwu.edu.cn [Northwest University, National Key Laboratory of Photoelectric Technology and Functional Materials (Culture Base), National Photoelectric Technology and Functional Materials & Application International Cooperation Base, Physics Department, Institute of Photonics & Photon-Technology (China)

2015-01-15

A novel sulfur/graphene/carbon nanotube (S/GN/CNT) composite was successfully prepared by a facile hydrothermal co-assembling route. When used as cathode for lithium–sulfur battery, the S/GN/CNT composite can be pressed directly onto nickel foam without binder and conductive additive, thereby simplifying the manufacturing process. The resulting S/GN/CNT composite exhibited high and stable-specific discharge capacities of 670 mAh g{sup −1} after 80 cycles at 0.2 C and good rate capability. This enhanced electrochemical performance could be attributed to the combinative effects of GN and CNT, which not only function as a flexible conductive matrix, favoring the ion transport and electrolyte diffusion, but also for provide a porous three-dimensional architecture with open channels to effectively confine the soluble polysulfides.

A novel three-dimensional sulfur/graphene/carbon nanotube composite prepared by a hydrothermal co-assembling route as binder-free cathode for lithium–sulfur batteries

International Nuclear Information System (INIS)

Yuan, Guanghui; Wang, Gang; Wang, Hui; Bai, Jintao

2015-01-01

A novel sulfur/graphene/carbon nanotube (S/GN/CNT) composite was successfully prepared by a facile hydrothermal co-assembling route. When used as cathode for lithium–sulfur battery, the S/GN/CNT composite can be pressed directly onto nickel foam without binder and conductive additive, thereby simplifying the manufacturing process. The resulting S/GN/CNT composite exhibited high and stable-specific discharge capacities of 670 mAh g −1 after 80 cycles at 0.2 C and good rate capability. This enhanced electrochemical performance could be attributed to the combinative effects of GN and CNT, which not only function as a flexible conductive matrix, favoring the ion transport and electrolyte diffusion, but also for provide a porous three-dimensional architecture with open channels to effectively confine the soluble polysulfides

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

Directory of Open Access Journals (Sweden)

Nurgul Balci

2017-08-01

Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

Gamma Radiolytic Degradation of Heptachlor in Methanol and Monitoring of Degradation by HPLC

International Nuclear Information System (INIS)

Riaz, M.; Butt, S.B.

2014-01-01

Removal of known insecticide Heptachlor (HPTC) in methanol solution by gamma-rays under varied experimental conditions has been optimized. Air saturated solution of HPTC was irradiated at x-rays dose from 1 to 10 kGys. The extent of radiolytic degradation was monitored by reversed phase high performance liquid chromatography (HPLC) coupled with UV detector. At dose of 10 kGys gamma 98 % of HPTC was degraded. The degradation of HPTC occurs by CH/sub 3/O and CH/sub 2/OH radicals generated by methanol radiolysis. It is concluded that gamma-rays can remove Persistent Organic Pollutants (POPs) form environmental matrices. It can decrease the harmful properties of these POPs by their transformation into less resistant fragments to biological / natural elimination in the aquatic atmosphere. (author)

Evaluate the role of organic acids in the protection of ligands from radiolytic degradation

Energy Technology Data Exchange (ETDEWEB)

Miller, Anneka [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stehpen [Idaho National Lab. (INL), Idaho Falls, ID (United States); Peterman, Dean [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2016-08-01

In the Advanced TALSPEAK process, the bis(2-ethylhexyl)phosphoric acid (HDEHP) extractant used in the traditional TALSPEAK process is replaced by the extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]). In addition, the aqueous phase complexant and buffer used in traditional TALSPEAK is replaced with the combination of N-(2-hydroxyethyl)ethylenediamine-N,N’,N’-triacetic acid (HEDTA) and citric acid. In order to evaluate the possible impacts of gamma radiolysis upon the efficacy of the Advanced TALSPEAK flowsheet, aqueous and organic phases corresponding to the extraction section of the proposed flowsheet were irradiated in the INL test loop under an ambient atmosphere. The results of these studies conducted at INL, led INL researchers to conclude that the scarcity of values of rate constants for the reaction of hydroxyl radical with the components of the Advanced TALSPEAK process chemistry was severely limiting the interpretation of the results of radiolysis studies performed at the INL. In this work, the rate of reaction of hydroxyl radical with citric acid at several pH values was measured using a competitive pulse radiolysis technique. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation. The results reported here demonstrate the importance of obtaining hydroxyl radical reaction rate data for the conditions that closely resemble actual solution conditions expected to be used in an actual solvent extraction process. This report describes those results and is written in completion of milestone M3FT-16IN030102028, the goal of which was to evaluate the role of organic acids in the protection of ligands from radiolytic degradation.

Radiolytic stabilization of poly(methyl methacrylate) using commercial additives

International Nuclear Information System (INIS)

Aquino, Katia Aparecida da Silva

2000-04-01

Poly(methyl methacrylate), PMMA, Acrigel, a Brazilian polymer, is used in the manufacture of medical supplies sterelizable by ionizing radiation. However, when PMMA is gamma-irradiated it undergoes main chain scissions, which promote molecular degradation causing reduction in its mechanical properties. Therefore, radiolytic of PMMA is important for it to become commercially radiosterizable. In this work some commercial additives, originally used in photo-and thermo-oxidate stabilization of polymers, were tested. Only two additives, type HALS (Hindered Amine Light Stabilizer), denoted Scavenger, showed a good protective quality. The investigation of radiation-induced main scissions was carried out by viscosimetric method. The most effective additive, added to the polymer system at 0.3 w/w%, promotes a great molecular radioprotection of 93%. That means a reduction of G-value (scissions/100 eV) from 0.611 to 0.053. In addition, the glassy transition temperature (T g ) of PMMA (no additive) significantly changed by radiation does not change when PMMA (with additive) is irradiated. The spectroscopy analysis, FT-IR and NMR ( 1 H), showed that the radioprotector added to the system does not change the PMMA structure. (author)

Toward High-Performance Lithium-Sulfur Batteries: Upcycling of LDPE Plastic into Sulfonated Carbon Scaffold via Microwave-Promoted Sulfonation.

Science.gov (United States)

Kim, Patrick J; Fontecha, Harif D; Kim, Kyungho; Pol, Vilas G

2018-05-02

Lithium-sulfur batteries were intensively explored during the last few decades as next-generation batteries owing to their high energy density (2600 Wh kg -1 ) and effective cost benefit. However, systemic challenges, mainly associated with polysulfide shuttling effect and low Coulombic efficiency, plague the practical utilization of sulfur cathode electrodes in the battery market. To address the aforementioned issues, many approaches have been investigated by tailoring the surface characteristics and porosities of carbon scaffold. In this study, we first present an effective strategy of preparing porous sulfonated carbon (PSC) from low-density polyethylene (LDPE) plastic via microwave-promoted sulfonation. Microwave process not only boosts the sulfonation reaction of LDPE but also induces huge amounts of pores within the sulfonated LDPE plastic. When a PSC layer was utilized as an interlayer in lithium-sulfur batteries, the sulfur cathode delivered an improved capacity of 776 mAh g -1 at 0.5C and an excellent cycle retention of 79% over 200 cycles. These are mainly attributed to two materialistic benefits of PSC: (a) porous structure with high surface area and (b) negatively charged conductive scaffold. These two characteristics not only facilitate the improved electrochemical kinetics but also effectively block the diffusion of polysulfides via Coulomb interaction.

Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids

International Nuclear Information System (INIS)

Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P.

2014-01-01

Highlights: • Extractive de-sulfurization and de-ashing process for cleaning high sulfur coals. • The process removes inorganic as well as organic sulfur components from high sulfur coals. • The process has less risk to chemists and other surroundings. - Abstract: The environmental consequences of energy production from coals are well known, and are driving the development of desulfurization technologies. In this investigation, ionic liquids were examined for extractive desulfurization and de-ashing in industrially important high sulfur sub-bituminous Indian coals. The ionic liquids, namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (IL1) and 1-n-butyl 3-methylimidazolium chloride (IL2) were employed for desulfurization of a few Indian coal samples in presence of HCOOH/H 2 O 2 and V 2 O 5 . Results show the maximum removal of 50.20% of the total sulfur, 48.00% of the organic sulfur, and 70.37 wt% of the ash in this process. The ionic liquids were recovered and subsequently used for further desulfurization. FT-IR spectra reveal the transformation of organic sulfur functionalities into the sulfoxides (S=O) and sulfones (-SO 2 ) due to the oxidative reactions. The sulfate, pyrite and sulfides (aryls) signals in the near edge X-ray absorption fine structure (NEXAFS) of the oxidized coal samples showed sulfur transformation during the desulfurization process. The study demonstrates the removal of significant amount of inorganic as well as organic sulfur (aryls) components from the original high sulfur coal samples to make them cleaner

Effects of aerobic-anaerobic transient conditions on sulfur and metal cycles in sewer biofilms

NARCIS (Netherlands)

Nielsen, A.; Lens, P.N.L.; Vollertsen, J.; Hvitved-Jacobsen, Th.

2005-01-01

Interactions between sulfur and metals were studied in aerobic and anaerobic biofilms grown on domestic waste water at 15°C. The dominant metals in the waste water were iron, zinc and copper, which were present in average concentrations of 0.5mg/l, 0.6mg/l and 0.1m/l, respectively. Copper and zinc

Natural environment and the biogeochemical cycle s. Pt. A

Energy Technology Data Exchange (ETDEWEB)

Hutzinger, O [ed.

1980-01-01

At the moment three volumes of the handbook are planned. Volume 1 deals with the natural environment and the biogeochemical cycles therein, including some background information such as energetics and ecology. The individual chapters are dealing with the atmosphere, the hydrosphere, chemical oceanography, chemical aspects of soil, the cycle of oxygen, sulfur, and phosphorus, metal cycles and biological methylation, and natural organohalogen compounds. Separate abstracts are prepared for 5 chapters of this book.

Molecular analysis of the diversity of sulfate-reducing and sulfur-oxidizing prokaryotes in the environment, using aprA as functional marker gene.

Science.gov (United States)

Meyer, Birte; Kuever, Jan

2007-12-01

The dissimilatory adenosine-5'-phosphosulfate reductase is a key enzyme of the microbial sulfate reduction and sulfur oxidation processes. Because the alpha- and beta-subunit-encoding genes, aprBA, are highly conserved among sulfate-reducing and sulfur-oxidizing prokaryotes, they are most suitable for molecular profiling of the microbial community structure of the sulfur cycle in environment. In this study, a new aprA gene-targeting assay using a combination of PCR and denaturing gradient gel electrophoresis is presented. The screening of sulfate-reducing and sulfur-oxidizing reference strains as well as the analyses of environmental DNA from diverse habitats (e.g., microbial mats, invertebrate tissue, marine and estuarine sediments, and filtered hydrothermal water) by the new primer pair revealed an improved microbial diversity coverage and less-pronounced template-to-PCR product bias in direct comparison to those of the previously published primer set (B. Deplancke, K. R. Hristova, H. A. Oakley, V. J. McCracken, R. Aminov, R. I. Mackie, and H. R. Gaskins, Appl. Environ. Microbiol. 66:2166-2174, 2000). The concomitant molecular detection of sulfate-reducing and sulfur-oxidizing prokaryotes was confirmed. The new assay was applied in comparison with the 16S rRNA gene-based analysis to investigate the microbial diversity of the sulfur cycle in sediment, seawater, and manganese crust samples from four study sites in the area of the Lesser Antilles volcanic arc, Caribbean Sea (Caribflux project). The aprA gene-based approach revealed putative sulfur-oxidizing Alphaproteobacteria of chemolithoheterotrophic lifestyle to have been abundant in the nonhydrothermal sediment and water column. In contrast, the sulfur-based microbial community that inhabited the surface of the volcanic manganese crust was more complex, consisting predominantly of putative chemolithoautotrophic sulfur oxidizers of the Betaproteobacteria and Gammaproteobacteria.

Radiolytic degradation of gallic acid and its derivatives in aqueous solution

International Nuclear Information System (INIS)

Melo, R.; Leal, J.P.; Takacs, E.; Wojnarovits, L.

2009-01-01

Polyphenols, like gallic acid (GA) released in the environment in larger amount, by inducing some unwanted oxidations, may constitute environmental hazard: their concentration in wastewater should be controlled. Radiolytic degradation of GA was investigated by pulse radiolysis and final product techniques in dilute aqueous solution. Subsidiary measurements were made with 3,4,5-trimethoxybenzoic acid (TMBA) and 3,4,5-trihydroxy methylbenzoate (MGA). The hydroxyl radical and hydrogen atom intermediates of water radiolysis react with the solute molecules yielding cyclohexadienyl radicals. The radicals formed in GA and MGA solutions in acid/base catalyzed water elimination decay to phenoxyl radicals. This reaction is not observed in TMBA solution. The hydrated electron intermediate of water decomposition adds to the carbonyl oxygen, the anion thus formed protonates on the ring forming cyclohexadienyl radical or on the carbonyl group forming carbonyl centred radical. The GA intermediates formed during reaction with primary water radicals in presence of oxygen transform to non-aromatic molecules, e.g., to aliphatic carboxylic acids.

Radiolytic degradation of gallic acid and its derivatives in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Melo, R. [Instituto Tecnologico e Nuclear, UCQR, Estrada Nacional No. 10, Apartado 21, 2686-953, Sacavem (Portugal); Leal, J.P. [Instituto Tecnologico e Nuclear, UCQR, Estrada Nacional No. 10, Apartado 21, 2686-953, Sacavem (Portugal); Centro Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, 1749-016 Lisboa (Portugal); Takacs, E., E-mail: takacs@iki.kfki.hu [Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest (Hungary); Wojnarovits, L. [Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest (Hungary)

2009-12-30

Polyphenols, like gallic acid (GA) released in the environment in larger amount, by inducing some unwanted oxidations, may constitute environmental hazard: their concentration in wastewater should be controlled. Radiolytic degradation of GA was investigated by pulse radiolysis and final product techniques in dilute aqueous solution. Subsidiary measurements were made with 3,4,5-trimethoxybenzoic acid (TMBA) and 3,4,5-trihydroxy methylbenzoate (MGA). The hydroxyl radical and hydrogen atom intermediates of water radiolysis react with the solute molecules yielding cyclohexadienyl radicals. The radicals formed in GA and MGA solutions in acid/base catalyzed water elimination decay to phenoxyl radicals. This reaction is not observed in TMBA solution. The hydrated electron intermediate of water decomposition adds to the carbonyl oxygen, the anion thus formed protonates on the ring forming cyclohexadienyl radical or on the carbonyl group forming carbonyl centred radical. The GA intermediates formed during reaction with primary water radicals in presence of oxygen transform to non-aromatic molecules, e.g., to aliphatic carboxylic acids.

Sulfur poisoning in cattle

Energy Technology Data Exchange (ETDEWEB)

Julian, R J; Harrison, K B

1975-01-01

A case of sulfur poisoning is described in which 12 of 20 cattle died following the feeding of sulfur. Respiratory distress and abdominal pain were the prominent signs. Examination of one animal revealed vasculitis and necrosis of the rumen and abomasal wall. The possible toxic effects of sulfur are discussed.

Studies on the radiation chemistry of biomolecules in aqueous solution with specific objective of minimizing their radiolytic degradation. Coordinated programme for Asia and the Pacific Region on radiation sterilization practices significant to local medical supplies and conditions

International Nuclear Information System (INIS)

Narayana Rao, K.

1979-01-01

As part of a study of radiolytic degradation of pharmaceuticals during radiosterilization, the basic radiation chemistry of the B-group vitamins, nicotinamide, pyridoxin, riboflavin and thiamine, and the reaction of hydrogen peroxide with these same materials has been investigated. The various aspects studied were - radiolysis under controlled conditions, effects of phase, temperature, pH and nature and concentration of additives. Some of the conclusions are: 1) with oxygen saturated aqueous solutions containing glucose, the radiolytic degradation of the vitamins is reduced: 2) results a similar for N 2 O saturated aqueous solutions; 3) in glucose-containing solutions, the protective effect is considerably modified at higher temperatures; and 4) irradiation of air-saturated aqueous solutions in the frozen state leads to reduced decomposition. It is concluded that in the presence of oxygen, in frozen matrices at low temperature, it appears possible to reduce the radiolytic breakdown of vitamins to low levels

Account of the intratrack radiolytic processes for interpretation of the AMOC spectrum of liquid water

International Nuclear Information System (INIS)

Zvezhinskiy, D S; Stepanov, S V; Butterling, M; Wagner, A; Krause-Rehberg, R

2013-01-01

Recent development of the Gamma-induced Positron Spectroscopy (GiPS) setup significantly extends applicability of the Age-Momentum Correlation technique (AMOC) for studies of the bulk samples. It also provides many advantages comparing with conventional positron annihilation experiments in liquids, such as extremely low annihilation fraction in vessel walls, absence of a positron source and positron annihilations in it. We have developed a new approach for processing and interpretation of the AMOC-GiPS data based on the diffusion recombination model of the intratrack radiolytic processes. This approach is verified in case of liquid water, which is considered as a reference medium in the positron and positronium chemistry.

Account of the intratrack radiolytic processes for interpretation of the AMOC spectrum of liquid water

Science.gov (United States)

Zvezhinskiy, D. S.; Butterling, M.; Wagner, A.; Krause-Rehberg, R.; Stepanov, S. V.

2013-06-01

Recent development of the Gamma-induced Positron Spectroscopy (GiPS) setup significantly extends applicability of the Age-Momentum Correlation technique (AMOC) for studies of the bulk samples. It also provides many advantages comparing with conventional positron annihilation experiments in liquids, such as extremely low annihilation fraction in vessel walls, absence of a positron source and positron annihilations in it. We have developed a new approach for processing and interpretation of the AMOC-GiPS data based on the diffusion recombination model of the intratrack radiolytic processes. This approach is verified in case of liquid water, which is considered as a reference medium in the positron and positronium chemistry.

Sulfur Earth

Science.gov (United States)

de Jong, B. H.

2007-12-01

Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

Thermal and Radiolytic Gas Generation Tests on Material from Tanks 241-U-103, 241-AW-101, 241-S-106, and 241-S-102: Status Report

International Nuclear Information System (INIS)

King, C.M.; Bryan, S.A.

1999-01-01

This report summarizes progress in evaluating thermal and radiolytic flammable gas generation in actual Hanford single-shell tank wastes. The work described was conducted at Pacific Northwest National Laboratory (PNNL) for the Flammable Gas Safety Project, whose purpose is to develop information to support DE and S Hanford (DESH) and Project Management Hanford Contract (PHMC) subcontractors in their efforts to ensure the safe interim storage of wastes at the Hanford Site. This work is related to gas generation studies performed by Numatec Hanford Corporation (formerly Westinghouse Hanford Company). This report describes the results of laboratory tests of gas generation from actual convective layer wastes from Tank 241-U-103 under thermal and radiolytic conditions. Accurate measurements of gas generation rates from highly radioactive tank wastes are needed to assess the potential for producing and storing flammable gases within the tanks. The gas generation capacity of the waste in Tank 241-U-103 is a high priority for the Flammable Gas Safety Program due to its potential for accumulating gases above the flammability limit (Johnson et al, 1997). The objective of this work was to establish the composition of gaseous degradation products formed in actual tank wastes by thermal and radiolytic processes as a function of temperature. The gas generation tests on Tank 241-U-103 samples focused first on the effect of temperature on the composition and rate of gas generation Generation rates of nitrogen, nitrous oxide, methane, and hydrogen increased with temperature, and the composition of the product gas mixture varied with temperature

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

Science.gov (United States)

Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker

2008-02-01

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the

Sulfur problems in Swedish agriculture

Energy Technology Data Exchange (ETDEWEB)

Johansson, O

1959-01-01

The present paper deals with some aspects of the sulfur situation in Swedish agriculture with special emphasis on the importance of and relationships among various sources of sulfur supply. An inventory of the sulfur content of Swedish soils and hay crops includes 649 soil samples and a corresponding number of hay samples from 59 locations. In a special investigation the samples were found to be representative of normal Swedish farm land. It is concluded that the amount of sulfur compounds in the air is the primary factor which determines the amount of sulfur added to the soil from the atmosphere. Compared with values obtained in other countries, the amount of sulfur added by the precipitation in Sweden is very low. The distribution in air and precipitation of sulfur from an industrial source was studied in a special investigation. An initial reason for the present study was the damage to vegetation caused by smoke from an industrial source. It was concluded that the average conditions in the vicinity of the industrial source with respect to smoke constituents in the air and precipitation were unfavorable only to the plants directly within a very narrow region. Relationships among the sulfur contents of air, of precipitation, of soils and of plants have been subject to special investigations. In the final general discussion and conclusions it is pointed out that the results from these investigations indicate evident differences in the sulfur status of Swedish soils. The present trend toward the use of more highly concentrated fertilizers poor in sulfur may be expected to cause a considerable change in the sulfur situation in Swedish agriculture. 167 references, 40 figures, 44 tables.

Sulfate- and Sulfur-Reducing Bacteria as Terrestrial Analogs for Microbial Life on Jupiter's Satellite Io

Science.gov (United States)

Pikuta, Elena V.; Hoover, Richard B.; Six, N. Frank (Technical Monitor)

2001-01-01

Observations from the Voyager and Galileo spacecraft have revealed Jupiter's moon Io to be the most volcanically active body of our Solar System. The Galileo Near Infrared Imaging Spectrometer (NIMS) detected extensive deposits of sulfur compounds, elemental sulfur and SO2 frost on the surface of Io. There are extreme temperature variations on Io's surface, ranging from -130 C to over 2000 C at the Pillan Patera volcanic vent. The active volcanoes, fumaroles, calderas, and lava lakes and vast sulfur deposits on this frozen moon indicate that analogs of sulfur- and sulfate-reducing bacteria might inhabit Io. Hence Io may have great significance to Astrobiology. Earth's life forms that depend on sulfur respiration are members of two domains: Bacteria and Archaea. Two basic links of the biogeochemical sulfur cycle of Earth have been studied: 1) the sulfur oxidizing process (occurring at aerobic conditions) and 2) the process of sulfur-reduction to hydrogen sulfide (anaerobic conditions). Sulfate-reducing bacteria (StRB) and sulfur-reducing bacteria (SrRB) are responsible for anaerobic reducing processes. At the present time the systematics of StRB include over 112 species distributed into 35 genera of Bacteria and Archaea. Moderately thermophilic and mesophilic SrRB belong to the Bacteria. The hyperthermophilic SrRB predominately belong to the domain Archaea and are included in the genera: Pyrodictium, Thermoproteus, Pyrobaculum, Thermophilum, Desulfurococcus, and Thermodiscus. The StRB and SrRB use a wide spectrum of substrates as electron donors for lithotrophic and heterotrophic type nutrition. The electron acceptors for the StRB include: sulfate, thiosulfate, sulfite, sulfur, arsenate, dithionite, tetrathionate, sulfur monoxide, iron, nitrite, selenite, fumarate, oxygen, carbon dioxide, and chlorine-containing phenol compounds. The Sulfate- and Sulfur-reducing bacteria are widely distributed in anaerobic ecosystems, including extreme environments like hot springs

A Comparison of Organic and Steam Rankine Cycle Power Systems for Waste Heat Recovery on Large Ships

DEFF Research Database (Denmark)

Andreasen, Jesper Graa; Meroni, Andrea; Haglind, Fredrik

2017-01-01

%) fuel case. The processes were compared based on their off-design performance for diesel engine loads in the range between 25% and 100%. The fluids considered in the organic Rankine cycle process were MM(hexamethyldisiloxane), toluene, n-pentane, i-pentane and c-pentane. The results of the comparison....... The net power production from the waste heat recovery units is generally higher for the low-sulfur fuel case. The steam Rankine cycle unit produces 18% more power at design compared to the high-sulfur fuel case, while the organic Rankine cycle unit using MM produces 33% more power....

Molecular Analysis of the Diversity of Sulfate-Reducing and Sulfur-Oxidizing Prokaryotes in the Environment, Using aprA as Functional Marker Gene▿ †

Science.gov (United States)

Meyer, Birte; Kuever, Jan

2007-01-01

The dissimilatory adenosine-5′-phosposulfate reductase is a key enzyme of the microbial sulfate reduction and sulfur oxidation processes. Because the alpha- and beta-subunit-encoding genes, aprBA, are highly conserved among sulfate-reducing and sulfur-oxidizing prokaryotes, they are most suitable for molecular profiling of the microbial community structure of the sulfur cycle in environment. In this study, a new aprA gene-targeting assay using a combination of PCR and denaturing gradient gel electrophoresis is presented. The screening of sulfate-reducing and sulfur-oxidizing reference strains as well as the analyses of environmental DNA from diverse habitats (e.g., microbial mats, invertebrate tissue, marine and estuarine sediments, and filtered hydrothermal water) by the new primer pair revealed an improved microbial diversity coverage and less-pronounced template-to-PCR product bias in direct comparison to those of the previously published primer set (B. Deplancke, K. R. Hristova, H. A. Oakley, V. J. McCracken, R. Aminov, R. I. Mackie, and H. R. Gaskins, Appl. Environ. Microbiol. 66:2166-2174, 2000). The concomitant molecular detection of sulfate-reducing and sulfur-oxidizing prokaryotes was confirmed. The new assay was applied in comparison with the 16S rRNA gene-based analysis to investigate the microbial diversity of the sulfur cycle in sediment, seawater, and manganese crust samples from four study sites in the area of the Lesser Antilles volcanic arc, Caribbean Sea (Caribflux project). The aprA gene-based approach revealed putative sulfur-oxidizing Alphaproteobacteria of chemolithoheterotrophic lifestyle to have been abundant in the nonhydrothermal sediment and water column. In contrast, the sulfur-based microbial community that inhabited the surface of the volcanic manganese crust was more complex, consisting predominantly of putative chemolithoautotrophic sulfur oxidizers of the Betaproteobacteria and Gammaproteobacteria. PMID:17921272

Research and development on process components for hydrogen production. (1) Test-fabrication of sulfuric acid transfer pump

International Nuclear Information System (INIS)

Iwatsuki, Jin; Terada, Atsuhiko; Hino, Ryutaro; Kubo, Shinji; Onuki, Kaoru; Watanabe, Yutaka

2009-01-01

Japan Atomic Energy Agency has been conducting a research and development on hydrogen production system using High Temperature Gas-Cooled Reactor. As a part of this effort, thermochemical water-splitting cycle featuring iodine- and sulfur-compounds (IS process) is under development considering its potential of large-scale economical hydrogen production. The IS process constitutes very severe environments to the materials of construction because of the corrosive nature of process chemicals, especially of the high temperature acidic solutions of sulfuric acid and hydriodic acid dissolving iodine. Therefore, selection of the corrosion-resistant materials and development of the components have been the crucial subjects of process development. This paper concerns the sulfuric acid transfer pump. The development has been implemented of a pump for transporting concentrated sulfuric acid at temperatures of higher than 300degC and at elevated pressure. Recent progress of these activities will be reported. (author)

Thermal and combined thermal and radiolytic reactions involving nitrous oxide, hydrogen, nitrogen, and ammonia in contact with tank 241-SY-101 simulated waste

International Nuclear Information System (INIS)

Bryan, S.A.; Pederson, L.R.

1996-02-01

Work described in this report was conducted at Pacific Northwest National Laboratory (PNNL) for the Flammable Gas Safety Project, the purpose of which is to develop information needed to support Westinghouse Hanford Company (WHC) in their efforts to ensure the safe interim storage of wastes at the Hanford Site. Described in this report are the results of tests to evaluate the rates of thermal and combined thermal and radiolytic reactions involving flammable gases in the presence of Tank 241-SY-101 simulated waste. Flammable gases generated by the radiolysis of water and by the thermal and radiolytic decomposition of organic waste constituents may themselves participate in further reactions. Examples include the decomposition of nitrous oxide to yield nitrogen and oxygen, the reaction of nitrous oxide and hydrogen to produce nitrogen and water, and the reaction of nitrogen and hydrogen to produce ammonia. The composition of the gases trapped in bubbles in the wastes might therefore change continuously as a function of the time that the gas bubbles are retained

Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

International Nuclear Information System (INIS)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian; Pujals, Daniel Codorniu; Mikosch, Hans; Hernández, Mayra P.

2014-01-01

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO 2 gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage

Sulfur dimers adsorbed on Au(111) as building blocks for sulfur octomers formation: A density functional study

Energy Technology Data Exchange (ETDEWEB)

Hernandez-Tamargo, Carlos E.; Montero-Alejo, Ana Lilian [Laboratory of Computational and Theoretical Chemistry (LQCT), Faculty of Chemistry, Havana University, Havana 10400 (Cuba); Pujals, Daniel Codorniu [Higher Institute of Technologies and Applied Sciences (InSTEC), Havana 10400 (Cuba); Mikosch, Hans [Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/E164-EC, 1060 Vienna (Austria); Hernández, Mayra P., E-mail: mayrap@imre.oc.uh.cu [Instituto de Ciencias y Tecnologías de Materiales (IMRE), Havana 10400 (Cuba)

2014-07-28

Experimental scanning tunneling microscopy (STM) studies have shown for more than two decades rectangular formations when sulfur atoms are deposited on Au(111) surfaces. The precursors have ranged from simple molecules or ions, such as SO{sub 2} gas or sulfide anions, to more complex organosulfur compounds. We investigated, within the framework of the Density Functional Theory, the structure of these rectangular patterns assuming them entirely composed of sulfur atoms as the experimental evidence suggests. The sulfur coverage at which the simulations were carried out (0.67 ML or higher) provoked that the sulfur-sulfur association had to be taken into account for achieving a good agreement between the sets of simulated and experimental STM images. A combination of four sulfur dimers per rectangular formation properly explained the trends obtained by the experimental STM analysis which were related with the rectangles' size and shape fluctuations together with sulfur-sulfur distances within these rectangles. Finally, a projected density of states analysis showed that the dimers were capable of altering the Au(5d) electronic states at the same level as atomic sulfur adsorbed at low coverage. Besides, sulfur dimers states were perfectly distinguished, whose presence near and above the Fermi level can explain both: sulfur-sulfur bond elongation and dimers stability when they stayed adsorbed on the surface at high coverage.

Genomic and Evolutionary Perspectives on Sulfur Metabolism in Green Sulfur Bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Bryant, Donald A.

2008-01-01

Green sulfur bacteria (GSB) are anaerobic photoautotrophs that oxidize sulfide, elemental sulfur, thiosulfate, ferrous iron, and hydrogen for growth. We present here an analysis of the distribution and evolution of enzymes involved in oxidation of sulfur compounds in GSB based on genome sequence......, in combination with phylogenetic analyses, suggests that the Dsr system in GSB could be a recent acquisition, which was obtained by lateral gene transfer in part from sulfideoxidizing bacteria and in part from sulfate-reducing bacteria. All thiosulfate-utilizing GSB strains have an identical sox gene cluster...

Acidithiobacillus caldus sulfur oxidation model based on transcriptome analysis between the wild type and sulfur oxygenase reductase defective mutant.

Directory of Open Access Journals (Sweden)

Linxu Chen

Full Text Available Acidithiobacillus caldus (A. caldus is widely used in bio-leaching. It gains energy and electrons from oxidation of elemental sulfur and reduced inorganic sulfur compounds (RISCs for carbon dioxide fixation and growth. Genomic analyses suggest that its sulfur oxidation system involves a truncated sulfur oxidation (Sox system (omitting SoxCD, non-Sox sulfur oxidation system similar to the sulfur oxidation in A. ferrooxidans, and sulfur oxygenase reductase (SOR. The complexity of the sulfur oxidation system of A. caldus generates a big obstacle on the research of its sulfur oxidation mechanism. However, the development of genetic manipulation method for A. caldus in recent years provides powerful tools for constructing genetic mutants to study the sulfur oxidation system.An A. caldus mutant lacking the sulfur oxygenase reductase gene (sor was created and its growth abilities were measured in media using elemental sulfur (S(0 and tetrathionate (K(2S(4O(6 as the substrates, respectively. Then, comparative transcriptome analysis (microarrays and real-time quantitative PCR of the wild type and the Δsor mutant in S(0 and K(2S(4O(6 media were employed to detect the differentially expressed genes involved in sulfur oxidation. SOR was concluded to oxidize the cytoplasmic elemental sulfur, but could not couple the sulfur oxidation with the electron transfer chain or substrate-level phosphorylation. Other elemental sulfur oxidation pathways including sulfur diooxygenase (SDO and heterodisulfide reductase (HDR, the truncated Sox pathway, and the S(4I pathway for hydrolysis of tetrathionate and oxidation of thiosulfate in A. caldus are proposed according to expression patterns of sulfur oxidation genes and growth abilities of the wild type and the mutant in different substrates media.An integrated sulfur oxidation model with various sulfur oxidation pathways of A. caldus is proposed and the features of this model are summarized.

Interactions of C, N, P and S biogeochemical cycles and global change

International Nuclear Information System (INIS)

Wollast, R.; Mackenzie, F.T.

1993-01-01

The biochemical cycles of carbon, nitrogen, phosphorus and sulfur are tied to each other through biological productivity and to problems of global environmental change. Both natural changes in the cycles of the elements and interference and distortion of these cycles by human activities (e.g. disturbancies by agricultural, industrial and urbanization activities) will have impacts on ecosystems and human society. (UT)

Promotional role of Li4Ti5O12 as polysulfide adsorbent and fast Li+ conductor on electrochemical performances of sulfur cathode

Science.gov (United States)

Zeng, Tianbiao; Hu, Xuebu; Ji, Penghui; Shang, Biao; Peng, Qimeng; Zhang, Yaoyao; Song, Ruiqiang

2017-08-01

Lithium-sulfur (Li-S) batteries attract much attention due to its high specific capacity and energy density compared to lithium-ion batteries (LiBs). Herein, a novel composite named as (void/nano-Li4Ti5O12 pieces)@C [(v/n-L)@C] was designed and prepared as a sulfur host. Spinel Li4Ti5O12 here as a multifunctional additive played as polysulfide adsorbent agent and fast Li+ conductor, and carbon shell was designed as electronic conductor, as well as volume barrier to limit the volume expansion caused by sulfur. As-prepared (S/nano-Li4Ti5O12 pieces)@C [(S/n-L)@C] are core-shell spheres, which are about 200 nm in size. Nano-Li4Ti5O12 and sulfur were coated by the outer carbon shell with a thickness of about 20 nm. The experimental results show that electrochemical performances of (S/n-L)@C cathode were enhanced effectively compared to S@C cathode. At 0.5C and 1C, the discharge capacity of (S/n-L)@C was 33.5% and 40.1% higher than that of S@C at 500th cycle. Even at 2C, its capacity reached 600.9 mAh g-1 at 1000th cycle. Li+ conductivity of (S/n-L)@C was one order of magnitude higher than that of S@C, which was reach to 2.55 × 10-8 S cm-1. The experiment results indicate Li4Ti5O12 plays a promotional role on electrochemical performances of sulfur cathode, especially for stable cycling performance and high rate performance.

Conceptual design model of the sulfur-iodine S-I thermochemical water splitting process for hydrogen production using nuclear heat source

International Nuclear Information System (INIS)

Gonzalez Rodriguez, Daniel; Parra, Lazaro Garcia

2011-01-01

Hydrogen is the most indicated candidate for its implementation as energy carrier in a future sustainable scenario. The current hydrogen production is based on fossils fuels; they have a huge contribution to the atmosphere pollution. Thermochemical water-splitting cycles do not have this issue because they use solar or nuclear heat; their environment impact is smaller than conventional fuels. The software based on chemical process simulation (CPS) can be used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. In the paper is developed a model for Sulfur-Iodine process in order to analyze his sensibility and calculate the efficiency and the influence of many parameters on this value. (author)

Conceptual design model of the sulfur-iodine S-I thermochemical water splitting process for hydrogen production using nuclear heat source

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Rodriguez, Daniel; Parra, Lazaro Garcia, E-mail: dgr@instec.cu, E-mail: lgarcia@instec.cu [Departamento de Ingenieria Nuclear, Instituto Superior de Ciencias y Tecnologias Aplicadas, La Habana (Cuba)

2011-07-01

Hydrogen is the most indicated candidate for its implementation as energy carrier in a future sustainable scenario. The current hydrogen production is based on fossils fuels; they have a huge contribution to the atmosphere pollution. Thermochemical water-splitting cycles do not have this issue because they use solar or nuclear heat; their environment impact is smaller than conventional fuels. The software based on chemical process simulation (CPS) can be used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. In the paper is developed a model for Sulfur-Iodine process in order to analyze his sensibility and calculate the efficiency and the influence of many parameters on this value. (author)

Flexible carbon nanofiber/polyvinylidene fluoride composite membranes as interlayers in high-performance Lithiumsbnd Sulfur batteries

Science.gov (United States)

Wang, Zhenhua; Zhang, Jing; Yang, Yuxiang; Yue, Xinyang; Hao, Xiaoming; Sun, Wang; Rooney, David; Sun, Kening

2016-10-01

Traditionally polyvinylidene fluoride membranes have been used in applications such as membrane distillation, wastewater treatment, desalination and separator fabrication. Within this work we demonstrate that a novel carbon nanofiber/polyvinylidene fluoride (CNF/PVDF) composite membrane can be used as an interlayer for Lithiumsbnd Sulfur (Lisbnd S) batteries yielding both high capacity and long cycling life. This PVDF membrane is shown to effectively separate dissolved lithium polysulfide with the high electronic conductivity CNF not only reducing the internal resistance in the sulfur cathode but also helping immobilize the polysulfide through its abundant nanospaces. The resulting Lisbnd S battery assembled with the CNF/PVDF composite membrane effectively solves the polysulfide permeation problem and exhibits excellent electrochemical performance. It is further shown that the CNF/PVDF electrode has an excellent cycling stability and retains a capacity of 768.6 mAh g-1 with a coulombic efficiency above 99% over 200 cycles at 0.5C, which is more than twice that of a cell without CNF/PVDF (374 mAh g-1). In addition, the low-cost raw materials and the simple preparation process of CNF/PVDF composite membrane is also amenable for industrial production.

Sulfur amino acid deficiency upregulates intestinal methionine cycle activity and suppresses epithelial growth in neonatal pigs.

Science.gov (United States)

We recently showed that the developing gut is a significant site of methionine transmethylation to homocysteine and transsulfuration to cysteine. We hypothesized that sulfur amino acid (SAA) deficiency would preferentially reduce mucosal growth and antioxidant function in neonatal pigs. Neonatal pi...

Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

Science.gov (United States)

Yan, Jianhua; Liu, Xingbo

2016-01-01

Rechargeable lithium–sulfur (Li–S) batteries are receiving ever‐increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their rapid capacity fade has been one of the key barriers for their further improvement. It is well accepted that the major degradation mechanisms of S‐cathodes include low electrical conductivity of S and sulfides, precipitation of nonconductive Li2S2 and Li2S, and poly‐shuttle effects. To determine these degradation factors, a comprehensive study of sulfur cathodes with different amounts of electrolytes is presented here. A survey of the fundamentals of Li–S chemistry with respect to capacity fade is first conducted; then, the parameters obtained through electrochemical performance and characterization are used to determine the key causes of capacity fade in Li–S batteries. It is confirmed that the formation and accumulation of nonconductive Li2S2/Li2S films on sulfur cathode surfaces are the major parameters contributing to the rapid capacity fade of Li–S batteries. PMID:27981001

Sulfur contents and sulfur-isotope compositions of thiotrophic symbioses in bivalve molluscs and vestimentiferan worms

Science.gov (United States)

Vetter, R.D.; Fry, B.

1998-01-01

Total sulfur (S(TOT)), elemental sulfur (S??) and sulfur-isotope compositions (??34S) of marine animals were analyzed to determine whether these chemical characteristics could help distinguish animals with a sulfur-based, thiotrophic nutrition from animals whose nutrition is based on methanotrophy or on more normal consumption of phytoplankton-derived organic matter. The presence of S??was almost entirely confined to the symbiont-containing tissues of thiotrophs, but was sometimes undetectable in thiotrophic species where sulfide availability was probably low. When S??contents were subtracted, the remaining tissue-sulfur concentrations were similar for all nutritional groups. ??34S values were typically lower for thiotrophs than for other groups, although there was overlap in methanotroph and thiotroph values at some sites. Field evidence supported the existence of small to moderate (1 to 10???)34S fractionations in the uptake of sulfides and metabolism of thiosulfate. In general, a total sulfur content of >3% dry weight, the presence of elemental sulfur, and ??34S values less than + 5??? can be used to infer a thiotrophic mode of nutrition.

Demand outlook for sulfur and high-sulfur petroleum coke

Energy Technology Data Exchange (ETDEWEB)

Koshkarov, V.Ya.; Danil' yan, P.G.; Feotov, V.E.; Gimaev, R.N.; Koshkarova, M.E.; Sadykova, S.R.; Vodovichenko, N.S.

1980-01-01

The feasibility of using sulfur and high-sulfur petroleum coke fines in pyrometallurgical processes and also in the chemical and coal-tar chemical industry is examined. Results of industrial tests on briquetting fines of petroleum coke with a petroleum binder are presented. The feasibility of using the obtained briquets in shaft furnace smelting of oxidized nickel ores, production of anode stock, and also in the chemical industry are demonstrated.

SULFUR POLYMER ENCAPSULATION

International Nuclear Information System (INIS)

KALB, P.

2001-01-01

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

Stability of sulfur slopes on Io

Science.gov (United States)

Clow, G. D.; Carr, M. H.

1980-01-01

The mechanical properties of elemental sulfur are such that the upper crust of Io cannot be primarily sulfur. For heat flows in the range 100-1000 ergs/sq cm sec sulfur becomes ductile within several hundred meters of the surface and would prevent the formation of calderas with depths greater than this. However, the one caldera for which precise depth data are available is 2 km deep, and this value may be typical. A study of the mechanical equilibrium of simple slopes shows that the depth to the zone of rapid ductile flow strongly controls the maximum heights for sulfur slopes. Sulfur scarps with heights greater than 1 km will fail for all heat flows greater than 180 ergs/sq cm sec and slope angles greater than 22.5 deg. The observed relief on Io is inconsistent with that anticipated for a predominantly sulfur crust. However, a silicate crust with several percent sulfur included satisfies both the mechanical constraints and the observed presence of sulfur on Io.

40 CFR 52.1881 - Control strategy: Sulfur oxides (sulfur dioxide).

Science.gov (United States)

2010-07-01

....0 pounds of sulfur dioxide per million BTU actual heat input for the coal-fired boiler and 0.4... BTU actual heat input for coal-fired boiler C exiting through stack 5. (3) 2.24 pounds of sulfur dioxide per million BTU acutal heat input for coal-fired boiler D exiting through stack 6. (E) In lieu of...

Concerted effects in the reaction of ·OH radicals with aromatics: radiolytic oxidation of salicylic acid

International Nuclear Information System (INIS)

Albarran, G.; Schuler, R.H.

2003-01-01

Liquid chromatographic and capillary electrophoretic studies have been used to resolve the products produced in the radiolytic oxidation of salicylic acid in aqueous solution. These studies have shown that, as in the case of phenol, · OH radicals preferentially add to the positions ortho and para to the OH substituent. However, in contrast to its reaction with phenol, addition at the ortho position is favored over addition at the para position. Because · OH radical is a strong electrophile this difference suggests that the electron population at the ortho position in the salicylate anion is enhanced as a result of the hydrogen bonding in salicylic acid

Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

Science.gov (United States)

Hackley, Keith C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W.

1990-01-01

Hot tetrachloroethene (perchloroethylene, PCE) extracts significant amounts of elemental sulfur (So) from weathered coals but not from pristine coals. The objective of this study was to determine whether So extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted So was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The So was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, So and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. ?? 1990.

Process for removing sulfur from sulfur-containing gases: high calcium fly-ash

Science.gov (United States)

Rochelle, Gary T.; Chang, John C. S.

1991-01-01

The present disclosure relates to improved processes for treating hot sulfur-containing flue gas to remove sulfur therefrom. Processes in accordance with the present invention include preparing an aqueous slurry composed of a calcium alkali source and a source of reactive silica and/or alumina, heating the slurry to above-ambient temperatures for a period of time in order to facilitate the formation of sulfur-absorbing calcium silicates or aluminates, and treating the gas with the heat-treated slurry components. Examples disclosed herein demonstrate the utility of these processes in achieving improved sulfur-absorbing capabilities. Additionally, disclosure is provided which illustrates preferred configurations for employing the present processes both as a dry sorbent injection and for use in conjunction with a spray dryer and/or bagfilter. Retrofit application to existing systems is also addressed.

A novel strategy for high-stability lithium sulfur batteries by in situ formation of polysulfide adsorptive-blocking layer

Science.gov (United States)

Jin, Liming; Li, Gaoran; Liu, Binhong; Li, Zhoupeng; Zheng, Junsheng; Zheng, Jim P.

2017-07-01

Lithium sulfur (Lisbnd S) batteries are one of the most promising energy storage devices owing to their high energy and power density. However, the shuttle effect as a key barrier hinders its practical application by resulting in low coulombic efficiency and poor cycling performance. Herein, a novel design of in situ formed polysulfide adsorptive-blocking layer (PAL) on the cathode surface was developed to tame the polysulfide shuttling and promote the cycling stability for Lisbnd S batteries. The PAL is consisted of La2S3, which is capable to chemically adsorb polysulfide via the strong interaction of Lasbnd S bond and Ssbnd S bond, and build an effective barrier against sulfur escaping. Moreover, the La2S3 is capable to suppress the crystallization of Li2S and promote the ion transfer, which contributes to the reduced internal resistance of batteries. Furthermore, the by-product LiNO3 simultaneously forms a stable anode solid and electrolyte interface to further inhibit the polysulfide shuttle. By this simple and convenient method, the resultant Lisbnd S batteries achieved exceptional cycling stability with an ultralow decay rate of 0.055% since the 10th cycle.

Modified sulfur cement solidification of low-level wastes

Energy Technology Data Exchange (ETDEWEB)

1985-10-01

This topical report describes the results of an investigation on the solidification of low-level radioactive wastes in modified sulfur cement. The work was performed as part of the Waste Form Evaluation Program, sponsored by the US Department of Energy's Low-Level Waste Management Program. Modified sulfur cement is a thermoplastic material developed by the US Bureau of Mines. Processing of waste and binder was accomplished by means of both a single-screw extruder and a dual-action mixing vessel. Waste types selected for this study included those resulting from advanced volume reduction technologies (dry evaporator concentrate salts and incinerator ash) and those which remain problematic for solidification using contemporary agents (ion exchange resins). Process development studies were conducted to ascertain optimal process control parameters for successful solidification. Maximum waste loadings were determined for each waste type and method of processing. Property evaluation testing was carried out on laboratory scale specimens in order to compare with waste form performance for other potential matrix materials. Waste form property testing included compressive strength, water immersion, thermal cycling and radionuclide leachability. Recommended waste loadings of 40 wt. % sodium sulfate and boric acid salts and 43 wt. % incinerator ash, which are based on processing and performance considerations, are reported. Solidification efficiencies for these waste types represent significant improvements over those of hydraulic cements. Due to poor waste form performance, incorporation of ion exchange resin waste in modified sulfur cement is not recommended.

Modified sulfur cement solidification of low-level wastes

International Nuclear Information System (INIS)

1985-10-01

This topical report describes the results of an investigation on the solidification of low-level radioactive wastes in modified sulfur cement. The work was performed as part of the Waste Form Evaluation Program, sponsored by the US Department of Energy's Low-Level Waste Management Program. Modified sulfur cement is a thermoplastic material developed by the US Bureau of Mines. Processing of waste and binder was accomplished by means of both a single-screw extruder and a dual-action mixing vessel. Waste types selected for this study included those resulting from advanced volume reduction technologies (dry evaporator concentrate salts and incinerator ash) and those which remain problematic for solidification using contemporary agents (ion exchange resins). Process development studies were conducted to ascertain optimal process control parameters for successful solidification. Maximum waste loadings were determined for each waste type and method of processing. Property evaluation testing was carried out on laboratory scale specimens in order to compare with waste form performance for other potential matrix materials. Waste form property testing included compressive strength, water immersion, thermal cycling and radionuclide leachability. Recommended waste loadings of 40 wt. % sodium sulfate and boric acid salts and 43 wt. % incinerator ash, which are based on processing and performance considerations, are reported. Solidification efficiencies for these waste types represent significant improvements over those of hydraulic cements. Due to poor waste form performance, incorporation of ion exchange resin waste in modified sulfur cement is not recommended

Sulfur gained from flue gas, a demonstration unit of the Wellman-Lord process annexed to a black coal power plant

Energy Technology Data Exchange (ETDEWEB)

Schulte, H

1977-12-16

Details of reducing air pollution by desulfurization of flue gases are presented. The demonstration unit is annexed to a 115 MW block at the Gary power plant in Indiana, USA. A second unit is being installed at the larger coal power plant in San Juan, New Mexico. The Wellman-Lord technology achieves a higher than 90% desulfurization of industrial waste gases. The technology is based on washing the gases with sodium sulfide. The resulting concentrated sulfur dioxide gas is used for pure sulfur and sulfuric acid production. Sodium sulfate is another commercial by-product obtained from the sodium sulfide regeneration cycle. Chemical details and the technological flow sheet are discussed. Electricity production costs in the power plants due to desulfurization of waste gases will increase by an estimated 15%. Advantages, in addition to reducing air pollution and marketing sulfur products, are also seen in the absence of sulfur containing wastes for disposal. (In German)

Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

Energy Technology Data Exchange (ETDEWEB)

Hackley, K.C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W. (Eastern Illinois University, Charleston, IL (USA). Chemistry Dept.)

1990-01-01

Hot tetrachloroethene (perchloroethylen PCE) extracts significant amounts of elemental sulfur (S{sup o}) from weathered coals but not from pristine coals. The objective of this study was to determine whether S{sup o} extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted S{sup o} was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The S{sup o} was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, S{sup o} and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. 21 refs., 2 tabs.

Seed recovery and regeneration in coal-fired, open-cycle magnetohydrodynamic systems

International Nuclear Information System (INIS)

Sheth, A.C.; Jackson, D.M.; Attig, R.C.

1986-01-01

Coal-fired magnetohydrodynamic (MHD) power systems not only have high cycle efficiency, but they also have an inherent sulfur removal capability. The potassium compound uses as ''seed'' plays a dual role. It 1) increases the electrical conductivity of the plasma needed to produce power in the MHD electrical topping cycle, and 2) reacts with sulfur dioxide to form potassium sulfate, thereby eliminating most of the sulfur oxides from the gaseous effluent. For economical reasons, the spent seed must be recovered, desulfurized and recycled to the MHD power plant. This paper reviews some of the available experimental results and literature relating to SO 2 removal and seed recovery, and will also discuss several potential seed regeneration processes. Three methods of potassium extraction are discussed, i.e., hot aqueous digestion with CA(OH) 2 /NaOH, acid washing, and aqueous extraction. The selected candidate regeneration systems are discussed from the viewpoint of energy and process water requirements and environmental considerations such as waste discharges and emissions of gaseous, particulate and trace element pollutants

Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

Energy Technology Data Exchange (ETDEWEB)

Abedinzadeh, Z. [Lab. de Chimie Physique, UMR, Univ. Rene Descartes, Paris (France)

2001-02-01

Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS{sup .}, RSS{sup .}, RS{sup .+}, (RSSR){sup .+}] and their implications for biological systems. (author)

Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

International Nuclear Information System (INIS)

Abedinzadeh, Z.

2001-01-01

Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS . , RSS . , RS .+ , (RSSR) .+ ] and their implications for biological systems. (author)

Danburite decomposition by sulfuric acid

International Nuclear Information System (INIS)

Mirsaidov, U.; Mamatov, E.D.; Ashurov, N.A.

2011-01-01

Present article is devoted to decomposition of danburite of Ak-Arkhar Deposit of Tajikistan by sulfuric acid. The process of decomposition of danburite concentrate by sulfuric acid was studied. The chemical nature of decomposition process of boron containing ore was determined. The influence of temperature on the rate of extraction of boron and iron oxides was defined. The dependence of decomposition of boron and iron oxides on process duration, dosage of H 2 SO 4 , acid concentration and size of danburite particles was determined. The kinetics of danburite decomposition by sulfuric acid was studied as well. The apparent activation energy of the process of danburite decomposition by sulfuric acid was calculated. The flowsheet of danburite processing by sulfuric acid was elaborated.

Sulfur polymer cement concrete

International Nuclear Information System (INIS)

Weber, H.H.; McBee, W.C.

1990-01-01

Sulfur-based composite materials formulated using sulfur polymer cement (SPC) and mineral aggregates are described and compared with conventional portland cement based materials. Materials characteristics presented include mechanical strength, chemical resistance, impact resistance, moisture permeation, and linear shrinkage during placement and curing. Examples of preparation and placement of sulfur polymer cement concrete (SC) are described using commercial scale equipment. SC applications presented are focused into hostile chemical environments where severe portland cement concrete (PCC) failure has occurred

Radiolytic preparation of ETFE and PFA based anion exchange membranes for alkaline fuel cell

International Nuclear Information System (INIS)

Ko, Beom-Seok; Sohn, Joon-Yong; Nho, Young-Chang; Shin, Junhwa

2011-01-01

In this study, a versatile monomer, vinylbenzyl chloride (VBC) was radiolytically grafted onto a partially fluorinated ETFE and perfluorinated polymer PFA films. The VBC grafted films were treated with trimethylamine to prepare the alkaline anion exchange membranes (AAEMs). No significant differences in the ion exchange capacities and water uptakes were observed between the ETFE and PFA based AAEMs with similar degree of grafting (DOG). However, the distribution patterns of the graft chains over the cross-section of the ETFE and PFA based AAEMs were found to be quite different; the even distribution was observed from the ETFE based AAEMs while the uneven distribution was observed from the PFA based AAEMs. It was also found that the PFA based AAEMs have the higher ionic conductivity and chemical stability, compared to the ETFE based AAEMs.

Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

Science.gov (United States)

Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

2017-12-01

The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested

Formation of CuxS Layers on Polypropylene Sulfurized by Molten Sulfur

Directory of Open Access Journals (Sweden)

Rasa ALABURDAITĖ

2011-11-01

Full Text Available The processes of formation of electrically conductive layers of copper sulfides CuxS by the sorption-diffusion method on polypropylene (PP using molten sulfur as sulfurizing agent was investigated. The amount of sorbed sulfur increased with the increase of the duration of treatment. Copper sulfide layers were formed on the surface of polypropylene after the treatment of sulfurized polymer with Cu(II/I salt solution. The amount of copper sulfide in layer increased with the increase of treatment duration in copper salt solution. XRD spectra of PP films treated for 3 min with molten sulfur and then with Cu(II/I salt solution for the different time showed that the copper sulfide phases, mostly digenite, Cu2-xS and a-chalcocite, Cu2S were formed in the layers. Electromotive force measurement results confirmed the composition of formed CuxS layers on PP. The phase composition of layers also changed after the annealing. The value of electrical resistance of copper sulfide layers on PP varied from 20 W/cm2 to 80 W/cm2 and after annealing at 80 °C - in the interval of 10 W/cm2 - 60 W/cm2.http://dx.doi.org/10.5755/j01.ms.17.4.776

Calculus of radiolytic products generation in water due to alpha radiation. Determination of the spent nuclear fuels matrix alteration rate Determination of velocity of spent fuel matrix; Calculo de la generacion de productos radioliticos en agua por radiacion {alpha}. Determinacion de la velocidad de alteracion de la matriz del combustible nuclear gastado

Energy Technology Data Exchange (ETDEWEB)

Quinones, J.; Serrano, J.; Diaz Arocas, P.; Rodriguez Almazan, J. L. [Ciemat. Madrid (Spain); Bruno, J.; Cera, E.; Merino, J.; Esteban, J. A.; Martinez-Esparza, A. [Enresa. Madrid (Spain)

2000-07-01

The generation of radiolytic products as a result of alpha radiation in the surface of the spent fuel is a key process in order to understand how the it becomes degraded in repository conditions. The present work has established a radiolytic model based on a set of reactions involving fuel oxidation-dissolution and radiolytic products recombination. It also includes the decrease of the dose rates as the main alpha emitters decay away. Four cases, with varying parameters of the system, have been assessed. The results show a decrease in both the concentration of the radiolytic products in the gap water and the degradation of the fuel matrix. It has been estimated that in the period of the evaluation (10''6 years) up to 52% of the pellet is altered in the conservative cases, whereas only 11% is altered in the realistic cases. No significant differences were observed when the carbonates reactions were included in the system. (Author)

High Mass-Loading of Sulfur-Based Cathode Composites and Polysulfides Stabilization for Rechargeable Lithium/Sulfur Batteries

International Nuclear Information System (INIS)

Hara, Toru; Konarov, Aishuak; Mentbayeva, Almagul; Kurmanbayeva, Indira; Bakenov, Zhumabay

2015-01-01

Although sulfur has a high theoretical gravimetric capacity, 1672 mAh/g, its insulating nature requires a large amount of conducting additives: this tends to result in a low mass-loading of active material (sulfur), and thereby, a lower capacity than expected. Therefore, an optimal choice of conducting agents and of the method for sulfur/conducting-agent integration is critically important. In this paper, we report that the areal capacity of 4.9 mAh/cm 2 was achieved at sulfur mass loading of 4.1 mg/cm 2 by casting sulfur/polyacrylonitrile/ketjenblack (S/PAN/KB) cathode composite into carbon fiber paper. This is the highest value among published/reported ones even though it does not contain expensive nanosized carbon materials such as carbon nanotubes, graphene, or graphene derivatives, and competitive enough with the conventional LiCoO 2 -based cathodes (e.g., LiCoO 2 , <20 mg/cm 2 corresponding to <2.8 mAh/cm 2 ). Furthermore, the combination of sulfur/PAN-based composite and PAN-based carbon fiber paper enabled the sulfur-based composite to be used even in carbonate-based electrolyte solution that many lithium/sulfur battery researchers avoid the use of it because of severer irreversible active material loss than in electrolyte solutions without carbonate-based solutions, and even at the highest mass-loading ever reported (the more sulfur is loaded, the more decomposed sulfides deposit at an anode surface).

Developing porous carbon with dihydrogen phosphate groups as sulfur host for high performance lithium sulfur batteries

Science.gov (United States)

Cui, Yanhui; Zhang, Qi; Wu, Junwei; Liang, Xiao; Baker, Andrew P.; Qu, Deyang; Zhang, Hui; Zhang, Huayu; Zhang, Xinhe

2018-02-01

Carbon matrix (CM) derived from biomass is low cost and easily mass produced, showing great potential as sulfur host for lithium sulfur batteries. In this paper we report on a dihydrogen phosphate modified CM (PCM-650) prepared from luffa sponge (luffa acutangula) by phosphoric acid treatment. The phosphoric acid not only increases the surface area of the PCM-650, but also introduces dihydrogen phosphate onto PCM-650 (2.28 at% P). Sulfur impregnated (63.6 wt%) PCM-650/S, in comparison with samples with less dihydrogen phosphate LPCM-650/S, shows a significant performance improvement. XPS analysis is conducted for sulfur at different stages, including sulfur (undischarged), polysulfides (discharge to 2.1 V) and short chain sulfides (discharge to 1.7 V). The results consistently show chemical shifts for S2p in PCM-650, suggesting an enhanced adsorption effect. Furthermore, density functional theory (DFT) calculations is used to clarify the molecular binding: carbon/sulfur (0.86 eV), carbon/Li2S (0.3 eV), CH3-O-PO3H2/sulfur (1.24 eV), and CH3-O-PO3H2/Li2S (1.81 eV). It shows that dihydrogen phosphate group can significantly enhance the binding with sulfur and sulfide, consistent with XPS results. Consequently a CM functionalised with dihydrogen phosphate shows great potential as the sulfur host in a Li-S battery.

Effect of commercial activated carbons in sulfur cathodes on the electrochemical properties of lithium/sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Icpyo [School of Materials Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Kim, Ki-Won; Nam, Tae-Hyun; Cho, Kwon-Koo; Ahn, Jou-Hyeon [Department of Materials Engineering and Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Ryu, Ho-Suk [Department of Material and Energy Engineering, Gyeongwoon University, 730, Gangdong-ro, Sandong-myeon, Gumi, Gyeongbuk, 39160 (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of); Department of Materials Engineering and Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju, Gyeongnam 52828 (Korea, Republic of)

2016-10-15

Highlights: • The sulfur/activated carbon composite is fabricated using commercial activated carbons. • The sulfur/activated carbon composite with coal shows the best performance. • The Li/S battery has capacities of 1240 mAh g{sup −1} at 1 C and 567 mAh g{sup −1} at 10 C. - Abstract: We prepared sulfur/active carbon composites via a simple solution-based process using the following commercial activated carbon-based materials: coal, coconut shells, and sawdust. Although elemental sulfur was not detected in any of the sulfur/activated carbon composites based on Thermogravimetric analysis, X-ray diffraction, and Raman spectroscopy, Energy-dispersive X-ray spectroscopy results confirmed its presence in the activated carbon. These results indicate that sulfur was successfully impregnated in the activated carbon and that all of the activated carbons acted as sulfur reservoirs. The sulfur/activated carbon composite cathode using coal exhibited the highest discharge capacity and best rate capability. The first discharge capacity at 1 C (1.672 A g{sup −1}) was 1240 mAh g{sup −1}, and a large reversible capacity of 567 mAh g{sup −1} was observed at 10 C (16.72 A g{sup −1}).

Sulfur isotope in nature. Determination of sulfur isotope ratios in coal and petroleum by mass spectrometry

International Nuclear Information System (INIS)

Derda, M.

1999-01-01

Elementary sulfur or in chemical compounds is one of the elements widespread in the earth's crust and biosphere. Its participation in earth's crust amounts to 0.26 % by weight. Measurement of isotope composition of natural samples can deliver many information about origin, creation and transformation ranges of rocks and minerals. Sulfur isotope ratio contained in minerals is variable and for this reason investigation of isotope sulfur composition can deliver useful information about the geochemistry of each component. Therefore in the investigated sample it is necessary to determine not only the content of sulfur but also the isotope composition of each component. Differentiation of contents of sulfur-34 in natural sulfur compounds can reach up to 110 per mile. So large divergences can be explained by a kinetic effect or by bacterial reduction of sulphates. In this report a wide review of the results of investigations of isotope sulfur compositions in coal and petroleum are presented as well as the methods for the preparation of samples for mass spectrometry analysis are proposed. (author)

Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules

Science.gov (United States)

Adam, P.; Schneckenburger, P.; Schaeffer, P.; Albrecht, P.

2000-10-01

Macromolecular fractions, isolated from the solvent extract of sulfur-rich Recent (Siders Pond, USA; Lake Cadagno, Switzerland; Walvis Bay, Namibia) and immature sediments (Gibellina, Messinian of Sicily; Vena del Gesso, Messinian of Italy), were investigated by chemical degradation using sodium ethanethiolate/methyliodide. This mild reagent which cleaves polysulfide bonds to yield methylsulfides has the advantage over other methods of leaving intact other functionalities (like double bonds) and preserving sulfur atoms at their incorporation site. The method is, therefore, well-suited to the molecular level investigation of sulfur-rich macromolecules from Recent sediments containing highly functionalized polysulfide-bound subunits. In Recent anoxic sulfur-rich sediments, the release of various methylthioethers clearly demonstrates that intermolecular sulfurization of organic matter does occur at the earliest stages of diagenesis. Steroids and phytane derivatives are the major sulfurized lipids, a feature also observed in more mature sulfur-rich sediments. Several phytene derivatives, such as cis and trans 1-methylthiophyt-2-enes, as well as methylthiosteroids, including 5α- and 5β-3-(methylthio)-cholest-2-enes, were identified by comparison with synthesized standards. Steroid methylthioenolethers are released from polysulfide-bound steroid enethiols present in the macromolecular fractions. The latter, which correspond to thioketones, can be considered as intermediates in the reductive sulfurization pathway leading from steroid ketones to polysulfide-bound saturated steroid skeletons and are characterized for the first time in the present study. Thus, it could be shown that the major part of the polysulfide-bound lipids occurring in Recent sediments is apparently the result of sulfurization processes affecting carbonyls (aldehydes and ketones). The unsaturated methylthioethers obtained from Recent sediments were not present in more mature evaporitic samples, which

Sulfur equilibrium desulfurization of sulfur containing products of combustion

International Nuclear Information System (INIS)

Woodroffe, J.A.; Abichandani, J.S.

1990-01-01

This patent describes the method for the combustion of a carbon- and sulfur-containing fuel for substantially reducing emission of gaseous sulfur compounds formed during combustion of the fuel in a combustion zone. The zone having one or more fuel inlets and one or more oxidizer inlets, and having a combustion products outlet spaced therefrom, and having one or more inorganic sorbent inlets downstream of the fuel inlet(s) and oxidizer inlet(s) and upstream of the combustion products outlet

Radiolytic studies of the cumyloxyl radical in aqueous solutions

International Nuclear Information System (INIS)

Neta, P.; Dizdaroglu, M.; Simic, M.G.

1984-01-01

Formation and reactions of the cumyloxyl radical in aqueous solutions were studied by steady-state and pulse radiolytic techniques. Cumene hydroperoxide reacts with esub(aq)sup(-) (k = 4.4x10 9 M -1 s -1 ) to yield the cumyloxyl radical. The spectrum recorded after the pulse indicates formation of a species absorbing at 250 nm. This product was identified as acetophenone, which is formed by the fragmentation of the cumyloxyl radical. By comparison of the pseudo-first-order rates of esub(aq)sup(-) decay at 600 nm with the rate of production of acetophenone at 245 nm at increasing concentrations of cumene hydroperoxide, it was possible to derive a rate constant of 1.0x10 7 s -1 for the cleavage of cumyloxyl to acetophenone and methyl radical. This value is higher than that measured previously in organic solvents (1x10 6 s -1 ), as expected. HPLC analysis of the radiation products acetophenone and cumyl alcohol permitted determination of rate constants for hydrogen abstraction by the cumyloxyl radical, in competition with the fragmentation. The rate constants for H abstraction from i-PrOH, EtOH, and MeOH by CmO were found to be 9.9x10 6 , 3.8x10 6 , and 8.5x10 5 M -1 s -1 , respectively

Aircraft exhaust sulfur emissions

Energy Technology Data Exchange (ETDEWEB)

Brown, R C; Anderson, M R; Miake-Lye, R C; Kolb, C E [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A A; Buriko, Y I [Scientific Research Center ` Ecolen` , Moscow (Russian Federation)

1998-12-31

The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

Aircraft exhaust sulfur emissions

Energy Technology Data Exchange (ETDEWEB)

Brown, R.C.; Anderson, M.R.; Miake-Lye, R.C.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A.A.; Buriko, Y.I. [Scientific Research Center `Ecolen`, Moscow (Russian Federation)

1997-12-31

The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

Monitoring of gamma radiolytic degradation products of methoxychlor pesticide in water by solid phase micro-extraction using hplc and GC-MS (abstract)

International Nuclear Information System (INIS)

Butt, S.B.; Zafar, A.

2011-01-01

Monitoring, removal and management of toxic chemicals is an essential area of study regarding sustainable progress. Different approaches are adopted to eliminate these water born toxics from water and waste water. Among these gamma radiolytic is an emerging option. This ionization radiation generates highly reactive radicals that reacts with pollutants and hence eliminates these. A solid-phase micro-extraction (SPME) procedure has been developed for the successful preconcentration of organic pollutant irradiated water. A SPME fused-silica fiber coated with Polyacrylate was used as a probe to extract the organic pollutant after irradiation. In this reference, degradation of priority organic pollutant methoxychlor (1, 1, 1-Trichloro 2, 2-bis (p-methoxyphenyl) ethane, in water by gamma irradiation under varied experimental conditions has been investigated. The degree of gamma radiolytic degradation was monitored by HPLC-UV and GC-MS. For 4 kGy and 5 kGy gamma radiation dose at a rate of 200 kGyh/sup -1/ greater or equal to 95 % and 98 % MXC was degraded respectively. The degradation products were identified by Mass Spectrometry after comparing their MS spectras with the NIST 98 library. The major degradation occurs via dechlorination, dehydro chlorination, by the detachment of methoxyphenyl from MXC and by interaction of other radicals generated by the water radiolysis. (author)

Temperature and radiolytic corrosion effects on the chlorine behaviour in nuclear graphite: consequences for the disposable of irradiated graphite from UNGG reactors

International Nuclear Information System (INIS)

Vaudey, C.E.

2010-10-01

This work concerns the dismantling of the UNGG reactor which have produced around 23 000 t of graphite wastes that ave to be disposed of according to the French law of June 206. These wastes contain two long-lived radionuclides ( 14 C and 36 Cl) which are the main long term dose contributors. In order to get information about their inventory and their long term behaviour in case of water ingress into the repository, it is necessary to determine their location and speciation in the irradiated graphite after the reactor shutdown. This work concerns the study of 36 Cl. The main objective is to reproduce its behaviour during reactor operation. For that purpose, we have studied the effects of temperature and radiolytic corrosion independently. Our results show a rapid release of around 20% 36 Cl during the first hours of reactor operation whereas a much slower release occurs afterwards. We have put in evidence two types of chlorine corresponding to two different chemical forms (of different thermal stabilities) or to two locations (of different accessibilities). We have also shown that the radiolytic corrosion seems to enhance chlorine release, whatever the irradiation dose. Moreover, the major chemical form of chlorine is inorganic. (author)

Nanostructured nitrogen-doped mesoporous carbon derived from polyacrylonitrile for advanced lithium sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ying; Zhao, Xiaohui; Chauhan, Ghanshyam S. [Department of Chemical Engineering and Research Institute for Green Energy Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of); Ahn, Jou-Hyeon, E-mail: jhahn@gnu.ac.kr [Department of Chemical Engineering and Research Institute for Green Energy Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of); Department of Materials Engineering and Convergence Technology and RIGET, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of)

2016-09-01

Graphical abstract: Well-ordered nitrogen-doped mesoporous carbon materials were prepared by in-situ polymerization of polyacrylonitrile in SBA-15 template. The composite of sulfur and nitrogen-doped carbon was successfully used as a cathode material for lithium sulfur battery. - Highlights: • N-doped mesoporous carbons were prepared with PAN as carbon source. • Highly ordered pore system facilitates sulfur loading. • Ladder-type carbon matrix provides good structural stability for confining sulfur. • N-doping ensures an improved absorbability of soluble polysulfides. - Abstract: Nitrogen doping in carbon matrix can effectively improve the wettability of electrolyte and increase electric conductivity of carbon by ensuring fast transfer of ions. We synthesized a series of nitrogen-doped mesoporous carbons (CPANs) via in situ polymerization of polyacrylonitrile (PAN) in SBA-15 template followed by carbonization at different temperatures. Carbonization results in the formation of ladder structure which enhances the stability of the matrix. In this study, CPAN-800, carbon matrix synthesized by the carbonization at 800 °C, was found to possess many desirable properties such as high specific surface area and pore volume, moderate nitrogen content, and highly ordered mesoporous structure. Therefore, it was used to prepare S/CPAN-800 composite as cathode material in lithium sulfur (Li-S) batteries. The S/CPAN-800 composite was proved to be an excellent material for Li-S cells which delivered a high initial discharge capacity of 1585 mAh g{sup −1} and enhanced capacity retention of 862 mAh g{sup −1} at 0.1 C after 100 cycles.

Li+-Permeable Film on Lithium Anode for Lithium Sulfur Battery.

Science.gov (United States)

Yang, Yan-Bo; Liu, Yun-Xia; Song, Zhiping; Zhou, Yun-Hong; Zhan, Hui

2017-11-08

Lithium-sulfur (Li-S) battery is an important candidate for next-generation energy storage. However, the reaction between polysulfide and lithium (Li) anode brings poor cycling stability, low Coulombic efficiency, and Li corrosion. Herein, we report a Li protection technology. Li metal was treated in crown ether containing electrolyte, and thus, treated Li was further used as the anode in Li-S cell. Due to the coordination between Li + and crown ether, a Li + -permeable film can be formed on Li, and the film is proved to be able to block the detrimental reaction between Li anode and polysulfide. By using the Li anode pretreated in 2 wt % B15C5-containing electrolyte, Li-S cell exhibits significantly improved cycling stability, such as∼900 mAh g -1 after 100 cycles, and high Coulombic efficiency of>93%. In addition, such effect is also notable when high S loading condition is applied.

Radiolytic degradation of paracetamol in dilute aqueous solution

International Nuclear Information System (INIS)

Szabo, L.; Toth, T.; Homlok, R.; Takacs, E.; Wojnarovits, L.

2011-01-01

Complete text of publication follows. Paracetamol or with name acetaminophen is widely used as analgesic and antipyretic drug. Due to its heavy use it is regularly detected in the surface waters. The degradation of the compound formerly was studied in several advanced oxidation processes (UV/H 2 O 2 , UV/TiO 2 , electrochemical oxidation, ozonation). Here we report on the radiolytic degradation. In the experimental work we combined a wide variety of techniques. For the investigation of the intermediates pulse radiolysis, for end-product experiments (decolouration, mineralization) gamma irradiation were used together with UV-Vis spectroscopy, HPLC separation (with diode array and MS-MS detection), chemical oxygen demand, total organic carbon content and toxicity measurements. · OH radicals are the main oxidative species during irradiation. They add to the aromatic ring producing hydroxycyclohexadienyl type radicals. These radicals either transform to hydroxy-paracetamol stable products in several reaction steps, or after water elimination transform to semi-iminoquinone radical. The reaction of hydroxycyclohexadienyl radicals with O 2 yields peroxi radicals. The latter radicals may eliminate HO 2 · or undergo ring opening and transformation, first to different carboxylic acids, and finally (mineralization) to CO 2 , H 2 O and NH 3 or NO 2 . Paracetamol has a relatively low toxicity. In 10 -3 mol dm -3 DCF solution after irradiation some products (e.g. hydroquinone, acetamide) are more toxic than paracetamol. By increasing the dose the toxicity suddenly decreases. It seems that the toxic products are highly sensitive to irradiation treatment.

Parameters Influencing Sulfur Speciation in Environmental Samples Using Sulfur K-Edge X-Ray Absorption Near-Edge Structure

Directory of Open Access Journals (Sweden)

Siwatt Pongpiachan

2012-01-01

Full Text Available This paper aims to enhance the credibility of applying the sulfur K-edge XANES spectroscopy as an innovative “fingerprint” for characterizing environmental samples. The sensitivities of sulfur K-edge XANES spectra of ten sulfur compound standards detected by two different detectors, namely, Lytle detector (LyD and Germanium detector (GeD, were studied and compared. Further investigation on “self-absorption” effect revealed that the maximum sensitivities of sulfur K-edge XANES spectra were achieved when diluting sulfur compound standards with boron nitride (BN at the mixing ratio of 0.1%. The “particle-size” effect on sulfur K-edge XANES spectrum sensitivities was examined by comparing signal-to-noise ratios of total suspended particles (TSP and particulate matter of less than 10 millionths of a meter (PM10 collected at three major cities of Thailand. The analytical results have demonstrated that the signal-to-noise ratios of sulfur K-edge XANES spectra were positively correlated with sulfate content in aerosols and negatively connected with particle sizes. The combination of hierarchical cluster analysis (HCA and principal component analysis (PCA has proved that sulfur K-edge XANES spectrum can be used to characterize German terrestrial soils and Andaman coastal sediments. In addition, this study highlighted the capability of sulfur K-edge XANES spectra as an innovative “fingerprint” to distinguish tsunami backwash deposits (TBD from typical marine sediments (TMS.

Electrochemical properties of ether-based electrolytes for lithium/sulfur rechargeable batteries

International Nuclear Information System (INIS)

Barchasz, Céline; Leprêtre, Jean-Claude; Patoux, Sébastien; Alloin, Fannie

2013-01-01

Highlights: ► Liquid electrolyte composition for lithium/sulfur secondary batteries. ► Carbonate-based electrolytes prove not to be compatible with the sulfur electrode. ► Poor electrochemical performances related to low polysulfide solubility. ► Increase in the discharge capacity using ether solvents with high solvating ability such as PEGDME. ► Evidence of DIOX polymerization during cycling. -- Abstract: The lithium/sulfur (Li/S) battery is a promising electrochemical system that has a high theoretical capacity of 1675 mAh g −1 . However, the system suffers from several drawbacks: poor active material conductivity, active material dissolution, and use of the highly reactive lithium metal electrode. In this study, we investigated the electrolyte effects on electrochemical performances of the Li/S cell, by acting on the solvent composition. As conventional carbonate-based electrolytes turned out to be unusable in Li/S cells, alternative ether solvents had to be considered. Different kinds of solvent structures were investigated by changing the ether/alkyl moieties ratio to vary the lithium polysulfide solubility. This allowed to point out the importance of the solvent solvation ability on the discharge capacity. As the end of discharge is linked to the positive electrode passivation, an electrolyte having high solvation ability reduces the polysulfide precipitation and delays the positive electrode passivation

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water

International Nuclear Information System (INIS)

Nakajima, Hayato; Imai, Yoshiyuki; Kasahara, Seiji; Kubo, Shinji; Onuki, Kaoru

2007-01-01

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water, which is a unit reaction in the IS process for thermochemical hydrogen production, was studied experimentally at 323 K under iodine saturation. Quasi-equilibrium state was observed in the presence of sulfur dioxide gas at constant pressure. The composition of the poly-hydriodic acid solution formed was discussed assuming an ideal desulfurization by the reverse reaction of the Bunsen reaction. The value of HI/(HI+H 2 O) of the desulfurized solution was large at high sulfur dioxide pressure and reached the maximum of 15.7 ± 0.3 mol%. (author)

The Radiolytic Destruction of Glycine Diluted in H2O and CO2 Ice: Implications for Mars and Other Planetary Environments

Science.gov (United States)

Gerakines, Perry A.; Hudson, R. L.

2013-10-01

Future missions to Mars and other planetary surfaces will probe under the surfaces of these worlds for signs of organic chemistry. In previous studies we have shown that glycine and other amino acids have radiolytic destruction rates that depend on temperature and on dilution within an H2O ice matrix (Gerakines et al., 2012; Gerakines and Hudson 2013). In the new work presented here, we have examined the destruction of glycine diluted in CO2 ice at various concentrations and irradiated with protons at 0.8 MeV, typical of cosmic rays and solar energetic particles. Destruction rates for glycine were measured by infrared spectroscopy in situ, without removing or warming the ice samples. New results on the half life of glycine in solid CO2 will be compared to those found in H2O ice matrices. The survivability of glycine in icy planetary surfaces rich in H2O and CO2 ice will be discussed, and the implications for planetary science missions will be considered. References: Gerakines, P. A., Hudson, R. L., Moore, M. H., and Bell, J-L. (2012). In-situ Measurements of the Radiation Stability of Amino Acids at 15 - 140 K. Icarus, 220, 647-659. Gerakines, P. A. and Hudson, R. L. (2013). Glycine's Radiolytic Destruction in Ices: First in situ Laboratory Measurements for Mars. Astrobiology, 13, 647-655.

Decoupling the Impacts of Heterotrophy and Autotrophy on Sulfuric Acid Speleogenesis

Science.gov (United States)

Jones, A. A.; Bennett, P.

2013-12-01

Within caves such as Movile Caves (Romania), the Frasassi Caves (Italy), and Lower Kane Cave (LKC, Wyoming, USA) the combination of abiotic autoxidation and microbiological oxidation of H2S produces SO42- and H+ that promotes limestone dissolution through sulfuric-acid speleogenesis (SAS). Microbial sulfide oxidation by sulfur-oxidizing bacteria (SOB) has been shown recently to be the dominant process leading to speleogenesis in these caves. However, due to the inherently large diversity of microbial communities within these environments, there are a variety of metabolic pathways that can impact limestone dissolution and carbon cycling to varying degrees. In order to investigate these variations we outfitted a continuous flow bioreactor with a Picarro Wavelength-Scanned Cavity Ring Down Spectrometer (WS-CRDS) that continuously monitored and logged 12CO2 and 13CO2 at ppmv sensitivity and isotope ratios at consumed resulting in lighter CO2 in the headspace. 16S rRNA sequences confirm that heterotrophic sulfur-reducing bacteria dominate the community within this reactor. When both acetate and CO2 were supplied the heterotrophic behavior appeared to dominate the system which resulted in a significant drop (15‰) in δ13C and a correlative drop in limestone dissolution rate. These results suggest that chemoautotrophy increases the rate of SAS and CO2 flux within the cave environment while heterotrophy leads to slower SAS or even calcite precipitation. Furthermore, changes in carbon substrate (CO2 vs. Acetate) or sulfur substrate concentrations caused an immediate microbial response that could be observed in all measured chemical variables.

Flow injection gas chromatography with sulfur chemiluminescence detection for the analysis of total sulfur in complex hydrocarbon matrixes.

Science.gov (United States)

Hua, Yujuan; Hawryluk, Myron; Gras, Ronda; Shearer, Randall; Luong, Jim

2018-01-01

A fast and reliable analytical technique for the determination of total sulfur levels in complex hydrocarbon matrices is introduced. The method employed flow injection technique using a gas chromatograph as a sample introduction device and a gas phase dual-plasma sulfur chemiluminescence detector for sulfur quantification. Using the technique described, total sulfur measurement in challenging hydrocarbon matrices can be achieved in less than 10 s with sample-to-sample time ideal for fast analysis or trace sulfur analysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A primer on sulfur for the planetary geologist

Science.gov (United States)

Theilig, E.

1982-01-01

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

Mercury adsorption properties of sulfur-impregnated adsorbents

Science.gov (United States)

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

Lanthanum Nitrate As Electrolyte Additive To Stabilize the Surface Morphology of Lithium Anode for Lithium-Sulfur Battery.

Science.gov (United States)

Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2016-03-01

Lithium-sulfur (Li-S) battery is regarded as one of the most promising candidates beyond conventional lithium ion batteries. However, the instability of the metallic lithium anode during lithium electrochemical dissolution/deposition is still a major barrier for the practical application of Li-S battery. In this work, lanthanum nitrate, as electrolyte additive, is introduced into Li-S battery to stabilize the surface of lithium anode. By introducing lanthanum nitrate into electrolyte, a composite passivation film of lanthanum/lithium sulfides can be formed on metallic lithium anode, which is beneficial to decrease the reducibility of metallic lithium and slow down the electrochemical dissolution/deposition reaction on lithium anode for stabilizing the surface morphology of metallic Li anode in lithium-sulfur battery. Meanwhile, the cycle stability of the fabricated Li-S cell is improved by introducing lanthanum nitrate into electrolyte. Apparently, lanthanum nitrate is an effective additive for the protection of lithium anode and the cycling stability of Li-S battery.

Deposition and cycling of sulfur controls mercury accumulation in Isle Royale fish

Energy Technology Data Exchange (ETDEWEB)

Paul E. Drevnick; Donald E. Canfield; Patrick R. Gorski (and others) [Miami University, Oxford, OH (United States). Department of Zoology

2007-11-01

Mercury contamination of fish is a global problem. Consumption of contaminated fish is the primary route of methylmercury exposure in humans and is detrimental to health. Newly mandated reductions in anthropogenic mercury emissions aim to reduce atmospheric mercury deposition and thus mercury concentrations in fish. However, factors other than mercury deposition are important for mercury bioaccumulation in fish. In the lakes of Isle Royale, U.S.A., reduced rates of sulfate deposition since the Clean Air Act of 1970 have caused mercury concentrations in fish to decline to levels that are safe for human consumption, even without a discernible decrease in mercury deposition. Therefore, reductions in anthropogenic sulfur emissions may provide a synergistic solution to the mercury problem in sulfate-limited freshwaters. 71 refs., 3 figs., 1 tab.

46 CFR 151.50-21 - Sulfuric acid.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

Applicability test of glass lining material for high-temperature acidic solutions of sulfuric acid in thermochemical water-splitting IS process

International Nuclear Information System (INIS)

Iwatsuki, Jin; Tanaka, Nobuyuki; Terada, Atsuhiko; Onuki, Kaoru; Watanabe, Yutaka

2010-01-01

A key issue for realizing the thermochemical IS process for hydrogen production is the selection of materials for working with high-temperature acidic solutions of sulfuric acid and hydriodic acid. Glass lining material is a promising candidate, which is composed of steel having good strength and glass having good corrosion resistance. Since the applicability of glass lining material depends strongly on the service condition, corrosion tests using glass used in glass lining material and heat cycle tests using glass lining piping were carried out to examine the possibility of using the glass lining material with high-temperature acidic solutions of sulfuric acid. It was confirmed that the glass lining materials exhibited sufficient corrosion resistance and heat resistance in high-temperature sulfuric acid of the IS process. (author)

46 CFR 153.1046 - Sulfuric acid.

Science.gov (United States)

2010-10-01

... 46 Shipping 5 2010-10-01 2010-10-01 false Sulfuric acid. 153.1046 Section 153.1046 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK....1046 Sulfuric acid. No person may liquefy frozen or congealed sulfuric acid other than by external tank...

Sensing sulfur oxides and other sulfur bearing pollutants with solid electrolyte pellets. I. Gas concentration cells